US4528373A
Expired / Lapsed
US
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Vinylacetylene-terminated polyimide derivatives
Assignee: Plastics Engineering Co
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Filing: 1983-12-27
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Granted: 1985-07-09
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Expires: 2003-12-27
Abstract
Abstract Novel, unsaturated vinylacetylene-terminated polyimides and processes for their preparation are disclosed herein. These new polyimides are derivatives of anhydride-terminated aromatic polyimides from which they can be prepared by amidation to provide new unsaturated amide groups having a terminal group containing the structure--CH═CH--C.tbd.C-- or--C.tbd.C--CH═CH--, hereinafter sometimes referred to as "conjugated enynes". These new compositions are more tractable than the original anhydride-terminated polyimides and can be converted at appropriate lower temperatures to crosslinked, insoluble, infusible polymers without by-product formation, thereby extending greatly the applications for which the aromatic polyimides can be employed. Moreover, these new polyimides can undergo the Diels-Alder type of addition with a large number of dienophiles. Certain monomeric materials are also described.
Inventors
- 👤 Gaetano F. D'Alelio, deceased
- 👤 Phillip A. Waitkus
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 15:28
CPC Classifications
C; C07; C07D; C07D209/00; C07D209/02; C07D209/44; C07D209/48; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1003; C08G73/1007; C08G73/101; C08G73/1067
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
215 words
The polyimide comprising the Diels-Alder addition product of (1) a conjugated enyne selected from the class consisting of C 6 H 5 --CH═CHC.tbd.CC 6 H 5 C 6 H 5 CH 2 CH═CHC.tbd.CCH 2 C 6 H 5 CH 3 CH═CHC.tbd.CCH 3 and C 2 H 5 CH═CHC.tbd.CC 2 H 5 with (2) an aromatic polyimide dienophile having the formula: ##STR55## wherein: Ar° is a monovalent aromatic radical; Ar' is a tetravalent aromatic radical, the four carbonyl groups being attached directly to separate carbon atoms and each pair of carbonyl groups being attached to the adjacent carbon atoms in Ar' except in the case of Ar' being a naphthalene radical, one or both pairs of the carbonyl groups may be attached to pericarbon atoms; Ar is a divalent aromatic radical; D is a divalent dienophile group selected from the class consisting of --C(R)═CH-- and a non-conjugated --C.tbd.C--; R is hydrogen or an organic moiety containing 1 to 21 carbon atoms; R' is a divalent hydrocarbon group of 1-12 carbon atoms; R° is hydrogen or a hydrocarbon moiety containing one to 21 carbon atoms; and n is zero or an integer having a value of one to 20, the addition being primarily between the unsaturated groups in said conjugated enyne and the unsaturation in the dienophile.
Claim 2
Dependent Claim
215 words
The polyimide comprising the Diels-Alder addition product of (1) a conjugated enyne selected from the class consisting of C 6 H 5 --CH═CHC.tbd.CC 6 H 5 C 6 H 5 CH 2 CH═CHC.tbd.CCH 2 C 6 H 5 CH 3 CH═CHC.tbd.CCH 3 and C 2 H 5 CH═CHC.tbd.CC 2 H 5 with (2) an aromatic polyimide dienophile having the formula: ##STR55## wherein: Ar° is a monovalent aromatic radical; Ar' is a tetravalent aromatic radical, the four carbonyl groups being attached directly to separate carbon atoms and each pair of carbonyl groups being attached to the adjacent carbon atoms in Ar' except in the case of Ar' being a naphthalene radical, one or both pairs of the carbonyl groups may be attached to pericarbon atoms; Ar is a divalent aromatic radical; D is a divalent dienophile group selected from the class consisting of --C(R)═CH-- and a non-conjugated --C.tbd.C--; R is hydrogen or an organic moiety containing 1 to 21 carbon atoms; R' is a divalent hydrocarbon group of 1-12 carbon atoms; R° is hydrogen or a hydrocarbon moiety containing one to 21 carbon atoms; and n is zero or an integer having a value of one to 20, the addition being primarily between the unsaturated groups in said conjugated enyne and the unsaturation in the dienophile.
Claim 3
Dependent Claim
10 words
The polyimide of claim 1, in which R is H.
Claim 4
Dependent Claim
14 words
The polyimide of claim 1, in which R is C 6 H 5 .
Claim 5
Dependent Claim
12 words
The polyimide of claim 1, in which R is CH 3 .
Claim 6
Dependent Claim
12 words
The polyimide of claim 1, in which n is at least two.
Claim 7
Dependent Claim
12 words
The polyimide of claim 1, in which n is at least three.
Claim 8
Dependent Claim
18 words
The polyimide of claim 5, in which Ar' is a radical selected from the class consisting of: ##STR56##
Claim 9
Dependent Claim
10 words
The polyimide of claim 1, in which Ar' is ##STR57##
Claim 10
Dependent Claim
42 words
The polyimide of claim 1, in which the Ar is selected from the class consisting of --C 6 H 4 --, --C 6 H 4 OC 6 H 4 -- and --C 6 H 4 SO 2 C 6 H 4 --.
Claim 11
Dependent Claim
15 words
The polyimide of claim 5, in which the Ar is --C 6 H 4 --.
Claim 12
Dependent Claim
122 words
The polyimide of claim 1, in which the polyimide dienophile is prepared by the reaction of a dianhydride of an aromatic tetracarboxylic acid and a diamine selected from the class consisting of: 1,3- and 1,4-(NH 2 ) 2 benzene; 2,3-; 2,4-; 2,6- and 3,5-(NH 2 ) 2 -toluene; 3,3'-; 4,4'- and 3,4'-methylene dianiline; 4,4'-; 3,3'- and 3,4'-oxydianiline; 4,4'-; 3,3'- and 3,4'-sulfonyldianiline; 1,3-; 1,4- and 1,2-bis(3-aminophenoxy) benzene; 1,3- and 1,4-bis(4-aminophenoxy) benzene; and H 2 NC 6 H 4 OC 6 H 4 SO 2 C 6 H 4 OC 6 H 4 SO 2 C 6 H 4 OC 6 H 4 NH 2 in which the respective attachments to a C 6 H 4 ring are meta or para to each other.
Claim 13
Dependent Claim
13 words
The polyimide of claim 11, in which the diamine is a methylene dianiline.
Claim 14
Dependent Claim
13 words
The polyimide of claim 11, in which the diamine is a sulfonyl dianiline.
Claim 15
Dependent Claim
12 words
The polyimide of claim 11, in which the diamine is an oxydianiline.
Claim 16
Dependent Claim
12 words
The polyimide of claim 11, in which the diamine is 2,4-toluene diamine.
Claim 17
Dependent Claim
10 words
The polyimide of claim 11, in which R is H.
Claim 18
Dependent Claim
14 words
The polyimide of claim 11, in which R is C 6 H 5 .
Claim 19
Dependent Claim
15 words
The polyimide of claim 1 in which n has a value of one to 10.
Claim 20
Dependent Claim
15 words
The polyimide of claim 5 in which n has a value of one to 10.
Claim 21
Dependent Claim
15 words
The polyimide of claim 7 in which n has a value of one to 10.
Claim 22
Dependent Claim
15 words
The polyimide of claim 11 in which n has a value of one to 10.
Claim 23
Dependent Claim
14 words
The polyimide of claim 1 in which Ar° is --C 6 H 5 .
Claim 24
Dependent Claim
18 words
The polyimide of claim 1 in which Ar° is --C 6 H 4 OC 6 H 5 .
Claim 25
Dependent Claim
16 words
The polyimide of claim 1 in which R°--D--R'-- represents CH 2 ═CHC 6 H 4 --.
Claim 26
Dependent Claim
13 words
The polyimide of claim 1 in R°--D--R'-- represents CH 2 ═CHCH 2 --.
Claim 27
Dependent Claim
12 words
The polyimide of claim 1 in which R' is --CH 2 --.
Claim 28
Dependent Claim
14 words
The polyimide of claim 1 in which R' is --C 6 H 4 --.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-07-08 | 1989-01-07 | 1989-07-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-07-08 | 1993-01-07 | 1993-07-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-07-08 | 1997-01-07 | 1997-07-09 | $7700.00 | Window Closed / Lapsed |