Curable compositions containing a polyepoxide and a halogenated bisphenol

Claim 1

A composition comprising (A) at least one of (1) at least one epoxy resin represented by the following formulas I, II, III, IV, V or VI wherein each Aʹ is independently a divalent hydrocarbyl group having from 1 to 12 carbon atoms, -S-­, -S-S-, -SO-, -SO₂-, -CO- or -O-; each B is represented by the formula each Bʹ is represented by the formula each Bʺ is represented by the formula each R is independently hydrogen or an alkyl group having from 1 to 4 carbon atoms; each Q is independently hydrogen or a hydrocarbyl group having from 1 to 10 carbon atoms; each Rʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10 carbon atoms or a halogen; m has a value of n-1; mʹ has a value of nʹ-1; mʺ has a value of nʺ-1 whereby each of m, mʹ and mʺ has at least the value zero; each n, nʹ and nʺ independently has a value from zero to 3; q has a value from zero to 4; each y independently has an average value from 1 to 5; yʹ has an average value of from zero to 3 and each z and zʹ independently has a value from zero to 3; (2) the reaction product of (a) at least one epoxy resin as defined in component (A-1) and b) at least one dihydric or polyhydric phenol represented by the following formulas VII, VIII or IX wherein A is a divalent hydrocarbon group having from 1 to 12 carbon atoms, -O-, -­ S-, -S-S-, -SO-, -SO₂-, or -CO-; each Y is independently hydrogen, a halogen or a hydrocarby or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each Aʺ is independently a divalent hydrocarbon group having from 1 to 6 carbon atoms; each Yʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10, preferably from 1 to 4 carbon atoms, a halogen atom or a hydroxyl group; and n has a value of 0 or 1; and wherein components (A-2-a) and (A-2-b) are present in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from 0.01:1 to 0.5:1; or (3) mixtures thereof; and (B) at least one halogenated dihydric phenol represented by the following formulas X, XI or XII wherein A, Aʺ, Y, Yʹ and n are as defined above; each X is a halogen; with the proviso that at least one X or Y in Formula XI and at least one X or Yʹ in Formula XII is a halogen; and wherein components (A) and (B) are present in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from above 0.7:1 to about 1.1:1; characterized by employing as at least a portion of component (B) a halogenated dihydric phenol wherein at least 5 weight percent of the halogen atoms present in component (B) are in the meta position with respect to the hydroxyl groups.

Claim 12

A method for preparing a composition said composition comprising (A) at least one of (1) at least one epoxy resin represented by the following formulas I, II, III, IV, V or VI wherein each Aʹ is independently a divalent hydrocarbyl group having from 1 to 12 carbon atoms, -S-­, -S-S-, -SO-, -SO₂-, -CO- or -O-; each B is represented by the formula each Bʹ is represented by the formula each Bʺ is represented by the formula each R is independently hydrogen or an alkyl group having from 1 to 4 carbon atoms; each Q is independently hydrogen or a hydrocarbyl group having from 1 to 10 carbon atoms; each Rʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10 carbon atoms or a halogen; m has a value of n-1; mʹ has a value of nʹ-1; mʺ has a value of nʺ-1 whereby each of m, mʹ and mʺ has at least the value zero; each n, nʹ and nʺ independently has a value from zero to 3; q has a value from zero to 4; each y independently has an average value from 1 to 5; yʹ has an average value of from zero to 3 and each z and zʹ independently has a value from zero to 3; (2) the reaction product of (a) at least one epoxy resin as defined in component (A-1) and b) at least one dihydric or polyhydric phenol represented by the following formulas VII, VIII or IX wherein A is a divalent hydrocarbon group having from 1 to 12 carbon atoms, -O-, -­ S-, -S-S-, -SO-, -SO₂-, or -CO-; each Y is independently hydrogen, a halogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each Aʺ is independently a divalent hydrocarbon group having from 1 to 6 carbon atoms; each Yʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10, preferably from 1 to 4 carbon atoms, a halogen atom or a hydroxyl group; and n has a value of 0 or 1; and wherein components (A-2-a) and (A-2-b) are present in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from 0.01:1 to 0.5:1; or (3) mixtures thereof; and (B) at least one halogenated dihydric phenol represented by the following formulas X, XI or XII wherein A, Aʺ, Y, Yʹ and n are as defined above; each X is a halogen; with the proviso that at least one X or Y in Formula XI and at least one X or Yʹ in Formula XII is a halogen; by mixing components (A) and (B) in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from about 0.7:1 to about 1.1 :1 said method being characterized by employing as at least a portion of component (B) a halogenated dihydric phenol wherein at least 5 weight percent of the halogen atoms present in component (B) are in the meta position with respect to the hydroxyl groups.

Claim 13

A method for preparing a composition said composition comprising (A) at least one of (1) at least one epoxy resin represented by the following formulas I, II, III, IV, V or VI wherein each Aʹ is independently a divalent hydrocarbyl group having from 1 to 12 carbon atoms, -S-­, -S-S-, -SO-, -SO₂-, -CO- or -O-; each B is represented by the formula each Bʹ is represented by the formula each Bʺ is represented by the formula each R is independently hydrogen or an alkyl group having from 1 to 4 carbon atoms; each Q is independently hydrogen or a hydrocarbyl group having from 1 to 10 carbon atoms; each Rʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10 carbon atoms or a halogen; m has a value of n-1; mʹ has a value of nʹ-1; mʺ has a value of nʺ-1 whereby each of m, mʹ and mʺ has at least the value zero; each n, nʹ and nʺ independently has a value from zero to 3; q has a value from zero to 4; each y independently has an average value from 1 to 5; yʹ has an average value of from zero to 3 and each z and zʹ independently has a value from zero to 3; (2) the reaction product of (a) at least one epoxy resin as defined in component (A-1) and b) at least one dihydric or polyhydric phenol represented by the following formulas VII, VIII or IX wherein A is a divalent hydrocarbon group having from 1 to 12 carbon atoms, -O-, -­ S-, -S-S-, -SO-, -SO₂-, or -CO-; each Y is independently hydrogen, a halogen or a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbon atoms; each Aʺ is independently a divalent hydrocarbon group having from 1 to 6 carbon atoms; each Yʹ is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10, preferably from 1 to 4 carbon atoms, a halogen atom or a hydroxyl group; and n has a value of 0 or 1; and wherein components (A-2-a) and (A-2-b) are present in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from 0.01:1 to 0.5:1; or (3) mixtures thereof; and (B) at least one halogenated dihydric phenol represented by the following formulas X, XI or XII wherein A, Aʺ, Y, Yʹ and n are as defined above; each X is a halogen; with the proviso that at least one X or Y in Formula XI and at least one X or Yʹ in Formula XII is a halogen; by mixing components (A) and (B) in quantities such that the ratio of phenolic hydroxyl groups to epoxide groups is from about 0.7:1 to about 1.1 :1 said method being characterized by employing as at least a portion of component (B) a halogenated dihydric phenol wherein at least 5 weight percent of the halogen atoms present in component (B) are in the meta position with respect to the hydroxyl groups.

Claim 16

A method according to anyone of Claims 1 to 3 wherein component (A) is component (A-1) represented by formula I or II wherein Q, R and Rʹ are hydrogen; q has an average value of from 0.1 to 2 and component (B) is represented by formula XI wherein A is a divalent hydrocarbyl group having from 1 to about 6 carbon atoms, and each X is bromine.

Claim 17

A method according to anyone of Claims 1 to 3 wherein component (A) is component (A-1) represented by formula III wherein Aʹ has from 1 to 4 carbon atoms and each R and Rʹ is hydrogen and component (B) is represented by formula XI wherein A is a divalent hydrocarbyl group having from 1 to 6 carbon atoms and each X is bromine.

Claim 18

A method according to anyone of Claims 1 to 3 wherein component (A) is component (A-1) represented by formulas IV or V wherein each Q, R and Rʹ is hydrogen and component (B) is represented by formula XI wherein A is a divalent hydrocarbyl group having from 1 to about 6 carbon atoms and each X is bromine.

Claim 19

A method according to anyone of Claims 1 to 3 wherein component (A) is component (A-1) represented by formula VI wherein each Q and Rʹ is hydrogen and component (B) is represented by formula XI wherein A is a divalent hydrocarbyl group having from 1 to about 6 carbon atoms and each X is bromine.

Claim 20

A method according to anyone of Claims 4-7 wherein component (B) is 2,2ʹ,6,6ʹ-tetrabromo-­3,3ʹ,5,5ʹ-tetramethyl-4,4ʹ-biphenol or 2,2ʹ,6-tribromo-­3,3ʹ,5,5ʹ-tetra-methyl-4,4ʹ-biphenol or 4,4ʹ-methylene-­bis-3,5-dibromo- -2,6-dimethylphenol, or mixture thereof and said stabilizer is methyl p-toluene sulfonate.

Claim 21

A method for preparing a composition which method comprises mixing (I) a composition of any one of Claims 1-8 and (II) a catalytic quantity of at least one catalyst for effecting the reaction between components (I-A) and (I-­B).