WO1995005403A1 - Radiation curable alk-1-enyl ether polyester prepolymers - Google Patents

Radiation curable alk-1-enyl ether polyester prepolymers Download PDF

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Publication number
WO1995005403A1
WO1995005403A1 PCT/US1994/008203 US9408203W WO9505403A1 WO 1995005403 A1 WO1995005403 A1 WO 1995005403A1 US 9408203 W US9408203 W US 9408203W WO 9505403 A1 WO9505403 A1 WO 9505403A1
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prepolymer
och
formula
coc
cho
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PCT/US1994/008203
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French (fr)
Inventor
Jeffrey S. Plotkin
Mark M. Miller
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Isp Investments Inc.
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Priority claimed from US08/108,212 external-priority patent/US5373032A/en
Priority claimed from US08/107,867 external-priority patent/US5342860A/en
Application filed by Isp Investments Inc. filed Critical Isp Investments Inc.
Priority to AU73687/94A priority Critical patent/AU7368794A/en
Publication of WO1995005403A1 publication Critical patent/WO1995005403A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44Adipic acid esters
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80Phthalic acid esters
    • C07C69/82Terephthalic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32Monomers containing two or more unsaturated aliphatic radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/675Low-molecular-weight compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to novel prepolymers containing polyurethanyl groups and a plurality of alk-1-enyl ether crosslinking sites.
  • the invention relates to the preparation of said prepolymers and in still another aspect the invention relates to cured coatings of said prepolymers.
  • polyester coating materials can be cured thermally or by radiation in the presence of a free radical photoinitiator but these materials do not lend themselves to cationically induced polymerization. It is well recognized that thermal curing is not cost efficient and that radiation curing in free radical systems is oxygen inhibited, thus requiring an inert atmosphere or the minimizing affect of a hydrogen donating component. The later expedient is not completely satisfactory since such hydrogen donating components significantly reduce the rate of reaction. Also, it has been found that polymerization or curing in free radical systems ceases almost immediately upon removing the source of radiation; thus, the cured product often contains significant amounts of unpolymerized components.
  • Another object is to provide a polyester prepolymer containing many crosslinking sites which is rapidly cured to a high density material under mild conditions.
  • Another object of this invention is to provide a convenient process for the preparation of the present prepolymer.
  • Still another object of this invention is to provide a protective coating with a cured high density prepolymer having improved hardness, flexibility, resistance to abrasion and chemical attack.
  • A is C 2 to C 12 alkylene, C 6 to C 1 aryl, both groups optionally substituted with lower alkyl, halo lower alkyl, alkyleneoxy, halogen or aryl;
  • R x is alkylene containing from 1 to 6 carbon atoms
  • R 2 is a saturated or unsaturated divalent radical containing from 1 to 14 carbon atoms and is selected from the group of alkylene, alkenylene and arylene, each group optionally substituted with oxygen, halogen, lower alkyl and/or hydroxy and
  • R 3 is hydrogen or C ⁇ to C 6 alkyl.
  • hydroxylated alk-1-enyl ether compounds of this invention are dihydroxylated and most preferred are those wherein R-L and R 2 are lower alkyl and R 3 is hydrogen, methyl or ethyl.
  • Suitable hydroxylated alk-1-enyl ether reactants include: 1,2-dihydroxyethyl ethyl prop-1-enyl ether, 1,2-dihydroxypropyl butyl prop-1-enyl ether, 1,2-dihydroxypropyl ethyl vinyl ether, 1,3-dihydroxybutyl ethyl prop-1-enyl ether.
  • 1,3-dihydroxybutyl octyl vinyl ether 1,3-dihydroxyhexyl dodecyl but-1-enyl ether, 1,2-dihydroxybutenyl ethyl prop-1-enyl ether, 1,3-dihydroxyoctenyl ethyl vinyl ether, 1,3-dihydroxydecyl hexyl hex-1-enyl ether, 1,2-dihydroxyethyl phenyl vinyl ether, 1,3-dihydroxypropyl bromophenyl vinyl ether, 1,3-dihydroxyethyl chlorophenyl vinyl ether, 1,3-dihydroxyethyl tolyl vinyl ether, 1,3-dihydroxyethyl hydroxyphenyl vinyl ether, 1,3-dihydroxyethyl oxyphenyl vinyl ether, 1,3-dihydroxyethyl dibromohexyl vinyl ether, 1,3-dihydroxyethyl di
  • Suitable examples of reactant II include dimethyl terephthalate, dimethyl-amino-terephthalate, dimethyl-amino-isophthalate, dimethyl adipate, dibutyl malonate, diethyl oxalate, dioctyl oxalate, didecyl malonate, diethyl succinate, dimethyl glutarate, dibutyl adipate, dioctyl succinate, didodecyl phthalate, etc.
  • the transesterification reaction of I and II is carried out in the liquid phase with agitation under a blanket of an inert gas.
  • a temperature of between about 95° and about 210°C, preferably, between about 140° and about 180°C, for a period of from about 1 to about 5 hours.
  • the alcohol by-product is continuously removed by distillation; or, when the reaction is conducted in a sealed system, the by-product can be subsequently distilled off at above its vaporization temperature.
  • the mole ratio of the polyhydroxy alk-1-enyl ether (I) to diester (II) is dependent on the number of functional -OH and R 3 COO-groups in the respective reactants.
  • a -OH to R 3 COO- mole ratio of between about 1:1 and about 1:2.5 can be employed, however, a slight excess of reactant II is preferred. Further, this reaction can be carried out in the presence of from about 0.1 to about 3 wt. %, based on reaction mixture, of a catalyst such as titanium isopropoxide, titanium butoxide, titanium methoxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, potassium methoxide, potassium butoxide, sodium phenoxide, potassium phenoxide, zinc, zinc acetate, manganese acetate, dibutyl tin dioxide or another base catalyst.
  • a catalyst such as titanium isopropoxide, titanium butoxide, titanium methoxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, potassium methoxide, potassium butoxide, sodium phenoxide, potassium phenoxide, zinc, zinc acetate, manganese a
  • the intermediate monomer or oligomer (III) is then reacted with an end capping compound, preferably a monohydroxy alk-1-enyl ether of the formula
  • R 4 is C ⁇ to C 6 alkylene, C 6 to C 14 arylene, xylylene, each optionally substituted with alkyl, halogen or alkenyl and R 6 is hydrogen or C ⁇ to C 4 alkyl.
  • the monohydroxy alk-1-enyl ether reactants (IV) include hydroxyhexyl prop-1-enyl ether, 1-hydroxy- dimethylene-propylene vinyl ether, hydroxyethyl-prop-1- enyl ether, hydroxycyclohexyl vinyl ether, hydroxybutyl- vinyl ether, hydroxybutyl but-1-enyl ether, hydroxypropyl prop-1-enyl ether, ⁇ -hydroxyoctyl-vinyl ether, 2-hydroxypropyl prop-1-enyl ether, hydroxyphenyl prop-1-enyl ether, hydroxy tolyl but-1-enyl ether, hydroxybutyl but-1-enyl ether, the vinyl ether or prop-1-enyl ether of hydroxymethyl benzyl alcohol, cyclohexane dimethanol mono vinyl ether, etc.
  • the end capping reaction involving reactant IV is carried out under conditions similar to the reaction between reactants I and II including the presence
  • the Brookfield viscosity of the liquid prepolymeric product which ranges from about 5,000 to about 500,000 cps, is inversely affected by the amount of end capping diluent added.
  • the above reactions can be effected in a single stage or in a two-stage process.
  • the polyhydroxylated alk-1-enyl ether, the difunctional ester and the end capping component diluent are contacted with constant agitation under a pressure of from about atmospheric to about 20 psig.
  • the cationically curable prepolymer of this invention exhibits many advantages over the polyester prepolymers of the art in that the present prepolymer offers an increased number of crosslinking sites, which, when polymerized, provides a coating of extremely high density having excellent resistance to abrasion and chemical attack.
  • the present prepolymer obtained in a liquid state, allows for improved uniform coating applications on a substrate of metal, plastic, ceramic, wood, paper, glass, etc.
  • the cured prepolymer also maintains flexibility resulting from their many unsaturated sites where polymer units are extended by addition to double bonds. Further, coatings of the present cured polymer preserve the finish of a painted surface, e.g. as automotive, aircraft and ship coatings.
  • the present prepolymers III are prepared for curing by the addition of a cationic initiator and between about 10 and about 80 wt. % of a diluent.
  • the present prepolymers which are useful as high density curable molding resins and highly solvent resistant adhesive coatings.
  • the product can be diluted with a suitable solvent, applied to a surface in a thickness of between about 0.1 to about 5 mils and cured by exposure to a source of radiation such as UV light, electron beam, laser emission. X-rays, gamma-rays, etc.
  • an onium photoinitiator such as, for example a diary1 iodonium salt, a polyphenyl sulphonium fluoride, a triaryl sulphonium salt and the like.
  • Curing by UV light exposure is generally effected at between about 300 and about 3,000 milli joules/cm 2 . Radiation curing of the prepolymer is extremely rapid, so that a coated substrate can be processed at a rate of up to 700 feet/sec and; whereas curing by heat requires a longer treatment up to about 2 hours.
  • Examples of the reactive diluents employed in formulations of the present curable products are divinyl ether of triethylene glycol (DVE) and cyclohexane dimethanol divinyl ether (CHVE) , the propenyl propylene ether of propylene carbonate (PEPC) , tetrahydrofurfuryl vinyl ether and epoxides, e.g. 3,4-epoxycyclohexyl-3,4-epoxycyclohexane.
  • the present coatings are clear, colorless, flexible films which find many applications as indicated above.
  • EXAMPLE 4 The products of Examples 1-3 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) . The resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table. TABLE
  • EXAMPLE 1 H 100 1/8 >200 64 880 6.4
  • Example 5 The procedure of Example 5 was repeated using 7.8 grams of 1,2-propanediol in place of 1-propenyloxy propanediol.
  • the product of this example was identified as having the formula
  • Example 6 The procedure of Example 6 was repeated using 15.5 grams of 1,2-propanediol in place of 1-propenyloxy propanediol.
  • the product of this example is identical to that obtained in Example 7
  • Example 6 The procedure of Example 6 was repeated using 37.06 grams of n-butanol in place of hydroxybutyl vinyl ether. The product of this example
  • CH 2 OCH CHCH 3 CH 3 possesses a non-reactive end-capping group but would retain internal cross-linking properties because of the reactive-chain extender. However, this product exhibits poor pencil hardness, little or no adhesive properties and low tensile properties.
  • Examples 5-9 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) .
  • the resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table.
  • Example 5 is repeated, except that 3 moles of -hydroxybutyl vinyl ether, 2 moles of toluene diisocyanate and 0.8 grams of dibutyl tin dilaurate are substituted for the amounts shown therein (a 4-fold excess) .
  • the product of this reaction has the formula

Abstract

This invention relates to alk-1-enyl ether-polyester block prepolymers which are curable by cationically initiated radiation and which are defined by formula (I), wherein m has a value of from 1 to 25; A is C2 to C12 alkylene, C6 to C14 arylene, both groups optionally substituted with lower alkyl, halo lower alkyl, alkyleneoxy, halogen, aryl or NHA'NH wherein A' is the same as A; R1 is alkylene containing from 1 to 6 carbon atoms; R2 is a saturated or unsaturated divalent radical containing from 1 to 14 carbon atoms and is selected from the group of alkylene, alkenylene and arylene, each group optionally substituted with oxygen, halogen, lower alkyl and/or hydroxy; R5 is hydrogen or C1 to C6 alkyl; R4 is C1 to C6 alkylene, C6 to C14 arylene, lower alkyl substituted phenylene or xylylene and R6 is hydrogen or C1 to C4 alkyl. The invention also relates to the method of preparing and curing the above prepolymer and to the use of the cured prepolymer as a hard, flexible protective coating possessing high density and superior resistance to abrasion and chemical attack.

Description

RADIATION CURABLE ALK-1-ENYL ETHER POLYESTER PREPOLYMERS
In one aspect, the present invention relates to novel prepolymers containing polyurethanyl groups and a plurality of alk-1-enyl ether crosslinking sites. In another aspect the invention relates to the preparation of said prepolymers and in still another aspect the invention relates to cured coatings of said prepolymers.
BACKGROUND OF THE INVENTION
It is known that certain polyester coating materials can be cured thermally or by radiation in the presence of a free radical photoinitiator but these materials do not lend themselves to cationically induced polymerization. It is well recognized that thermal curing is not cost efficient and that radiation curing in free radical systems is oxygen inhibited, thus requiring an inert atmosphere or the minimizing affect of a hydrogen donating component. The later expedient is not completely satisfactory since such hydrogen donating components significantly reduce the rate of reaction. Also, it has been found that polymerization or curing in free radical systems ceases almost immediately upon removing the source of radiation; thus, the cured product often contains significant amounts of unpolymerized components. Accordingly, it is an aim of research to develop monomers or oligomers which provide stable polymerizable formulations with polyester containing materials while incorporating other beneficial properties in the finished cured product. Additionally, it is desirable that such monomers or their oligo ers be amenable to radiation curing at a rapid rate under mild temperature conditions by cationically induced polymerization which is not oxygen inhibited and which permits continued polymerization after removal from the source of radiation exposure.
Accordingly, it is an object of the present invention to overcome the disadvantages of previous polyester prepolymers and to provide a novel polyester prepolymer which is cationically curable at room temperature by radiation.
Another object is to provide a polyester prepolymer containing many crosslinking sites which is rapidly cured to a high density material under mild conditions.
Another object of this invention is to provide a convenient process for the preparation of the present prepolymer.
Still another object of this invention is to provide a protective coating with a cured high density prepolymer having improved hardness, flexibility, resistance to abrasion and chemical attack.
These and other objects will become apparent from the following description and disclosure.
THE INVENTION
In accordance with this invention, a polyhydroxylated alk-1-enyl ether having the formula
HOR^CH (OH) -R2OCH=CHR5 I
is reacted with a difunctional ester having the structure
R3OOC-A-COOR3 II or isocyanate having the structure 0=C=N-A-N=C=0 to form an intermediate monomer or oligomer defined by the formula
(R3OCOACO-)2 -[ (ORjCHO-COACO)^OR^HO]-
R2OCH=CHR5 R2OCH=CHR5 III
and the corresponding alcohol by-product HOR3 wherein m' has a value of from 1 to 25;
A is C2 to C12 alkylene, C6 to C1 aryl, both groups optionally substituted with lower alkyl, halo lower alkyl, alkyleneoxy, halogen or aryl;
Rx is alkylene containing from 1 to 6 carbon atoms;
R2 is a saturated or unsaturated divalent radical containing from 1 to 14 carbon atoms and is selected from the group of alkylene, alkenylene and arylene, each group optionally substituted with oxygen, halogen, lower alkyl and/or hydroxy and
R3 is hydrogen or Cλ to C6 alkyl.
The polyhydroxylated alk-1-enyl ether reactant (I) may contain an additional OH group in the R2 group which would result in an intermediate monomer or oligomer of more complex structure, i.e. where R3OOC-A-COOR3 reacts with the additional -OH group to provide another -OR1-CHO- group in the side chain of the intermediate R2OCH=CHR5
compound. However, the preferred hydroxylated alk-1-enyl ether compounds of this invention are dihydroxylated and most preferred are those wherein R-L and R2 are lower alkyl and R3 is hydrogen, methyl or ethyl. Suitable hydroxylated alk-1-enyl ether reactants include: 1,2-dihydroxyethyl ethyl prop-1-enyl ether, 1,2-dihydroxypropyl butyl prop-1-enyl ether, 1,2-dihydroxypropyl ethyl vinyl ether, 1,3-dihydroxybutyl ethyl prop-1-enyl ether. 1,3-dihydroxybutyl octyl vinyl ether, 1,3-dihydroxyhexyl dodecyl but-1-enyl ether, 1,2-dihydroxybutenyl ethyl prop-1-enyl ether, 1,3-dihydroxyoctenyl ethyl vinyl ether, 1,3-dihydroxydecyl hexyl hex-1-enyl ether, 1,2-dihydroxyethyl phenyl vinyl ether, 1,3-dihydroxypropyl bromophenyl vinyl ether, 1,3-dihydroxyethyl chlorophenyl vinyl ether, 1,3-dihydroxyethyl tolyl vinyl ether, 1,3-dihydroxyethyl hydroxyphenyl vinyl ether, 1,3-dihydroxyethyl oxyphenyl vinyl ether, 1,3-dihydroxyethyl dibromohexyl vinyl ether, 1,3-dihydroxyethyl hydroxyoctyl vinyl ether, 1,2-dihydroxybutyl tolyl prop-1-enyl ether and the like.
Suitable examples of reactant II include dimethyl terephthalate, dimethyl-amino-terephthalate, dimethyl-amino-isophthalate, dimethyl adipate, dibutyl malonate, diethyl oxalate, dioctyl oxalate, didecyl malonate, diethyl succinate, dimethyl glutarate, dibutyl adipate, dioctyl succinate, didodecyl phthalate, etc.
The transesterification reaction of I and II is carried out in the liquid phase with agitation under a blanket of an inert gas. A temperature of between about 95° and about 210°C, preferably, between about 140° and about 180°C, for a period of from about 1 to about 5 hours. During reaction, the alcohol by-product is continuously removed by distillation; or, when the reaction is conducted in a sealed system, the by-product can be subsequently distilled off at above its vaporization temperature. The mole ratio of the polyhydroxy alk-1-enyl ether (I) to diester (II) is dependent on the number of functional -OH and R3COO-groups in the respective reactants. Generally, a -OH to R3COO- mole ratio of between about 1:1 and about 1:2.5 can be employed, however, a slight excess of reactant II is preferred. Further, this reaction can be carried out in the presence of from about 0.1 to about 3 wt. %, based on reaction mixture, of a catalyst such as titanium isopropoxide, titanium butoxide, titanium methoxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, potassium methoxide, potassium butoxide, sodium phenoxide, potassium phenoxide, zinc, zinc acetate, manganese acetate, dibutyl tin dioxide or another base catalyst.
The intermediate monomer or oligomer (III) is then reacted with an end capping compound, preferably a monohydroxy alk-1-enyl ether of the formula
HO-R4-OCH=CHR6 IV
wherein R4 is Cλ to C6 alkylene, C6 to C14 arylene, xylylene, each optionally substituted with alkyl, halogen or alkenyl and R6 is hydrogen or Cχ to C4 alkyl. The resulting monomer or block oligomer of this invention having the formula
(R6CH=CHOR40-)2 -[ (COACO-OR-^HO)mCOACO}-
R2OCH=CHR5
is obtained in quantitative yield.
The monohydroxy alk-1-enyl ether reactants (IV) include hydroxyhexyl prop-1-enyl ether, 1-hydroxy- dimethylene-propylene vinyl ether, hydroxyethyl-prop-1- enyl ether, hydroxycyclohexyl vinyl ether, hydroxybutyl- vinyl ether, hydroxybutyl but-1-enyl ether, hydroxypropyl prop-1-enyl ether, α-hydroxyoctyl-vinyl ether, 2-hydroxypropyl prop-1-enyl ether, hydroxyphenyl prop-1-enyl ether, hydroxy tolyl but-1-enyl ether, hydroxybutyl but-1-enyl ether, the vinyl ether or prop-1-enyl ether of hydroxymethyl benzyl alcohol, cyclohexane dimethanol mono vinyl ether, etc. The end capping reaction involving reactant IV is carried out under conditions similar to the reaction between reactants I and II including the presence of the base catalyst.
In the reaction between intermediate compound III and the end capping monohydroxy alk-1-enyl ether, a mole ratio of -COOR3 to -0CH=CHR5 between about 4:1 and about 1:4, preferably between about 1:1.5 and about 1:2 is employed. The Brookfield viscosity of the liquid prepolymeric product, which ranges from about 5,000 to about 500,000 cps, is inversely affected by the amount of end capping diluent added.
The above reactions can be effected in a single stage or in a two-stage process. In the single stage, the polyhydroxylated alk-1-enyl ether, the difunctional ester and the end capping component diluent are contacted with constant agitation under a pressure of from about atmospheric to about 20 psig.
The cationically curable prepolymer of this invention exhibits many advantages over the polyester prepolymers of the art in that the present prepolymer offers an increased number of crosslinking sites, which, when polymerized, provides a coating of extremely high density having excellent resistance to abrasion and chemical attack. The present prepolymer, obtained in a liquid state, allows for improved uniform coating applications on a substrate of metal, plastic, ceramic, wood, paper, glass, etc. The cured prepolymer also maintains flexibility resulting from their many unsaturated sites where polymer units are extended by addition to double bonds. Further, coatings of the present cured polymer preserve the finish of a painted surface, e.g. as automotive, aircraft and ship coatings. The present prepolymers III are prepared for curing by the addition of a cationic initiator and between about 10 and about 80 wt. % of a diluent. The present prepolymers which are useful as high density curable molding resins and highly solvent resistant adhesive coatings. The product can be diluted with a suitable solvent, applied to a surface in a thickness of between about 0.1 to about 5 mils and cured by exposure to a source of radiation such as UV light, electron beam, laser emission. X-rays, gamma-rays, etc. in the presence of an onium photoinitiator such as, for example a diary1 iodonium salt, a polyphenyl sulphonium fluoride, a triaryl sulphonium salt and the like. Curing by UV light exposure is generally effected at between about 300 and about 3,000 milli joules/cm2. Radiation curing of the prepolymer is extremely rapid, so that a coated substrate can be processed at a rate of up to 700 feet/sec and; whereas curing by heat requires a longer treatment up to about 2 hours. Examples of the reactive diluents employed in formulations of the present curable products are divinyl ether of triethylene glycol (DVE) and cyclohexane dimethanol divinyl ether (CHVE) , the propenyl propylene ether of propylene carbonate (PEPC) , tetrahydrofurfuryl vinyl ether and epoxides, e.g. 3,4-epoxycyclohexyl-3,4-epoxycyclohexane. The present coatings are clear, colorless, flexible films which find many applications as indicated above.
Having thus generally described the invention, reference is now had to the accompanying examples which illustrate comparative examples and preferred embodiments which are not construed as limiting to the scope of the invention as more broadly set forth above and in the appended claims. EXAMPLE 1
Aromatic Polyester Resin (Prepolymer^ Synthesis
Into a 500 cc round bottom flask, equipped with an agitator, temperature control, nitrogen sparge and a distillation head, was added 65.05 grams (0.50 moles) of 3-(l-propeneoxy)-l,2-propanediol; 194.19 grams (1.0 moles) or dimethyl terphthalate; 0.56 grams (0.0018 moles) of titanium (IV) isopropoxide; and 116.1 grams of 4-hydroxy butyl vinyl ether. The reaction was heated to 90°C. at which point methanol began to distill overhead. The reaction temperature was increased incrementally over a period of 16 hours to a temperature of 180°C. after which 95.0% of the stoichiometric methanol by-product was distilled overhead, and the reaction was terminated. The product,
(CH2=CHOC4H80-)2 -[ (COC6H4CO-OCH2CHO)COC6H4CO]-
CH2OCH=CHCH3
(305.2 grams) was recovered and its structure identified by H1NMR and FTIR analysis. The product obtained in 97.9% yield was of high purity.
EXAMPLE 2
Aliphatic Polyester Resin fPrepolvmer) Synthesis
Into a 500 cc round bottom flask, equipped with an agitator, temperature control, nitrogen sparge and a distillation head, was added 65.05 grams (0.50 moles) of 3-(l-propeneoxy)-l,2-propanediol; 174.19 grams (1.0 moles) or dimethyl adipate; 0.56 grams (0.0018 moles) of titanium (IV) isopropoxide; and 116.1 grams of 4-hydroxy butyl vinyl ether. The reaction was heated to 90°C. at which point methanol began to distill overhead. The reaction temperature was increased incrementally over a period of 16 hours to a temperature of 180°C. after which 95.0% of the stoichiometric methanol by-product was distilled overhead, and the reaction was terminated. The product,
(CH2=CHOC4H80-)2 -[ (COC4H8CO-OCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
(285.2 grams) was recovered and its structure identified by H1NMR and FTIR analysis. The product obtained in a yield of 97.9% was of high purity.
When H0CH2- <j—I > -CH2OCH=CH2 is
- & substituted in the same molar amount in the above Example 2 for 4-hydroxybutyl vinyl ether, the product has the structure
-CH20-)2 -[(COC4H8COOCH2CHO)C0C4H8C0]-
Figure imgf000011_0001
CH2OCH=CHCH3
EXAMPLE 3 Halo-Aromatic Polyester Resin (Prepolymer) Synthesis
Into a 500 cc round bottom flask, equipped with agitation, temperature control, nitrogen sparge and a simple distillation head, was added 80.05 grams (0.50 moles) of 4-(l-buteneoxy)-l,2-butanediol; 262.2 grams (1.0 moles) of 2-(trifluoromethyl)-l,4-dimethyl terphthalate; 0.56 grams (0.0018 moles) of titanium (IV) isopropoxide; and 116.1 grams (1.0 moles) of 2-(l- buteneoxy)-l-ethanol. The reaction was heated to 90°C. after which methanol began to distill overhead. The reaction temperature was increased incrementally over a period of 16 hours to 180°C. At this point 95.0% of the stoichiometric methanol was distilled overhead, and the reaction was terminated. 385.9 grams product having the formula
(C2H5CH=CHOC2H40-)2 -[ -
Figure imgf000012_0001
was recovered. H1NMR and FTIR analysis confirmed the structure and high purity of the product. An overall yield of 97.9% was obtained.
EXAMPLE 4 The products of Examples 1-3 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) . The resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table. TABLE
TENSILE PROPERTIES
PRODUCT PENCIL ADHESION MANDRELL MEK YOUNGS TENSILE ELONGATION OF HARDNESS % BEND RUBS MODULUS STRENGTH %
EXAMPLE 1 H 100 1/8 >200 64 880 6.4
EXAMPLE 2 HB 80 1/8 >200 50 700 5.3
EXAMPLE 3 70 1/8 >200 50 650 5.1
Merely by increasing the mole ratio of the intermediate with respect to the end capping hydroxy alk-1-enyl ether in the above examples, a product where m has a value greater than 1 can be obtained. Accordingly, a 25-fold increase in the intermediate concentration produces a product where m is 25.
EXAMPLE 4 Preparation of Dihydroxy Alk-1-Enyl Ether
Into a 1500 cc stainless steel reaction vessel, equipped with a mechanical stirrer, high pressure gas feed lines, internal cooling, and temperature control, was added 1140.6 grams (10 moles) of propenyl glycidyl ether (PGE) , 198.0 grams (11 moles) of water, 5.7 grams of tetrabutyl ammonium bromide, and 3.0 grams of sodium bicarbonate. The mixture was heated to 100°C. under a C02 pressure of 200 psig for 6 hours, with continuous C02 feed. Analysis by gas chromatography showed quantitative conversion of PGE. This material was then flash distilled at a temperature of 120°C. at 5.0 mm Hg, to remove water and separate the product from the catalyst. l-Propenyloxy-2,3-propanediol 1250 grams of 98.5% purity was recovered, and its structure was confirmed by FTIR and H1NMR spectroscopic methods.
EXAMPLE 5 Preparation of Uncured Prepolymer
Into a 250 cc round bottom flask equipped with agitation, reflux condenser, nitrogen sparge, and temperature control was added 87.08 grams (0.5 moles) of toluene diisocyanate. To this was added 87.08 grams (0.75 moles) of 4-hydroxybutyl vinyl ether, 16.53 grams (0.125 moles) of 1-propenyloxy propanediol from Example 4 and 0.2 grams of dibutyl tin dilaurate at a controlled rate so as to maintain a temperature of 60-80°C. The reaction was monitored by volumetric isocyanate analysis, and proceeded to completion after 4 hours. The viscous product,
Figure imgf000015_0001
was recovered, and the above structure was confirmed by H1NMR and FTIR spectroscopy.
EXAMPLE 6 Prepolymer Preparation
Into a 250 cc round bottom flask equipped with agitation, reflux condenser, nitrogen sparge, and temperature control was added 87.98 g (0.5 moles) of toluene diisocyanate. To this was added 58.05 grams (0.50 moles) of 4-hydroxybutyl vinyl ether 33.05 grams (0.25 moles) of 1-propenyloxy propanediol from Example 4 and 0.2 grams of dibutyl tin dilaurate at a controlled rate so as to maintain a temperature of 60-80°C. The reaction was monitored by volumetric isocyanate analysis, and proceeded to completion after 4 hours. The same viscous product as obtained in Example 5 was recovered, and the structure was confirmed by H***NMR and FTIR spectroscopy
(CH2=CHOC4H80-)2-[
Figure imgf000016_0001
When HOCH2- (jr\ ) -CH2OCH=CH2
is substituted in the same molar amount in the above Example 6 for 4 -hydroxybutyl vinyl ether, the product has the structure
(CH2=CHOCH2- ]-
Figure imgf000016_0002
When OCN(CH2)6CNO is substituted in the same molar amount in the above Example 6 for toluene diisocyanate, the product has the structure
(CH2=CH0C4H8O-)2 -[CONH(CH2)6NHCOOCH2CHO-CONH(CH2)6NHCO]-
CH2OCH=CHCH3
When OCN-C6H4-CH2-C6H4-NCO is
substituted in the same molar amount in the above Example 6 for toluene diisocyanate, the product has the structure
(CH2=CHOC4H80-)2
- [ CONH-C6H4-CH2-C C66HH44NNHHCCOOOOCCHH22CCHOCONH-C6H4-CH2-C6H4-NHCO] -
CH2CH=CHCH3 EXAMPLE 7
The procedure of Example 5 was repeated using 7.8 grams of 1,2-propanediol in place of 1-propenyloxy propanediol. The product of this example was identified as having the formula
(CH2=CHOC4H80-)2 -[ (CONH-C6H4-NHCOOCH2CHO)CONH-C6H4-NHCO]•
CH,
and is useful as a non-reactive chain extender resin.
EXAMPLE 8
The procedure of Example 6 was repeated using 15.5 grams of 1,2-propanediol in place of 1-propenyloxy propanediol. The product of this example is identical to that obtained in Example 7
(CH2=CHOC4H80-)2 -[(CONH-C6H4-NHCOOCH2CHO)2CONH-C6H4-NHCO]-
CH,
COMPARATIVE EXAMPLE 9
The procedure of Example 6 was repeated using 37.06 grams of n-butanol in place of hydroxybutyl vinyl ether. The product of this example
Figure imgf000017_0001
CH2OCH=CHCH3 CH3 possesses a non-reactive end-capping group but would retain internal cross-linking properties because of the reactive-chain extender. However, this product exhibits poor pencil hardness, little or no adhesive properties and low tensile properties.
EXAMPLE 10
The products of Examples 5-9 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) . The resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table.
TABLE
TENSILE PROPERTIES
PENCIL ADHESION MANDRELL MEK YOUNGS TENSILE ELONGATION
OLIGOMER HARDNESS % BEND RUBS MODULUS STRENGTH %
EXAMPLE 5 2H 100 1/8 >200 89 1250 7.6
EXAMPLE 6 3H 70 1/8 >200 76 1150 8.4
EXAMPLE 7 H 70 1/8 >200 65 1000 5.1
EXAMPLE 8 H 50 1/8 >200 55 800 4.8
EXAMPLE 9 B 1/8 >200 10 600 8.5
EXAMPLE 11
Example 5 is repeated, except that 3 moles of -hydroxybutyl vinyl ether, 2 moles of toluene diisocyanate and 0.8 grams of dibutyl tin dilaurate are substituted for the amounts shown therein (a 4-fold excess) . The product of this reaction has the formula
(CH2*=CHOC4H80-)2 -[ (CONH-C6H4-NHCOOCH2CHO)4CONH-C6H4-NHCO]-
CH2OCH=CHCH3
Merely by increasing the mole ratio of the intermediate with respect to the end capping hydroxy alk-1-enyl ether, a product where m has a value greater than 1 can be obtained. Accordingly, a 25-fold increase in the intermediate concentration produces a product where m is 25.

Claims

WHAT IS CLAIMED IS:
1. A polyalk-1-enyl polyester prepolymer having the formula
(R6CH=CHOR40-)2 -[ (COACO-OR1CHO)mCOACO]-
R2OCH=CHR5
wherein m has a value of from 1 to 25;
A is c2 to C12 alkylene, C6 to C14 arylene, both groups optionally substituted with lower alkyl, halo lower alkyl, alkyleneoxy, halogen, aryl or NHA'NH wherein A' is the same as A;
R is alkylene containing from 1 to 6 carbon atoms;
R2 is a saturated or unsaturated divalent radical containing from 1 to 14 carbon atoms and is selected from the group of alkylene, alkenylene and arylene, each group optionally substituted with oxygen, halogen, lower alkyl and/or hydroxy;
R5 is hydrogen or Cλ to C6 alkyl;
R is C-L to C5 alkylene, C6 to C14 arylene, lower alkyl substituted phenylene or xylylene and
R6 is hydrogen or Cλ to C alkyl.
2. The prepolymer of Claim 1 wherein A is arylene and has a value of 2.
3. The prepolymer of Claim 1 wherein A is an aliphatic radical and m has a value of 2.
4. The prepolymer of Claim 1 having the formula:
(CH2=CHOCH2- ]
Figure imgf000022_0001
5. The prepolymer of Claim 1 having the formula:
(CH2=CH0C4H80-)2 -[ (COC4H8CO-OCH2CHO)C0C4H8C0]-
CH2OCH=CHCH3
6. The prepolymer of Claim 1 having the formula:
(C2H5CH=CHOC2H40-)2 -[ (CO-< 0 >-CO-OCH2CH0)CO- O/ "CO]
C2H4OCH=CHC2H5
7. The prepolymer of Claim 1 having the formula:
(CH2=CHOC4H80-)2 -[ (COC6H4CO-OCH2CHO)COC6H4CO]-
CH2OCH=CHCH3
8. A radiation curable composition containing the prepolymer of Claim 1 and an effective amount of a cationic polymerization initiator.
9. The composition of Claim 8 wherein said initiator is an onium salt initiator.
10. The composition of Claim 9 wherein said initiator is the triphenylsulfonium salt of hexafluorophosphate.
11. The composition of Claim 9 wherein said prepolymer has the formula:
(CH2=CHOC4H80-)2 -[ (COC6H4CO-OCH2CHO)COC6H4CO]-
CH2OCH=CHCH3
12. The composition of Claim 9 wherein said prepolymer has the formula:
(CH2=CHOC4H80-)2 -[ (COC4H8CO-OCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
13. The composition of Claim 9 wherein said prepolymer has the formula:
(C2H5CH=CHOC2H40-)2 -[
Figure imgf000023_0001
14. The composition of Claim 9 wherein said prepolymer has the formula:
(CH2=CHOCH2- \H/ -CH 2°")2 ~[ (COC4H8COOCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
15. A substrate having a hard, durable and flexible coating of the cured prepolymer of Claim 1.
16. The substrate of Claim 15 which is coated with the cured prepolymer having the formula:
(CH2=CHOC4H80-)2 -[ (COC6H4CO-OCH2CHO)COC6H4CO]-
CH2OCH=CHCH3
17. The substrate of Claim 15 which is coated with the cured prepolymer having the formula:
(CH2=CHOC4H80-)2 -[(COC4H8CO-OCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
18. The substrate of Claim 15 which is coated with the cured prepolymer having the formula:
(C2H5CH=CHOC2H40-)2 -[
Figure imgf000024_0001
19. The substrate of Claim 15 which is coated with the cured prepolymer having the formula:
(CH2=CHOCH2 G-|/"""-CH20-)2 -[ (COC4H8COOCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
20. The prepolymer of Claim 1 wherein A is NHA'NH; m has a value of from 1 to 4, A' is alkylene, R5 is lower alkyl, R4 is alkylene and R6 is hydrogen or methyl.
21. The prepolymer of Claim 1 wherein A is NHA'NH; m has a value of from 1 to 4, A' is arylene, R5 is lower alkyl, R4 is alkylene and R6 is hydrogen or methyl.
22. The prepolymer of claim 1 having the formula
(CH2=CHOCH2- ];
Figure imgf000025_0001
23. The prepolymer of Claim 1 having the formula
(H9C40-)2 -[ (CONH-
Figure imgf000025_0002
24. The prepolymer of Claim 1 having the formula
(CH2=CHOC4H80-)2 -[ (CONH-C6H4-NHCOOCH2CHO)4CONH-CβH4-NHCO]•
CH2OCH=CHCH3
25. The prepolymer of Claim 1 having the formula
(CH2=CHOC4H80-)2 -[CONH(CH2)6NHCOOCH2CHO-CONH(CH2)6NHCO]
CH2OCH=CHCH3
26. The composition of Claim 8 wherein A is NHA'NH and the initiator is diphenyl-4-thiophenoxy phenyl sulfonium salt.
27. The composition of Claim 8 containing the prepolymer wherein m has a value of 2, A' is aryl, R5 and R4 are each lower alkyl and R6 is hydrogen or methyl.
28. The composition of Claim 27 which additionally contains a diluent having the formula
(CH2=CHOC4H80-)2 -[(CONH-C6H4-NHCOOCH2CHO)CONH-C8H4-NHCO]-
CH3
29. The composition of Claim 27 wherein said prepolymer is
2 "[CONHC6H4NHCOOCH2CHOCONHC6H4CO]-
Figure imgf000026_0001
CH2OCH=CHCH3
30. The composition of Claim 27 wherein said prepolymer is
(CH2=CHOC4H80-)2
-[CONH-C6H4-CH2-C6H4NHCOOCH2CHOCONH-C6H4-CH2-CβH4-NHCO]-
CH2CH""*"CHCH-j
31. The composition of Claim 27 wherein said prepolymer is
(CH2=CH0C4H80-)2 -[ (CONH-C6H4-NHCOOCH2CHO)4C0NH-C6H4-NHC0]
CH2OCH=CHCH3
32. The composition of Claim 27 wherein said prepolymer is
(CH2=CHOC4H80-)2 -[C0NH(CH2)6NHCOOCH2CHO-CONH(CH2) 6NHC0]-
CH2OCH=CHCH3
33. The substrate of Claim 15 wherein said coating is the cured poly(alk-l-enyl) /urethanyl prepolymer having the formula
(CH2=CHOCH2- H/-CH2°~)2 ~[ (COC4H8COOCH2CHO)COC4H8CO]-
CH2OCH=CHCH3
PCT/US1994/008203 1993-08-18 1994-07-20 Radiation curable alk-1-enyl ether polyester prepolymers WO1995005403A1 (en)

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US08/108,212 1993-08-18
US08/108,212 US5373032A (en) 1993-08-18 1993-08-18 Radiation curable alk-1-enyl urethanyl prepolymers
US08/107,867 1993-08-18
US08/107,867 US5342860A (en) 1993-08-18 1993-08-18 Radiation curable alk-1-enyl ether polyester prepolymers

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