Epoxide photopolymerizable compositions containing cyclic amides as gelation inhibitor and methods of polymerizing

Claim 2

A stabilized polymerizable composition, comprising a polymerizable material consisting essentially of: a major proportion of a monomeric or prepolymeric epoxide, mixtures thereof or mixture thereof with a monomer selected from the group consisting of lactones and vinyl-containing compounds, said mixture being polymerizable to higher molecular weights through the action of a cationic catalyst; a radiation-sensitive catalyst precursor which decomposes upon application of energy to provide a Lewis acid effective to initiate polymerization of said polymerizable material, said precursor being an aromatic diazonium salt of a complex halogenide and present in an amount sufficient to effect said polymerization; and a stabilizing amount of a monomeric gelation inhibitor for counteracting prematurely formed Lewis acid, said inhibitor being selected from compounds of the general formula ##EQU13## R' is hydrogen or an unreactive group; R is hydrogen, an unreactive group, or a double bond to an adjacent carbon atom; and n is an integer of 3 to 11; said stabilizing amount of the inhibitor being substantially inert to said polymerizable material and said catalyst precursor.

Claim 3

The composition of claim 1, in which the monomeric or prepolymeric epoxide is a mixture of epoxides.

Claim 4

The composition of claim 1, in which the polymerizable material is a mixture of epoxides and a lactone.

Claim 5

The composition of claim 3, in which said lactone is propiolactone.

Claim 6

The composition of claim 1, in which the polymerizable material is a mixture of epoxides and a vinyl-containing compound.

Claim 7

The composition of claim 5, in which said vinylcontaining compound is selected from compounds having the general formula ##EQU14## wherein R 1 and R 2 are selected from the group consisting of hydrogen, alkyl, alkoxy, aryl, aryloxy, halogen, haloalkyl and haloaryl.

Claim 8

The composition of claim 1, in which said catalyst precursor is present in an amount equal to between about 0.5% and about 5% of the weight of said polymerizable material present in the composition.

Claim 9

The composition of claim 1 in which n is 3.

Claim 10

The composition of claim 1 in which n is 4.

Claim 11

The composition of claim 1 in which n is 5.

Claim 12

The composition of claim 1 in which n is 6.

Claim 13

The composition of claim 1 in which n is 11.

Claim 14

The composition of claim 1 in which said cyclic amide is selected from the group consisting of E-caprolactam, 2-pyrrolidinone, δ-valerolactam, 2-azacyclooctanone and 2-azacyclotridecanone.

Claim 15

The composition of claim 1, in which said gelation inhibitor is present in an amount by weight equal to between about 5% mole and about 65% mole based on the molar concentration of the catalyst precursor.

Claim 16

The composition of claim 1, in which the total amount of any unpolymerizable volatile solvents present in said composition is less than about 4% by weight of the composition.

Claim 17

The process of polymerizing a polymerizable material consisting essentially of a major proportion of a monomeric or prepolymeric epoxide, mixtures thereof or mixtures thereof with a monomer selected from the group consisting of lactones and vinyl-containing compounds, said mixtures being polymerizable to higher molecular weights through the action of a cationic catalyst, comprising: forming a mixture of a polymerizable material with a radiationsensitive catalyst precursor which decomposes upon application of energy to provide a Lewis acid effective to initiate polymerization of said polymerizable material, said precursor being an aromatic diazonium salt of a complex halogenide and present in an amount sufficient to effect said polymerization, and with a stabilizing amount of a monomeric gelation inhibitor for counteracting prematurely formed Lewis acid, said inhibitor being selected from compounds of the general formula ##EQU15## R' is hydrogen or an unreactive group; R is hydrogen, an unreactive group, or a double bond to an adjacent carbon atom; and n is an integer of 3 to 11 said stabilizing amount of the inhibitor being substantially inert to said polymerizable material and said catalyst precursor and subsequently applying energy to the resulting mixture to release said Lewis acid in sufficient amounts to effect substantial polymerization of the polymerizable material.

Claim 18

The process of polymerizing a polymerizable material consisting essentially of a major proportion of a monomeric or prepolymeric epoxide, mixtures thereof or mixtures thereof with a monomer selected from the group consisting of lactones and vinyl-containing compounds, said mixtures being polymerizable to higher molecular weights through the action of a cationic catalyst, comprising: forming a mixture of a polymerizable material with a radiationsensitive catalyst precursor which decomposes upon application of energy to provide a Lewis acid effective to initiate polymerization of said polymerizable material, said precursor being an aromatic diazonium salt of a complex halogenide and present in an amount sufficient to effect said polymerization, and with a stabilizing amount of a monomeric gelation inhibitor for counteracting prematurely formed Lewis acid, said inhibitor being selected from compounds of the general formula ##EQU15## R' is hydrogen or an unreactive group; R is hydrogen, an unreactive group, or a double bond to an adjacent carbon atom; and n is an integer of 3 to 11 said stabilizing amount of the inhibitor being substantially inert to said polymerizable material and said catalyst precursor and subsequently applying energy to the resulting mixture to release said Lewis acid in sufficient amounts to effect substantial polymerization of the polymerizable material.

Claim 19

The process of claim 16, in which the monomeric or prepolymeric epoxide is a mixture of epoxides.

Claim 20

The process of claim 16, in which the polymerizable material is a mixture of epoxides and a lactone.

Claim 21

The process of claim 16, in which the polymerizable material is a mixture of epoxides and a vinyl-containing compound.

Claim 22

The process of claim 16, in which said vinylcontaining compound is selected from compounds having the general formula ##EQU16## wherein R 1 and R 2 are selected from the group consisting of hydrogen, alkyl, alkoxy, aryl, aryloxy, halogen, haloalkyl and haloaryl.

Claim 23

The process of claim 16, in which said catalyst precursor is mixed with said polymerizable material in an amount equal to between about 0.5% and about 5% of the weight of the polymerizable material.

Claim 24

The process of claim 16, in which n is 3.

Claim 25

The process of claim 16, in which n is 4.

Claim 26

The process of claim 16, in which n is 5.

Claim 27

The process of claim 16, in which n is 6.

Claim 28

The process of claim 16, in which n is 11.

Claim 29

The process of claim 16, in which said cyclic amide is selected from the group consisting of E-caprolactam 2-pyrrolidinone, δ-valerolactam, 2-azacyclooctanone and 2-azacyclotridecanone.

Claim 30

The process of claim 16 in which said gelation inhibitor is mixed with said polymerizable material and said catalyst precursor in an amount equal to between about 5% mole and about 65% mole based on the molar concentration of the catalyst precursor.