CA2151151A1 - Photodefineable polymers containing perfluorocyclobutane groups - Google Patents

Photodefineable polymers containing perfluorocyclobutane groups

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Publication number
CA2151151A1
CA2151151A1 CA002151151A CA2151151A CA2151151A1 CA 2151151 A1 CA2151151 A1 CA 2151151A1 CA 002151151 A CA002151151 A CA 002151151A CA 2151151 A CA2151151 A CA 2151151A CA 2151151 A1 CA2151151 A1 CA 2151151A1
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CA
Canada
Prior art keywords
trifluoroethenyloxyphenyl
bis
beta
acetophenone
trifluoroethenyloxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002151151A
Other languages
French (fr)
Inventor
David A. Babb
W. Frank Richey
Katherine S. Clement
Eric S. Moyer
Marius W. Sorenson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2151151A1 publication Critical patent/CA2151151A1/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
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    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
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    • C07C43/00—Ethers; Compounds having groups, groups or groups
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
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    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
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    • C07C50/00—Quinones
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    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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    • C07C59/40—Unsaturated compounds
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    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • C07C65/28—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups having unsaturation outside the aromatic rings
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    • C07—ORGANIC CHEMISTRY
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    • C07C65/40—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups containing singly bound oxygen-containing groups
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
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    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Abstract

A polymer has at least one photoactive site and more than one perfluorocyclobutane group. New monomers containing photoactive sites or photoactive precursors and at least one perfluorovinyl group are useful for making such polymers. Processes of making such polymers and the monomers from which they are made are disclosed. The polymers are useful in coatings, in coating, photoresists, and other photoactive applications.

Description

~WO 94/15t58 2 ~ 5 ~ PCT/US93/11562 PHOTODEFINABLE POLYMERS CONTAINING PERFLUOROCYCLOBUTANE GROUPS

This invention relates to photoimageable polymers, particularly those polymers having perfluorocyclobutane groups.
,.
Photoimageable polymers are widely used, especially in the electronics industry to apply coatings of polymer to exact portions of an electronic device, often such that other materials, for instance metals can be applied in regions not coated with polymer. There are a number of ways of achieving the desired results, conveniently classified into positive 10 photoresists, in which the area exposed to light is removed, and negative photoresists, in which the area exposed to light is insolubilized and remains after the unexposed area is removed.

Polyimide negative photoresists are widely used in electronics. Because most polyimides are nearly insoluble in common organic solvents, a soluble precursor is generally used. The precursor has a photosensitive group such as a methacrylate ester group. The photosensitive group results in crosslinking of the precursors on exposure to light of a certain wavelength, such that unexposed precursor can be removed by solvent washing. Then the remaining precursor is converted to polyimide by exposure to heat of 400C. Exposure to such heat results in loss of the photosensitive groups and water. Loss of such materials requires 20 removal of them and often results in bubbles and shri nkage of from 15 to 50 percent.
Photodefinable polyimides that are not subjected to a high temperaure post-cure contain unreacted polyamic acid groups that contri bute to i ncreases in the dielectric constant and water absorption of the polymer. Such systems are described in references such as Rohde et al "RecentAdvancesinPhotoimageablePolyimides,"SPlEVol.539AdvancesinResistTechnology25 and Processing ll (1985).

Those skilled in the art recognize that polyimides, though widely used have various disadvantages. For instance, D. Makino has stated, Though many kinds of photosensitive polyimides, including positive working or preimidized, have been proposed, their processing latitudes are narrow and theirproperties are sti ll i nferior to thermal cure polyimides, and their application has been limited to a small portion of microelectronics.
"Recent Progess of the Application of Polyimides to Microelectronics, Proceedings of the American Chemical Society Division of Polymeric Materials: Science and Engineering, vol. 66, 35 April 1992, p.233.
Furthermore, when the optical density of the photosensitive material is high in the region of excitation and does not show a hypsochromic shift when irradiated, then most of the photochemistry will occur on the surface. Light intensity will be significantly attenuated 40,23~ 21511~1 and thus the level of crosslinking will be decreased as a function of depth into the photosensitive layer. This results in undercutting of pattern features and creates problems in line width control and integrated circuit fabrication.

A number of other polymers have been suggested for use as photoimageable polymers; however, they have not offered properties suitable for use in electronics. For instance, certain photoimageable polyesters disclosed by J. G. Jegal, L. H. Lin and A. Blumstein, Polymer Preprints, Vol. 32, No.3, August 1991, pp.205-206, were formed by reaction of 4,4'-Dihydroxy-a-methylstilbene with various dicarboxylic acids, and subsequently crossliriked via 10 irradiation with UV light at 254 nm. The resulting polyesters have not been used in thin film dielectric or microelectronic applications because polyesters in general exhibit relatively higher water absorption and dielectric values than polymers currently used in these applications.

Although notteaching photoimaging,WO 91/18859 disclosessome compounds 15 havi ng perfl uorovi nyl grou ps and rad i cal Iy i niti ated polymers thereof The com pou nds i ncl ude 4,7-dioxa-5-trifluoromethyl-2,2,3,3,5,6,6,8,9,9-decafluoronon-8-enyl methacrylate (Example 13) which is polymerized using benzoyl peroxide radical initiator (Example 15). The specification discloses that the monomers contain "both an acrylic, styryl, acetylenic, or olefinic functionality as well as a trifluorovinyl ether both of which may polymerize in free radical 20 polymerizations, crosslinked polymers may result." Those skilled in the art recognize that radically polymerized perfluorovinyl groups results in linear polymers rather than perfluorocyclobutane groups containing polymers. The document states methacrylate groups and the like can result in crosslinking of these linear polymers during the free radical polymeri zation.
It would be desi rable to have a photoimageable polymer which does not lose water or other materials in its formation or insolubilization, and therefore has less resulting shrinkage, which does not require heating to 300 or 400C, shows a hypsochromic or bathochromic shift (that is a shift of the absorption maxi umum to shorter or longer 30 wavelengths respectively) when irradiated and which has properties such as low dielectric constant, low dissipation factor, low moisture absorbance, low ionic mobility or ionic transport properties, optical clarity (to visible light) good planarizability, good compatibility of the prepolymer with a wide variety of organic solvents (such as ethers, ketones, aromatics, that is, compounds containing a benzene ring, either substituted or unsubstituted, including fused 35 ring systems such as naphthalene, as is described by Andrew Streitwieser, Jr. and Clayton Heathcock in Introduction to Organic Chemistry, Macmillan Publishing Co., Inc.,1976, p.35 and p. 577, polar aprotic solvents to facilitate application methods such as spin coating, spray coating, dip coating, roll coating, pad printing and the like, but after thermal curing and/or no - - AMENDED SHEE~
IPE~/EP

40,23~ ~ -2 ~
- curing yields a finished polymer with good solvent resistance and good resistance to chemical etchants such as acids and bases.
-In one aspect the invention is a polymer having at least one photoactive site and 5 more than one perfluorocyclobutane group. The invention also includes monomers containingphotoactive sites or photoactive precursors for making such polymers.
In another aspect, the invention includes the uses of such polymers in coatings and in negative photoresists.

In yet another aspect the invention includes processes of making such polymers and the monomers from which they are made.

-2a-AMENDE~3~HEET
IPE~EP

~)WO 94/15258 215 1151 PCT/US93/11562 Polymers of the invention have at least one photoactive site, that is a grouping of atoms capable of absorbing energy from incident photonic radiation such that the polymer becomes less soluble or dispersible in at least one solvent or dispersing medium than it was 5 before exposure to the incident photonic radiation. Compounds of the invention also have such photoactive sites or photoactive precursors; in which case, a polymer made at least partially from such compounds containing photoactive sites becomes less soluble or dispersible upon photonic irradiation. Decreasing solubility or dispersibility is also evidenced by differential solubility between exposed and unexposed polymer, for example in a layer, a first 10 portion of which is exposed to incident photonic radiation and second portion of which remains unexposed.

The term "incident photonic radiation" or "actinic radiation" refers to energy in the form of electromagnetic waves of a wavelength capable of exciting bonding or non-15 bonding electrons in certain functional groups refer. ed to herei n as photoactive sites or theactive portion of such sites to produce a chemical reaction.

The term polymer is used herein to include any compound or compounds comprised of two or more like or di rreren~ monomer units. Thus the term polymer includes 20 prepolymers, dimers, trimers, tetramers and other oligomers.

Determining reduced solubility or dispersibility is within the skill in the art. For instance, a solid, gel, or organic phase separates from a liquid medium; more solvent is required to dissolve or disperse the same weight of polymer; latex particles coalesce; an z5 emulsion separates or requires additional stirring. The polymer is optionally dissolved or dispersed in any medium effective therefor. For instance, polymers of the invention are advantageously dissolved in solvents such as ethers, ketones, aromatic hydrocarbons, polar aprotic solvents, halocarbon solvents and the like. Among these solvents, mesitylene, diglyme, n-methylpyrrolidinone, and dimethylformamide are advantageously used in electronic 30 applications such as depositing a layer of polymer on a substrate such as a metal (for example copper, aluminum, indium, tin, silver, gold, platinum, cadminum and alloys thereofl, silicon, silicon oxide, gallium arsenide, germanium arsenide, barrium ferrite, alloy of chromium and at least one other metal, ceramitized glass, indium tin oxide, glass, quartz, a like, similar, or different polymer (particularly epoxy resins, polycarbonates, polyesters, polyimides, 35 polystyrenes (particularly syndiotactic), benzocyclobutenes, acrylics, other perfluorocyclobutane-containing polymers having differenct aryl groups and combinations thereof), graphite, combinations of the.above and the like. Similarly, the polymer may be dispersed in an aqueous and/or organic medium particularly in an aqueous medium. For WO 94/15258 2~ 51151 PCTIUS93111562 ~

instance, in the form of a latex or emulsion. Reduced solubility or dispersibility is believed to be associated with increased molecular weight of the polymer, for instance from increasing chai n length, or preferably crosslinking. Preferably, the decreased solubility or dispersibility is a result of chemical changes (chemical reactions), which more preferably result in the formation 5 of covalent bonds. Formation of coatings and other layers of this type of polymer is advantageously as disclosed in U.S. Patent 5,246,782 (Kennedy et al.).

Polymers of the invention additionally have more than one perfluorocyclobutane group. Methods of making polymers having perfluorocyclobutane groups are disclosed in U.S.
10 Patents5,021,602; 5,023,386; 5,037,917, 5,037,918and 5,037,919. U.S. Patent5,021,602 (Clement et al.) discloses compounds of the formula:

fF2--TF2 Gn R X CF--CF X' R'--(-G' )n' (hereinafter Formula 1) wherein R and R' independently represent optionally inertly substituted hydrocarbyl groups; X
and X' represent any molecular structures which link R and R' with the perfluorocyclobutane ring; n and n' are the number of G and G' groups, respectively; and G and G' independently represent any reactive functional groups or any groups convertible into reactive functional 25 group and methods for making such compounds and forming polymers Lhereflo,l,.
U.S. Patent 5,023,380 (Babb et al) discloses compounds of the formula:

CF2 = CF-X-R-(X-CF = CF2)m (hereinafter Formula ll) wherein R represents an unsubstituted or inertly substituted hydrocarbyl group; each X is 35 independently selected from the group consisting of groups having at least one non-carbon ~WO 94/15258 21~ 1 PCT/US93/11562 atom between R and -CF = CF2; and m is an integer of from 1 to 3 and methods for making such compounds and forming polymers therefrom U.S. Patent 5,037,919 (Clement, et al.) discloses compounds of the formula (G)n-R-(X-CF = CF2)m (hereinafter Formula lll) 10 wherein R represents an optionally substituted hydrocarbyl group, X represents any group which links R and a trifluorovinyl (perfluorovinyl, trifluoroethenyl, or perfluoroethenyl) group;
n is the number of G groups, m is the number of (XCF = CF2) groups; and G represents any reactive functional group or a group convertible into a reactive functional group and methods for making such compounds and forming polymers therefrom.

These patents and U.S. Patent 5,037,917 (Babb et al.) and 5,037,918 (Babb) all of which are incor~.o-dled herein by reference in their entireties disclose methods of forming polymers having perfluorocyclobutane rings by heating monomers having trifluorovinyl groups, by reacting compounds having perfluorocyclobutane groups such as compounds of 20 Formula I with di- or polyfunctional compounds reactive with the groups designated G andlor G'; and by reacting compounds having a reactive group (G) and at least one trifluorovinyl group such as compounds of Formula lll with oligomers or polymerizable compounds followed by polymerization.

The disclosed methods are applicable for forming polymers of the invention. In the practice of the present invention, however; at least a portion of the compounds used i n forming the polymers have photoactive sites. In the practice of the invention R and R' preferably have from 6 to 100 carbon atoms, more preferably from 6 to 50 carbon atoms, most preferably from 6 to 25 carbon atoms. For instance, the molecular fragments designated R and 30 R' in Formulas l-lll optionally have photoactive sites. Photoactive sites include those having at leasttwo conjugated multiple bonds (wherein the term "multiple bonds" is used to include double, triple or aromatic bonds between two carbon atoms, between a carbon atom and a heteroatom such as an oxygen, nitrogen, sulfur, phosphorus or between two or more heteroatoms such as between sulfur and oxygen, phosphorus and oxygen or sulfur, nitrogen 35 and oxygen, or nitrogen and nitrogen such that incident photonic radiation is absorbed by the molecule.

Exemplary photoactive sites include molecular groups such as:

WO 94115258 21511~1 PCTIUS93/11562 ~

R"

~' (stilbenes) R"
(styrenes) ~} ~/ (1 -aryl propenyl) o (bischalcone, o, ~}~/ y~S substituted) (chalcones including hydroxy chalcones) ~3\\ 0 koumarins) ~/~0 (benzylidenecyclohexanones) (1,5-diaryl-1,4-pentadiene-3-~ ~ 'a/ ~ /~ ones) O (2,6-bis(benzylidene)cyclohexanones) Y'~

40,23~ 21S1151 ~ ` ~

~11~ CH2 O I (for example acrylates, methacrylates, such RN as:
O O
~ o C-f = CH2 CF2=CF ~~ ~',1 R
R=H,CH3 O
¢\(maleimides) ~3 (naphthoquinones) \///\~\~\ (polyacetylenes) (cinnamic acids, when y = OH;
~P J cinnamate esters when y = O-R", /~ R" = hydrocarbyl; or cinnamaldehydes when y = H) O O
bis(benzoyl) \ ~// ~ ~ivinylbenzene, for ~ J \ / ~ ~ example with o, m, or p `'\ substituted mi~dre ring~

AMENDEb SHEET
IPE~IEP

4~),23~
. -- 2~ S ~ ' .

~ O (2-cinnamvlidene and higher wherein n is an integer of from 1 to 11.

n /~/3n (1,9-bis(aryl)-1,3-6,8-nonatetraene-5-one and higher polyaryl alkyl polyenones) where each n is independently an integer O to 11.

~n O (/\~
(2,6-bis(cinnamylidene and higher) cyclohexanones) where each n is independently an integer of from O to 11.
(C~Oy//\~
~ n (polyenone cycloalkylenes) where each n is independently an integer of from 1 to 12 and with optional addition unsaturation in the cycloalkylring O O ~,/
CH2 = CH-C-O --CH2-CH2-C O ~[
O (1-acrylato-2-benzoyloxyethanes) ~ (benzophenones) in each case wherein each R" is H or a hydrocarbyl group which is optionally inertly substituted, preferably H or a hydrocarbyl group of from 1 to 12 carbon atoms, more preferably H or an alkyl hydrocarbyl group of from 1 to 6 carbon atoms; and Y stands for a bond to any other atom or group of atoms (for example H, OH, OR, R", SH, SR", NHR~, and the like).

AME~ED SHFET
IPE~/EP

~ WO 94/15258 2 1~1 1 S 1 PCT/US93/11562 Any photoactive site or compound containing such a site is optionally inertly substituted, that is substituted with any group which does not undesirably affect the function of the photoactive site.

The photoactive site (represented hereinafter as "PAS") is optionally any part of a compound and optionally becomes part of a polymer backbone or side chain. For instance, when the photoactive site corresponds to at least a portion of R in Formula ll, a monomer is represented:

CF2 = CF-X-PAS-(X-CF = CF2)q (Formula IV) wherein X is as defined for Formula l; PAS is a photoactive site or photoactive precursor as defined previously; and q is an integer of from 0 to 4. When such a compound is polymerized by formation of perfluorocyclobutane groups from the trifluorovinyl groups, the photoactive sites are in the polymer backbone. Alternatively, the photoactive sites are in side chains such as when a compound such as CF2 = CF2-X-R"--(X-CF = CF2)q (PAS)r (Formula V) wherein X is as defined for Formula l; RN is as defined for R and R' of Formula I except that it is substituted with PAS which is as defined for Formula IV; q is an integer of from 0 to 4; and r is 30 an integer from 1 to 4 is similarly polymerized. Compounds of Formula IV or V are novel compounds of the invention.

Alternatively, photoactive sites are formed on already formed polymers having plural perfluorocyclobutane groups, such as by reaction of compounds having photoactive sites - 35 or photoactive precursors that are subsequently converted to photoactive sites with any polymer formed by a process taught in any of the already cited patents disclosing perfluorocyclobutane containing polymers.

WO 94/1~;258 PCT/US93111562 2~

When the polymer of the invention is formed at least partially from compounds corresponding to Formulas 1, ll or lll wherein R and/or R' contain at least one photoactive site (as in Formula IV or V), the compounds are suitably formed by methods disclosed in the cited references from starting materials having the desired photoactive site(s) or from starting materials having precursors for the photoactive sites. When zinc is used to form tri fl uorovi nyl groups from bromotetrafluoroethyl groups, it is preferable to use precursors for photoactive sites containing carbon-carbon double bonds conjugated with aromatic rings and carbon-oxygen double bonds because such double bonds are often attacked by zinc under reaction conditions. For instance, para-perfluoroethenyloxybenzaldehyde can be formed by reaction of zinc with para-bromotetrafluoroethoxybenzaldehyde; then for instance, the para-perfluoroethenyloxybenzaldehyde can be condensed in an aldol condensation with a ketone, either two moles of the aldehyde with a ketone like acetone or one mole of the aldehyde with a trifluoroethenyl compound containing a ketone group e.q. para-perfluoroethenyloxyacetophenone to form } ocF = CF2 (1 ,5-(4-trifluoroethenyl-CF - CF oxyphenyl)-1,4-2- or pentadiene-3-one) o Il CF2=CF--o--(~ \=
\~3 0--CF = CF2 (4,4'-bis(trifluoroethenyloxy)chalcone) respectively.

WO 94/15258 . 21~ 1 PCT/US93/11562 A process for making such compounds is then:

(a) forming a salt having an anion corresponding to a compound (acid) of Formula Vl:

HX-PAP-(XH)q Vl wherein X and q are defined as for Formula IV; and PAP and PAP' are photoactive precursors (any group(s) which can react to form a photoactive group), where PAPrepresents a group which can be modified to become photoactive (either a single group or a group illustrated by the benzaldehyde and acetophenone groups in the above illustration which can react, optionally with other reactants, to become a photoactive site);

(b) reactingthesaltwitha 1,2-dihalo-1,1,2,2-tetrafluoroethanewherein the halo groups are iodine, bromine, chlorine or mixtures thereof, at least one halo group being a bromi ne or an iodine atom, to form a compound of Formula Vll;

Z-cF2cF2-x-pAp~x-cF2cF2-z)q Vll wherein PAP, X and q are defined as for Formula Vl; and each Z is independently iodine or bromine;

(c) eliminating the halogen atorns represented by Z to form the trifluorovinyl compound(s); and CF2 = CF-X-PAP-(X-CF = CF2)q Vlll wherein X, PAP, and q are as defined for Formula Vl.

(d) modifying the photoactive precursors (PAP) to form photoactive sites (PAS) to form compounds represented by Formula IV.

WO 94/15258 215 115 ~ PCT/US93/11562 CF2 = CF--X-PAS-(X-CF = CF2)q Step d is suitably before or after step(s) b and/or c Those skilled in the art are able 5 to ascertain suitable order of steps from chemical sensitivity and reactivities of groups present with reactants used in the steps.

Itshould be noted that groups represented by PAP, and PAS optionally include groups which are not photoactive along with the photoactive groups. For instance the 10 molecular structure between the X's i n Formula IV is optional Iy not itsel f total Iy photoactive but has, for instance a pendant photoactive group or a reactive group to which a photoactive site may be attached.

The step of modifying the photoactive precursor(s) optionally incl udes reactions which combi ne like or different precursors to form a photoactive site as ill ustrated by the condensation of aldehydes and ketones already discussed. Alternatively, one site in a molecule is chemically modified. For instance, a photoactive site of unsaturation (carbon-carbon double bond) may be generated from a non-photoactive precursor by the acid catalyzed C~dehydration of an alkyl alcohol. Alternatively, a photoactive site may be modified via reactive 20 substitution to change the quantum yield or absorption maximum of the chromophore. For instance, the compound 4-(trifluoroethenyloxy)-~-(4-nitrobenzylidene) acetophenone, formed by the Aldol condensation of 4-(trifluoroethenyloxy)acetophenone with 4-nitrobenzaldehyde, is suitably catalytically hydrogenated using palladium on carbon to reduce the nitro group to an amine, thereby changing the absorption spectrum of the chromophore. The resulting 25 amine is optionally subsequently reacted with iodomethane to form the dimethylamine compound to further change the absorption characteristics of the chromophore.

Steps (a) through (c) of the process are advantageously carried out as described in U.S. Patent 5,023,380.

Compounds of Formula IV where q is at least 1 are homo or copolymerized to form polymers having photoactive sites and perfluorocyclobutane groups In a variation on this process, a compound of Formula Vl where q is 0 is used to35 form a compound of Formula IV where q is 0 and wherein the molecular structure represented by PAP includes a group reactive with at least one compound to become a photoactive site.
The compound CF2 = CF-X-PAP has one trifluorovinyl group which is reacted into perfluorocyclobutane-containing polymers (by processes such as those disclosed in U.S. Patents WO 94/15258 2 ~ 1 PCT/US93/11562 5,037,917and 5,037,918),whichpolymersthenhavesidechainscorrespondingtomolecular structures represented by PAP. Exemplary of compounds of Formula Vl where q is 0 are p-perfluoroethenyloxyacetophenones (optionally substituted for instance with cyano, nitro, sulfonate ester, sulfonamide, trifluoromethyl, carboxylic ester, aldehyde, ketone, or halo 5 (preferably fluoro, bromo or chloro) groups in the ortho and/or meta positions) which are reactive, for instance under acid conditions (including hydrochloric acid in ethanol) with optionally substituted benzaldehydes. Such electron donating substituents as methoxy, ethoxy, or dimethylamino groups para to an aldehyde or propenaldehyde group act to move the wavelength of light absorbed by the resulting chalcone group from 300-320 nm to 340-420 10 nm wavelengths, for i nstance 414 nm in the case of the p-dimethylami no substituted aldehyde.
Electron releasing groups such as secondary or tertiary amines, hydroxy groups, ethers, alkoxy groups preferably of from one to 12 carbon atoms or alkyl groups preferably having from 1 to 12 carbon atoms, on the benzaldehyde act to further i nduce charge separation and cause the resulting compound to absorb light at longer wavelengths. Benzaldehyde is illustrative of 15 aldehydes useful in the process; such aldehydes include unsubstituted or inertly substituted, cinnamaldehydes, acroleins, furfural, heptadienals (and other polyene aldehydes), retinals, phenyl-2,4-pentadienal terepl,lhaldehyde, naphthalenedicarboxaldehyde, furylpolyene aldehydes and combinations thereof.

In yet another variation of the process, a compound of Formula Vl where q is 0 is reacted with a compound having at least two, preferably at least three, trifluorovinyl groups such that a perfluorocyclobutane group is formed in a compound having at least one, preferably at least two, more preferably two, trifluorovinyl groups for subsequent polymer formation. Such compounds include reaction products of 1,1,1-tris (4'-25 trifluoroethenyloxyphenyl) ethane with compounds of Formula IV such as 1-acroyloxy-2-(4-trifluoroethenyloxy)-benzoyloxyethane and 1-methacroyloxy-2-(4-trifluoroethenyloxy)-benzoyloxyethane and the like.

Similarly, compounds of Formula lll are advantageously formed by the process 30 disclosed i n U .S. Patent 5,037,919 wherein R contains a photoactive site or by a modification of that process wherein steps a' through c' are advantageously carried out as described therein and step d' involves formation of the photoactive site:

(a') preparing a 2-halotetrafluoro compound of the Formula IX

(Q-CF2-CF2--X-)m-PAp-(G )n or at least two compounds, at least one of each of Formula X and Xl WO 94/15258 21511 5 ~ PCT/US93/11562 (Q-CF2-CF2-X)m-PAP' X

and pAp-(G )n Xl wherein X, PAP, m and n are as defined for Formulas I and ll, and Q is bromine, chlorine or iodine: and G" is a functional group G, as previously defined, or a functional group suitable for 10 conversion into G: and each PAP' is independently the same or different photoactive precursor which react with one another to form a photoactive site;

(b') chemically modifying group G" to produce functional group G;

(c') dehalogenating the 2-halotetrafiuoro compound to form the corresponding trifluorovinyl compound; and (d') modifying the photoactive precursors to form photoactive sites thus forming novel compounds of the invention represented by Formula Xll:

(G)n~PAS~(X~CE=CF2)m Step d' is carried out as step d in the process for making compounds of Formula Vlll and optionally takes place between steps a' and b', b' and c', after c', or simultaneously with steps b' 25 or c', but preferably after step c'. Also, step b' may take place before or after step c' or step d':
For instance; the hydroxy group of ~(4-hydroxybenzylidene)-4-trifluoro-ethenyloxyacetophenone may be converted to an acetate by treatment with acetyl chloride i n tetrahydrofuran.

Exemplary of compounds of Formula Xll are ~-(4-hydroxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-Acetylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-Acetyloxybenzylidene)-4-(trifluoroethenyloxy) acetophenone, ~-(4-aminobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ,~-(4-carboxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-isocyanatobenzylidene)-4-35 (trifluoroethenyloxy)acetophenone, ~-(4-chlorocarboxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-carboxymethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-carboxyethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, 4-hydroxy-~-(4-~ WO 94/15258 2 1~11 51 PCTtUS93/11562 trifluoroethenyloxybenzylidene)acetophenone, 4-amino-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxy-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-chlorocarboxy-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-isocyanato-,~-(4-5 trifluoroethenyioxybenzylidene)acetophenone, 4-carboxymethyl-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxyethyl-13-4-(trifluoroethenyloxybenzylidene)acetophenone, 1-(4-hydroxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-hydroxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-l-propene, 1-(4-aminophenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-aminophenyl)-l-l O (4-trifluoroethenyloxyphenyl)- l -propene, l -(4-carboxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-carboxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-l-propene, 1-(4-chlorocarboxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-chlorocarboxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-isocyanatophenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-isocyanatophenyl)-1-(4-trifluoroethenyloxyphenyl)-1 -propene, 1-(4-carboxymethylphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-carboxymethylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 4-hydroxy-4'-trifluoroethenyloxystilbene, 4-aminophenyl-4'-trifluoroethenyloxystilbene, 4-carboxyphenyl-4'-trifluoroethenyloxystilbene, 4-isocyanato-4'-trifluoroethenyloxystilbene, 4-carboxymethyl-4'-trifluoroethenyloxystilbene, 20 5-hydroxy-8-trifluoroethenyloxynaphthoquinone, 1-(4-hydroxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-aminophenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-carboxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-carboxymethylphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-isocyanatophenyl)-5-(4-25 trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 5-hydroxy-8-trifluoroethenyloxycoumarin, 8-hydroxy-5-trifluoroethenyloxycoumarin, S-amino-8-trifluoroethenyloxycoumarin, 8-amino-5-trifluoroethenyloxycoumarin, 5-isocyanato-8-trifluoroethenyloxycoumarin, 8-isocyanato-5-trifluoroethenyloxycoumarin, 2-(4-hydroxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-hydroxybenzylidene)-6-(4-30 trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-aminobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-aminobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-carboxymethylbenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-carboxymethylbenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-isocyanatobenzylidene)-6-(4-35 trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-isocyanatobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-chlorocarboxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-chlorocarboxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone WO 94/15258 PCT/US93/11562 ~
21~i~5~ --Compounds of Formula Xll are optionally dimerized as discussed in U.S. Patent S,02 1,602 to form compounds of Formula 1 Polymers are formed as described in U.S. Patents 5,037,919; 5,021,602; 5,037,917and 5,037,918,whichareincorporated byreferenceintheir 5 entirities Alternatively, compounds of Formula Xll wherein X is oxygen, PAS =
ArC(O)CH = CH-Ar wherein Ar is preferably of from 6 to S0 carbon atoms, and G is a reactive site such as hydroxyl, amine, carboxylic acid, carboxylic acid halide, cyanate, or isocyanate are 10 reacted (through the group represented by G) with such compounds as alkyl diamines, diols, dicarboxylic acids, dicarboxylic acld halides, phosgene, etc. to form polyesters, polyethers, polycarbonates, polyamides, polyurethanes, end capped with trifluoroethenyloxy groups.
These compounds are then heated to cause dimerization of the trifluoroethenyloxy end groups, thereby creating perfluorocyclobutane ring containing polymers with photoactive sites included in the polymer backbone. These polymers are suitably dissolved and applied as coatings by any means within the skill in the art such as spin-coating, roll coating, spray coating, pad printing and the like. The coating is then exposed to light of the appropriate wavelength to crosslink the polymer. This photocuring process crosslinks the exposed polymer and thereby imparts increased solvent resistance, increased mechanical properties, and modified optical 20 properties with respect to the unexposed polymer or prepolymer.

Alternative methods for preparing polymers of the invention include a process ofpreparing a compound of Formula Xlll:

PAS-R(-X-CF = CF2)t wherein PAS, R, and X are as defined for Formula IV and t is an integer of from 1 to 4 by (a") forming the salt of an anion correspondi ng to a compound (acid) of formula XIV:

H-x-fi-(x-H)t ~AP

35 wherein X, R, and t are as defined for Formula Xlll and PAP is as defined for Formula Vl;

~ WO 94/15258 2 t S 1 1 ~1 PCT/US93/11562 (b") reacting the salt with a 1,2-dihalo-1,1 ,2,2-tetrafluoroethane wherein the halo groups are iodine, bromine, chlorine or mixtures thereof, at least one halo group being a bromine or an iodine atom, to form a compound of Formula XV:

5 Z-cF2-cF2-R-(x-cF2-cF2-z) PAP

10 wherein R, X, PAP and t are as defined for Formula XIV are as each Z is independently bromine or iodine (c") eliminating the halogen atoms represented by Z to form the trifluorovinyl compound; and 5 (d ") modifying the photoactive precursor to form a photoactive site, forming compounds represented by Formula Xlll.

PAs-R-(x-cF = CF2)t Step (dN) is carried out as steps (d) and (d') and optionally occurs before step a", between steps a~ and b" or b~ and CN, simultaneous with steps a~, b", or c" or, preferably,after step c". For instance, the acetyl group of 1-(4-acetophenyl)-1,1-bis(4-trifluoroethenyloxy)phenyl ethane is optionally combined via Aldol condensation with benzaldehyde or variously substituted benzaldehydes to form 1-(4-(~-25 benzylidene)acetophenyl)-1,1-bis(4-trifluoroethenyloxy phenyl)ethane.

In an important embodiment of the process of the invention PAP is a molecular structure having a group reactive with at least one compound having or suitable for forming a photoactive site (a photoactive site-containing or photoactive precursor-containing 30 compound). In this embodiment, the step of reacting with such a compound is represented as at least a part of step d" . When there are steps of reacting such a PAP with at least one such compound and of converting a resulting PAP into a PAS, the reacting and converting steps are optionally consective or separated by one or more of steps b" and c" .

Preferred species formed by such a process are compounds of the formula XVI:

4(~,23-- 21 5~

S CF2 = CF{~{~}C{~}o~F = CF2 ~, PAS

which compounds are novel . Wherein R is an unsubstituted or i nertly substituted hydrocarbyl group preferably of from 1 to 10, more preferably of from 1 to 4 carbon atoms. R is optionalIy and advantageously substituted with functional groups which provide additional desirable 15 properties to the polymer, for example a photosensitizing group such as those within the skill intheart.

Compounds exemplary of Formula Xlll include 1 -(4-acryloxyphenyl)-1,1 -bis(4-trifluoroethenyloxyphenyl)ethane, 1-(4-methacryloxyphenyl)-1,1-bis(4-20 trifluoroethenyloxyphenyl)ethane, 1-(4-acrylphenyl)-1, 1 -bis(4-trifluoroethenyloxyphenyl)ethane, 1-(4-methacrylphenyl)- 1,1 bis(4-trifluoroethenyloxyphenyl)ethane, 4-(1,1-bis(4-trifluoro~t~r,y~ henyl)ethyl)-~-(benzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-dimethylaminobenzylidene) acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-25 methoxybenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-trifluoromethylbenzylidene) acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-carboxymethylbenzylidene) acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-nitrobenzylidene)acetophenone, 4-(1,1-bis(4-trifll~oroethenyloxyphenyl)ethyl)-~-(4-chlorobenzylidene)acetophenone, 4-(1,1-bis(4-tl'ifluoroethenyloxyphenyl)ethyl)-~-(4-30 fluorobenzylidene)acetophenone, 4-(l,l-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-acetylbenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4-cyanobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)styrene, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-N-phenyl maleimide, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-S-phenyl-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-35 trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(dimethylamino)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-methoxyphenyl)- 1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(carboxymethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-AMENDED SHEET
IPE~/EP

2~

(carboxyethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(trifluoromethyl)phenyl)-1 ,4-pentadiene-3-one, 1-(4-(1 ,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-nitrophenyl)-1 ,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-chlorophenyl)-1,4-- 5 pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-fiuorophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-acetophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-cyanophenyl)-1,4-pentadiene-3-one, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl acetylene, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl buta-1,3-diyne, 4-(1,1-bis(4-10 trifluoroethenyloxyphenyl)ethyl)phenyl hexa-1,3,5-triyne, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl octa-1,3,5,7-tetrayne, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl-1,3,5,7,9-pentayne, 6-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)naphthoquinone, 6-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)coumarin, 7-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)coumarin, 2-(4-(1,1-bis(trifluoroethenyloxyphenyl)ethyl)benzylidene)cyclohexanone, 2-(4-(4-(1,1-bis(trifluoroethenyloxyphenyl)ethyl)phenoxy)benzylidene)cyclohexanone, 1-acroyloxy-2-(4-trifluoroethenyloxy)benzoyloxyethane, 1-methacroyloxy-2-(4-trifluoroethenyloxy)benzoyloxyethane, N-(4-trifluoroethenyloxyphenyl)acrylamide, N-(4-20 trifluoroethenyloxyphenyl)methacrylamide, 4-trifluoroethenyloxyphenyl acrylate, 4-trifluoroethenyloxyphenyl methacrylate, N-(4-trifluoroethenyloxyphenyl)maleimide, N-(4-trifluoroethenyloxybenzoyl)maleimide, ~-(4-methoxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-dimethylaminobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-carboxymethylbenzylidene)-4-25 (trifluoroethenyloxy)acetophenone, ~-(4-carboxyethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-nitrobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-chlorobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-fluorobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-acetylbenzylidene)-4-30 (trifluoroethenyloxy)acetophenone, i~-(4-cyanobenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(3-trifluoromethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-trifluoromethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, ~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-methoxy-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-dimethylamino-~-(4-35 trifluoroethenyloxybenzylidene)acetophenone, 4-carboxymethyl-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxyethyl-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-chloro-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-nitro-~-(4-WO 94/15258 2 ~ 1 PCT/US93111562 trifluoroethenyloxybenzylidene)acetophenone, 4-fluoro-13-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-acetyl-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-cyano-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-trifluoromethyl-~-(4-5 trifluoroethenyloxybenzylidene)acetophenone, 3-trifluoromethyl-~-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-trifluoroethenyloxycinnamaldehyde, 4-trifluoroethenyloxycinnamic acid, 4-trifluoroethenyloxycinnamic acid, methyl ester, 4-trifluoroethenyloxycinnamic acid, ethyl ester, 4-trifluoroethenyloxycinnamic acid, isopropyl ester, 4-trifluoroethenyloxycinnamic acid, phenyl ester, 1-(4-trifluoroethenyloxyphenyl)-l O propen-1 -one, 1 -(4-trifluoroethenyloxyphenyl)-1 -buten-3-one, S-(trifluoroethenyloxy)naphthoquinone, 6-(trifluoroethenyloxy)naphthoquinone, 5-(4-(trifluoroethenyloxy)benzoyloxy)naphthoquinone, 6-(4-(trifluoroethenyloxy)benzoyloxy)naphthoquinone, 5-(trifluoroethenyloxy)coumarin, 6-(trifluoroethenyloxy)coumarin, 7-15 (trifluoroethenyloxy)coumarin, 8-(trifluoroethenyloxy)coumarin, 5-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 6-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 7-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 8-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 2-(4-trifluoroethenyoxylbenzylidene)cyclohexanone, 1-(4-trifluoroethenyloxyphenyl)-5-phenyl-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(dimethylamino)phenyl)-20 1 ,4-pentadiene-3-one, 1 -(4-trifluoroethenyloxyphenyl)-5-(4-methoxyphenyl)-1 ,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(carboxymethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(carboxyethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(trifluoromethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(3-(trifluoromethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-25 trifluoroethenyloxyphenyl)-5-(4-nitrophenyl)-1 ,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-chlorophenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-fluorophenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-acetophenyl)-1,4-pentadiene-3-one, 1-(4-methoxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-methoxyphenyl)-1-(4-30 trifluoroethenyloxyphenyl)-1 -propene, 1 -(4-dimethylaminophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-dimethylaminophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-carboxymethylphenyl)-2-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-carboxymethylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-chlorophenyl)-2-(4-trifluoroethenyloxyphenyl)-l-35 propene, 2-(4-chlorophenyl)- l -(4-trifluoroethenyloxyphenyl)-l -propene, 1 -(4-nitrophenyl)-2-(4-trifiuoroethenyloxyphenyl)-l-propene, 2-(4-nitrophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-fluorophenyl)-2-(4-trifluc~roethenyloxyphenyl)-l-propene, 2-(4-fluorophenyl)-l-(4-trifluoroethenyloxyphenyl)-l-propene, 1-(4-cyanophenyl)-2-(4-trifluoroethenyloxyphenyl)-~WO 94115258 ~ 51 PCT/US93/11562 l-propene, 2-(4-cyanophenyl)-1-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-acetylphenyl)-1-(4-trifluoroethenyloxyphenyl)-l-propene, 2-(4-acetylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 4-methoxy-4'-trifluoroethenyloxystilbene, 4-dimethylaminophenyl-4'-trifluoroethenyloxystilbene, 4-carboxymethylphenyl-4'-- 5 trifluoroethenyloxystilbene, 4-carboxyethylphenyl-4'-trifluoroethenyloxystilbene, 4-nitro-4'-trifluoroethenyloxystilbene, 4-chloro-4'-trifluoroethenyloxystilbene, 4-fluoro-4'-trifluoroethenyloxystilbene, 4-cyano-4'-trifluoroethenyloxystilbene, 4-acetyl-4'-trifluoroethenyloxystilbene, 4-trifluoromethyl-4'-trifluoroethenyloxystilbene, 1-(4-dimethylaminophenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one, 1-(4-methoxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one, ~-cinnamylidene-4-trifluoroethenyloxyacetophenone, ~-(4'-dimethylaminocinnamylidene)-4-trifluoroethenyloxyacetophenone, ~-(2'-methoxycinnamylidene)-4-tri fl uoroethenyloxyacetophenone"~-(4'-methoxyci nnamyl idene)-4-trifluoroethenyloxyacetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(benzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-methoxybenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-dimethylaminobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-cyanobenzylidene)aceLophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-nitrobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(cinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(2'-methoxycinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-methoxycinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~(4'-dimethylaminocinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-~-(4'-nitrocinnamylidene)acetophenone, 1,1-bis(4-trifluoroethenyloxyphenyl)-1-(4-(3-(2-furanyl)-2-propene-1-onyl)phenyl)ethane, 1 ,1-bis(4-trifluoroethenyloxyphenyl)-1-(4-(5-(2-furanyl)-2,4-pentadiene-1-onyl)phenyl)ethane, 3,5-bis(trifluoroethenyloxy)-~(benzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(4'-methoxybenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(4'-dimethylaminobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(4'-cyanobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-,~-30 (4'-nitrobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(cinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(2'-methoxycinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(4'-methoxycinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-(4'dimethylaminocinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-~-35 (nitrocinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-1-(3-(2-(furanyl)-2-propene-1-onyl)benzene, 3,5-bis(trifluoroethenyloxy)-1-(5-(2-(furanyl)-2,4-pentadiene-1-onyl)benzene, 2-(3-phenyl-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(2-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-dimethylaminophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-cyanophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-nitrophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-phenyl-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(2-methoxyphenyl)-2-propene- 1 -onyl)-9,9-bis(4-trifl uoroethenyloxyphenyl)fl uorene, 2,7-bis(3-(4-dimethylaminophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-cyanophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-nitrophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-phenyl-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-methoxyphenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(2-methoxyphenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-dimethylaminophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-cyanophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-nitrophenyl)-2,4-pentadiene-l-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-phenyl-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4-methoxyphenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4-dimethylaminophenyl)-2,4-pentadiene-1 -onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(2-dimethylaminophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4-cyanophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, and 2,7-bis(5-(4-nitrophenyl)-2,4-pentadiene-1 -onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene.

When R is part of PAS and t is 2, compounds of Formula Xlll correspond to Formula IV. Exemplary compounds of Formula IV include 4,4'-bis(trifluoroethenyloxy)-a-methylstilbene; 4,4'-bis(trifluoroethenyloxy)stilbene; 4-Trifluoroethenyloxy-~-(4-trifluoroethenyloxybenzylidene)acetophenone; 2,6-bis(4-trifluoroethenyloxybenzylidene)cyclohexanone; 2,6-bis(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone; 1,4-bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1,3-bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1,4-bis(3-(4-trifluoroethenyloxyphenyl)-1-propene-3-onyl)benzene; 1,3-bis(3-(4-trifluoroethenyloxyphenyl)-1-propene-3-onyl)benzene; 1,5-bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one; 4-Trifluoroethenyloxy-,~-(4-35 trifluoroethenyloxybenzylidene)acetophenone; 4,4'-bis-(trifluoroethenyloxy)stilbene; 4,4'-bis(trifluoroethenyloxy)-~-methylstilbene; ~,~'-bis(4-trifluoroethenyloxybenzylidene)-1,4-diacetylbenzene; ~,~'-bis(4-trifluoroethenyloxybenzylidene)-1,3-diacetylbenzene; ~"~'-bis(4-trifluoroethenyloxybenzylidene)-1,2-diacetylbenzene; 5,8-bis(trifluoroethenyloxy)coumarin;

~ WO 94/15258 2 1 51151 PCT/US93/11562 2,6-bis(4,trifluoroethenyloxybenzylidene)cyclohexanone; 2,6-bis(4,trifiuoroethenyloxybenzylidene)-4-methylcyclohexanone; 5,8-bis(trifluoroethenyloxy)naphthoquinone; ~,~'-bis(4-trifluoroethenyloxybenzoyl)-1,4-d i vi nyl benzene .
Polymers of the invention include those formed according to the teachings of U.S.
Patent 5,037,917 by copolymerizing or reacting such compounds with compounds of Formula ll wherein m is greater than 1 to form polymers having (in the case of m = 2) repeating units of Formula XV:

215115~

l fF2 I F2 --CF CF-X-R-X

X

X

PAS

wherein X, R, and PAS are as defined for Formulas I and IV.

For instance, the reaction products of compounds of Formula Xlll where t = 1 with compounds such as 1,1,1-tris (4'-trifluoroethenyloxyphenyl)ethane, (1,3,5-tris(2-(4-25 trifluoroethenyloxy)phenylene)-2-propyl benzene), or the (trifluorovinyl etherified) polyphenolic compounds such as Novolac compounds, exemplify polymers of Formula XV.
Preferred Novolac compounds correspond to Formula XVI:

~ R4 ~/ R4 wherei n p is an integer of from 0 to 10; each R4 is i ndependently a linear or cyclic hydrocarbylidene or group preferably of from 1 to 20 carbon atoms (more preferably WO 94/15258 ~ L ~ 1 PCT/US93/11562 methylene, dicyclopentadienylene, isopropylideneiene, fluorenylidene; and the like); and each R5 is independently a hydrogen or an unsubstituted or inertly substituted alkyl or alkyl ether group preferably of from 1 to 6 carbon atoms, preferably of 1 to 3 carbon atoms - 5 Monomers containing trifluorovinyl or perfluorocyclobutane groups and photoactive groups are suitably homopolymerized or copolymerized, preferably copolymerized, for instance, with any monomer of the types disclosed by U S Patents 5,021,602; 5,023,380; 5,037,917; 5,037,918; or 5,037,919; by methods disclosed therein.
Preferably sufficient monomer having at leàst one photoactive site or photoactive precursor to 10 formapolymerwhichbecomeslesssolubleordispersibleuponexposuretophotonicradiation is used. Advantageously, at least 0.1 percent by molar composition of such monomers are used in a polymer, preferably at ieast 1, more preferably from 1 to 100, most preferably from 5 to 25 mole percent of photoactive site containing monomers are used. The polymer is suitably linear, branched, crosslinked, or a mixture thereof.

To avoid solubility of at least a portion of a photoactive polymer after treatment with actinic radiation, it is advantageous to avoid having low molecular weight oligomers and polymers after photoactive sites have reacted. When a photoactive monomer containing two trifluorovinyl groups is ho.,.opolymerized or copolymerized with another monomer containing 20 two trifluorovinyl groups to form a substantially linear thermoplastic polymer with photoactive siteseitherpendanttoorinccr~.o,dted inthepolymerbackbone,themolecularweightofsuch a system is advantageously made as high as possible while still maintaining desirable properties for processability, such as solubility in a solvent suitable for solution coating processes which are within the skill in the art, or melt processability such as extrusion, injection molding or melt 25 blowing. In addition, the molar percent composition of the photoactive site is advantageously optimized to maintain the same features of processability. Optimization of molecular weight and molar composition of the photoactive site enhance the photochemical sensitivity as defined by Minsk et al. in The Journal of Applied Polymer Science, Volume 2, p.302 (1959), or by Robertson et al. ibid, p.308.

Similarly, in systems where the photoactive monomer has three or more trifluorovinyl groups, or is polymerized in a system containing a comonomer with three or more trifluorovinyl groups in sufficient quantity to result in a thermoset polymer, the molecular weight of the polymer (preferably prepolymer) is advantageously as close to the gel 35 point of the system as possible while still maintaining processability as defined above, including solvent solubility and/or melt processability. In this case, processability also involves the exclusi on of gels or very high molecular weight fractions which may form before the gel poi nt, but which adversely affect the processability of the polymer and the quality of the coatings and -25- .

WO 94/15258 ; PCT/US93111562 ~115~ --Iaminates obtained from these prepolymers in applications where properties such as planarization and optical uniformity are important. In addition, the molar content of the photoactive site is optimized to provide maximum photochemical sensitivity as defined for the linear polymers. In general, weight average molecular weights on the order of 5,000 to 500,000, most preferably from 10,000 to 300,000 are useful in these systems When the polymer is a thermoplastic, however, it is advantageously applied in a liquid media as described but at a weight average molecular weight greater than 20,000, preferably greater than 60,000. Such high molecular weight polymers are advantageously 10 applied in liquid media, preferably solutions such as by spin coating, spray coating, dip coating, pad printing and other methods known to those skilled in the art. Whereas a post application baking step is used forthermoset resins of the invention, thermoplastics are advantageously applied i n a sufficiently high mol ecular weight to obviate the need for a post bake step Alternatively, thermoplastic polymers of the invention are applied in melted form such as in a melt extruder, by melt coextrusion of a multilayer laminate, or by spin coating, di p coating or spray coating the polymer directly from the melt phase. The polymer may also be formed into a free standing film by melt extrusion, blow molding or other means known to those skilled in the art.

Alternatively, the polymer is applied as a dry film as is within the skill in the art for instance as discussed in Printed Circuits Handbook, C. F. Combs, Jr., ed., second ed., McGraw-Hill, New York, 1979, pages 6-12 through 6-13. In a dry film application, a film of photoactive polymer is advantageously supplied as a layer on one, or preferably between two, polymer sheets. The film is advantageously applied to a material such as a conductor, for example 25 copper, is exposed to light such that the viscosity of the exposed photoactive polymer i ncreases leaving the unexposed polymer unchanged for removal Photoactive polymers prepared by any of the foregoing methods are advantageously used as coatings. For use as coating, the polymer is preferably prepared in an 30 organic solvent, aqueous medium, emulsion, or latex or is dissolved or dispersed after formation or used as a dry film. The coating is applied to a surface by means within the state of the art, such as by spin coating, spray coating, plasma deposition, roll coating, pad printing, dip coating and the like. Then the polymer is exposed or at least a portion of the polymer is selectively exposed to photonic radiation of a wavelength which interacts directly or indirectly 35 with the photoactive sites. Preferably, sufficient photonic radiation is used to render the polymer less soluble or dispersible, more preferably essentially insoluble or not dispersible (that is insufficiently soluble or dispersible to be removed from the surface by rinsing in the solvent ~ WO 94/15258 ~15 1 1 5 ~ PCT/US93/11562 used for application or any other solvent(s) effective for removal of the unexposed portion of the polymer) or more viscous The polymer is suitably applied to any surface such as the surface of flat, sphericai, 5 irregular shapes, such as glass plates, silicon or silicon oxide wafers such as those used in the production of semiconductor devices, giass beads, copper film, other polymers including for instance polycarbonate, polyimide, polyester, polytetrafluoroethylene or other fluoropolymers, polyquinolines, poiybenzoxazoles, polybenzimidazoles, polyaryl sulfones, microelectronic circuitry including multilayer microelectronic circuitry devices or other surfaces 10 of the like which optionally may be prepared by processes such as cleaning by washing with soap followed by rinsing with deionized water and then drying, either in an oven or with a stream of dry gas such as air, or cleaning by a plasma cleaning process such as oxygen plasma or sulfur hexafluoride plasma cleaning. Other surface treatments may include preparing the surface with an adhesion promoter such as bis[3-(triethoxysilyl)propyl~amine using standard 15 conditions such as those outlined i n ~Si I icon Com pou nds - Register and Review, " pu bl ished by Petrarch Systems Silanes and Silicones (1987), Pel. ~r~l, Systems.

Any incident photonic radiation which is effective to render the polymer less soluble or dispersible (hereinafter effective wavelength) is suitably used. Such radiation is 20 advantageously at a wavelength which is absorbed by the photoactive site, preferably from 250 nm to 5û0 nm, for instance 405-436 nm for sites having the 4-dimethylaminochalcone group, 300-365 nm for sites having the 4-methoxychalcone group, 254-280 nm for sites having the ~-methylstilbene group, 3û0-365 nm for sites having the (unsubstituted) chalcone group, 3û0-365 nm for sites having the 1,4-pentadiene-3-one group, and the like. Alternatively, another 25 compound can absorb the photonic radiation and change the available energy. For instance, compounds referred to as photosensitizers, such as benzophenone,1,2-benzanthraquinone, or Michler's ketone are known in the art to absorb light at a wavelength di ffefent from the absorption of the photoactive site, and transfer the absorbed energy via collision processes from the photosensitizer to the photoactive site, activating the photoactive site for covalent 30 reaction with an appropriate site for crosslinking. Thus, the photonic energy is suitably used directiy or indirectly.

While the photosensitizer compounds are effective to increase the effective wavelength to those more commonly used in industry, use of wavelengths in the mid and deep 35 ultraviolet (UV), that is wavelengths such as the 313 nm (nanometer) line for mid UV, and the 254 nm line for deep UV are advantageous especially for formation of coatings having very fine definition because resol ution is improved. Most commonly used photoimageable polymers are active in the near UV region rather than the more desirable mid and deep UV. In a preferred W O 94/15258 . PCTrUS93/11562 21Sl~
~
embodiment of this invention, the photoactive group is active with a wavelength of incident photonic radiation of from 235 to 260 or from 250 to 275 to avoid optical density from the presence of aromatic groups Advantageously, to reduce solubility or dispersibility, the photoactive group acts such that crosslinking occurs as a result of incident photonic energy. Crosslinking optionally occurs between like photoactive groups or between a photoactive group and a group which is not photoactive. Most photoactive compounds of the invention react to crosslink through chemical reactions at the photoactive site, and generally involve lower energy (longer 10 wavelength, for example greater than 320 nm) absorptions of molecules with large and diffuse molecular orbitals, usually spread out over one or more aromatic ring systems. Abenzophenone chromophore reacts somewhat differently however, irradiation of benzophenone with light excites the benzophenone carbonyl group to the excited singlet state, which crosses to the chemically active triplet state. During this excitation of the carbonyl group, the ~I bond is broken and the triplet state can be considered as a 1,2 diradical, which is believed to abstract hydrogen from hydrogen-donor molecules such as hydrocarbons, alcohols, ethers, amines, thiols, sulphides, and phenols and produce a benzophenone ketyl radical, also called a diphenylhydroxymethyl radical or semipinacal radical which radical reacts with another part of the polymer such that crossl inking occurs.

In the practice of the invention, it is preferred that crosslinking occurs such that the resulting group is not photoactive or photoabsorptive at the effective wavelength, preferably not photoactive at any wavelength. When photoactive groups continue to absorb photonic radiation at substantially the same wavelength (a wavelength sufficiently close to the 25 effective wavelength to absorb at least a portion of the incident photonic radiation) after solubility or dispersibility is reduced, they prevent that photonic radiation from going deeper into the polymer to cause another photoactive group to react. A material having groups which absorb photonic radiation at a given wavelength are referred to as having optical density at that wavelength. At reduced optical density, there is transparency that permits the photonic radiation to go deeper within a polymer. The deeper penetration of photonic radiation permits curing of thicker films or layers of polymer than is possible in a polymer with a higher optical density. Thus, practice of this preferred embodiment of the invention permits formation of thicker films than is possible in systems where optical density remains after solubility or dispersibility is reduced. For instance films having a high optical density are 35 generally limited to a thickness of less than 10 llm, but films of greater than 2 ~m preferably greater than S ~m more preferably greater than 10 llm are formed in the practice of the invention. Films of the invention are advantageously at least 0.01 llm, preferably at least 0.1 ~m, more preferably at least 0.5 llm thick. Formation of ~ WO 94/15258 2151~ ~1 PCT/US93/11562 such thick films also is facilitated by the lack of volatiles (water or molecules eliminated in formation of the final polymer film) formed in the practice of the invention.

Photoactive groups that result in crosslinking not having optical density at the 5 effective wavelength include chalcones; cinnamates; acrylates; cinnamaldehydes; maleimides;
l ,5-aryl-l ,4-pentadiene-3-ones naphthoquinones; coumarins; (benzylidene) cyclohexanones;
2,6-bis(benzylidene)cyclohexanones; 2-cinnamylidene cyclohexanones; l ,9-bis(aryl)- l ,3,6,9-nonatetraene-5-ones; 2,6-bis(cinnamylidene)cyclohexanones; and stilbenes.

l O For use as a negative photoresist, only a portion of the photoactive polymer is exposed to sufficient photonic radiation to render it less soluble or dispersible. The remaining portion is referred to as unexposed and is removed by means within the skill in the art such as by a process known as developing, such as by spray development, which includes steps of spraying a film-coated substrate with a continuous stream of atomized or otherwise dispersed stream of a developing solvent for a sufficient time to efficiently remove the uncrosslinked portion of a polymer, followed by a drying step comprised of for instance either oven drying the substrate, or drying with a continuous stream of dry gas such as air or nitrogen, or a combination of both oven-drying and gas drying. Alternative means of removing the less soluble portion of polymer include dunk rinsing, which involves immersing the substrate in a 20 bath of the developing solvent for sufficient time to dissolve the uncrosslinked portion of the polymer.

When the polymer has remaining trifluorovinyl groups, such as in the case of oligomers or B-staged polymers, the polymer is advantageously heated sufficiently to allow at 25 least a portion of the trifluorovinyl groups to form perfluorocyclobutane groups, advantageously further building molecularweight of the polymer such that it becomes less soluble, more oxidatively and thermally stable, less swellable by contact with solvent, and attains a low dielectric constant and a dissipation factorwhich is characteristic of the perfluorocyclobutane ring containing polymers. Temperatures and conditions for forming 30 perfluorocyclobutane groups are those disclosed in the previously cited patents.

Such coatings are also advantageously optically transparent and may be suitable as scratch resistant or chemically resistant coatings on optical lenses or other devices where optical transparency is an important feature.
Polymers formed in the practice of the invention advantageously have low moisture absorption, preferably moisture absorption of less than 2 percent, low dielectric constant, preferably below 3.5, low dissipation factor, preferably below WO 94115258 21 511 ~ PCTIUS93/11562 .01, flame retardency, good mechanical properties such as tensile modulus and flexural modulus of at least 150,000 psi (1,034,213 kPa) chemical resistance, such as resistance to hydrocarbon, aromatic ring-containing solvents including benzene, chlorobenzene,nitrobenzene, toluene, xylene, mesityiene, and the like, ketone or halocarbon solvents, and high thermal-oxidative stability, preferably above 100C, preferably 150C, more preferably 200~C, (advantageously formulated without added antioxidant). Polymers with at least some of these properties are particularly usefui in fabrication of dielectric polymer films for microelectronics applications.

The following examples are offered to illustrate but not limit the invention.
Examples (Ex.) of the invention are designated numerically, while Comparative Samples (CS) are not examples of the invention and are designated alphabetically. All parts, ratios, percentages and fractions are by weight unless designated otherwise.

15 Example 1: Synthesis and Polymerization of 4,4'-Bis(trifluoroethenyloxy)-a-methylstilbene 4,4'-Bis(2-bromotetrafluoroethoxy)-a-methylstilbene:

4,4'-bis(hydroxy)-a-methylstilbene (100.0 9, 0.442 mole) was added to a 3 liter, 4 20 necked round bottomed flask along with DMSO (dimethylsulfoxide) (1150 ml) and toluene (350 ml). The resulting mixture was deoxygenated with nitrogen for 15 minutes, then KOH (58.4 9, 0.884 mole as 85 percent pellets, the remaining 15 percent being water) was added all at once.
The mixture was stirred and heated to reflux, and water was removed azeotropically by distillation of the waterltoluene azeotrope for a total of 10 hours. A Soxhlet extractor 25 containing a drying bed of anhydrous Na2SO4was placed on the reactor, and the toluene was refluxed through this drying bed to remove residual water. Toluene (260 ml) was removed by simple distillation, then the remaining mixture was cooled to 24C.1,2-Dibromotetrafluoroethane (276 9,1.06 mole) was added slowly over 30 minutes, and the reaction mixture was stirred at 24C for 8 hours. After filtration and evaporation, the residue 30 was flushed through a column of alumina using hexane as the eluent. Hexane was removed by evaporation, and the resulting residue weighed 109.4 9 (0.19 mole) for an isolated yield of 42 percent.

Mass Spectrometric Analysis: m/e(masslcharge ratio) = 165 (9.6 percent); 179 (9.5 percent);
35 387(10.0percent); 389(10.0percent); 582(41.1 percent); 583 (21.5 percent); 584(100 percent); 585 (20.6 percent); 586 (47.1 percent) 4,4'-Bis(trifluoroethenyioxy)-a-methylstilbene:

WO 94/1~258 2 ~ 1 PCT/US93/11562 The intermediate product 4,4-bis(2-bromotetrafluoroethoxy)-a-methylstilbene (106.43 9,0 18 mole) was added to 100 ml of acetonitrile in a 250 ml dropping addition funnel attached to a 11iter 5-necked round bottomed flask. Zinc granules (40 mesh,25.0 9,0.38 mole) 5 were added to the reactor along with 100 ml of acetonitrile, and the resulting stirred suspension was deoxygenated with nitrogen for 10 minutes by introducing nitrogen gas through a gas dispersion tube. The suspension was then heated to 75C, at which point the addition of intermediate product solution in acetonitrile was begun. The addition was carried out over 20 minutes, and the resulting mixture was heated at 75C overnight. After 10 centrifugationtoremovesuspendedsolids,theresultingsupernatantwasevaporatedto dryness, leaving a crude product which was filtered through a short bed (4 cm) of alumina in a 600 ml sintered glass filter funnel using hexane as the eluent. After removal of the hexane by evaporation, the product was heated at 55C under high vacuum for 3û minutes.

15 MassSpectrometricAnalysis: m/e = 191 (20.7 percent); 192(12.2 percent); 386(100percent);
387 (22.2 percent).

Q-Methylstilbene Perfluorocyclobutyl Ether Polymer:

A small sample (2.09) of the 4,4'-bis(trifluoroethenyloxy)-a-methyl-stilbene monomer was placed in a S0 ml 3-necked round bottomed flask fitted with a mechanical stirrer and a temperature controller. The monomer was agitated slowly as nitrogen was bubbled throughtheliquidfor5minutes. Thetemperatureoftheflaskwasraisedto160Cfor90 minutes, then to 180C for 60 minutes, and finally to 200C for 90 minutes. After it was cooled 25 to room temperature, the resulting polymer was recovered by breaking pieces of the polymer out of the reaction flask, and a small portion of the polymer was dissolved in benzene. The benzene solution was filtered to remove any insoluble portion of the polymer and deposited on a salt plate for infrared (IR) analysis. The benzene was evaporated at 130C in an oven to leave a thin polymer film deposited on the salt plate.

Examination of the IR spectrum of the polymer revealed a medium absorption at 837 cm-1, indicative of a carbon-hydrogen stretch associated with the hydrogen attached to a carbon-carbon olefin bond between two aromatic rings in the Q-methylstilbene structure. The salt plate was then placed under UV irradiation at 254 nm for 3 hours. Analysis of the UV-cured 35 film by IR indicated a significant decrease in the carbon-hydrogen absorption at 837 cm-1. This loss of intensity at 837 cm-1 was attributed to the disappearance of the carbon-carbon double bond between the aromatic rings of the ~l-methylstilbene as this structure dimerized WO 94/15258 2 ~ S ~ PCT/US93/11562 upon irradiation with UV light at 254 nm. Subsequent irradiation overnight with light of 254 nm waveiength produced little change in the spectrum as compared to irradiation for 3 hours.

The resulting polymer fil m deposited on the salt plate was washed extensively 5 with benzene in an effort to dissolve and thereby remove the polymer film which had originally been deposited from benzene solution After being washed in 50 ml of benzene for 5 minutes, the salt plate was removed and the benzene allowed to evaporate to dryness. The IR spectrum of the salt plate was taken again, and no measurable loss of absorption intensity of the polymer film was observed with respect to the film before washing with benzene. This 10 demonstratedthatthepolymerfilmwassubstantiallyintactafterbeingwashedwiththe solvent originally used to deposit the soluble form of the polymer, and indicated a degree of crosslinking in the polymer sufficient to render it insoluble in a solvent in which it was soluble prior to irradiation with UV light at 254 nm.

Example 2: Copolymerization of 20 Mole Percent4,4'-Bis(trifluoroethenyloxy)~
methylstilbenewith80molePercent 1,1,1-Tris(4-trifluoroethenyloxyphenyl)ethane(TVE
Monomer) and Subsequent Photocrosslinking of the Copolymer A mixture of 4,4'-bis(trifluoroethenyloxy)-~1-methylstilbene (1.01 9, 0.0026 mole) 20 and 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane (prepared here and in all examples as described in U.S. Patent 5,066,746) (5.66 9, 0.010 mole) was placed in a 100 ml round bottomed flask equipped with a mechanical stirrer and and deoxygenated by introducing nitrogen into the flask through a gas dispersion tube for 10 minutes. The resulting mixture was then heated to 15ûC with stirring for one hour. The resulting prepolymer was cooled to room temperature, 25 and a 1.0 9 sample of the prepolymer was removed from the flask. This sample was combined with10mlofbenzeneina100mlErhlenmeyerflaskandheatedto45Cwithstirringforl hour. The resulting polymer solution was deposited on a NaCI salt plate and the benzene solvent was evaporated to dryness in a drying oven at 120C. Infrared (IR) analysis of this salt plate showed an absorption spectrum of the copolymer, with characteristic IR absorptions at 30 1605cm-1,1594cm-1,and 1505cm-1,correspondingtothearomaticringabsorptionsofthepolymersystem,andat1206cm-1,1175cm-1,and 1141 cm-1,correspondingtotheabsorption of the carbon-fluorine bonds. After irradiation of the film with UV lightat 254 nm wavelength for 64 hours, a broad absorption band of moderate i ntensity from 1685 cm- 1 to 1772 cm- 1 appeared. The sait plate was immersed in benzene and washed by swirling the benzene 35 solvent over the salt plate for two minutes. Subsequent IR analysis of the washed plate revealed no decrease in the absorbance i ntensity, indicati ng that the polymer fil m was sti l l substantially intact. This example demonstrated that the polymer was WO 94/1~258 ~ lPCT/US93/11562 rendered insoluble to a solvent in which it was soluble before irradiation by irradiation with UV
light at 254 nm wavelength Example 3: Synthesis of 1,5-Bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one 4-(2-bromotetrafl uoroethoxy)benzaldehyde:

Method 1:
Dimethylsulfoxide (210 ml) and toluene (75 ml) were placed in a 500 ml 5-necked 0 round bottomed flask equipped with a mechanical stirrer, a BarreK trap topped with a nitrogen padded reflux condenser, and a thermocouple attached to a temperature controller which controls a heating mantle on the flask through a Variac rheostat power supply. The solution was deoxygenated by bubbling nitrogen into the reactor for 10 minutes Potassium hydroxide (KOH) (23.0 9, 0.35 mole as 85.5 percent pellets, the remainder was water) was added to the solution and the mixture was heated to 110C to dissolve the KOH. 4-Hydroxybenzaldehyde (42.7 9) was added in two equal portions. The solution was heated to reflux to begin water removal. When 14 ml of lower phase had been collected in the Barrett trap, the trap was replaced with a Soxhlet extractor containing anhydrous Na2SO4 (sodium sulfate), and the residual water in the toluene was removed by distilling the toluene through 20 this Na2504 drying bed. Toluene (50 ml) was removed by simple distillation, and the resulting mixture was cooled to 60C.1,2-Dibromotetrafluoroethane (140 9, 0.538 moles) was added slowly and the mixture was heated to 70C. After 2.5 hours of heating at 70C, the mixture was heated to 85C overnight. The resulting reaction mixture was cooled, filtered and extracted with hexane (4 times,400 ml each). The hexane extracts were combined and washed with 25 distilled water (6 times, 500 ml each). After evaporation of the hexane a yellow oil remained, which was flash distilled on a Kugelrohr apparatus (80-90C, 0.20 mm Hg (26.6 Pa)) to provide a colorless liquid (8.359, 0.028 mole) in 7.9 percent yield.

Method 2:
Powdered 4-hydroxybenzaldehyde (351.4 9, 2.584 mole) was added slowly to a stirred solution of KOH (169.59, 2.584 mole as 85.5 percent pellets also containing 15 percent water) in 1600 ml of methanol which had been thoroughly deoxygenated by introducing nitrogen through a gas dispersion tube for a period of 15 minutes. The mixture was stirred for l hour under a nitrogen atmosphere, then evaporated to yield a purple solid This solid product was placed in a vacuum drying oven at 5 mm Hg (665 Pa) and 110C for 5 hours, then removed, ground into a fine powder and placed in the vacuum drying oven at 5 mm Hg (665 Pa) and 110C overnight. A total of 410.5 9 (2.56 mole,99.3 percent yield) of the potassium salt of p-hydroxybenzaldehyde was isolated by this method.

WO 94/15258 21~115 I PCT/US93/11562 ~

A portion of this salt (208.0 9, l .3 mole) was added to 1200 ml of DMSO in a 3-liter round bottomed flask fitted with a vacuum sealed mechanical stirrer, a thermocouple well, a gas inlet valve and a Soxhlet extractor and condenser unit which was connected to a vacuum 5 pump An oven dried ceramic thimble in the Soxhlet extractor contained activated 5A
molecular sieves The mixture was stirred slowly under high vacuum and heated to distill the DMSO through the Soxhlet drying apparatus. This distillation was continued until the DMSO
solution measured 500 ppm H20 by Karl-Fishertitration.

After the system was vented to ambient pressure under dry nitrogen and the reaction mixture was cooled to 45C,1,2-dibromotetrafluoroethane (390 g, 1.S0 mole) was slowly added to the reaction mixture through a dropping addition funnel. A temperature of 45C was mai ntained throughout the addition, and thereafter for 1 hour. The temperature was then raised to 50C for 30 minutes, then to 55C for 20 minutes, then to 65C for l hour, and finally to 75C overnight. After being cooled to room temperature, the resulting crude reaction mixture was extracted with hexane (6 times with 1 liter portions). The hexane extracts were combined and evaporated to leave a portion of the product as a yellow oil. The remainder of the product was codistilled from the crude reaction mixture with the DMSO solvent. This DMSO/product mixture (1 liter) was diluted with 1200 ml of water and extracted again with 20 hexane (4 times with 1 liter portions). These hexane extracts were combined with the yellow oil from the first extraction and washed with 250 ml of distilled water. After evaporation of the hexane layer, a light yellow oil remained. This oil was flash evaporated on a rotary evaporator (75C, 0.5 mm Hg (66.5 Pa)) to provide a water white oil (136.07 g, 0.452 mole, 34.8 percent yield),98.6 percent pure by gas chromatography (GC) analysis.
Mass Spectrometric Analysis: m/e = 299 (58 percent); 300 (33 percent); 301 (100 percent); 302 (13 percent); 303 (31 percent) .

4-Trifluoroethenyloxybenzaldehyde:
Acetonitrile (300 ml) and granular zinc (30.0 g) were combined in a 1 liter round bottomed flask and stirred at 75C under nitrogen as 4-(2-bromotetrafluoroethoxy)benzaldehyde (111.39 g,0.37 mole) was added slowly by dropping addition funnel. The resulting mixture was stirred and heated at 79C for 12 hours After 35 filtration to remove zinc salts and unreacted zinc, the acetonitrile was removed under vacuum on a rotary evaporator. The resulting oily residue was flash distilled on a rotary WO 94/15258 ~ lPCT/US93111562 evaporator under high vacuum (26.6 Pa) to provide 47.339 (0.234 mole) of a water white oil in 63.3 percent yield MassSpectrometricAnalysis: m/e = 51 (56percent); 77(65percent); 105(31 percent); 127(37 5 percent); 154(21 percent); 201 (34percent); 202(100percent); 203(70percent).

- Alternatively the compound was prepared from methyl-4-hydroxy-benzoic acid, salts or esters thereof or from phenol.

10 1,5-Bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one:

Method l:

Acetone (û.70g, û.012 mole) and 4-trifluoroethenyloxybenzaldehyde (5.09, 0.0247 mole) were combined in reagent alcohol (90 percent ethanol, 5 percent methanol, and 5 percent isopropyl alcohol, available from Fisher Scientific) (30 ml) in a 250 ml jacketed 3-necked round bottom flask equipped with a mechanical stirrer, a nitrogen padded reflux condenser with a downstream gas flow indicator (a bubbler)and an inlet gas dispersion tube. The solution was cooled to 0C with stirri ng by circulating chilled glycol through the jacket of the reaction 20 vessel, and was deoxygenated by introducing nitrogen through a gas dispersion tube into the solutionfor15minutes. AtemperatureofO-5Cwasmaintainedasthenitrogengasflowwas ceased and the alcohol solution was saturated with HCI (hydrochloric acid) by introducing gaseous anhydrous HCI through the gas inlet tube. The solution was stirred at 5C for 5 hours, then filtered, and the precipitate washed with 20 ml of fresh alcohol. The white crystalline 25 product thus obtained (1.4 9, 0.0032 mole, 27.4 percent yield) had a melting point of 113-114.5C.

MassSpectrometricAnalysis: m/e = 76 (16 percent); 1û2 (33 percent); 203 (13 percent); 329 (11 percent); 426 (100 percent); 427 (24 percent).

Method 2:

Reagent alcohol (110 ml) and 4-trifluoroethenyloxybenzaldehyde (20.09, O.Og9 mole) were combined in the apparatus of Method 1 (with the addition of a septum on one 35 neck of the apparatus, through which was introduced the needle of a syringe containing the reagent acetone), deoxygenated as in Method 1 and cooled to 0C with sti rring. The temperature was maintained at 0-5C as the alcohol solution was saturated with anhydrous HCI as in Method 1. When the alcohol solution had reached saturation, as was WO 94/15258 PCT/US93/11562indicated by excess HCI exiting the reaction flask through the downstream gas TIOW malCatOr,the addition of acetone (2.879,0 0495 mole) was begun. The acetone was added in small portions (0.50 ml each) at 30 minute intervals, for a total addition time of 3.5 hours.The ~ contlnuousfeedofanhydrousHClgaswasallowedtocontinueovernightataslowpace(lOml ,_~ 5 per minute). The HCI feed was then stopped and nitrogen gas was bubbled through the L.~ solution for 1 hour to remove some of the dissoived HCI. The reaction mixture was then filtered, and the precipitate was washed twice with deionized water (50 ml each). The precipitate was air dried for 20 minutes to provide 10.469 (0.0245 mole) of the desired product.
The filtrate was evaporated to a red oil, which was dissolved in acetonitrile (70 ml) and 10 extracted with two portions of hexane (600 ml each). The extracts were combined and evaporated to provide an additional 0.559 of the product, for a total of 11.019 (0.0258 mole, 52.2 percent yield) as a light pink crystalline solid with a melting point of 111 ^113C.

Example 4: Preparation and Photocrosslinking of a Copolymer of 1,5-Bis(4-15 trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one and 4,4'-Bis(trifluoroethenyloxy)biphenyl A sample of the monomer 4,4'-bis(trifluoroethenyloxy)biphenyl, prepared as described in U.S. Patent 5,023,380 (1.42 9, 0.0041 mole) was combined with the monomer 1,5-bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one (0.58 9, 0.00136 mole) in a 100 ml 3 20 necked round bottomed flask fitted with a mechanical stirrer, a temperature controller and a nitrogen inlet. The reactor was swept with nitrogen as the mixture of monomers was heated to 155C. The temperature was controlled at 155C for 2 hours; then the heat was removed. A
portion of the resulting yellow prepolymer was removed, dissolved in dichloromethane (CH2CI2) and deposited between two NaCI salt plates for IR analysis. The two salt plates were 25 rubbed together with the solutioF~ of prepolymer between them, then separated . The sol vent was allowed to evaporate from each plate, leaving roughly identical films of prepolymer on each of the two plates.

One plate was placed in a plastic bag and stored in the dark as a control for the 30 experiment. The second plate was placed in a round bottomed flask, and the flask was deoxygenated carefully with nitrogen. This plate was then subjected to irradiation with a 15 watt GE F1 ST8/BLB blacklight (360 nm) for 90 minutes. The two salt plates were then analyzed by IR spectroscopy. The first salt plate (experimental control) exhibited a complex absorption structure in the region normally associated with carbon-carbon double bonds, with small to 35 medium absorptions at 1674cm-1,1657 cm-1,1623 cm-1, 1604 cm-1, and 1585 cm-1. By contrast, the IR spectrum of the plate which had been subjected to irradiation at 360 nm showed only a single absorption band in this region at 1606 cm-1, all other absorptions in this region becoming minimal. This indicated that irradiation of the polymer film on the second salt WO 94/15258 ~ 1 5 115 1 PCT/US93/1 1562 plate had effected a change in the absorbance of the carbon-carbon double bond region of the IR spectrum by causing a light-induced intermolecular dimerization of some of the pentadienone carbon-carbon double bonds.

The second salt plate was then placed back in the round bottomed flask and irradiated with the blacklight for an additional 16 hours, while the first plate was returned to dark storage for the same period of time. Subsequent IR analysis of the two plates showed no noticeable differences from the spectra taken previously, after the second plate had experienced only 90 minutes of irradiation at 360 nm.
~O
The two salt plates were then simultaneously placed in a 250 ml evaporating dishcontaining 50 ml of CH2CI2, just enough to completely immerse the plates. The evaporating dish was then swirled gently for 1 minute to wash the solvent back and forth across the surfaces of the salt plates. The two plates were then removed and analyzed again by IR spectroscopy The first plate, which had been stored in the dark, shows no absorption spectrum at all, indicating that the polymer film which was deposited there had been completely washed away by the CH2CI2 treatment. The second salt plate, which had been subjected to irradiation with light at 360 nm, showed no decrease in the absorption spectrum after the CH2CI2 treatment, indicating that the irradiated film was still substaintally intact. This example demonstrated 20 that a polymer film which had been subjected to photonic radiation was rendered insoluble in a solvent in which it was initially soluble.

Example S: Synthesis of ~-(4-trifluoroethenyloxy-benzylidene)-4-trifluoroethenyloxyacetophenone Method 1:

4-(2-Bromotetrafl uoroethoxy)acetophenone ~Hydroxyacetophenone(351.4g,2.584mole)wasaddedslowlytoasolutionof KOH(169.5g, 2.584 mole as 85.5 percent pellets (remainder water)) in 1600 ml of methanol which had been thoroughly deoxygenated by bubbling nitrogen through a gas dispersion tube. The solution was stirred for 1.5 hours, then evaporated to a wet powder. This powder was dried overnight in a vacuum drying oven at 115C, removing once after 2 hours to grind it 35 to a fine powder with a mortar and pestle. The powder was cooled to room temperature under vacuum in the oven. A total of 448.2 9 (2.576 mole, 99.7 percent yield) was recovered as a pink/orange solid 21511~;~

A portion of this solid (228.2 9,1.31 mole) was added to 1250 ml of DMSO in a 3-liter round bottomed flask equipped with a vacuum-sealed mechanical stirrer, a thermocouple in a glass thermocouple well, a gas dispersion tube, and a Soxhlet extractor topped with a 5 reflux condenser. A ceramic thimble in the Soxhlet extractor was filled with activated 5A
molecular sieves After the mixture was thoroughly deoxygenated by introducing nitrogen through the gas dispersion tube for 15 minutes, the tube was removed and replaced by a glass stopper. The mixture was stirred slowly under high vacuum (266 Pa) and heated to distill the DMSO through the Soxhlet drying apparatus for 4 hours. The solution was vented to 10 atmospheric pressure under nitrogen and cooled to room temperature. Analysis of the DMSO
solution indicates a water content of 420 ppm (parts per million by weight) by Karl Fisher titration. The reaction mixture was chilled to 18C in an ice water bath, and addition of 1,2-dibromotetrafluoroethane (400.0 9, 1.54 mole) was carried out over 45 minutes. The mixture was held at 18C for 30 minutes, then allowed to warm to room temperature. Over the course of onehourthetemperaturewasraisedto50Candwasmaintainedat50Cfor18hours. The temperature was then raised to 65C for 8 hours, after which the mixture was cooled to room temperature. The DMSO solvent was removed from the product at 85C/2.0 mm Hg, (266 Pa) and the resulting dark residue was distilled on a Kugelrohr apparatus to provide 82.6 9 (0.262 mole,20.0 percent yield) of the 4-(2-bromotetrafluoroethoxy)-acetophenone.

Mass Spectrometric Analysis: m/e = 299 (85.8 percent); 300 (30.1 percent); 301 (100 percent);
315 (19.9 percent),317 (19.9 percent).

Infrared spectral analysis (cm- 1): C = O (1690); Ar (1605,1504); C-F (1203,1167,1132).

4-Trifluoroethenyloxyacetophenone 4-(2-Bromotetrafluoroethoxy)acetophenone (82.0 9, 0.406 mole) was combined with 175 ml of acetonitrile and placed in an addition funnel attached to a 500 ml round 30 bottomed flask equipped with a reflux condenser, a mechanical stirrer, and a thermocouple attached to a temperature controller which controls a heating mantle on the flask through a Variac rheostat power supply. An additional 25 ml of acetonitrile was placed in the 500 ml flask along with granular zinc (32.0 9, 0.4895 mole). The resulting zinc slurry was stirred and heated to 78C, at which point the addition of 4-(2-bromotetrafluoroethoxy)acetophenone was 35 begun. The addition was carried out over a period of 45 minutes, during which time the heat was increased to the reflux temperature of the mixture (82C). After the resulting mixture was stirred at reflux for 5 hours, analysis of ~ WO 9411~258 2 ~ 511~ I PCT/US93/11562 the reaction mixture by gas chromatography indicates that all of the starting acetophenone product had been consumed The reaction mixture was then cooled to room temperature and decanted away from the unreacted zinc granules into water (400 ml) which had been acidified with 20 ml of 12 5 N HCI. This aqueous mixture was extracted with dichloromethane (2 times,250 ml each). This extract was evaporated to provide a yellow oil which was distilled on a rotary evaporator at 85C and 2 mm Hg (266 Pa). The resulting product was flushed through a short bed of neutral aluminum oxide using hexane as an eluent to provide 27.9 g (û.138 mole, 34 percent yield) of the 4-trifluoroethenyloxyacetophenone product as a water white oil.

Mass SpectrometricAnalysis: m/e = 76 (22.4 percent); 91 (41.0 percent); 104(38.5 percent); 201 (100percent); 216(22.1 percent); 217(12percent).

InfraredSpectralAnalysis(cm-1): C=0(1689);Ar(16û2, 1502);C-F(1203,1169, 1144).

Alternatively, the compound was prepared from ethyl phenol or phenol.

,~-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone Reagent alcohol (150 ml, Fisher Scientific) was combined in a 11iter jacketed round bottomed flask with 4-trifluoroethenyloxyacetophenone (25.0 9,0.116 mole) and 4-trifluoroethenyloxybenzaldehyde (23.4 9, 0.116 mole). The flask was equipped with a mechanical stirrer, a thermometer, and a gas dispersion tube. The mixture was stirred as chilled glycol coolant was circulated through the flask jacket to cool the mixture to 3-5C. Nitrogen 25 gas was bubbled into the mixture through the gas dispersion tube to deoxygenate the solution. The inlet gas was then switched from nitrogen to anhydrous HCI and the feed rate was controlled to maintain a solution temperature of 5C. This HCI feed was continued for 4.5 hours, at which point the HCI feed was stopped and the stirring was continued for an additional hour.

Cold water ~250 ml) was then added slowly to the reactor. The resulting light yellow precipitate was filtered from the liquid, washed twice with 200 ml each of cold deionized water, then dissolved in 1000 ml of hot (60C) hexane. The resulting hexane layer was decanted away from the water layer and chilled in an ice bath to recrystallize the product.
35 After filtration to remove the precipitate, the hexane filtrate was concentrated by evaporation on a rotary evaporator at 60C and chilled again to cause the crystallization of the product.
Three batches of crystals were thus collected from the hexane phase and were W O 94/15258 21~ 1 PCTrUS93/11562 combined to provide 26.9 g, (0.067 mole, 58.0 percent yield) of a fluffy white powder, melting point 93.5-94.0C

Mass Spectrometric Analysis: m/e = 102 (20.4 percent); 104 ( l 7. l percent); 178 ( l 9.8 percent);
201 (17.2 percent); 206 (21.0 percent); 303 (37.3 percent); 399 (51.4 percent); 400 (100 percent); 401 (50.9%).

Method 2:

10 ~-(4-(2-bromotetrafluoroethoxy)benzylidene)-4-(2-bromotetrafluoroethoxy)acetophenone A sample of ~hydroxy-,~-(4-hydroxybenzylidene)acetophenone (4,4'-dihydroxychalcone, prepared according to the procedure of Zahir in Journal of Applied Polymer Science, volume 23, page 1355, (1979)) (229.09, 0.954 mole) was added todimethylsulfoxide (DMSO) and toluene in a 2 liter 5-necked round bottom flask equipped with a mechanical stirrer, a Barrett trap topped with a nitrogen padded refl ux condenser, and a thermocouple attached to a temperature controller which controls the power output to a heating mantle on the reaction vessel through a variable rheostat power source. The solution was deoxygenated by introducing nitrogen through a gas dispersion tube for 15 minutes.
20 Potassi um hydroxide pellets (125.4g,85 percent KOH by weight, the balance being water) were added to the solution and heating was begun. The nitrogen gas dispersion tube was removed and replaced with a glass stopper when the KOH pel lets were completely dissolved, that was when the solution temperature reaches 110C. The solution was heated to reflux (138C), and water was removed through the Barrett trap via azeotropic distillation with the toluene. A
25 total of 99 ml of lower phase was removed from the Barrett trap over the course of 6 hours.
The Barrett trap was then removed and replaced with a Soxhlet extractor containing activated 5A molecular sieves. The toluene was then distilled through the Soxhlet extractor drying bed for 3 hours. The Soxhlet extractor was then removed and replaced with the Barrett trap, and toluene (200 ml) was removed through the Barrett trap by simple distillation. The resulting 30 solution was then cooled to 30C, and the addition of 1,2-dibromotetrafluoroethane (600.09, 2.31 mole) was begun. The addition was carried out at 30-35C over a period of 45 minutes.
When the addition was complete, the mixture was heated slowly to 75C over 1 hour and stirred at 75C overnight.

After being cooled the mixture was added to a large excess of distilled water (4.0 L) and dichloromethane (500 mL) was added to the solution to facilitate phase separation. The dichloromethane phase was removed from the bottom and evaporated to provide crude product as a dark brown oil. The oil was dissolved in acetonitrile (1500mL) and WO 94/152~8 ~ PCT/US93/11562 placed in a continuous liquid/liquid extractor as the heavy source phase in an apparatus as described for continuous extraction for solvents lighter than water by F. Kutscher and H
Steudel in Zeitschrift fur Physiologische Chemie, volume 39, page 474, (1903). The light phase which was continuously evaporated and recirculated was hexane. The extraction was run for 5 48 hours, and the hexane was evaporated. The residue remaining after evaporation was dissoived in toluene (300 ml) and flushed through a short bed of alumina. The toluene was evaporated, and a yeilow crystalline product remains and was dissolved in a minimum amount of hot hexane (60C). The hexane was chilled in an ice bath to cause the crystallization of the product. After filtration to remove the precipitate, the hexane filtrate was concentrated by 10 evaporation on a rotary evaporator at 60C and chilled again to cause the crystallization of the product. After filtration the precipitate fractions were combined to afford 208.6g (0.35 mole, 36.6 percent yield) of the product ~-(4-(2-bromotetrafluoroethoxy)benzylidene)-4-(2-bromotetrafluoroethoxy)acetophenone as a light green solid with a melting point of 89-90C.

MassSpectrometricAnalysis: m/e = 63(16.9percent);92(14.3percent); 165(15.8percent);
299 (17.0 percent); 401 (55.0 percent); 402 ~23.4 percent); 403 (60.5 percent); 404 (20.8 percent);417(12.7percent); 419(16.1percent);596(62.3percent); 597(75.1percent);598 (100.0 percent); S99 (47.7 percent); 600 (47.6 percent).

20 ~-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone The product of the above reaction"~-(4-(2-bromotetrafluoroethoxy)benzylidene)-4-(2-bromotetra-fluoro-ethoxy)acetophenone (5.09, 0.00836 mole) was combined in a 200 ml 3-necked round bottom flask with 2-methoxy ethyl ether (20 ml) and granular zinc (4.37g, 0.067 25 mole). The slurry was heated to 120C and stirred with a mechanical stirrer under a nitrogen atomsphere for 24 hours. The resulting reaction mixture was filtered and the filtrate was evaporated at 90C under reduced pressure (2.0 mm,266 Pa) to remove the solvent. The residue remaini ng after evaporation was dissolved in acetonitri le (150 ml) and extracted with hexane (5 portions, 200 ml each). The hexane extracts were combined and evaporated at 60C
30 and reduced pressure (20 mm,2670 Pa) to a volume of 100 ml which was then allowed to cool to room temperature from 60C. The product which crystallized out of the hexane was collected by filtration and washed with cold hexane (25 ml, 5C). The hexane filtrates were combined and concentrated by evaporation at 60C and reduced pressure (20 mm, 2670 Pa) to a volume of 75 ml, then allowed to cool again to room temperature. A second batch of crystals 35 was thereby collected after filtration of the hexane concentrate. The combined solids weighed 0.609 (0.0015 mole, 17.9 percentyield) and had a melting pointof 93.5-94C.

W O 94/15258 PCTrUS93/11562 2 1 ~
Examples 6-10: Preparation of Copolymers of 1,1,1 -Tris(trifluoroethenyloxyphenyl)ethane with ,~-(4-trifluoroethenyloxybenzylidene)-4-trifiuoroethenyloxyac etophenone, and a Copolymer of 1,1,1 -Tris(trifluoroethenyloxyphenyl)ethane with 1,5-Bis(4-trifluoroethenyloxyphenyl)- 1,4-pentadiene-3-one For each of Examples 6-11, solid white 1,1,1 -tris(trifluoroethenyloxy-phenyl)ethane (TVE Monomer, 200 9) was added to a 500 mL one necked round bottom flask connected to a Kuglerohr apparatus and then deoxygenated at 80C under vacuum (0.20 mm Hg,26.6 Pa) for 2 hours to give a colorless oil The TVE monomer was then mixed with the 10 stated amounts indicated in each example of ~-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone (hereinafter chalcone monomer) prepared by the process of Example 5 or 1,5-Bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one (hereinafter bischalcone monomer) prepared by the process of Example 3 and B-staged accordi ng to the procedure outlined below.

Example 6: 5 Mole percent Chalcone/9S Mole percent TVE.

TVE monomer (30 g) and chalcone monomer (1.18 9) were placed in a long cyiindrical reaction vessel equipped with a three necked glass head, a Teflon'U
20 (polytetrafluoroethylene commercially available from E.l. DuPont de Nemours and Co.) seal, a stirrer with a Teflon '~ paddle, a screw clamp, a nitrogen inlet, and a vacuum outlet. The mixture was stirred at a constant speed, evacuated, vented two times with nitrogen, immersed in a fluidized aluminum oxide sand bath (preheated to 150C) to 2/3 its height and then heated at 150C with stirring for 3.50 hours under nitrogen. (Heating to achieve partial polymerization 25 was referred to as B-stagi ng .) U pon cool i ng, the prepolymer was a yel low 91 ass-l i ke sol id . After the temperature of the prepolymer reaches room temperature (22-24C), the reactor was cooled with dry ice to facilitate removal of the prepolymer by cracking the embrittled prepolymer, thereby making it easier to remove from the reaction vessel. The prepolymer was ground to a fine powder with a mortar and pestle to give 28.45 9 of a yellow solid. Analysis of 30 the prepolymer by gel permeation chromatography (GPC) indicated a weight average molecular weight of 7,810 for this sample as standardized against polystyrene.

Example 7: 10 Mole percent Chalcone/90 Mole percent TVE.
~.
TVE Monomer (30 9) and chalcone monomer (2.50 9) were combined and B-staged at 150C for 4 hours using the procedure of Example 6 to give 29.05 9 of yellow solid prepolymer. Analysis of the prepolymer by GPC indicated a weight average molecular weight of 13,800 for this sample as standardized against polystyrene.

~ WO 94tl5258 2 ~ ~1 1 5 ~ PCT/US93/11562 Example 8: 10 Mole Percent Chalcone/90 Mole Percent TVE.

TVE Monomer (30 9) and chalcone monomer (2.50 g) were combined and B-staged at 150C for 4.75 hours using the procedure of Example 6 to give 28.02 9 of yellow sol id prepolymer. Analysis of the prepolymer by GPC indicated a weight average molecular weight of 34,800 for this sample as standardized against polystyrene.

Example 9: 50 Mole percent Chalcone/50 Mole percent TVE.

TVE Monomer (30 9) and chalcone monomer (11.24 9) were combined and B-staged at 150C for 4.25 hours using the procedure of Example 6 to give 40.00 9 of yellow solid prepolymer. Analysis of the prepolymer by GPC indicated a weight average molecular weight of 3,160 for this sample as standardized against polystyrene.

Example 10: 10 Mole percent Bischalcone/90 Mole percent TVE.

TVE Monomer (20 9) and bischalcone monomer (1.77 9) were combined and 8-staged at 150C for 4 hours using the procedure of Example 6 to give 19.00 9 of yellow solid 20 prepolymer. Analysis of the prepolymer by GPC indicated a weight average molecular weight of 4,400 for this sample as standardized against polystyrene.

Examples 11 - 15: Spi n coating a photosensitive prepolymer onto a 1 û-centi meter diameter silicon oxide wafer and photocrosslinking the prepolymer film In the following examples the silicon oxide wafers were pretreated with an adhesion promoteraccordingtothe following method:

Bis[3-(triethoxysilyl)propyllamine(commerciallyavailablefrom HulsAmerica Inc.) 30 (O.S0 9) was combined with distilled water (0.50 g) for 14 minutes to promote some prehydrolysis and condensation of the silane functionality. This solution was then diluted with 24 ml of methanol to form a 2 weight percent solution of the adhesion promoter in methanol.
A portion of the adhesion promoter solution (5 ml) was drawn into a syringe and filtered through a 1.0 micron (0.001 mm) filter onto the surface of the silicon wafer which was spinning 35 at 5000 revolutions per minute (rpm) on a Solitec Model 5100 Spin Coater. After the adhesion promoter was applied, the substrate continues to spin at 5000 rpm for 90 seconds to evaporate the water and methanol from the adhesion promoter coating.

40,2~F 21 Sl 1~1 Example 11: Photocrosslinking of a Copolymer of 5 Mole Percent Chalcone Monomer/95 Mole Percent TVE Monomer The prepolymer of 5 mole percent chalcone/95 mole percent TVE monomer from 5 Example 6 above (weight average molecular weight = 7,810 g/mole) was dissolved to make a 50 percent solid solution in mesitylene. The prepolymer solution was filtered from a syringe through a 0.2 micron (0.0002 mm) fi Iter (to remove small particles) i nto a 100 m L clean bottle.
The term 'clean bottle' isused to refer to a bottle which hasbeen cleaned to contain less than 0.001 particle of size 0.30 micron or larger per milliliter of volume. The prepolymer solution (2 10 mL)wasthendepositedontoa10cmroundsiliconoxidewaferusingaspreadcycleof500rpm for 3 seconds and a spin cycle of 5000 rpm for 30 seconds to give a film of excellent quality (no large variation in film thickness as noted by the absence of unassisted visually detected colored interference patterns on the wafer). The prepolymer film was prebaked at 80C for 30 minutes to remove residual solvent and to enhance adhesion of the prepolymer onto the subtrate. The prepolymer fi I m thickness as determi ned by an Al pha Step-200 Prof i I emeter was 1 572 m i crons.

The prebaked prepolymer (5 mole percent chalcone/95 mole percent TVE) was exposed to UV light (wavelength range = 290-350 nanometers (nm),1000 Watts) using a high pressure mercury xenon short arc lamp for an exposure time of 250, 500,800, and 999 seconds 20 (seconds.) using a fused silica quartz test mask for pattern transfer. The exposed film was then developed by soaking in xylene solvent for 15 seconds and then dried under a stream of nitrogen at a tem perature of 25C. A negative relief of the pattern on the quartz mask was sucessfully transferred to the polymer upon development as indicated by uncrosslinked areas within the pattern which were washed away by the developing solvent (xylene). The pattern 25 results indicated that an exposure time of 999 seconds was sufficient to crosslink the prepolymer to an extent sufficient to render it i nsol uble i n the developi ng solvent. Exposure times of 800 seconds or less under these conditions were found to be insufficient to pattern the fil m. Other solvents such as dichloromethane and 2-methoxyethyl ether were also excellent solvents for development under the same development conditions. The film thickness 30 measured after lJV exposure and development was determi ned to be 1.485 microns. The loss in film thickness was 6 percent after solvent development.

Following the general procedure of Example 11, further examples of processing good quality thin films of photodefinable prepolymers onto 10 cm silicon oxide substrates were 35 outlined in the following examples of the invention:
.

Example 12: (10 mole percent chalcone / 90 mole percent TVE) AMEN~ED SHEET
IPE~/EP

WO 94/15258 ~ l S l 151 PCT/US93/11~62 B-Staging Conditions: 4 0 hours at 1 50C;

Spin Coating Conditions:
5 Spread cycle: 500 rpm for 45 seconds.
Spin cycle: 1500 rpm for 30 seconds to yield a 1.4 micron coating after photocrosslinking.

Polymer Prebake and Solvent Evaporation = 80C for 30 minutes;

10 UV exposure time: 999 seconds;

Developing solvent: 2-methoxyethyl ether for 15 seconds;

Thermal Cure: 2hr(hour)rampto210C(hold 1 hr). ["2hourrampto210C" referstoraising the temperature from room temperature to 210C over a 2 hour period; then "hold 1 hr"
means the plate was held at 21 0C for 1 hour.l Example 13: (10 mole percent chalcone / 90 mole percent TVE) 20 B-Staging Conditions: 4.75 hours at 1 50C;

Spin Coating Conditions:
Spread cycle: 500 rpm for 3 seconds.
Spin cycle: 9000 rpm for 30 seconds to yield a 4.4 micron coating after photocrosslinking.

Polymer Prebake and Solvent Evaporation: 80C for 30 minutes;

UV exposure time: 999 seconds;

30 Developing solvent: 2-methoxyethyl ether for 15 seconds;

Thermal Cure: 2 hr ramp to 210C (hold 1 hr).

Examplel4:(10mole percentchalcone/9Omole percentTVE) B-Stagi ng Conditions: 4.0 hours at 1 50C;

Spin Coating Conditions:

WO 94/15258 21 ~ 1 PCT/US93/11562 Spread cycle: 500 rpm for 45 seconds.
Spin cycle: 1500 rpm for 30 seconds to yield a 1.4 micron coating after photocrosslinking.

Polymer Prebake and Solvent Evaporation: 2 hours ramp from 50C to 120C (hold 1 hour);

UV exposure time: 999 seconds;

Developing solvent: 2-methoxyethyl ether for 15 seconds;

l O Thermal Cure: 2 hr ramp to 210C (hold l hr) Example 15: (lOmole percentchalcone/9Omole percentTVE) B-Staging Conditions: 4.75 hours at 150C;

Spin Coating Conditions:
Spread cycle: 500 rpm for 3 seconds.
Spin cycle: 9000 rpm for 30 seconds to yield a 4.4 micron coating after photocrosslinking.

20 Polymer Prebake and Solvent Evaporation: 2 hours ramp from 50C to 120C (hold 1 hour);

UV exposure time: 999 seconds;

Developing solvent: 2-methoxyethyl ether for 15 seconds;

Thermal Cure: 2hrrampto210C(hold 1 hr).

Example 16: (50 mole percent chalcone / 50 mole percent TVE) 30 B-Staging Conditions: 4 25 hours at 150C;

Spin Coating Conditions:
Spread cycle: 500 rpm for 3 seconds.
Spin cycle: 9000 rpm for 30 seconds to yield a coating of unknown thickness after 35 phOtocrosslinking Polymer Prebake and Solvent Evaporation: 30 minutes ramp from 50C to 120C (hold 30 minutes);

WO 94/1~258 ~ ~ 51 151 lPCT/US93/11562 UV exposure time: 999 seconds;

Developing solvent: 2-methoxyethyl ether for 15 seconds;

Thermal Cure: 2 hr ramp to 21 0C (hold 1 hr).

Example 17: (10 mole percent bischalcone/90 mole percentTVE) B-Staging Conditions: 4.00 hours at 1 50C;

Spin Coating Conditions:
Spread cycle: S00 rpm for 3 seconds.
Spin cycle: 9000 rpm for 30 seconds to yield a 1.0 micron coating after photocrosslinking.

Polymer Prebake and Solvent Evaporation: 2 hours ramp from 50C to 1 20C (hold 1 hour);

UV exposure time: S00 seconds;

20 Developing solvent: 2-methoxyethyl ether for 15 seconds;

Thermal Cure: 2 hrrampto210C(hold 1 hr). (SeeTable 1).

Conditions for photodefining the copolymer of the bischalcone (10 mole percent) with TVE (90 25 mole percent) in Example 17 were si milar to those in the previous examples, except that the wavelength range of 350-450 nm used for pattern transfer (see Table 2). In an exposure time of 500 seconds, the energy dosage required for crosslinking 10 mole percent bischalcone / 90 mole percent TVE prepolymer fi I m of 4400 weight average molecular weight and 1.0 micron thickness was 30 J/cm2 (at 365 nm).

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WO 94/15258 ~ S~ PCT/US93/11562 In the last column, F, D = the quality of the wafer was fair and the polymer film delaminated duringdevelopement; E = excellentquality; ND = nodelamination; NDT = nodelamination on the top side of the wafer; however, some dissolving of the polymer closest to the silicon 5 oxide wafer was observed. G = a good quality film was obtained. The difference between G
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~o WO 9411S258 ~151151 PCT/US93/11562 Examples 18-20 and Comparative Sample A: Optical Density Measurements and Photobleaching of Photocrosslinkable Prepolymer Films Sol utions of prepolymer (50 percent by weight) with the followi ng compositions;
5 100 mole percent TVE (Comparative Sample A, not an example of the invention), S mole percentchalcone/95moiepercentTVE(Example 18), 10molepercentchalcone/9Omole percent TVE (Example 19), 50 mole percent chalcone/50 mole percent TVE (Example 20) were each separately prepared i n mesitylene. The solutions were filtered through a 0.20 micron filter and then spin coated on 10 centimeter quartz substrates using a spread cycle of 500 rpm for 3 seconds and a spin cycle of 9000 rpm for 30 seconds to yield the following film thicknesses before exposure to uv light; 1.042,1.482,1.398, 1.280, and 1.000 microns, respectively Each coated quartz wafer was exposed to UV light for 999 seconds between the wavelengths of 290-350 nm. The UV absorption spectra for each wafer was analyzed between 200 and 500 nm wavelengths with a Perkin Elmer Model Lambda 3B UVNIS Spectophotometer before and after UV exposure. The spectra of the photocrosslinkable copolymer before photoexposure had the characteristic lambda max (that was the wavelength of maximum absorbance of the prepolymer film in the region of 260 nm to 450 nm); the spectra of the photoexposed prepolymer films had a decrease of absorbance at the position of the lambda 20 max of the photocrosslinkable copolymer. The lambda max for the chalcone and bischalcone contai ni ng prepolymers were 314 and 330 nm, respectively.

The spectra and the optical density measurements for both photodefinable materials before and after UV exposure indicated thatthe copolymer "bleaches" (that is, it 25 turns colorless from 260 nm to 500 nm) upon exposure to UV light. Data for the optical density measurementsofthechalconeandbischalconecontainingprepolymerfilmsat313nm,334 nm, and 365 nm before and after exposure to UV light appear in Tables 3 and 4, respectively.

These examples demonstrated bleaching of these photocrosslinkable copolymers 30 after photoexposure WO 94/15258 2~5 ~5 ~ PCT/US93/11562 .~
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o WO 94/15258 21~ 115 ~ PCT/US93/11562 Example 21: Preparation of ,~-(4-dimethylaminobenzylidene)-4-trifiuoroethenyloxyacetophe none 4-Trifluoroethenyloxyacetophenone (prepared in Example 5 above,10.0 9,0.046 5 mole) was combined with dimethylaminobenzaldehyde (commercially available from Aldrich Chemical Co., 7.59 9, O.OS l mole) in 60 ml of reagent alcohol in the apparatus described for the preparation of ,~-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone in Example S, Method l, and stirred at 0-5C with a slow feed of anhydrous HCI for 78 hours.
Nitrogen was blown through the reaction mixture to remove some HCI, then the alcohol was 10 evaporated to provide the crude prod uct mi xtu re. This mixture was dissolved in dichloromethane and carefully washed with aqueous potassium carbonate to neutralize the acid. The dichloromethane was evaporated, and the residue was subjected to column chromatography on alumina using hexane saturated with acetonitrile as an eluent, to provide 11.4 g (71 percent) of the ~-(4-dimethylaminophenyl)-4-trifluoroethenyloxyacetophenone as an orange crystalline sol id with a melting poi nt of 68-72C.

Spectral analysis of this product indicated a lambda max of 412 nm in acetonitrile solution, with an extinction coefficient of 29,560.

20 MassSpectrometricAnalysis: m/e = 121 (7.4percent); 146(6.1 percent); 174(6.1 percent); 250 (12.3 percent); 347 (100 percent); 348 (30.8 percent) was consistent with identification as ~-(4-dimethylamino-benzylidene)-4-trifluoroethenyloxyacetophenone.

Example 22: Copolymerization of ~-(4-dimethylaminobenzylidene)-4-trifluoroethenyloxy-25 acetophenone and TVE monomer ~ -(4-dimethylaminobenzylidene)-4-trifluoroethenyloxyacetophenone (1.4052 9, 0.00404 mole) prepared according to the procedure of Example 21 was combined with the TVE
monomer (20.01 9, 0.0366 mole) and mesitylene solvent (21.4 9) in a 200 ml round bottomed 30 flask equipped with a reflux condenser and a thermocouple attached to a temperature controller which controls a heati ng mantle on the flask through a Variac rheostat power supply. A magnetic stirring bar was placed in the flask, and the flask was placed on a magnetic stirrer to provide agitation during the polymerization process. The mixture was thoroughly deoxygenated by bubbling nitrogen through a gas dispersion tube into the stirred solution, 35 and was thereafter maintained under a nitrogen atmosphere. The solution was heated to 160C with stirring for 5 hours, then cooled WO 94/15258 ~l S~l PCT/US93/11562 The molecular weight of the prepolymer was checked by gel permeationchromatography (GPC) as standardized against polystyrene. The weight average molecular weightwasfoundtobe6,316 Thesolutionwasheatedtol60Cforanadditional65minutes, after which time it was cooled and the molecular weight tested again. The weight average 5 molecular weight of the prepolymer was 12,434 as determined by GPC as standardized against polystyrene. The solution was heated to 160C for an additional 60 minutes, then cooled to test the molecular weight. The weight average molecular weight of the prepolymer was 38,442 Example 23: Preparation of i3-(4-methoxybenzylidenej-4-trifluoroethenyloxyacetophenone 4-Trifiuoroethenyloxyacetophenone (l O.0 9, 0.0463 mole) was combined with 4-anisaldehyde (commercially available from Aldrich Chemical Co.) (6.9 g,0.050 mole) in reagent alcohol in the apparatus described for the preparation of ,~-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxy-acetophenone in Example 5, Method 1 above, and was cooled to 0C-5C with stirring. After the solution was deoxygenated by bubbling nitrogen through a gas dispersion tube for 10 minutes, anhydrous HCI was introduced into the solution at a rate that maintained a solution temperature of 5C. After 1.5 hours the solution turned red, and a solid precipitate began to form. The HCI feed was stopped after 4 hours, and nitrogen was blown through the solution to remove some of the HCI. The 20 alcohol was evaporated, and the remaining solid was dissolved in 100 ml of dichloromethane.
The dichloromethane solution was carefully washed with aqueous potassium carbonate to neutralize the acid. The dichloromethane was then removed from the product by evaporation on a rotary evaporator. Analysis of the fi nal product by gas chromatography indicates that the material was greater than 97 percent pure and requires no further purification.

This product had a melting point of 70.0-71.5C.

Spectral analysis of this product indicated that it exhibits a lambda max of 338 nm in acetonitrile solution, with an extinction coefficient of 20,029.

Mass Spectrometric Analysis: m/e = 89 (6.2 percent); 165 (8.6 percent); 303 (8.1 percent); 333 (9.8 percent); 334 (100 percent); 335 (51.3 percent); 336 (8.15 percent) was consistent with identification as ~-(4-methoxybenzylidene)-4-trifiuoroethenyloxyacetophenone.

35 Example 24: Copolymerization of ~-(4-methoxybenzylidene)-4-trifluoroethenyloxyacetophenone with TVE Monomer:

W O 94/15258 21~ PCTrUS93/11562 i3-(4-methoxyben~ylidene)-4-ttifluoroethenyloxyacetophenone(1.3544 9, 0.00405 mole) was combined with TVE monomer (20.02 9,0.0366 mole) and mesitylene solvent (21.37 9) in the apparatus of Example 2Z, and was deoxygenated thoroughly by introducing nitrogen through a gas dispersion tube for 10 minutes, and thereafter maintaining the soiution under a nitrogen atmosphere. The solution was heated to 160C for 3 hours and 10 minutes, after which time it was cooled and the solution was checked by GPC analysis to ascertain the molecular weight of the prepolymer. The weight average molecular weight of the prepolymer was 379,400.

Claims

1. A polymer comprising at least one photoactive site and more than one perfluorocyciobutane group.

2 The polymer of Claim 1 wherein photoactive sites are in side chains.

3. A polymer of Claim 2 comprising repeating units represented by the formula:

wherein PAS is a photoactive site or photoactive precursor; R is an optionally inertly substituted hydrocarbyl group; and X is a bond or any group which links R and a perfluorocyclobutane group.

4. The polymer of Claim 3 wherein each R is an aromatic hydrocarbyl group of from 6 to 50 carbon atoms and X includes at least one S, O, Si, N or P atom between R and the perfluorocyclobutane group.

5. The polymer of Claim 1 which are reaction products of compounds of Formula XIII:
PAS-R(-X-CF = CF2)t wherein PAS is a photoactive site or photoactive precursor, R is an optionally inertly substituted hydrocarbyl group, X is a bond or linking group which links R and a perfluorovinyl group, and t is 1, reacted or copolymerized with 1,1,1-tris (4'-trifluoroethenyloxy phenyl)ethane, (1,3,5-tris(2-(4-trifluoroethenyloxy)phenylene)-2-propyl)benzene), the trifluorovinyl etherified Novolac polyphenolic compounds, or mixtures thereof.

6. The polymer of Claim 2 which are prepared from monomers comprising those of the formula:

(Formula V) wherein X is a bond or linking group which links R" and a perfluorovinyl group; R" is an unsubstituted or inertly substituted hydrocarbyl group substituted with PAS which is a photoactive site or precursor; q is an integer of from 0 to 4; and r is an integer from 1 to 4.

7. The polymer of Claim 2 formed by polymerization or copolymerization of compounds of Formula XVI:

wherein PAS is a photoactive site or photoactive precursor and R is an unsubstituted or inertly substituted hydrocarbyl group.

8. The polymer of Claim 2 comprising at least one reaction product of a compound having at least three trifluorovinyl groups with 1-acryloxy-2-(4-trifluoroethenoxy)-benzoyloxyethane; 1-methacryloxy-2-(4-trifluoroethenoxy) benzoyloxyethane, or mixtures thereof.

9. The polymer of Claim 1 wherein the photoactive sites are in the polymer backbone.

10. The polymer of Claim 9 prepared from monomers comprising those of a formula:

CF2 = CF-X-PAS-(X-CF = CF2)q (Formula IV) wherein PAS is a photoactive site or photoactive precursor; X is any bond or group which links PAS and the perfluorovinyl group; and q is an integer of from 0 to 4 11. The polymer of Clalm 1 whlch comprises at least one of 4,4'-bis(trifluoroethenyloxy)-.alpha.-methylstilbene, 1,5-bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one; .beta.-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone, ~-(4-dimethylaminobenzylidene)-4-trifluoroethenyloxy-acetophenone; .beta.-(4-methoxybenzylidene)-4-trifluoroethenyloxyacetophenone or mixtures thereof.

12. The polymer of Claim 11 which is a copolymerization product also comprising 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane, 4,4'-bis(trifluoroethenyloxy)biphenyl or mixtures thereof.

13. The polymer of Claim 1 havlng moisture absorption less than 2 percent, dielectric constant below 3.5, dissipation factor below 0.01, flame retardency, tensile modulus orflexuralmodulusofatleast150,000psi(1,034,213kPa),orthermal-oxidativestabilityabove 100°C.

14 A compound having at least one trifluorovinyl group and at least one photoactive site or photoactive precursor excluding compounds of the formula:

CF2=CF-[OCF2CF(CF3)]p-[O(CF2)q]r-CH2OR1 wherein:
R1 is alkyl or cycloalkyl containing 1 to 30 carbon atoms, C-C=CH2, or -(CH2)tR5;

R2 is hydrogen or methyl;

R3 is-C=CH, -CH = CH2, styryl or ;

R5 is aryl or substituted aryl;
p is an integer of 0 to 20;
q is an integer of 1 to 10;
r is 0 or 1;
s is 1, 2, 3 or4; and t is 0, 1, 2, 3 or 4;

provided that when r is 0, p is not 0.

and excluding compounds of the formula CF2XCFX-[OCF2CF(CF3)]p-[O(CF2)q]r-CH2OR1 wherein:

R1 is alkyl or cycloalkyl containing 1 to 30 carbon atoms, -C-C = CH2, , -(CH2)tR5 or hydrogen;

R2 is hydrogen or methyl;
R3 is -C?CH, -CH=CH2, styryl or ;

R5 is aryl or substituted aryl;
each X is independently chlorine or bromine;

-59a-p is an i nteger of 0 to 20;
q is an integer of 1 to 10;
r is 0 or 1;
s is 1, 2, 3 or 4; and t is 0, 1, 2, 3 or 4;

provided that when r is 0, p is not 0, and further provided that when p is 0, q is three, r is 1, and R1 is not hydrogen.

-59b-15. The compound of Claim 14 having at least one photoactive site or photoactive precursor which is an unsubstituted or inertly substituted stilbene, styrene, 1-aryl propenyl, bischalcone, chalcone, coumarin, (benzylidene)cyclohexanone, bis(benzylidene)cyclohexanones, cinnamylidene cyclohexanone, bis(aryl)nonatetraene, bis(cinnamylidene cyclohexanone), 1,5-diaryl-1,4-pentadiene-3-one, cyclohexadienone, acrylate, methacrylate, maleimide, naphthoquinone, polyacetylene, cinnamic acid, cinnamate ester, cinnamaldehyde,.beta.,.beta.'-bis(benzoyl) divinylbenzene, benzophenone or combination thereof.

16. The compound of Claim 14 represented by at least one of the Formulae:

PAS-R(-X-CF = CF2)t (Formula XIII) wherein PAS is a photoactive site or photoactive precursor, R is an optionally inertly substituted hydrocarbyl group, and X is a bond or linking group which links R and a perfluorovinyl group; t is 1;

(Formula V) wherein X is as defined for Formula XIII; R" is an unsubstituted or inertly substituted hydrocarbyl group substituted with PAS which is as defined for Formula XII; q is an integer of from 0 to 4; and r is an integer from 1 to 4;

CF2 = CF-X-PAS-(X-CF=CF2)q (Formula IV) wherein PAS is a photoactive site or photoactive precursor; X is any bond or group which links PAS and the perfluorovinyl group; and q is an integer of from 0 to 4;
(G)n-PAS-(X-CF=CF2)m (Formula XII) wherein X and PAS are as defined for Formula IV; G is a reactive functional group or precursor thereof; n and m are independently integers of from 1 to 3; or (Formula XVI) wherein PAS is a photoactive site or photoactive precursor and R is an unsubstituted or inertly substituted hydrocarbyl group.

17. The compound of Claim 16 represented by Formula XVI wherein R is substituted with at least one photosensitizing group.

18. The compound of Claim 16 which is selected from 4,4'-bis(trifluoroethenyloxy)-a-methylstilbene, 1,5-bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one; .beta.-(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone;
.beta.-(4-dimethylaminobenzylidene)-4-trifluoroethenyloxy-acetophenone; .beta.(4-methoxybenzylidene)-4-trifluoroethenyloxyacetophenone.

19. The compound of Claim 14which is formed from a perfluoroethenyloxy-substituted acetophenone and an aldehyde 2û. The compound of Claim 19 wherein the acetophenone is substituted with at least one cyano, nitro, sulfonate ester, sulfonamide, trifluoromethyl, carboxylic ester, aldehyde, ketone, or halo group, or the benzaldehyde is substituted with at least one tertiary amine, hydroxy group, ether, or alkoxy group para to the aldehyde or propenaldehyde group.

21. The compound of Claim 16 selected from .beta.-(4-hydroxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-acetylbenzylidene)-4-(trifiuoroethenyloxy)acetophenone, .beta.-(4-Acetyloxybenzylidene)-4-(trifluoroethenyloxy) acetophenone, .beta.-(4-aminobenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-carboxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-isocyanatobenzylidene)-4-(trifiuoroethenyloxy)acetophenone, .beta.-(4-chlorocarboxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-carboxymethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-carboxyethylbenzylidene)-4-ttrifiuoroethenyioxy)acetophenone, 4-hydroxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-amino-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-chlorocarboxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-isocyanato-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxymethyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxyethyl-.beta.-4-(trifluoroethenyloxybenzylidene)acetophenone, 1-(4-hydroxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-hydroxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-aminophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-aminophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-carboxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-carboxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-chlorocarboxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-chlorocarboxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-isocyanatophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-isocyanatophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-carboxymethylphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-carboxymethylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 4-hydroxy-4'-trifluoroethenyloxystilbene, 4-aminophenyl-4'-trifluoroethenyloxystilbene, 4-carboxyphenyl-4'-trifluoroethenyloxystilbene, 4-isocyanato-4'-trifluoroethenyloxystilbene, 4-carboxymethyi-4'-trifluoroethenyloxystilbene, 5-hydroxy-8-trifluoroethenyloxynaphthoquinone, 1-(4-hydroxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-aminophenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-carboxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-carboxymethylphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 1-(4-isocyanatophenyll-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadien-3-one, 5-hydroxy-8-trifluoroethenyloxycoumarin, 8-hydroxy-5-trifluoroethenyloxycoumarin, 5-amino-8-trifluoroethenyloxycoumarin, 8-amino-5-trifluoroethenyloxycoumarin, 5-isocyanato-8-trifluoroethenyloxycoumarin, 8-isocyanato-5-trifluoroethenyloxycoumarin, 2-(4-hydroxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-hydroxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-aminobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-aminobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-carboxymethylbenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-carboxymethylbenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-isocyanatobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-isocyanatobenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone, 2-(4-chlorocarboxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)cyclohexanone, 2-(4-chlorocarboxybenzylidene)-6-(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone.

22. The compound of Claim 16 selected from 1-(4-acryloxyphenyl)-1,1-bis(4-trifluoroethenyloxyphenyl)ethane, 1-(4-methacryloxyphenyl)-1,1-bis(4-trifluoroethenyloxyphenyl)ethane, 1-(4-acrylphenyl)-1,1-bis(4-trifluoroethenyloxyphenyl)ethane, 1-(4-methacrylphenyl)-1,1-bis(4-trifluoroethenyloxyphenyl)ethane, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-,.beta.-(benzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-dimethylaminobenzylidene) acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-methoxybenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-trifluoromethylbenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-carboxymethylbenzylidene) acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-nitrobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-chlorobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-fluorobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4-acetylbenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl) .beta.-(4-cyanobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)styrene, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-N-phenyl maleimide, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-phenyl-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(dimethylamino)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-methoxyphenyl)- 1,4-pentadiene-3-one, 1-(4(1,1-bis(4-trifiuoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(carboxymethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(carboxyethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-(trifluoromethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-nitrophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-chlorophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-fluorophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-acetophenyl)-1,4-pentadiene-3-one, 1-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl)-5-(4-cyanophenyl)-1,4-pentadiene-3-one, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl acetylene, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl buta-1,3-diyne, 4-(1,1-bis(4-trifl uoroethenyloxyphenyl)ethyl)phenyl hexa-1,3,5-triyne, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl octa-1,3,5,7-tetrayne, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenyl-1,3,5,7,9-pentayne, 6-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)naphthoquinone, 6-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)coumarin, 7-(4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)phenoxy)coumarin, 2-(4-(1,1-bis(trifluoroethenyloxyphenyl)ethyl)benzylidene)cyclohexanone, 2-(4-(4-(1,1-bis(trifluoroethenyloxyphenyl)ethyl)phenoxy)benzylidene)cyclohexanone, 1-acroyloxy-2-(4-trifluoroethenyloxy)benzoyloxyethane, 1-methacroyloxy-2-(4-trifluoroethenyloxy)benzoyloxyethane, N-(4-trifluoroethenyloxyphenyl)acrylamide, N-(4-trifluoroethenyloxyphenyl)methacrylamide, 4-trifluoroethenyloxyphenyl acrylate, 4-trifluoroethenyloxyphenyl methacrylate, N-(4-trifluoroethenyloxyphenyl)maleimide, N-(4-trifluoroethenyloxybenzoyl)maleimide,.beta.-(4-methoxybenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-dimethylaminobenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-carboxymethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-carboxyethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-nitrobenzyl idene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-chlorobenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-fluorobenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-acetylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-cyanobenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(3-trifluoromethylbenzylidene)-4-(trifluoroethenyloxy)acetophenone, .beta.-(4-trifluoromethylbenzylidene)-4-(trifluoroethenyloxy)acetophenorie, .beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-methoxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-dimethylamino-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxymethyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-carboxyethyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-chloro-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-nitro-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-fluoro-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-acetyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-cyano-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-trifluoromethyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 3-trifluoromethyl-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone, 4-trifluoroethenyloxycinnamaldehyde, 4-trifluoroethenyloxycinnamic acid, 4-trifluoroethenyloxycinnamic acid, methyl ester, 4-trifluoroethenyloxycinnamic acid, ethyl ester, 4-trifluoroethenyloxycinnamic acid, isopropyl ester, 4-trifluoroethenyloxycinnamic acid, phenyl ester, 1-(4-trifluoroethenyloxyphenyl)-propen-1-one, 1-(4-trifluoroethenyloxyphenyl)-1-buten-3-one, 5-(trifluoroethenyloxy)naphthoquinone, 6-(trifluoroethenyloxy)naphthoquinone, 5-(4-(trifluoroethenyloxy)benzoyloxy)naphthoquinone, 6-(4-(trifluoroethenyloxy)benzoyloxy)naphthoquinone, 5-(trifluoroethenyloxy)coumarin, 6-(trifluoroethenyloxy)coumarin, 7-(trifluoroethenyloxy)coumarin, 8-(trifluoroethenyloxy)coumarin, 5-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 6-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 7-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 8-(4-(trifluoroethenyloxy)benzoyloxy)coumarin, 2-(4-trifluoroethenyoxylbenzylidene)cyclohexanone, 1-(4-trifluoroethenyloxyphenyl)-5-phenyl-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(dimethylamino)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-methoxyphenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(carboxymethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(carboxyethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-(trifluoromethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(3-(trifluoromethyl)phenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-nitrophenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-chlorophenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-fluorophenyl)-1,4-pentadiene-3-one, 1-(4-trifluoroethenyloxyphenyl)-5-(4-acetophenyl)-1,4-pentadiene-3-one, 1-(4-methoxyphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-methoxyphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-dimethylaminophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-dimethylaminophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-carboxymethylphenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-carboxymethylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-chlorophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-chlorophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-nitrophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-nitrophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-fluorophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-fluorophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 1-(4-cyanophenyl)-2-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-cyanophenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-acetylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 2-(4-acetylphenyl)-1-(4-trifluoroethenyloxyphenyl)-1-propene, 4-methoxy-4'-trifluoroethenyloxystilbene, 4-dimethylaminophenyl-4'-trifluoroethenyloxystilbene, 4-carboxymethylphenyl-4'-trifluoroethenyloxystilbene, 4-carboxyethylphenyl-4'-trifluoroethenyloxystilbene, 4-nitro-4'-trifluoroethenyloxystilbene, 4-chloro-4'-trifluoroethenyloxystilbene, 4-fluoro-4'-trifluoroethenyloxystilbene, 4-cyano-4'-trifluoroethenyloxystilbene, 4-acetyl-4'-trifluoroethenyloxystilbene, 4-trifluoromethyl-4'-trifluoroethenyloxystilbene, 1-(4-dimethylaminophenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one, 1-(4-methoxyphenyl)-5-(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one, .beta.-cinnamylidene-4-trifluoroethenyloxyacetophenone, .beta.-(4'-dimethylaminocinnamylidene)-4-trifluoroethenyloxyacetophenone, .beta.-(2'-methoxycinnamylidene)-4-trifluoroethenyloxyacetophenone, .beta.-(4'-methoxycinnamylidene)-4-trifluoroethenyloxyacetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(benzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-methoxybenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-dimethylaminobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-cyanobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-nitrobenzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(cinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(2'-methoxycinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-methoxycinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-dimethylaminocinnamylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)-.beta.-(4'-nitrocinnamylidene)acetophenone, 1,1-bis(4-trifluoroethenyloxyphenyl)-1-(4-(3-(2-furanyl)-2-propene-1-onyl)phenyl)ethane, 1,1-bis(4-trifluoroethenyloxyphenyl)-1-(4-(5-(2-furanyl)-2,4-pentadiene-1-onyl)phenyl)ethane, 3,5-bis(trifluoroethenyloxy)-.beta.-(benzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'-methoxybenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'-dimethylaminobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'-cyanobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'-nitrobenzylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(cinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(2'-methoxycinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'-methoxycinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(4'dimethylaminocinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-.beta.-(nitrocinnamylidene)acetophenone, 3,5-bis(trifluoroethenyloxy)-1-(3-(2-(furanyl)-2-propene-1-onyl)benzene, 3,5-bis(trifluoroethenyloxy)-1-(5-(2-(furanyl)-2,4-pentadiene-1-onyl)benzene, 2-(3-phenyl-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(2-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-dimethylaminophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-cyanophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(3-(4-nitropheny1)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-phenyl-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(2-methoxyphenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-dimethylaminophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-cyanophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(3-(4-nitrophenyl)-2-propene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-phenyl-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-methoxyphenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(2-methoxyphenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-dimethylaminophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-cyanophenyl)-2,4-pentadiene-l-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2-(5-(4-nitrophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-phenyl-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4 methoxyphenyl)-2,4-pentadiene-l-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4-dimethylaminophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(2-dimethylaminophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, 2,7-bis(5-(4-cyanophenyl)-2,4-pentadiene 1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene, and 2,7-bis(5-(4-nitrophenyl)-2,4-pentadiene-1-onyl)-9,9-bis(4-trifluoroethenyloxyphenyl)fluorene.

23. The compound of Claim 16 selected from 4,4'-bis(trifluoroethenyloxy)-.alpha.-methylstilbene; 4,4'-bis(trifluoroethenyloxy)stilbene; 4-Trifluoroethenyloxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone; 2,6-bis(4-trifluoroethenyloxybenzylidene)cyclohexanone; 2,6-bis(4-trifluoroethenyloxybenzylidene)-4-methylcyclohexanone; 1,4-bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1, bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1,4-bis(3-(4-trifluoroethenyloxyphenyl)-1-propene-3-onyl)benzene; 1,3-bis(3-(4-trifluoroethenyloxyphenyl)-1-propene-3-onyl)benzene; 1,5-bis(4-trifluoroethenyloxyphenyl)-1,4-pentadiene-3-one; 4-Trifluoroethenyloxy-.beta.-(4-trifluoroethenyloxybenzylidene)acetophenone; 4,4'-bis-(trifluoroethenyloxy)stilbene; 4,4'-bis(trifluoroethenyloxy)-a-methylstilbene; .beta.,.beta.'-bis(4-trifluoroethenyloxybenzylidene)-1,4-diacetylbenzene; .beta.,.beta.'-bis(4-trifluoroethenyloxybenzylidene)-1,3-diacetylbenzene; .beta.,.beta.'-bis(4-trifluoroethenyloxybenzylidene)-1,2-diacetylbenzene; 5,8-bis(trifluoroethenyloxy)coumarin;
2,6-bis(4,trifluoroethenyloxybenzylidene)cyclohexanone; 2,6-bis(4,trifluoroethenyloxybenzylidene)-4-methylcyclohexanone; 5,8-bis(trifluoroethenyloxy)naphthoquinone; .beta.,.beta.'-bis(4-trifluoroethenyloxybenzoyl)-1,4-divinylbenzene, and 4,4'-bis(trifluoro-ethenyloxy)benzophenone.

24. The compound of Claim 16 represented by the formula:
(G)n-PAS-(X-CF = CF2)m (Formula XII) wherein X is oxygen, PAS is ArC(O)CH = CH-Ar wherein Ar is an aromatic hydrocarbyl group of from 6 to 50 carbon atoms.

25. A compound selected from 4,4'-bis(2-bromotetrafluoroethoxy)-.alpha.-methylstilbene; 4-(2-bromotetrafluoroethoxy)benzaldehyde; 4-(2-bromotetrafluoroethoxy)acetophenone; .beta.-(4-(2-bromotetrafluoroethoxy)benzylidene)-4-(2-bromotetrafluoroethoxy)acetophenone.

26. A method of using a polymer having at least one photoactive site and plural perfluorocyclobutane groups as a coating comprising application of at least one such polymer, which polymer is at least partially soluble or dispersible, to a surface and exposing at least a portion of said polymer to incident photonic radiation sufficient to render the polymer so exposed less soluble or dispersible.

27. The method of Claim 26 wherein the polymer is formed from monomers including at least one monomer having at least one photoactive site or precursor and three or more trifluorovinyl groups or is polymerized in a system containing with a comonomer having at least three or more trifluorovinyl groups in sufficient quantity to result in a thermoset polymer.

28. The method of Claim 26 wherein the polymer is formed from monomers having two perfluorovinyl groups and at least one photoactive site or precursor optionally with different monomers having at least two perfluorovinyl groups which polymer is irradiated to form a crosslinked polymer.

29. The method of Claim 26 wherein photosensitizer compounds are also used with the polymer in a quantity sufficient to increase the effect wavelength of the incident photonic radiation.

30. A method of using a polymer having at least one photoactive site and more than one perfluorocyclobutane group as a negative photoresistant comprising the steps of (1) applying at least one such polymer, which polymer is at least partially soluble or dispersible in a solvent, to a surface or substrate (2) exposing a portion of said polymer to incident photonic radiation such that the exposed portion of the polymer becomes less soluble or dispersible than a remaining unexposed portion, and (3) removing the unexposed portion.

31. A process of preparing a compound represented by at least one of the Formulae.

PAS-R(-X-CF = CF2)t (Formula XIII) wherein PAS is a photoactive site or photoactive precursor, R is an optionally inertly substituted hydrocarbyl group, and X is a bond or iinking group which links R and a perfluorovinyl group; t is 1;

(Formula V) wherein X is as defined for Formula XIII; R" is an unsubstituted or inertly substituted hydrocarbyl group substituted with PAS which is as defined for Formula XIII; q is an integer of from 0 to 4; and r is an integer from 1 to 4;

CF2=CF-PAS-(X-CF=CF)q (Formula IV) wherein PAS is a photoactive site or photoactive precursor; X is any bond or group which links PAS and the perfluorovinyl group; and q is an integer of from 0 to 4;

(G)n-PAS-(X-CF=CF)m (Formula XV) wherein X and PAS are as defined for Formula IV; G is a reactive functional group or precursor thereof; n and m are independently integers of from 1 to 3; or (Formula XVI) wherein PAS is a photoactive site or photoactive precursor and R is an unsubstituted or inertly substituted hydrocarbyl group by a process comprising:

(a) forming a salt having an anion corresponding to a compound (acid) of Formula VI, or XIV:

HX-PAP-(XH)q or wherein X is a bond or group linking the hydrogen to the PAS or PAP; PAS is a photoactive site or photoactive precursor; PAP is a photoactive precursor R" is an unsubstituted or inertly substituted hydrocarbyl group; q is an integer of from 0 to 4; t and r are independently integers of from 1 to 4;
(b) reacting the salt with a 1,2-dihalo-1,1,2,2-tetrafluoroethane wherein the halo groups are iodine, bromine, chlorine or mixtures thereof, at least one halo group being a bromine or an iodine atom, to form a compound of Formula VII, or XV;

Z-CF2CF2-X-PAS-(X-CF2CF2-Z)q wherein PAS, X, R" and q are defined as for Formulas VI and XIV; and each Z is independently iodine or bromine;

(c) eliminating the halogen atoms represented by Z to form the corresponding trifluorovinyl compound.

32. A process of preparing a compound of Formula XII
(G)n-PAS-(X-CF=CF2)m wherein G is a reactive functional group or group convertible into a reactive functional group;
PAS is a group containing photoactive site or photoactive precursor; X is a group linking PAS
with the trifluorovinyl group; m is the number of trifluorovinyl groups and n is the number of functional groups; by (a') preparing a 2-halotetrafluoro compound of the Formula IX

(Q-CF2-CF2-X-)m-PAS-(G')n or at least two compounds, at least one of each of Formulas X and XI

(Q-CF2-CF2-X)m-PAS' (Formula X) and PAS"-(G")n (Formula XI) wherein X, m and n are as defined for Formula XII; G" represents any reactive functional group or any group convertible into a reactive functional group; PAS and PAS" are independently photoactive sites or photoactive precursors; PAS' and PAS" are groups reactive with one another to form a photoactive site or photoactive precursor; and Q is bromine, chlorine or iodine; and (b') eliminating the halogen atom represented by Q to form the corresponding trifluorovinyl compound.
CA002151151A 1992-12-24 1993-12-01 Photodefineable polymers containing perfluorocyclobutane groups Abandoned CA2151151A1 (en)

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