CA2027918A1

CA2027918A1 - Vinyl ethers

Info

Publication number: CA2027918A1
Application number: CA 2027918
Authority: CA
Inventors: James A. Dougherty; Kou-Chang Liu; Fulvio J. Vara; Paul D. Taylor
Original assignee: GAF Chemicals Corp
Current assignee: GAF Chemicals Corp
Priority date: 1989-10-20
Filing date: 1990-10-18
Publication date: 1991-04-21
Also published as: EP0496828A4; WO1991005814A1; AU646824B2; AU5389394A; AU6729890A; AU662670B2; EP0496828A1

Abstract

VINYL ETHERS
.

ABSTRACT

This invention relates to vinyl ethers (I) 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 C1 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 when p is one, and is or a mixture of and when p is greater than one;
vinyl ethers (II) 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 one of Y and Y' is while any remaining Y and Y' can be or . The invention also relates to the synthesis and uses of the above polyphenyl vinyl ethers; and fluorinated vinyl ethers (III) having the formula wherein t has a value of from 1 to 22; R' is C2 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 -CH2-, and where each of R1, R2, R3 and R4 is independently hydrogen or

Description

2 ~

VINYL ETHERS

BACKGROUND OF THE INVENTION

Certain radiation curable coatings and films such as those ~ormed from the acrylates, particularly propane trimethanol triacrylate, trimethacrylate, pentaerythritol triacrylate, and hPxanediol diacylate or methacryla~e, are in great demand because o~ 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 o~ nitrogen. Although formulation with a photoinitiator which undergoes bimolecular reacti.on with a hydrogen donor minimizes the inhibitory effect o~ air, this benefit is realiæed 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 o~ 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 bene~icial properties of acrylates but which i5 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.

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THE INVENTION

Accsrding to this invention there is provided epoxy vinyl ethers haviny the formula (I) 2 ~)P~af C82~ 2CIICH2~n~ ~ ~ N2(Y3~p l ~ ) 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 is branched or linear C1 to C4 alkylene; B is halogen or lower alkyl;
m has a value of from O ~o 4; n has a value of from O to 20; p has a value of from 1 to 5 and Y is ~0~
-CH-CH2 when p is 1 and is -CH-CH2 or a mixture of~ .

-CH-/CH2 and -CH-CH20ROCH=CH2 when p is greater than O OH
one. Of the above defi~ed epoxy vinyl ethers, those wherein R is C to C6 alkylene, A is -CH2- or ~ C(CH3)2, m has a value of 0; n has a value of from o to 12 are pre~erred. Most preferred of this group are the products wherein Y is - \-~H2 and p is 1-5.

The method of synthesizing the above vinyl ethers (I) involves the reaction of a hydroxylated vinyl e~her reactant, ~HO~pROCH=CH2, and a diepoxy aryl hydroxyalkyl ether coreactant, C~ HCi~2 (o~A~oc~28HCH2)/~0~ 2 ~2 wherein R, A~ B, m, n and p are a~ de~ined.

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.- ~ -, .

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..

J a ;~
~ 3 ~

The mole ratio of reactants i5 critical and is the ratio where the number of epoxy groups in the reaotion mixture exceeds the number of hydroxy groups in the reaction mixture by at least one. Hence, wher the hydroxyvinyl ether reactant is (HO)3ROC~=C~2, the mole ratio of reactant to coreactant is between 1:2 and 1:3;
~hen (HO)5ROCH=C~2 is substituted, the ratio is between 1:3 and 1:5 and when HOROC~=CH~ 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 o~
air or in the absence of oxygen under a blanket o~ inert gas. Generally, the present condensation reaction is carried out at a temperature of between about 100 and about 175C. under atmospheric pressure ~or a period o~
from 0.5 to 200 hours. Preferred reaction parameters include a temperature of from about 120 to about 160C.
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 Prom about 0.01 to about 2 wt r % ~ preferably ~rom about 0.1 to about 1 wt. %
o~ the total mixture. When the reactan~s 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 o~ cyclohexanedimethanol, the monovinyl ether o~ tris-(hydroxymethyl) ethane, the divinyl ether of 2-ethyl-2(hydroxymethyl)1,3-propanediol, the divinyl ether of tris(hydroxymethyl) ethane, tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxypropyl) vinyl ether, the monovinyl ether o~ 3-ethyl-1,6-hexanediol, . . ,, :

,~
::

(4-hydroxybutyl) vinyl ether, the monovinyl ether of 2-methyl-1,8-octanediol, (vinyloxy) cresol, (vinyloxy) xylol and alkoxylated derivatives thereof containing ~rom 1 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 i~
substituted with halo or Cl 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.
Thase resins have the ~ollowing structure CH~ O--Ctll--C~--C?~o~3Cl~30--Ci`~. -CA--C~t~

These epoxy reactants are readily prepared by well known procedures, such as the procedure outlined on pages 10 through 21 o~ Chapter 2 of H~NDBOOK OF EPOXY R~SINS, 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 copolymerization~ can be carried out in the presence of air to produce highly desirable films and coatin~s which r~tain the desirable properties of both monomers or their polymerized derivative~ Curable compositions containing between about O and about 80% o~ a vinyl ether, an epoxide, an acrylate or a methacrylate 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 ar~ suitable radiation curable coatings which are polymerized by exposure to W light, electron beam, laser emission or other source of radiation. Between about 2 and about 50 wt. % oP the present product with from about 0.1 to about 5 ~t. % of a conventional photoinitiator, such a~ 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-1-phenyl-1-propan 1 one, 2,2-dichloro-1-(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 effeck 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 materials2 Curing of the present ~ompounds 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 W light, between about 0.5 and about 5 megarads of electron beam exposure or equivalent radiation exposures.

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According to another embodiment of this invention there is provided epoxy vinyl ethers having the ~ormula (II) CH29C~O~(O~ ~ ~2lHCH2O ~ H~[ ~ ~2]n ~ 0C~2( 0~
OC~2 ~Y) - P

wherein R is a polyvalen~ linear, branched or cyclic hydrocarbon radical having ~rom 2 to 20 carbon atom~, optionally substituted with alkyleneoxy; n ha~ a value of rom 1 to 20; p has a value o~ from 1 to 6; and at least one of Y and Y' is -CH-CH2 while each of any remaining Y
/ ~
and Y'can be -CH-CH2 or CHCH2OROCH=CH2. Of the OH
above de~ined 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 -CH-CH2 are pre~erred. 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 polyepoxy aryl hydroxyalkyl ether coreactant, of the ~ormula C~2 ~ C~20 ~ H2_[ ~ H~l ~ OC~2 ~ ~ 2 OCH CH ~ CH
~0/

wherein R, p and n are as defined.

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.

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.J,.~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 epoxy groups, -CH~CH2, 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 l,.there can be 21 epoxy GRoUPS/OH. In the latex 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 unraact2d epoxy groupsO
In another case where (HO)3ROCH-CH2 is the reactant and n in the coreactant is 6, the ratio of reactant to cor~actant 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 t-o 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 desixed.
In accordance with another embodiment of this invention there is provided a fluorinated vinyl ether (III) having the formula CF3(cF2)tRlocH2lHR'locH=cH~
OH

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"~' ' ' ' ' ~ " ', .

~ ~ ~ J~

wherein t has a value of from 1 to 22, R' is C2 to C20 alkylene, alkoxyalkylene, arylene or aryloxyalkylene which radicals are optionally fl~orinated; R" is a divalent radical having from 1 to 100 carbon atomR and is selected from the group of alkylene, arylene, alkarylene, aralkylene which groups are optionally substituted with lower alkyl or the radical OH ~ 2 ~C8cH2 ~ n~ c~2 ~8)m ~ ~ (3)~ 19)~E~

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 CH2 ~ ~c(CH3)2 and R~ R2 where each of Rl, R2, R3 and R~ is independently hydrogen or . -C6H4cH2 \-~H2 B is lower alkyl; m has a value of from 0 to 4 and n has a value of from 0 to ~0.
The above compounds can be synthesized according to following equation A.

CF3 ~CF2 ) tR' 0}~ ~ C~2--CHRUOCH¢H2 ~ CP3 (CP2 ) tR ' C~2 ~ HR"OCE~=CH2 . .
I II

, wherein R', R" and t are as defined. When coreactant II is an oligomer, as described ahove for R'!, e.g.
l-[ttt2,3-ePoxypropoxy]phenyl]alkyl]pheno~y]-3-~[vinyloxy]
alkoxy]-2-propanol, the reaction can be illustrated by equation B below.

3~ 2~tR Oi~ + CN2~C~IO~ c~l2cHcHa~ocH2c~c~2)n~H2c~cH~

~

CF3(CF2)t~ 0cH2cHcH2o~A~cH2lHc~2o~A~;o~nc82~cH2oRocH C~12 ( m t~)m I )m The synthesis is carried out under mild conditions such as a temperature of between about 50 and 160C. under atmospheric pressure for a period o~ from about 2 to about 50 hours, preferably at a temperature from 120 to about 150C. 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. % o~ 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 o~ inert gas such as nitrogen~

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Examples of the vinyl ether epoxide r2actant include [(vinyloxy) methyl] oxirane, [tvinyloxy) 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, penta~lusrohexanol, nonafluoropentanol, heptafluorodecanol, heptadeca~luorodecanol, 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 o~ equation B wherein n has a value o~ O 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 ~abrics, 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 surfac~s 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 effec~ed at room temperature under ambient pressure .
: `:: ` :

conditions by exposure to a source of radiation such as W
light, an electron beam, lazer emission and the like in the presence of from about 0.05 to about 5 w~. % of a photoinitiator. Suitable photoinitiators are the onium 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.
Tha amount of initiator employed is pre~erably between about 0.1 and about 2 wt. % with respect to reactantsO
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 W light or between about 0.5 and about 5 meg~rads 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 al~o be cured by conventional thermal prooesses employing a temperature of from about 50C. to about 160C.
Having generally described the inven~ion reference is now had to the accompanying examples which illustrate preferred embodiments which are not ko be construed as limiting to the scope of the invention more broadly defined above and in the appended claims.

EXAMPL~ 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 120C. for 12 hours and 150C. for :, . . . .

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48 hours under a blanket of nitrogen. Greater than 95%
conversion was obtained. The gel-like product containi~g CE12'CBOC4Bl30~2cElc~2 ~0~El3~:H2cHcEl2]o-2o~ (~CH2CH ~C~2 is recovered.
. .

Epon 828 epoxy resin (2 mole), monovinyl ether of cyclohexane trimethanol (l mole~ and potassium hydroxide (0.4 g, 85~ pellets) are charged into a 1-liter flask equipped as in Example l. The ~olution is heated at 145C.
for 40 hours. Greater than 95% conversion is obtained.
The gel-like product containing 2~0C9~1S02~ C~C1l2~ 2C~C82)o ~}~ o=2~C~212 i~ recovered.

EX~MPLE 3 Epon 826 epoxy resin (364 g, 1 mole), monovin~l 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 i~ heated at 120C. for 42 hours and at 150C. for an additional 10 hours under a blanket o~ nitrogen.
-.: . . . :

Greater than 95% conversion is obtained. The gel~like product containing C~2~0c8}~l4oc~2c~ ~20 ~CN2~c~2c~--c~2 is recovered.

EX~MPLE 4 The product of Example 1 is mixed with 1~ of triphenyl sulfonium salt of phosphorous hexafluoride coated on an aluminum panel in a thicknes~ 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 whîch the coated substrate is removed. A completely homopolymerized protective coating having resistance to chemical attack is achieved.

.
The procedure described in Example 4 is repeated except that 50% of tha product of Example 2 was prsmixed with 50~ o~ the divinyl ether of triethylene glycol. The coated substrate is complately cured in less than 1 second to a strong protective coatin~ having high resistance to chemical attack.

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The general procedure in Example 2 is repsated, except that 2 moles o~ monovinyl ether of triethylene glycol are used. The product S~ (C~2~20t3c~2c~ca2o~~0C~2~C~20~0-2 ~ ~ /\

is obtained in at least 70% yield.

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 ~lask equipped with a mechanical stirrerr.nitrog~n inlet, thermometer, a condenser and a drying tube. The solution was heated at 150C. for 72 hours under a blanket of nitrogen. Greater than 90% conversion to a gel-like product comprisin~

Hoc4~8ocH2c ~cH2o~ 2~ }l2)l-3~ocH2cE~c~2(:~c4H8oc}I CH2 OC}~2C~--~CHi was obtained.

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, .. , ,; .................. ~ . ' :

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D.E.N. 439 Epoxy Novolac Resin (1231.2 g.), the monovinyl eth~r of triethylene glycol (352.3 g.) and 3 g.
of potassium hydroxide are charged into a 2-liter ~lask.
The solution is heated at 120C. for 2~ hours and then at 150C. for 72 hours. Greater than 90% conversion ko a qel-like product comprising ' 0}~
cs2 -C~ aocR2~H2~)cH2~cE~2) 1 3~) ~\

OCH

was obtained.

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 ~ [~2,3-epoxypropoxy] phenyl]-2-propyl]-phenoxy]
-3-~vinyloxy] butoxy]-2-propanol, 1 mole of heptafluoro pentanol, and 0.5 gram o~ 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 ~he fo~mula ctl2D'CK~C4~ 2C~C~12~ 2cl~c~Gc2a4 ~C~2) 2C~3 according to NMX, is recovered.

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EX~MPLE 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~ conversio~ is achieved. A product having the structure CN2-CUOC~ 0CH2CHCH2-1O~ 2~ 2 12~ oC~2~Hc~2oc}~ F2)4cF3 H 0}~

is recovered.

Example 9 was repeated except that heptadecyl fluorodecanol was substituted for heptafluoropentanol of Example 9. About lO0~ conversion was achieved. The corresponding product is recovered.
Example 9 is repeated with substitution of each of the following alcohol reactants:

HOC2H4C6F13 ' HOC2~4C8F17 ' H0c2H4cloF2l and H0C2H4Cl2F25 In each case about 100% conversion i5 achieved and the corresponding products are recovered.

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C~ "' $ '~ fP

Example 9 is repeated except that [(vinyloxy) methyl] oxiran~ is substituted for Epon 828 in Example 90 About 100% conversion is achieved and a product having the structure CF3(cF2)2c2H4ocH2lH_~H20~=CH2 OH

is recovered.

Into a one liter flask equipped with a mechanical stirrer, nitrogen inlet, thermometer and a conden~er attached to a drying tube, is introduced 377 grams (1 mole) of Epon 828 epoxy resin, 107 grams (0.5 mole~ of heptafluoro pentancl, 58.1 gram (0.5 mole) o~
4-hydroxybutyl vinyl ether and 0.5 gram o~ 85% potassium : ~ hydroxide pellets. The mixture i5 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 ~ormula C1~ 8 ~tCN2C~lK Z 5 ~ C113 OCH21 C~2-1~ f~ f 0-OC~112c~cl320c2a4 ~2~ 2 3 according to NMR, is recovered.

.: .

. .
.

c~ 3 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 ~rom a medium pressure vapor lamp provids a cured soil and stain resistant barrier.

:
:., . . ~ .

.

Claims

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 C1 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 when p is 1 and is or a mixture of and when p is greater than one;

the compounds (II) having the formula 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 o~ Y and Y'is while any remaining Y and Y' can be or ;

and the compounds (III) having the formula:

wherein t has a value of from 1 to 22; R' is C2 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 -CH2-, and whare each of R1, R2, R3 and R4 is independently hydrogen or B is lower alkyl; m has a value of from O to 4 and n has a value of from O to 20.

2. The compound of Claim 1 wherPin in (I) R is a C2 to C6 aliphatic hydrocarbon, A is -CH2- or , 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 C6 aliphatic hydrocarbon, n has a value of from 1 to 12 and Y and Y' are each .

4. The compound of Claim 1 wherein in (III) R' is each alkylene and R" is C1 to C4 alkylene.

5. The compound .

6. The compound .

7. The compound .

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 (HO)pROCH=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°C. 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 , 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 -CH2-, 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 comonomer 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 (HO)pROCH=CH2 and a polyepoxy aryl hydroxyalkyl ether coreactant of the formula 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 pxesence 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 dimethansl.

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 l 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 presance 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.