AU662670B2

AU662670B2 - Vinyl ethers synthesized from hydroxylated vinyl ethers and polyepoxides

Info

Publication number: AU662670B2
Application number: AU53893/94A
Authority: AU
Inventors: James A. Dougherty; Kou-Chang Liu; Paul D. Taylor; Fulvio J. Vara
Original assignee: ISP Investments LLC
Current assignee: ISP Investments LLC
Priority date: 1989-10-20
Filing date: 1994-01-19
Publication date: 1995-09-07
Anticipated expiration: 2010-10-11
Also published as: WO1991005814A1; EP0496828A4; CA2027918A1; AU646824B2; AU6729890A; EP0496828A1; AU5389394A

Description

VINYL ETHERS SYNTHESIZED FROM HYDROXYLATED

VINYL

ETHERS AND POLYEPOXIDES BACKGROUND OF THE INVENTION Certain radiation curable coatings and films such X as those formed from the acrylates, particularly propane trimethanol 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 1ocationically 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 bimolecular reaction with a I ~1 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 o 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 2fpolymerization which is not oxygen inhibited and which permits continued polymerization after removal from the source of radiation exposure.

<K

S2 THE INVENTION According to this invention there is provided epoxy vinyl ethers having the formula 82-aCo(0to)p-2"ca to -(o-DocBC )no a a)) (on (Br O (b (B) wherein R is a polyvalent linear, branched or cyclic hydrocarbon radical having from 2 to 20 carbon atoms, optionally substituted with alkyleneoxy; A isbranched or linear C 1 to C 4 alkylene; B is halogen or lower alkyl; m has a value of from 0 to 4; n has a value of from 0 to /o 20; p has a value of from 1 to 5 and Y is 0

-CH-CH

2 when p is 1 and is -CH-CH 2 or a mixture of 2O/

-CH-CH

2 and -CH-CH 2

OROCH=CH

2 when p is greater than I l 0 OH one. Of the above defined epoxy vinyl ethers, those wherein R is C 2 to C 6 alkylene, A is -CH 2 or FS ;C(CH 3 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- H 2 and p is 0 .The method of synthesizing the above vinyl ethers involves the reaction of a hydroxylated vinyl ether t reactant, (HO)pROCH=CH 2 and a diepoxy aryl hydroxyalkyl ether coreactant,

OH

2 C 2 OCHC H0 OCH wherein R, A, B, n and p are OCas defined)

J

wherein R, A, B, m, n and p are as defined.

3 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 6 hydroxyvinyl ether reactant is (HO) 3

ROCH=CH

2 the mole ratio of reactant to coreactant is between 1:2 and .1:3; when (HO) 5

ROCH=CH

2 is substituted, the ratio is between 1:3 and 1:5 and when HOROCH=CH 2 is the reactant, the ratio is 1:1. In accordance with the species of products 1o in this invention, the overall mole ratio of reactant to coreactant is from 1:1 to The reaction can be carried out in the presence of S. air or in the absence of oxygen under a blanket of inert gas. Generally, the present condensation reaction is /5carried out at a temperature of between about 1000 and about 175 0 C. under atmospheric pressure for a period of from 0.5 to 200 hours. Preferred reaction parameters include a temperature of from about 1200 to about 1600C.

for a period of from about 2 to about 100 hours.

s. 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. I o 2S-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.

i 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 -T-hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxypropyl) vinyl ether, the monovinyl ether of 3-ethyl-l,6-hexanediol, 4 (4-hydroxybutyl) vinyl ether, the.monovinyl ether of 2-methyl-1,8-octanediol, (vinyloxy) cresol, (vinyloxy) xyloi and alkoxylated derivatives thereof containing from 1 to 6 ethyleneoxy or propyleneoxy units. Suitable aromatic Spolyepoxy 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 C 1 to C 4 alkyl radicals.

A commercially available group of diepoxy 0 reactants suitable.for use in the present reaction are the Epon epoxy resins supplied by Shell Chemical Company.

These resins have the following structure Ic C oX I -c U C" O- O These epoxy reactants are readily prepared by well known /procedures, such as the procedure outlined on pages 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 S o and can be homopolymerized to hard chemically resistant S.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 S-2scuring 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 3 derivatives. Curable compositions containing between about 0 and about 80% of a vinyl ether, an epoxide, an acrylate or a methacrylate comonomer or a polymer thereof and Si i i: ic; YI 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, f 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 /o 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 :o 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 2Stheir 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 go millijoules/cm 2 of UV light, between about 0.5 and about megarads of electron beam exposure or equivalent radiation exposures.

r

I

6 According to another embodiment of this invention there is provided epoxy vinyl ethers having the formula (II) CH 2 -CHOR (O HH 2 CHCH20 2 HI CH 2 2 2

OCH

2

(Y)

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-CH 2 while each of any remaining Y 0 and Y'can be -CH-CH 2 or -CHCH20ROCH=CH 2 Of the

OH

/0 above defined polyphenyl vinyl ethers, those wherein R is

C

2 to C 6 alkylene, n has a value of from 1 to 12 and Y and Y' are -CH-CH 2 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, (HO)pROCH=CH2, and a pplyepoxy aryl Shydroxyalkyl ether coreactant, of the formula dH- 22 1 C0 C- OC2 2 OCg CH- CH 2 i h e\ 2 2 owherein R, p and n are as defined.

L I 1 7 The amounts of reactant and coreactant employed in the synthesis process to produce the epoxy polyphenyl product are critical. Specifically, the total'number of

O

epoxy groups, -CH-CH 2 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 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) 3

ROCH=CH

2 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) 3

ROCH=CH

2 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 S* coreactant, or vice versa, all of the hydroxy groups of the hydroxylated vinyl ether will 15 be reacted and the product will always contain at least one epoxy group. It is essential to S, retain an epoxy group in the product where derivatives of the present products are desired.

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

CF

3

(CF

2 t

R'OCH

2

CHR"OCH=CH

2 20

OH

f 9 b A 'I3':L M< UI wherein t has a value of from 1 to 22; R' is C 2 to C 20 alkylene, alkoxyalkylene, arylene or aryloxyalkylene which radicals are optionally fluorinated; R" is a divalent radical selected from the group of alkylene, arylene, alkarylene, aralkylene radicals having from 1 to 100 carbon atoms, which radicals are optionally substituted with lower alkyl or the radical

-R-O-CH

2

CHCH

2 0 -A OCH 2 9HCH 2 )nO-Q A )-OCH 2 OH OH B)m (B)m (B)m (B)m wherein R is a polyvalent linear, branched or cyclic hydrocarbon radical having from 2 to carbon atoms, optionally substituted with alkyleneoxy; A is a divalent radical selected from the group of I I -CH2- /C(CH 3 2 and R1--C-CR 2

R

3

R

4 where each of R 1

R

2

R

3 and R 4 is independently hydrogen or

-C

6

H

4 0CH 2

CH-CH

2 0 B is lower alkyl; m has a value of from 0 to 4 and n has a value of from 0 to The above compounds can be synthesized according to following equation A.

0

CF

3

(CF

2 )tR'OH CH 2

-CHR"OCH=CH

2

CF

3

(CF

2 )tR'OCH 2

CHR"OCH=CH

2

O

OH

t t 6 Ic V 4 6t *9 a t *c 6 LarL

L

IN:\LIBXX]00368:JJN

I

9 wherein R" and t are as defined. When coreactant II is an oligomer, as described above for e.g.

1-[[l[2,3-epoxypropoxy]phenyl]alkyl]phenoxy]-3-[[vinyloxy] alkoxy]-2-propanol, the reaction can be illustrated by S equation B below.

cr cr,) R'aO CHc -HOc-0 -CHCHCaI on a W/ o a\

CH

a t fK 3 c r 2 tR OC N 2 CHC H 2 O C H CH2 0N SA CH 2 CH 2 0 ROCH*C H2 .t The synthesis is carried out under mild conditions such as a temperature of between about 500 and 1600C. under atmospheric pressure for a period of from about 2 to about /o 50 hours, preferably at a temperature from 120° to about 150°C. 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 2oparticulate 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.

I 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] Soxirane, [(vinyloxy) dodecyl] oxirane, ((vinyloxy) tolylj 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, 162-(pentafluorophenyl) ethanol, 2-[4-(pentacosafluorododecyl) tetrafluorophenoxy] ethanol, etc.

Of the above named reactants, tC ~pentadecafluorooctanol, heptadecafluorodecanol are -Vpreferred 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(CH 3 2 and R is butylene.

The above compounds have been found to be .u 25excellent 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 easily removed from paper surfaces or backing materials for adhesive tapes and the like and many other applications T 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 -I I; 11 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 X salts such as the triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodium salt, tetrazolium 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.

w 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/cm 2 UV light or between about 1 4 C 0.5 and about 5 megarads 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 160C.

Having generally described the invention reference -'bis now had to the accompanying examples which illustrate preferred embodiments -which are not to be construed as S| 'limiting to the scope of the invention more broadly defined 4 above and in the appended claims.

EXAMPLE 1 s- .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 o3 solution was heated at 1200C. for 12 hours and 150°C. for..

j. r _I 1- ~L~L~ -12- 48 hours under a blanket of nitrogen. Greater than conVersion was obtained. The gel-like product containing 53 3 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 i-liter flask cr equl -led as in Example 1. The solution is heated at 145 0

C.

Sfoy ours. Greater than 95% conversion is obtained.

The like product containing cH _.cMoc R 5 O CE OCR CUCHO 4. 5 OCH CHCH 0) o-K 2 Q HCH- CH 2

I

is recovered.

EXAMPLE 3 is- Epon 826 epoxy resin (364 g, 1 mole), monovinyl 4 ether of'cyclohexane dimethanol'(170 g, 1 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 1200C. for 42 hours and at 150 0 C. for i .~an additional 10 hours under a blanket of nitrogen.

13 13 Greater than 95% conversion is obtained. The gel-like product containing CH 2 -COCg H 1 4

OCH

2

CHCH

2 0-&CH 2

OCH

2 CH_ Ci2 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 'o temperature to 400 millijoules/cm 2 radiation from a tc medium pressure mercury vapor lamp, after which the coated c substrate is removed. A completely homopolymerized protective coating having resistance to chemical attack is achieved.

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

A

i 1 l l 14 EXAMPLE 6 except glycol The general procedure in Example 2 is repeated, that 2 moles of monovinyl ether of triethylene are used. The product ft CC I C

C

4' 44 C 4- 4* 4 4 V 44 44 4 2CR2013 2 2 2211 2) 0-2 CHD 2 2 CH 3 C3 3 is obtained in at least 70% yield.

EXAMPLE 7 D.E.N. 438 Epoxy Novolac Resin (1095 4-hydroxybutyl vinyl ether (446.5 and potassium Ihydroxide 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 0 C. for 72 hours under a blanket of nitrogen. Greater than 90% conversion to a gel-like product comprising A 4 I AtICA A* 4

(I

''CC

4 44 .4 *4~444 4

OH

CH 2

-CHOC

4 H 8 OCH 2

CHI

OH

3 CHCH OC H OCHAAACH 2 was obtained.

15 EXAMPLE 8 D.E.N. 439 Epoxy Novolac Resin (1231.2 the monovinyl ether of triethylene glycol (352.3 and 3 g.

of potassium hydroxide are charged into a 2-liter flask.

I The solution is heated at 1200C. for 24 hours and then at 150°C. for 72 hours. Greater than 90% conversion to a gel-like product comprising

OH

CH

2

=CHOC

4

H

8 0CH 2

HCH

2 o cH( c) 1-3 )CH)C 2 C CH 2 OCH 2 H- 2 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 l-[[[[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 120O-for 24 hours and at a 1500 for an additional 48 hours after which heating was discontinued. Greater than 99% conversion is obtained. A product having the formula 2c 4CHg OCoCHCH 2

M

2 cC 2

C

2 8 4 C N OH v C8 3 on according to NMR, is recovered.

Yri -16 EXAMPLE 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 .I resin) of Example 9. Also, decafluorohexanol is substituted for heptafluoropentanol in Example 9. About 100% conversion is achieved. A product having the structure c2 C H 2 C

OC

2 C2 12

-OC

H 2 H C H 2(CF 2 4CF 3 OH H H H O o 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 S',,corresponding product is recovered.

Example 9 is repeated with substitution of each of the following alcohol reactants: I HOC 2

H

4

C

6 FI3, HOC 2

H

4

C

8

F

1 7'

HOC

2

H

4

C

10

F

21 and HOC 2

H

4

C

12

F

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

1 a 17 EXAMPLE 12 Exaiple 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

CF

3

(CF

2 2

C

2

H

4

CH

2

CH-CH

2

OCH=CH

2

OH

is recovered.

EXAMPLE 13 S| Into a one liter flask equipped with a mechanical /o stirrer, nitrogen inlet, thermometer and a condenser Sattached 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 S' hydroxide pellets. The mixture is heated at 1200 for 24 hours and at a 1500 for an additional 48 hours after which heating was discontinued. Greater than 99% conversion is obtained. A product having the formula caoCaCHOC OaCHCHCr 2 0-d40o CH2CHo-1r.4- c"^ SCH 3

OH

according to NMR, is recovered.

I

-I

4.,l -18- 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/cm 2 radiation from a medium pressure vapor lamp provide a cured soil and stain resistant barrier.

OC C

CC

(Ct CC tC' Ct t s :1 1~ 6! i i i

Claims

2. The compound of claim 1 wherein R' is each alkylene and R" is C 1 to cC 4 alkylene.
3. The compound of claim 1 wherein R' is alkylene and R" is an oligomeric radical having the formula -R-O-CH 2 CCH 2 (O Q A OCH 2 CHCH 2 )n'O A OCH2- OH 7 OH I S .B)m (B)m (B)m (B)m m has a value of from 0 to 4 and n' has a value of from 2 to 4.
4. The compound of claim 1 wherein m is 0; n has a value of 0 or 1 and A is -CH 2 or -C(CH 3 2
5. The compound of claim 4 wherein R is alkylene.
6. The process for synthesizing the compound of claim 1 which comprises contacting a fluorinated alcohol having the formula CF 3 (CF 2 )tR'OH S 1N:\LIBXX10368:JJN Ls 1 1 1 f," with a vinyl ether epoxide having the formula CH 2 -CHR"OCH=CH 2 'O 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 500 to about 160 0 C for a period of from about 2 to about 50 hours.
7. The process of claim 6 wherein R' is alkylene.
8. The process of claim 6 wherein said vinyl ether epoxide is [(vinyloxy)methyl] oxirane.
9. The process of claim 6 wherein R" of said vinyl ether epoxide is -R-O-CH 2 CHCH 2 (O -A OCH 2 CHCH 2 )nO Q -A -OCH 2 OH y W OH I (B)m (B)m (B)m (B)m
10. The process of claim 9 wherein A is 2 r m is and n The process of claim 9 wherein A is -CH2- or -C(CH3)2-; m is 0 and n J 4 i I rI C N I( 4 r I 41 N, has a value of 0 or 1.
11. A compound as defined in claim 1 and substantially as herein described with reference to any one of the Examples. Dated 5 July, 1995 ISP Investments Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON I- I 41 V, 0 6: a a'r ii i IN:\LIBXXIO0368JJN ABSTRACT Vinyl Ethers Synthesized from Hydroxylated Vinyl Ethers and Polyepoxides 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 bishphenols 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. t c I t Cf It 4 r i t *«KI *i In: Iibxx0O36S:SEF