Polyisocyanato/imido compositions and imide group containing polymers prepared therefrom

Claim 2

A composition of matter comprising (A) at least one organic polyisocyanate, and (B) at least one unsaturated imide selected from the group consisting of: (i) a monoimide of the formula: ##STR15## wherein D represents ##STR16## in which Y is H, CH 3 or Cl, and Z is either 0, 1 or 2, and R 1 is hydrogen or a monovalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing up to 20 carbon atoms; and (ii) a polyimide of the formula: ##STR17## wherein D is as above, n is a number ranging from 2 to 5 and R 2 is a radical having the valence n, such R 2 radical being selected from the group consisting of a wholly hydrocarbon radical, a heteroatom interrupted hydrocarbon radical, and a heterocycle containing hydrocarbon radical, and wherein in said composition the ratio r of total isocyanate functions in the polyisocyanate (A) to total polymerizable double bonds in the unsaturated imide (B) is in the range of from 0.3 to 15.

Claim 3

The composition of matter as defined by claim 1, wherein the polyisocyanate is a monomeric polyisocyanate of the formula: R.sub.3 --NCO).sub.m [III] in which m is a number of from 2 to 5, and R 3 represents a radical with the valence m and is an aliphatic, cycloaliphatic or aromatic radical having up to 50 carbon atoms, said R 3 radical being selected from the group consisting of a wholly hydrocarbon radical, a heteroatom interrupted hydrocarbon radical, and a heterocycle containing hydrocarbon radical.

Claim 4

The composition of matter as defined by claim 2, wherein the number m is either 2 or 3.

Claim 5

The composition of matter as defined by claim 2, wherein R 3 is a straight or branched chain aliphatic radical having up to 12 carbon atoms, a C 1 -C 12 alkylene radical, a cycloaliphatic radical having 5 to 6 ring carbon atoms, a monocyclic or fused bicyclic aromatic radical, a ##STR18## radical where p is 1, 2 or 3, a polycyclic aromatic radical as defined above, the individual rings of which are either fused or linked by a simple valence bond, or linked by an atom or bridge selected from the group consisting of --O--, --S--, --SO 2 -- or an alkylene radical containing 1 to 4 carbon atoms, or further wherein the various aromatic nuclei are substituted with one or more halogen atoms, or with one or more alkyl radicals having 1 to 4 carbon atoms, or with a methoxy group.

Claim 6

The composition of matter as defined by claim 2, wherein the polyisocyanate is selected from the group consisting of toluene-2,4-diisocyanate, mixtures of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, bis(4-isocyanatophenyl)methane, paraphenylene diisocyanate, metaphenylene diisocyanate, 1,5-di-isocyanatonaphtalene, tris(4-isocyanatophenyl)methane, 2,4-diisocyanato-chlorobenzene, bis(4-isocyanatophenyl)ether, 1,6-diisocyanatohexane, 3,3'-dimethyl-4,4'-diisocyanato-biphenyl, bis(4-isocyanatocyclohexyl)methane, bis(3-methyl-4-isocyanatophenyl)methane, bis(4-isocyanatophenyl)propane, 4,4'-diisocyanato-3,3'-dichlorodiphenyl, and polyisocyanates of the formula: ##STR19## where w is a number ranging from 0.1 to 4.

Claim 7

The composition of matter as defined by claim 1, wherein the polyisocyanate is a polyisocyanate prepolymer selected from the group consisting of those of the formulae: ##STR20## wherein Σ 1 comprises a divalent organic radical derived from a polymer containing at least two reactive hydroxyl or amino groups, said prepolymer resulting from the reaction of a molar excess of a diisocyanate of the formula OCN--R 3 --NCO with said reactive hydroxyl or amino group-containing polymer.

Claim 8

The composition of matter as defined by claim 6, wherein Σ 1 is the reaction product of a dihydroxylated polymer selected from the group consisting of hydroxylated polybutadiene, castor oil, hydroxylated epoxy resin containing at least two 1,2-epoxy groups per molecule, hydroxylated polyester prepared from a diacid and a diol and α,ω dihydroxylated polyether.

Claim 9

The composition of matter as defined by claim 7, wherein the dihydroxylated polymer is a hydroxylated polyester, said polyester being the condensation product of a dicarboxylic acid and a diol, and the amounts of such reactants being that their OH/COOH ratio is greater than 1.

Claim 10

The composition of matter as defined by claim 8, wherein the OH/COOH ratio ranges from 1.1 to 2, the dicarboxylic acid is selected from the group consisting of succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric, methyliminodiacetic, dimethylamino-3-hexanedioic, cyclohexane-1,4-dicarboxylic acid, 3-dimethylaminocyclopentane-1,2-dicarboxylic acid, the phthalic acids, naphthalene-1,5-dicarboxylic acid, pyrimidine dicarboxylic acids and imidazole dicarboxylic acid, and the diol is selected from the group consisting of 1,2-ethanediol, the 1,2- and 1,3-propanediols, the 1,2-, 2,3-, 1,3- and 1,4-butanediols, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, butenediol, butynediol, ethyldiethanolamine, and an αω-hydroxylated polyether.

Claim 11

The composition of matter as defined by claim 7, wherein the dihydroxylated polymer is an α,ω-dihydroxylated polyether selected from the group consisting of poly(oxyalkylene)glycol, poly(oxytetramethylene)glycol, and a nitrogen containing α,ω-dihydroxylated polyether.

Claim 12

The composition of matter as defined by claim 6, wherein Σ 1 is the reaction product of an α,ω-diamine polymer.

Claim 13

The composition of matter as defined by claim 1, wherein the component (A) further comprises up to 30% of a monoisocyanate of the formula: G--NCO [VII] wherein the symbol G is a substituted or unsubstituted, saturated or unsaturated, linear or branched chain aliphatic radical, having up to 8 carbon atoms, a C 1 -C 8 alkyl radical, a cycloalkyl radical with 5 or 6 carbon atoms, a phenyl radical, an alkylphenyl or phenylalkyl radical with up to 12 carbon atoms, said substituents being one or two chlorine atoms or a methoxy group.

Claim 14

The composition of matter as defined by claim 1, wherein the unsaturated imide has the formula I, and R 1 represents a substituted or unsubstituted, linear or branched chain alkyl or alkenyl radical containing up to 20 carbon atoms, a cycloalkyl radical containing 5 or 6 carbon atoms in the ring, a mono- or bicyclic aryl radical or aralkyl radical containing up to 20 carbon atoms, ##STR21## a monovalent radical selected from the group consisting of a phenyl radical and at least one phenylene radical joined together by a simple valence bond or by an atom or an inert bridge selected from the group --O--, --S--, an alkylene radical with 1 to 3 carbon atoms, --CO--, --SO 2 --, --NR 4 --, --N═N--, --CONH--, --COO--, where R 4 represents H, CH 3 , phenyl or cyclohexyl, said substituents being selected from the group F, Cl, CH 3 , OCH 3 , OC 2 H 5 , OH, NO 2 , --COOH, --NHCOCH 3 , and ##STR22##

Claim 15

The composition of matter as defined by claim 1, wherein the unsaturated imide is selected from the group consisting of maleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-phenylchloromaleimide, N-p-chlorophenylmaleimide, N-p-methoxyphenylmaleimide, N-p-methylphenylmaleimide, N-p-nitrophenylmaleimide, N-p-phenoxyphenylmaleimide, N-p-phenylcarbonylphenylmaleimide, maleimido-1-acetoxysuccinimido-4-benzene, maleimido-4-acetoxysuccinimido-4'-diphenylmethane, maleimido-4-acetoxysuccinimido-4'-diphenylether, maleimido-4-acetamido-4'-diphenylether, maleimido-2-acetamido-6 pyridine, maleimido-4-acetamido-4'-diphenylmethane, N-methylmaleimide, N-ethylmaleimide, N-vinylmaleimide, N-allylmaleimide, N-cyclohexylmaleimide, N-decylmaleimide.

Claim 16

The composition of matter as defined by claim 1, wherein the unsaturated imide has the formula II, and R 2 is an alkylene radical, linear or branched, containing up to 13 carbon atoms; a cyclohexylene or cyclopentylene radical; a phenylene or naphthylene radical; ##STR23## where s is equal to 1, 2 or 3; a radical containing two phenylene or cyclohexylene radicals joined to each other by a simple valence bond or by a linking atom or inert bridge selected from the group consisting of --O--, --S--, an alkylene group having 1 to 3 carbon atoms, --CO--, --SO 2 --, --NR 5 --, --N═N--, --CONH--, --COO--, --P(O)R 5 , --CONH--X--NHCO--, ##STR24## where R 5 represents a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, phenyl or cyclohexyl and X represents an alkylene radical having up to 13 carbon atoms.

Claim 17

The composition of matter as defined by claim 1, wherein the unsaturated imide is selected from the group consisting of N,N'-ethylene-bis-maleimide, N,N'-metaphenylene-bis-maleimide, N,N'-hexamethylene-bis-maleimide, N,N'-paraphenylene-bis-maleimide, N,N'-4,4'-biphenylene-bis-maleimide, N,N'-4,4'-diphenylmethane-bis-maleimide, N,N'-4,4'-diphenylmethane-bis-tetrahydrophthalimide, N,N'-4,4'-diphenylether-bis-maleimide, N,N'-4,4'-diphenylthio-bis-maleimide, N,N'-4,4'-diphenylsulfone-bis-maleimide, N,N'-4,4'-dicyclohexylmethane-bis-maleimide, N,N'-α,α'-4,4'-dimethylene cyclohexane-bis-maleimide, N,N'-paraxylylene-bis-maleimide, N,N'-4,4'-diphenyl-1,1-cyclohexane-bis-maleimide, N,N'-4,4'-diphenylmethane-bis-citraconimide, N,N'-4,4'-diphenylether-bis-endomethylene tetrahydrophthalimide, N,N'-4,4'-diphenylmethane-bis-chloromaleimide, N,N'-4,4'-diphenyl-1,1-propane-bis-maleimide, N,N'-4,4'-triphenyl-1,1,1-ethane-bis-maleimide, N,N'-4,4'-triphenylmethane-bis-maleimide, N,N'-3,5-triazole-1,2,4-bis-maleimide, N,N'-dodecamethylene-bis-maleimide, N,N'-trimethyl-2,2,4-hexamethylene-bis-maleimide, bis(maleimido-2-ethoxy)-1,2-ethane, bis(maleimido-3-propoxy)-1,3-propane, N,N'-4,4'-benzophenone-bis-maleimide, N,N'-pyridinediyl-2,6-bis-maleimide, N,N'-naphthylene-1,5-bis-maleimide, N,N'-cyclohexylene-1,4-bis-maleimide, N,N'-methyl-5-phenylene-1,3-bis-maleimide, and N,N'-methoxy-5-phenylene-1,3-bis-maleimide.

Claim 18

The composition of matter as defined by claim 1, wherein the unsaturated imide has the structural formula: ##STR25## wherein y is a number from 0.1 to 4, and R 6 is a divalent hydrocarbon radical having 1 to 8 carbon atoms.

Claim 19

The composition of matter as defined by claim 1, wherein the ratio r is in the range of from 0.5 to 10.

Claim 20

The composition of matter as defined by claim 1, further comprising a catalytic amount of an isocyanate polymerization catalyst.

Claim 21

The composition of matter as defined by claim 1, further comprising a catalytic amount of a vinylpyridine catalyst.

Claim 22

A homogeneous solution comprising the composition of matter as defined by claim 1.

Claim 23

The composition of matter as defined by claim 1, further comprising a polymerization inhibitor.

Claim 24

The composition of matter as defined by claim 1, wherein at least a portion of the total --NCO functions in the polyisocyanate are blocked.

Claim 25

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 1 and characterized by recurring units having the structure ##STR26##

Claim 26

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 2 and characterized by recurring units having the structure ##STR27##

Claim 27

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 3 and characterized by recurring units having the structure ##STR28##

Claim 28

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 4 and characterized by recurring units having the structure ##STR29##

Claim 29

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 5 and characterized by recurring units having the structure ##STR30##

Claim 30

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 6 and characterized by recurring units having the structure ##STR31##

Claim 31

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 7 and characterized by recurring units having the structure ##STR32##

Claim 32

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 8 and characterized by recurring units having the structure ##STR33##

Claim 33

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 9 and characterized by recurring units having the structure ##STR34##

Claim 34

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 10 and characterized by recurring units having the structure ##STR35##

Claim 35

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 11 and characterized by recurring units having the structure ##STR36##

Claim 36

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 12 and characterized by recurring units having the structure ##STR37##

Claim 37

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 13 and characterized by recurring units having the structure ##STR38##

Claim 38

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 14 and characterized by recurring units having the structure ##STR39##

Claim 39

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 15 and characterized by recurring units having the structure ##STR40##

Claim 40

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 16 and characterized by recurring units having the structure ##STR41##

Claim 41

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 17 and characterized by recurring units having the structure ##STR42##

Claim 42

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the polyisocyanate and the unsaturated imide as defined in claim 18 and characterized by recurring units having the structure ##STR43##

Claim 43

A hard, thermally stable, solvent resistant imido polymer, comprising the polyaddition product of the composition of matter as defined by claim 23 and characterized by recurring units having the structure ##STR44##

Claim 44

A hard, thermally stable, solvent resistant imido group containing polymer, characterized by the recurring unit: ##STR45## wherein Y is H, CH 3 or Cl.

Claim 45

A hard, thermally stable, solvent resistant imido group containing polymer, characterized by the recurring unit: ##STR45## wherein Y is H, CH 3 or Cl.

Claim 46

A hard, thermally stable, solvent resistant reticulated imido polymer, comprising the polyaddition and cross-linked product of the polyisocyanate and the unsaturated imide as defined by claim 1.

Claim 47

A molded shape article comprising the composition of matter as defined by claim 1.

Claim 48

A substrate coated with a film comprising the composition of matter as defined by claim 1.

Claim 49

A substrate coated with a film comprising the imido polymer as defined by claim 24.

Claim 50

A molded shaped article comprising the imido polymer as defined by claim 24.

Claim 51

A laminate comprising the composition of matter as defined by claim 1.

Claim 52

A laminate comprising the imido polymer as defined by claim 24.

Claim 53

A process for the preparation of an imido polymer, comprising heating the composition of matter as defined by claim 1 to a temperature of at least 100° C.

Claim 54

A coating, molding or adhesive composition, comprising the composition of matter as defined by claim 1.

Claim 55

A coating, molding or adhesive composition, comprising the imido polymer as defined by claim 24.

Claim 56

A molded shaped article comprising the imido polymer as defined by claim 44.

Claim 57

A substrate coated with a film comprising the imido polymer as defined by claim 44.