CA2075367A1 - Vinyl ether compounds - Google Patents

Abstract

Alkenyl ether carbonates having formula (A) wherein A is RHC=CHO(B)n-, lower alkyl or a mixture thereof; B is (a) divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or polyalkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy; R is hydrogen or lower alkyl and n is from 1 to 10. These are provided alkenyl ether polycarbonate, a polymerizable compound formed from reaction of a dialkenyl ether monocarbonate and a polyhydroxy alcohol having at least three hydroxy groups, a polymerizable compound formed from the reaction of a hydroxylated polymeric polyether, polyurethane, polycarbonate, polyester of an alkanedioic acid or polybutadiene and a dialkenyloxy carbonate co-reactant, and polyaryloxypolyvinyl ethers. The polymerized compounds are intermediates for hard abrasion resistant films and coatings. The monomers and oligomers are intermediates for hydrogels or photoresist materials.

Description

207~31J 7 VINYL ETHER COMPOUNDS

Alkenyl ether carbonates having the formula A-OCO(B)nOCH=CHR tA) wherein A is RHC=CHO(B)n-, lower alkyl or a mixture thereof; ~ is a divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or polyalkoxylated alkylene, alken~lene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy; R is hydrogen or lower alkyl and n has a value of from 1 to 10.
Preferred species of these alkenyl ether carbonates are those wherein n has a value of one and A is RHC=CHO(B)n-, where B is butylene or dimethylene cyclohexane or A is methyl or ethyl and B is butylene.
Most preferred of this group are those wherein R is hydrogen.
There is also provided alkenyl ether polycarbonates having the formula o O
A-OCO[R"(OR")mOCO]nROCH=CHR' (B) wherein A is R'HC=CHOR-, lower alkyl or a mixture thereof;
R and R" are each independently a divalent radical having from 2 to 20 carbon atoms and are selected from the group of alkylene, mono- or poly- alkoxylated alkylene, alkenylene, alkynylene, arylene, alXarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy; R' is hydrogen or lower alkyl; (n) has a value of from 1 to 10 and (m) has a value of from 0 to 10; with the proviso that R" contains at least 3 carbon atoms when m is zero.

20~S3~7 W091/1~2 PCT/US91/~

Preferred species of the present alkenyl ether polycarbonates are those wherein R' is hydrogen and A is R'HC=CHOR- or -CH3; R is C2 to C8 alkylene; R" is C2 to C6 alkylene; m has a value of from 0 to 6 when R"
contains at least 3 carbon atoms and m has a value of from l to 6 when R" contains 2 carbon atoms.
Also provided is a polymerizable compound having the formula ~ O-R'HC=CHO(B)m-OCO- R"(OH)n-b (C) b which is the reaction product-:of a p~ly~ydroxylated reactant (I) having the formula ROH and a dialkenyloxy carbonate coreactant (II) having the formula:

R'HC=CHO(B)mOCO(B)mOCH=CHR' wherein R is a C3 to C50 saturated or unsaturated, linear, branched or cyclic polyhydroxylated hydrocarbon radical optionally substituted with halo, alkoxy, lower alkyl, cyano or nitro;
R' is hydrogen or lower alkyl R" is the same as R except that it contains at least one less hydroxy group.
B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono- or poly- alkoxylated alkylene, .: , 2Q7~3~7 WO91/13052 PCT/US9l/0~39 alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals ar~ optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy (m) has a value of from 1 to 10; (b) has a value of from at least 1 up to the number of hydroxy groups in ROH and (n) represents the number of hydroxy groups in ROH, generally from 3 to 10 hydroxy groups.
Polyhydroxylated reactant (I) contains at least 3, preferably not more than 10, hydroxy ~roups and includes hydroxylated derivatives of alkylene, alkenylene, alkynylene, arylene, alkarylene, aralkylene and ethoxylated or propoxylated species of these radicals. Specific examples of hydroxylated reactant (I) are represented by trihydroxy benzene, trihydroxy nitrDhen2ene, tetrahydroxy diphenyl dimethyl methane, hexahydroxy diphenyl methane, tetrahydroxy styrene, tetrahydroxy--tolu~ne, dichlorotrihydroxy benzene, trihydroxy cyanomethyl benzene, dinitrotrihydroxybenzene, hexahydroxy anthranol, and alkoxylated derivatives thereof 1,2,5,7,9-penta-hydroxynonane, 1,2,4-trihydroxybutane, 4,5-dichloro-1,3,6,10-tetrahydroxydecane, decahydroxy tetracosane, decahydroxy pentacontane, 1,2,11,12-tetrahydroxy dodec-6-yne, 3,5-bromo-1,2,13,14-tetradecane, trimethylol ethane, trimethylol propane, 3-ethoxy-1,2,4,5-tetrahydroxypentane, pentaerythritol, starches, cellulose, sugars and alkoxylated drivatives thereof.
The dialkenyloxy carbonate coreactants (II) are preferably those wherein R' is hydrogen or methyl, m is 1 and B is butylene, dimethylene cyclohexane or ethoxylated or propoxylated derivatives thereof.

2 ~
W091/13~2 PCT/US91/0~_ -- 4 -- .

Examples of suita~le coreactants include bis(ethenyloxy butyl) carbonate, bis(ethenyloxy dimethylcyclohexyl) carbonate, bis(prop-l-enyloxy butyl) carbonate, and the polyethoxylated or polypropoxylated derivatives thereof, such as for example the polyethoxylated derivative of bis(ethenyloxy butyl) carbonate, having the formula [CH2=CHOC4H8(0CH2CH2) 3 -oco-wherein p has a value of from l to l0.
Also provided is a pclymerizahle compound having the formula (D) r 0l l R'HC=CHO(B)m-OCO-~ -R-(A)a I.
2-a which is the reaction product of a hydroxylated reactant (I) having the formula A-ROH and a dialkenyloxy carbonate coreactant (II) having the formula:

O
R'HC=CHO(B)mOeO(B)mOCH=CHR' II.

wherein R is a polymeric radical selected from the group of polyester, polyacetal, polyurethane, polyether, polybutadiene and polycarbonate, said polymers containing from about l0 to 50 repeating monomer units;
A is hydrogen, lower alkyl or hydroxy;
R' is hydrogen or lower alkyl;

`' 2~3~7 W091/13052 PCT/US91/~639 _ 5 B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or poly alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy (m) has a value of from l to l0; ~a) is zero when A is hydroxy and (a~ is one when A is hydrogen or lower alkyl.

Reactant (I), AROH, includes hydroxylated compounds having the formulae:

O o HO[(R'''OC-R"-~O)nOR''']OH, a p~lye~ter;

O O
HO[(R'''-OChHR"NHCO)nOR' "]OH, a polyurethane;

X X
H(OCH2CH)nOH, alkyl(OCH2CH)nOH and HO[(CH2)40 ~H, polyethers;

H[(OR"OC)nOR"]OH, a polycarbonate;

H[OR'''OClHOR"OCH)nOR''']OH, a polyacetal, etc.

WO91/13052 2 ~ 7 5 3 ~ 7 PCT/USg1/o~

In the above formulae, X is hydrogen or methyl; R"
i5 C2 to C20 alkylene or arylene; R''' is C2 to C20 alkylene and n has a value of from about l0 to 50. Of these hydroxylated polymers, the polyethers, polyesters, polycarbonates and polyurethanes are preferred.
An aryloxy polyvinyl ether also is provided having the formula (E) CH20ROC8=CE~2 CH2=CHORO-CR2 CHCH2- L--~OC~i2CHCH2~ ~}A~OC}I2CH

wherein R is a linear, branched or:cyclic radical having from 2 to 20 carbon atoms and is selec~ed from the group of alkylene, alkyleneoxy alkylene, polya,kylene~xy alkylene, arylene, alkarylene, alkarylalkylene and aralkylene; X is oxygen or sulfur; A is branched or linear alkylene having from l to 20 carbon atoms; B is halo or lower alkyl; n has a value of from l to 20 and p has a value of from 0 to 4.
The invention also relates to the preparation and use of said aryloxy divinyl ethers.
Preferred compounds are those wherein X is oxygen;
A is >C(CH3)2; p is zero; n has a value ~f fro~ l to 4 and R is a radical having from 2 to 8 carbon atoms.
The above carbonates (A) are synthesized by reacting a hydroxylated al~-l-enyl ether with a dialkyl carbonate according to the following equation.

O O
x HO(B)nOCH=CHR + R'OCOR' `A-OCO(B)nOCH=CHR + x R'OH

REACTANT I REACTANT II PRODUCT III

.

.: ' ~3~S7 WO91/1~2 PCT/US91/00639 wherein x is l or 2; each R' is represented by lower alkyl and R, A, B and n are ac defined above. The reaction is carried out under mild conditions such as a temperature of between about 65C. and about 150C. under a pressure ranging from about atmospheric to about 50 psig. for a period of from about l to about 30 hours, preferably at a temperature of between about 75 and about 125C. under ambient pressure for a period of from about l.5 to about lO
hours. This reaction is effected in an oxygen-free atmosphere under a blanket of inert gas, e.g. nitrogen.
The reaction is promoted with between about O.Ol and about 5 wt. %, preferably between about 0.3 and about 2 wt. % of a base catalyst including such catalysts as sodium or potassium alkoxides, particularly methoxides; sodium or potassium metal; sodium or potas~ium hydrQxide, hydride or phenoxide, alkaline earth metal hydr~xides or alkoxides and alkaline or alkali earth salts of reactant I.
Generally, the ratio of reactant I to II can vary within the range of between about l:5 and about 15:l, preferably between about l.2:l and about 5:l. Although the reaction does not require the use of a diluent, an inert liquid at a concentration of up to 50 wt. % of the reaction mixture can be employed. Suitable diluents include toluene, xylene, ben~ene, alkyl ethers, N-methyl-pyrrolidone, butyrolactone, ethyl acetate and the like which are normally liquid and have a boiling point below that of the reaction product.
It is found that the product composition can be varied depending uyon the initial ratio of reactant I with respect to reactant II. Specifica]ly an excess of reactant II produces a moncsubstituted carbonate wherein A is lower alkyl; whereas an excess of reactant I produces a disubstituted product wherein A is RCH=CHO(B)n-.

W091/13052 ~ PCT/US91/00~

Alternatively, the compounds of this invention where A is lower alkyl can be prepared by reacting a Cl to C6 alcohol with a divinyloxy carbonate according to the equation:

~1 O
R'OH + RHC=C~O(B)n~OCO~(B)nOCH=CHR -)RHC=CHO(B)n-OCO-R' The present polycarbonates (B) are synthesized by reacting a hydroxyalkyl alk-l-enyl ether, a diol and a dialkyl carbonate according to the following equation.

o o o HOROCH~CHR' l HOR"OH + R~OR"I_~.A-OClJtR'-t~ mOCO]nROCH~CHR' ~ R~H

REACSANS I REACl'ANT ~I REACTANT III PROD~lCr wherein each R " ' is represented by lower alkyl and R, R', R", A, m and n are as defined above.
Generally, the mole ratio of reactant I to II to reactant III can vary within the range of between about l:l0:20 and about l:0.5:2, preferably between about 4:l:4 and about 2:l:2. Although the reaction does not require the use of a diluent, an inert liquid at a concentration o~
up to 50 wt. % of the reaction mixture can be employed.
Suitable diluents include toluene, xylene, benzene, alkyl ethers, N-methylpyrrolidone, butyrolactone, ethyl acetate and the like which are normally liquid and have a boiling point below that of the reaction product.
It is found that the product composition can be varied depending upon the initial ratio of reactants I, II
and III. Specifically an excess of reactant III produces polycarbonates wherein A is lower alkyl; whereas an excess :....................................... ~, ..... .
.

WO91/1~52 2~ 7 3 ~ 7 PCT/US91/~639 of reactant I produces a disubstituted product wherein A is R'CH=CHOR-. Also, n in the alkenyloxy polycarbonate product largely depends on the mole ratio of reactant III
with respect to reactant II. Thus, where a high proportion of III is employed, the value of n is increased.
Conversely, where a low proportion of III is employed, the value of n is low.
Alternatively, the dialkenyloxy dicarbonate products can be prepared by reacting the diol (HOR"OH) with a dialkenyloxy monocarbonate (A) above. The reaction conditions for this alternative reaction are substantially the same as those described above except that the mole ratio of diol to carbonate reactan~:is..about 1:2. This reaction can be defined by the ~equati~

HOR"OH + R'HC=CHOROCOROCH=CHR' O O
R'HC=CHOROCOR"OCOROCH=CHR' The reaction for synthesizing the above compounds (C) is conducted in the presence of between about 0.0l and about 5 wt. %, preferably between about 0.l and about l wt.
% of a basic catalyst such as particulate sodium, potassium or lithium metal, sodium, potassium or lithium hydroxide, hydride or alkoxide, e.g. methoxide, and the like. The reactants may be diluted with up to 80% of a suitable inert solvent such as xylene, toluene, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, etc. Although dilution is usually recommended for more viscous reaction mixtures, it is also within the scope of this invention to carry out the react1on in.the absence of solvent.

WO9l/13052 2 ~ 7 ~ ~ ~ 7 PCT/US91/~6~

The reaction conditions include a temperature of from about 50 to about 200c., a pressure of from about 1 mm Hg to about 100 atmospheres for a period of from about 0.5 to about 24 hours. Within the above operating parameters, between about 90 and about 120C. under from about 1 to about 10 mm Hg for a period of from about 3 to about 7 hours are preferred. High conversions in excess of 80% are achieved by the present reaction.
The ratio of polyhydroxylated reactant to dialkenyloxy alkyl carbonate is as close to stoichiometry of the product desired as is convenient to maintain.
Desirably, the amount of dialkenyloxy alkyl carbonate varies from about 1 to about 2 moles of carbonate per equivalent of hydroxyl groups. However, it is to be understood that excess amounts of the alkenyloxy alkyl carbonate, up to about a 10 mole excess, can be employed without detriment to the reaction; the only objection being that such high excesses of the carbonate reactant are wasteful and inefficient.
The crude product of the above reaction generally contains a mixture of products. Thus for example when ROH
is HOCH2-CH(OH)CH(OH)CH2OH the crude product contains one or more of the following derivatives, depending upon the amount of coreactant employed.

R'HC=CHO(B)mOCO-R(OH)3 [ R'HC--CHO~B)mOgO3 ~ R(OH)2 ... , . ~.;;
;,.
.
, 20753~7 R'HC=CHO(B)mOCO ~ ~

. ~ O-- ..
R'HC=CHO(B)mOCO- 4 _~_ The products can be separated by any conventional means, e.g. fractional distillation, if desired.
The synthesis of the present carbonate products (D) is expressed as follows:

AROH + R'HC=CHO(B)mOCO(B)mOCH=CHR' [R'HC-CHO(B)m-OC0]2_aR(A)a + R'HC=CHO(B)mOH

The dialkenyloxy alkyl carbonate coreactants (II) are the (A) compounds described above and are preferably those wherein R' is hydrogen or methyl, m is l and B is butylene, dimethylene cyclohexane or ethoxylated or propoxylated derivatives thereof.
Examples of suitable coreactants include bis(ethenyloxy butyl) carbonate, bis(ethenyloxy dimethylcyclohexyl) carbonate, bis(prop-l-enyloxy butyl) carbonate, bis(l-propenyloxy phenyl) carbonate, bis(ethenyloxy benzyl) carbonate, bis(ethenyloxy xylyl) carbonate and the polyethoxylated or polypropoxylated derivatives thereof, such as for example the polyethoxylated derivative of bis(ethenyloxy butyl) carbonate, having the formula i WO91J1~2 2 ~ 7 ~ 3 ~ 7 PCT/US91tO06 [cH2=cHOc4H8(ocH2cH2)p~ OCO

wherein p has a value of from 1 to 10.
The above divinyl ethers (E) are synthesized by reacting a hydroxyvinyl ether with a diepoxide of a bisphenol such as bisphenol A epoxy resin, or a bisphenol F
epoxy resin. The reaction is effected according to the following equation.

C82~CHOROH + CH2--CHCH~{ ~ } ~ 2~Ca2~ ~ } ~ C82CE~
~B) p ~B) p (3) p (8) p CH20ROCEI--CH2 CH2=cHoRo-cH2 C~2Ca2~~ca2caca2~ ~oca2c~

' ,.

.~: :
, . ! , . . . .
. ' ' . , ' ' ~ , , ,. ' ' . ~ ~ .' ' ` , . ,' ;' ' . ' ' . ' ' ' ' 2 3 ~ ~ 3 ~ ~
WO9l/13~2 PCT/US91/00639 The synthesis 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 175C. 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 160C.
for a period of from about 2 to about lO0 hours.
The reaction is also conducted in the presence of a base catalyst such as particulate sodium, potassium, or lithium ~etal, sodium or potassium hydroxide or hydride.
The catalyst is present in an amount of from about 0.01 to about 2 wt. ~, preferably f~om abQut:0 1 to about 1 wt. %
of the total mixture. When;th~ ~eactants and products included herein are liquids,- t~y-are generally synthesized in the absence of diluents or solvents which are otherwise required for more viscous or solid reactant~. Suitable solvents include toluene, xylene, triethylene glycol dimethyl ether, N-methylpyrrolidone and the like. Such solvents can be employed in concentrations up to about S0%
of the reaction mixture.
The hydroxy vinyl ether reactant and the phenylic coreactant of the present process are generally employed in a mole ratio of from about 1:1 to about 10:1, preferably from about 1.05:1 to about 3:1.
Suitable hydroxylated vinyl ether reactants include the mono vinyl ether of cyclohexanedimethanol, tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxypropyl) vinyl ether, the monovinyl ether of 3-ethyl-1,6-hexanediol, (4-hydroxybutyl) vinyl ether, 6-hydroxyhexyl vinyl ether, the monovinyl ether of 2-methyl-1,8-octanediol, (vinyloxy) cresol, vinyloxymethyl cyclohexyl methanol and alkoxylated derivatives thereof containing from l to 6 ethyleneoxy or propyleneoxy units.

:
.

2~7~3~7 WO91/13052 PCT/US~1/006~, Suitable coreactants include 1,3-{bis4-{2-[4-(2,3-epoxypropoxy)phenyl]prop-2-yl~phenoxy}-2-propanol, 1,3-bis{4-[4-(2,3-epoxypropoxy)benzyl]phenoxy}-2-propanol poly(phenylalkylphenoxy-2-propanol-3-oxy)epoxypropoxy epoxypropoxyphenylalkylphenyl and the like.

The initiators suitable to effect polymerization reactions of the present invention can also comprise a mixture including the above-~amed-.cat~onic initiators and a free radical initiator to pro~ide a hybrid initiated system. Suitable free radical initiators~include l~hydrocyclohexyl phenyl ketone (HPK), 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one (HMPP0), 2,2-dichloro-1-(4-phenoxyphenyl) ethanone (DPPE) and the like. When initiator mixtures are employed, the free radical component can comprise up to 75%, preferably between about 30 and about 70%, of the initiator component. The present cationic initiator or cationic/free radical initiator mixtures provide the benefits of this invention when used for cross-linking blends of the present vinyl ether carbonate and vinyl ether or epoxide monomers.
However, when the blend contains an acrylate polymerizable comonomer the initiator mixture is recommended. The total amount of initiator employed is generally between about 0.1 and about 5 wt. % with respect to reactant or reactants.
Usually, exposure for less than one second is suffic~ent to provide a completely cross-linked homopolymer or copolymer. W light radiation dosages at room temperature of from about 100 to about 1500 milli J/cm2 are effective and dosages of from about 200 to about 600 milli J/cm2 are preferred. Equivalent dosages for curing are employed when using alternative sources of radiation.

... .

. ~

2~753~7 For example, curing with electron beam radiation can be carried out at be'ween about 0.5 and about 20 Mrads, preferably between about 1 and about 10 Mrads. Specific techniques for radiation curing are well known, thus further amplification is not required.
As inferred above, the present products can be mixed with a vinyl ether, epoxide, acrylate or vinyloxy alkyl urethane monomer or polymer, or other monomers and oligomers which otherwise would not be amenable to cationic radiation curing, to incorporate and combine the advantages of instant compounds with the beneficial properties of those coating materials or other monomers and oligomers.
Examples of monomers or pol~mer~-with-.which the present products can be combined to fo~m-cc~tings include the 1,4-butanediol diglycidyl ether; ~,4-apoxycyclohexyl methyl-3~4-epoxy cyclohexane carboxylate; diglycidyl ethers of bisphenol A or bisphenol F; polyglycidyl ethers of phenol-formaldehyde, e.g. epoxy novolac resins and other functional monomers and polymers which possess properties beneficial in durabie protective coatings. When such comonomeric coatings are employed, the mixture contains at least 5% of the present alkenyl ether carbonate.
The homopolymerized and copolymerized products of this invention have high resistance to solvents, acids and bases and form hard abrasion resistant films and coatings, possessing good substrate substantivity. The individual products of this invention, as monomers or oligomers or as mixtures thereof are also useful as chemical intermediates and as materials which, upon hydrolysis, are capable of forming hydrogels. Also, because cf their high radiation sensitivity, the present compounds are suitable as photoresist materials.

2v7.j3~ ~
WO91/13052 PCT/US91/00~.

PREPARATION OF COMPOUNDS (A) A. A 250 ml three-necked round bottom glass flask, equipped with a thermometer, magnetic stirrer, distillation head, water condenser, receiver and a nitrogen inlet was charged with 116 g. (l mole) of hydroxybutyl vinyl ether, 45 g. (0.5 mole) of dimethyl carbonate and 0.5 g. of sodium methoxide. The mixture was heated under a blanket of nitrogen to 82C. for 2.5 hours. An azeotrope of methanol by-product, dimethyl carbonate and hydroxybutyl vinyl ether was distilled off at a head temperature of about 32C. The reaction mix.ure was then cooled and filtered. The separated flltrate (130 g.) was f-las~ distilled at 65-85C.
under 3 mm Hg. The resulting distillate was subjected to gas chromatography analysis which indicated 70% unreacted hydroxybutyl vinyl ether and 30~ product. Fractional distillation under 3 mm Hg resulted in a fraction separated at 150-160C. (34 g.) which was analyzed as 82.4%
bis~(ethenyloxy)butyl] carbonate and 15.7%
mono[(ethenyloxy)butyl] methyl carbonate. Four grams of methanol and dimethyl carbonate were collected in the trap.

'. .- .

' ' ' , :

WO9l~13052 2a7~3~7 PCT/US91/~639 B. The product fraction separated at 150-160C. was then evaluated for a radiation cured coating according to the following procedure. The product mixed with 2 wt. % of triphenyl sulfonium hexafluorophosphate was coated in about 0.15 mil thickness on an aluminum panel and then subjected to less than 1 second exposure at room temperature to 400 milli J/cm2 radiation from 2 medium pressure mercury vapor lamps. The cured coating had strong adhesion to the substrate and had excellent resistance to chemical attack from acids and bases.

EXAMP_LE 2 The procedure describe~ in Example 1 was repeated except that the reaction was carried out with an excess of dimethyl carbonate 100 g. (1.11 mole) of dimethyl carbonate together with 116 g. (1 mole) of hydroxybutyl vinyl ether and 0.5 g. sodium methoxide was charged into the reactor and progressively heated from 85C. to 110C. The reaction mixture was distilled over a 26 hour period at a head temperature of from 40 to 63C. to remove 38.4 g. of methanol/dimethyl carbonate azeotrope. The filtered product t117 g.) was then distilled in an Oldershaw 5 plate column and the fraction separated (38.3 g.) at pot temperature of 112-125C. and head temperature of 59C.
under 1.5 mm Hg was analyzed and found to be 99% pure methyl [(ethenyloxy)butyl] carbonate, whose structure was confirmed by IR and lH and 13C NMR spectral data and elemental analysis.

2 ! 7 r ~ ~ 7 WO91/l30s2 PCT/US91/00~_, In the apparatus described in Example 1 was char~ed 250 g. ~2.15 mole) of hydroxybutyl vinyl ether, ~30 g. (1 mole) of dimethylcarbonate and 1 g. of sodium ~ethylate. The reaction mixture, under a blanket of nitrogen was heated for 18 hours at a head temperature of about 45C. to remove 39 g. of azeotropic distillate from the reaction pot containing 48% hydroxybutyl vinyl ether, 46% bis[(ethenyloxy)butyl] carbonate and 4%
mono[(ethenyloxy)butyl] methyl carbonate. The pot temperature was gradually raised from 85C. to 148C. over a period of 18 hours and the product-mixture filtered to remove undissolved catalyst and 240 g. of filtrate, containing CH2 CHO(cH2)4oco(cH2)4ocH=cH2 product was collected.

Example 3 was repeated using a 2 liter glass flask, except that 1000 g. (8.6 moles) of hydroxybutyl vinyl ether, 360 g. (4 moles) of dimethylcarbonate and 4 g.
of NaOCH3 were charged and heated under a blanket of nitrogen. In this example 243 g. of the azeotrope were removed at a head temperature of 28-65C. Also, the pot temperature was gradually increased over a 27 hour period.
The reaction product was filtered and the resulting product mixture was found to contain 34%
hydroxybutyl vinyl ether, 5.5% mono[(ethenyloxy)butyl]
methyl carbonate and 58% bis[(ethenyloxy)butyl] carbonate.

.

.

~7~357 WO91/130s2 PCT/US9t/00639 This product CH2=CH(CH2)4C(CH2)4CH=CH2 tlO70 g.) was then combined with 240 g. of the product obtained in Example 3 and 1295 g. of the combined product mixture was fractionally distilled in a 15 plate column Oldershaw distillation apparatus at a pot temperature of 110 to 180C. and a head temperature of 70-76C. under 5-7 mm Hg to recover 385 g. of hydroxybutyl vinyl ether of 99% purity. Upon further heating, the fraction collected at the pot temperature of 185-~lQC and head temperature of 143-145C. under 1 mm Hg (T67 ~. ) was found to be 99.7%
pure bis[(ethenyloxy)butyl]-c3r~cn~e. During the distillation unreacted hydroxybutyl vinyl e~her reacted with the mono[(ethenyloxy)butyl] methyl carbonate product to increase the bis[(ethenyloxy)butyl] carbonate content from 730 g. to 767 g. of 99% purity. The product was established with IR, 1H and 13C NMR spectra and elemental analysis.

Example 4 was repeated except that a charge of 900 g. of hydroxybutyl vinyl ether, 472 g. of diethylcarbonate and 4.1 g. of NaOCH3 was s~bstituted.
Also, the resulting mixture was heated at a pot temperature gradually increasing from 115 to 155C. over 28.5 hours.
The head temperature varied from 42C. to 100C. The corresponding ethanol/diethylcarbonate azeotrope (318 g.) ~as removed. The remaining product mixture was found to be 20% hydroxybutyl vinyl ether, 14.8% mono[(ethenyloxy)butyl]
ethyl carbonate and 63.5% bis[(ethenyloxy)butyl] carbonate.

WO91/13052 2 ~ 7 ~j 3 i~ 7 PCT/US91/00~.~

After filtering this product mixture and distilling as described in Example 4, the major fraction (572 g.) boiling off at 143-144C. under 1 mm Hg (pot temperature of 185-200C.) was found to be 99.2% pure bis[(ethenyloxy)butyl~ carbonate. A minor fraction (218 g.) boiling off at 160C. under 2.5 mm Hg (Pot temperature of 190C.) contained 97% bis[(ethenyloxy)butyl] carbonate and about 3% hydroxybutyl vinyl ether. A lighter fraction (75 g.) taken off at 66C. under 4-5 mm Hg (pot temperature of 130-190C. ) was found to be 95% pure hydroxybutyl vinyl ether.

The product from Exam~l-e 4 was mixed with an equal weight amount of a diglycidyl et~er of hisphenol A, 1 part 2er hundred parts of resin of a fluorochemical surfactant, and 4 parts per hundred parts of resin of a cationic photoinitiator at 50C. until a homogeneous low viscosity liquid was obtained. This mixture was then coated on an aluminum substrate at a thickness of 1.2 mil. The coated surface was exposed for less than 1 second to 400 millijoules/cm2 from a mercury vapor lamp. A tack free, film was produced. Coating properties reported in the following table were determined immediately after W
exposure and after a post cure at 177C. for 15 minutes.

TABLE

After W After Property xposure Post Cure Pencil Hardness (ASTM D 3363) 2B 2H
% Adhesion (ASTM D 3359)0 100 Double MEX Rubs 49 >100 Reverse Impact - 30 Mandrel Bend ~in.) (AS~M D 3111) 1/8 1/8 ;

wo gl/l3052 ~ 3 S 7 PCT/US91/00639 The mixture described in Example 6 was coated on a polyester substrate at a thickness of 0.5 mil. The coated c;urface was exposed to 400 millijoules/cm2 W light for less than 1 second and post cured for 2 hours at 50C.
Chemical resistance was tested by the covered spot test ~ASTM D 1308). ~o attack was observed after 24 hours exposure to 1% H2SO4, 1% NaOH, 10% acetic acid, or distilled water.

The product from Ex~pl~ 4 (2.5.0 gm) was mixed with the divinyl ether of triethylen~.glycol (25.0 gm) a bisphenol A epoxy acrylate oligomer, 2 ~hr* cationic photoinitiator, 2 phr* free radical photo-in;tiator and 1 phr* fluorochemical surfactant at 50C. until a homogeneous low viscosity liquid was obtained. this mixture was then coated on a polyester substrate at a thickness of 0.5 mil.
The coated surface was exposed to 400 millijoules/cm2 from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced.

Pencil Hardness 3H
Adhesion 100%
Double MEK Rubs >100 *parts/100 parts resin WO9l/l30s2 2 0 7 ,3 3 ~3 7 PCT/USg~ J

EXAMPLE g The product from Example 4 (12.5 gm) was mixed with the divinyl ether of triethylene glycol (12.5 gm) and a divinyl ether urethane oligomer (25.0 gm); 4 phr cationic photoinitiator, and 1 phr fluorochemical surfactant at 50C. until a homogeneous low viscosity liquid was obtained. This mixture was then coated on a aluminum panel (0.50 mil) and exposed to 400 millijoules/cm2 from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced Pencil Hardness 3B
Mandrel Bend 3~8 inch Double MEK Rubs 18 PREPARATION OF COMPOUNDS (B) A 500 ml, round bottom flask was charged with 30 g of triethylene glycol (0.2 mole), 105 g bis(ethenyloxy-butyl) carbonate (0.41 mole) and 0.1 g sodium methoxide.
The flask was heated under vacuum of 3 mm Hg at 100-105C.
in a Kugelrohr apparatus for a period of 4.5 hours, after which a total of 44.3 g of distillate was collected. The distillate was analyzed by gas chromatography (GC), and identified as a mixture of 95% hydroxybutyl vinyl ether, 3.8% bis(ethenyloxybutyl) carbonate and 0.8~ triethylene glycol.
The residue containing carbonate product weighed 90 g. To the residue was added 2 g Nuchar charcoal and the mixture was heated to 60C. under vacuum for 30 minutes and filtered.

2,~3;~7 WO91/1~52 PCT/US91/00639 The filtrate was a colorless liquid, weighing 83.0 g (yield of about 90%). lH NMR and IR data identified the product as having the structure O O
CH2=cHoc4H8oco (CH2CH2o) 3COC4H80CH CH2 The IR spectrum showed absence of OH frequency. About 98%
conversion was achieved.

Example l was repe~t~d e~r~pt that 21 g of diethylene glycol (0.2 mb~é) was used-in-the place of 30 g triethylene glycol.
The flask contents-~ere heated under vacuum, 3-5 ~m Hg at 100C. for a period of 4.5 hours and 43.1 g distillate containing a mixture of hydroxybutyl vinyl ether and the carbonate reactant was removed.
The contents of the flask was worked up as described in Example l. The filtrate was a clear colorless liquid weighing 83.3 g indicating about 90% yield.
IR spectrum analysis of the product showed total absence of OH signals. lH NMR and IR data identifed the product as having the structure O O
CH2=cHoc4H8oco(cH2cH2o) 2COC4H80CH CH2 More than 99% conversion was obtained.

WO91/13052 2 a I 3 3 ~ ~ PCT/US91/~639 A 500 ml round bottom flask was charged with 36 g butenediol (0.41 mole), 220 g bis(ethenyloxybutyl) carbonate (0.85 mole) and 0.4 g sodium methoxide. The procedure described in Example l was repeated except that the flask was heated at 100C. under vacuum of 6 mm Hg for 2 hours.
During this period, 166.5 g of distillate was collected. The reaction mixture was heated at 130C. under O.5 mm Hg vacuum, until distillation ceased and an additional 12.5 g of distillate was collected.
The pot content was worke~ u~ as described in Example 1 except that only 1 g of char~oal was used. A
colorless viscous liquid (67 g) which solidified on standing was obtained. The product was identified by lH
NMR and IR spectral data as having the structure O O
Il 11 CH2=CHGC4H80CoCH2CH=CHcH2ococ4H8ocH=cH2 A 500 ml round bottom flask was charged with 28.8 g cyclohexane dimethanol (0.2 mole), llO g bis(ethenyloxybutyl) carbonate (0.43 mole) and NaOCH3 0.2 g. The procedure desc~ibed in Example l was repeated except that the reaction mixture was heated at 100C. for only 2.5 hours. Recovery of distillate (65.9 g) was found to contain a m~xture Gf reactants, (~bout 20.0 g of bis(ethenyloxybutyl) carbonate) and 43.5 g of bis(hydroxybutyl vinyl ether).

~ ~ 7 ~ t~, ~
WO91/130s2 PCT~VS91/00639 The residue was worked up as in Example 1 with 1 g charcoal (Nuchar) heated to 90C. for 30 minutes and filtered. The filtrate was a clear colorless viscous liquid weighing 62 g. IR and lH NMR spectral data identified the product as having the structure O O
CH2=cHoc4H8ococH2-c6Hlo-cH2ococ4H8ocH CH2 IR spectrum showed total absence of OH frequency.
Greater than 98% conversion was achieved.

EX~MPIE 5 The product from Example 4 (46.7 g) ~as charged into a 100 ml round bottom flask and heated to 130C. under a vacuum of 3 mm Hg for 1 hour. Distillate welghing 5 g, primarily bis(ethenyloxybutyl carbonate) was removed.
Spectral analysis of the pot content showed oligomerization of Example 5 product, i.e.

O O
CH2=cHoc4H8oco ( CH2 -C6Hlo~CH20CO) 2 _3C4H80CH CH2 The procedure described in Example 1 was repeated except that the reaction mixture charged to the flask was 11 g of bisphenol A, 32.5 g bis(ethenyloxybutyl carbonate) and 1 g of KOH. The mixture was heated at 130C. under 5 mm Hg for a period of 7 hours. The distillate was removed and lH NMR identified the pot content as a mixture of the following products WO91/130s2 2 ~ 7 .~ 3 ~ ~ PCT/US91/0063Y

CH3 o-l-o(CH2)4cH=cH2]2 and CO(CH2)40-~H-0 ~ ~ OCo(cH2)4ocH=cH2 The procedure des~ribed in Example 1 was repeated except that the reaction mixture-c~arg~d:to the flask was 18.6 g. l-dodecanol and 25.8 g bisethenyloYy~utyl carbonate and O.l g sodium methoxide. The flask was heated at 90C.
under vacuum of S mm Hg for 5 hours.
During this period 13 g distillate containing a mixture of hydroxybutylvinyl ether and the carbonate reactant was removed.
The contents of the flask was worked up as in Example l using l g charcoal (Nuchar), heated to 60C. for 30 minutes and filtered. The filtrate was a clear colorless liquid which solidified on cooling weighing 26 g.
IR and lH NMR spectral data identified the product as having the structure H2C=CH0(CH2)40C0(CH2)llCH3 ~f~7.~.~'J7 WO91/13~s2 PCT/US9l/00639 EXAM~LE 8 Example 1 was repeated except that 62.6 g of the bis-ethoxylate of bisphenol A was used in place of triethylene glycol. The reaction mixture was heated under vacuum at 3-5 mm Hg at 100C. After 2 hours 52 grams of distillate was removed. The resulting yellowish liquid was treated with charcoal at 50C., and filtered. The final product was a clear viscous liquid. The 1H NMR spectrum is consistent ~ith the following struct- ~.

CH3 O(cH2)2oco(cH2)4ocH=cH2]2 A four-necked 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, distillation head and water condenser, additional funnel and nitrogen inlet was charged with 76 g of butanediol (0.86 mole), 150 g of dimethyl carbonate (1.7 mole), 11.6 g of hydroxybutyl vinyl ether (0.1 mole), and 1 g of sodium methoxide. The pot temperature was maintained at about 100C. under a blanket of nitrogen for a period of 12 hours, during which an azeotrope containing methanol and dimethyl carbonate was distilled off at a head temperature of 31-35C.
The reaction mixture was filtered and flash distilled at 120-150C. under 3 mm Hg. A solid residue (A) weighing 85 g was recovered.

2a~ ~357 WO91/13052 PCT/US91/~Ob~9 The residue (A) comprised 66% of H2C=HCo(cH2)4-[o-lcl-o(cH2)4]4ollocH3 O O

and 33% of H2C CHO(CH2)4 [o-lcl-o(cH2)4]4o - lcl-o(cH2)4ocH=cH2 O o which mixture was confirmed by HNMR analysis.

~'' 1,0 A 28 g portion of the r~si~u~:~A) described in Example 10 was charqed into a 250 ml, 3 necked round bottom flask equipped with mechanical stirrer, thermometer and a vertical condenser attached to a vacuum line.
Hydroxybutyl vinyl ether (100 g) and sodium methoxide (0.2 g) were added to the residue. The flask was then heated and maintained at a temperature of 100C., under a vacuum of 100 mm Hg, for a period of about 6.5 hours.
The content of the flask was flash distilled at 150C. under 3 mm Hg leaving 30 g of final product (B) which was a liquid at 30-40C. and slowly solidified at room temperature. During the flash distillation about 90 g hydroxybutyl vinyl ether was recovered. Product B, i.e.

H2C=CHO(CH2)4 -o--fi-o- [(CH2)4-0-1cl-0]8-9(cH2)4OcH=cH2 O O

was identified by 1HNMR analysis.

2~7~3 37 WO9l/13~2 PCT/US91/~639 A four necked, 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, distillation head with a water condenser and a N2 inlet was charged with 70 g of butanediol (0.78 mole), 150 g of dimethyl carbonate (1.67 mole), 11.6 g of hydroxy butyl vinyl ether (0.1 mole) and 0.5 g of sodium methoxide. The flask was heated under N2 by gradually raising the temperature to 105C., and maintained at 90~C. for 1 hour followed by continued heating up to 105C. for a total period of 12.5 hours.
During this period 90.4 g of distillate was removed at a head t lperature of about ~C_.. No...distillate, (an azeotrcpe of methanol and dimethylcarbonate) came off during the distillation.
The reaction mixture was filtere~ and 141.6 g of the filtrate was flash distilled at 120C. under a reduced pressure of 3 mm Hg over a period of 2 hours, after which 98 g of a solid mixture was obtained. The solid product (C) H3Co-lC-[o(cH2)4o-lcl-]6-go(cH2)4ocH CH2 O O

and H3COICI [(CH2)40 ICI ]6_9ocH3 O O

was identified by 'HNMR analysis.

:' -'' 2 ~
WO91tl3052 PCT/US91/00 The solid product C (75.4 g) was charged into a 500 ml 3-necked round-bottom flask equipped with a mechanical stirrer, thermometer-vertical water condenser and N2 inlet. The condenser was connected to a source of vacuum via a trap and 100 g of hydroxybutyl vinyl ether and 0.3 g of sodium methoxide were added to the flask. The flask was heated and maintained at 100C. at a reduced pressure of 150 mm Hg for a period of 9.5 hours. The contents of the flask was then filtered and 162.4 g of filtrate was flash distilled at 110C. under reduced pressure of 3 mm Hg during which unreacted hydroxy vinyl ether was removed, leaving 89.4 g residue which solidified on cooling. This solid prod~ct ~as:f~nd to be 2C CHO(CH2)40~C~O[ (cH2)4olcl-o]7 - 9(cH2)4ocH=cH2 O O

EXAMP~E 12 Example 11 was repeated except that the charge to the reactor was 50 g of residue A obtained from Example ~, 100 g of hydroxy butylvinyl ether and 0.2 g sodium methoxide. The mixture was heated to 105C. under a vacuum of 160 mm Hg for a period of 12 hours and the crude product was then filtered. The filtrate, weighing 141 g, was flash-distilled at 100C. under a reduced pressure of 3 mm Hg for a period of 2.5 hours. The resulting product, H2c=cHoc4H8oc~o[c4Hgo~c~o]5-6c4H8ocH CH2 O O

(5~.7 g) was recovered and solidified on cooling to room temperature.

2~7, )57 Wogl/13052 PCTtUS91/00639 Example 9 was repeated except that the charge to the reactor contained excess dimethyl carbonate. 90 g butanediol (l mole), 360 g dimethyl carbonate (4 moles) and 1 g sodium methoxide. The flask was heated gradually heated and maintained at 85-95C. for 20.5 hours during which 165.6 g distillate, an azeotrope of methanol and unreacted dimethyl carbonate, was collected at a head temperature of 42-45C. Analysis of a 5 g aliquot of the remaining liquid in the flask showed it to be a methyl end-capped carbonate oligomer intermediate having the structure H3COCIiO[(cH2)4olclo]3-4c~3 Hydroxy butylvinyl ether (250 g, 2.15 mole) was added to the flask and the temperature was raised to 135-140C. under a blanket of nitrogen for a period of 4 hours, during which 33 g of distillate was removed. The reaction product was filtered under suction and 350 g of the filtrate was flash-distilled at 100C. under 3 mm Hg to remove 201 g of distillate. The oligomeric product t139 g) having the formula CH2=cHo(c4H8)o~c~o[(c4Hg)o~co~3-4(c4H8)ocH=cH2 O o was recovered from the flask.

WO 91/13052 2 ~ -15 3 G ~I P~/USgl/oo~-~

A four-necked 1 liter flask equipped with a mechanical stirrer, thermometer, distillation head with a horizontal condenser, nitrogen inlet and a receiver was charged with 250 g of commercially available poly THF*
(polyoxybutylene diol - 250 having an average molecular weight about 250), 360 g t4 moles) of dimethyl carbonate (DMC) and 1 g titanium isopropoxide. The flask was heated and maintained at 90C. for a period of 9 hours during which 169.5 g of distillate (an azeotrope of methanol and dimethyl carbonate) was collected at a head-temperature of 36C.
Progress of the reactiDn~was m~nitored periodically by lHNMR data a~d:O~ ~nmher. The reaction product was found to be a mixture- af~ methyl terminated and OH terminated carbonate oligomers.

.
* Ho(c4H8o)3-4H

A second addition of DMC (100 g) was made to the flask and heating continued at a pot temperature 95-97C.
under a blanket of nitrogen for 6 hours, during which 55.4 g distillate was removed. Analysis of the reaction mixture indicated residual OH group.
A third addition of DMC (100 g) was then made and heating continued at a pot temperature of 95-101C. for 3 hours under N2 during which an additional 118.4 g of distillate was removed. Analysis showed the OH number of tries reaction mixture to be 85.5 mg KOH/g. indicating almost 80% conversion.

wo sl/13nsz ~1~ 7 ~ 7 Pcr/l ssl/~u639 A final addition of DMC (100 g) made and, heating continued under N2 at pot temperature 105-115C., during which 101.5 g distillate was collected at a head temperature of 67-75C~ over a period of 6 hours. Thus, a total of 445 g distillate was collected. The reaction mixture, analyzed by 1HNMR data, showed practically complete methyl terminated polycarbonate of the poly THF
diol as an intermediate product, (i.e. polyoxybutylene diol). The OH number was found to be 20.8 mg KOH/g.
Hydroxy.~tyl vinyl ether (240 g, 2.~' moles) was then added to the flask and heating was continued at a pot temperature from 130 to 156C. for 6.5 hours under N2.
During this period 59 g distillat~..~ostly methanol was removed at a head temperat~re ahout.67C. The remaining liquid was then flash distilled at.15.0C. under a reduced pressure of 3 mm Hg, leaving 311 g of a yellow oil in the flask as the final product (D).
Product D was found to have the formula Ol O
H2c=cHoc4H8oco[c4H8(oc4H8)2-3oco]2-3c4H8ocH 2 The OH number of product D 2.8 was 8.0 mg KOH/g.

Example 9 was repeated except that 75 g commercially available triethylene glycol (0.5 mole), 360 g dimethyl carbonate (4 moles), and 0.4 g sodium methoxide were charged to the flask. The flask was heated under N2 at 85C. and 96 g of distillate was collected over a period of 5 hours at a head temperature of 51C. The remaining W091/13052 2 ~ 7 ~ 3 6 7 PCT/US91/00~

volatile components were removed by heating under vacuum (140-180 mm Hg) at a temperature 50-550c. whereupon 42.5 g additional distillate was removed at a head temperature of 42C. 1HNMR analysis of the intermediate product showed the composition to be methyl terminated carbonate oligomer having the formula H3coc-o[c2H4 (C2H4) 20~1o]2CH3 Hydroxybutyl vinyl ether (120 g, 1.04 moles) was then addecd to the flask and heating under N2 was continued at 110C.-160C... over.. ~ ~e i~d.of 11 hours during which period 188 g of dis~i~t~:was ~ollected at a head temperature varying from 43 t~ 94C..until no more distillate came off at atmospheric pressure.
The reaction mixture was then filtered and 208 g of filtrate was flash-distilled at 170C. under 3 mm Hg over a period of 4 hours to provide 130 g of final product in the flask as pale yellow oil having the formula O O
H2C=CHOC4H80CO [ C2H4 (C2H4 ) 2C] 3-4C2H40CH CH2 This product had an OH number = 19.5 mg KOH/g, indicating greater than 97~0 conversion.

2 ~ 7 J ~ ~
WO91/1~52 PCT/US9l/00639 The product of Example 2 was mixed with an equal amount of a diglycidyl ether of bisphenol A, 1 phr~ of a fluorochemical surfactant and 4 phr of cationic photoinitiator until a homogeneous low viscosity liquid was obtained. This mixture was then coated on an aluminum substrate in a thickness of 1.6 mil. The coated surface was exposed for less than l second to 400 llijoules/cm2 radiation from a mercury vapor lamp. A tack-free film was produced. Coating properties reported in the following table were determined immediately after W exposure and after a post cure of 177C. for. l~ minutes.

Propertv After ~VPost Cured Pencil Hardness (ASTM D3363) 4B H
Double MEX Rubs >lO0 >100 % Adhesion (ASTM D 3359) 0 100 Reverse Impact (in-lbs) - 55 Mandrel Bend (in.) (ASTM D3111) 3/16 1/8 * parts/hundred parts of resin The product of Example 3 was mixed with an equai weight of triethylene glycol divinyl ether, 1 phr fluorochemical surfactant and 4 phr cationic photoinitiator until a homogeneous low viscosity liquid was obtained.
This mixture was then coated on an aluminum substrate in a thickness of 1.4 mil. Th~ coated surface was exposed for less than 1 second to 4~0 millijoules/cm2 radiation fror.
a mercury vapor lamp. A tack-free film was produced.

wo 91/13052 2 ~ 7 .~ 7 Pcr/usgl/0o6J~ ;

Coating properties reported in the fGllowing table were determiend immediately after W exposure and after a post cure of 177C. for 15 minutes.

Pro~rtY After W Post Cured Pencil Hardness (ASTM D3363) <4B F
Double MEK Rubs 150 >100 % Adhesion (ASTM D 3359) 0 100 Reverse Impact (in-lbs) - 15 Mandrel Bend (in.) (ASTM D3111) 3/4 3/16 Example 10 was repeated e~cept that the reaction product of Example 1 is substituted for-the reaction product of Example 3. The following properties were determined for the product.

ProPertv After W Post Cured Pencil Hardness <4B <4B
Double MEK Rubs 4 lO
% Adhesion o '70 Reverse Impact (in-lbs) - 15 Mandrel Bend (in.) 7/16 5/16 Example 10 is repeated except that the reaction product of Example 4 is substituted for the reaction product of Example 3. The following properties for the product were determined.

WO91/13~2 PCT/US91/~639 PropertY After W Post Cured Pencil Hardness <4B F
Double MEK Rubs 12 80 % Adhesion o o Reverse Impact (in-lbs) - lS
Mandrel Bend (in.) l/4 l/8 The product of Example 2 (50.0 gm) is mixed with 50 g of a bisphenol a epoxy acrylate oligomer, 2 phr cationic photoinitiator, 2 phr free radical photoinitiator*
and 1 phr fluorochemical s~,Iactant at 50C. until a homogeneous, low viscosity li~ui~ is obtained. This mixture is then coated on a pol~e~ter.substrate at a thickness of 0.5 mil. The coate~ s~r~ace is exposed to 400 millijoules/cm2 radiation free coating haviny a good pencil hardness of about 3H, 100% adhesion and high chemical resistance is obtained.

* hydroxycyclohexyl phenyl ketone EXAMPLE 2l The product from Example 3 (50.0 gm) is mixed with 25 g of a divinyl ether urethane oligomer, 4 phr cationic photoinitiator and l phr fluorochemical surfactant at 50C.
until a homogeneous low viscosity liquid is obtained. This mixture is then coated on a aluminum panel in a thickness of 0.50 mil and exposed to 400 millijoules/cm2 radiation from a mercury vapor lamp for less than l second. A tack free coating havinq a good pencil hardness of about 3B, a Mandrel bend of at least 3/8 inch is obtained.

WOgl/130s2 2 ~ 7 i~ 7 PCT/US91/~6 PREPARATION OF COMPOUNDS (C) In a 250 ml round bottom flask 25 g. of 3,3,3-trimethylolpropane was charged along with 143 g. of bis(ethenyloxybutyl) carbonate and 0.1 g. of sodium methoxide. The contents of the flask was heated to 100-105C. under a vacuum of 3 mm Hg. After 6 hours, 54 g.
of hydroxybutyl vinyl ether had been distilled out of the reaction flask. After cooling, the crude reaction product was treated with 2 g. of charcoal at 45C. and filtered, leaving a yellowish viscous li~ui~. The lH NMR and IR
spectrum of this material i~dicat-ed the mixture of products shown C~H2 80% ~CH2=CHOC4H80C0]3-cH2cl-cH2 15% [CH2=cHoc4H8oco]2-cH2cî-cH2 O C~ 2H5 5% CH2=C~Oc4HgococH2-c-cH2oH

.

WO91/1~K2 PCT/US91/00639 The product from Example l is mixed with an equal weight of triethylene glycol divinyl ether, l phr (part per hundred) fluorochemical surfactant and 4 phr cationic photoinitiator. The resulting low viscosity liqu J is coated on a polyester substrate (2.0 mil thicknes: and exposed to 400 millijoules/cm2 from a mercury vapor lamp. A tack free, chemically resistant coating is produced.

Example l was repe~ted eYcept that 25 g. of 1,2,6-trihydroxyhexane was substi-~ut~d for trimethylolpropane. The resulti~g pr~duct was a yellow viscous oil. The lH NMR and IR spectra of this material indicated a mixture of the compounds:

[CH2=CHOC4H8OCO]3-CH2-CH(CH2)4-[CH2=CHOC4H8OCO]2-CH2-~CH(CH2)4-OH

CH2=cHoc4H8oco-cH2-lH-(cH2)4OH
OH

and isomers thereof.

.

2~7.,3~ 7 .
WO91/130~2 PCT/US91/00 PREPARATION OF COMPOUNDS (D) .

In a 250 ml, one necked, round bottom flask, 80 g.
(0.08 mole) polyethylene glycol with an average molecular weight of 1000 was charged along with 56 g.
bis(ethenyloxybutyl) carbonate (0.22 mole) and 0.2 g.
sodium ethoxide. The flask was heated under vacuum at 3 mm Hg, at 100-105C. in a Kugelrohr apparatus for a period of 7 hours after which a total of 22.5 g. distillate was collected. The distillate was ide~tified by GC analysis as a mixture containing 75-~0% hy~r~xybutyl vinyl ether and 20-25% of bis(ethenyloxybutyl) c~rbonate. About 90%
conversion was achieved. -The contents of the fla~sk c~ntaining the majorproduct of the reaction was treated with ~ g. (Nuchar) charcoal and filtered at about 45C. The filtrate solidified on standing yielding 98 g. of a clear colorless waxy solid which was identified as product having the formula O O
CH2=cHoc4H8oco(cH2cH2o)2ococ4H8ocH CH2 by lH NMR and IR spectral analysis. a conversion of 87.6% was achieved.

In a 100 ml, one-necked, round bottom flask, 20 g.
of Duracarb 120 (a hydroxy terminated lower alkyl polycarbonate of molecular weight ~ 850 g/mol) and 125 g.
bis(ethenyloxybutyl) carbonate were mixed together with 0.1 g. of sodium methoxide. The contents of the flask was 2 ~7 ~J `3 ~7 heated to 100C. while under a vacuum of 3 mm Hg. After 3 hours, 3.4 g. of hydroxybutyl vinyl ether by-product had been distilled from the reaction mixture.
The contents o f the flask containing the product of this invention was treated with 1 g. of (Nuchar) charcoal and filtered at 45C. Upon standing the filtrate solidified to give 25 g. of a white, waxy solid. Analysis by lH NMR indicated the polycarbonate bis(ethenyoxybutyl) end capped product.

PREPARATION OF COMPOUNDS (E) Hydroxybutyl vinyl et~er (19O0 g), bisphenol A
epoxy resin (345.6 g) and potassium hy~roxide (0.5 g) were chargwd to a three liter flask~e~uippe~ with a mechanical stirrer, thermometer, nitrogen inlet a~ a condenser adapted with a drying tube. The solution was heated at 120C. for 24 hours and 150C. for 48 hours, after which 400 g of the resulting solution was transferred to a one liter flask. Unreacted hydroxybutyl vinyl ether was stripped off and 300 ml of toluene was added. The resulting solution was washed five times with 300 ml of water, dried over calcium sulfate and filtèred. After stripping off toluene solvent, the substantially pure divinyl ether product having the structure:

CH =CHOC4~ -~2 C~2OC1H8OCH=CH2 2 8 C C~2- ~ ~ (CH3) ~ CH2CHCH2~ ~ _(C:~3 ~ OH

was obtained as a yellow viscous oil.

WO91/l3052 2 ~ 7 .i 3 i~ 7 PCT/US91/00~

The above product was then evaluated for a radiation cured coating by coating in about 0.15 mil thickness on an aluminum panel and then exposing for less than 1 second at room temperature to 400 milli J/cm2 radiation from 2 medium pressure mercury vapor lamps. The cured coating had strong adhesion to the substrate and had excellent resistance to chemical attack from acids and bases.

Cyclohexanedimethanol (1802.6 g) and potssium hydroxide (85~ pellets, 36 g) werOE-c~&rged into a one gallon stainless steel autocla~e. The autoclave was initially purged with nitrogen at roo~-temperature and then twice at 110C. under 20 mm Hg vacuum for 0.5 hour.
Propane (100 psig) was added, the solution was heated to 160C., after which the propane pressure was readjusted to lO0 psig and acetylene (100 psig) was added to initiate the vinylation. After 4 hours, the reaction was halted and 46%
(642 g) of product was then recovered in 99% purity by twice distilling the crude mixture in a 15 plate Oldershaw column at 103C. under 4 mm Hg.
The cyclohexanedimethanol monovinyl ether product (469.3 g), bisphenol A epoxy resin (150 g) and potassium hydroxide (85% pellets, 0.5 g) were charged into a flask equipped as described in Example 1. The solution was heated to 150C. for 48 hours and then cooled to room temperature. The resulting crude product (300 g), 500 ml of toluene and 2 g of magnesium silicate were then transferred into a 1 liter flask wherein the mixture was stirred for 1 hour at room temperature and then filtered.

2 i~ 7 After toluene and unreacted cyclohexane methanol vinyl ether were stripped off, the divinyl ether of bisphenol A
epoxy resin product having the structure CH2OCH ~ CH ~CH=CH
1 2 2 CH2=cHocH2 ~ CH201:i2 CHCH2 - L~ 3 2~0CH2 ,C~CH~ _~ (CH3)2 ~ OCH2Ci was obtained as a pale yellow jelly.

EX~MPr~ 3 Hydroxyethyl vinyl ether (4.3~ .g), bisphenol A
epoxy resin (282 g) and potassium hydroxi~e (0.5 g, 85%
pellets) were charged into a 1 liter flask eyuipped as described as in Example 1. The solution was heated and held at reflux for 56 hours, after which the solution was cooled to room temperature, stirred with 5 g of magnesium silicate for 1 hour and filtered. Unreacted, excess hydroxyethyl vinyl ether was stripped off and the divinyl ether of bisphenol A epoxy product having the structure:

1~2OC2~4OCH-CH2 CH2'C~OC2H4 O-C1~2 C~C~2~ r ~ (C~3) ~ ~2C CR23 ~ C(CH3 ~ CC~2c was obtained as a pale yellow oil.

, ~ . , .

- ' -2 3 7 ,; ~
WOgl/13052 PCT/US9l/OOo~Y

Hydroxybutyl vinyl ether (648 g), bisphenol epoxy resin (498 g) and potassium hydroxide (0.5 g) were charged into a two liter flask equipped as described in Example 1.
The solution was heated at 120C. for 24 hours and then at 158C. for 48 hours. Magnesium silicate (10 g) was added to the solution, the resulting mixture was stripped for 1 hour at 40C. and then filtered. The unreacted excess hydroxybutyl vinyl ether was st~ipped off and the divinyl ether product having the structure:

1~2 C4~8ocH=cH2 2 4 3 0-C:~2 C~CH2- r ~ 2 ~ H2C~C~2~ ~ 2 ~ ~C~2l,~

was recovered as a yellow viscous oil.

Claims (4)

WHAT IS CLAIMED IS:

1. The compounds having the formulas (A) wherein A is RHC=CHO(B)n-, lower alkyl or a mixture thereof; B is a divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or polyalkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy; R is hydrogen or lower alkyl and n has a value of from 1 to 10, or, (B) wherein A is R'HC=CHOR-, lower alkyl or a mixture thereof;
R and R" are each independently a divalent radical having from 2 to 20 carbon atoms and are selected from the group of alkylene, mono- or poly- alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy; R' is hydrogen or lower alkyl; (n) has a value of from 1 to 10 and (m) has a value of from 0 to 10; with the proviso that R" contains at least 3 carbon atoms when m is zero, or (C) WO 91/13052 PCT/US91/00?

wherein R" is a C3 to C50 saturated or unsaturated, linear, branched or cyclic hydrocarbon radical optionally substituted with halo, alkoxy, lower alkyl, cyano or nitro;
R' is hydrogen or lower alkyl B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono- or poly- alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy; (m) has a value of from 1 to 10; (b) has a value of from at least one up to the number of hydroxyl groups in R" and (n) represents the number of hydroxy groups in R", or (D) wherein R is a polymeric radical selected from the group of polyester, polyacetal, polyurethane, polyether, polybutadiene and polycarbonate, said polymers containing from about 10 to 50 repeating monomer units;
A is hydrogen, lower alkyl or hydroxy;
R' is hydrogen or lower alkyl;
B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or poly alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy; (m) has a value of from 1 to 10 and (a) is zero when A is hydroxy and is 1 when A is hydrogen or lower alkyl, or an aryloxy polyvinyl ether having the formula (E) (E) wherein R is a linear, branched or cyclic radical having from 2 to 20 carbon atoms and is selected from the group of alkylene, alkyleneoxy alkylene, polyalkyleneoxy alkylene, arylene, alkarylene and aralkylene; X is oxygen or sulfur;
A is branched or linear alkylene having from 1 to 10 carbon atoms; B is halo or lower alkyl; n has a value of from 1 to 20 and p has a value of from 0 to 4.

2. The compound of claim 1 (A) having the formula , or ; or the compound of claim 1 (B) having the formula , , , or ;

the compound of Claim 1 wherein in (D) R is selected from the group of polyether, polyester, polycarbonate and polyurethane;
wherein in (D) B is butylene or

3. The aryloxy polyvinyl ether of Claim 1 (E) wherein X is oxygen, or R is a radical having from 2 to 8 carbon atoms, or p is zero, or n has a value of from 1 to 4, or A is >C(CH3)2.

4. The aryloxy polyvinyl ether of Claim 1 (E) having the formula or or