Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes

Claim 2

A vinyl ether terminated oligomeric ester of the formula, R.sub.1 CH═CR.sub.2 OXO(O)CYC(O)O--[--ZO(O)CYC(O)O--].sub.p --XOCR.sub.2 ═CHR.sub.1, or a vinyl ether terminated oligomeric urethane of the formula, R.sub.1 CH═CR.sub.2 OXO(O)CNH[QNHC(O)OZO(O)CNH].sub.p QNHC(O)OXOCR.sub.2 ═CHR.sub.1 where: R 1 and R 2 are independently selected from the group consisting of hydrogen and lower alkyl moieties containing up to about 10 carbon atoms; HOXOH is a diol of formula [HO(CH 2 ) n ] 2 R 3 where n is an integer from 1 to about 6, and R 3 is a divalent radical whose parent is a saturated cyclic hydrocarbon of ring size 5 to 8 carbons; HOZOH is the same as HOXOH; or is an alkylene diol of the formula HO(C q H 2q )OH, where q is an integer from 2 to about 10; or a poly(ethyleneoxy) or poly(propyleneoxy)glycols, HO--[--CH 2 CH 2 O--] m --H or HO--[--CH(CH 3 )CH 2 O--] m --H, respectively, where m is an integer from 1 to about 50;

Claim 3

p is 0 or an integer from 1 to about 200;

Claim 4

p is 0 or an integer from 1 to about 200;

Claim 5

HO 2 CYCO 2 H is a dicarboxylic acid selected from the group consisting of phthalic acids, polymethylene dicarboxylic acids, HO 2 C(CH 2 ) r CO 2 H, where r is an integer from 2 to about 8, para-phenylene diacetic acid, para-phenylene dipropionic acid, 5-t-butylisophthalic acid and 4,4'-dibenzylic acid; OCNQNCO is selected from the group consisting of toluene diisocyanates, p- and m-phenylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenedicyclohexyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4'-diisocyanate, bis(2-methyl-3-isocyanatephenyl)methane, bis(3-methyl-4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate and polyphenyl polyisocyanates.

Claim 6

HO 2 CYCO 2 H is a dicarboxylic acid selected from the group consisting of phthalic acids, polymethylene dicarboxylic acids, HO 2 C(CH 2 ) r CO 2 H, where r is an integer from 2 to about 8, para-phenylene diacetic acid, para-phenylene dipropionic acid, 5-t-butylisophthalic acid and 4,4'-dibenzylic acid; OCNQNCO is selected from the group consisting of toluene diisocyanates, p- and m-phenylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenedicyclohexyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4'-diisocyanate, bis(2-methyl-3-isocyanatephenyl)methane, bis(3-methyl-4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate and polyphenyl polyisocyanates.

Claim 7

The vinyl ether terminated oligomer of claim 1 where R 2 is hydrogen and R 1 is an alkyl group of 1 to about 4 carbon atoms.

Claim 8

The vinyl ether terminated oligomer of claim 1 where R 1 and R 2 are hydrogen.

Claim 9

The vinyl ether terminated oligomer of claim 1 where R 1 is hydrogen and R 2 is methyl, or R 1 is methyl and R 2 is hydrogen.

Claim 10

The vinyl ether terminated oligomer of claim 1 where X is the same as Z.

Claim 11

The vinyl ether terminated oligomer of claim 1 where the diol of formula [HO(CH 2 ) n ] 2 R 3 has n=1 to 3.

Claim 12

The vinyl ether terminated oligomer of claim 6 where the diol is a bis(hydroxymethyl)cyclohexane.

Claim 13

The vinyl ether terminated oligomer of claim 7 where the diol is 1,4-bis(hydroxymethyl)cyclohexane.

Claim 14

The vinyl ether terminated oligomer of claim 1 where m is an integer from 1 to about 5.

Claim 15

The vinyl ether terminated oligomer of claim 1 where p is an integer from 1 to about 20.

Claim 16

The vinyl ether terminated oligomer of claim 1 where HO 2 CYCO 2 H is a phthalic acid.

Claim 17

The vinyl ether terminated oligomer of claim 11 where the acid is terephthalic acid.

Claim 18

The vinyl ether terminated oligomer of claim 12 where the acid is isophthalic acid.

Claim 19

The vinyl ether terminated oligomer of claim 1 where HO 2 CYCO 2 H is adipic acid.

Claim 20

The vinyl ether terminated oligomer of claim 1 where OCNQNCO is 4,4'-methylenedicyclohexyl diisocyanate.

Claim 21

The vinyl ether terminated oligomer of claim 1 where OCNQNCO is toluene diisocyanate.

Claim 22

A vinyl ether terminated oligomeric ester containing fewer than 5% unreacted alcoholic hydroxyl groups which is the reaction product of a mixture of alcohols containing 1 molar proportion of a vinyl ether terminated alcohol of the formula, R.sub.1 CH═CR.sub.2 OXOH, and from 0.5 to about 100 molar proportions of a polyol of formula Z(OH) t with a sufficient amount of a dicarboxylic acid such that there are fewer than 5% free alcoholic hydroxyl groups in the resulting ester, where: R 1 and R 2 are independently selected from the group consisting of hydrogen and lower alkyl moieties containing up to about 10 carbon atoms; HOXOH is a bis(hydroxyalkyl)cycloalkane of formula [HO(CH 2 ) n ] 2 R 3 where n is an integer from 1 to about 6, and R 3 is a divalent radical whose parent is a saturated cyclic hydrocarbon of ring size 5 to 8 carbons; Z(OH) t is HOXOH; or is (a) an alkylene diol of the formula HO(C q H 2q )OH, where q is an integer from 2 to about 10; or (b) a poly(ethyleneoxy) or poly(propyleneoxy)glycol, HO--[--CH 2 CH 2 O--] m --H or HO--[--CH(CH 3 )CH 2 --] m --H, respectively, where m is an integer from 1 to about 50; or (c) a higher polyol, where t is an integer which is at least 3.

Claim 23

A vinyl ether terminated oligomeric ester containing fewer than 5% unreacted alcoholic hydroxyl groups which is the reaction product of a mixture of alcohols containing 1 molar proportion of a vinyl ether terminated alcohol of the formula, R.sub.1 CH═CR.sub.2 OXOH, and from 0.5 to about 100 molar proportions of a polyol of formula Z(OH) t with a sufficient amount of a dicarboxylic acid such that there are fewer than 5% free alcoholic hydroxyl groups in the resulting ester, where: R 1 and R 2 are independently selected from the group consisting of hydrogen and lower alkyl moieties containing up to about 10 carbon atoms; HOXOH is a bis(hydroxyalkyl)cycloalkane of formula [HO(CH 2 ) n ] 2 R 3 where n is an integer from 1 to about 6, and R 3 is a divalent radical whose parent is a saturated cyclic hydrocarbon of ring size 5 to 8 carbons; Z(OH) t is HOXOH; or is (a) an alkylene diol of the formula HO(C q H 2q )OH, where q is an integer from 2 to about 10; or (b) a poly(ethyleneoxy) or poly(propyleneoxy)glycol, HO--[--CH 2 CH 2 O--] m --H or HO--[--CH(CH 3 )CH 2 --] m --H, respectively, where m is an integer from 1 to about 50; or (c) a higher polyol, where t is an integer which is at least 3.

Claim 24

The vinyl ether terminated oligomer of claim 17 where R 2 is hydrogen and R 1 is an alkyl group of 1 to about 4 carbon atoms.

Claim 25

The vinyl ether terminated oligomer of claim 17 where R 1 and R 2 are hydrogen.

Claim 26

The vinyl ether terminated oligomer of claim 17 where R 1 is hydrogen and R 2 is methyl, or R 1 is methyl and R 2 is hydrogen.

Claim 27

The vinyl ether terminated oligomer of claim 17 where the diol of formula [HO(CH 2 ) n ] 2 R 3 has n=1 to 3.

Claim 28

The vinyl ether terminated oligomer of claim 21 where the diol is a bis(hydroxymethyl)cyclohexane.

Claim 29

The vinyl ether terminated oligomer of claim 22 where the diol is 1,4-bis(hydroxymethyl)cyclohexane.

Claim 30

The vinyl ether terminated oligomer of claim 17 where m is an integer from 1 to about 5.

Claim 31

The vinyl ether terminated oligomer of claim 17 where p is an integer from 1 to about 20.

Claim 32

The vinyl ether terminated oligomer of claim 17 where the dicarboxylic acid is selected from the group consisting of phthalic acids, polymethylene dicarboxylic acids, HO 2 C(CH 2 ) r CO 2 H, where r is an integer from 2 to about 8, para-phenylene diacetic acid, para-phenylene dipropionic acid, 5-t-butylisophthalic acid and 4,4'-dibenzylic acid.

Claim 33

The vinyl ether terminated oligomer of claim 17 where the dicarboxylic acid is a phthalic acid.

Claim 34

The vinyl ether terminated oligomer of claim 27 where the acid is terephthalic acid.

Claim 35

The vinyl ether terminated oligomer of claim 27 where the acid is isophthalic acid.

Claim 36

The vinyl ether terminated oligomer of claim 17 where the acid is adipic acid.

Claim 37

A vinyl ether terminated oligomeric urethane containing fewer than 5% unreacted alcoholic hydroxyl groups which is the reaction product of a mixture of alcohols containing 1 molar proportion of a vinyl ether terminated alcohol of the formula, R.sub.1 CH═CR.sub.2 OXOH, and from 0.5 to about 100 molar proportions of a polyol of formula Z(OH) t with a sufficient amount of a diisocyanate such that there are fewer than 5% free alcoholic hydroxyl groups in the resulting urethane, where: R 1 and R 2 are independently selected from the group consisting of hydrogen and lower alkyl moieties containing up to about 10 carbon atoms; HOXOH is a bis(hydroxyalkyl)cycloalkane of formula [HO(CH 2 ) n ] 2 R 3 where n is an integer from 1 to about 6, and R 3 is a divalent radical whose parent is a saturated cyclic hydrocarbon of ring size 5 to 8 carbons; Z(OH) t is HOXOH; or is (a) an alkylene diol of the formula HO(C q H 2q )OH, where q is an integer from 2 to about 10; or (b) a poly(ethyleneoxy) or poly(propyleneoxy)glycol, HO--[--CH 2 CH 2 O--] m --H or HO--[--CH(CH 3 )CH 2 --] m --H, respectively, where m is an integer from 1 to about 50; or (c) a higher polyol, where t is an integer which is at least 3.

Claim 38

A vinyl ether terminated oligomeric urethane containing fewer than 5% unreacted alcoholic hydroxyl groups which is the reaction product of a mixture of alcohols containing 1 molar proportion of a vinyl ether terminated alcohol of the formula, R.sub.1 CH═CR.sub.2 OXOH, and from 0.5 to about 100 molar proportions of a polyol of formula Z(OH) t with a sufficient amount of a diisocyanate such that there are fewer than 5% free alcoholic hydroxyl groups in the resulting urethane, where: R 1 and R 2 are independently selected from the group consisting of hydrogen and lower alkyl moieties containing up to about 10 carbon atoms; HOXOH is a bis(hydroxyalkyl)cycloalkane of formula [HO(CH 2 ) n ] 2 R 3 where n is an integer from 1 to about 6, and R 3 is a divalent radical whose parent is a saturated cyclic hydrocarbon of ring size 5 to 8 carbons; Z(OH) t is HOXOH; or is (a) an alkylene diol of the formula HO(C q H 2q )OH, where q is an integer from 2 to about 10; or (b) a poly(ethyleneoxy) or poly(propyleneoxy)glycol, HO--[--CH 2 CH 2 O--] m --H or HO--[--CH(CH 3 )CH 2 --] m --H, respectively, where m is an integer from 1 to about 50; or (c) a higher polyol, where t is an integer which is at least 3.

Claim 39

The vinyl ether terminated oligomer of claim 31 where R 2 is hydrogen and R 1 is an alkyl group of 1 to about 4 carbon atoms.

Claim 40

The vinyl ether terminated oligomer of claim 31 where R 1 and R 2 are hydrogen.

Claim 41

The vinyl ether terminated oligomer of claim 31 where R 1 is hydrogen and R 2 is methyl, or R 1 is methyl and R 2 is hydrogen.

Claim 42

The vinyl ether terminated oligomer of claim 31 where the diol of formula [HO(CH 2 ) n ] 2 R 3 has n=1 to 3.

Claim 43

The vinyl ether terminated oligomer of claim 35 where the diol is a bis(hydroxymethyl)cyclohexane.

Claim 44

The vinyl ether terminated oligomer of claim 36 where the diol is 1,4-bis(hydroxymethyl)cyclohexane.

Claim 45

The vinyl ether terminated oligomer of claim 31 where m is an integer from 1 to about 5.

Claim 46

The vinyl ether terminated oligomer of claim 31 where p is an integer from 1 to about 20.

Claim 47

The vinyl ether terminated oligomer of claim 31 where the diisocyanate is selected from the group consisting of toluene diisocyanates, p- and m-phenylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenedicyclohexyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4'-diisocyanate, bis(2-methyl-3-isocyanatephenyl)methane, bis(3-methyl-4-isocyanatephenyl)methane, and 4,4'-diphenylpropane diisocyanate and polyphenyl polyisocyanates.

Claim 48

The vinyl ether terminated oligomer of claim 40 where the diisocyanate is 4,4'-methylenedicyclohexyl diisocyanate.

Claim 49

The vinyl ether terminated oligomer of claim 40 where the diisocyanate is toluene diisocyanate.