Monomers and oligomers containing a plurality of vinylbenzyl ether groups, method for their preparation and cured products therefrom

Claim 2

A monomer of oligomer containing a plurality of vinylaryl ether groups represented by the following formulas I, II or III ##STR5## wherein A is a hydrocarbyl group having from 1 to about 25 carbon atoms, --O--, --S--, --S--S--, ##STR6## R is hydrogen or a hydrocarbyl group having from 1 to about 12 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms or a halogen atom; m' has a value of from zero to about 200; each m and n independently has a value of zero or one; with the proviso that when m' and n have a value of zero, then A is a dicyclopentadienyl group or a dicyclopentadienyl oligomer group.

Claim 3

A monomer or oligomer of claim 1 wherein A is a hydrocarbyl group having from 1 to about 15 carbon atoms; R is hydrogen or a hydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms or a halogen atom; each m and n independently has a value of zero or 1; and m' has a value of from zero to about 50.

Claim 4

A monomer or oligomer of claim 1 wherein A is a hydrocarbyl group having from 1 to about 10 carbon atoms; R is hydrogen or a hydrocarbyl group having from 1 to about 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms or a halogen atom; and m' has a value of from zero to about 20.

Claim 5

A monomer or oligomer selected from the group consisting of the bis(vinyl benzyl) ether of dicyclopentadienyl bis(2,6-dimethyl phenol), bis(vinyl benzyl) ether of dicyclopentadienyl bis(o-cresol), bis(vinylbenzyl)ether of 3,3,',5,5'-tetramethyl-2,2',6,6'-tetrabromobiphenol, and bis(vinylbenzyl)ether of 2,6-dibromo-3,3',5,5'-tetramethyl bisphenol F. and

Claim 6

A monomer or oligomer selected from the group consisting of the bis(vinyl benzyl) ether of dicyclopentadienyl bis(2,6-dimethyl phenol), bis(vinyl benzyl) ether of dicyclopentadienyl bis(o-cresol), bis(vinylbenzyl)ether of 3,3,',5,5'-tetramethyl-2,2',6,6'-tetrabromobiphenol, and bis(vinylbenzyl)ether of 2,6-dibromo-3,3',5,5'-tetramethyl bisphenol F. and

Claim 9

A method of claim 5 wherein the reaction is conducted at a temperature of from about -30° C. to about 100° C. for from about 0.5 to about 20 hours.

Claim 10

A method of claim 5 wherein the reaction is conducted at a temperature of from about 0° C. to about 80° C. for from about 0.5 to about 15 hours.

Claim 11

A method of claim 5 wherein the reaction is conducted at a temperature of from about 15° C. to about 60° C. for from about 0.5 to about 6 hours.

Claim 12

A method of claim 6 wherein (a) said alkali metal phenoxide of a material containing a plurality of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR7## wherein A is a hydrocarbyl group having from 1 to about 25 carbon atoms, --O--, --S--, --S--S--, ##STR8## R is hydrogen or a hydrocarbyl group having from 1 to about 12 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms or a halogen atom, preferably bromine; each m independently has a value of zero or 1; and m' has a value of from zero to about 200; (b) said vinylbenzyl halide is vinylbenzyl chloride or vinylbenzyl bromide; and (c) said polar aprotic solvent is dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl pyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxy propane, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone or mixtures thereof.

Claim 13

A method of claim 7 wherein (a) said alkali metal phenoxide of a material containing a plurality of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR9## wherein A is a hydrocarbyl group having from 1 to about 15 carbon atoms; R is hydrogen or a hydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms or a halogen atom, preferably bromine; each m independently has a value of zero or 1; and m' has a value of from zero to about 50; (b) said vinylbenzyl halide is vinylbenzyl halide is vinylbenzyl chloride or vinylbenzyl bromide; and (c) said polar aprotic solvent is dimethylformamide, dimethyl acetamide, dimethylsulfoxide, N-methyl pyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxy propane, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ether ketone, methyl isobutyl ketone, acetone or mixtures thereof.

Claim 14

A method of claim 8 wherein (a) said alkali metal phenoxide of a material containing a pluraity of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR10## wherein A is a hydrocarbyl group having from 1 to about 10 carbon atoms; R is hydrogen or a hydrocarbyl group having from 1 to about 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms or a halogen atom, preferably bromine; each m independently has a value of zero or 1; and m' has a value of from zero to about 20; (b) said vinylbenzyl halide is vinylbenzyl chloride or vinyl benzyl bromide; and (c) said polar aprotic solvent is dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone or mixtures thereof.

Claim 17

A method of claim 12 wherein the reaction is conducted at a temperature of from about -30° C. to about 100° C. for from about 0.5 to about 20 hours.

Claim 18

A method of claim 13 wherein the reaction is conducted at a temperature of from about 0° C. to about 80° C. for from about 0.5 to about 15 hours.

Claim 19

A method of claim 14 wherein the reaction is conducted at a temperature of from about 15° C. to about 60° C. for from about 0.5 to about 6 hours.

Claim 20

A method of claim 13 wherein (a) said alkali metal phenoxide of a material containing a plurality of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR12## wherein A is a hydrocarbyl group having from 1 to about 25 carbon atoms, --O--, --S--, --S--S--, ##STR13## R is hydrogen or a hydrocarbyl group having from 1 to about 12 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 12 carbon atoms or a halogen atom; each m independently has a value of zero or 1; and m' has a value of from zero to about 200; (b) said extender material is 4-bromomethyl-3,5-dibromo-2,6-dimethyl phenol, 2,4-bis(chloromethyl)mesitylene, 1,2-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 4,6-bis-(chloromethyl)-m-xylene, 2,5-bis-(chloromethyl)-p-xylene, and combinations thereof; (c) said vinylbenzyl halide is vinylbenzyl halide is vinylbenzyl chloride or vinylbenzyl bromide; and (d) said polar aprotic solvent is dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone or mixtures thereof.

Claim 21

A method of claim 14 wherein (a) said alkali metal phenoxide of a material containing a plurality of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR14## wherein A is a hydrocarbyl group having from 1 to about 15 carbon atoms, --O--, --S--, --S--S--, ##STR15## R is hydrogen or a hydrocarbyl group having from 1 to about 6 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 6 carbon atoms or a halogen atom, preferably bromine; each m independently has a value of zero or 1; and m' has a value of from zero to about 50; said extender material is 4-bromomethyl-3,5-dibromo-2,6-dimethyl phenol, 2,4-bis(chloromethyl) 1,2-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 2,4-bis(chloromethyl)-mesitylene, 4,6-bis(chloromethyl)-m-xylene, 2,5bis-(chloromethyl)-p-xylene, and combinations thereof; (c) said vinylbenzyl halide is vinylbenzyl halide is vinylbenzyl chloride or vinylbenzyl bromide; and (d) said polar aprotic solvent is dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone or mixtures thereof.

Claim 22

A method of claim 15 wherein (a) said alkali metal phenoxide of a material containing a plurality of aromatic hydroxyl groups is an alkali metal phenoxide of a material represented by the following formulas V, VI or VII ##STR16## wherein A is a hydrocarbyl group having from 1 to about 10 carbon atoms, --O--, --S--, --S--S--, ##STR17## R is hydrogen or a hydrocarbyl group having from 1 to about 4 carbon atoms; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbon atoms or a halogen atom, preferably bromine; each m independently has a value of zero or 1; and m' has a value of from zero to about 20; (b) said extender material is 4-bromomethyl-3,5-dibromo-2,6-dimethyl phenol, 2,4-bis(chloromethyl) 1,2-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 2,4-bis-(chloromethyl)mesitylene, 4,6-bis-(chloromethyl)-m-xylene, 2,5-bis-(chloromethyl)-p-xylene, and combinations thereof; (c) said vinylbenzyl halide is vinylbenzyl halide is vinylbenzyl chloride or vinylbenzyl bromide; and (d) said polar aprotic solvent is dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidinone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dimethoxy propane, tetramethylene sulfone, hexamethyl phosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone or mixtures thereof.