Process for hardening a resin which is the reaction product of an epoxy resin, an olefinically unsaturated monocarboxylic acid and a polycarboxylic acid anhydride unit

Claim 2

A process for hardening (I) a resin which is the reaction product of a first reaction of a) an epoxy resin which contains at least two epoxy groups, with b) an olefinically unsaturated monocarboxylic acid followed by a reaction of free hydroxyl groups formed from the epoxidecarboxylic acid reaction with c) a polycarboxylic acid anhydride unit, by copolymerising said resin (I) with (II) a copolymerisable olefinically unsaturated monomer under the action of irradiation of an electron beam of a minimum radiation dose of 0.25 Mrad/g of reaction product, one polycarboxylic acid anhydride unit being attached to at least two molecules of the epoxy resin, the number of epoxy groups being approximately equal to the sum of the number of free carboxyl groups and the number of anhydride groups of the polycarboxylic acid anhydride units, the epoxide being in the proportion of about 1.25 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.25 to 0.5 mol of polycarboxylic acid anhydride units.

Claim 3

A process for hardening (I) a resin which is the reaction product of a first reaction of (a) an epoxy resin which contains at least two epoxy groups, with (b) an olefinically unsaturated monocarboxylic acid having 3 to 6 carbon atoms followed by a reaction of free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c) a polycarboxylic acid anhydride unit having 4 to 10 carbon atoms, by copolymerising said resin (I) with (II) a copolymerisable olefinically unsaturated monomer under the action of irradiation of an electron beam of a radiation dose of from 0.25 to 2.0 Mrad/g of reaction product, one polycarboxylic acid anhydride unit being attached to at least two molecules of the epoxy resin, the number of the epoxy groups being approximately equal to the sum of the number of free carboxylic groups and the number of anhydride groups of the polycarboxylic acid anhydride units, the epoxide being in the proportion of about 1.25 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.25 to 0.5 mo. of polycarboxylic acid anhydride units.

Claim 4

A process for hardening (I) a resin which is the reaction product of a first reaction of (a) an epoxy resin which contains at least two epoxy groups, with (b) an olefinically unsaturated monocarboxylic acid having 3 to 6 carbon atoms followed by a reaction of free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c) a polycarboxylic acid anhydride unit having 4 to 10 carbon atoms, by copolymerising said resin (I) with (II) a copolymerisable olefinically unsaturated monomer under the action of irradiation of an electron beam of a radiation dose of from 0.25 to 2.0 Mrad/g of reaction product, one polycarboxylic acid anhydride unit being attached to at least two molecules of the epoxy resin, the number of the epoxy groups being approximately equal to the sum of the number of free carboxylic groups and the number of anhydride groups of the polycarboxylic acid anhydride units, the epoxide being in the proportion of about 1.25 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.25 to 0.5 mo. of polycarboxylic acid anhydride units.

Claim 5

A process as claimed in claim 1 wherein the epoxy resin is a condensation product of a compound selected from the group consisting of novolak, diphenylolpropane, di- and triphenylolmethane 3,5-3',5'-tetrachloro-or -bromo- diphenylolpropane.

Claim 6

A process as claimed in claim 1 wherein the molecular weight of the epoxy resin is from 312 to 2000.

Claim 7

A process as claimed in claim 1 wherein the unsaturated monocarboxylic acid contains 3 to 6 C atoms.

Claim 8

A process as claimed in claim 1 wherein the polycarboxylic acid anhydride unit is selected from the group consisting of polycarboxylic acid anhydride and polycarboxylic acid anhydride containing in addition at least one carboxylic group.

Claim 9

A process as claimed in claim 1 wherein the polycarboxylic acid anhydride unit is selected from the group consisting of polycarboxylic acid anhydride and polycarboxylic acid anhydride containing in addition at least one carboxylic group.

Claim 10

A process as claimed in claim 1 wherein the reaction between the epoxy resin, the unsaturated monocarboxylic acid and the polycarboxylic acid anhydride unit is carried out at a temperature from 70° to 140° C.

Claim 11

A process as claimed in claim 1 in which the epoxy resin is reacted with the olefinically unsaturated monocarboxylic acid and the polycarboxylic acid anhydride in the presence of a catalyst, and a compound selected from the group consisting of hydroquinone and t-butyl hydroquinone and mixtures thereof.

Claim 12

A process as claimed in claim 1, in which the epoxy resin is formed by dehydrochlorination of a condensation product of phenoxychlorhydrine and formaldehyde.

Claim 13

A shaped body whenever obtained by a process as claimed in claim 1.

Claim 14

A shaped body as claimed in claim 11 which is a film or fibre.

Claim 15

A shaped body as claimed in claim 11 which is a coating.

Claim 16

A process for hardening a resin (I0) which is the reaction product of: a. an epoxy resin which is the bisglycidyl ether of diphenylolpropane or diphenylol methane which is first reacted with b. an olefinically unsaturated monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, and crotonic acid, followed by a reaction of free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c. a polycarboxylic acid anhydride unit selected from the group consisting of trimellitic anhydride, phthalic anhydride, and succinic anhydride and a mixture thereof by copolymerising said resin (I) with (II) a copolymerisable monomer selected from the group consisting of esters of acrylic or methycrylic acid with an alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, ethylhexyl alcohol, dodecyl alcohol, ethane diol, 1,2-propane diol, 1,3-propane, 1,2-butane diol, 1,4-butane diol, glycerol, pentaerythritol, and sorbitol; styrene; acrylonitrile; vinyl toluene; divinyl benzene maleic acid, esters of alcohols having 1 to 4 carbon atoms and alkyl esters of phthalic acid; wherein on polycarboxylic unit of said polycarboxylic acid anhydride units is attached to at least two molecules of the epoxy resin, wherein the resin is irradiated with an electron beam to a dose of from 0.25 to 2.0 Mrad/g of resin, wherein one mole of the epoxy resin (a) is reacted with less than 2 moles of monocarboxylic acid (b), the remaining free epoxy groups being reacted with an amount of the polycarboxylic acid anhydride unit such that the number of free epoxy groups approximately equals the total of the anhydride groups of the polycarboxylic acid anhydride units and the free carboxylic groups of the polycarboxylic acid anhydride unit, the number of the epoxide groups of resin (a) being in the proportion of about 1.25 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.25 to 0.5 mol of polycarboxylic acid anhydride units.

Claim 17

A process for hardening a resin (I0) which is the reaction product of: a. an epoxy resin which is the bisglycidyl ether of diphenylolpropane or diphenylol methane which is first reacted with b. an olefinically unsaturated monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, and crotonic acid, followed by a reaction of free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c. a polycarboxylic acid anhydride unit selected from the group consisting of trimellitic anhydride, phthalic anhydride, and succinic anhydride and a mixture thereof by copolymerising said resin (I) with (II) a copolymerisable monomer selected from the group consisting of esters of acrylic or methycrylic acid with an alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, ethylhexyl alcohol, dodecyl alcohol, ethane diol, 1,2-propane diol, 1,3-propane, 1,2-butane diol, 1,4-butane diol, glycerol, pentaerythritol, and sorbitol; styrene; acrylonitrile; vinyl toluene; divinyl benzene maleic acid, esters of alcohols having 1 to 4 carbon atoms and alkyl esters of phthalic acid; wherein on polycarboxylic unit of said polycarboxylic acid anhydride units is attached to at least two molecules of the epoxy resin, wherein the resin is irradiated with an electron beam to a dose of from 0.25 to 2.0 Mrad/g of resin, wherein one mole of the epoxy resin (a) is reacted with less than 2 moles of monocarboxylic acid (b), the remaining free epoxy groups being reacted with an amount of the polycarboxylic acid anhydride unit such that the number of free epoxy groups approximately equals the total of the anhydride groups of the polycarboxylic acid anhydride units and the free carboxylic groups of the polycarboxylic acid anhydride unit, the number of the epoxide groups of resin (a) being in the proportion of about 1.25 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.25 to 0.5 mol of polycarboxylic acid anhydride units.

Claim 18

A process for hardening (I) a resin which is the reaction product of a first reaction of a) an epoxy resin which contains at least two epoxy groups, with b) an olefinically unsaturated monocarboxylic acid followed by a reaction free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c) a polycarboxylic acid anhydride unit, by copolymerising said resin (I) with (II) a copolymerisable olefinically unsaturated monomer under the action of irradiation of an electron beam of a radiation dose of 0.25 to 2.0 Mrad/g of reaction product, one polycarboxylic acid anhydride being attached to at least two molecules of the epoxy resin, the number of epoxy groups being approximately equal to the sum of the number of free carboxyl groups and the number of anhydride groups of the polycarboxylic acid anhydride units, the epoxide being in the proportion of about 1.33 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.33 to 0.5 mol of polycarboxylic acid anhydride units.

Claim 19

A process for hardening (I) a resin which is the reaction product of a first reaction of a) an epoxy resin which contains at least two epoxy groups, with b) an olefinically unsaturated monocarboxylic acid followed by a reaction free hydroxyl groups formed from the epoxide-carboxylic acid reaction with c) a polycarboxylic acid anhydride unit, by copolymerising said resin (I) with (II) a copolymerisable olefinically unsaturated monomer under the action of irradiation of an electron beam of a radiation dose of 0.25 to 2.0 Mrad/g of reaction product, one polycarboxylic acid anhydride being attached to at least two molecules of the epoxy resin, the number of epoxy groups being approximately equal to the sum of the number of free carboxyl groups and the number of anhydride groups of the polycarboxylic acid anhydride units, the epoxide being in the proportion of about 1.33 to 1.5 equivalents of epoxide per equivalent of unsaturated monocarboxylic acid and about 0.33 to 0.5 mol of polycarboxylic acid anhydride units.

Claim 20

A process as claimed in claim 1 wherein said reaction product is prepared by the successive esterifying steps of: (I) an epoxy resin which contains at least two epoxy groups with less than one equivalent amount of unsaturated monocarboxylic acid, based on the epoxy groups, (II) the product of I, which contains the resulting hydroxyl groups from process Step I with polycarboxylic acid anhydride units and (III) the product of II which contains the resulting carboxylic groups from process Step II with the remaining unchanged epoxy groups from process Step I.