US5011905A
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Polyimide oligomers and blends
Assignee: Boeing Co
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Filing: 1990-08-13
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Granted: 1991-04-30
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Expires: 2010-08-13
Abstract
Abstract Polyimide oligomers include (1) linear, monofunctional crosslinking oligomers prepared by condensing a monoanhydride end cap with a diamine that includes alternating ether and "sulfone" (--SO 2 --, --S--, --CO--, --(CF 3 ) 2 C--, or --(CH 3 ) 2 C--) linkages connecting alternating aromatic radicals and with a dianhydride (or dianhydride mixture), particularly the unsaturated, aliphatic dianhydride commonly known as MCTC; (2) linear, mono- or difunctional crosslinking oligomers prepared by condensing an amine end cap with a diamine and a dianhydride; and (3) multidimensional, crosslinking oligomers having an aromatic hub and at least three radiating arms connected to the hub, each arm including a crosslinking end cap at its distal end and at least one imide linkage. Blends, prepregs, and composites can be prepared from the oligomers. Multidimensional oligomers can be prepared using etheranhydride intermediates or etheramine intermediates formed by reacting a suitable hub with nitrophthalic anhydride or aminophenol.
Inventors
- 👤 Hyman R. Lubowitz
- 👤 Clyde H. Sheppard
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 06:08
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1057; C08G73/1064; C08G73/1003; C08G73/1007; C08G73/101; C08G73/1014; C08G73/1067; C08G73/1071; C08G73/14; C08L; C08L79/00; C08L79/04; C08L79/08
Claims Analysis
Total Claims: 37
Claim 1
Independent Claim
181 words
A monofunctional crosslinkable, thermoplastic, polyimide oligomer which is the product formed by reacting under an inert gas atmosphere a mixture comprising: (a) two moles of a crosslinkable monoanhydride selected from the group consisting of: ##STR35## wherein Me=methyl; G=--O--, --SO 2 --, --CH 2 --, or --S--; E=allyl or methallyl; R 1 =lower alkoxy, aryl, substituted aryl, lower alkyl, substituted alkyl, aryloxy, or halogen; and j=0, 1, or 2; (b) n+1 moles of a polyaryl diamine having terminal amino groups, the diamine including alternating aryl radicals (--Ar--) connected together by alternating ether (--O--) and sulfone (--L--) linkages, wherein each sulfone linkage (--L--) is selected from the group consisting of --SO 2 --, --S--, --CO--, --(CF 3 ) 2 C--, and --(CH 3 ) 2 C--, so that the dimaine has a general formula: H.sub.2 N--Ar--O--Ar--L--Ar--O].sub.m Ar--NH.sub.2 wherein Ar=an aromatic radial, and m=a small integer greater than or equal to 1; and (c) n moles of at least one dianhydride, wherein n=an integer selected so that the oligomer prossesses thermoplastic properties and has an average formula weight of between about 5,000 to 40,000.
Claim 2
Dependent Claim
181 words
A monofunctional crosslinkable, thermoplastic, polyimide oligomer which is the product formed by reacting under an inert gas atmosphere a mixture comprising: (a) two moles of a crosslinkable monoanhydride selected from the group consisting of: ##STR35## wherein Me=methyl; G=--O--, --SO 2 --, --CH 2 --, or --S--; E=allyl or methallyl; R 1 =lower alkoxy, aryl, substituted aryl, lower alkyl, substituted alkyl, aryloxy, or halogen; and j=0, 1, or 2; (b) n+1 moles of a polyaryl diamine having terminal amino groups, the diamine including alternating aryl radicals (--Ar--) connected together by alternating ether (--O--) and sulfone (--L--) linkages, wherein each sulfone linkage (--L--) is selected from the group consisting of --SO 2 --, --S--, --CO--, --(CF 3 ) 2 C--, and --(CH 3 ) 2 C--, so that the dimaine has a general formula: H.sub.2 N--Ar--O--Ar--L--Ar--O].sub.m Ar--NH.sub.2 wherein Ar=an aromatic radial, and m=a small integer greater than or equal to 1; and (c) n moles of at least one dianhydride, wherein n=an integer selected so that the oligomer prossesses thermoplastic properties and has an average formula weight of between about 5,000 to 40,000.
Claim 3
Dependent Claim
22 words
The oligomer of claim 1 wherein the aromatic radical (--Ar--) is selected from the group consisting of phenyl or substituted phenyl radicals.
Claim 4
Dependent Claim
10 words
The oligomer of 2 wherein --L-- is --SO 2 --.
Claim 5
Dependent Claim
10 words
The oligomer of 2 wherein --L-- is --SO 2 --.
Claim 6
Dependent Claim
18 words
The oligomer of claim 3 wherein the oligomer has an average formula weight between about 20,000 to 30,000.
Claim 7
Dependent Claim
22 words
The oligomer of claim 1 wherein the diamine is a phenoxyphenyl sulfone diamine of the general formula: ##STR36## wherein m=a small integer.
Claim 8
Dependent Claim
12 words
The oligomer of claim 1 wherein the dianhydride is an aliphatic dianhydride.
Claim 9
Dependent Claim
11 words
The oligomer of claim 6 wherein the aliphatic dianhydride is MCTC.
Claim 10
Dependent Claim
9 words
The oligomer of claim 7 wherein the monoanhydride ##STR37##
Claim 11
Dependent Claim
67 words
The oligomer of claim 1 wherein the diamine is selected from the group of diamines consisting of: ##STR38## wherein A and B are aromatic radicals, at least one of A and B being a diaryl radical having a sulfone linkage selected from the group consisting of --SO 2 --, --S--, --CO--, --(CH 3 ) 2 C--, and --(CF 3 )C-- linking the aryl moieties, and wherein q=0-27.
Claim 12
Dependent Claim
49 words
The oligomer of claim 5 wherein the diamine is a phenoxyphenylsulfone diamine selected from the group consisting of: ##STR39## wherein m=an integer such that the diamine has an average formula weight between about 2,000 to 10,000, and wherein the diamine is formed by reacting aminophenol, bisphenol A, and 4,4'-dichlorodiphenylsulfone.
Claim 13
Dependent Claim
10 words
The oligomer of claim 10 wherein the dianhydride is MCTC.
Claim 14
Dependent Claim
15 words
The oligomer of claim 10 wherein the dianhydride is a mixture of MCTC and BTDA.
Claim 15
Dependent Claim
83 words
A crosslinkable polyimide oligomer having the general formula: ##STR40## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR41## wherein X is selected from the group consisting of: ##STR42## A is the residue of a dianhydride; B is the residue of a diamine; n=2, R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl.
Claim 16
Dependent Claim
83 words
A crosslinkable polyimide oligomer having the general formula: ##STR40## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR41## wherein X is selected from the group consisting of: ##STR42## A is the residue of a dianhydride; B is the residue of a diamine; n=2, R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl.
Claim 17
Dependent Claim
49 words
The oligomer of claim 13 wherein the diamine is selected from the group consisting of: ##STR43## wherein ##STR44## q=--SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--; Me=methyl; m=an integer, generally less than 5; and D=any of --CO--, --SO 2 --, or --(CF 3 ) 2 C--.
Claim 18
Dependent Claim
22 words
The oligomer of claim 13 wherein the dianhydride is selected from the group consisting of pyromellitic dianhydride, MCTC, BTDA, or mixtures thereof.
Claim 19
Dependent Claim
17 words
A prepreg comprising the oligomer of claim 1 and a reinforcing additive in fiber or particulate form.
Claim 20
Dependent Claim
17 words
A prepreg comprising the oligomer of claim 13 and a reinforcing additive in fiber or particulate form.
Claim 21
Dependent Claim
19 words
The prepreg of claim 1 further comprising a coreactant selected from the group consisting of p-phenylenediamine, benzidine, or 4,4'-methylenedianiline.
Claim 22
Dependent Claim
148 words
A process for making thermoplastic, solvent-resistant, polyimide oligomers suitable for advanced composites, comprising the step of reacting substantially stoichometric amounts of a crosslinkable monoanhydride, a diamine, and a dianhydride under an inert atmosphere at reduced temperature, wherein the monoanhydride is selected from the group consisting of: ##STR45## wherein X= ##STR46## R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl; wherein the diamine has: terminal amino (--NH 2 ) groups, a plurality of aromatic radicals, and alternating ether and sulfone linkages connecting the aromatic radicals, wherein each sulfone linkage is selected from the group consisting of: --SO 2 --, --S--, --CO--, --(CF 3 ) 2 C--, or --(CH 3 ) 2 C--; and wherein the oligomer has an average formula weight in excess of about 5000.
Claim 23
Dependent Claim
148 words
A process for making thermoplastic, solvent-resistant, polyimide oligomers suitable for advanced composites, comprising the step of reacting substantially stoichometric amounts of a crosslinkable monoanhydride, a diamine, and a dianhydride under an inert atmosphere at reduced temperature, wherein the monoanhydride is selected from the group consisting of: ##STR45## wherein X= ##STR46## R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl; wherein the diamine has: terminal amino (--NH 2 ) groups, a plurality of aromatic radicals, and alternating ether and sulfone linkages connecting the aromatic radicals, wherein each sulfone linkage is selected from the group consisting of: --SO 2 --, --S--, --CO--, --(CF 3 ) 2 C--, or --(CH 3 ) 2 C--; and wherein the oligomer has an average formula weight in excess of about 5000.
Claim 24
Dependent Claim
35 words
The process of claim 19 further comprising the steps of preparing the diamine by reacting aminophenol with a dihydric phenol and a dihalophenylsulfone under an inert atmosphere at an elevated temperature, and cooling the diamine.
Claim 25
Dependent Claim
19 words
The process of claim 20 wherein the step of preparing the diamine occurs on the presence of a base.
Claim 26
Dependent Claim
33 words
The process of claim 19 wherein the dianhydride comprises a mixture of BTDA and MCTC and wherein the monoanhydride and dianhydride mixture are combined prior to addition of the combination to the diamine.
Claim 27
Independent Claim
73 words
A method for making a difunctional, crosslinkable, polyimide oligomer, comprising the step of condensing a difunctional end cap amine of the general formula: ##STR47## wherein X= ##STR48## R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl, with substantially stoichiometric amounts of a dianhydride and a diamine under an inert atmosphere.
Claim 28
Independent Claim
73 words
A method for making a difunctional, crosslinkable, polyimide oligomer, comprising the step of condensing a difunctional end cap amine of the general formula: ##STR47## wherein X= ##STR48## R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and E=methallyl or allyl, with substantially stoichiometric amounts of a dianhydride and a diamine under an inert atmosphere.
Claim 29
Dependent Claim
15 words
The method of claim 23 wherein the dianhydride comprises a mixture of BTDA and MCTC.
Claim 30
Dependent Claim
22 words
The method of claim 23 wherein the end cap amine and diamine are mixed prior to adding the mixture to the dianhydride.
Claim 31
Dependent Claim
97 words
A prepreg comprising a crosslinkable polyimide oligomer and a reinforcing additive in fiber or particulate form, said oligomer having the general formula: ##STR49## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR50## wherein X is selected from the group consisting of: ##STR51## A is the residue of a dianhydride; B is the residue of a diamine; n=2; R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and T=methallyl or allyl.
Claim 32
Dependent Claim
97 words
A prepreg comprising a crosslinkable polyimide oligomer and a reinforcing additive in fiber or particulate form, said oligomer having the general formula: ##STR49## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR50## wherein X is selected from the group consisting of: ##STR51## A is the residue of a dianhydride; B is the residue of a diamine; n=2; R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and T=methallyl or allyl.
Claim 33
Dependent Claim
104 words
A prepreg comprising a crosslinkable polyimide oligomer and a reinforcing additive in fiber or particulate form, said oligomer having the general formula: ##STR52## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR53## wherein X is selected from the group consisting of: ##STR54## A is the residue of a dianhydride; B is the residue of a diamine other than a phenylene diamine; n=1 or 2; R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and T=methallyl or allyl.
Claim 34
Dependent Claim
104 words
A prepreg comprising a crosslinkable polyimide oligomer and a reinforcing additive in fiber or particulate form, said oligomer having the general formula: ##STR52## wherein E is the residue of an amine end cap selected from the group consisting of: ##STR53## wherein X is selected from the group consisting of: ##STR54## A is the residue of a dianhydride; B is the residue of a diamine other than a phenylene diamine; n=1 or 2; R 1 =lower alkyl, lower alkoxy, aryl, substituted aryl, substituted alkyl, aryloxy, or halogen; j=0, 1, or 2; Me=methyl; G=--SO 2 --, --CH 2 --, --S--, or --O--; and T=methallyl or allyl.
Claim 35
Dependent Claim
7 words
The prepreg of claim 27 wherein n=2.
Claim 36
Dependent Claim
49 words
The prepreg of claim 27 wherein the diamine is selected from the group consisting of: ##STR55## wherein ##STR56## q=--SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--; Me=methyl; m=an integer, generally less than 5; and D=any of --CO--, --SO 2 --, or --(CF 3 ) 2 C--.
Claim 37
Dependent Claim
7 words
The prepreg of claim 29 wherein n=2.
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