EP0496828A4

EP0496828A4 - Vinyl ethers synthesized from hydroxylated vinyl ethers and polyepoxides

Info

Publication number: EP0496828A4
Application number: EP19900916980
Authority: EP
Inventors: Kou-Chang Liu; Fulvio J. Vara; James A. Dougherty; Paul D. Taylor
Original assignee: ISP Investments LLC
Current assignee: ISP Investments LLC
Priority date: 1989-10-20
Filing date: 1990-10-11
Publication date: 1993-03-31
Also published as: AU6729890A; WO1991005814A1; EP0496828A1; AU646824B2; AU662670B2; CA2027918A1; AU5389394A

Abstract

Epoxy vinyl ethers are synthesized by the reaction of a hydroxylated vinyl ether and a diepoxy aryl hydroxyalkyl ether coreactant such as a diepoxy compound of bisphenols or an epoxy novolac resin in a ratio of the total number of epoxy groups to hydroxyl groups of in excess of at least one. A fluorinated vinyl ether is synthesized by the reaction of a vinyl ether epoxide and a fluoro alkanol. The vinyl ethers are cationically induced radiation cured, resulting in products which are not oxygen inhibited and which are polymerizable after removal from radiation, unlike free radical systems. They are used as release agents and stain protective coatings.

Description

VI_NYL E_TH_{ERS SY}N_TH_ESIZED FROM HYDROXYLATED VI^NYL ETHERS AND POLYEPOXIDES

BACKGROUND OF THE INVENTION

Certain radiation curable coatings and films such as those formed from the acrylates, particularly propane tri ethanol triacrylate, trimethacrylate, pentaerythritol triacrylate, and hexanediol diacylate or methacrylate, are in great demand because of their rapid curing properties.

Since acrylate compounds are not conducive to cationically induced radiation curing, they require more costly free radical systems which are oxygen inhibited unless effected in an inert atmosphere, generally under a blanket of nitrogen. Although formulation with a photoinitiator which undergoes bi olecular reaction with a hydrogen donor minimizes the inhibitory effect of air, this benefit is realized at the expense of a greatly reduced cure rate. Also, it is found that polymerization or curing in free radical systems ceases almost immediately upon removal from the source of radiation; thus, the cured product likely contains significant amounts of unpolymerized components. Accordingly, it is an aim of research to develop a compound having the beneficial properties of acrylates but which is amenable to radiation curing at a rapid rate by cationically induced polymerization which is not oxygen inhibited and which permits continued polymerization after removal from the source of radiation exposure. THE INVENTION

According to this invention there is provided epoxy vinyl ethers having the formula

wherein R is a polyvalent linear, branched or cyclic hydrocarbon radical having from 2 to 20 carbon atoms, optionally substituted with alkyleneoxy; A is branched or linear C± to C alkylene; B is halogen or lower alkyl; m has a value of from 0 to 4; n has a value of from 0 to

20; p has a value of from 1 to 5 and Y is

O / \

-CH-CH, when p is 1 and is -CH-CH or a mixture of

_. \ / ²

O

-CH-CH₂ and -CH-CH₂OROCH=CH₂ when p is greater than

O OH one. Of the above defined epoxy vinyl ethers, those wherein R is C₂ to C₆ alkylene, A is -CH₂- or

^•C(CH₃)₂, m has a value of 0; n has a value of from 0 to 12 are preferred. Most preferred of this group are the products wherein Y is -CH-CH₂ and p is 1-5.

0 The method of synthesizing the above vinyl ethers (I) involves the reaction of a hydroxylated vinyl ether reactant, (H0)_R0CH=CH₂, and a diepoxy aryl hydroxyalkyl ether coreactant.

wherein R, A, B, m, n and p are as defined. The mole ratio of reactants is critical and is the ratio where the number of epoxy groups in the reaction mixture exceeds the number of hydroxy groups in the reaction mixture by at least one. Hence, where the hydroxyvinyl ether reactant is (HO)₃ROCH=CH₂, the mole ratio of reactant to coreactant is between 1:2 and 1:3; when (HO)₅ROCH=CH₂ is substituted, the ratio is between 1:3 and 1:5 and when HOROCH=CH₂ is the reactant, the ratio is 1:1. In accordance with the species of products in this invention, the overall mole ratio of reactant to coreactant is from 1:1 to 1:5.

The reaction can be carried out in the presence of air or in the absence of oxygen under a blanket of inert gas. Generally, the present condensation reaction is carried out at a temperature of between about 100° and about 175°C. under atmospheric pressure for a period of from 0.5 to 200 hours. Preferred reaction parameters include a temperature of from about 120° to about 160°C. for a period of from about 2 to about 100 hours.

The reaction is also conducted in the presence of a base catalyst such as particulate sodium, potassium, or lithium metal, sodium or potassium hydroxide or hydride. The catalyst is present in an amount of from about 0.01 to about 2 wt. %, preferably from about 0.1 to about 1 wt. % of the total mixture. When the reactants and products included herein are liquids, they are generally synthesized in the absence of diluents or solvents which are otherwise required for more viscous or solid reactants.

Suitable hydroxylated vinyl ether reactants include the mono vinyl ether of cyclohexanetrimethanol, the monovinyl ether of cyclohexanedimethanol, the monovinyl ether of tris-(hydroxymethyl) ethane, the divinyl ether of 2-ethyl-2(hydroxymethyl)l,3-propanediol, the divinyl ether of tris(hydroxymethyl) ethane, tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxypropyl) vinyl ether, the monovinyl ether of 3-ethyl-l,6-hexanediol, (4-hydroxybutyl) vinyl ether, the.monovinyl ether of 2-methyl-l,8-octanediol, (vinyloxy) cresol, (vinyloxy) xylol and alkoxylated derivatives thereof containing from l to 6 ethyleneoxy or propyleneoxy units. Suitable aromatic polyepoxy reactants include the terminally substituted diepoxy compounds of bisphenol A and bisphenol F, resins and compounds wherein one or more of the phenyl groups is substituted with halo or C₁ to C₄ alkyl radicals.

A commercially available group of diepoxy reactants suitable for use in the present reaction are the Epon epoxy resins supplied by Shell Chemical Company. These resins have the following structure

These epoxy reactants are readily prepared by well known procedures, such as the procedure outlined on pages 10 through 21 of Chapter 2 of HANDBOOK OF EPOXY RESINS, by Henry Lee and Kris Neville, published by McGraw Hill Book Company, 1967.

These products are useful chemical intermediates and can be homopolymerized to hard chemically resistant films and coatings which have good substrate substantivity. Alternatively, the present compounds can be mixed with alkenyl ether, alkenyl ester, epoxide or acrylate monomers or polymers to impart rapid radiation curing properties in the presence of a cationic photoinitiator. Cross-linking copolymerizations can be carried out in the presence of air to produce highly desirable films and coatings which retain the desirable properties of both monomers or their polymerized derivatives. Curable compositions containing between about 0 and about 80% of a vinyl ether, an epoxide, an acrylate or a ethacrylate comonomer or a polymer thereof and between about 20% and about 100% of the present epoxy vinyl ether in the presence of from about 0.05 to about 5 wt. % of a cationic photoinitiator are suitable radiation curable coatings which are polymerized by exposure to UV light, electron beam, laser emission or other source of radiation. Between about 2 and about 50 wt. % of the present product with from about 0.1 to about 5 wt. % of a conventional photoinitiator, such as an onium salt including the triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodium salt, tetrazolium chloride, phenyl onium salts or aryl alkyl onium salts, cationic initiators and/or free radical initiators such as 1-hydrocyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenyl-l-propan-l-one, 2,2-dichloro-l-(4-phenoxyphenyl) ethanone and other free radical and cationic initiators which are suitably employed in this invention can be admixed with an acrylic compound normally not conducive to rapid cationic radiation curing, such as an acrylate or methacrylate comonomer, to effect curing within a few seconds exposure to a source of radiation. These coatings are applied to a substrate such as glass, ceramic, wood, plastic, metal and the like in thicknesses of from about 0.1 to about 5 mils. Additionally, the compounds of this invention, because of their sensitivity to polymerization by radiation, find application as photoresist materials.

Curing of the present compounds or their admixtures with comonomers can be effected in less than 1 second by exposure to between about 100 and about 800 millijoules/cm² of UV light, between about 0.5 and about 5 megarads of electron beam exposure or equivalent radiation exposures. According to another embodiment of this invention there is provided epoxy vinyl ethers having the formula

wherein R is a polyvalent linear, branched or cyclic hydrocarbon radical having from 2 to 20 carbon atoms, optionally substituted with alkyleneoxy; n has a value of from 1 to 20; p has a value of from 1 to 6; and at least

0 one of Y and Y' is -CH-CH₂ while each of any remaining Y

O and Y'can be -CH-CH₂ or -CHCH₂OROCH=CH₂. Of the

OH above defined polyphenyl vinyl ethers, those wherein R is C₂ to C₆ alkylene, n has a value of from 1 to 12 and Y

and Y' are -C _/H°-CH₂ are preferred. Most preferred of this group are those compounds where n and p have a value of from 1 to 4.

The synthesis of the above epoxy vinyl ether (II) involves the reaction of a hydroxylated vinyl ether reactant, (H0)_pR0CH=CH₂, and a polyepoxy aryl hydroxyalkyl ether coreactant, of the formula

wherein R, p and n are as defined. The amounts of reactant and coreactant employed in the synthesis process to produce the epoxy polyphenyl product are critical. Specifically, the total number of

0 / \ epoxy groups, -CH-CH , with respect to the total amount of -OH groups in the system, must be in excess of at least one. For example, as an upper limit, when n is 20 and p is 1, there can be 21 epoxy GROUPS/OH. In the later case, where p is 1, only one epoxy group, of the original 22 epoxy groups, reacts. When a polyhydroxylated reactant is employed, e.g. (HO)₃ROCH=CH₂, and n has a positive value, e.g. 2, the ratio of reactant to coreactant is 1:1, whereby the product has one unreacted epoxy group; however when 2 moles of the coreactant to 1 mole of the reactant is employed, the product contains 5 unreacted epoxy groups. In another case where (HO)₃ROCH=CH is the reactant and n in the coreactant is 6, the ratio of reactant to coreactant can vary from 1:0.5, where the product contains 1 remaining epoxy group, up to 1:1 where the product contains 5 remaining epoxy groups. Hence by controlling the amount of reactant to coreactant, or vice versa, all of the hydroxy groups of the hydroxylated vinyl ether will be reacted and the product will always contain at least one epoxy group. It is essential to retain an epoxy group in the product where derivatives of the present products are desired.

In accordance with another embodiment of this invention there is provided a fluorinated vinyl ether (III) having the formula

CF₃(CF₂)_tR'OCH₂CHR"OCH=CH₂

OH wherein t has a value of from 1 to 22; R' is C to C₂₀ alkylene, alkoxyalkylene, arylene or aryloxyalkylene which radicals are optionally fluorinated; R" is a divalent radical having from 1 to 100 carbon atoms and is selected from the group of alkylene, arylene, alkarylene, aralkylene which groups are optionally substituted with lower alkyl or the radical

wherein R is a polyvalent linear, branched or cyclic hydrocarbon radical having from 2 to 20 carbon atoms, optionally substituted with alkyleneoxy; A is a divalent radical selected from the group of

where each of R_lf R₂, R₃ and R₄ is independently hydrogen or

-C₆H₄CH₂CH-CH2

B is lower alkyl; m has a value of from 0 to 4 and n has a value of from 0 to 20.

The above compounds can be synthesized according to following equation A.

II wherein R', R" and t are as defined. When coreactant II is an oligomer, as described above for R", e.g. l-[[[[2,3-epoxypropoxy]phenyl]alkyl]phenoxy]-3-[[vinyloxy] alkoxy]-2-propanol, the reaction can be illustrated by equation B below.

cr₃<cP₂)_tROH +

The synthesis is carried out under mild conditions such as a temperature of between about 50° and 160°C. under atmospheric pressure for a period of from about 2 to about 50 hours, preferably at a temperature from 120° to about 150^βC. for a period of from 2 to about 10 hours. The reactants may be contacted in the absence or in the presence of an inert solvent. When used, the solvent can be employed in an amount up to 70% of the reaction mixture. Suitable solvents include, toluene, xylene, the dimethyl ether of tri- or tetra- ethylene glycol and the like. The reaction is carried out in the presence of between about 0.01 and about 3 wt. %, preferably between about 0.05 and about 1 wt. % of a base catalyst such as particulate sodium, potassium or lithium metal, a sodium, lithium or potassium hydroxide or hydride, and similar base catalysts. While the present reaction is not oxygen inhibited, it is preferred to conduct the reaction under a blanket of inert gas such as nitrogen. Examples of the vinyl ether epoxide reactant include [(vinyloxy) methyl] oxirane, [(vinyloxy) benzyl] oxirane, [(vinyloxy) phenyl] oxirane, [(vinyloxy) butyl] oxirane, [(vinyloxy) ethyl] oxirane, [(vinyloxy) octyl] oxirane, [(vinyloxy) dodecyl] oxirane, [(vinyloxy) tolyl] oxirane, [(vinyloxy)-2,3-dimethyl hexyl] oxirane, [2-(vinyloxy) ethoxy] phenyl oxirane, and [[(vinyloxy) phenoxy]phenyl] oxirane.

Suitable fluoro alkanol reactants include pentafluoropropanol, pentafluorohexanol, nonafluoropentanol, heptafluorodecanol, heptadecafluorodecanol, pentadecafluorodecanol, undecafluoroheptanol, 2-(undecafluorocyclohexyl) ethanol, heptatricontafluoroeicosanol, nonadecafluoroeicosanol, 2-(pentafluorophenyl) ethanol,

2-[4-(pentacosafluorododecyl) tetrafluorophenoxy] ethanol, etc.

Of the above named reactants, pentadecafluorooctanol, heptadecafluorodecanol are preferred flourinated alcohols. Preferred species of the oxirane reactant are [(vinyloxy) methyl] oxirane and the oligomers of equation B wherein n has a value of 0 or 1; m is zero; A is -C(CH₃)₂- and R is butylene.

The above compounds have been found to be excellent release coating materials. Accordingly, they can be coated on a suitable substrate such as glass, ceramic, wood, metal, woven fabrics, paper and the like in thicknesses ranging from 0.05 up to 5 mils to provide products having stain and soil resistance or labels which are easily removed from paper surfaces or backing materials for adhesive tapes and the like and many other applications which are apparent from their properties. As coating agents, curing the products of the present invention is easily effected at room temperature under ambient pressure conditions by exposure to a source of radiation such as UV light, an electron beam, lazer emission and the like in the presence of from about 0.05 to about 5 wt. % of a photoinitiator. Suitable photoinitiators are the onium salts such as the triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodium salt, tetrazoliu chloride, phenyl onium salts or aryl alkyl onium salts and the like. The amount of initiator employed is preferably between about 0.1 and about 2 wt. % with respect to reactants.

The present products can be cured in a period of less than 1 second, e.g. by exposure to between about 100 and about 800 millijoules/cm² UV light or between about 0.5 and about 5 egarads of electron beam emission. The sensitivity of the present compounds to radiation curing makes them excellent candidates for use as photoresists.

The products of this invention can also be cured by conventional thermal processes employing a temperature of from about 50°C. to about 160°C.

Having generally described the invention reference is now had to the accompanying examples which illustrate preferred embodiments which are not to be construed as limiting to the scope of the invention more broadly defined above and in the appended claims.

EXAMPLE 1

Epon 828 epoxy resin (1131 g, 3 moles) , 4-hydroxybutyl vinyl ether (348.5 g, 3 moles) and potassium hydroxide (0.5 g, 85% pellets) were charged into a 2-liter flask equipped with a mechanical stirrer, nitrogen inlet, thermometer and a condenser with a drying tube. The solution was heated at 120°C. for 12 hours and 150°C. for 48 hours under a blanket of nitrogen. Greater than 95% conversion was obtained. The gel-like product containing

is recovered.

EXAMPLE 2

Epon 828 epoxy resin (2 mole) , monovinyl ether of cyclohexane trimethanol (1 mole) and potassium hydroxide (0.4 g, 85% pellets) are charged into a 1-liter flask equipped as in Example 1. The solution is heated at 145°C. for 40 hours. Greater than 95% conversion is obtained. The gel-like product containing

is recovered.

EXAMPLE 3

Epon 826 epoxy resin (364 g, 1 mole) , monovinyl ether of cyclohexane dimethanol (170 g, l mole) and potassium hydroxide (0.4 g of 85% pellets) are charged into a one liter glass flask equipped as in Example 1. The solution is heated at 120^βC. for 42 hours and at 150^βC. for an additional 10 hours under a blanket of nitrogen. Greater than 95% conversion is obtained. The gel-like product containing

is recovered.

EXAMPLE 4

The product of Example 1 is mixed with 1% of triphenyl sulfonium salt of phosphorous hexafluoride coated on an aluminum panel in a thickness of 0.15 mil and the coated substrate is exposed for less than 1 second at room temperature to 400 millijoules/cm² radiation from a medium pressure mercury vapor lamp, after which the coated substrate is removed. A completely homopolymerized protective coating having resistance to chemical attack is achieved.

EXAMPLE 5

The procedure described in Example 4 is repeated except that 50% of the product of Example 2 was pre ixed with 50% of the divinyl ether of triethylene glycol. The coated substrate is completely cured in less than 1 second to a strong protective coating having high resistance to chemical attack. EXAMPLE 6

The general procedure in Example 2 is repeated, except that 2 moles of monovinyl ether of triethylene glycol are used. The product

is obtained in at least 70% yield.

EXAMPLE 7

D.E.N. 438 Epoxy Novolac Resin (1095 g.), 4-hydroxybutyl vinyl ether (446.5 g.) and potassium hydroxide 1.0 g. were charged into a 2-liter flask equipped with a mechanical stirrer,. nitrogen inlet, thermometer, a condenser and a drying tube. The solution was heated at 150°C. for 72 hours under a blanket of nitrogen. Greater than 90% conversion to a gel-like product comprising

was obtained. EXAMPLE 8

D.E.N. 439 Epoxy Novolac Resin (1231.2 g.), the monovinyl ether of triethylene glycol (352.3 g.) and 3 g. of potassium hydroxide are charged into a 2-liter flask. The solution is heated at 120°C. for 24 hours and then at 150°C. for 72 hours. Greater than 90% conversion to a gel-like product comprising

was obtained.

EXAMPLE 9

Into a one liter flask equipped with a mechanical stirrer, nitrogen inlet, thermometer and a condenser attached to a drying tube, is introduced 1 mole of 1~[[C[2,3-epoxypropoxy] phenyl]-2-propyl]-phenoxy] -3-[vinyloxy] butoxy]-2-propanol, 1 mole of heptafluoro pentanol, and 0.5 gram of 85% potassium hydroxide pellets. The mixture was heated at 120° for 24 hours and at a 150° for an additional 48 hours after which heating was discontinued. Greater than 99% conversion is obtained. A product having the formula

according to NMR, is recovered. EXAMPLE 10

The procedure described in Example 9 is repeated except that the corresponding glycidyl ether of bisphenol F is substituted for the bisphenol A resin (Epon 828 epoxy resin) of Example 9. Also, decafluorohexanol is substituted for heptafluoropentanol in Example 9. About 100% conversion is achieved. A product having the structure

is recovered.

EXAMPLE 11

Example 9 was repeated except that heptadecyl fluorodecanol was substituted for heptafluoropentanol of Example 9. About 100% conversion was achieved. The corresponding product is recovered.

Example 9 is repeated with substitution of each of the following alcohol reactants:

HOC₂H C₆F₁₃, H0C₂H₄C₈F₁₇,

H0C₂H₄C₁₀F₂₁ and H0C₂H₄C₁₂F₂₅ .

In each case about 100% conversion is achieved and the corresponding products are recovered. EXAMPLE 12

Example 9 is repeated except that [(vinyloxy) methyl] oxirane is substituted for Epon 828 in Example 9. About 100% conversion is achieved and a product having the structure

CF₃(CF₂)₂C₂H₄OCH₂CH-CH₂OCH=CH₂

OH

is recovered.

EXAMPLE 13

Into a one liter flask equipped with a mechanical stirrer, nitrogen inlet, thermometer and a condenser attached to a drying tube, is introduced 377 grams (1 mole) of Epon 828 epoxy resin, 107 grams (0.5 mole) of heptafluoro pentanol, 58.1 gram (0.5 mole) of 4-hydroxybutyl vinyl ether and 0.5 gram of 85% potassium hydroxide pellets. The mixture is heated at 120° for 24 hours and at a 150° for an additional 48 hours after which heating was discontinued. Greater than 99% conversion is obtained. A product having the formula

according to NMR, is recovered. The above products are clear liquids or gel-like materials which, when coated on a substrate in a thickness of from about 0.15 to about 0.5 mil and exposed for less than one second at room temperature to 400 millijoules/cm² radiation from a medium pressure vapor lamp provide a cured soil and stain resistant barrier.

Claims

WHAT IS CLAIMED IS:

1. The compounds (I) having the formula

wherein R is a polyvalent linear, branched or cyclic hydrocarbon or alkoxylated hydrocarbon radical containing from 2 to 20 carbon atoms; A is branched or linear C_χ to

C₄ alkylene;

B is halogen or lower alkyl; m has a value of from 0 to 4; n has a value of from 0 to 20; p has a value of from 1 to 5 and Y is -CH-CH₂ when p is 1 and is -CH-CH₂

O 0 or a mixture of -CH-CH₂ and -CHCH₂OROCH=CH₂ when

O OH p is greater than one;

the compounds (II) having the formula

CH₂-CH0R H₂rø

wherein R is a polyvalent linear, branched or cyclic hydrocarbon or alkoxylated hydrocarbon radical having from 2 to 20 carbon atoms; n has a value of from 1 to 20; p has a value of from 1 to 6 and at least one of Y and Y'is -CH-CH₂ while any remaining Y and Y' can O

be -CH-CH₂ or -CHCH₂OROCH=CH₂ O OH

and the compounds (III) having the formula:

CF₃(CF₂)_tR•OCH₂CHR^MOCH=CH₂ OH

wherein t has a value of from 1 to 22; R' is C to C₂₀ alkylene, alkoxyalkylene, arylene or aryloxyalkylene which radicals are optionally fluorinated; R^H is a divalent radical having from 1 to 100 carbon atoms and is selected from the group of alkylene, arylene, alkarylene, aralkylene which groups are optionally substituted with lower alkyl or the radical

where each of R_{l f} R₂, R₃ and R₄ is independently hydrogen or

2. The compound of Claim 1 wherein in (I) R is a C₂ to C₆ aliphatic hydrocarbon, A is -CH₂- or

^TC(CH₃)₂, m has a value of 0, n has a value of from 0 to 12 and p has a value of 1 to 3.

3. The compound of Claim 1 wherein in (II) R is a C₂ to Cg aliphatic hydrocarbon, n has a value of from 1 to 12 and Y and Y^» are each -0CH 2-_>CH-/CH2,.

O

4. The compound of Claim 1 wherein in (III) R¹ is each alkylene and R" is C to C₄ alkylene.

5. The compound

6. The compound

7. The compound

OH

^CH₂^HOC₈H₁₄ ⁽ H₂(!:HCH₂( _H2--_0._OCH2C^ _CH2

8. The compound

9. The compound

10. The compound of Claim 1 wherein in (III) R' is alkylene and R" is an oligomeric radical having the formula

11. The compound of Claim 10 wherein m is zero; n has a value of zero or one and A is -CH₂- or -C(CH₃)₂-.

12. The compound of Claim 11 wherein R is alkylene.

13. The process for synthesizing the compound (I) of Claim 1 by contacting a hydroxylated vinyl ether reactant of the formula

(H0)_R0CH=CH₂

and a diepoxy aryl hydroxyalkyl ether coreactant of the formula

wherein R, A, B, m, n and p are as defined, and wherein the number of epoxy groups exceeds the number of hydroxy groups in the reaction mixture by 1 to 5 and reacting said reactant and coreactant at a temperature of from about 100^βC. to 175°C. in the presence of from about 0.01 to about 2 wt. % of a base catalyst.

14. The process of Claim 13 wherein said hydroxylated vinyl ether is

CH₂=CHOC₄H₈OH

15. The process of Claim 13 wherein said hydroxylated vinyl ether is the monovinyl ether of cyclohexane dimethanol.

16. The process of Claim 13 wherein said hydroxylated vinyl ether is the monovinyl ether of cyclohexane trimethanol.

17. The process of Claim 13 wherein A of the aromatic polyepoxide is ^C(CH₃), m has a value of zero and n has a value of from 0 to 4.

18. The process of Claim 13 wherein A of the aromatic polyepoxide is -CH -, m has a value of zero and n has a value of from 0 to 4. 19. A substrate coated with an effective chemically resistant cured layer of the compound (I) of Claim 1.

20. A substrate having coated on its surface an effective chemically resistant layer comprising a mixture of from about 20 to about 100% of the compound (I) of Claim 1 and from about 0 to about 80% of a polymerizable co onomer selected from the group of a vinyl ether, epoxide, acrylate and methylmethacrylate.

21. The process for synthesizing the compound (II) of Claim 1 which comprises contacting a hydroxylated vinyl ether reactant of the formula

(H0)_pR0CH=CH₂

and a polyepoxy aryl hydroxyalkyl ether coreactant of the formula

_fi

wherein R, p and n are as defined and wherein the total number of epoxy groups with respect to the total number of hydroxy groups in the reaction system is in excess of at least one and reacting said reactant and coreactant at a temperature of from about 100°C. to 175°C. in the presence of from about 0.01 to about 2 wt. % of a base catalyst. 22. The process of Claim 21 wherein the number of epoxy groups with respect to the number of hydroxy groups in the reaction system is in excess of from 1 to 21.

23. The process of Claim 21 wherein said hydroxylated vinyl ether is

CH₂=CHOC₄H₈OH

24. The process of Claim 21 wherein said hydroxylated vinyl ether is the monovinyl ether of cyclohexane dimethanol.

25. The process of Claim 21 wherein said hydroxylated vinyl ether is the monovinyl ether of triethylene glycol.

26. The process of Claim 21 wherein n has a value of from 1 to 4.

27. The process for synthesizing the compound (III) of Claim 1 which comprises contacting a fluorinated alcohol having the formula

CF₃(CF₂)_tR'OH

with a vinyl ether epoxide having the formula

wherein t, R' and R" are as defined, and reacting said fluorinated alcohol and said vinyl ether epoxide in the presence of a base catalyst at a temperature of from about 50° to about 160°C. for a period of from about 2 to about 50 hours.

28. The process of Claim 27 wherein R' is alkylene.

29. The process of Claim 27 wherein said vinyl ether epoxide is [(vinyloxy)methyl] oxirane.

30. The process of Claim 27 wherein R" of said vinyl ether epoxide is

31. The process of Claim 30 wherein A is -CH₂- or -C(CH₃)₂-; m is zero and n has a value of zero or one.