EP0328020A2 — Use of a catalyst in epoxy compositions

Claim 1

Independent Claim 299 words

A composition comprising (A) at least one compound containing an average of more than one epoxide group per molecule; (B) at least one compound containing an average of more than one aromatic hydroxyl group per molecule other than an alkenylphenol polymer; and (C) a catalytic quantity of the product resulting from contacting (1) at least one compound selected from (a) an onium compound of the element nitrogen, phosphorus, sulfur or arsenic, (b) a non-heterocyclic amine compound or an acid adduct thereof and (c)a heterocyclic nitrogen-containing compound or an acid adduct thereof, with (2) at least one compound selected from (a) an inorganic acid free of boron or a metal salt thereof, said inorganic acid having a weak-nucleophilic anion, (b) an inorganic acid containing boron or a metal salt thereof, said inorganic acid being represented by the formula BR₃R′ wherein each R is independently hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbyl group having from 1 to 12 carbon atoms or a halogen and R′ is a group other than a hydrocarbyl group, and (c) any combination of components (a) or (b); wherein (i) components (C-1) and (C-2) are contacted in quantities which permit the composition to satisfy the viscosity requirements of the composition after storage at 50°C for 14 days; (ii) components (A) and (B) are present in quantities which provide a ratio of aromatic hydroxyl groups to epoxide group of from 0.05:1 to 20:1; and (iii) a mixture of components (A), (B), and (C), when dissolved in 20 to 40 percent by weight of a suitable solvent or solvent mixture has a viscosity measured at 25°C of 75 percent or less than the viscosity of a like composition except that the catalyst consists only of component (C-1), said viscosity being determined after storage for 14 days at 50°C.

Claim 2

Dependent Claim 299 words

A composition comprising (A) at least one compound containing an average of more than one epoxide group per molecule; (B) at least one compound containing an average of more than one aromatic hydroxyl group per molecule other than an alkenylphenol polymer; and (C) a catalytic quantity of the product resulting from contacting (1) at least one compound selected from (a) an onium compound of the element nitrogen, phosphorus, sulfur or arsenic, (b) a non-heterocyclic amine compound or an acid adduct thereof and (c)a heterocyclic nitrogen-containing compound or an acid adduct thereof, with (2) at least one compound selected from (a) an inorganic acid free of boron or a metal salt thereof, said inorganic acid having a weak-nucleophilic anion, (b) an inorganic acid containing boron or a metal salt thereof, said inorganic acid being represented by the formula BR₃R′ wherein each R is independently hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbyl group having from 1 to 12 carbon atoms or a halogen and R′ is a group other than a hydrocarbyl group, and (c) any combination of components (a) or (b); wherein (i) components (C-1) and (C-2) are contacted in quantities which permit the composition to satisfy the viscosity requirements of the composition after storage at 50°C for 14 days; (ii) components (A) and (B) are present in quantities which provide a ratio of aromatic hydroxyl groups to epoxide group of from 0.05:1 to 20:1; and (iii) a mixture of components (A), (B), and (C), when dissolved in 20 to 40 percent by weight of a suitable solvent or solvent mixture has a viscosity measured at 25°C of 75 percent or less than the viscosity of a like composition except that the catalyst consists only of component (C-1), said viscosity being determined after storage for 14 days at 50°C.

Claim 3

Dependent Claim 75 words

A composition of Claim 1, wherein component (A) is a glycidyl ether of dihydroxy phenol, biphenol, bisphenol, halogenated bisphenol, alkylated bisphenol, trisphenol, phenol-aldehyde novolac resin, halogenated phenol-aldehyde novolac resin, alkylated phenol-aldehyde novolac resin, phenol-hydroxybenzaldehyde resin, alkylated phenol-hydroxybenzaldehyde resin, hydrocarbon-phenol resin, hydrocarbon-halogenated phenol resin, hydrocarbon-alkylated phenol resin, aliphatic diol, aliphatic triol, polyetherdiol, polyethertriol, the alkylene oxide adduct of a compound containing an average of more than one aromatic hydroxyl group per molecule, or any combination thereof.

Claim 4

Dependent Claim 47 words

A composition of Claim 1, wherein component (B) is a dihydroxy phenol, biphenol, bisphenol, halogenated bisphenol, alkylated bisphenol, trisphenol, phenol-aldehyde novolac resin, halogenated phenol-aldehyde novolac resin, alkylated phenol-aldehyde novolac resin, phenol-hydroxybenzaldehyde resin, alkylated phenol-hydroxybenzaldehyde resin, hydrocarbon-phenol resin, hydrocarbon-halogenated phenol resin, hydrocarbon-alkylated phenol resin, or any combination thereof.

Claim 5

Dependent Claim 145 words

A composition of Claim 1 wherein (a) component (C-1-a) is a compound represented by the following formulas IA or IB wherein each R, R¹, R² and R³ is independently a hydrocarbyl group having from 1 to 18, preferably from 1 to 9, carbon atoms, or a hydrocarbyl group having from 1 to 18, preferably from 1 to 9 carbon atoms which group also contains one or more oxygen, sulfur, halogen, or nitrogen atoms or two of such R, R¹, R² and R³ groups can combine to form a heterocyclic ring containing one or more atoms other than carbon atoms; each X is the anion portion of a relatively strong nucleophiic acid; Z is phosphorus, nitrogen, sulfur or arsenic; m has a value equal to the valence of the anion X, and z has a value of zero or 1 depending on the valence of Z.

Claim 6

Dependent Claim 20 words

A composition of Claim 1, wherein component (C-1-b) is a primary, secondary or tertiary aliphatic, cycloaliphatic, or aromatic non-heterocyclic amine.

Claim 7

Dependent Claim 43 words

A composition of Claim 1, wherein component (C-1-c) is selected from imidazoles, imidazolidines, imidazolines, oxazoles, pyrroles, thiazoles, pyridines, pyrazines, morpholines, pyridazine, pyrimidine, pyrazoles, quinoxalines, quinazolines, phthalozines, quinolines, purines, indazoles, indoles, indolazines, phenazines, phenarsines, phenothiazines, pyrrolines, indolines, piperidines, piperazines, pyrrolidine or any combination thereof.

Claim 8

Dependent Claim 52 words

A composition of Claim 1, wherein component (C-2) is selected from the group consisting of fluoboric acid, fluoarsenic acid, fluoantimonic acid, fluophosphoric acid, chloroboric acid, chloroarsenic acid, chloro-antimonic acid, chlorophosphoric acid, perchloric acid, chloric acid, bromic acid, iodic acid, Group I or II metal salts of such acids, and any combination thereof.

Claim 9

Dependent Claim 110 words

A catalyst resulting from contacting (1) at least one heterocyclic nitrogen-containing compound other than pyridine or an acid adduct thereof with (2) at least one compound selected from (a) an inorganic acid free of boron or a metal salt thereof, said inorganic acid having a weak-nucleophilic anion, (b) an inorganic acid containing boron or a metal salt thereof, said inorganic acid being represented by the formula BR₃R′ wherein each R is independently hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbyl group having from 1 to 12 carbon atoms or a halogen and R′ is a group other than a hydrocarbyl group, and (c) any combination of components (a) or (b).

Claim 10

Dependent Claim 110 words

A catalyst resulting from contacting (1) at least one heterocyclic nitrogen-containing compound other than pyridine or an acid adduct thereof with (2) at least one compound selected from (a) an inorganic acid free of boron or a metal salt thereof, said inorganic acid having a weak-nucleophilic anion, (b) an inorganic acid containing boron or a metal salt thereof, said inorganic acid being represented by the formula BR₃R′ wherein each R is independently hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbyl group having from 1 to 12 carbon atoms or a halogen and R′ is a group other than a hydrocarbyl group, and (c) any combination of components (a) or (b).

Claim 11

Dependent Claim 41 words

The catalyst of Claim 8 wherein components (1) and (2) are contacted in quantities which provide from 0.6 to 1.4 moles of acid or metal acid salt per mole of heterocyclic nitrogen-containing compound or acid adduct of a heterocyclic nitrogen-containing compound.

Claim 12

Dependent Claim 89 words

The catalyst of Claim 8 wherein (a) component (1) is selected from imidazoles, imidazolidines, imidazolines, oxazoles, pyrroles, thiazoles, pyridines, pyrazines, morpholines, pyridazines, pyrimidines, pyrazoles, quinoxalines, quinazolines, phthalozines, quinolines, purines, indazoles, indoles, indolazines, phenazines, phenarsines, phenothiazines, pyrrolines, indolines, piperidines, piperazines, pyrrolidine or any combination thereof; and (b) component (2) is selected from fluoboric acid, fluoarsenic acid, fluoantimonic acid, fluophosphoric acid, chloroboric acid, chloroarsenic acid, chloroantimonic acid, chlorophosphoric acid, perchloric acid, chloric acid, bromic acid, iodic acid, Group I or Group II metal salt of such acids, or any combination thereof.

Claim 13

Dependent Claim 143 words

The catalyst of Claim 10 wherein component (1) is an imidazole represented by the following formula I wherein R a is hydrogen, halogen, cyano or a hydrocarbyl group having from 2 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substitutent; each R b , R c and R d is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent, or R b and R c can combine to form a 5 or 6 membered ring with the carbon and nitrogen atoms from the imidazole ring to which they are attached or R c and R d can combine to form a 5 or 6 membered ring with the two carbon atoms from the imidazole ring to which they are attached.

Claim 14

Dependent Claim 19 words

The catalyst of Claim 11 wherein said imidazole compound is 2-ethyl-4-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole ,4,5-diphenylimidazole, or any combination thereof.

Claim 15

Dependent Claim 195 words

The catalyst of Claim 11 which is represented by the following formula I′ wherein R a is hydrogen or a hydrocarbyl group having from 2 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent; each R b , R c and R d is independently hydrogen or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent, or R b and R c can combine to form a 5 or 6 membered ring with the carbon and nitrogen atoms from the imidazole ring to which they are attached or R c and R d can combine to form a 5 or 6 membered ring with the two carbon atoms from the imidazole ring to which they are attached; and X is the anion portion of (a) an inorganic acid free of boron having a weak nucleophilic anion or (b) a boron containing inorganic acid represented by the formula HBR₃R′ wherein each R is independently hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbyl group having from 1 to 12 carbon atoms or a halogen and R′ is a halogen.

Claim 16

Dependent Claim 119 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrazole compound represented by the following formula II wherein each R a , R b , R c and R d is independently hydrogen or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent, or R b and R c can combine to form a 5 or 6 membered ring with the carbon and nitrogen atoms from the pyrazole ring to which they are attached or R c and R d can combine to form a 5 or 6 membered ring with the two carbon atoms from the pyrazole ring to which they are attached.

Claim 17

Dependent Claim 60 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an oxazole represented by the following formula III wherein each R a , R b , R c and R d is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 18

Dependent Claim 73 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an imidazolidine compound represented by the following formula IV wherein each R a , R b , R c , R d , R e , R f , R g and R h is independently hydrogen or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen or the like substituent.

Claim 19

Dependent Claim 64 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an imidazoline compound represented by the following formula V wherein each R a , R b , R c , R d , R e and R f is independently hydrogen or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent.

Claim 20

Dependent Claim 61 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a thiazole compound represented by the following formula VI wherein each R a , R b , R c and R d is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 21

Dependent Claim 62 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrrole compound represented by the following formula VII wherein each R a , R b , R c , R d and R e is independently hydrogen or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 22

Dependent Claim 89 words

The catalyst of claim 10 wherein said heterocyclic nitrogen-containing compound is a pyridine compound represented by the following formula VIII wherein R a , R b , R c , R d and R e is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent with the proviso that at least one of the R a , R b , R c , R d or R e is other than hydrogen.

Claim 23

Dependent Claim 59 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrazine compound represented by the following formula IX wherein each R a , R b , R c and R d is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 24

Dependent Claim 60 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyridazine compound represented by the following formula X wherein each R a , R b , R c , and R d is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 25

Dependent Claim 75 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrrolidine compound represented by the following formula XI wherein each R a , R b , R c , R d , R e , R f , R g , R h and R i is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur or halogen substituent.

Claim 26

Dependent Claim 99 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a morpholine compound represented by the following formula XII wherein R a is hydrogen, a hydrocarbyl group having from 2 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, or halogen substituent; each R b , R c , R d , R e , R f , R g , R h and R i is independently hydrogen, halogen, cyano or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, halogen or the like substituent.

Claim 27

Dependent Claim 63 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrimidine compound represented by the following formula XIII wherein each R a , R b , R c , R d , and R e is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 28

Dependent Claim 65 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a quinoxaline compound represented by the following formula XIV wherein each R a , R b , R c , R d , R e ,and R f is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 29

Dependent Claim 66 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a quinazoline compound represented by the following formula XV wherein each R a , R b , R c , R d , R e , and R f is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 30

Dependent Claim 65 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a phthalozine compound represented by the following formula XVI wherein each R a , R b , R c , R d , R e ,and R f is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 31

Dependent Claim 68 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a quinoline compound represented by the following formula XVII wherein each R a , R b , R c , R d , R e , R f and R g is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 32

Dependent Claim 62 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a purine compound represented by the following formula XVIII wherein each R a , R b , R c and R d is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen or the like substituent.

Claim 33

Dependent Claim 65 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an indazole compound represented by the following formula XIX wherein each R a , R b , R c , R d , R e and R f is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 34

Dependent Claim 68 words

The product of Claim 10 wherein said heterocyclic nitrogen-containing compound is an indole compound represented by the following formula XX wherein each R a , R b , R c , R d , R e , R f and R g is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 35

Dependent Claim 68 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an indolazine compound represented by the following formula XXI wherein each R a , R b , R c , R d , R e , R f and R g is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 36

Dependent Claim 71 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a phenazine compound represented by the following formula XXII wherein each R a , R b , R c , R d , R e , R f , R g and R h is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 37

Dependent Claim 71 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a phenarsazine compound represented by the following formula XXIII wherein each R a , R b , R c , R d , R e , R f , R g and R h is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 38

Dependent Claim 74 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a phenothiazine compound represented by the following formula XXIV wherein each R a , R b , R c , R d , R e , R f , R g , R h and R i is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 39

Dependent Claim 68 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a pyrroline compound represented by the following formula XXV wherein each R a , R b , R c , R d , R e , R f and R g is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 40

Dependent Claim 74 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is an indoline compound represented by the following formula XXVI wherein each R a , R b , R c , R d , R e , R f , R g , R h and R i is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 41

Dependent Claim 80 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a piperidine compound represented by the following formula XXVII wherein each R a , R b , R c , R d , R e , R f , R g , R h , R i , R j and R k is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Claim 42

Dependent Claim 77 words

The catalyst of Claim 10 wherein said heterocyclic nitrogen-containing compound is a piperazine compound represented by the following formula XXVIII wherein each R a , R b , R c , R d , R e , R f , R g , R h , R i and R j is independently hydrogen, or a hydrocarbyl group having from 1 to 18 carbon atoms or such hydrocarbyl groups containing an oxygen, sulfur, cyano or halogen substituent.

Use of a catalyst in epoxy compositions

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