Polyimide precursor compositions, their manufacture, the resultant polyimides and their use, particularly for manufacturing enamelling varnishes for electric wires

Claim 2

A process for preparing a polyimide precursor composition comprising: (a) a first step of reacting, within a solvent, at least one biprimary aromatic diamine of general formula (2): NH.sub.2 --Ar'--NH.sub.2 ( 2) with at least one tetracarboxylic aromatic compound of general formula (3): ##STR4## and, (b) a second step of reacting the product obtained in step (a) with at least one dianhydride of a tetracarboxylic aromatic acid of general formula (1): ##STR5## wherein Ar' is a divalent aromatic radical formed of one or more rings, the two valencies Ar' are on separate carbon atoms, not in ortho or peri position; Ar and Ar" are tetravalent aromatic radicals formed of one or more rings, the four valencies of which are on separate carbon atoms placed by pairs in ortho or peri position; R is a hydrogen atom or a monovalent hydrocarbon radical, and the arrows indicate the isomerism possibilities, the reactants proportions being from 0.05 to 50 moles of compound of formula (3) and 90 to 110 moles of compound of formula (2) per 100 moles of all the compounds of formulas (1) and (3).

Claim 3

A process according to claim 1, wherein R is a hydrogen atom.

Claim 4

A process according to claim 1, wherein R is a hydrocarbon radical of 1 to 13 carbon atoms.

Claim 5

A process according to claim 3, wherein R is a methyl radical.

Claim 6

A process according to claim 1, wherein, the the operating temperature is maintained between 5° and 40° C.

Claim 7

A process according to claim 1, wherein 1 to 15 moles of compound of formula (3) are used for 100 moles of all the compounds of formulas (1) and (3).

Claim 8

A process for manufacturing a polyimide, comprising heating a composition according to claim 1 at a temperature higher than 120° C.

Claim 9

A process according to claim 7, characterized in that the heating temperature is from 160° to 400° C.

Claim 10

A process for manufacturing a a coated substrate, comprising coating said substrate with a solution of a composition of claim 1, evaporating the solvent and heating at a temperature of at least 120° C.

Claim 11

A method according to claim 9, wherein 10-15 mole % of a compound of formula (3) is used in the products of the precursor composition resulting in a substrate having a varnish or adhesive layer.

Claim 12

A method according to claim 9, wherein 4-10 mole % of a compound of formula (3) and 96-90% of a compound of formula (1) are used in the production of the precursor composition, and the substrate is metal, resulting in an insulated metal surface.

Claim 13

A method according to claim 9, for enamelling electric or magnetic wires, wherein 2-7 mole % of a compound of formula (3) and 98-93% of a compound of formula (1) are used in the production of the precursor composition.

Claim 14

An alpha, omega-diamino polyamide-acid of the formula 4: ##STR6## wherein Ar' is a divalent aromatic radical formed of one or more rings, the two valencies of Ar' are on separate carbon atoms, not in ortho or peri position; Ar and Ar" are tetravalent aromatic radicals formed of one or more rings, the four valencies of which are on separate carbon atoms placed by pairs in ortho or peri position; R is a hydrogen atom or a monovalent hydrocarbon radical, and the arrows indicate the isomerism possibilities, and n is 1-2,000.

Claim 15

An alpha, omega-diamino polyamide-acid of the formula 4: ##STR6## wherein Ar' is a divalent aromatic radical formed of one or more rings, the two valencies of Ar' are on separate carbon atoms, not in ortho or peri position; Ar and Ar" are tetravalent aromatic radicals formed of one or more rings, the four valencies of which are on separate carbon atoms placed by pairs in ortho or peri position; R is a hydrogen atom or a monovalent hydrocarbon radical, and the arrows indicate the isomerism possibilities, and n is 1-2,000.

Claim 16

A process according to claim 13, wherein R is hydrogen atom.

Claim 17

A process according to claim 13, wherein R is a hydrocarbon radical of 1 to 13 carbon atoms.

Claim 18

A process according to claim 13, wherein R is a methyl radical.

Claim 19

An alpha, omega-diamino polyamide-acid according to claim 13, wherein n is about 5-100.

Claim 20

A process for the preparation of a polyimide precursor comprising: reacting simultaneously in a solvent at least one biprimary aromatic amine of the formula 2: NH.sub.2 --Ar'--NH.sub.2 ( 2) at least one tetracarboxylic aromatic compound of the formula 3: ##STR7## and at least one dianhydride of a tetracarboxylic aromatic acid of the formula 1: ##STR8## wherein Ar' is a divalent aromatic radical formed of one or more rings, the two valencies of Ar' are on separate carbon atoms, not in ortho or peri position; Ar and Ar" are tetravalent aromatic radicals formed of one or more rings, the four valencies of which are on separate carbon atoms placed by pairs in ortho or peri position; R is a hydrogen atom or a monovalent hydrocarbon radical, and the arrows indicate the isomerism possibilities, the reactants proportions being from 0.05 to 50 moles of compound of formula (3) and 90 to 110 moles of compound of formula (2) per 100 moles of all the compounds of formulas (1) and (3).

Claim 21

A process for the preparation of a polyimide precursor comprising: reacting simultaneously in a solvent at least one biprimary aromatic amine of the formula 2: NH.sub.2 --Ar'--NH.sub.2 ( 2) at least one tetracarboxylic aromatic compound of the formula 3: ##STR7## and at least one dianhydride of a tetracarboxylic aromatic acid of the formula 1: ##STR8## wherein Ar' is a divalent aromatic radical formed of one or more rings, the two valencies of Ar' are on separate carbon atoms, not in ortho or peri position; Ar and Ar" are tetravalent aromatic radicals formed of one or more rings, the four valencies of which are on separate carbon atoms placed by pairs in ortho or peri position; R is a hydrogen atom or a monovalent hydrocarbon radical, and the arrows indicate the isomerism possibilities, the reactants proportions being from 0.05 to 50 moles of compound of formula (3) and 90 to 110 moles of compound of formula (2) per 100 moles of all the compounds of formulas (1) and (3).

Claim 22

A process according to claim 18, wherein the amine of formula 2 is (1,3) or (1,4)-diamine benzene; (2,4)diamino, (2,6)diamino or (3,5)-diamino toluene; diaminoxylene; (3,3')diamino or (4,4')-diamino diphenylmethane; bis(4-amino 3-methyl phenyl)methane; 2,2-bis(4-amino phenyl)propane; 4,4'-diamino biphenyl; 3,3'-dimethyl benzidine; 3,3'-dimethoxy benzidine; 3,3'-dichloro benzidine; (3,3') or (4,4)-diamno diphenylether; (3,3') or (4,4')-diamino benzophenone, (3,3') or (4,4')diamino benzhydrol; bis(4-amino phenyl)sulfide; bis(4-amino phenyl)sulfone; bis(3-amino phenyl)sulfone; (3,3') (3'4) (3,4') or (4,4)diamino benzanilidine; bis(4-amino phenyl)difluoromethane; (3,3') (3,4') (3'4) or (4,4')-diamino phenyl benzoate; bis(3-amino phenyl)dimethylsilane; bis(4-amino-phenyl)dimethylsilane; 2,2-bis(4-amino phenyl)hexafluoropropane; (1,3) or (1,4)-meta or para aminophenoxy benzene; (1,3) or (1,4)-meta or para aminobenzoyl benzene; or (1,3) or 1,4 (1,4)-meta or para aminophenyl hydroxymethyl benzene.

Claim 23

A process according to claim 18, wherein the tetracarboxylic compound of formula (3) is tetracid.

Claim 24

A process according to claim 18, wherein the tetracarboxylic compound of formula (3) is an alkyl bis(ortho-acid-ester) obtained by reacting an anhydride with an aliphatic alcohol.

Claim 25

A process according to claim 21, wherein the bis(ortho-acid-ester) is a methyl, ethyl, isopropyl, n-butyl, tert-butyl, neopentyl, octyl or dodecyl ester.

Claim 26

A process according to claim 18, wherein the dianhydride of formula (1) is a dianhydride of: (a) (1,2,3,4)- or (1,2,4,5)-tetracarboxy benzene, (b) 3-phenyl or 3,6-diphenyl pyromellitic acid (c) (1,2,5,6)-, (2,3,6,7)-, (1,2,4,5)- or (1,4,5,8)-tetracarboxy naphthalene, (d) (2,2',3,3')- or (3,3',4,4')-tetracarboxy diphenyl, (e) (3,4,9,10)-tetracarboxy perylene, (f) (2,2')-bis(3,4-dicarboxy phenyl)propane, (g) bis(3,4-dicarboxy phenyl)methane (h) bis(3,4-dicarboxy phenyl)ether, (i) bis(3,4-dicarboxy phenyl)sulfide, (j) bis(3,4-dicarboxy phenyl)sulfone, (k) (2,2',3,3')- or (3,3',4,4')-tetracarboxy benzophenone, (l) (3,3',4'4')-tetracarboxy benzhydrol, (m) (1,8,9,10)-tetracarboxy phenanthrene, (n) (2,35,6)-tetracarboxy pyrazine, (o) (2,3,4,5)-tetracarboxy thiophene, (p) (2,2)-bis(3,4-dicarboxy phenyl)hexafluoropropane, (q) (1,3)- or (1,4)-bis(3,4-dicarboxy benzoyl)benzene, (r) (4,4)'-bis(3,4-dicarboxy benzoyl)diphenylether, (s) (1,3)- or (1,4)-bis(3,4-dicarboxy phenyl hydroxymethylene)benzene, (t) bis(3,4-dicarboxy phenyl)dimethylsilane, (u) (3,3'4,4')-tetracarboxy benzanilide, (v) bis(3,4-dicarboxy phenyl)difluoromethane, or (w) (1,3)- or (1,4)-bis(3,4-dicarboxy phenoxy)benzene.

Claim 27

A polyamide precursor composition produced according to the process of claim 1.

Claim 28

A polyamide precursor composition produced according to the process of claim 2.

Claim 29

A polyamide precursor composition produced according to the process of claim 3.

Claim 30

A polyamide precursor composition produced according to the process of claim 4.

Claim 31

A polyamide precursor composition produced according to the process of claim 5.

Claim 32

A polyamide precursor commposition produced according to the process of claim 5.