US4876328A
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Polyamide composition
Assignee: Boeing Co
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Filing: 1987-06-12
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Granted: 1989-10-24
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Expires: 2007-06-12
Abstract
Abstract Polyamide advanced composites are formed by the condensation of diacid halides (or dicarboxylic acids) and diamines in a linear or multidimensional morphology with crosslinkable end caps that provide improved solvent- resistance. The diamines and diacid halides generally include "sulfone" linkages in aryl chains to impart the desired combination of physical properties to the oligomers, prepregs, and composites. Linear oligomers have mono- or difunctional crosslinking end caps at the ends of polyarylamide chains. Multidimensional oligomers have a hub and three or more radiating amide arms, each arm having a mono- or difunctional crosslinking end cap at its distal end.
Inventors
- 👤 Hyman R. Lubowitz
- 👤 Clyde H. Sheppard
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 18:45
CPC Classifications
C; C08; C08G; C08G69/00; C08G69/02; C08G69/26; C08G69/42; C08J; C08J5/00; C08J5/24; C08J5/241; C08J5/243; C08J5/249; C08L; C08L77/00; C08J2377/00
Claims Analysis
Total Claims: 60
Claim 1
Independent Claim
155 words
A composition of matter, comprising a compound selected from the group consisting of: E--CONH--P--NHCO-- m --E; E--NHCO--Q--CONH-- m --E; Ar-- n ; Ar-- n ; Ar-- n ; Ar-- n ; Ar-- n ; or Ar-- n ; wherein m is a small integer; Ar is an aromatic moiety; n is 3 or 4; E is a crosslinkable end cap monomer for improving solvent resistance of the cured oligomer in an the advanced composite selected from the group consisting of: ##STR53## R 1 is lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substituted aryl, halogen, or mixtures thereof; j is 0, 1, or 2; i is 1 or 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; T is allyl or methallyl; P is a linear, aromatic, organic, divalent residue of a diamine; and Q is a linear, aromatic, organic, divalent residue of a diacid halide or dicarboxylic acid.
Claim 2
Dependent Claim
155 words
A composition of matter, comprising a compound selected from the group consisting of: E--CONH--P--NHCO-- m --E; E--NHCO--Q--CONH-- m --E; Ar-- n ; Ar-- n ; Ar-- n ; Ar-- n ; Ar-- n ; or Ar-- n ; wherein m is a small integer; Ar is an aromatic moiety; n is 3 or 4; E is a crosslinkable end cap monomer for improving solvent resistance of the cured oligomer in an the advanced composite selected from the group consisting of: ##STR53## R 1 is lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substituted aryl, halogen, or mixtures thereof; j is 0, 1, or 2; i is 1 or 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; T is allyl or methallyl; P is a linear, aromatic, organic, divalent residue of a diamine; and Q is a linear, aromatic, organic, divalent residue of a diacid halide or dicarboxylic acid.
Claim 3
Dependent Claim
95 words
The composition of claim 1 wherein the diacid halide includes a radial selected from the group consisting of: phenylene; naphthylene; biphenylene; a divalent radical of the general formula: ##STR54## wherein D is --S--, --O--, --CO--, --SO 2 --, --(CH 3 ) 2 C--, --(CF 3 ) 2 C--; a divalent radical compound having at least one conductive linkage selected from the group consisting of Schiff base, thiazole, oxazole, or imidazole linkages; or a divalent radical of the general formula: ##STR55## wherein R' is a C 2 to C 12 divalent aliphatic, alicyclic, or aromatic radical.
Claim 4
Dependent Claim
57 words
The composition of claim 2 wherein the conductive linkage is a Schiff base selected from the group consisting of: ##STR56## wherein R is selected from the group of radicals consisting of: phenylene; naphthylene; biphenylene or a divalent radical of the general formula: ##STR57## wherein W is --SO 2 -- or --CH 2 --; and b is 0-4.
Claim 5
Dependent Claim
17 words
The composition of claim 1 wherein the diacid halide is selected from the group consisting of: ##STR58##
Claim 6
Dependent Claim
52 words
The composition of claim 1 wherein the diamine is selected from the group consisting of: ##STR59## q is --SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--; Me is methyl; m is a small integer; and D is --CO--, --SO 2 --, --(CF 3 ) 2 C-- or mixtures thereof.
Claim 7
Dependent Claim
13 words
The composition of claim 5 wherein q is --SO 2 -- or --CO--.
Claim 8
Dependent Claim
52 words
The composition of claim 2 wherein the diamine is selected from the group consisting of: ##STR60## q is --SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--; Me is methyl; m is a small integer; and D is --CO--, --SO 2 --, --(CF 3 ) 2 C--, or mixtures thereof.
Claim 9
Dependent Claim
17 words
The composition of claim 5 wherein the diacid halide is selected from the group consisting of: ##STR61##
Claim 10
Dependent Claim
35 words
The composition of claim 5 wherein the diamine is selected from the group consisting of: ##STR62## q is --SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--; and m is a small integer.
Claim 11
Dependent Claim
30 words
The composition of claim 5 wherein the diamine is selected from the group consisting of: ##STR63## wherein q is --SO 2 --, --CO--, --S--, or --(CF 3 ) 2 C--.
Claim 12
Dependent Claim
41 words
The composition of claim 1 wherein the compound is selected from the group consisting of: E--CONH--P--NHCO[Q--CONH--P--NHCO] m E; or E--NHCO--Q--CONH[P--NHCO--Q--CONH] m E; so that the polyamide is a linear polyamide composition including terminal end caps having one or two crosslinking functionalities.
Claim 13
Dependent Claim
43 words
The composition of claim 1 wherein the compound is selected from the group consisting of: Ar[CONH--P--NHCO--Q--CONH--E] n ; Ar[NHCO--Q--CONH--P--NHCO--E] n ; Ar[COHN--E] n ; Ar[NHCO--E] n ; Ar[CONH--P--NHCO--Q--E] n ; or Ar[NHCO--Q--CONH--E] n , so that the polyamide is a multidimensional polyamide composition.
Claim 14
Dependent Claim
15 words
The composition of claim 1 wherein E is selected from the group consisting of: ##STR64##
Claim 15
Dependent Claim
14 words
The composition of claim 1 wherein R 1 is aryl and j is 1.
Claim 16
Dependent Claim
9 words
The composition of claim 1 wherein i is 2.
Claim 17
Dependent Claim
39 words
The composition of claim 1 further comprising a suitable amount of a dopant mixed with the composition to make the composition conductive or semiconductive, and wherein at least one of the diamine or diacid halide inlcudes a conductive linkage.
Claim 18
Dependent Claim
15 words
The composition of claim 16 wherein the conductive linkage includes a Schiff base (--CH═N--) radical.
Claim 19
Dependent Claim
22 words
The multidimensional composition of claim 12 wherein the composition is selected from the group consisting of: Ar[CONH--P--NHCO--Q--CONH--E] n or Ar[NHCO--Q--CONH--P--NHCO--E] n .
Claim 20
Dependent Claim
24 words
The composition of claim 12 wherein Ar is selected from the the group consisting of phenyl, biphenyl, naphthyl, a triazine derivative, or an aryletheramine.
Claim 21
Dependent Claim
20 words
The composition 19 wherein Ar is ##STR65## and n is 3, and wherein Ar is the residue of an amine.
Claim 22
Dependent Claim
20 words
The composition 19 wherein Ar is ##STR65## and n is 3, and wherein Ar is the residue of an amine.
Claim 23
Dependent Claim
17 words
A prepreg comprising the composition of claim 1 and a reinforcing additive in fiber or particulate form.
Claim 24
Dependent Claim
17 words
A prepreg comprising the composition of claim 8 and a reinforcing additive in fiber or particulate form.
Claim 25
Dependent Claim
10 words
A composite formed by curing the composition of claim 1.
Claim 26
Dependent Claim
10 words
A composite formed by curing the prepreg of claim 21.
Claim 27
Dependent Claim
9 words
The composition of claim 1 wherein i is 2.
Claim 28
Dependent Claim
17 words
A prepreg comprising the composition of claim 25 and a reinforcing additive in fiber or particulate form.
Claim 29
Dependent Claim
9 words
A composite comprising the cured prepreg of claim 26.
Claim 30
Dependent Claim
44 words
A polyamide composition which is the product of the process of the condensation of: (a) 2 moles of a crosslinkable end cap phenylamine; (b) n moles of a linear, polyaryl diamine; and (c) n+1 moles of a linear, polyaryl diacid halide or dicarboxylic acid.
Claim 31
Dependent Claim
44 words
A polyamide composition which is the product of the process of the condensation of: (a) 2 moles of a crosslinkable end cap phenylamine; (b) n moles of a linear, polyaryl diamine; and (c) n+1 moles of a linear, polyaryl diacid halide or dicarboxylic acid.
Claim 32
Dependent Claim
48 words
A polyamide composition which is the product of the process of the condensation of: (a) 2 moles of a crosslinkable end cap phenyl acid halide or carboxylic acid; (b) n moles of a linear, polyaryl diacid halide or dicarboxylic acid; (c) n+1 moles of a linear, polyaryl diamine.
Claim 33
Dependent Claim
48 words
A polyamide composition which is the product of the process of the condensation of: (a) 2 moles of a crosslinkable end cap phenyl acid halide or carboxylic acid; (b) n moles of a linear, polyaryl diacid halide or dicarboxylic acid; (c) n+1 moles of a linear, polyaryl diamine.
Claim 34
Dependent Claim
112 words
A multidimensional polyamide composition, comprising: a cyclic central hub having at least three substantially identical arms radiating from the hub, each arm including at least one amide linkage and having a terminal crosslinking end cap that can be chemically or thermally activated in the composition to form a crosslinked composite, the end cap including a residue selected from the group consisting of: ##STR66## wherein R 1 is lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substitued aryl, halogen, or mixtures thereof; j is 0, 1, or 2; i is 1 or 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; and T is allyl or methallyl.
Claim 35
Dependent Claim
112 words
A multidimensional polyamide composition, comprising: a cyclic central hub having at least three substantially identical arms radiating from the hub, each arm including at least one amide linkage and having a terminal crosslinking end cap that can be chemically or thermally activated in the composition to form a crosslinked composite, the end cap including a residue selected from the group consisting of: ##STR66## wherein R 1 is lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substitued aryl, halogen, or mixtures thereof; j is 0, 1, or 2; i is 1 or 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; and T is allyl or methallyl.
Claim 36
Dependent Claim
12 words
The composition of claim 30 wherein the hub is an aromatic compound.
Claim 37
Dependent Claim
52 words
The composition of claim 30 wherein each arm includes at least one conductive linkage selected from the group consisting of Schiff base, oxazole, thiazole, and imidazole, and further comprising a suitable amount of a dopant mixed with the composition to produce conductive or semiconductive properties in a composite formed from the composition.
Claim 38
Dependent Claim
14 words
The composition of claim 30 wherein each arm includes a plurality of aryl groups.
Claim 39
Dependent Claim
14 words
The composition of claim 30 wherein R 1 is aryl and j is 1.
Claim 40
Dependent Claim
62 words
The composition of claim 30, wherein the composition is selected from the group consisting of: ##STR67## i is 1 or 2 R 1 is lower alkyl, lower alkoxy, aryloxy, substituted alkyl, substituted aryl, halogen, or mixtures thereof; j is 0, 1, 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; and T is allyl or methallyl.
Claim 41
Dependent Claim
63 words
A multidimensional polyamide composition which is the product of the process of the condensation of substantially: (a) 1 mole of an aromatic hub having at least three, terminal amine substituents; (b) m moles of a crosslinking end cap phenylamine; and (c) m moles of a linear, polyaryl diacid halide or dicarboxylic acid, wherein m equals the number of amine substituents on the hub.
Claim 42
Dependent Claim
63 words
A multidimensional polyamide composition which is the product of the process of the condensation of substantially: (a) 1 mole of an aromatic hub having at least three, terminal amine substituents; (b) m moles of a crosslinking end cap phenylamine; and (c) m moles of a linear, polyaryl diacid halide or dicarboxylic acid, wherein m equals the number of amine substituents on the hub.
Claim 43
Dependent Claim
62 words
A multidimensional polyamide composition formed by the condensation of substantially: (a) 1 mole of an aromatic hub having at least three --COX or --COOH substituents; (b) m moles of a crosslinking end cap including either a ##STR68## (c) m moles of a linear, polyaryl diamine, wherein m equals the number of --COX or --COOH substituents on the hub, and X is halogen.
Claim 44
Dependent Claim
62 words
A multidimensional polyamide composition formed by the condensation of substantially: (a) 1 mole of an aromatic hub having at least three --COX or --COOH substituents; (b) m moles of a crosslinking end cap including either a ##STR68## (c) m moles of a linear, polyaryl diamine, wherein m equals the number of --COX or --COOH substituents on the hub, and X is halogen.
Claim 45
Dependent Claim
17 words
A prepreg comprising the composition of claim 28 and a reinforcing additive in fiber or particulate form.
Claim 46
Dependent Claim
18 words
A prepreg formed with the composition of claim 29 and a reinforcing additive in fiber or particulate form.
Claim 47
Dependent Claim
17 words
A prepreg comprising the composition of claim 31 and a reinforcing additive in fiber or particulate form.
Claim 48
Dependent Claim
66 words
The composition of claim 36 wherein the phenylamine includes a residue selected from the group consisting of: ##STR69## R 1 is lower alkyl, lower alkoxy, aryl, aryloxy, substituted alkyl, substituted aryl, halogen, or mixtures thereof; j is 0, 1, or 2; i is 1 or 2; Me is methyl; G is --CH 2 --, --O--, --S--, or --SO 2 --; and T is allyl or methallyl.
Claim 49
Dependent Claim
30 words
The composition of claim 36 wherein the aromatic hub is selected from the group consisting of: ##STR70## wherein R 2 is a divalent hydrocarbon residue containing 1-12 carbon atoms; ##STR71##
Claim 50
Dependent Claim
17 words
The composition of claim 42 wherein the diacid halide is selected from the group consisting of: ##STR72##
Claim 51
Independent Claim
69 words
A method for synthesizing a polyamide composition, comprising the step of: condensing a mixture having a molar ratio of substantially about: (a) 2 moles of a crosslinkable end cap phenylamine, (b) n+1 moles of a diacid halide or dicarboxylic acid containing one or more groups; and (c) n moles of a diamine containing one or more aryl groups, wherein n is an integer greater than or equal to one.
Claim 52
Independent Claim
69 words
A method for synthesizing a polyamide composition, comprising the step of: condensing a mixture having a molar ratio of substantially about: (a) 2 moles of a crosslinkable end cap phenylamine, (b) n+1 moles of a diacid halide or dicarboxylic acid containing one or more groups; and (c) n moles of a diamine containing one or more aryl groups, wherein n is an integer greater than or equal to one.
Claim 53
Dependent Claim
47 words
The method of claim 44 wherein the molar ratio of the mixture comprises substantially: (a) about 2 moles of a crosslinkable end cap phenyl acid halide or carboxylic acid; (b) about n moles of the diacid halide or dicarboxylic acid; (c) about n+1 moles of the diamine.
Claim 54
Dependent Claim
64 words
The method of claim 44 wherein the molar ratio of the mixture comprises substantially: (a) about 1 mole of an aromatic hub having m terminal amine substituents; (b) about m moles of the diacid halide or dicarboxylic acid; (c) about m moles of the diamine; and (d) about m moles of a crosslinkable end cap phenyl acid halide; wherein m is 3 or 4.
Claim 55
Dependent Claim
51 words
The method of claim 44 further comprising the steps of: (a) dissolving the diacid halide or dicarboxylic acid in a suitable solvent to form an acid solution; (b) mixing the phenylamine and the diamine together; and (c) under an inert atmosphere, adding the mixed phenylamine and diamine to the acid solution.
Claim 56
Dependent Claim
51 words
The method of claim 45 further comprising the steps of: (a) dissolving the diamine in a suitable solvent; (b) mixing the phenyl acid halide or carboxylic acid and the diacid halide or dicarboxylic acid to form a premix; and (c) under an inert atmosphere, adding the premix to the diamine solution.
Claim 57
Dependent Claim
68 words
The method of claim 46 further comprising the steps of: (a) dissolving the diacid halide or dicarboxylic acid in a suitable solvent to form an acid solution; (b) mixing the phenyl acid halide end cap with the acid solution to form a reaction solution; (c) mixing the hub and the diamine to form a premix; and (d) under an inert atmosphere, adding the premix to the reaction solution.
Claim 58
Independent Claim
58 words
A method of synthesizing a multidimensional polyamide composition comprising the step of: condensing a mixture having a molar ratio of substantially about: (a) 1 mole of an aromatic, organic hub having an terminal acid halide functionalities, (b) m moles of a diamine, and (c) m moles of a crosslinking end cap anhydride, wherein m is 3 or 4.
Claim 59
Independent Claim
58 words
A method of synthesizing a multidimensional polyamide composition comprising the step of: condensing a mixture having a molar ratio of substantially about: (a) 1 mole of an aromatic, organic hub having an terminal acid halide functionalities, (b) m moles of a diamine, and (c) m moles of a crosslinking end cap anhydride, wherein m is 3 or 4.
Claim 60
Dependent Claim
44 words
The method of claim 50 wherein the mixture comprises about: (a) 1 moles of an aromatic, organic hub having m terminal amine functionalities, (b) m moles of a diacid halide, (c) m moles of a diamine, and (d) m moles of a crosslinking anhydride.
References Cited (Backward Citations)
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