Preparation of bis (2-cyanoacrylate)monomers

Claim 2

In the preparation of bis (2-cyanoacrylate) monomer represented by the General Formula VI ##EQU10## from 2-cyanoacrylic acid ester of the General Formula I ##EQU11## the steps comprising: a. introducing a blocking group by means of a Diels-Alder reaction in which a cyclic 1,3-diene is reacted with said cyanoacrylic ester of Formula I to give a compound of the General Formula II ##EQU12## b. converting said compound of General Formula II by hydrolysis to a compound represented by Formula III ##EQU13## converting the compound of Formula III to an acyl halide represented by the General Formula IV(B): ##EQU14## c. coupling two acyl groups of compounds of Formula IV(B) to each other through an -- O -- R -- O -- linkage by esterification with a difunctional alcohol to form a compound represented by the General Formula V ##EQU15## d. and then heating the compound of Formula V with maleic anhydride to displace said blocking groups and form said bis (2-cyanoacrylate) of Formula VI; wherein said blocking group ##SPC18## of Formula II, III, and V is any one of the group consisting of ##SPC19## where R 1 and R 2 are the same R 1 and R 2 are selected from the group consisting of H, an alkyl group of 1 to 5 carbons, phenyl, Br or Cl and where R 1 and R 2 are different, R 1 is H and R 2 is a member selected from any of the group consisting of an alkyl group of 1 to 5 carbons, phenyl, Br and Cl; ##SPC20## where R 3 is H or CH 3 ; and ##SPC21## wherein the organo linking group R of Formulas VI and V is the same and is any one of the group consisting of: --(CH.sub.2).sub.m --, where m is an integer of from 1 to 20 inclusive; ##EQU16## where n is an integer of from 0 to 18 inclusive, and R 4 and R 5 are independently hydrogen or a C 1 to C 5 alkyl group, R 4 and R 5 not simultaneously being hydrogen; --(CH.sub.2).sub.r --Z--(CH.sub.2).sub.s --, where Z is --O--, --S--, --CH=CH--; --C.tbd.C--; ##EQU17## and ##SPC22## where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R 6 and R 7 are independently hydrogen or a straight or branched chain C 1 and C 5 alkyl group ##SPC23## where x and y are integers of from 1 to 6 inclusive; ##SPC24## where x and y are as hereinbefore defined; --CH.sub.2 --(CF.sub.2).sub.z --CH.sub.2 --, where z is an integer of from 1 to 10 inclusive; and ##EQU18## and wherein R' of Formula I and II is an alcohol moiety selected from C 1 to C 16 alkyl, cyclohexyl or phenyl.

Claim 3

A method according to claim 1 in which the cyclic 1,3 diene is selected from the group consisting of anthracene, 9-methylanthracene, 9-bromoanthracene, 9-phenylanthracene, 9,10-dimethylanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, cyclopentadiene, methylcyclopentadiene, and norbornadiene.

Claim 4

A method according to claim 2 in which the diene is cyclopentadiene.

Claim 5

A method according to claim 1 where the difunctional alcohol is of the formula Ho[r"].sub. t OH where when t is = to or > 1, R" is propylene, and when t is > 2, R" is propylene, tetramethylene and ethylene, and t is a range average such that the molecular weight is from about 76 to about 2000.

Claim 6

A method according to claim 1 wherein from 25 to 200 mole percent excess of maleic anhydride is employed.

Claim 7

A method according to claim 1 where the cyanoacrylic ester is isobutyl 2-cyanoacrylate.

Claim 8

A method according to claim 1 in which the diene is anthracene.

Claim 9

A method according to claim 1 wherein the glycol is HO--(CH 2 ) m --OH, where m is an integer of from 1 to 20 inclusive.

Claim 10

A method according to claim 1 in which the difunctional alcohol is selected from the group consisting of Ho--(ch 2 ) m --OH where m is an integer of from 1 to 20 inclusive; ##EQU19## where n is an integer of from 0 to 18 and R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1 to C 5 alkyl, but R 4 , and R 5 not simultaneously being hydrogen; Ho--(ch 2 ) r --Z--(CH 2 ) s --OH where Z is --O--, --S--, --CH=CH--, --C.tbd.C--, ##EQU20## and ##SPC25## where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R 6 and R 7 being as heretofore defined; ##SPC26## where x and y are integers of from 1 to 6 inclusive; ##SPC27## where x and y are as hereinbefore defined; Ho--ch 2 --(cf 2 ) z --CH 2 --OH where z is an integer of from 1 to 10 inclusive; and Ho--ch 2 --si(CH 3 ) 2 --O--Si(CH 3 ) 2 --CH 2 --OH.

Claim 11

In the preparation of bis (2-cyanoacrylate) monomer represented by the General Formula VI ##EQU21## from 2-cyanoacrylic acid ester of the General Formula I ##EQU22## the steps comprising: a. introducing a blocking group D by means of a Diels-Alder reaction in which a cyclic 1,3-diene is reacted with said cyanoacrylic ester of Formula I to give a compound of the General Formula II ##EQU23## b. converting said compound of General Formula II by hydrolysis to a compound represented by Formula III ##EQU24## neutralizing the compound of Formula III with a metal base of which the designation M is the metal to form a metal salt compound of the General Formula IV(A): ##EQU25## c. coupling two carboxyl groups of compounds of Formula IV(A) to each other through an organo-linking group - R - by ester formation through reaction with a dihalide to form a compound represented by the General Formula V ##EQU26## and then heating the compound of Formula V with maleic anhydride to displace said blocking groups and form said bis (2-cyanoacrylate) of Formula VI; wherein said blocking group ##SPC28## of Formula II, III, IV(A) and V is any one of the group consisting of ##SPC29## where R 1 and R 2 are the same, R 1 and R 2 are selected from the group consisting of H, an alkyl group of 1 to 5 carbons, phenyl, Br or Cl and where R 1 and R 2 are different, R 1 is H and R 2 is a member selected from any of the group consisting of an alkyl group of 1 to 5 carbons, phenyl, Br and Cl; ##SPC30## where R 3 is H or CH.sub. 3 ; and ##SPC31## wherein the organo linking group R of Formulas VI and V is the same and is any one of the group consisting of: --(CH.sub.2).sub.m --, where m is an integer of from 1 to 20 inclusive; ##EQU27## where n is an integer of from 0 to 18 inclusive, and R 4 and R 5 are independently hydrogen or a C 1 to C 5 alkyl group, R 4 and R 5 not simultaneously being hydrogen; --(CH.sub.2).sub.r --Z--(CH.sub.2).sub.s --, where Z is --O--, --S--, --CH=CH--;--C.tbd.C--; ##EQU28## and ##SPC32## where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R 6 and R 7 are independently hydrogen or a straight or branched chain C 1 to C 5 alkyl group ##SPC33## where x and y are integers of from 1 to 6 inclusive; ##SPC34## where x and y are as hereinbefore defined; --CH.sub.2 --(CF.sub.2).sub.z --CH.sub.2 --, where z is an integer of from 1 to 10 inclusive; and ##EQU29## and wherein R' of Formula I and II is an alcohol moiety selected from C 1 to C 16 alkyl, cyclohexyl or phenyl.

Claim 12

In the preparation of bis (2-cyanoacrylate) monomer represented by the General Formula VI ##EQU21## from 2-cyanoacrylic acid ester of the General Formula I ##EQU22## the steps comprising: a. introducing a blocking group D by means of a Diels-Alder reaction in which a cyclic 1,3-diene is reacted with said cyanoacrylic ester of Formula I to give a compound of the General Formula II ##EQU23## b. converting said compound of General Formula II by hydrolysis to a compound represented by Formula III ##EQU24## neutralizing the compound of Formula III with a metal base of which the designation M is the metal to form a metal salt compound of the General Formula IV(A): ##EQU25## c. coupling two carboxyl groups of compounds of Formula IV(A) to each other through an organo-linking group - R - by ester formation through reaction with a dihalide to form a compound represented by the General Formula V ##EQU26## and then heating the compound of Formula V with maleic anhydride to displace said blocking groups and form said bis (2-cyanoacrylate) of Formula VI; wherein said blocking group ##SPC28## of Formula II, III, IV(A) and V is any one of the group consisting of ##SPC29## where R 1 and R 2 are the same, R 1 and R 2 are selected from the group consisting of H, an alkyl group of 1 to 5 carbons, phenyl, Br or Cl and where R 1 and R 2 are different, R 1 is H and R 2 is a member selected from any of the group consisting of an alkyl group of 1 to 5 carbons, phenyl, Br and Cl; ##SPC30## where R 3 is H or CH.sub. 3 ; and ##SPC31## wherein the organo linking group R of Formulas VI and V is the same and is any one of the group consisting of: --(CH.sub.2).sub.m --, where m is an integer of from 1 to 20 inclusive; ##EQU27## where n is an integer of from 0 to 18 inclusive, and R 4 and R 5 are independently hydrogen or a C 1 to C 5 alkyl group, R 4 and R 5 not simultaneously being hydrogen; --(CH.sub.2).sub.r --Z--(CH.sub.2).sub.s --, where Z is --O--, --S--, --CH=CH--;--C.tbd.C--; ##EQU28## and ##SPC32## where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R 6 and R 7 are independently hydrogen or a straight or branched chain C 1 to C 5 alkyl group ##SPC33## where x and y are integers of from 1 to 6 inclusive; ##SPC34## where x and y are as hereinbefore defined; --CH.sub.2 --(CF.sub.2).sub.z --CH.sub.2 --, where z is an integer of from 1 to 10 inclusive; and ##EQU29## and wherein R' of Formula I and II is an alcohol moiety selected from C 1 to C 16 alkyl, cyclohexyl or phenyl.

Claim 13

A method according to claim 10 in which the dihalide is selected from the group consisting of X--(ch 2 ) m --X, where m is an integer of from 1 to 20 inclusive; ##EQU30## where n is an integer of from 0 to 18 and R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1 to C 5 alkyl, but R 4 , and R 5 not simultaneously being hydrogen; X--(ch 2 ) r --Z--(CH 2 ) s --X, where Z is --O--, --S--, --CH=CH--, --C.tbd.C--, ##EQU31## and ##SPC35## where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R 6 and R 7 are independently hydrogen or a straight or branched chain C 1 to C 5 alkyl group ##SPC36## where x and y are integers of from 1 to 6 inclusive; ##SPC37## where x and y are as hereinbefore defined; X--ch 2 --(cf 2 ) z --CH 2 --X, where z is an integer of from 1 to 10 inclusive; and X--ch 2 --si(CH 3 ) 2 --O--Si(CH 3 ) 2 --CH 2 --X; and X is either independently selected from the halogens chlorine, bromine, and iodine.

Claim 14

A method according to claim 11 wherein the dihalide is X--(CH 2 ) m --X, where m is an integer of from 1 to 20 inclusive.

Claim 15

A method according to claim 10 in which the cyclic 1,3 diene is selected from the group consisting of anthracene, 9-methylanthracene, 9-bromoanthracene, 9-phenylanthracene, 9,10-dimethylanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, cyclopentadiene, methylcyclopentadiene, and norbornadiene.

Claim 16

A method according to claim 13 in which the diene is cyclopentadiene.

Claim 17

A method according to claim 10 wherein from 25 to 200 mole percent excess of maleic anhydride is employed.

Claim 18

A method according to claim 10 where the cyanoacrylic ester is isobutyl 2-cyanoacrylate.

Claim 19

A method according to claim 10 in which the diene is anthracene.