CA2057309A1 - Laminates of polymers having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings - Google Patents

Abstract

ABSTRACT

A laminate has at least two layers, at least one of which comprises a polymer having more than one perfluorocyclobutane group. Such polymers impart quantities of environmental protection, chemical and solvent resistance, hydrolytic stability, lubricity, low dielectric, hydrostatic stability, weatherability, flame resistance, chemical resistance, hydrolytic stability, scratch resistance, surface passivation, water repellancy, lower surface refractive index, lower surface coefficient of friction, fluid barrier properties, oil repellancy, thermal stability, and/or reduced moisture pick-up. Additionally, the coatings are optically clear, easy to apply either neat, in a solvent or otherwise, have relatively low cure temperatures for their temperature resistance, and exhibit insulating and planarizing capabilities.

39,066-F

Description

LAMINATES OF POLYMFRS HAVING PERFLUOR~CYCLOBUTANE RING~
,iND POLYME~S CONTAINING PERFLUOROCY~LOBUTANE RrNGS

This invention relates to laminates of ?o.~mers containing more than one perfluorocyclobutane ring.

Laminates are materials having more than on~
layer. While in the simplest form i laminate has mutually coextensive discrete laye:-_. the term also includes layered materials wherein one or more ]avers may have dimensions different from at least one other layer. For instance, a middle layer of three layers may extend beyond the edges of the other two layers or one or more of the other layers may extend beyond the edges of the middle layer. Also, layers may not remain discrete after formation of a laminate. For instance.
in a laminate of three layers, a middle layer may be discontinuous, e.g. a loosely woven material. and layers contiguous thereto may be of the same or miscible compositions such that in a lamination process, those layers merge through discontinuities in the middle layer. Laminates also include coated objects where'n one layer may cover all or substantially all surfaces of another layer or wherein whal may be considered l~1ers above and below an object may join in at leas~ one place or along one or more edges. Laminates in their simplest 39,o6~-F -1-` ` ` 2057309 form have relatively planar layers. but the term includes non-planar materials of any shape includin~
wires, fibers, pipes, tubes, bowls. pots. spneres, cubes, bricks, irregularly shaped objects, discontinuous , - . materials and the like.

A wide variety of laminates are known. Their properties and uses depend on the materials used for the layers. While laminates having layers Ol polymers are often formed and useful for the properties of the polymers. polymers seldom have high temperature resistance, fire retardancy and other properties that would be desirable in laminates.

Polymers having more than one perPluorocyclobuta~e group have recently been disco~ered and include polymers thermally formed from monomers having at least two perfluorovinyl groups and interpolymers of compounds having at least one perfluorocyclobutane ring and at least two functional groups reactive with di- or poly- functional compounds to form polymers.

The present invention, in one aspect, is a laminate having at least two layers at least one of which comprises a polymer having more than one perfluorocyclobutane group. Such laminates are particularly u~eful in electronics. building materials, optics for applications requiring heat or weather resistance and the like.
The crosslinked polymers exhibit enhanced solvent resistance and increased mechanical strength.

39,066-F -2-without loss of advantageous electrical properties. such as low dielectric constant and dissipation fac~or.
The invention includes electronic devices and computers comprising such laminates.

In another aspect the invention include.s a process of preparing a laminate comprising a step of coating at least one material ~itn a polymer having more than one perfluorocyclobutane group. In yet another aspect, the invention includes a process ~or preparlng a laminate comprising adhering at least one layer of a polymer having more than one perfluorocyclobutane group and at least one layer of a material ha~ing a composition different from the polymer.

Laminates of the inven~ion have at least two layers, at least one of which is a polymer having perfluorocyclobutane rings. The other layer(s) are any material, preferably at least one layer is a material having properties, preferably physical or chemical properties different from the layer having perfluorocyclobutane rings. More preferably the properties are such that the layer(s) of polymer improves at least one property of the laminate relative to the properties of the rest of the laminate without the polymer layer(s). For instance, a layer of polymer may be added to effect, preferably to improve, passivity, mechanical strength, flame retardancy.
smoothing or planarity, receiving an image, selective removal, hydrolytic stability, moisture resistance, chemical resistance. heat resistance, weatherabitily.
low dielectric nature (insulating),wear resistance.
scratch resistance.

39,066-F -3_ 2~73Q~

The layer(s) other than the layer(s) of polymer having perfluorocyclobutane rings are suitably sucn materials as wood. metal~ ceramics. glass. other polymers, paper. paper board cloth. woven fibers, non-5 woven fiber mats. synthetic fibers, Ke~lar~, carbon fibers. silicon and other inorganic substrates and the like. The materials selected for the layers depend on the desired application. Preferred materials include glass, including glass fibers!(wo-ven, no7n-~o~en or strands), ceramics such as metals such as Ai (alu~i~um).
MJ (magnesium), Ti (titanium). ~u (copper). Cr (chromium), Au (gold), Ag (silver), W (tungsten).
stainless steel. Hastalloy. carbon steel and polymers such as epoxy resins. polyimides, benzocvclobutane 1~ polymers, other thermosets, nd polystyrene. polyamides.
polycarbonates, polyesters and other thermoplastlcs.
Optionally, the other layer(s) may incluae at leas one layer of polymer containing perfluorocyclobutane rirgs.
said layer(s) preferably having a different composition.
for instance different in polymer structure, molecular weight, additives, crosslir,king type or density.

It should be noted that the layer(s) other thar at least one o~ a polymer having perfluorocyclobutane rings can be of any shape, generally determined by the purpose of the laminate. For instance, the other layer(s) are suitably disks, plates, wires. tubes, boards, spheres, rods, pipes, cylindrical, bricks, 3 fibers, woven or non-woven fabrics. yarns including comingled yarns, ordered polymers, woven or non woven mat. In each case the shape is optiona]ly. hollow or solid, in the case of hollow objects, the polymer layer(s) is optionally inside and/or outside. The other layer is optionally porous such that the polymer 39,066-F -4-- ` 20~7309 layer(s) penetrate, such as graphite mat or fabric, glass mat or fabric, a scrim. particulate material and the like.

Laminates of the invention have at least one 5 layer of polymer having at least two perfluorocyclo-butane rings. Such polymers and the methods of making them and monomers Iseful in their preparation are disclosed in U.S. Patent Number 5,021.602 dated Ju~e 4.
l991; U.S. Patent Number 5,923,380 dated June 11. 1991;
U.S. Patent Numbers 5,037,917, 5,037,918: 5,037,919, all dated August 6, 1991 and U.S. Patent Number 5,066,~46 dated November 19, 1991.

Preferably, polymers used in the practice of the invention are formed by thermal reaction of monomers, including oligomers or low molecular weight polymers, having at least two dimerizable perfl~arovinyl groups such that perfluorocyclobutane groups are formed.
A dimerizable perfluorovinyl group is a perfluorovinyl group which reacts with another such group to form a perfluorocyclobutane ring. Alternatively, the polymers are prepared by reacting monomers having at leas~ one perfluorocyclobutane ring and at least two functional groups reactive with di- or poly-functional compounds to form interpolymers therewith.

Properties of the polymers vary with the proportion of perfluorocyclobutane rings, the nature of other portions of the polymer and other chemical and structural features of the polymers. For instance, the relative proportion by weight of the perfluorocyclobutane groups to the other molecular components of the resulting products can vary over a 39,066-F -5-20~730~

wide range of from 12 to 1 to 0.01 to 1, preferably from 5 to 1 to 0.02 to 1 and most preferably from 2 ~n 1 to 0.03 to 1. High proportion~ of perfluorocyclo~ane groups, preferably at least 0.1 to 1 more prefer~bly lt ,~ least 0.25 to 1 are desirable for instarce. when fluorocarbon character such as low dielectric constant is beneficial in the products. Exemplary of such products are low dielec ric fluids and lubricants.
Medium ranges of ratios of weights of perfluorocyclobutane groups to other molecular structures of 2 to 1 to 1 to 4 are desirable. for instance, when higher physical strength and relatively lower dielectric constants (for example~ relative to conventional engineering thermoplasticsj are deslred.
for example. in low dielectric plastics. These relatively low dielectric plastics are particularly preferred and are preferably achieved by using ~romatic compounds substituted with trifluorovinyl groups. most preferably, with trifluorovinyl ether groups. ~ery low proportions of the perfluorocyclobutane groups result, for instance, when low molecular weight oligomers (for example, in the range of 1000 to 20,000) are terminated by trifluorovinyl groups and then thermally dimeri~ed to form higher molecular weight polymers.

Any monomer having at least two dimerizable perfluorovinyl groups is suitably used to form polymers used in the practice of the present invention.
3o In the thermal polymerization of diperfluorovinyl compounds, substantially linear polymers having little branching are believed to be formed. In the practice of some embodiments of the present invention, it is preferred to crosslink such 39,o66-F -6-- -` 2~7309 polymers to achieve properties such as ir?roved (relative to the uncrosslinked polymer) mechani~al strength, solvent resistance, hydrolytic stablllty, thermal stability, and/or wear resistance. At least two - types of crosslinking are observed. A first type of crosslinking involves the use of monomers having at least three perfluorovinyl groups; such crosslinking is referred to herein as "polyfunctional crosslinking." A
second type of crosslinking is observe~ ~hen nertain types of monomers are used, and because it is believed that this second type of crosslinking involves certain aromatic structures in the backbone of the polymer, it is referred to herein as "backbone crosslinking."

Without crosslinking, solid polymers useful in ;~ the nvention are generally thermoplastic except in the case of partially polymerized monomers which are referred to herein as prepolymers or B-staged polymers, which may be partially crosslinked and/or not thermoplastic. Viscosity of either a melt or solution of the polymer increases as crosslinking occurs until the gel point and resulting insolubility is reached.
Backbone crosslinked polymers are preferably elastomeric, that is. the polymer can generally regain its shape after deformation. That deformation is indicated by elongation measurements greater than lO0 percent at temperatures above the glass transition temperature (Tg) of the polymer. Backbone crosslinked polymers preferably retain their elastomeric properties at temperatures of from their glass transition temperatures to the temperatures at which they are observed to degrade, preferably 400C. The glass 39,066-F -7-~ 20~7309 transition temperature varies with the composition of the polymer.

Backbone crosslinking also increases a -- ~polymer's tensile strength as measured by the procedures of ASTM Dd82-83. The increase is preferably up to lO00 percent. more preferably from lO percent to 500 percent.~mcst preferably of from 10 percent to 100 percen~ increase. Also the polymer's~tensile and flexural modulus as measured by the procedures of ASTM
D882-83 and AST~ D790-81, respectively, also increases.
preferably up to 1000 percent, more preferably of from lO percent to 500 percent, most preferably of from 10 percent to 100 percent. Additionally, the fluorine-containing strucSures of such crosslinked polymerspreferabl~ retain relatively low dielectric constants.

Such properti s are useful in laminates such as disk substrates, media binders, optical waveguides, fiber bundles~ circuit boards, optical cladding, encapsulated objects and the like.

Although any monomer having two dimerizable perfluorovinyl groups and which is crosslinkable is suitably used for backbone crosslinking, polymers used in the invention are preferably prepared from monomers having two perfluorovinyl groups separated by at least one hydrocarbyl group having at least one carbon atom between the perfluorovinyl groups.

When the perfluorovinyl groups are attached to aliphatic carbons or separated from aliphatic carbons by single atoms such as oxygen, the perfluorovinyl groups are preferably primary or secondary. Preferably, to 39,066-F -8-/

- 2~573a~
_9_ avoid rearrangement and facilitate polymer formation and crosslinking the monomers have structures such that resulting polymers have hy~rocarbyl groups (preferably aromatic rings), perfluorocyclobutane rings and at least one non-carbon atom such as oxygen, silicon, boron.
phosphorus, nitrogen, selenium, tellurium and/or sulfur atom (each optionally substituted) in the backbones.

The monomers preferably have a st,ructure represented by the following Formula I:

Formula I
CF2=CF-X-R-(X-CF~CF2)m wherein R represents an, optionally inertly substituted group; each X is independently a bond or any group which links R and a perfluorovinyl group (hereinafter linking structures), said structures being inert; mt1 is the number of -X-CF=CF2 units. Advantageously, m is an integer of from 1 to 3, preferably from 1 to 2. While compounds represented by Formula I wherein m is one are especially useful for forming linear polymers, compounds wherein m is 2 or more part.cularly 2 or 3 are e~pecially useful for polyfunctional crosslinking. By "inert" it is meant that the structures or substituents do not react undesirably with perfluorovinyl groups or interfere undesirably with polymerization (perfluorocyclobutane formation) of the monomers.
3o Linking structures X are each independently a linking structure such as a bond, an oxygen atom, carboxylic and thiocarboxylic ester groups, other suifur containing structures, perfluoroalkylene, perfluoroalkylene ether, alkylene, acetylene, phosphorus 39,066-F _3_ containing groups such as phosphines. carbonyl and thiocarbonyl groups; seleno; telluro: nitrido: silicon-con~aining groups such as silanediyl, trisilaneaLy tetrasilanetetrayl, siloxanediyl. disiloxanedivl.
trisiloxyl, trisilazanyl. or silylthio groups: boron-containing groups such as boranediyl or methylboranediylgroups; a combination thereof, or any other group which is inert, ~hich~molecularly links R to a perfluorovinyl group, and wnich provides a molecular structure in which the perfluorovinyl group is sufficiently reactive to form a Derfluorocyclobutane ring. For instance. X is preferably other than a perfluoroalkylene group because perfluorovinyl groups attached to perfluoroalkyLene groups generally require temperatures greater than ~00C
to dimerize and are subject to isomerization.

It is preferred that at least one of X is not a bond. More preferably, X is independently selected from the group consisting of groups having at least one non-carbon atom between the perfluorovinyl groups and R,such as groups containing oxygen, sulfur. selenium atoms, tellurium atoms, silicon, boron. phosphorus or nitrogen between R and the per~luoroviry group, for example, oxygen atoms. sulfur atoms, (thio) carboxylic ester groups, phosphines, (thio) carbonyl groups, seleno, telluro, silanediyl, trisilanediyl. trisilazanyl or silylthio, boranediyl groups. Preferred groups have S, 0, Si. N or P, more preferably S, 0. or Si between R
and the perfluorovinyl group. such as carbonyl, thiocarbonyl, sulfoneJ sulfoxy, silanediyl, amines (optionally inertly substituted), oxygen or sulfur ! atoms. Most preferably there is a single atom oth~r than carbon between R and each perfluorovinyl group;
even .nore preferably the single atom is oxygen or 39 ~ o66-F - l o---~`` 2057309 sulfur, among those groups preferably an ether or sulfide linkage, because monomers having such lin~ing structures advantageously form perfluorocyclobutane groups at lo.~er temperatures than are needed with such groups as perfluoroalkyl groups and are more stable than monomers where the perfluorovinyl group is attached directly to R, particularly when R is aromatic.
Monomers having~such linking structures are also relatively easily prepared.

R is suitably any inert molecular structure, preferably a molecular structure which facilitates formation of perfluorocyclobutane rings and/or polyfunctional crosslinking and/or imparts desirable physical properties to polymers or oligomers prepared from the monomers. For the purpose of imparting desirable physical properties to polymers, R preferably contains at least one carbon atom. Preferably, the carbon atom is in the molecular chain between X's because monomers having at least one carbon atom between X's when X i~ other than a bond, tend to have desirable stability and to produce polymers having desirable physical propertie~. Alternatively, the carbon atom is in a side chain: for.instance, -R- can be -N(CH3)-.
-N(CH2CH3)-, -P(CH3)- or -P(CH2CH3)-. The carbon atoms(s) in R are suitably in aliphatic, cycloaliphatic.
aromatic, heterocyclic groups or combinations thereof.
Additionally, R optionally contains groups or has substituents which are inert, that is which do not undesirably interfere with the formation of perfluorocyclobutane rings from perfluorovinyl groups.
i Inert substituents include ether, carbonyl, ester.
tertiary amide, carbonate, sulfide, sulfoxide, sulfone, nitrile, alkyl phosphonate, tertiary amine, alkyl 39,066-F

phosphate, alkyl silyl, chlorine, bromine. fluorine, alkyl, arylalkyl, alkylaryl, cycloalkyl. aromatic.
heterocyclic, alkoxyl and aryloxy groups, which inert substituents are suitably in any position. for instance, in a polymer backbone between X's and/or appended to such a backbone. Carbon-containing inert substituents on R preferably contain from 1 to 50. more preferably from 1 to 12 carbon atoms because of the stability and ease of working with monomers of lower molecular weight.
R, including inert substituents preferably has a molecular weight (MW) of from 14 to 20,000, more preferably from 75 to 15,000 and most preferably from 75 tc 5,000. These ranges include monomeric and oligomeric R groups. In the case of monomers which are other than oligomeric. R preferably has from 1 to 50.
more preferably from 6 to 50. carbon atoms because molecular weights above this reduce the contribution to properties made by the fluorine-containing substituents when R i~ alkyl or aromatio hydrocarbon. As previously discussed, the nature of R as well as the perfluorocyclobutane content of the polymers can vary broadly according to the type of products desired.

Preferably, for polymers having good plastic properties such as tensile strength and flexibility, at least one carbon atom of R is in the molecular chain between X's and is part of an aromatic nucleus.
Aromatic groups are desirable because of improved physical properties of the polymers and ease of manufacture of the monomers. For both ease of manufacture of the monomer and monomer stability, when R
is aromatic, each X is preferably independently sulfur or oxygen. The aromatic group can be any molecular structure having aromatic character, advantageously 39,o66-F -'2-20~73~9 having at least one six-membered aromatic r ng, suitably having any number of such six-membered rings fused together or connected by bonds or linking strustures. R
preferably has from 1 to 50 such rings, more preferably from 1 to 10 rings, more preferably containing frcm 6 to 25 carbon atoms, most preferably R has at least 2 to 4 aromatic rings to impart properties such as hardness and/or stiffness to a polymer. The aromatic fragment i3 slitably unsubstituted or inertly substit~uted. Inert substituents on an aromatic R include. for ins~ance. the inert substituents listed for R generally. Exemplary aromatic molecular fragments include. for instance, perchlorophenylene, phenylene, biphenylene, naphthylene.
dichlorophenylene, nitrophenylene, p.p'(2,2-diphenylene propane) [-C6H4-C(CH3)2-C6H4-]; p,p'-(2,2-diphenylene-1,1,1,3,3.3 hexafluoropropane) [-C6H4-C(rF3)2-C6H4-1 preferably biphenylene; phenylene; 9.~'-d;phenyl-fluorene, oxydiphenylene; thiodiphenylene; 1,1,'-triphenyleneethane; 1,3,5-triphenylenebenzene; 1,3,5-(2-phenylene-2-propyl)benzene; 1,1,1-triphenylenemethane;
1,1,2,2-tetraphenylene-1,2-diphenylethane: bis(1.1-diphenyleneethyl)benzene; 1-(2-phenylene-2-propyl)-4-(1,1-diphenyleneethyl)benzene: 2,2-diphenylene propane;
2,2'-diphenylene, 1-,1,1,3,3,3-hex~fluoropropane; 1,1-diphenylene- -phenylethane; naphthalene; and anthracene.
Molecular weights of aromatic ring containing polymers are preferably at least 10,000. Such aromatic groups are preferably present because they generally impart high temperature glass transition properties (Tg) and good mechanical strength (for example, as measured by differential scanning calorimetry (DSC) and tensile/flexural tests) to the polymer.

39,066-F -13-20~730~

Such properties are preferred for laminales such as circuit boards, optical waveguides, and the like.

For the purpose of facilitating backbone crosslinking, more preferably, R is a group which reacts with perfluoroviny groups residual in a substantially iinear polymer to form a crosslin~ed or branche~
molecular structure. The reaction of R ~ith the perfluorovinyl groups is suitably initiated by he~t.
free radicals, wave energy, or any other cross :nking initiating means, but preferably by heat. Most preferably R includes a structure having two double~
triple or aromatic bonds (hereafter multiple bonds) separated by a single bond and capable of attaining a cisoid conformation. Such structures are recogni~e~ in the art as latent Diels-Alder dienes. Preferably the latent dienes are suitable for reactions of the Diels-Alder type, more preferably suitable for such reactionswith perfluorovinyl groups in the monomers, most preferably suitable for such reactions with perfluorovinyl ether groups under conditions used for crosslinking. The single bond is preferably a carbon to carbon single bond. Each of the multiple bonds is independently suitably a multiple bond between any two atoms, preferably between a carbon atom and any other atom (for example, -C=0, -C=C-, -CsN), more preferably a carbon to carbon bond. Exemplary of preferred R
3 groups include, for instance, biphenylene, 9,9'-diphenylfluorene, fluorene, cyclopentadienylene, furan and anthracene.

Most preferably, at least one aromatic carbon atom of R is bonded directly to X, most preferably 39, o66-F - l4-2 0 ~ 9 aromatic carbon atoms of R are bonded directly to each X
because perfluorovinyl groups bonced to X. said ~ being bonded to aromatic groups are generally more rea ~ive in forming perfluorocyclobutane rings.

Some specific combinations of X and R are especially preferred: when R is aromatic, at least one X
is preferably other than a oond. more preferably neither X is a bond. because attachment of perfluorovinyl groups directly to aromatic R renders the perfluorovinyl groups more thermally an~ oxidatively unstable than when said groups are attached, for instance to oxygen or sulfur.
When R is a perfluoroalkyl group or a perfluoroalkyle,her group, at least one X is pref-~ably other than a bond. most preferably no X is a bond or a perfluoroalkyl group, because perfluorovinyl groups linked directly to perfluoroalkyl groups require temperature in excess of 300C to dimerize and are subject to isomerization.

Monomers preferred for use in preparing polymers useful in the practice of the present invention are suitably prepared by any method which links molecular structures having perfluorovinyl groups to other molecular structures or which forms perfluorovinyl groups.

An exemplary method of preparing a tris-perfluorovinyl ether (exemplary of monomers having morethan one perfluorovinyl group) is illustrated by a process having the following steps:
i (A) A trihydroxy compound such as 1,1,1-tris(4-hydroxyphenyl)ethane is converted to its sodium 39,066-F -15-` 2057309 or potassium salt in a solvent such as water, methanol or a mixture thereof. The methanol or another solven~
for the trihydroxy compound is used when the compound is not water soluble, to keep the trihydroxy compound in solution. Salt formation occurs conveniently at from 0C to 120C at atmospheric pressure, preferably under a nitrogen atmosphere to avoid oxidation in the case of an oxidizable trihydroxy compound.

(B) When methanol or other solvent other than water is used, it is removed, e.g. under reduced pressure at any convenient temperature and pressure with replacement of water as it is lost.

(C) The salt is dried and powdered by means within the skill in the art for example, in a drum dryer or other apparatus which provides ~gitation and water removal, e.g. by heat and/or reduced pressure. A
dryness of less than 1 weight percent water, preferably less than 0.1 percent, more preferably less than 0.02 weight percent is preferably attained in this step. If such dryness is not attained in this step, step E is alternatively used to attain said dryness.

~ D) The salt is slurried in a polar, aprotic solvent suitable for achieving reaction such as DMSO
~dimethyl sulfoxide), ethers, DMF (dimethyl formamide), HMPA (hexamethylphosphoramide), diglyme, tetraglyme or glyme.

(E) If dryness to less than 1 weight percent water is not attained in step (C), an aprotic azeotropic medium such as toluene or chlorobenzene in a solvent to azeotrope medium ratio of from 10 to 1 to 1.5 to 1 is 39~066-F -,6-20~7309 added, and the solution dried by the azeotropic removal of water. Half of the azeotropeic medium is removed, for example, by distillation, and ~he mixture is cooled below 50C, preferably below 20C.

tF) A dihalotetrafluoroethane such as 1,2-dibromotetrafluoroethane is added to form a mixture as the reaction temperature is controlle at a temperature suitable for the reaction to occur substantially without the side reaction of aromatic ring halogenation; in the case of l,l,l-tris~4-hydroxyphenyl)ethane a tempe~ature preferably below 20C is used initially. The mixture is stirred at e.g. 18C to 25C, preferably until the amount (yield) of product stops increasing (the reaction is complete) as indicated by gas chromatographic analysis of product tris-bromide.

(G) The tris-bromide is purified by means within the skill in the art:

(Gl) For instance, the mixture is poured into an equal volume of cold water, conveniently from 0.5 to 3 times the volume of the solution, and the product falls out as the lower layer. There is preferably sufficient cooling to offset the heat generated by admixing DMSO (or other solvent) and water. The product, a tris-bromide, is then distilled, for example, at 190C to 195C/0.05 mm Hg. When tris-bromides are heat stable as observed in the case of 1,1,1-tris(4-(2-bromotrifluoroethoxy)phenyl)ethane, the degree of vacuum is selected to give a convenient boiling point. Such selection is within the skill in the art.

39, o66-F -17 -20~7309 (G2) Alternatively, the solution of product is extracted with a non-polar solvent such as a hydrocarbon, for instance hexane, using means within the skill in the art such as countercurrent extraction. The solvent is conveniently used in an amount of from l to 5 times the volume of solution of product, and the product is extracted into the hydrocarbon. The hydrocarbon is then removed by means within the skill in tne art such as evaporatlon, conveniently under reduced pressu-re.
(H) The tris-bromide is used directly or, if desired, in cases where the tris-bromide is a solid it may be dissolved for ease of addition in a polar, aprotic solvent such as diglyme, tetraglyme, glyme, or a nitrile such as acetonitrile, glutaronitrile, or 3-methoxypropionitrile and added to a hot (for example 40-135C) mixture of the same solvent and granular zinc to form the tris-perfluorovinyl ether (TVE).
Alternatively, the tris-bromide can be added to a hot (for example 120C) mixture of, for example, diglyme or nitrile and granular zinc as a melt without dilution if heated above its melting point, for example to 120C in the case of l,l,l-tris(4-(2-bromotrifluoroethoxy)phenyl) ethane. Temperatures above 135C are preferably avoided to avoid dimerization of perfluorovinyl groups.

(I) The TV~ is isolated by removing the zinc salts for example by centrifugation, evaporating the 3 diglyme under reduced pressure, diluting the TV~ with a, preEerably low boiling, solvent such as hexane, and flushing the solution through a pad of neutral alumina or other absorbent for color bodies and residual ionic species. Alternatively, the zinc salts are removed by filtration and the TVE distilled under vacuum, for 39,066-F -18-2~73~9 _19_ example in two stages, the firs~ ~o remove solvent and the second to purify the TVE. Prefe!ably, temperatures above 110C are avoided to avoid dimeriza~ion of perfluorovinyl groups. Especially when a very pure product is desired, these methods of purification are suitably combined.

Alternativel~l, the TVE is isoLated by removing the zinc sal~s by filtration, evaporatinq the gly~e (if used~ under reduced pressure, diluting ~he TVE or its solution in a nitrile with hydrocarbon solvent for the TVE such as hexane and purifying b~l countercurrent extraction or similarly extracting the hydrocarbon with polar organic materials such as acetonitrile or DMSO.
The pure TVE in hydrocarbon is then L lushed through a pad of absorbent for color bodies and residual ionic species such as decolorizing carbon, ion exchange resins, alumina or the like.
Z (J) The hexane or other hydrocarbon, if used, is removed from the TVE e.g. by evaporation under reduced pressure.

Polymers produced from the preferred monomers preferably have a formula represented by the following Formula II:

Formula II
3o lX~R~[X~Q]m In wherein R, X, and m, are defined above, Q is a perfluorocyclobutane group: and n i3 an integer representing the number of repeating units, which is 39,o66-F -19-- DEC-06-199~ 16:14 FROM PRTENT DEPT. B-1210 TO 81613232a440 P.03 preferably from 2 to 100.000. More preferably from 2 to 10,000, most proferably from 3 to 5,00~. More preferablg m is onè or two. Formula II is ~eneralized3 when D~ i9 greater than one, ome o~ the -X- Q s-tructure~
represent branching and~or cros~linklng.

The monomers are heated to a temperature and for a time sufficient to ~orm perfluoroQyclobutane rings. Temperatures ~uitable for ~ormlng per~luorocyclobutane r~nt~ dif~er with the structure of thc monomer. ln gen~ral~ temperatures abo~e 40C are suitable ~or Pormation of per~luorocyclobutane rings, preferably the ~emperature is above 50C, more pre~erably above 100C, because these temperatures re~ult ln formation of the rings at success~vely ~aster rates. Temperatures abo~e 450C are prefera~ly a~olded becau~e perfluorocyclobutane ~roups aro generally thermally un~table above such temperatures.
Monomer~ having three or more dlmerlzable perfluorovlnyl g~oup~ (herei~after re~erred to as polyfunational) are especially useful to form poly~er~
ha~ing relati~ely high Tg believed ~o be due to z5 polyfun~tlonal cros~linklng. From 0 to tO0 poroent by weight o~ ~uch monomer~ are ~uitably used, preferably ~u~floient of the monomers haYing at least three perfluorovinyl groups to mea~urably increase the chemlcal re~istance and/or m~chanica~ strength o~ the polymer over that of a polymer of monomers hav~ng aorre3pondLng structure~ but with only two perfluorov~nyl groups, more preferably at least 0.05 mole percent, most pre~erably fro~ 0.1 to 100 mole percent Or Such wonomers i~ u~ed. While u~e o~ lower proportion~ Or polyfunotional monomer~s) produ¢es, 39~o66-F _~o_ 20~7303 generally thermoplastic, polymers having crosslinking and corresponding properties of toughness and solllent resistance, use of sufficient polyfunctional monomers to form thermosetting polymers is useful to produce crosslinked polymers having greater chemical resi~tance and/or mechanical strength. The relative proportions of polyfunctional monomer which produce such polymers varies with the structure of the monomers. However.
from 0.5 to 75 mole percent polyfunctional monomers u ed with monomers having 2 perfluorovinyl groups is sufficient to result in sufficient crosslinking in a thermoplastic polymer to reduce its solubility in a solvent.

More than one stage of polymerization is often advantageous particularly for polyfunctional monomers.
to achieve desired viscosity for forming laminates. A
first stage of polymerization is conveniently carried out at temperatures of from 50C to 400C, pre~erably from 105C to 250C, more preferably from 120C to 170C.
At least one later stage follows the first stage and is preferably carried out at a higher temperature than the first to lllow the polymerization to proceed toward completion. Such later stage(s) are conveniently carried out at temperatures from that sufficient to result in additional polymerization up ~o the decomposition temperature of a resulting polymer, preferably from 100C to 450C, preferably from 120C to 400C, more preferably from 200C to 375C. Those skilled in the art will recognize that the first and later stages can represent more than one stage or can be carried out using two or more temperatures and that a series of stages or a continuum of temperatures are suitably used. In addition to these stages a postcure 39,066-F -21--` 20~309 at relatlve high temperature such as from 200C to 450C
is optionally used. The postcure is suitably for any duration sufficient to change physical properries and insufficient to decompose the polymer, preIerably from 1 minute to 1 week. more ~referably at high temperatures such as from 2~0C to 450C for duration of from 1 minute to 2Y hours. St~ges of polymerization are conveniently run under conditions preliously described for polymeri2ation of the monomers. When a sol~/enS is ~sed in an early stage, and it is desirable to avoid bubbles that may occur as a solvent is driven off.
advantageously the so vent is removed before or during a later stage.

It is found that solvent, degree of polymerization, and other parameters, for instance conditions of coating, effect coating quality and thickness. Those skilled in the art are able to determine optimum conditions for each particular polymer and coating desired. An illustrative example ~"ith variations in solvent, degree of polymerization and parameters of spin coating is given in the Examples of this invention.

Dielectric constants and static dissipation factors (as measured according to the procedures of ASTM
D150-87) preferably range from 2.2 to 3.0 and from 0.0001 to 0.005 respectively. Glass transition temperatures increase from ambient when R is phenyl, to 170C when R is biphenyl, to 230C when R is 9,9-diphenylfluorene, to 286C or higher than 286~C when R is 1,1,1-triphenyl~thane.

39,066-F -22-The linear polymers advantageously a~e cast from solvents such as ethers. esters, aromatic hydrocarbons and ch.orinated solvents, mesitylene.
diglyme, o-xylene, n-butyl acetate. tetrahydrofuran or dichloromethane.

Before backbone cross]inking, substantially linear polymers or oligomers are thermally produced from the preferred monomers. The polymers can-be crosslinked by any crosslinking initiating means such as by heat, by free radicals, or by wave energy. Thermally backbone crosslinked polymers are prepared from such thermally formed polymers containing perfluorocyclobutane rings by heating the polymers to a temperature sufficient to result in crosslinking, that is for chemical bonds to form between at least some of the polymer molecules.
The temperature for such crosslinking is higher than that required for thermal (linear) polymerization, preferably it is at least 50C degrees higher than the temperature required for thermal (linear) polymerization, more preferably from 250C to 400C, most preferably from 280C to 380C, even more preferably from 280aC to 340C. These temperatures are suitably maintained for a time sufficient to achieve a praselected degree of crosslinking. Such times are preferably from 1 minute to 10 days, more preferably from 15 minutes to 1 day (24 hours), most preferably from 15 minutes to 8 hours.

In alternative embodiments of the invention, the polymer is formed from monomers having at least one perfluorocyclobutane ring, preferably of the formula:

39,o66-F -23-bEC-'a6-1991 16: 15 FROM P~TENT DEPT. ~-1210 TO E~1613232a440 P. 04 ~
20~7309 ~

FORMULA 111 fFZ-CF2 Gn-~-X-CF ~CF~~ '(-G')n' wherein R and R~ independently repre~ent optio~ally inertly ~u~stltuted group~ and X' represent molecular strùctures which llnk fl and R' w~th the perfluorocyclobutane rin~; n and n' are the n~mber of and G' groups, r~3pecti~ely, and preferably aro ~ndependently integers o~ from 1 to 4, more preferably from 1 to 2 most preferably 1; and & and G' independently represent any reactl~e ~unc~ional groups cr any ~roups convertible into reactlve ~unotional groups, preferably any ~unctional group suitable for reactlon with d~- or poly-functional compounds So for~
polymer~. Alternatively, G and/or G' is a group sultable ~or chemlcal conversion 1nto a functlonal group suitable for reaction to rorm a polymer.

G and G' are pre~erably independently seleo~ed from the group oonslstin~ of reactlvo runctional groups including hydroxyl ~roups (both alcoholic and phenollc) and ester~ thereof, oarboxyllc ac$d ~roup~, th;o-carboxylic acid groups, thiocarboxylic and carbaxyllo e~ters, preferably lower alkyl esters of from one to 12 carbon atoms, such a~ methyl and ethyl esters, acyl 3~ hslides such as chlorlde~, isooyanates, acyl azides, acetyl groups, tr$haloacetyl groups, primary or secondary a~nes, sulfide groups, sulronic acld ~roups, sulfona~lde groups, ketone9, aldehydes, spoxy groups, pri~ary or seoondary amides, halo ~roups (e.g.chloro~
bromo, ~odo, and fluoro groups), nitro groups, oyano 39,o66-F -24-20~309 groups, anhrdrides, imides, cyanate groups, ~inyL, allyl, acetylene groups; silicon-containing subsiituents such as alkyl silanes. siloxanes, cnlor~s;lanes, phosphorus-containing groups such as phosphines, phosphate, phosphonate, boron-containins groups 3uch as boranes; and groups convertible into reactive functional groups including e3ters: trihalomethyl groups; alkoxy groups, alkyl groups when R is aromatic said alkyl and alkoxy groups preferably containlng from 1 to 12 carbon atoms; and the like. More preferably, for ease in preparation of the c~mpounds and polymers thereof. G and G' are independently selected from hydroxyl groups and esters thereof, carboxylic or thiocarboxylic acid ester groups, carboxylic acid groups, ~cyl chlorides, isocyanates, acetylenic groups, alkoxy groups~alkyl groups when R is aromatic, and primary or secondary amines. Most preferably, for ease in preparation of the compounds and polymers thereof, G and G' are the same and are selected from hydroxyl and esters thereof, carboxylic acid ester groups, carboxylic acid groups, acyl chlorides, isocyanates, acetylenic groups, and primary or secondary amines.

Preferred X and X' are independently generally as described for X in Formula I and preferred R and R' are independently generally as described for R in Formula I.

Such monomers are preferably prepared from monomers of the Formula:

Gn-R-X-CF=CF2 Formula I~

39.066-F -25-20~7309 wherein R and X are as defined for Formula I; and G and n are as defined ~or ~ormula ~II.

Conveniently, the process for preparirg such monomers çomprises the steps of:

(a) preparing a 2-halotetrafluoro compound of Formula V:

Q-CF2-C~2-X-R-(-G")n Formula V
wherein X, R ~nd n are as previously defined for X, X', R, R' and n in Formula I~; Q is bromine, chlorine or iodine; preferably bromine or iodine, most preferably bromine; and G" is a functional group G, as previously defined, or a functional group suitable for conversion into G or G'; and (b) chemically modifying group G" to produce functional group G or G';

(c) dehalogenating the 2-halotetrafluoro compound to form the corresponding trifluorovinyl compound (d) thermally dimerizing the perfluorovinyl compound to form a perfluorocyclobutane ring.

Step (b) optionally precedes or follows step (c) and/or (d), or steps (b) and (c) are simultaneous, generally depending on the relative ease of the reactions required and the relative sensitivity of the 2-halotetrafluoro group or the trifluorovinyl group to the chemical reactions required for step (b).

39,066-F -26-7~09 ~ onomers of Formula III are suitably reacted with di- or poly-functional compounds reactive wl~h the groups represented by G and G' to form pol~mers therewith by means within the skill in the art of polymerization. Preferably, the polymers are condensation polymers such as polyesters, polyamides.
polycarbonates, polyethers. epoxy resins and the like.

In the practice of the invention. polymers having perfluorocyclobutane ring3 are found to ad~re directly to materials such as compatible polymers~
polymers having a common solvent, metals, particularly textured metals, silicon or silicon dioxide. especiaily etched silicon or silicon oxides, glass, silicon nitride, aluminum nitride, alumina, gallium arsenide, quart7, ceramics, etc. Alternatively, an additional material or layer may be introduced between a layer having perfluorocyclobutane groups and an adjacent layer to improve adherence; exemplary of such layers or materials are primers, adhesion promoters such as a ~ilane, preferably an organo silane such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane [(CH3)3-Si-NH-Si(CH3)3], or an aminosilane coupler such as y-aminopropyltriethoxy silane or a chelate compound such as aluminum monoethylacetoacetatediisopropylate [((isoC3H70)2Al(OCOC2HsCHCOCH3)] are useful in the practice of the invention. A toluene solution of the chelate is, for instance, spread on a substrate. The substrate is then baked at 350C for 30 minutes in oxygen to form a very thin (e.g. 5 nm) layer of aluminum oxide on the surface. Other means for depositing aluminum oxide are likewise suitable. Polymer is then 39,066-F -27-2~573~9 deposited or otherwi~ie applied. Other adhesion promoters are suitably applied as layers on a substrate or on a layer of polymer having per~luorocyclo~tane groups. Alternatively, the promoter is blended with the monomer before polymerization, negating the need for formation of an additional layer. The adhesion promoter may be blended e.g. at from 0.05 ~eight percent to 5 weight percent. In general less than 0.05 wei~ht percen~ is ineffective.~and more than 5 wei~ht percent adversely a:~ects other desirable properties of the polymer, such as low dielisctr c constant or low water absorption. Additional adhesion promoters useful in the practice of the invention include Chemloc speci~lity elastomer adhesives, fluoroepoxides including fluorodiepoxide adhesives, vinyl tri-tert-butyl silane peroxide, neoalcoxytitanates, neoalkoxyzi~conates, iminoxyl radical compounds, polyarylene sulfide resins, aromatic polyether-sulfone resins, aromatic polyether ketone resins; alkoxy containing silicon compounds, organotitanates, organohydrogensilicon compounds, m-aminophenol (optionally in an adhesive blend such as a phenoplast blend), chromic acid, phosphoric acid, polyalkylsilicate containing finely divided met~l such as zinc, chromium III complexes of such compounds as filmaric acids, epoxy resin with curing agents such as dianhydrides, ammonium chromate, ammonium phosphate, chromium/chromium oxide mixtures, carboxyl-containing alpha-olefin polymers, fluorinated acids and alcohols, organic complexes of metals of groups 2B or 8 on the periodic table of the elements, porous layers of fluoropolymer particles, adhesive cements; optionally fluorinated rubber optionally with tackifiers such as urethane, epoxy or acrylic resins; hydrocarbon polymer with halogenating agent, tri-allyl cyanurate, tri-allyl 39,066-F -28---` 2~57309 _~9_ isocyarurate, silicon tack agent, perfluoroalkoxy -esin with resin conta ning imide linkages, polysulfidic silane compounds, epoxy adhesive, alkali nd/or alkaiine earth alumino-borosilicate glass, bis-chloroalkyl viny phosphonate, polyurethane mastic, polyester film ~ases, polyamide acid salt, metal oxides, fluorine resin promoters optionall~ containing oxidants and/or inorganic acids,~ methylmethacrylate copolymers, zinc phosphate, zinc dispersion,~water-hardening cements, peroxy organic compounds, fluorine resin containing asbestos paper, lithium polysilicate, powdered acid and alkali-resistant inorganic substance (such as silica, graphite, molybdenum sulfate, or chromium oxide3, aluminum borophosphate, alkyl silicates, alkali metal silicates, polyamine-imide primers, polyvinylcinnamic acid ~optionally exposed to ultraviolet light), deposited carbon layers and the like. Alternatively, fillers including superfine inert fillers, glass fillers, copper oxide and other metal oxides, colloidal silica, glass fibers, water hardening cements; mineral fibrils such as potassium titanate, titanium dioxide or boehmite; boehmite in other forms, asbestos improve adhesion. Such fillers are optionally coated or treated (e.g. with surfactant or adhesion promoter) to improve adherence to the polymer. Processes involving grafting such monomers as acrylic esters and/or other vinyl compounds to the polymer (e.g. using catalysts or radiation), and optionally treating the grafted molecules (e.g. saponification)~ also is suitable to increase adhesion to the polymer.

Adhesion is also coveniently enhanced by surface preparation, texturizing a substrate, for instance, by scratching, etching, pla~ma treating, 39,066-F -29-2~7309 -3o-bu~fing and the like. Other means o~ sur~aee prepa~ati3n include degreasins, plasma treating. sonic cleaning, solvent treatment, SO3 treatment (e3~ecially of silicon oxide), plasma glow discharge (PGD); PGD
followed by adhesive monomers; air, oxygen, or ammonia plasma; gas plasma etching; sodium treatment; wet chemical etching; electrochemical reduction; grafting;
application and removal of metals such as aluminum; ion and ei~ctron beam techniques sucA as 6 MeV fluorine ions, electrons at intensities of 50-2000V, hydrogen cations at 0.2-500 ev to 1 MeV, hellum cations at 200 KeV to 1 MeV, fluorine or c~lorine ions at 0.5 MeV; neon at 280 KeV; oxygen enriched flame treatment; Accelerated Argon Ion treatment: low pressure plasma; irradiation in adhesive monomer vapor (radiation induced grafting);
Fastblast Process; depositing carbon layer(s); arc treatment; plasma polymerizing in the presence of materials such as alkyl silanes or stannanes; sodium naphthalemide; roughening and/or oxidizing; treating with organic peroxide or polyamine optionally followed by coating with silicone adhesives or adhesion promoters; rough chromate coating; plasma depositing e.g. a hydrocarbon film; inert gas glow discharge (e.g.
argon, helium, neon); low temperature plasma treatment;
corona discharge treatment; microwave discharge plasma;
irradiating with high energy ions e.g. of at l?ast 0.1 meV/amu; abrasion optionally followed by a polymer such as polyvinylcinnamic acid which is optionall~ cured, e.g. by ultraviolet light; reaction of metal oxide with aqueous aldehyde optionally with electrical potential treatment; noble metal activator treatment; treatment with alkali metal (e.g. in organic solvent) and e.g.
naphthalene, followed by contact with an ox dative mineral acid or mixture thereof; sand blasting; heat 39,066-F -30-2~5~3~9 treating in solution o~ alkali metal hydroxide;
treatment with alkali metal or hydroxide thereof and hexamethylpho photriamide and or aromatic hydrocarbon:
and ozone treatment.

In the cases ~here the polymer having perfluorocyclobutane groups is applied as a coating, the other layer(s) are optionally referred to as a substrate(s).

Polymers having perfluorocyclobutane groups, particularly those formed from monomers having at least three perfluorovinyl groups, have densities approximating those of the monomer; therefore, when the monomer or prepolymer is applied to an object and polymerized thereon there is insufPicient dimensional change (shrinking or expansion) to result in internal stres~. Because of this property, the polymers are useful as layers in situations where dimensional stability is important, such as a layer between other layers, e.g. an adhesive.

Polymers containing perfluorocyclobltane rings are suitably applied to the other layer(s) by any means.
Means for application are within the skill in the art.
For instance~ layers are suitably placed adjacent to one another, preferably they are contiguous or adhered in some manner such as by use of an inner layer between them. Laysrs of polymer having perfluorocyclobutane groups are applied by methods such as vapor deposition (chemical or physical), sputtering, solution deposition, liquid-phase epitaxy, screen printing, melt spinning, dip coating, roll coating, spinning, solution casting, brushing (e.g. varnish), spray coating, powder coating, 39,066-F -31-2 ~ 0 9 plasma deposition, dispersion spraying, solution casting, vacuum deposition, slurry spraying, dry-~owder-spraying, fluidized bed techniques, radio frequency (RF) plasma deposition, welding, explosion methods including the Wire Explosion Spraying Method and e~plosion bonding, press-bonding with heat; plasma polymerization:
dispersion in a dispersion media with subsequent removal of dispersion media; pressure bonding e.g. at soLtening point of polymer; adhesively joining a~pair of surfaces one of which contains a polymerization or crosslinking catalyst or initiator such that polymerization is initiated on contact; heat bonding with pressure e.g. in a reduced pressure gaseous environment; vulcanization;
extruding molten polymer onto a surface; hot-~as welding; baking-coating; sintering; placing one layer and the polymer layer (optionally in particulate form) between hot rollers; application in a binder which is optionally subsequently removed e.g. by pyrolysis, and the like. Mono- and multilayer films are also deposited on a substrate using a Langmuir-Blodgett technique, at an air-water or other interface. Spin coating, spray coating, solvent casting, screen printing and casting from solvents are particularly useful. The polymer (monomer or prepolymer)-is suitably applied to an object heated sufficiently hot to evaporate a solvent and/or polymerize the prepolymer or monomer or cure the polymer. For instance, an object such as a hot wire is suitably passed through polymer, prepolymer, or monomer in a liquid state (e.g. molten or in solution), optionally as a spray or other comminuted form, at a rate calculated to result in deposition of a layer of predetermined thickness. Alternatively, other materials such as metals including aluminum, gold, copper, titanium, chromium, iron, tellurium, polymers, silicon, 39,066-F -32-20~730~

or 3ilicon dioxide are applied to polymers having perfluorocylobutane groups by methods including those listed for applications of the polymers, particularly by sputtering, vapor deposition and other means within the skill in the art for such depositions. Use of such techniques and other suitable coating techniques is within the skill in the art.

Any solvent for the monomer, prepolymer or polymer may suitably be used. Solvents ~nclude hydrocarbons such as o-; m- or p-xylene. mesitylene toluene, benzene; chlorinated hydrocarbons such as chlorobenzene, dichloromethane; ketones such as methyl ethyl ketone, isopherone, acetone, methyl isobutyl ketone, and cyclohexanone; esters such as isoamyl acetate, n-butyl acetate, ethyl acetate, cellosolve acetate, methyl cellosolve acetate; ethers such as diglyme, tetrahydrofuran; amides such as N,N-dimethylformamide; and other polar solvents such as nitromethane, or l-methyl-2-pyrrolidinone; and the like.
The range of solvents facilitates smooth coatings in a variety of applications.

The polymer having perfluorocyclobutane groups optionally contains other materials (materials of composition different from that of the polymer.
preferably non-polymeric materials) such as additives to change the chemical or physical properties of the polymer, for instance stabilizers, adhesion promoters or, preferably, metal-containing compounds such as magnetic particles, such as barium ferrite (BaFe) iron oxide (e.g. Fe203, optionally with Co), or other metal containing particles for use in magnetic media, optical media, or other recording media; conductive particles 39,066-F -33-2~3a~

such as metal or carbon for use as conductive sealants, conductive adhesives, conductive coatings, electromagnetic interference (EMI)/~adio frequency interference (~FI) shielding coating, static dissipation, or electrical contacts. In these respects the polymer can conveniently act as a binder resin.
C-rtain materials may be residual in the layers from means for coating the polymers, for instance fillers.
thickeners, or surfactants may be used in screen printing, or spray coating.

Polymers having perfluorocyclobutane groups in their backbones, particularly such solid polymers, preferably those also having aromatic group and non-carbon atoms in their backbones are useful in compositeswherein the polymer surrounds, thus forms layers around such materials as fiber glass, particularly fiber glass mats (woven or non-woven), graphite, partlcularly grapite mat (woven or non-woven), KevlarrM, Nomex'~, gla~s spheres. Such composites are especially useful because of properties such as low viscosity, good wetting, and lack of volatile materials formed during polymerization. The polymers offer properties such as toughness, thermal oxidative stability. low dielectric, ignition resistance, flexural and tensile modulus, and environmental protection. Composites can be made from e.g. mats or other layers by means such as use of preforms, dipping mats in monomer or prepolymer, resin transfer molding (where the mat is placed into the mold and monomer or prepolymer is added and heated to polymerize) and the like. While the polymers are particularly useful as exterior layers, dielectric layers and the like, they are also useful as reinforcing or other interior layers such as reinforcements in 39,066-F -34-- - 2 ~ 0 9 tires, drive belts and the like. Layers within composites are referred to herein as reinforcing or filling layers.

Polymer having perfluorocyclobutane groups are particularly useful as a coating for glass and other transparent materials because of the polymer's clarity.
Coatings for transparent materials are useful for scratch resistance, environmental protection including protection from moisture and chemicals. flexibility, toughness, and thermal stability. The coatings are useful on windows, green houses, skylights, oven windows, solar stills, and the like. Additionally, the polymer is useful in anti-fouling coatings on such objects as boats; underwater insulation, particularly electrical insulation; and on vessels, helmets, valves (valve liners), molds, turbine blades and other parts.
light bulbs, carpet, tubs (e.g. for washers or driers), electrical switch enclosures, batteries, battery se~arators: Pilm such as photographic and photovoltaic film; bathtubs and shower coatings, tiles, swimming pool (liners), siding, roofing, UV filter, sleeping bags, sails, raincoats, and in mildew resistant coatings. The flame resistance of the polymers renders them useful in ignition resistant paints and as coatings on protective clothing, sick room equipment, medical and other clothing, bed linens, instruments, mattresses, furniture, draperies, carpet, pillows, toys, tents, campers, fuel containers (liners), building materials, and the like. Because of the range of temperature resistance of the polymers, they are suitably coated on cryogenic containers, autoclaves. ovens. used in retortable pouches, cookware, utensils for coated cookware, heat exchangers and other heated or cooled 39,066-F -35--`" 2~303 -3~-surfaces. Microwave a~21ications include roasting bass, microwave cookware and containers, popcorn bags. boiling bags, frozen food trays, microwavable food containers because of resistance to degradation by heat or microwave radiation. Coatings of the polymer are additionally useful on food processing equipment.
refrigerators (inside or outside) and the like.

Applied to layers such as film, electronic components. mirrors, glass, polymers of other composition, metals and alloys thereof~ silicon oxides.
silicon and the like, the polymer having perfluorocyclobutane groups is useful in components including: non-glare or antireflection coatings (e.g.
for photographic film) because of optical clarity and refractive index; reflection coatings for metal or dielectric reflectors because of properties of low dielectric, hydrolytic stability, clarity, or colorlessness; interference filters when applied to other polymers because of properties of optical clarity and low refractive index; polarizers; beam splitters;
passive devices such as couplers because of its index of refraction; photon detectors including photoconductive and photoemissive detectors because of properties of optical clarity; photovoltaic devices such as solar cells because of properties of hydrolytic stability, optical clarity; in imaging applications, e.g. in electrophotography including Xerography and Electrofax because of properties of low dielectric and optical clarity; in thin film displays (e.g. electroluminescent and electrochromic) because of properties of ! planarization and low dielectric; in information storage devices because of properties of planarization, environmental stability; in thin film active components 39,o66-F -36-2~7309 such as transistors and diodes because of properties of low dielectric; dopant diffusion layers in implant masks; in thin film integrated circuits as dielectris interlayers because of low dielectric and ability to planarize; in micr-wave.circuits such as microwave integrated circuits (e.g. as microwave circuit boards) because of properties of low dielectric low dissipation factor, and in other microwave applications such as telecommunications equipment.. including.~.ce.i.vers (e.g.
antennas and probes) and transmitters (broadcasting and power), particularly as coatings for these. because of resistance to degradation by microwaves, tran~mission of such waves and lack of absorption in the microwave range; in surface acoustic wave devices such as transducers, delay lines, band-pass filters, pulse-compression filters, amplifiers, guiding components and other applications because of properties of low dielectric, refractive index, optical density; in charge-couple devices as scanners because of properties of planarization and optical clarity; in thermal detectors, thermal imaging devices, photothermal conversion devices because of properties of temperature stability; because of low diele tr c properties the polymer is useful as passivation layer in high speed electrical switches; as a non-linear optical (NL0) polymer backbone to produce active device structures for optical interconnects because of properties of low dielectric, high heat stability, and good optical transmission; fiber optic sensors.

Polymers having perfluorocyclobutane groups are useful in seals and gaskets, preferably used as a layer of a seal or gasket, e.g. around a scrim, but alternatively used alone. As a seal or gasket, the 39,066-F -37-. ` 2~5~309 polymer offers advantages such as chemical resistance, high thermal stability, oxidative stability, solvent resistance and the like.

Polymers having perfluorocyclobutane rings have properties of resisting transport of chemical species that could attack an underlying layer, such as hydrolytic stability. hydrostatic stability. chemical resistance, low moisture absorption~ or weatherability (hereinafter referred to collectively as environmentally protective, meaning protective from at least one substance or force to which an object is exposed in its environment, including conditions of manufacture, storage and use) that result in utility as coatings to impart surface passivation for instance to metals, semiconductors, capacitors. inductors, conductors, solar cells, glass and glass fibers, quartz and quartz fibers, polymers such as polycarbonate to improve corrosion resistance, reduce sensitivity to chemicals, protect from scratches. Because of optical clarity, the polymers are suitable environmentally protective and/or scratch resistant coatings even for devices such as photovoltaics, optical disks, windows. eye glasses, mirrors (especially those used outdoors), optical fibers and the like. The polymers have properties of low coefficient of friction (for instance, less than 0.25 static coefficient and less thar 0.16 dynamic coefficient of friction), scratch resistance, high heat resistance, chemical resistance, and colorlessness that result in utility as coatings for tribological applications (interfacing surfaces in relative motion) such as wear-resistant coatings and lubricating coatings. They are also useful in decorative applications such as clear coating for preserving 39,066-F -38-20~730~

automobile finishes e.g. as an overcoat to paint. as an undercoat to smooth paint or in automotive body panels.
building materials, wall papers or other wall s~/erings, siding, display materials and the like; in fabrication of structural ~orms as coatings for flame resistance t weather resistance, moisture resistance and such as on thermoplastics, wood, metal, ~ibers, and powders.
Because of low temperature curing. low dielectric, low moisture absorbar--e, chemical resistance and optical clarity, layer(s) of polymers having perfluorocyclo-butane groups or materials having such layers are particularly useful in electronic packaging such as multichip modules, multi-layer chips, microwave circuits, planarization layers, optical interconnect l nes, circuit boards, cable insulation and the like.
The polymers are also useful as environmentally protective layers and impact absorbing layers for micromachines.
Resistance of polymers having perfluorocyclo-butane rings to radiation (e.g. electron-beam, gamma-waves and alpha parti¢les) results in their usefulness as layers in objects exposed to radiation, such as instruments or-packaging to be sterilized by radiation, as substrates for films, in electronics exposed to radiation and the like. For instance, the polymers are useful as passivation coatings on medical instruments and in packaging for medical devices such as bandages, operating equipment and the like. Similarly, the polymers are useful in e.g. X-ray films. Because the polymers are both radiation and heat resistant, as well as resistant to chemicals, including oxygen and moisture, their usefulness extends to labware including petri dishes; incubator windows, window coatings and 39,o66-F -39-` ` 20~30~

linings; oxygen tents and masks; sterilizable (gamma ray and~or autoclavable) equipment such as trays, ~urgical drapes, medical table surfaces, medical clothing;
surgical packs; body fluid containers; and the like.

The chemical resistance of polymers having perfluorocyclobutane polymers, particularly polymers having pGrfluorocyclobutanQ groups, aromatic groups and non-carbon atoms, preeerably oxygen or sulfur in the backbones Ihereof. renders such polymers useful for protection from chemical àttack. In addition to passivation, such use includes masking of underlying layers for solder, for etching, for module fabrication graphs device and the like. The polymers are useful as cable jacketting for e.g. optical, electronic, and superconductive wires or fibers.

In electronics applications, varieties of substrates are coated with polymeric materials either for selective etching or for passivation. Typical substrates include silicon, silicon oxides, gallium arsenide or other compounds of metals of Groups IIIA and IVA of the periodic table as basic semiconducting materials for forming transistors. diodes. and capacitors; silicon dioxide, silicon nitride. or phosporus-doped silicon dioxide as dielectric materials for interlayer insulation and passivation; aluminum or polycrystalline silicon as conducting materials for e.g.
contacts, interconnections, and electrodes; chromium or alloys thereof e.g. used in optical masks for photolithography; or copper as conducting material used ! e.g. in printed circuit boards. Silicon s a major semiconducting material in microelectronic devices. It advantageously begins microfabrication in the shape of 39,o66-F -40_ 20~3~9 wafers. The surface of a silicon wafer or that of a epitaxially grown silicon layer is cleaned for polymer film depos tion. A 3ilicon surface is generally coated with an oxide layer, e.g. by thermal oxidation or by chemical vapor deposition, before being coated with a resist. Highly doped polycrystalline silicon is, however, generally coated with resist to be patterned to form electrodes or interconnections in integrated circuits. Such a material (also called ~olysilicon) is deposited e.g. on an oxide layer from the vapor phase by pyrolyzing silane. Polycrys~alline silicon is use~ul e.g. to form electrodes in capacitors and tran3istors.
To form electrodes, before patterning, the layer is preferably doped e.g. by thermal diffusion or by ion inplantation to increase conductivity.

Typically, surface flatness of a silicon wafer used in a semiconductor device does not deviate from optical flatness more than 70 ~m. Additional deviation is generally caused by oxide layer deposition because of a difference in thermal expansion coefficient between oxide and silicon. Polymers having perfluorocyclobutane groups are suitably used to planarize the wafer. which allows the production of smaller circuitry (higher density). Such polymers can be applied and allowed to adhere during thermal cycling.

Gallium arsenide (GaAs) and its homologues are also frequently used in semiconductor devices such as high-speed transistors, high speed integrated circuits, light-emitting diodes, and laser diodes, and thus is a useful substrate for layer(s) of polymer having perfluorocyclobutane groups. Silicon dioxide, as a common insulator in semiconductor devices, is also a 39,066-F -41-suitable substrate for polymer layers according to the practice of the invention. It is often fo~med on silicon by thermal oxidation of the surface with o~ygen or water vapor at a temperature between 1000 and 1200C
or is, optionall~. chemically deposited onto a substrate, not necessarily silicon, e.g. from the vapor phase, e.g. by the oxidation of silane with oxygen at a temperature between~400 and 500C. Silicon dioxide is hydrophobic but reacts with water vapor in the atmosphere to form silanol (Si-OH), or a silanolated surface is formed in the chemical vapor deposition of silicon dioxide. Surface treatment to enhance adhesion is preferred before applying a polymer layer. Sil con nitride is conveniently deposited vapor phase ~rom e.g.
silan~ and ammonia at a temperature between 700 and - 800C. Silicon nitride is often a barrier for selective oxidation of silicon surface. Phosphorus-doped silicon dioxide is advantageously deposited vapor phase by the reaction of oxygen with silane and phospine (PH3). It is useful for e.g. interlayer insulation and passivation of device~. A surface treatment is preferred prior to polymer film deposition. Chromium is a useful opaque layer in optical masks conveniently at a thickness of 0.08 to 0.01-~m, e.g. deposited by vacuum evaporation or sputtering. Copper is widely used as a conductor in electric and electronic industries. In printed circuit boards, a copper foil is conveniently patterned lithographically to form interconnections between electronic components. Polymers having perfluorcyclobutane groups are advantageously deposited on any of these substrates.

The surface onto which a po:ymer film is applied is preferably clean and free from dust particles 39,066-F -42-2~57309 to avoid adhesion problems and/or defects in t~e film.
Cleaning of a silicon wafer surface may. ~or instance, involve: (1) boiling in a solvent, e.g. trichl~ro-ethylene, ~2) washing in ano~her solvent, e.g. acetone (room temperature). followed by (3) boiling in an acid, e.g. concentrated nitric acid. In a typical process, steps 1 and 2 take 5 minutes each and step 3 taKes 15 minutes. Other-substrate treaments include, fo~
instance, etching silicon dioxide, with aqueous hydrofluoric acid (HF); hexamethyl disilane (HMDS) treatment of polysilicon, silicon dioxide, phosporus doped silicon dioxide or silicon nitride.

Practice of the invention is particularly useful as one or more layers~ optionally with layers of different composition, on substrates such as wires, fibers (synthetic and natural), cables, and other elongated objects which can be coated on all exposed surfaces. The polymers are useful as sleeving, cladding, flame resistant coatings and in addition to being applied by coating means already enumerated can be applied, for instance as tape wound around the elongated object(s). High thermal stability with continuous service at 200C or greater being possible, while maintaining excellent electrical and dielectric properties combined with high resistance to chemicals and solvents, and low coefficients of friction and surface energy of polymers having perfluorocyclobutane groups result in utility, for instance~ including tape and wire insulations (particularly in high temperature, high frequency applications) capacitor dielectrias, coaxial connectors, coil wrappers, transformers and as a glass fiber laminate for printed circuit boards. As a material having a low index of refraction as measured by 39,066-F -43---` 20573~

refractometer, in addition to its thermal, hydrolytic and chemical stability, flame resistance, ea3y curability and compatibility with other materials such as other polymers. polymers having perfluorocyclobutane groups are particularly useful in wave guides as coatings (both claddings and buffering) ~or c?tical fibers or in multichip modules or passive devices.
Because of the low refractive index, hydrolytic stability and heat stability, the polymers are suitable for use in multilayer optical films for band pass filters and interference coatings.

Coatings can be applied, for instance, as colloidal aqueous dispersions by such means as spraying, dipping, flowing or casting and to obtain a, preferably continuous and/or uniform, coating followed by an initial heating is used to remove solvents e.g. at 100 to 200C and then by curing at 190 to 300C. The polymer~ can also be applied by extrusion, electrostatic spraying and fluidised bed techniques. A particularly preferred embodiment of the invention include layers of polymers having perfluorocyclobutane groups over optical fibers, e.g. glass fibers. Without an effective coating, the fibers deteriorate from exposure to moisture, e.g. SiO2 develops hydroxy groups and there is a large resulting optical loss. Such a coating is typically applied as a prepolymer solution, preferably of sufficient viscosity to spread evenly to form a uniform coating, from which the solvent is removed (some curing optionally occurs) to form a, preferably tackless, coated fiber by rapid heating, e.g. in a plasma (UV, electron beam), infrared (IR) oven or the like; this heating is optionally followed by additional heating or other curing to achieve a polymer which is 39,066-F -44-2~573~9 prefera~ly at least 50 percent cured. more preferably at least 80 percent cured, most preferably at least 99 percent cured. The polymer is a suitable outer coating for such optical fibers because of the polymers' flame retardancy, flexi~ility, heat durability. low moisture uptake and hydrolytic stability. Such outer coatings are applied by means within the skill in the art such as by extrusion.

For high-density integrated circuit applications, multiple interconnections, which preferably consist of alternating metal and dielectric layers, are very important. Such interconnections enhance efficiency of chip utilization and increase design flexibility. Multilevel structures now have feature sizes of 1 ~m, and it is projected that future feature sizes will reach the range of 0.5 ~m.
Metallization of dielectrics makes it possible to obtain highly packed, multilevel interconnectors. Polymers applied according to the practice of the invention, e.g.
by spin coating, planarize underlying topography to provide a surface suitable for the next metal deposition. The degree of planarization is determined by the ratio of the ~tep height with the polymer coating to the initial step height of the metal pattern without the coating. For multilevel applications, vias for metal connections have to be formed to make contact between interconnection levels. Subtractive photolithography techniques in which a photoresist is r applied on top of a polymer coating are suitable. Then a cured polymer film is etched, e.g. using a photoresist I as an etching mask. A middle layer in a trilevel or ; multilayer resist system is often silicon dioxide. The layer can be deposited e.g. by vacuum evaporation or 39,066-F -45-2~5730~

deposition~ but is conveniently deposited by spin coating. Such a coating is called spin-on glass and is tetraethoxysilane dissolved in ethanol, whicn when deposited and baked, results in a layer of silicon dioxide.

Polymers having perfluorocyclobutane groups, particularly those having perfluorocyclobutane groups in a polymer backbone, which also has non-carbon atoms and aromatic hydrocarbon groups, preferably separating the perfluorocyclobutane groups exhibi~ dielectric properties suitable for electronic applications such as insulators in multichip packaging (multichip modules), multilayer electronic structures 7 capacitors, ring oscillators and the like.

Multichip packaging offers the potential for fabricating circuits with increased density and higher performance at lower cost than is presently feasible.
Z Multichip packaging designs reduce the distance between the chips, thus reducing the necessary wire length.
Many multichip circuit designs require multiple levels of interconnection due to the wiring density of the design. This wiring density can be achieved with current thin film technology. The interlevel dielectric material determines the maximum density of the circuit through the line impedance and spacing necessary to minimize crosstalk between signal lines. A material with lower dielectric constant allows closer packing of interconnect lines, and thus provides higher density.
Higher density and shorter interconnect lengths also permit the circuit to operate at higher speeds.
Conveniently, polymerization of monomers containing perfluorovinyl functional groups is a thermal process 39,066-F -46-2~573~

which does not require catalysis and does not generate any volatile by-products. To cast the material as a thin film on a substrate, it is convenient to prepolymerize the monomer to an intermediate degree of conversion of the functional groups. The prepoly~er can be handled either as a melt or in solution, and can be fully cured to the final thermoset after being cast as a film. Prepolymerization, or B-staging, is performed by heating the neat monomers to a temperature between 100C
and 190C for from l min. to 8 hours, depending upon the temperature. The extent of reaction can be determiend from the reduction of the residual heat of reaction measured by differential scanning calorimetry (DSC).

Polymers having perfluorocyclobutane groups exhibit low water absorption (for instance 0.325 weight percent water uptake by poly[1,1,1-tris(4-trifluoroethyloxyphenyl)ethaneJ and 0.04 percent by weight water uptake by poly[4,4'-bis(trifluorovinyloxy)biphenyl] as measured by ASTM D-570-81) and desorption of the water within 24 hours.
Such low water absorption avoids the increase in dielectric constants associated with water absorption and the resulting degradation of electrical characteristics of structures in which they are used as a dielectric. The chemical resistance of such polymers is also excellent, such that thin films easily withstand typical metal etching processes. These films withstand hours at elevated temperatures in acid and alkaline baths with apparently little effect.

Thermogravimetric Analysis (TGA) measures the weight of a bulk sample as a function of temperature and 39,066-F -47-`DEC~ 1991 16:15 FROM PflTENT DEPT. ~-1210 TO 81613232~440 P, 05 ~
2057309 ~' t$me. At a 10C per minute ra~p rate, the on~et of welght los~ is observed above 350C in air and nltrogen.

Isothermal wei~ht lo~s is a more repre~entati~e indication o~ the abllity o~ any polymer to withstand 5 proces3ing a~ a ~iven temperature. In both air and nitrogen environment-~ at 350C, after 1000 minutes in the~e environments poly{1,1,1-tris(4-trlfluoroethenyl-oxyphenyl)cthane] lo~e~ less than 1.2 weight percent, preferably les3 than 1 percent weight in nitrogen and 6 percent by we~tht in air. The polymers exhibit ~tabllity at temperatures up to 400C, a~ observed ln annealing of alumlnum.

In ~abrication Or microele¢tronlc device~, relatively thin de~ect ~ree film~. generally 1 ~ thlck, ar~ advanta~eou~ly deposlted on a supporting lnorganlc ~ubstrate e,g. ~ilicon, or ~ilicon-contalning materials such as ~illcon dloxide, alum~na, ¢oppe~, sllicon nitride; aluminum nitrlde~ alu~inum~ quartz, galllum arsenide and the like. In the practice of the invention, coating~ are conveniently prepared ~rom prepolymer~ reaoted to a moleoular weight, for ~nstance, of 1600 Mn (number a~era~e~, 4900 Mw (welght a~erage)~
11300 Mz (high avera~e) prererably greater thQn 50~0 Mw.
These prepolym~rs are completely misclble w~th a variety of organic ~olvents ~uch a3 ~ylene, mesitylene, n-butyl acetate and the like. The dis~olved prepolymer can be cast onto a ~ub~trate by common spin and ~pray coating techniques. The vi~cosity Or the~e ~olut~ons is i~portant in controlling coatin~ thickne~s ~y elther depo~itlon teohnique.

39,o66-F -4~-.. .. ...

2~57309 Films of polymers of perfluorovinyl-containing monomers are coated on salt substrate3 by spray deposition and cured in air at 250C for 2 hours. This cure period i3 selected as corresponding to the minimum time for the elimination of the reaction ex~therm-as measured by DSC. After curing the films are re~oved by dissolving the substrate in water bath. The resulting films are between 25 ~m and 50 ~m thick. Samples f?r dielectric spectroscopy are metallized films prepared by sputtering 100 nm of Au (gold) in an Ar (argon) plasma onto both sides of the films. Disks 9.5 mm in diameter are punched out of the metallized films. These disks are used to measure both the dielectric permittivity with an HP 4192 Impedance Analyzer and the dissipation factor with a GenRad 1615-A Capacitance Bridge, both according to manufacturer's directions. Spectroscopy shows a dielectric constant of 2.45 and dissipation factor of 0.0005 for poly[1,1,1-tris(4-perfluorovinyloxyphenyl)ethane].

Samples for dielectric breakdown measurementsare not metallized, but are placed between a copper plate and a 6.4 mm steel ball as electrodes. The voltage source is a Bertan Model 20~A-10R Power supply driven by a ramp generator at 200 V/S (volts/second).
Interpretation and meaning of such dielectric measurements is within the skill in the art such as reflected in "Dielectric Materials and Applications" ed.
3 by A. R. von Hippel, The MIT Press, Cambridge. MA, 1966.

To form a sample illustrative of multichip modules, silicon substrates (100 mm diameter) having 1 ~m of thermal oxide are cleaned with an organic solvent.
Then they are metalized using 2 micron Al, Cu 1 39,o66-F -49--` - 2~730~

--~o--percentwhich is sputtered then patterned and etched using an aluminum etch solution of (50 weight percent water, 42 weight percent phosphoric acid, 5 weight percent acetic acid and 3 weight percent nitric acid) to i, , form ground plane and bond pad areas. Under the given conditions, 2 ~m of undercut occurs on each of the exposed sides of the Al wiring traces.

After remo~ral of the photoresist,,a coupling agent e.g. vinyltriethoxysilane is applied to the substrate surface and is followed by a prepolymer solution. The coupiing agent preferably has an end attached to the SiO2 and A102 surfaces, and another attached to the polymer. The prepolymer is spin coated under conditlons which result in 5.5 ~m final polymer thickness. The low viscosity, high solids content prepolymer solution affords a very high degree of planarization. The polymer is thermally cured to 95 percent, such that remaining unreacted perfluorovinyl groups crosslink into the subsequent polymer layer to enhance polymer-to-polymer adhesion.

Via~ are etched into the polymer by sputter depositing a 0.3-0.5 ~m copper transfer mask over the surface. The copper mask is defined and etched using a bath solution of the following weight percent of ingredients: 89, water; 8, nitric acid; and 3, acetic acid. After the photoresist is stripped. the substrate ; 30 is subjected to a barrel plasma etcher (EFE 301C) using I a 86 percent 02~ 14 percent SF6 gas mixture.

-i The copper mask is subsequently removed by an acid bath 59 weight percent water and 41 weight percent nitric acid. This acid bath mask has less effect on the 39,066-F -50-~73~

exposed Al via pads than the weaker bath used to define the via cuts. Next an in-situ Ar back-3put~er is u3ed to deposit a layer of metal and the process above is repeated. Each new polymer layer is subjected to a full :~ cure. The Si substrate is adhered to a alumina base with a low temperature cure epoxy. Wire bonds are made between the external Si substrate pads and the thlck-film conductors on the alumina package. Hermeticaily sealing is optional because of...the hydrophohic nature of the polymer. The module package is placed on an interface printed wiring boa~d consisting of power supply, monitor, keyboard and external floppy drive interconnects.

The low dielectric, air curability, low moisture absorbance, thermal stability, and planarity of polymers having perfluorocyclobutane groups makes them particularly useful in such applications as dielectrics, espe¢ially in multichip modules; protective coatings;
planarizing layers; substrates and the like.

Layer(s) of polymers having perfluorocyclobutane groups are optionally patSerned such as for:photoresists;and by.such means as wet etching, plasma etching, reactive ion etching (RIE), dry etching, photo laser ablation, which are within the skill in the art as illustrated by Polymers for Electronic Applications, Lai, CRC Press (1989) pp. 42-47. Patterning can be accomplished by multileveltechniques in which the pattern is lithographically defined in a resist layer coated on the polymeric dielectric layer and then etched into the bottom layer.
A particularly useful technique involves masking the portions of polymer (or prepolymer) not to be removed, 39 ~ o66-F _51-205`7~9 removing the unmasked portions of polymer, then curing remaining polymer, e.g. thermally. Methods within the skill in the art such as wet-etching or oxygen plas~a techniques such as reactive-ion etching, other plasma etching, reactive ion etching (RIE) wherein substrate3 are placed between electrodes (usually plate electrodes which sustain a radio frequency (RF) plasma), reac~ive ion beam etchin~ (RIBE). ion beam etching (IBE) in which a beam of reactive ions (e.g~. 0+)-are beamed-onto the substrate, processes such as laser ablation are suitable for etching. The polymers can provide a flexible, X-ray transparent substrate for an '~-ray absorbant like gold which is patterned onto a polymer film, preferably on a substrate, e.g. a silicon wafer which is o~tionally removed, e.g. by etching.

Polymers having perfluorocyclobutane groups are particularly useful for forming planar layers, that is layers which are very smooth as indicated by meaqurements of surface smoothness using a profilemeter commercially available form such companies as Tencor Instruments. A surface may be thought of as having peaks and valleyq. A pen follows the surface up and down as it goes~across the surface measuring distances up and down. Average roughness (surEace roughness) is the average of such distances measured from the center line outward and is referred to as RA. The biggest peak to valley measurement made in a pass over a surface is referred to as RT. Layers of perfluorocyclobutane containing polymers on substrates originally having a surface roughness of 100-150 Angstroms (such as aluminum or polished nickel) preEerably have a planarity after 39,066-F -52-2~57309 coating of less than l~O Angstroms, mor~e pre~erabl- less than 50 Angstroms.

To achieve such planarity, a coating is advantageously applied such that the polymer can flow to level roughness introduced in applying the polymer or roughness in the substrate or in metals or ceramics processed onto the substrate.~ Thus, coatings for planarity are preferably applied by means such as spin coating or spray coating in which the surface tension can function to keep the surface of the coating flat.
Other coating means which allow planarity to result include spraying and dipping. These methods and spin coating are within the skill in the art, spin coating art being illustrated by such references as Jenekhe, S.A., "Polymer Processing to Thin Films for Microelectronic Applications" in Polymers for Hi~h Technolo~v, Bowden et al. ed., American Chemical Society 1987, pp. 261-269.

A solution, preferabl~7 of prepolymer, is spread onto the substrate which is held on a vacuum spindle.
The substrate is then accelerated up to a constant rotating speed,~which is advantageously held for a time sufficient to allow preceding to an even thickness, e.g.
30-60 sec. The solution film, thinned by centrifugal force, is dried to form a solid polymer film. The film thickness decreases with increasing time, rapidly approaching a uniform film thickness.

After a polymer film is formed e.g. by a spin-coating process, the film is conveniently baked. The baking evaporates solvent remaining in the film and generally polymerizes the monomer or prepolymer ~ore 39,066-F -53-, 2~730~

completely. Baking temperatures are preferably from 180C to 300C. more pre~erably from 250C to 300C.
Polymers having perfluorocyclobutane groups advantageously have sufficient hardness to allow polishing o~ a coating to further improve plan~ri~y.

Polymers having perfluorocyclobutane ri~gs (?referably polymers having such rinr,s in the backbone along with linking~groups. preferably o~ygen or sul~ur, and aromatic rings) are particularly useful in magnetic media or other information storage media, e.g. tapes or disks, especially hard disks. The planarization properties; thermal, water and chemical stability;
mechanical properties such as hardness, flexural and tensile modulus, flexibility, toughness, elongation, and flexural strength; cure temperatures; lack of volatiles or other by-products produced in polymerization or curing; and low coefficient of friction make the polymers useful for any or all of several layers on hard disks. Hard disks are generally made up of a substrate, one or more undercoat layers (often nickel or nick~l phosphorus), at least one magnetic coating (often an alloy of cobalt and a ron-magnetic metal like chromium), and at least one overcoat (often carbon. e.g. sputtered or wet-coated). The polymers are useful as undercoat and planarization layer(s) on any substrate suitable for disks such as ceramic, glass, canacite (ceramitized glass), or metal such as aluminum, titanium, magnesium, nickel coated aluminum, nickel, plastic (e.g.
polyetherimide), or the like. Used as a planarizing coating, the polymer replaces metals such as nickel now used and grolnd or oolished to the desired smoothness (generating waste nickel). A polymer planarization layer is optionally additionally smoothed as by 39,~5~-F -54-~ 2~5~3~

polishing, e. g. with very fine grit pads such lS 8000 grit pads. A planarization layer is preferably from 20 to 1000 Angstroms thick, more preferably from 50 to 100 Angstroms. The planarity offered by polymer layers according to the practice of the invention is ill~strated by the planarity of an unpolished spin coating of poly[1,1,1-tris(~-trifluoroethenyloxyphenyl)ethanel on an aluminum disk which has a planarity of 40 Angstroms as measured by a profilemeter. The substrate is optionally treated as previously outlined to improve~ adhesion. The polymer advantageously lends mechanical strength without introducing curvature or roughness so that thin substrates are more suitably used. Independently, the polymers are also useful for intermediate layer(s), including magnetic layer(s)~ which ly contain or have adhered thereto, the media, e.g. particles or a layer, applied e.g. by sputtering, of iron oxide. optionally with cobalt (especially as a deposited layer), barium ferrite, a mixture or alloy of cobalt and e.g. chromium and/or tantalum, herein after referred to media containing layer(s). Media containing layer(s) are suitably used on one or more planarization layers of polymer, metal (e.g. nickel) or other material.
Alternatively, the media is used in or on the planarization layer to avoid a coating step. The media containing l~yer is optionally the outermost layer or optionally has overcoat(s). Independently of its use in other layers, the polymer is suitably used in one or more over coating layers which cover the media-containing layer(s) and provide smooth, protective, cushioning, planarizing and/or lubricating coating(s) to protect the media from environmental damage or damage from the reading and/or writing head of a disk assembly.

39,066-F -55-2~5~

-~6-Layers of polymer according to the practice of the invention are also useful as the substrate for the other layers. For use as a substrate, the polymer preferably has a hardness of at least 4 B as measured by AST~ D-3363.

Optical recording media including polycrystalline tellurium films show rapid degradation in high humidity or oxygen environments.~ Tellurium, for instance, is oxidized upon exposure to air, but under dry conditions a stable passivating layer is rapidly formed preventing further oxidation. Water destabilises this thin oxide layer, and oxidation of the tellurium metal proceeds until it is all consumed. In the practice of the invention, polymers are applied as a barrier or protecting layer to protect the thin layers of tellurium or other optical media from environmental gases and moisture. In one embodiment an air sandwich structure utilises a substrate on which the tellurium metal is deposited; annular spacers then provide the supports for the top polymer film and leave a cavity immediately above the metal. The polymer is optionally used to overcoat or encapsulate optical structures.

Because of their high dielectric strength, resistance to degradation by heat, oxygen and moisture and many chemicals polymers having perfluorocyclobutane groups are particularly useful as capacitor dielectric (films). To make a metallized film capacitor, for instance, the polymer has a layer of such metals as aluminum or zinc adhered to its surface e.g. by physical (preferably vacuum) deposition. Then the film is e.g.
wound and, preferably, a clearing voltage is applied to cause localized breakdown discharges at any weak spots 39,066-F -56-- ` ~0~73~9 in he dielectric to stop the discharge by causing evaporation of metal around the faults.

Polymers having perfluorocyclobutane groups are also useful in displays such as flat panel displays, especially liquid crystal (LC) displays, because of their clarity, resistance to temperatures experienced in fabricAtion, low temperature cure-, hydrolytic and chemical stability. A circuit for~ controlling the LC
display is advantageously assembled, then a layer of the polymer is applied over the circuit by means analogous to that now used for such polymers as polyimides.
Another polymer, e.g. a polyimide, is optionally applied over the perfluorocyclobutane ring-containing polymer, adjacent the liquid crystal material, or the liquid crystal material is used adjacent the perfluorocyclobutane ring-containing polymer. A polymer used adjacent a liquid crystal is preferably buffed or texturized to enhance alignment of liquid crystals.
When the polymer having perfluorocyclobutane groups (as a first poly~er) is used with another polymer (as a second polymer), the first polymer is advantageously a protective layer to lend e.g. hydrolytic stability, planarization ard good mechanical properties to the second polymer. Alternatively, whether or not a perfluorocyclobutane ring-containing polymer is used between the controlling circuit and the liquid crystal, such polymers are useful as outer layers, adjacent the liquid crystal and/or on a different layer which is adjacent the liquid crystal. An electrode, electroconductive grid or other display controlling device is optionally introduced into the polymer or between layers.

39,066-F -57--58- 20~730~

Because of their resistance to cnemicals and moisture, polymers having perfluorocyclobl-ane group3 in the backbones thereof are suitable as integrated circuit (IC) encapsulants. Encapsulants protect the electronic devices from ~oisture, mo~ile ions, ultraviolet ~nd visible irradiation, a particles, and/or hostile environmental conditions. An encapsulant preferably also enhances a fragile IC device, improves its mechanical properties, and increases device re~iability.
Encapsulants of the invention advantageously ha-Ye good electrical and mechanical properties; and are resistant to solvents, fluxes, and detergents.

High-density and/or high-speed integrated circuits (ICs) such as VLSIC (very large scale integrated circuit), VHSIC (very high speed integrated circuits), and GaAs ICs require fine-line, multilayer conductor patterns to interconnect large numbers of input/outputs (I/Os) on highly integrated circuits. A
package must provide effective removal of heat and environmental protection of the ICs. Layers of polymers having perfluorocyclobutane rings assist in achieving these ends. For instance in high density printed wiring boards (PWBs) with plated Cu conductor and glass-reinforced polymer dielectrics; thick film multilayer interconnects with screen-printed conductor pastes (e.g., Cu, Au) and ceramic/glass dielectrics; multilayer co-fired ceramic with refractory metals (W or Mo) and aluminia dielectric; ~,~afer scale integration using IC
metallization processes on silicon substrates; and thin film multilayer (TFML) interconnections using Cu, Au, or Al conductors and polymer dielectrics, specifically polymers having perfluorocylclobutane groups.

39,066-F -58-20573~9 Substrates suitably include ceramics, metals, or silicon wafers.

Using polymers having per~luorocyclobutane rings in electronic devices as described. particularly in integrated circuits~ memory or data storage means~ in multichip modules or multi- ayer chips, allows ~ore electronic devices to be more compact than would be the case without the polymers. Such compactness is particularly important in computers which can be smaller and/or lighter because of use of the polymers. For instance, the computers can have hard disk drives wherein data can be stored more compactly and/or using less weight because of the use of the polymers.
The polymers are also useful for example as powder coatings in the electronics industry for conformal coatings of electronic components such as resistor networks, capacitors and hybrids. Powder coatings are applied, for instance, by automatic fluidised beds, dipping equipment, and electrostatic spra-~ing. For use as a powder coating, the polymer preferably has a fusing temperature below the melting point of tin lead solder more preferably below 150C, most preferably below 1-3C. Alternatively, monomers having a melting point below 200C preferably within the preferred fusion ranges are applied as a powder and heated to effect polymerization. Other components of a desired coating optionally admixed with the monomers before polymerization such that such components remain in the final polymerized coating. Powder coatings are suitably used as slot liners, forming an integral coating over which windings can be directly laid. They are also used for the encapsulation of end windings of 39,o66-F -59_ 2~573~

motors e.g. for use in portable drills and other ~otor-containing equipment. Electrostatic powder coating offers an alternative to solvent-based enamels for insulating magnet wires. Cured powder coatings impart properties such as impact strenth, abrasion resistance, moisture resistance, temperature cycling ?erformance, electrical insulation char~cteristics and adhesion to a variety of substr~te and device types, making them particularly useful in both ~he electrical and electron cs industries.

Polymers having perfluorocyclobutane rings exhibit an unusual phenomenon which makes them particularly useful in a variety of applications and facilitates unusual methods of achieving coatings. The perfluorocyclobutane groups tend to segr~gate from hydrocarbon and polar portions of the molecules (analogous to the behavior of a surfactant). Thus, when coatings or layers are applied under conditions, such as heat or solution, which allow the polymer to assume its equilibrium conformation, there are layers of fluoropolymer and layers of e.g. hydrocarbon in the case of a polymer having a hydrocarbon portion of the molecule. This segregating behavior has many advantages. For instance, the hydrocarbon portion of the molecule will intermix with or adhere to other substances present, e.g other polymers like polystyrene, polyolefins, polyurethanes, polycarbonates. epoxy resins, polyesters, polyamines, polyimides, and the like, particularly hydrocarbon polymers such as polyolefins and polystyrene. The perfluorocyclobutane portions of the polymer, then, tend to align away from the hydrocarbon portions of the molecule, leaving a fluorocarbon-like coating thereon. Similarly, when the 39.066-F -60--61- 205730~

non-fluorocarbon portions of the molecule are functionalized, e.g. with groups such as sulfonyl groups; acid groups including carboxylate groups;
hydroxy groups; phosphonyl, phosphoryl, phosphine. or phosphate groups; silane groups such as vinyl or allyl silanes; siloxane groups; amine grou?s; sulfate!
sulfonated, sulfoxide or sulfide groups, such groups are attracted to similar substances or to substances.
preferably substrates, with which they are otherwise observed to be compatible. For instance, a perfluorocyclobutane ring-containing polymer having an aromatic portion having e.g. silane or siloxane groups adheres to such substrates as silica or silicon wafers such as are used in semiconductor applications and the like. Similarly, a perfluorocyclobutane ring-containing polymer having an aromatic portion having phosphonyl or phosphoryl groups adheres to such substrates as calcium salts such as bone or ceramics and the like. Such polymers having sulfur-containing functionality such as ~ulfate, sulfonate, sulfoxide or sulfide groups adhere to iron and iron-containing alloys like steel. ~he fluorocarbon por~ions of the molecules are, thus exposed in each of the cases, exhibiting properties of toughness, low dielectric, low dissipation factor.
lubricity, flame resistance, lower surface refractive index, lower surface tension, fluid barrier properties, repellence of water, oils, soil and the like; resistance to heat, chemical resistance and other environmental protection. Protection from substances such a~ oil and water reduces penetration of these and improves dimensional stability of the substrate, rendering the substrate stain resistant. Migration of substances such as plasticizers out of the substrate is reduced.
Fluorocarbon character on the exterior of an object also 39,066-F -61-20573Q~

-6~- 74069-47 imparts mold-release character. In addition. the coatings are scratch-resistant.

This phenomenon is ~Iseful~ for instarce, in coating fibers. fabrics or other layers such as wool, cotton. and artificial fibers such as polyesters. nylon, and rayon as well as forming layers on molded and other shaped articles. Portions of polymers containing perfluorocyclobutane rings more like the fiber, fabric or layer tend to adhere to the layer while the perfluorocyclobutane portions of the molecule tend to align outside the fiber, fabric or layer. Such properties as flame retardancy, or water repellency are observed in the coated fabric, fiber or layer.
One unusual consequence of the segregatlng phenomenon is that blends of the polymers having per~luorocyclobutane groups and other polymers result in layered materials. It is observed, for instance, that a blend of poly~ers having perfluorocyclobutane groups and e.g. polystyrene when ~haped under conditions allowing segregation of molecular species appears to result in a laye ed material having hydrocarbon portiors of the perfluorocyclebutane-containing polymer blended with the polystyrene while the perfluorocyclobutane groups form an outside layer. Because of this, e.g. 2 weight percent of poly [4,4'-bis(trifluorovinyloxy)biphenyl] in polystyrene re ults in resistance to the flame of a cigarette lighter for a period of 15 seconds in ambient air. For instance, fibers or microfibers of blends of the perfluorocyclobutane ring-containing polymers and another polymer. e.g. polystyrene are conveniently formed, e.g. by extrusion. The fibers may be prepared in a continuous or discontinuous manner and optionally 39,066-F -62-2~5730~

into e.g. a non-woven mat which is optionally further fabricated such as by compaction, stretching, calendering, embosslng, twisting, winding etc. to further alter or collect the resulting mat. When perfluorocyclobutane ring containing polymers are blended with other polymers it is preferable to select polymers of similar Tg (glass transition tem3erat re) such that both polymers are melted and segre~ation is facilitated.

While polymers having perfluorocyclobutane groups are generally useful as layers or coatings, the preferred polymers are generally those having linking structures and aromatic portions of the molecule. More preferably the polymers are formed by thermal polymeri-,~ zation of monomers of Formula I, most preferably where X
is oxygen or sulfur, preferably oxygen and R is an aromatic group. Among such polymers, both thermoplastic polymers such as polymers of bifunctional monomers such as 4,4'-bis(trifluorovinyloxy)biphenyl; 1,3-bis(tri-fluorovinyloxy) benzene; 9,9-bis(trifluorovi.~yloxy-phenyl) fluorene; and 1,1-bis(4-trifluorovinyloxy-phenyl)-1-phenyl ethane; 4.4'-bis(trifluorovinyloxy-phenyl) sulfide; 4.4'-bis(trifluarovinyloxyphenyl) isopropane; 2,6-bis(trifluorovinyoxy)naphthalene; or 2,7-bis(trifluorovinyloxy)naphthalene, preferably those which are crosslinked by additional hea~ such as polymers of 4,4'-bis(trifluorovinyloxy)biphenyl or 9,9-bis(tri~luorovinyloxyphenyl)fluorene and t~ermosetpolymers such as those containing trifuncticlal monomers, preferably more than 0.5 percent by weight trifunctional monomers are particularly useful. The thermoplastic monomers are particularly useful in applications such as molded circuit boards, film for 39,o66-F -63-20~7309 tape automated bonding, ignition resistant and water repellent coatings, where properties such as extrudability, melt processibility? tear strength~ flame resistance, or environmental protectiveness are useful.
- The polymers which can be crosslinked by additional heat are particularly useful in applications such as films and infrared coatings where properties such as chemical resistance, thermosettin~, solvent resistance are useful. The thermoset polymers are particularly useful in applications such as planarization coatings, passivation coatings, and scratch resistance where properties such as solution processibility, hardness, thermosetting, low moisture uptake, low dielectric, or passivation are usefui. Blends of the thermoset and l~ thermoplastic polymers as illustrated by blends of polymers of 1,1,1-tris(4-trifluorovinyloxyphenyl)ethane:
l,3,5-(2-(4-trifluorovinyloxyphenyl)-2-propyl)benzene and mixtures thereof with polymers of 4,4'-bis(tri-fluorovinyloxy)biphenyl; 9,9-bis(4-trifluorovinyl-oxyphenyl) fluorene; l,3-bis(trifluorovinyloxy)benzene;
2,7-bis(trifluorovinyloxy) naphthalene or mixtures thereof are useful when the high temperature physical (mechanical) properties, cb~lical resistance of the thermoset polym~r is needed but the thermoplastic imparts adhesion, lowered flexural modulus (toughness).
flexibility, preferably without loss of superior thermal oxidative stability or dielectric properties.

Some of the properties ~f perfluorocyclobutane-containing polymers which render them useful as layers and coatings are listed below for a representative thermoplastic pol~[4,4'-bis(trifluorovinyloxy)biphenyll, a representative thermoplastic poly[4,4'-bis(trifluoro-vinyloxy)biphenyl] backbone crosslinked at 280C for 1 39,066-F -64-2a5~303 hour and a representative thermoset polymer (poly~l,l.l-tris(4-trifluoroethenyloxyphenyl)ethane) ZO

39,066-F -65-~57303 ~ ~ I T ~ T ~
ti-o __ ~ ~ l ~ Ll V

I o o ~ o O .- o o :,~, I_ _ _ _ _ _ ~ l .~ ~ ~

O 00 03 00 D ~ C ~' e . ~ ~, ~, . O

T ~ 1~ j~ ¦~ ~ ~
_ _ _ _ , ._ _ _ ~ _ -,,, _ E ~ ~ ~ ~
~ ~ ` L~

39, 066-F -66--67- 2~7309 ~ , ~

39, 066-F -67--68- 2~730~

In no instance is the use of a term like fire retardant. fire r~tardancy? fl~me resistanc~ or the like to be interpreted as implying those qualities in any actual fire condi~ion, rather the terms indicate that at least some of the ~oly~ers perform relativeiJ better than controls in standardized tests. Numerical flame ratings are not lntended to reflect the ha,-~rds presented ~y these or o~her ma~erials under actual fire conditions.
The following examples are offered to illustrate but not to limit the present invention. In each case, percentages are weight percent unless otherwise indicated. Examples (Fx.) of the present inver,ion are indicated numerically, while comparative samples (C.S.) are not -xamples of the present invent.on and are indicated with letters.

Dielectric constant and dissipation factor measurement~ are conducted according to the procedures of ASTM D150-87. Tensile strength and modulus and percent elongation are measured on an Instron model 1125 according to the procedures of ASTM D-882-83.
Samples of [1,1,1-tris(4-trifluoroethenyloxy-phenyl)-ethane] (TVE) and of 4,4'-bis(trifluorovinyloxy) biphenyl prepared as taught in U.S. Patent Number 5,066,746 issued November 19, 1991 are used for the 3 following Examples:

Examples 1-9: Investigation,of the,effect,,of solvents and prepolymerization on the attributes of coatings of poly [1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane~

39,066-F -68-2~573~
_~9_ Various degrees of prepolymeriza.ion were achieved using a B-staging apparatus having an ou~er cylindrical insulated jacket with heat supply, open at one end to receive a vertical tubular reactor and a fluidized bed of aluminum oxide between inner walls o~
the B-staging apparatus and ~he tubular reactor. The apparatus was a Tecam model SBL-1 Fluidized Sand 8ath commerciall~J availa~le from Techne, Incorporated. A
thermocouple was inserted in the flui:iz~d ~ed to monitor temperature. The tubular reactor was immersed into the fluidized bed to a depth of 2/3 of its height.
such that the fluidi~ed bed was approximately 6 inches (15.2 cm) above the top o~ the TVE. ~he tubular reactor was equipped with a mechanical stirrer, a vacuum inlet and a nitrogsn inle~ each with valves. The vacuum inlet was used to remove the (xygen from the ~VE monomer before the reactor was immersed into the fluidized bed.
The nitrogen inlet allowed nitrogen to enter the reactor to purge the reactor during the deoxygenation procedure and to maintain an inert atmosphere during the reaction.
Before the reactor was immersed into the fluidized bed, the polymer was deoxygenated. Oxygen was removed from the TVE monomer by subjecting the monomer for 2 hours at room temperature (22C)~ under high vacuum and then ~or an additional hour at 40C under high vacuum. After that time, the reactor was purged twice with nitrogen for a period of 15 minutes each (this means that the vacuum valve was closed and then the nitrogen valve was 3a opened to allow nitrogen to enver the reactor). A
nitrogen atmosphere was maintained for 15 minutes before the nitrogen valve was closed.and the vacuum valve wasopened again. This was done two times to give two 15 minute nitrogen purgings.

39,066-F -69-2~730~

In each polymerization? a s~mple o~2 the wei~h~
of the TVE indicated in Table 1 was placed in the tubular reactor and immerqed in the fluiaized bed whic~
has been preheated ;o the temperature indicated in the table. The reactor was maintained at the indicated temperature ~or the time shown in the same table. In each instance, a glassy solid polymer W23 obtained.

A DuPont In~truments Model ~10 ~ifferential Scanning Calorimeter (DSC) commercially a~/ailable from DuPont Instruments. Inc. was used to determine reacti~/e groups (relative to TVE monomer) remaining after each prepolymerization reaction. Each prepolymer contained a certain percentage of reactive vinyl groups. The method for obtai~ing the total energy released and the percentage of reactive groups remaining~was as follow3:
A sample of each prepolymer was placed on a heating element of the DSC instrument and slowly heated from 20C to 400C at 10C/min. During the heating process, the reactive vinyl groups reacted and released energy in the process. A DSC program was used to calculate the total energy released (shown in Table 1) after all o~
the remaining reac~ive vinyl groups in the prepolymer ~ample had completely-reacted on the heatlng element,.
The percentage of reactive vinyl groups remaining wascalculated according to the formula:
Total energy released by Prepolymer = 61.43%
3o Total energy released by TVE Monomer 432 05 The sample calculation above wasfor Sample No. 1 from Tacle 1, 39,066-F -70-2n5730~

Table 1 Conditions The TVE
Sample Various for, otal Percent Exarn I Amount ~) B-Staging Energyd Remaining p e o Conditions Released Reactive Number (Joul/g) Groups (%) A all ~.lonomer, 432.û5 00 .Oo unheated 1 30 140"C, 3 ~rs 265.40 5 .~3 30 1 50CC, 1 llrs 32:1.10 74 32 , 3 301 50C, 2 hrs 277.C0 64 ' 1 4 30153C, 3 hrs, 246 10 ~6 96 80150 C, 3 hrs, 220.'5 50.98 6 801 50C, 3 hrs, 223.30 51.~8 R-3~
7 80150C, 3 hrs, 224.30 51.92 R-4~

8 801 50C, 3b hrs, 230.50 53.35 9 30160C, 30 min 325.65 75.34 a. Each value is an average of two DSC runs wherein all available perfluorov~nyl groups are reacted.
b. Run number Yellowing of the prepolymer wasobserved when the oxygen was not completely removed from the T~E
monomer, but the yelLowing did not appear to affect coating quality. The prepolymer was colorless when deoxygenation was complete.

Molecular weight distributions for the indicated prepolymers were determined using a Waters model M-6000 Size Exclusion Chromatograph (commercially 39,066-F -71-~730~
, , availaDle from -iaters, Inc.~ accord .~, to manu~acturer's directions. Results are shown in Tables 2 and 3.

Mn is the number a~rerage molecular wei~ht. lw is the weight avera~ molecular weight. Mz is the high average molecular weight.
Table2 Molecular Weight Dislributiond For B-Staged TVE

10 Ex. Conditions ¦ Mn Mw I Mz ~;~l _ .
1 140C,3 h rs 1200 2500 4800 2.11 2 150C,1 hrs ~380 1400 2400 1.62 _ _ 3 150C, 2 hrs 1300 2900 6000 2.30 4 150C,3 h rs, 1600 4900 11300 3 00 7 150 C,3 hrs, 2000 9300 27500 4.53 ._ .
8 150VC,3 hrs, 1900 6900 18200 3.65 _ 9 160C,30 min 900 1500 2600 1.67 a. as obtained by Size Exclusion Chromatography 3o 39, o66-F -72-20~73~

Table 3 Weight Percent of t3ch Oligomera Present n 3-St3ged TVE
Ex ~ ~ High . B-Staced Mc,nomer Dimer Trimer Molecular Conditions ~'"o) (%) (%) we~ght ___ 1143C,3hr; 25~ 203 ¦ 117 333 215~"C,lh~s A~,3 275 l ~ 1~.~
_, _ 3150C~2~s 2~.3 lg.~ ~ '15.1 41~
_ , _ 4150C, 3 hrs, l6.9 15.2 12.5 554 S1 50C, 3 hrs, 13.64 1 1.79 9.57 Na 615ûC, 3 hrs, 14.20 12.51 10.03 Na 7 R-4 1 4.û3 12.17 9 .87 Na 8150 C, 3 hrs, 15.36 13.77 11.09 Na _1 60C, 30 min 39.1 27.2 15.8 17.9 a. as obtained by Size Exclusion Chromatography Na. = not measu red To test the prepolymers in coatings. clean solutions of the indlcated prepolymerized polymers weremade in the indic,~ted solven~s at weight ratios of polymer to solvent of 70/30 percsnt, 60/40 percent and 50/50 percent. Diglyme, mesitylene, o-xylene and n-butyl acetate were selected for investigation because they represented a wide range of types of solvents, having different boil ng points. viscosities and polarities, were solvents for both the monomer and polymer and were known to be useful in coating processes. Each solution was tested using a Solitec model 5110 (horizontal) Spin Coater, commercially 39,066-F -73-205730~
~ _ 74069-47 available from S li-~ec. Inc. For each coating, a silicon oxide wafer subsrrate was centere onto ~ ~lat chuck. which was cor.nec~ed to a rotating s?indle iuring ~pin coating. and 0.2~ .ml o~ a soluiion of triethoxysilJl-ben~oc~clobutene (T2S-BCR) in the ~e3t soivent adhesion prcmocer was dr~pped onto the sur~a2e of the substrate from a s-vringe ~quipped with a I mi ron Gelman ~crodi,c fiite~ ~commerc all~ available from Gelman Science Company~. rhe fi_ter housing was made of polypropylene~ and the filter was made of polytetrafluoroethylene and was 25 mm in diame~er having inlet and outlet connections on the filter housing. The adhesion promoter W2S spread over the wafer at a spin speed indica~ed in the Tables. A sample of 12 mL
polymer solution was applied over ;he surface of the substrate using one of two methods:

For the examples in Tables 4 and 5 and E~les 6 and 7, the polymer was applied onto the surface of the wafer using a 10 mL syringe equipped with a filter (Method 1).
For Examples 5 and 8, the polymer solution was pre-filtered through a filter into a 100 g clean bottle;
then the polymer soiution was poured from the bottle over the surface of the silicon oxide substrate until the polymer solution covers approximately 3/4 of the entire surface of the substrate. (Method 2) For all examples: for polymer coatings of l.0 micron or less, a 0.20 micron filter was used; for polymer coatings 3C thicker than 1 micron but less than 5 microns, a l.0 microfilter was used; for polymer coatings thicker than 5 microns, a 5 micron filter was used. The filters wereused to remove particlas, which would degrade the coating quality.

39,066-F -74-2~5730~

Then the spin coater wa3 turned on which ~auses the substrate to go into a spread mode followed a spin mode. The polymer was spread over the surface o~` the substrate at a spre~d speed, spread time, spin speed~
and spin time as in~lcated in the Tables to giv~ a uniform spin coated polymer solution.

Each coating was aoplied to a silicon wafer ~substrate) 2 inches (5.08cm) in diameter. The silicon o~ide suDstrates were commercially available from Unisil Corporation, where the substrates were preheated and silicon oxide was deposited on the surface of the substrate. Each wafer was cleaned before spin coating using a LFE Plasma Systems model 301C Barrel Etcner (commercially available from, LFE Plasma Systems. A Mark IV Company) according to mlnulacturer's dlrections. The Spin Coater was run according to manufacturer' directions under the conditions indicated in the tables.
After being coated, each wafer was removed from the spin coater and placed in a Blue M model B-2730 Curing Oven (commercially avail~ble from Blue M, a Division of General Signal) having a programmable temperature contro . and being fitted with a filtered nitrogen inlet and outl~t such that a nitrogen atmosphere wasmaintained during curing with a flow of 100 standard cubic feet per hour (2.8 cubic meters/hour). The nitrogen was filtered using an HEPA 1 micron filter. The preoolymer was further cured at 50C for 5 minutes, then -he 3 temperature was raised to 100C over a period of 15 minutes and maintained at 100C for an additional 15 minutes, after which. the temperature was raised to 150C over a period of 15 minutes and maintained for a period of 60 minutes, after which the temperature wasraised to 250C o~er a period of 60 minutes and 39,066-F -75-~EC-~6-1991 16:16 FROM P~TENT DEPT. 8-1210 T0 8l6l3232a440 P.06 2057~0~ ~`

main~a~ned for a p~r~od o~ 1 ~inute, after whiah the oven temperature wa~ low~red to 20~C and ~aintained until the coated wafer cools to that temperature.

A~er the curing. the ~llm thickne~
wasmeasured uslng a Nanospec/AFT Model 210 elllpsomete~
~o~mercially available from Nano~etrlcs, Inc. and a Tencor Instr~ments ~odel Alpha-Step ~00 profilem~ter commerclally ava~lable from T~ncor Instrumenta, In¢.

Tables 4-5 indicate the re~ult~ o~ ~he Coatin~
proce~ses .

Table 4 _ _ Film Thicknesses (llm) of Different B-staged Runs from a 50/50% Solid soll~tion in Four Different Solvents at Various Spin Sp~eds _ 140C 1 50C 1 50~C 1 50C . .
20Solvent Sp;n Speed 3 hr 1 hr 2 hr 3 hr R-1 (rpm) (Ex. 1) tEx. 2) (Ex. 3) (Ex. 4) Diglyme 5000 i 0 94300.5906 1 ;036S 1.2080 1 ~00 1 .55861 .1~5 18296 Na 25Mesitylene 5000 1.06360,6728 1.1272 1 .434a 1500 1 .84g41 .2148 2, 1 330 Na o Xylene 5000 1.34120,9863 t.5~35 1.9180 1~00 Z ,49001.830 1 2 .97 12 Na _ 3oAcBtattYI 5000 1~5 1 11 .0962 1 .7 1 87 1972 1 S00 2,65051 .gi1~ 3.3026 Na _ _ For each s~in coating, the spin time was 30 seconds and the spread sneed and spread time are 500 rpnl and 3 0 seconds, respectively. Film Thicknesses were measured with the Nanospec/AFr Na = Not available Method 1 was used for spin coating the prepolymer onto the substrate.
1-micrc,n fillers ~re used for each experiment.

39, 066-~ -76-_ . , .

- 20~7~09 Table 5 Film Thicknesses (~m~ of Different B-staged Runs from l~ifferent Percent¦
Solid solutions in Four Different Solvents at Various Spin SPee~s _, _~_ _ 150C 150C 1,O''C 150C
Spin Speed 3 hr 3 hr ' hr 3 hr 6 `140 Solvent (rpm i 70/30 Rs-50/50 R-2 5û, -,0 R-3 R-~Ex. ~) ~Ex. ~ (Ex. 7) (E . .
. , _ Digiyme 9ûOO 5.75 1.2275 ~a 2.3342 _ __ _ 50ûO ' 70 1.5877 Na 3.1834 15Cû '2.22 3.0438 ~`la 6.82 Mesitylene9000 7.32 1.4573 1.3193 3.20 _ S000 10.30 1.9121 1 7732 4 25 lS00 24.53 3.5342 3.~3~4 8 31 _ o-Xylene ~000 7.75 1.8872 Na 3.95 S000 10.71 2.4954 Na 5.27 1500 22.22 4.5146 Na 9.98 20n-Butyl 9000 7.71 1.9907 Na 4.08 Acetate S000 10.73 2.5625 Na 5 38 1500 20.42 4.1041 Na lû.20 .
For each spin ~oating, the spm Ime was 30 second~ 3nd the spread 25 speed and spread tlme were 500 rpm and 3 0 seconds, respectlvely. Na = NotaYailable For experiments 6 and 7, spin coating Method 1 is used.
For experiments 5 and 8, spin coating Method 2 is used.
A 5 rnicron filter was used for experiment 5 while a l micron filler was used for experiments 6-8.

39,066-F -77-2~7~0~

Table 6 _ Film Thicknesses ~lm) of ~ifferent t3-stage~ uns from Different Percent Solid solutions in Four Differen~ Soivents at Various Spin Speeds _ __ 150C l 50C 150C
Spin Speed 3 hr 3 hr 3 hr Solvent (rpm~ 50/50 F~-4 4û/60 R-4 50/50 R-5 (Ex.3) ~Ex. lO) (~x.11) Diglyme 9000 1.2529 3.6526 Na 1 û
5000 1.5654 0.87~01 1.3791 15ûO 3.00û3 l .5175 Na Mesitylene 9000 1.3877 0.8751 I~la !
5000 1.8712 1.1225 I.bl95 15ûO 3 50,13 ~2.0482 Na I
o-Xylene 9000 1.8473 1 0619 Na 5000 2.4501 1.274 2.1485 1500 4.77 2.3979 Na 20n-Butyl 9000 2.0166 1.1234 Na Acetate 5000 2.6075 1.4257 2.3616 _ 1500 4.99 2.6439 Na For each spln coatin~, the spin time was 30 seconds and the 25 spread speed and spread t~me were 50û rpm and 3.0 seconds, respectively. Na = Notavailable 39, û66-F -78-73~9 --7~--Tabl~ 7 Film ~hic!~ness (~m) For B-st~ged Run #5 From a 50/50i'~
Solid Solution in Four Different Solvents at Various Spr~ad Times __ Film Thickness (~m~
Solvent Used 3 sec.
45 se~. 90 sec.
Mesityl~ne 1.61952.~043 5 j3 _ O-Xylene 2.14~5 7.1~ 7 ~1 Diglyme 1.38151.87463.3102 N-Butyl 2.3~1~ 8.39 8.34 Acet3te For each spin coating, the spread speecl ivas 500 rpm and the spin speed and spin ime were 5000 rpm and 30 seconds, respectively.

Data in Tables 4-7 show that the degree of B-staging of polymers of TVE was an important variable affecting the film thickness and coating quality.
Coating quality was determined from observed uniformity.
including absence of holes: a standard deviation of less than 0.1 among 5 thickness ~easurements on different portions of a disk was considered good quality. There were also few color patte~ns of the ty?e produced by thickness variations and no visible bumpiness. At a given reaction temperature of 150C, when the B staged prepolymer was dissolved in a given solvent at a given concentration, the prepolymer that had reacted longer gave thicker coatings. These results directly correlated with the results from size exclusion chromatography which showed a progressive increase in the concentration of high molecular weight oligomers as 39.o66-F -79- --`" 2~730~

the B-staging reaction time for forming the ~repolymer increases. The conver,e was true for the percentage of TVE monomer remalning after each prepolymerization reaction. Furthermore, it was believed that, thicker coatings were observed because the viscosi r, y of the prepolymer solution was directly propor~,ional tG the percentage of high molecular ~eight oligomers in the prepolymer. There was also a _orrelation of B-staging condition with observed coatlng quaiity. The better quality coatings ~,iare achieve~ ~rom prepolymers ~i~ich were polymerized at the longer reaction times ~3 hrs at 150C). Prepolymers that polymerized at 10~C higher or lower than 150C, regardless of the reaction time.
generally gave lower quality coatings. The prepolymer containing 50.98 percent unreacted trifluorovinyef,her groups (Ex. 5) was observed to give the best quality coatings for film thickneqses between 1 and 4 microns.

Two other important variables affecting the film thickness and coating quality were the solvent and prepolymer concentration. The order in which film thickness was observed to increase with solvent is: n-butyl acetate greacer than o-xylene greater than mesitylene greater t'nan diglyme. This order wasdirectly proportional to the boiling point of the solvents.
Prepolymer solutions of n-butyl acetate and o-xylene were believed to give thicker coatings because the solvent evaporated from the substrate more quickly. As the solvent evaporated, the viscosity of the prepolymer solution on the substrate increased; less prepolymer solution was spun off at higher viscosities: therefore.
coatings were thicker. When solutions of prepolymer in solvents with approximately the same boiling point (such as mesitylene and diglyme) were spin coated, the 39,066-F -80-2~573~9 ~ , solution containing the solvent with the higher solve~
viscosity generally developed thisker coatings.
Variations in fil~ thlckness from prepolymer solutions of different concentrations indicated that as the prepolymer concentration increased from 40 to 70 percenf by weight, the f lm thickness also increased.

Choice of sollent and the prepolymer concentration also affected the coating quality.
Prepolymer solutions in all of the solvents studied wereobserved to produce good quality coatings, with somewhat less quallty observed for coatings from solutions in diglyme. Prepolymer solutions of mesitylene tended to exhibit highest quality coatings between 40 and 70 percent by weight prepolymer for a wide range of film th.icknesses (1-25 microi1s). Hi~hest coating quality ~asobserved for psepolymer concentrations of between 50 and 60 percent by weight.
Results indicated that film thickness increased as spin speed decreased. For low spin speeds of 1500 rpm and for high concentrations of 70 percent by weight prepolymer~ the orde~ in thickness did not correlate with the ooiling point of the solvent. It is believed that the solution viscosities were sufficiently high to overcome the effect of solvent boilins points on film thickness. The order of film thickne,s observed for o-xylene and n-butyl acetate at a spin speed of 1500 rpm~
was believed to be a result of experimental error in the concentration of prepolymer in n-butyl acetate.
Furthermore, coatings from prepolymer solutions in n-butyl acetate and diglyme at concentrations greater than 60 percent by weight prepolymer and for spin speeds of 1500 rpm were observed to be of generally lower quality 39,066-F -81--~2- 205730~

than those cf other coatings from these solvents. Film thickness incr~ased with longer spread times for prepolymer solutions in mesitylene arl diglyme. At spread times longer than 45 seconds, the increase ~n film thickness was not as large for prepolymer solution~
of the lower boiling solvents as for solutions in higher boiling solvents. Shorter spread t mes ~enerally resul~
in better quality coating-~.

The differences in ~,hickness between R-2 and R-3 is believed to be a result of differing molecular weight distributions of R-2 and R-3.

Example 10: Planarity of a film of poly(TVE) An aluminum disk having ~ surface roughness of 100-150 Angstroms, as measured by a profilemeter commercially available from Tencor, Inc. used according to the manufacturer's directions, was coated with poly[1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane]
acoording to the procedure used in Example 8 with mesitylene as solvent, at a 60 percent by weight concentration of prepolymer in solvent, and was cured according to the,pracedures of Examples 1-9.

The planarity of the resulting coated disk wasmeasured using the profilemeter as for the disk and found to be 20-40 Angstroms. This measurement indicated that polymers having perfluorocyclobutane groups are useful as coatings to achieve planarization.

39,066-F -82--~3-Example 11: Planarity of a film of pclyfl,1,1-tris(4-trifluoroethenyloxyphenyl)ethanel over an aluminum conductor Aluminum (Al) contlining 1 weight percent copper (Cu) conductor lines were depositec on a silicon oxide substrate using standard techniques used in microelectronics using ~he steps of:

(A) Cleaning the wafers in an oxygen plasma for 15 minutes using a LFE 301C Barrel Plasma Etcher ~commercially available from LFE Plasma Systems) at a gas flow of 130 sccm oxygen, 260 watts, at 1 torr.

(B) Rinsing with ultra pure deionize~ water and spinning dry then 3 rinses in ultra pure deionized water and another spinning dry.

(C) Depositing an approximately 2 ~m metal layer of aluminum containing 1 weight percent copper as an alloy by sputter depositon with an ion gun in an argon atmosphere using a Leybold 560 ~ox Coater (commercially available from Leybold-Heraeus Technologies. Inc.) ha~ling a DC (direct current) magnetron using 10 standard cubic centimeters (sccm) of argon, at a pressure of 5X10-4 mbars, a 500 ~I potential.
40 ~mA current, for a 1 minute duration to clean the surface and promote metal adhesion followed by a sputter 3 process at 299 sccm argon, at a pressure of 2X10-3 mbar, an alloy of aluminum with 1 pecent by weight copper as metal source and 1500 watts for 60 minutes.

39,066-F -83--84- 2~73~

(D) Washing in a mixture of acetone and methanol, quickly dumping the rinse to remove particulates, and ~rying at 100C.

- 5 (E) Spin coating with a 4 ~m layer of Shipley Microposit S1400-37 Positive Photoresist tcommercial y available f:om Shi31ey ~ompany, Inc.) for 2 sec. at 500 rpm with dynamic dls~ense, then spin lng for 30 sec. at 2500 rpm to form a resist layer.
(F) ~aking the coating 30 minutes at 100C.

(G) Exposing the resist layer to determine the pattern of aluminum using a Canon PLA-501FA aligner (commercially available from Canon USA, Inc.) using proximity mode and a high pressure mercury lamp with an exposure of 47.2 mJ/cm2 over aluminum measured at 405 nm.

(H) Developing the resist layer using Shipley Microposit 454 Developer (2 percent potassium hydroxide) (commercially availa~le from Shipley Company, Inc.) by immersion at 18C ~or 90 sec.
(I) Flood exposing the resist layer using a Canon PLA-501FA aligner (commercially available from Canon USA, Inc.) using a high pressure mercury lamp with an exposure of 236 mJ/cm2 measured at 405 nm.
3o (J) Baking for 30 minutes in air at 120C such that the resist layer withstands metal etching.

(K) Wet etching the aluminum layer at 45C for a period of 13.5 min. in a slightly agitated bath of 3?.066-F -84--85- 20573~

phos3horic acid, 41.8 weight ?ercent in 50.1 perren~
water with 5.2 ?ercent acetic acid and 2.9 percenc nitric acid.
(L) Rinsing in ultr- pure deionized water and drying.

(M) Stripping t-ne resi,t by washing in acetone and mentanol.

(N) Oxygen plasma cleaning the resulting laminate for 15 minutes.

(O) Rinsing by dipping in ultrapure deionized water three times.

(P) Dr-Jing by spinning.

(Q) Dehydration baking at 200C for a period of 3o minutes.

Equipment used was that described in Exa~ples 1-10 unless stated otherwise.

The lines had a height of 1.7 microns (~m) abova the silicon oxide surface as measured using a profilemeter, as in Example 10. A 4 ~m thick layer of poly[1,1,1-tris(4-trifluoroethenyloxyphenyl)ethanel wascoated and cured over the silicon oxide and Al 'ines, using the procedure of Example 6 and mesitylene as a solvent at 60 percent by weight concentration of prepolymer in solvent, and the curing procedure of Examples 1-9. The final cured film was observed to cover the surface such that the Al line protruded above 39,066-F -85-the planarity of the surface by 0.047 ~m as ~leasured using the pro~ilemeter. This corresponds to a degree of planarization ~DOP) of 97 percent, and demonstra~ad t~e ability of the polymers to plan~rize large differences in topology as is important for microelectronic 5 applications such as multichip modules.

Example 12: Composite of poly[1.1,1-tris(4-trifluoro-ethenyloxyphenyl)ethane] and gl~ss fiber mat.

Two plies of woven E glass (electrical glass) mat were cut (4"x5") (9 X 12.7 cm) and saturated with poly~1.1,1-tris(4-trifluoroethenyloxyphenyl)ethanel monomer. The cloth was placed in a 5 mil mold with Kaptonr~ polyimide film commercially available from DuPont de Nemours as release layers. The mold wassandwiched between two 6"x6" (15.2 x 15.2 cm) aluminum 1/8" (0.32 cm) plates and pressurized to 15 tons gauge pressure (10,000 KPa) in a hydraulic press commercially available from Pasadena Hydraulics Inc.
preheated to 180C and maintained at that temperature for 1 hour. The temperature of the pres~ was then increased to 240C and held at that temperature for 1 hour. The composite was cooled to room temperature under pressure, unmolded, and trimmed. The resulting composite was solid, light amber in color and f axible, with no visible voids.

Example 13: Composite of prepolymerized poly[',1,1-tris(4-trifluoroethenyloxyphenyl)ethane] and glass mat.

The process of Example 12 was repeat~d using powdered poly[1,1,1-tris(4-trifluoroethenyloxyphenyl) ethane] oligomers (heated for 1 hour at 160C, cooled, 39,066-F -86--87- 20~73~9 and ground to a powder) and heating the mold and plates preheated to 2~0C at 10,000 K?a ~or 1 hour omitting the 180C heating of E~ample 12). The resultin~
composite was cooled to 150C and removed from ~he press. The ~esulting composite was solid, sli~htly yellow in color. flexible, and has no visible ~oids.

Example3 14-15: Polystyrene m crofibers having a coating of poly[4,~'-bis(trifluorovinyloxy)biphenyl]

Microfibers were prepared from a polystyrene resin commercially available from The Dow Chemical Company under the trade designation Styron 635D (for Example 14) and from syndiotactic polystyrene (for Exam3le 15), each containing 2 ~"eight percent poly[4,4'-bis(trifluorovinyloxy)biphenyl~. A homogeneous melt blend resulted. A microfiber or a nonwoven mat of microfibers was prepared by introducing an aromatic polymer resin in the form of powder or pellet into a hopper connected to an extruder. The resin was melted in the extruder and supplied to a spinpack, through a molten polymer supplying line by a pump. The term "spinpack" refers to an assembly comprising a die nozzle 2~ having an orifice for a molten polymer and having a gas slot for melt-blo~ing the molten polymer, and a heater for keeping the die nozzle at a prescribed. uniform, temperature of 220C. The extruder. the spinpack, and the molten polymer supply line also had a heater for melting a polymer or for keeping a polymer in a molten state.

A gas stream of hot air was introduced into the spinpack through a gas stream supplying llne. In the spinpack, the molten polymer was forced out of an 39,066-F -87-orifice of a nozzle o~f the spin?ack ~ntc the co-current gas stream which attenuatea re resin ir.to ;'i~ers.

The fibers were collected in the form of a nonwoven ~at. .he ~.oltan pol~v-mer was L orced out of an orifice ~f nozzle (dia openingj and into the ga3 strea~
which was passed througr. gas 310~. Conditions o the preparation are given in ~a ie 10.

3o 39,066-F -88-`_ -89- 2057~a~

~:~

'E ~ ' ~ '' --L
o ~

~~ m L~

E ~ ~t 1~

39, 066-F -89-~73~

-~o--The microfibers form a non-woven mass of fibe;^
analogous to a co~ton ball. A ciga ette lighcer was held to each mass for ~ period of 15 se onds. r~lei-;her of Examples 14 or 15 ignited, although some charr ng wasobserved. No dripping or burning was, however, observed. For comparison, non-wo~en masses of the polystyrene and syndiotactic polystyrene were form~d without the poly[4,4'-bis(trifluorcvinyloxy)biphenyl~ and werefound to ignite readily.
The limiting oxygen index (LOI) of poly~4,~'-bis(trifluorovinyloxy)biphenyll was determined by ;he procedures of ASTM D-2863-87 to be 0.419 which wasinterpreted to mean that the volume percent oxy-en required to sustain combustion of the poly[4,4'-bis(trifluorovinyloxy)biphenyl] in an oxygen/nitrogen atmosphere was 41.9.

NOTE: THESE NUMERICAL FLAME RATINGS ARE NOT INTENDED TO
REFLECT HAZARDS PRESENTED BY THESE 0~ ANY OTHER
MATERIALS UNDER ACTUAL FIRE CONDI:IONS.

Example 16: Composites of Poly ~ tris (4-trifluoroethenyloxyphenyi) ethane and graphite flber.

Eight plies, approximately 50 grams of graphite fabric, style G105 8HS (0/90) commercially available from Textile Technologies Inc. of Hatboro, PA, were 3 stacked together in alternating weft and warp orientation and sewn together. The G105 8HS fabric was prepared with 3K from Celion'M G30~500 PAN based graphite fiber designated HTA-7W EP01 commercially available from BASF Structural Materials, Inc. For each composite sample (hereinafter "composite panel" or 39,066-F -90--- 2~7~09 "part"), 44 grams of the liquid TVE monomer material was poured into the bottom of a 5"x 7" (13 ~ 1~ cm) resin transfer molec~lar ~old cavity and the .abric ~s placed on top. The mold 1,3~3 -~ssembled, the pressure was reduced to 20 mrn ~g (2700 Pa). and the ass~bly was placed into a press and cured in the manner listed in Table 11.

The panel ~.~as cut and tested for composite laminate properties such as short beam shear strength and flexural properties using the procedures of ASTM D-2344 - 84 (1989 and ~-790 - 86 respectively. In addition, the density of tle cured laminates was determined by water immersion and by geometrical calculations, to achieve an approximate determination of void volume in the lamlnates by difference.

The 5"x 7" (13 x 18 cm) composite panel was trimmed with a diamond saw and then cut into individual samples for testing. Prior to testing, the parts were measured for density by water immersion. The composite panel was found to have an average density o~ 1.603 g/cc. The theoretical density for one specific sample was calculated based on the weight of the individual component,. The fabric used, TTI Style ~105 (commercially available from Textile Technologies Inc.).
was known to have a weight ~f 367.2 g/m2 or 0.03672 g/cm2- This one sample measured 7.625 cm by 1.270 cm and weighed 4.39 g. The fabric weight per ply in this panel was 0.356 g, and the total fabri~ weight was 2.S4 g; therefore, the resin weight was 1.55 g. By dividing the weight of the component by its density (resin 1.39 g/cm3, graphite 1.78 g/cm3) the total volume of each component was found. Resin volume for the sample was 39,066-F -91-20~3~9 1.115 cc and the fiber volume was 1.596 cm3, which corresponds to 41 volume percent resin and 59 volume percent fiber.

The theoretical density was determined by the Rule of Mixtures, for this panel it was found to be 1.620 g/cc. The void volume W2S determined b;
subtracting the density determined by water immension from this theoretical density and multiplying by 100.
For a sample this void volume was de~ermined to be 1.05 percent.

Another similar approximace method for determining fiber volume was descri3ed in a manual of recommended composite materials test methods prepare-' by Suppliers of Advanced Composite Materials Associa~ion (SACMA), designated SRM 10-88. The following equation was used to determine the fiber volume (FV):

FV = (AW x B/Tp x Pf) x (3.94 x E-5) x (100%) where AW, B, Tp. and Pf, were the fabric area weight in g/m2 of plies, average thickness in inches, and density of the reinforcement material in g/cm3, respectively.
The factor of 3.94 x E-5 was a units conversion factor.
For this composite the AW was 367.2 g/m2, B was 8 plies, Tp was 0.110 in. (0.279 cm), and Pf was 1.78 g/cm3. FV
was determined to be 59 percent from this equation.

The Short Beam Shear Strength, SBSS, for the ; composite laminates was determined according to ASTM D-2344 - 84 (1989) using an Instron Model 1127 equipped with the Series IX software package commercially 39,066-F -92--93- 2~73~

available from ,nstron Corp. of Centon, Massachuset~3.
The sample dimensions were 0.110 in (0.279 cm) thick b-J
0.247 in (0.627 cm) wide by 0.750 in (1.905 cm) in length. The tool for SBSS measuremen^s has a 0.430 in (1.0~2 cm) gage length. The laminate had S3SS of 4.52 ksi (ksi=1000 psi) (3116 kP~). These measurements correspond to 8.D ksi (59,300 kPa) for epoxy Tac~ixr~
123/H31, commercially available from The Dow Chemical Company reinforced with o2 volume percent Herculesr~' AS-4 3K 8HS fabric commercially available from Hercules Inc., 12.5 ksi (86,190 kPa? for PR-500 one part epoxy, commercially available from 3M Aerospace Materials Department, reinforced with 57 volume percent of CelionTM 3K 8HS fabric commercially available from BASF
Structural Materials,Inc.. 8.2 ksi, (56,500 kPa) for Eponr~ DPL-862/RSC-763 commercially available from Shell Chemical Company of Houston, TX reinforced with 57-62 volume percent of Celion'~ 3K 8HS fabric commercially available from BASF Structural Materials, Inc.

The flexural properties were measured in a three point bend mode according to ASTM D-790-86 at room temperature with an Instron Model 1127 commercially available from Instron Corporation of Canton, MA, equipped with the Series IX software package commercially available fro Instron Corp. The test samples averaged 0.499 in (1.267 cm) in width by 0.114 in (0.29 cm) in thickness by 3.0 in (7.6 cm) in length.
A span of 2.0 in (5.1 cm) and a crosshead speed of 0.05 in (0.13 cm) per minute was used. The span to depth ratio (L/d) for the specimens averaged 18, and the rigorous ASTM method requires a L/d ratio of 16. The flexural strength for this laminate was 75.4 ksi (520,000 kPa, 5.2 x 105 kPa). This value compares with 39,966-F -93-20~7309 128 ksi for epoxy Tacti~xr" 123/H31, commercially available fro~ The Dow Chemical Company. reinforced witn 62 volume percent HerculesT~ I~S-4 3K 8HS fabric commercial'y available from Hercules, Inc.. 157 ksi ( 1 .o8 x 106 ~?a) for PR-500 one part epoxy ~ommercially available from 3M Aerospace Materials Department~
reinforced with 57 volume percent of Celionr`' 3K ~HS
fabric comme~cially avail~ble from BASF Structural Materials, Inc., 12~ ksi (841,000 kPa) for Eponr~ DPL-862/RSC-763 commercially available from Shell Ch_mical Co. reinforced with 57-62 volume perce~t of Celion'~ 3K
8HS fabric. The modulus for this system was at 7.9 Msi (Millions of psi) (5.45 x 107 kPa. Most typical resins reinforced with this ty?e of fabric give modulus in the 8-10 Msi range (5.5 to 7 x 107 kPa).

The TVE monomers exhibited low viscosity when molten and they are useful in resin transfer molding techniques, The ease of processing of the monomer and the excellent electrical properties of the polymer formed from TVE indicate that the composites are useful.

3o 39,o66-F -94-2~73~9 Hea~Rale Temperature ~ Force Nsteber m jF/ ¦ C rnin. ~ ¦ ~ b I kPa Time, 1.1 15 i 8.030~ 105 ~T~ 45 1.~ 5 3 374 1 gO 0.~,~ 15 ___ ~
1.3 5 3 392 200 ' .6 11 ,ûO0 15 .
1.4 5 3 428 2 20 3 2 22,0û0 15 1.S 5 3 1 482 2~0 7.4 51,300 50 2.! -5 3 ~ 70 21 7.4 51,~00 2 Examples 17-22:

Tests of the Adhesion-promoting abilities of Bisphenol A-Bishydroxyphenyl Fluorene (Bis A-BHPF) Polycarbonate 60-4C Copolymer compared with Biphenol Perfluorocyclobutyl Ether Oligomer.

A 1 weight percent solution of Bis A-BHPF
polycarbonate prepared by dissolving 0.5 g o.' BisA-BHPF
polycarbonate 6'~ - 40 copolymer in 49.5 grams of dichloromethane was applied to half of a polished sheet of aluminum (foil) using a Gardco #18 wet film applicator rod (commercially available from Paul N.
Gardner Comp~ny. Inc.). At 100 weight percent solids, this corresponds to a thickness of 1.8 mils (1.8 x 10~3 inches) or 46.2 microns (4.6 x 10~3 cm), so a 1 percent solids solution should produce a thickness of about 0.5 micron (5 x 10-5 cmj.

39,066-F -95--96- 2~573~9 On the other side of the sheet, a coat ng of 5 weigh~ percent bis (trifluorovinyloxy) biphen~Jl (B~E) was applied using a Gardco #18 rod to produce a ccating of about 2.5 micron (2.5 x 10-4 cm) tnicknes3. The coatings quickly air-dried, thar is within a period of 1-2 minutes at room temperature the coatings were determined to ~e dry by touch and visual inspection, giving an iridescent rainbow effect (caused by nonuniform thickness due to the rapid drying).
A film of TVE oligomer solution (60 weight percent solids in ~ylene) was applied over each of the previous coatings using a Gardco #52 wet film asplicator. When the TVE coating was applied. the rainbow effect disappeared. An oligomer was prepared from TVE monomer by heating a neat tpure) sample of TVE
monomer at 150C for 3 hours under nitrogen. The oligomer was then dissolved in xylene and filtered through a 0.2 micron (2 x 10-5 cm) filter (under the trade designation Acrodisc commercially available from Gellman, Inc.) before storage. At 100 weight percent solids, a Gardco #52 wet film applicator applied a coating of 5.2 mils (5.2 x 10-3 inches) or 133.3 microns (1.3 :~ 10-2 cm); therefore. a ~0 weight percent solids solution should produce a coating of approximately 3.12 mils or 93 microns (9.3 x 10-3 cm) thickness. The coatings were cured in a Varian 3700 GC oven commercially available from Varian Corp., modified for 3 an enriched nitrogen atmosphere (>90 percent N2). The cure schedule was: 160C for 3 minutes, then increased heat 10C/minute to 250C and held for 3 minutes.

The resulting foil laminates were allowed to sit over a weekend. After the weekend, the films were 39,066-F -96-~EC-06-1991 16:17 FRO~ PRTENT DEPT. ~-1210 TO al6132328440 P.07 _97_ 2~ 5~3 0 checked for adhesion. The coating uslng the polycarbonate as an adhe~ion promoter hat come loose ~rom the aluminum. The railure appeared to ha~e occurred at the polycarbonate-metal interface, a~
deter~ined by ~he obserYation that the irlde~cent ralnbow e~fe¢t seen ~rom the initial application Or the polycarbonate layer waa not ~i3ible on the metal surface~ below the loo~e coating. ~he coatin~ cast onto the biphenol oligomer a~ adhe~ion promoter had not ~ailed and could ~ ~lexed without causing Pail~re. An e%ce ~ive amoun~ of bending, rolling, and baok and forth ~lexing did cause the coating to break loose onc day later.

~ue to the thickness of the TVE layer and the hi~h poli~h Or the aluminum ~urrace, thi~ was a fairly stringent adhesion test, and the adheslon produced u~ing the blphenol oligomer aa adhesion promo~er i~
~lgni~icant. No moa~urement o~ adhes10n or durabllity ls made~

Coatlng~ of TVE were applied and cured onto alumlnum and copper plate~ in the same manner a-~ abo~e 2S both wlth blphenol oligomer adhe~ion promoter and wlthout. The metal plate~ were prepared by pollching success1~ely with 180 grit alumlnum oxide paper. 360 grit aluminum oxide paper, and ~inally carborundum paper (croaus cloth). The plates were immedlately cleaned w~th acetone, degreased by wiping with dichloromethane.
and coated as te~cribed for the ro~l laminates. Both the plate~ coated wLth adhesion promoter and those wlthout produced good coatlngs which were still adhered 3 days later. It was possible that a mechanlcal bond 39~066-F ~97_ _ . ... .

205730~
-~8- 74069-47 was produced since the ~tal surface did n~ nave a "mirror" finish.

Exam3le 23: Coatin,s of bis (trifluoroviny10xy) biphenyl (~VE) on A1uminum Foil Thin co2tlngs of 3VE ether po1ymer, as prepared by heating and qtirring a so'ution of 60 g cf 3ll~ in 75 mL of perfl~lorotetradecahyd~ophenanthrene (MultifluGr APF 215 commercially available from Alr Products~ to reflux under nitrogen. Initially, upon ~eating the melted monomer was not miscible with the solvent, but as the tempsrature rose. the two phases became homogeneous.
After ~eing stirred at reflux for approximately 45 minutes, a polymer phase separated; and, after stirring and reflux for a total of 3 hours, the phase ceparated polymer became viscous enough to cause the s~irring to cease. The cooled polymer was removed from the flask and evaporated uncer high vacuum (approximately 0.5 torr (67 Pa)) at about 220C for 3 hours to remove residual qolvent. The resulting polymer was of sufficiently high molecular weight to make good films. The polymer was dissolved to form an 80 per^ent solution in dichloromethane. Samples of She solution were cast onte aluminum foil from a ao weight percent solution in dichloromethane using a Cardco #52 wet film applicator rod (commercially available from Paul N. Gardner Company, Inc.). At 100 weight percent solids this correspond~ to a coating thickness of 5.2 mils (5.2 x 10-3 incnes) or (1.3 x 10-2 cm) or 133.3 microns.
There~ore, a 20 weight percent solids solution should give approximately 1.04 mil~ or 26.6 microns (2.66 x 10~3 cm) thickness. The solvent was evaporated and the coatings were heated to 160C for 5 minutes in a Varian 39,066-F -98--` 2~573~9 _99_ 3700 G~ oven commercially available from Vari~n Corp.
modifiei for an enriched(>90 percent) nitrogen atmosphere. The resulting foi laminates can be used as supported coatings.

Example 24: Coating3 of 1,1,1 Tris ((4-trifluoroethenyloxy)phenyl) ethane on Aluminum Foil Thin coatings of 1,1,1 Iris ((4-1~ trifluoroethenyloxy)phen~Jl) ethane oligomer were castonto aluminum foii from a 60 weight ?ercent solution in xylene. The coatings were made using a Gardco ~52 wet film applicator rod (commercially available from -'aul N.
Gardner Company, Inc.). At 100 weight percent solids this corresponds to a film thickness of 5.2 mils 5.2 x 10-3 inches) (1.33 x 10-2 cm) or 133.3 microns.

An oligomer was prepared from T~E monomer by heating a pure sample at 150C for 3 hours under nitrogen. The oligomer was then dissolved in xylene and filtered through a 0.2 micron (2 x 10~5 cm) filter (under the trade designation Acrodisc commercially available from Gellman. Inc.) before storage. Ak 100 weight percent soiids, a Gardco t52 wet film ~pplicator lays down a film of 5.2 mils (5.2 x 10-3 inches) or 133.3 microns (1.33 x 10-2 cm); therefore. a 60 weight percent solids solution should produce a coating of approximately 3.12 mils or 93 microns (9.3 x 10-3 cm) thickness.

The coatings were cured in a Varian 3700 GC
oven commerciall~ available from Varian Corp. modified for an enriched (>90 percent) nitrogen atmosphere. The cure schedule was: 160C for 3 minutes, then increased 39,o66-F -99-20~73~9 no-'neat 10C,minute to 250C and held for 8 minutes. Theresulting foil laminates can be use~ for supported co-tings.

3o 39,066-F _loo-

Claims (19)

1. A laminate having at least two layers characterized in that at least one of the layers (polymer layer) comprises a polymer having more than one perfluorocyclobutane group.

2. The laminate of Claim 1 wherein the polymer is formed from at least one monomer having a structure represented by Formula I or III:

Formula I

CF2=CF-X-R-(X-CF=CF2)m or Formula III

wherein R represents an unsubstituted or inertly substituted group; each X is independently a bond or any group which links R and a perfluorovinyl group; m+1 is the number of -X-CF=CF2 units: n and n' are the number of G and G' groups, respectively; and G and G' 39,066-F -101-independently represent any reactive functional groups or any groups convertible into reactive functional groups.

3. The laminate of Claim 2 wherein the polymer has an average molecular weight of at least 10,000 and there is at least one reinforcing or filling layer.

4. The laminate of Claim 2 or 3 comprising at least one layer of the polymer and at least one other layer having a composition different from the layer of the polymer said layer comprising wood, clay, stone, silicon, silicon oxide, metal oxide, alloy of metal or metal oxide, metal, semiconductor, polymer of different composition, ceramic, glass, optical fiber, paper, synthetic fibers, cloth, or combinations thereof.

5. The laminate of Claim 1, 2, 3 or 4 wherein the polymer forms an environmentally protective, moisture resistant, hydrostatically stable, radiation resistant or chemically resistant coating on at least one layer having a composition different from that of the polymer.

6. The laminate of Claim 1, 2, 3, 4, or 5 wherein the laminate is lined pipe, valve liner, a seal, a gasket, or combination thereof.

7. The laminate of Claim 1, 2, 3, 4, or 5 wherein the laminate is medical equipment, sick room equipment, medical or other clothing, bed linen, an 39,066-F -102-instrument, ignition resistant paint, or combination thereof.

8. The laminate of Claim 1, 2, 3, 4, or 5 wherein the lamina e is eyeglasses, a window, coated glass, greenhouse, skylight, oven window, solar still, UV filter, or combination thereof.

9. The laminate of Claim 1, 2, 3, 4, or 5 wherein the laminate is packaging, a roasting bag, popcorn bag, boiling bag, frozen food tray, microwavable food container, retortable pouch, or combination thereof.

10. The laminate of Claim 1, 2, 3, 4, or 5 wherein the laminate is material with anti-fouling coating, object with underwater insulation, object with electrical insulation, object with mildew resistant coating, or combination thereof.

11. The laminate of Claim 1, 2, 3, 4, or 5 wherein the laminate is automobile body part, vessel, mold, turbine blade, tub, food processing equipment, cryogenic container, autoclave, oven, heat exchanger, fuel container, or combination thereof.

12. The laminate of Claim 2, 3, 4 or 5 wherein the laminate is a light bulb, carpet, bathtub, shower, sleeping bag, sail, raincoat. protective clothing, mattress, furniture, draperty, pillow, toy, tent, camper, microwave cookware, refrigerator (inside or outside), cookware, utensil for coated cookware, tile, 39.066-F -103-swimming pool liner, siding, roofing, or combination thereof.

13. The laminate of Claim 1, 2, 3, 4 or 5 wherein the laminate is an electrical switch enclosure, battery, battery separator; photographic, X-ray, or other imaging film; or combination thereof.

14. An electronic device comprising a laminate of Claim 6 wherein at least one other layer comprises silicon, silicon oxide, a metal, a metal oxide, an alloy of a metal or metal oxide, a semiconductor, a polymer of different composition, ceramic, glass, paper, synthetic fibers, quartz or mixtures thereof.

15. The electronic device of Claim 14 wherein the polymer is an insulator in the device.

16. A computer comprising at least one electronic device of Claim 14 or 15.

17. The laminate of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 wherein the laminate is formed by segregation of the polymer from a material of different composition.

18. A process of preparing a laminate comprising a step of coating at least one material characterized in that the material is coated with a polymer having more than one perfluorocyclobutane group.

19. The process of Claim 18 wherein the polymer is prepolymerized to a stage of less than complete polymerization before the step of coating and 39,066-F -104-after coating is exposed to conditions under which polymerization procedes.

39,066-F -105-