CA1335893C - Polyetherimide oligomers and blends - Google Patents
Polyetherimide oligomers and blendsInfo
- Publication number
- CA1335893C CA1335893C CA 555820 CA555820A CA1335893C CA 1335893 C CA1335893 C CA 1335893C CA 555820 CA555820 CA 555820 CA 555820 A CA555820 A CA 555820A CA 1335893 C CA1335893 C CA 1335893C
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- moles
- aryl
- oligomers
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- polyetherimide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Abstract
Polyetherimide oligomers having crosslinking end cap moieties which provide improved solvent -resistance to cured composites are generally represented by the formula:
wherein X = -O- or -S-;
A = n = 1 or 2;
, or E = allyl or methallyl;
R = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
Blends generally comprise substantially equimolar amounts of the oligomers and a comparable, compatible, noncrosslinking, etherimide polymer of substantially the same backbone. The crosslinkable oligomers are made by reacting substituted phthalic anhydrides with hydroxyaryl amines and suitable crosslinking end cap reactants, or by self-condensation of phthalimide salts followed by capping the polymers. Related polyetherimides of the present invention can be prepared by the condensation of nitrophthalic anhydride, diamines, dialcohols, (dihydricphenols), and phenolic, crosslinking end caps (A-OH), or the condensation of bis(phenates) or dialcohols (bisphenols), diamines, nitrophthalic anhydride, and amine-terminated end caps (A-NH2) or nitro-terminated end caps (A-NO2).
The oligomers and blends can be prepregged, and can be cured to form advanced composites having aerospace applications.
wherein X = -O- or -S-;
A = n = 1 or 2;
, or E = allyl or methallyl;
R = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
Blends generally comprise substantially equimolar amounts of the oligomers and a comparable, compatible, noncrosslinking, etherimide polymer of substantially the same backbone. The crosslinkable oligomers are made by reacting substituted phthalic anhydrides with hydroxyaryl amines and suitable crosslinking end cap reactants, or by self-condensation of phthalimide salts followed by capping the polymers. Related polyetherimides of the present invention can be prepared by the condensation of nitrophthalic anhydride, diamines, dialcohols, (dihydricphenols), and phenolic, crosslinking end caps (A-OH), or the condensation of bis(phenates) or dialcohols (bisphenols), diamines, nitrophthalic anhydride, and amine-terminated end caps (A-NH2) or nitro-terminated end caps (A-NO2).
The oligomers and blends can be prepregged, and can be cured to form advanced composites having aerospace applications.
Description
1 ~ 66239-1364 POL~ ~IMIDE OLIGOMERS AND BLENDS
Technical Fleld and Background of the Invention The present lnventlon relates to polyetherlmlde ollgomers that are curable lnto hlgh performance composltes and to thelr method of manufacture. The ollgomers have crossllnklng end cap functlonalltles whlch lmprove the solvent-reslstance of the composltes. Blends of the ollgomers and polymers are also described.
Polyetherlmides can be prepared by the self-condensa-tlon of hydroxyaryl phthallmlde salts, as dlsclosed ln Unlted States Patent 4,297,474.
The polymers have the general formula:
XR ~ C ~ NR' C
wherein R ls a trlvalent C(6_13) aromatlc organlc radlcal, R' ls a dlvalent C(6-30) aromatlc organlc radlcal, and X ls -O- or -S-. The polymers have alternatlng lmlde and ether (or thlo-ether) llnkages between aromatic radlcals. Slmllar polyether-lmlde polymers are prepared by the reactlon of alkall metal dlhydrlc phenol and an organlc bls (fluorophthallmlde) ln the presence of a dlpolar aprotlc solvent, as dlsclosed ln Unlted States Patent 3,847,869.
Polysulfonelmldes of the same general type are prepar-ed by the reactlon of an aromatlc bls(sulfoneanhydrlde) wlth an organlc dlamlne, as dlsclosed ln Unlted States Patent 4,107,147.
~, ~
1335893 66239-l364 While these etherimide and sulfoneimide polymers are suitable for films, coatlngs, etc., thelr solvent-reslstance and other physlcal propertles ln composlte form can be lmproved by addlng crossllnklng end cap functlonalltles to the polymer backbones, thereby making the composltes (cured from the ollgomers) better sulted for hlgh performance appllcatlons, such as aerospace needs.
Summary of the Inventlon Polyetherlmide (or sulfonelmldes) ollgomers of the present lnventlon have the general formula:
l o C - 11 ll A-XR< > N--R'XR<C> N--R'XR <C~N-A
O O , O
whereln X = -O- or -S-;
A - (Z)n ~,;
n - 1 or 2;
Z =
O O
C~ ) j ~C
~ C
O O
Me 0 ~nè
O Me (Rl) j~/N , or ~C
HC~C 11 ~~C
O O
E = allyl or methallyl:
R = a trlvalent C(6-13) aromatlc organlc radlcal;
Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl (lncludlng hydroxyl or halo substltuents);
R' = a dlvalent C(6-30) aromatlc organlc radlcal;
~ = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
These ollgomers can be prepared by condenslng:
A-X-R < C > (I) o o A - N ~ > R - Y (II) ;
Il O
Y - R < C / (III); and O
(IV) N - R'-X-H
in the ratio of I:II:III:IV = l:l:m:m wherein m = an integer greater than or equal to one, and A, R, R', and X are as defined previously, and wherein Y = halo- or nitro-. This reaction occurs in a suitable solvent under an inert atmosphere.
Compounds of the formula (I) and (II) are novel compositions of matter. Those of formula (I) can be prepared by reacting- A-XH with a substituted phthalic anhydride of the formula:
Y-R ~ ~ O (V) O
wherein A, Y, and R are as previously defined. Carried aut in a suitable solvent substantially to completion by mixing substantially equimolar amounts of the reactants, the anhydride need not be recovered, but rather the product mixture can be added to the reaction mixture of the condensation reaction of the oligomer, if the solvents are compatible.
Compounds of formula (II) are prepared by s reacting A-NH2 with the substituted phthalic anhydride of formula (V). Again, the reaction product need not be separated from the reaction mixture to carry out the oligomer's condensation, if the solvents are compatible.
Blended compositions, preferably having substantially equimolar amounts of the oligomers and a compatible polymer, are also contemplated. These blends generally comprise one of the crosslinkable oligomers previously described and a noncrosslinking polymer of the type described in U.S. Patent 4,297,474 that has substantially the same backbone as the oli~omer. Such a polymer, however, does not possess crosslinking capability.
Polysulfoneimide oligomers of the present invention can be prepared by reacting:
n + 1 moles of a dianhydride;
n moles of a diamine; and 2 moles of an amine end cap, wherein the dianhydride and diamine are selected to form a polysulfone imide backbone of the following general formula:
R ll A - ~ < ~ S2- R 52 ~ \ ~R' - A
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms. These radicals include halogenated aromatic C(6-20) hydrocarbon derivatives;
alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms; C(2_8) alkylene terminated polydiorganosiloxanes; and radicals of the formula:
6 133~893 wherein q = -CyH2y~r -CO-, -S02-, -O-, or -S-; and y = 1 to 5.
Oligomers of the present invention can also be prepared by the condensation of nitrophthalic anhydride, -diamines, dialcohols, and phenolic end caps.
Prepregs and composites of these oligomers and blends can also be made.
Detailed Description of the Invention Polyetherimides and polysulfoneimides are capped with mono- and difunctional, crosslinking phenylimides to produce oligomers that are curable to composites ;
which exhibit improved solvent resistance. The end cap phenylimides can be selected to provide cure and use temperatures within a relatively wide range.
Preferred compounds have the general formula:
O O O .
I I . Il 11 A-XR / > N ~R'XR < > N -R'XR = N-A
C C m C
Il - 11 _ 11 O O O , wherein X = -O- or -S-;
n n = 1 or 2;
. . .::
.: . .. ...
:'. :- . . , . , ,:
71 33~893 66239-1364 (R ~; - C /Rl)j ~ C/
Me 0 1) i ~1C \ ( 1 ) j ~C \
N , ~ C~
0 Me 0 Me ( l)j ~ \N , or ~ C
HC _C 0 0 E = allyl or methallyl:
R = a trlvalent C(6_l3) aromatlc organlc radlcal;
Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl (includlng hydroxyl or halo substltuents);
R' = a dlvalent C(6-30) aromatlc organlc radlcal;
~ = 0, 1, or 2; and G = -CH2-, or -O-, -S-, or -SO2-.
The crossllnklng end cap radlcals (A) are readily prepared by the condensation of the corresponding anhydride and a suitable amine, as described in United States Patent 4,604,437 with respect to the allyl-substituted or methallyl-substituted methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximides.
The end cap radicals are unsaturated, substituted phenylimides, and are generally selected from the group consisting of:
s, (2)n ~)~
wherein n = 1 or 2;
( R 1 ) j~ \N
Ll.
. Me e ~j (R~ C~N
(Rl)j ~ \N--, or ~/
O O
and Rl, G, and j are as previously defined. The most preferred end caps (to provide the highest thermal stability) are those in which Z has the formulae:
133~893 , ~~ / N o r ~1 . O
wherein j preferably equals 1. These preferred end caps are conveniently prepared from relatively inexpensive starting materials. Recent work also indicates than an end cap radical of the formula:
o R~ ~ ~N
wherein R2 = ~ is a preferred compound.
The polyetherimide oligomers of the present invention can be prepared by several reaction schemes.
One such method comprises the simultaneous condensation of:
A-X-R ~ ~ (I);
A ~ N ~ C > R - Y (II);
o Y - R ~ > O (III); and H2N---R' X-~ (IV) in the ratio of I:II:III:IV = l:l:m:m, wherein m is an integer greater than or equal to one. The product has the general formula previously described. The reaction occurs in a suitable solvent under an inert atmosphere.
If necessary, the reaction mixture can be heated to facilitate the reaction. The reaction conditions are l33sss3 generally comparable to those descrlbed ln Unlted States Patents 3,847,869 and 4,107,147.
Preferably the ollgomer products possess thermoplastlc propertles, and, accordlngly, have an average formula welght of between about 5,000 - 40,000, and generally 20,000 - 30,000.
Alternatlvely, the polyetherlmldes can be prepared by reactlng a polyetherlmlde polymer made by the self-condensatlon of a phthallmlde salt of the formula:
o C
Y - R ~ C > NR'XM
o wlth crossllnklng end cap moletles of the formulae:
o A-X-R < > 0 and Ij AN ~ C \
C RY
lo whereln X = -0- or -S-;
A = (Z)n ~,~
-12 1 335893 66239-l364 n = 1 or 2:
Z =
O O
(R~ r (Rl);
O O
1 ) j ~ ( Rl ) j O Me ;Rl) j ~c/
HC -C O O
E = allyl or methallyl;
Y = halo- or nltro-Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl;
R' = a dlvalent C(6_30) aromatlc organlc radlcal;
~ = O, 1, or 2;
G = -CH2-, -O-, -S-, or -S02-; and M = an alkali metal lon or ammonlum salt or hydrogen.
~7 'i-~
i33ssg3 The self-condensation proceeds as described in United States Patent 4,297,474 in a dipolar aprotic solvent. The end cap moieties can be introduced during the self-condensation to quench the polymerization, or they might be added following completion of the polymerization and recovery of the polyetherimide polymer from methanol. Improved solvent resistance on the cured composites is best achieved, however, by the quenching sequence rather than by the post-polymerization capping sequence.
Yet another preferred method for synthesizing the polyetherimides of the present invention involves the simultaneous condensation of about 2m + 2 moles of nitrophthalic anhydride with about m+1 moles of diamine, about m moles of dialcohol, and 2 moles of A-OH in a suitable solvent under an inert atmosphere. Here, the dialcohol (hereinafter referred to also as a diol or a dihydric phenol) may actually be in the form of a phenate.
In this reaction, the diamines (which have, preferably, aromatic ethersulfone backbones) react with the anhydride to form intermediates of the following nature in the backbone:
~ =N R2 N ,~
wherein R2 = a residue of the diamine. Similarly, the dialcohol reacts with the nitro-functionality to form an ether linkage of the general formula:
~ \ R3 wherein R3 = a residue of the dialcohol.
The A-OH end caps quench the polymerization.
The resulting polyetherimides have the general formula:
A - ~ \;-R2-N/ ~ ~ ~ 0-A
Yet another preferred synthesis comprises the simultaneous condensation of about 2m + 2 moles of nitrophthalic anhydride with about m+1 moles of dialcohol, m moles of diamine, and 2 moles A-NH2 in a suitable solvent under an inert atmosphere. Again, the dialcohol may be in the phenate form. The resulting oligomer has a general formula:
O
Yet another preferred synthesis comprises the simultaneous condensation of 2m moles of nitrophthalic anhydride with about m+1 moles of dialcohol, m moles of diamine, and 2 moles of A-NO2 (a nitro-terminated end cap) in a suitable solvent under an inert atmosphere.
Again, the dialcohol may be in the phenate form or a 133~893 corresponding sulfhydryl can be used to form a thioether. The resulting oligomer has the general formula:
C ~ O-R3-O - A
A-O-R3-O ~ \N-R2-N\ ~
o In any of the synthesis, the dialcohol can be replaced by a comparable disulfhydryl of the formula.:
HS-R2-SH. Mixtures of dialcohols, or disulfhydryls, or of dialcohols and disulfhydryls can be used.
Suitable diamines are selected from the group consisting of:
H2 ~ NH2 H2N~H2 H2N ~H2 ~
H2N -~ ~ q - ~ H2 ) H2N ~ ~ ~NH2 H2N ~ 4 ~ q ~ NH
2 ~ ~ H2 H N ~ ~ ~ ~ NH2 133~893 H2N ~ q ~ ~ q ~NH2 H2N ~ O ~ q ~ O ~H2 H2N~ S02~S02~ 2 ~ MH2 D D D
H2N ~ I ~ ~ J~ -m~C~NH2, ~
Me Me _ _ 2 ~ --R -O--R"-O-- Rl-o~NH2 whereln Rl = ~q ~
R" = ~, ~, ~, ~0 ~, or CH 3 ~, q = -S02-, -CO-, -S-, or -(CF3)2C-, and preferably -S02- or -CO-, 17 1 33$893 66239-l364 Me = CH3-.
m = an lnteger, generally less than 5, and preferably 0 or 1;
any of -CO-, -SO2-, or -(CF3)2C ; a X = halogen.
Other dlamlnes that may be used, but that are not preferred, lnclude those descrlbed ln Unlted States Patents 4,504,632 and 4,058,505.
The aryl or polyaryl "sulfone" dlamines prevlously descrlbed are preferred, slnce these dlamlnes provlde hlgh thermal stablllty to the resultlng ollgomers and composltes.
Mlxtures of dlamlnes mlght be used.
The dlalcohol ls generally a polyaryl compound and preferably ls selected from the group conslstlng of HO - Ar - OH;
HO - Ar - L - Ar' - L - Ar - OH;
HO - Ar' - L - Ar - L - Ar' - OH;
whereln L = -CH2-~ -(CF3)2C-~ -(CH3)2C-~ ~ 2 -CO-;
Ar' = ~ L ~ Tl)q ~ ~ ~,,(Tl)k, ( T ) k T ( T ) 5~}_ ( T l ) j ( l)k (T)k ( l)k .~
;~,~( T 1 ) q ~_ _~T 1 ) q T and Tl = lower alkyl, lower alkoxy, aryl, aryloxy, substituted aryl, halogen, or mixtures thereof;
q = O - 4 k = O - 3; and j = O, 1, or 2;
hydroquinone;
bisphenol A;
p' p' - bisphenol 4' 4' - dihydroxydiphenylsulfide;
4' 4' - dihydroxydiphenylether;
4' 4' - dihydroxydiphenylisopropane;
4' 4' - dihydroxydiphenylhexafluoropropane;
a dialcohol having a Schiff base segment, the radical being selected from the group consisting of:
~N= CH~ CH=~N- R- N= CH~ CH--N~
~H=N- R-N=CH~ , or ~CH=N- R-N--CH~CH=N- R-N--CH~ ' wherein R is selected from the group consisting of:
phenyl;
biphenyl;
naphthyl; or a radical of the general formula:
~W~
-wherein W = -CH2- or -S02-; or a dialcohol selected from the group:
~ HO ~ O ~ 0 30H
HO ~ L ~L ~OH
HO ~ L ~0 ~OH
HO~ O _~0 ~0 ~O~j, HO~ O ~L ~0 ~0~, HO~ L ~ O -~ L ~OH, HO~ S02 ~2~52~
HO ~ CH~ ~` SO ~ ~[~\ ~OH" or CH3 CH~
HO ~ D ~ ~ D ~ ~ D
wherein L is as defined above;
Me = CH3-;
m = an integer, generally less than 5, and preferably O or 1; and D = any of -CO-, -S02-, or -(CF3)2C-.
While bisphenol A is preferred (because of cost and avallablllty)~ the other dlalcohols can be used to add rlgldlty to the ollgomer wlthout slgnlflcantly lncreaslng the average formula welght, and, therefore, can lncrease the solvent reslstance. Random or block copolymers are posslble.
Furthermore, the dlalcohols may be selected from the dlhydrlc phenol lmlde sulfone reslns descrlbed ln Unlted States Patent 4,584,364, or those dlhydrlc phenols descrlbed ln Unlted States Patents 3,262,914 or 4,611,048. In fact, the hydroxy-termlnated etherlmldes of U.S. Patent 4,611,048 can be reacted wlth A-NO2 to provlde crossllnklng etherlmldes of the present lnventlon.
Dlalcohols of thls nature are commerclally avallable.
Some may be easlly syntheslzed by reactlng hallde lntermedlates wlth bls-phenates, such as by the reactlon of 4,4'-chlorophenyl-sulfone wlth bls(dlsodlum blphenolate).
The ollgomers can be syntheslzed ln a homogeneous reaction scheme whereln all the reactants are mlxed at one tlme (and thls scheme ls preferred), or ln a stepwlse reactlon. The dlamlne and dlalcohols can be mlxed, for example, followed by addltlon of the nltrophthallc anhydrlde to lnltlate the poly-merlzatlon and thereafter the end caps to quench lt. Those skilled in the art will recognize the varlant methods that mlght be used. To the extent posslble, undeslrable competltlve reactlons should be mlnimized by controlling the reactlon steps (l.e., addltlon of reactants) and the reactlon condltlons.
'~.
20a 13 3 5 89 3 66239-1364 Instead of Schiff base linkages in the dialcohols, these compounds might include oxazole, thlazole, or lmldazole llnkages. All of these llnkages present the potentlal for creatlng conductlve or semlconductlve composltes, lf sultably doped.
.
Dopants for creating semiconductive or conductive composites are preferably selected from compounds commonly used to dope other polymers, namely (l) dispersions of alkali metals (for high activity) or (2) strong chemical oxidizers, particularly alkali perchlorates (for lower activity). Arsenic compounds and elemental halogens, while active dopants, are too dangerous for general usage, and are not recommended.
The dopants react with the polymers to form charge transfer complexes. N-type semiconductors result from doping with alkali metal dispersions. P-type semiconductive result from doping with elemental iodine or perchlorates.
While research into conductive or semiconductive polymers has been intense, the resulting compounds (mainly polyacetylenes, polyphenelenes, and polyvinylacetylenes) are unsatisfactory for aerospace applications because the polymers are:
(a) unstable in air;
(b) unstable at high temperatures;
(c) brittle after doping;
(d) toxic because of the dopants; or (e) intractable.
These problems may be overcome or significantly reduced with the conductive oligomers of the present invention.
While conventional theory holds that semiconductive polymers should have (l) low ionization potentials, (2) long conjugation lengths, and (3) planar backbones, there is an inherent trade-off between conductivity and toughness or processibility, if these constraints are followed. To overcome the processing and toughness shortcomings common with Schiff base, oxazole, imidazole, or thiazole oligomers, the oligomers of the present invention, include "sulfone" linkages interspersed along the backbone providing a mechanical swivel for the rigid, conductive segments of the arms.
Since it is difficult to include the oxazole, imidazole, or thiazole linkages in the reactants, Schiff base compounds are preferred. The principle focus of the invention is toward improved etherimide, thioetherimides, or sulfoneimides, and the conductive or semiconductive composites are not the preferred compounds of the present invention. They are but a small subset of the compounds that comprise the present invention.
Solubility of the oligomers becomes an increasing problem as the length of the backbones increases. Therefore, shorter backbones are preferred, so long as the resulting oligomers remain processible.
That is, the backbones should be long enough to keep the oligomers soluble to the reaction sequence.
Blends of the crosslinkable oligomers and noncrosslinking, compatible polymers can also be made.
These blends generally comprise substantially equimolar mixtures of the oligomer and polymer. The polymer should have a backbone substantially identical with the oligomer, and may be made in accordance with a process described in U.S. Patent 4,297,474 or 3,847,869.
Impact resistance of the cured composites formed from prepregs of the oligomers can be increased without deleterious loss of solvent resistance by forming the prepregs with such a blend. Generally, the blend includes capped oligomers to provide crosslinking upon curing and noncrosslinking polymers of a corresponding backbone to provide compatibility of the oligomer and polymer. A 50-50 blend on a molar basis of oligomers and polymer may be formed by (a) dissolving the capped oligomer in a suitable first solvent, (b) dissolving the capped polymer in a separate portion of the same solvent or in a solvent miscible with the first solvent, (c) 23 133~893 mixing the two solvent solutions to form a lacquer, and (d) applying the lacquer to fabric in a conventional prepregging process.
Although the polymer in the blend usually has the same backbone (structure and formula weight) as the oligomer, the properties of the composite formed from the blend can be adjusted by altering the ratio of formula weight for the polymer and oligomer.
The terminal groups of the polymer are unimportant so long as the polymer's terminal groups do not react with or impede the crosslinking of the oligomer end caps. Also, it is probably nonessential that the oligomer and polymer have identical repeating units (structure), but that the oligomer and polymer merely be compatible in the solution prior to sweeping out as a prepreg. Of course, if the polymer and oligomer have identical backbones, compatibility in the blend is more likely.
The noncrosslinking polymer can be made by the same synthetic method as the oligomer with the substitution of a quenching cap for the crosslinking end cap. For example, phenol can replace end caps of the formula A-OH; benzamine can replace end caps of the formula A-NH2; and, nitrobenzene can replace end caps of the formula A-NO2.
While the best blends are probably those in which the backbones are essentially identical and of modest formula weight and those in which the oligomer and polymer are in equimolar proportions, other variant blends may be prepared, as will be recognized by those of ordinary skills in the art.
Anhydrides of the formula:
1l A X R ~ > O
lcl wherein X = -O- or -S-;
R = a trivalent C(6-13) aromatic organic radical;
A = (Z
n = 1 or 2;
Z = 1 ~ ~\N (Rl)j ~C\N--( R ~ ~ ( R ~
O Me O
(Rl)j~ N--R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = O, 1, or 2; and G = -CH2-, -O-, -S-, or -S02-, are useful in the synthesis of the etherimides of the present invention, and are prepared by the condensation of the corresponding end cap phenol or thiol (-XH) with a nitro- or halo- anhydride that contains the R moiety.
In at least one synthesis of the etherimides of the present invention, a compound of the formula:
~\
A - N < ~ R - Y
~. ~
is an intermediate or reactant, wherein:
R = a trivalent C(6-13) aromatic organic radical' A = Zn n = l or 2;
(R~ /\N - , (R~ \ N - , ~1 0 ~? ~[~
HC_~b/ E
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
This intermediate if formed by reacting A-NH2 with a substituted phthalic anhydride of the formula:
o wherein Y = halo- or nitro-. These substituted anhydrides are described in United States Patents 4,297,474 and 3,847,869.
Polysulfoneimide oligomers can be prepared by reacting about m+1 moles of a dianhydride with about m moles of a diamine and about 2 moles of an amine end cap (A-NH2). The resulting oligomer has the general formula:
A--~1~C~S02 R--SO~z ~ NR' A
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms. R and R' may include halogenated aromatic C(6-20) hydrocarbon derivatives;
alkylene radicals and cycloakylene radicals having from 2-20 carbon atoms; C(2-8) alkylene terminated - polydiorganosiloxanes; and radicals of the formula:
~q~
wherein q = -CyH2y~l -CO-, -SO2-, -O-, or -S-; and y = 1 to 5.
Comparable polymers, usable in blends of the sulfoneimides, are described in United States Patent 4,107,147. - Other aromatic dithio dianhydrides are described in United S~ates Patent 3,933,862.
~ he oligomers of the present invention can be combined with reinforcing materials, such as fibers, chopped fibers, whiskers, or fabrics, and cured to composite materials using heat or chemicals to activate crosslinking between end caps. Prepregs can be prepared by conventional prepregging technigues. Curing generally is conducted in conventional vacuum bagging te~hn~ques at elevated temperatures. The curing temperature varies with the choice of end cap. If desired, mixtures of end caps might be used.
While ~- isomerism has generally been described, other isomers may be used. The phenyl or aryl moieties in the backbones can also include substituents so long as the substituents do not interfere with the crosslinking or synthesis. While polyaryl compounds are described, aliphatic moieties can be included in the backbones, in some cases, although the ultimate use temperatures of these oligomers or composites may bè lower than with entirely polyaryl backbones.
While preferred embodiments have been described, those skilled in the art will readily recognize alterations, variations or modifications which might be made to the embodiments without departing from the inventive concept. Therefore, the claims should be interpreted liberally with the support of the full range of equivalents known to those or ordinary skill based upon this description. The claims should be limited only as is necessary in view of the pertinent prior art.
Technical Fleld and Background of the Invention The present lnventlon relates to polyetherlmlde ollgomers that are curable lnto hlgh performance composltes and to thelr method of manufacture. The ollgomers have crossllnklng end cap functlonalltles whlch lmprove the solvent-reslstance of the composltes. Blends of the ollgomers and polymers are also described.
Polyetherlmides can be prepared by the self-condensa-tlon of hydroxyaryl phthallmlde salts, as dlsclosed ln Unlted States Patent 4,297,474.
The polymers have the general formula:
XR ~ C ~ NR' C
wherein R ls a trlvalent C(6_13) aromatlc organlc radlcal, R' ls a dlvalent C(6-30) aromatlc organlc radlcal, and X ls -O- or -S-. The polymers have alternatlng lmlde and ether (or thlo-ether) llnkages between aromatic radlcals. Slmllar polyether-lmlde polymers are prepared by the reactlon of alkall metal dlhydrlc phenol and an organlc bls (fluorophthallmlde) ln the presence of a dlpolar aprotlc solvent, as dlsclosed ln Unlted States Patent 3,847,869.
Polysulfonelmldes of the same general type are prepar-ed by the reactlon of an aromatlc bls(sulfoneanhydrlde) wlth an organlc dlamlne, as dlsclosed ln Unlted States Patent 4,107,147.
~, ~
1335893 66239-l364 While these etherimide and sulfoneimide polymers are suitable for films, coatlngs, etc., thelr solvent-reslstance and other physlcal propertles ln composlte form can be lmproved by addlng crossllnklng end cap functlonalltles to the polymer backbones, thereby making the composltes (cured from the ollgomers) better sulted for hlgh performance appllcatlons, such as aerospace needs.
Summary of the Inventlon Polyetherlmide (or sulfonelmldes) ollgomers of the present lnventlon have the general formula:
l o C - 11 ll A-XR< > N--R'XR<C> N--R'XR <C~N-A
O O , O
whereln X = -O- or -S-;
A - (Z)n ~,;
n - 1 or 2;
Z =
O O
C~ ) j ~C
~ C
O O
Me 0 ~nè
O Me (Rl) j~/N , or ~C
HC~C 11 ~~C
O O
E = allyl or methallyl:
R = a trlvalent C(6-13) aromatlc organlc radlcal;
Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl (lncludlng hydroxyl or halo substltuents);
R' = a dlvalent C(6-30) aromatlc organlc radlcal;
~ = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
These ollgomers can be prepared by condenslng:
A-X-R < C > (I) o o A - N ~ > R - Y (II) ;
Il O
Y - R < C / (III); and O
(IV) N - R'-X-H
in the ratio of I:II:III:IV = l:l:m:m wherein m = an integer greater than or equal to one, and A, R, R', and X are as defined previously, and wherein Y = halo- or nitro-. This reaction occurs in a suitable solvent under an inert atmosphere.
Compounds of the formula (I) and (II) are novel compositions of matter. Those of formula (I) can be prepared by reacting- A-XH with a substituted phthalic anhydride of the formula:
Y-R ~ ~ O (V) O
wherein A, Y, and R are as previously defined. Carried aut in a suitable solvent substantially to completion by mixing substantially equimolar amounts of the reactants, the anhydride need not be recovered, but rather the product mixture can be added to the reaction mixture of the condensation reaction of the oligomer, if the solvents are compatible.
Compounds of formula (II) are prepared by s reacting A-NH2 with the substituted phthalic anhydride of formula (V). Again, the reaction product need not be separated from the reaction mixture to carry out the oligomer's condensation, if the solvents are compatible.
Blended compositions, preferably having substantially equimolar amounts of the oligomers and a compatible polymer, are also contemplated. These blends generally comprise one of the crosslinkable oligomers previously described and a noncrosslinking polymer of the type described in U.S. Patent 4,297,474 that has substantially the same backbone as the oli~omer. Such a polymer, however, does not possess crosslinking capability.
Polysulfoneimide oligomers of the present invention can be prepared by reacting:
n + 1 moles of a dianhydride;
n moles of a diamine; and 2 moles of an amine end cap, wherein the dianhydride and diamine are selected to form a polysulfone imide backbone of the following general formula:
R ll A - ~ < ~ S2- R 52 ~ \ ~R' - A
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms. These radicals include halogenated aromatic C(6-20) hydrocarbon derivatives;
alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms; C(2_8) alkylene terminated polydiorganosiloxanes; and radicals of the formula:
6 133~893 wherein q = -CyH2y~r -CO-, -S02-, -O-, or -S-; and y = 1 to 5.
Oligomers of the present invention can also be prepared by the condensation of nitrophthalic anhydride, -diamines, dialcohols, and phenolic end caps.
Prepregs and composites of these oligomers and blends can also be made.
Detailed Description of the Invention Polyetherimides and polysulfoneimides are capped with mono- and difunctional, crosslinking phenylimides to produce oligomers that are curable to composites ;
which exhibit improved solvent resistance. The end cap phenylimides can be selected to provide cure and use temperatures within a relatively wide range.
Preferred compounds have the general formula:
O O O .
I I . Il 11 A-XR / > N ~R'XR < > N -R'XR = N-A
C C m C
Il - 11 _ 11 O O O , wherein X = -O- or -S-;
n n = 1 or 2;
. . .::
.: . .. ...
:'. :- . . , . , ,:
71 33~893 66239-1364 (R ~; - C /Rl)j ~ C/
Me 0 1) i ~1C \ ( 1 ) j ~C \
N , ~ C~
0 Me 0 Me ( l)j ~ \N , or ~ C
HC _C 0 0 E = allyl or methallyl:
R = a trlvalent C(6_l3) aromatlc organlc radlcal;
Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl (includlng hydroxyl or halo substltuents);
R' = a dlvalent C(6-30) aromatlc organlc radlcal;
~ = 0, 1, or 2; and G = -CH2-, or -O-, -S-, or -SO2-.
The crossllnklng end cap radlcals (A) are readily prepared by the condensation of the corresponding anhydride and a suitable amine, as described in United States Patent 4,604,437 with respect to the allyl-substituted or methallyl-substituted methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximides.
The end cap radicals are unsaturated, substituted phenylimides, and are generally selected from the group consisting of:
s, (2)n ~)~
wherein n = 1 or 2;
( R 1 ) j~ \N
Ll.
. Me e ~j (R~ C~N
(Rl)j ~ \N--, or ~/
O O
and Rl, G, and j are as previously defined. The most preferred end caps (to provide the highest thermal stability) are those in which Z has the formulae:
133~893 , ~~ / N o r ~1 . O
wherein j preferably equals 1. These preferred end caps are conveniently prepared from relatively inexpensive starting materials. Recent work also indicates than an end cap radical of the formula:
o R~ ~ ~N
wherein R2 = ~ is a preferred compound.
The polyetherimide oligomers of the present invention can be prepared by several reaction schemes.
One such method comprises the simultaneous condensation of:
A-X-R ~ ~ (I);
A ~ N ~ C > R - Y (II);
o Y - R ~ > O (III); and H2N---R' X-~ (IV) in the ratio of I:II:III:IV = l:l:m:m, wherein m is an integer greater than or equal to one. The product has the general formula previously described. The reaction occurs in a suitable solvent under an inert atmosphere.
If necessary, the reaction mixture can be heated to facilitate the reaction. The reaction conditions are l33sss3 generally comparable to those descrlbed ln Unlted States Patents 3,847,869 and 4,107,147.
Preferably the ollgomer products possess thermoplastlc propertles, and, accordlngly, have an average formula welght of between about 5,000 - 40,000, and generally 20,000 - 30,000.
Alternatlvely, the polyetherlmldes can be prepared by reactlng a polyetherlmlde polymer made by the self-condensatlon of a phthallmlde salt of the formula:
o C
Y - R ~ C > NR'XM
o wlth crossllnklng end cap moletles of the formulae:
o A-X-R < > 0 and Ij AN ~ C \
C RY
lo whereln X = -0- or -S-;
A = (Z)n ~,~
-12 1 335893 66239-l364 n = 1 or 2:
Z =
O O
(R~ r (Rl);
O O
1 ) j ~ ( Rl ) j O Me ;Rl) j ~c/
HC -C O O
E = allyl or methallyl;
Y = halo- or nltro-Rl = any of lower alkyl, lower alkoxy, aryl, or substltuted aryl;
R' = a dlvalent C(6_30) aromatlc organlc radlcal;
~ = O, 1, or 2;
G = -CH2-, -O-, -S-, or -S02-; and M = an alkali metal lon or ammonlum salt or hydrogen.
~7 'i-~
i33ssg3 The self-condensation proceeds as described in United States Patent 4,297,474 in a dipolar aprotic solvent. The end cap moieties can be introduced during the self-condensation to quench the polymerization, or they might be added following completion of the polymerization and recovery of the polyetherimide polymer from methanol. Improved solvent resistance on the cured composites is best achieved, however, by the quenching sequence rather than by the post-polymerization capping sequence.
Yet another preferred method for synthesizing the polyetherimides of the present invention involves the simultaneous condensation of about 2m + 2 moles of nitrophthalic anhydride with about m+1 moles of diamine, about m moles of dialcohol, and 2 moles of A-OH in a suitable solvent under an inert atmosphere. Here, the dialcohol (hereinafter referred to also as a diol or a dihydric phenol) may actually be in the form of a phenate.
In this reaction, the diamines (which have, preferably, aromatic ethersulfone backbones) react with the anhydride to form intermediates of the following nature in the backbone:
~ =N R2 N ,~
wherein R2 = a residue of the diamine. Similarly, the dialcohol reacts with the nitro-functionality to form an ether linkage of the general formula:
~ \ R3 wherein R3 = a residue of the dialcohol.
The A-OH end caps quench the polymerization.
The resulting polyetherimides have the general formula:
A - ~ \;-R2-N/ ~ ~ ~ 0-A
Yet another preferred synthesis comprises the simultaneous condensation of about 2m + 2 moles of nitrophthalic anhydride with about m+1 moles of dialcohol, m moles of diamine, and 2 moles A-NH2 in a suitable solvent under an inert atmosphere. Again, the dialcohol may be in the phenate form. The resulting oligomer has a general formula:
O
Yet another preferred synthesis comprises the simultaneous condensation of 2m moles of nitrophthalic anhydride with about m+1 moles of dialcohol, m moles of diamine, and 2 moles of A-NO2 (a nitro-terminated end cap) in a suitable solvent under an inert atmosphere.
Again, the dialcohol may be in the phenate form or a 133~893 corresponding sulfhydryl can be used to form a thioether. The resulting oligomer has the general formula:
C ~ O-R3-O - A
A-O-R3-O ~ \N-R2-N\ ~
o In any of the synthesis, the dialcohol can be replaced by a comparable disulfhydryl of the formula.:
HS-R2-SH. Mixtures of dialcohols, or disulfhydryls, or of dialcohols and disulfhydryls can be used.
Suitable diamines are selected from the group consisting of:
H2 ~ NH2 H2N~H2 H2N ~H2 ~
H2N -~ ~ q - ~ H2 ) H2N ~ ~ ~NH2 H2N ~ 4 ~ q ~ NH
2 ~ ~ H2 H N ~ ~ ~ ~ NH2 133~893 H2N ~ q ~ ~ q ~NH2 H2N ~ O ~ q ~ O ~H2 H2N~ S02~S02~ 2 ~ MH2 D D D
H2N ~ I ~ ~ J~ -m~C~NH2, ~
Me Me _ _ 2 ~ --R -O--R"-O-- Rl-o~NH2 whereln Rl = ~q ~
R" = ~, ~, ~, ~0 ~, or CH 3 ~, q = -S02-, -CO-, -S-, or -(CF3)2C-, and preferably -S02- or -CO-, 17 1 33$893 66239-l364 Me = CH3-.
m = an lnteger, generally less than 5, and preferably 0 or 1;
any of -CO-, -SO2-, or -(CF3)2C ; a X = halogen.
Other dlamlnes that may be used, but that are not preferred, lnclude those descrlbed ln Unlted States Patents 4,504,632 and 4,058,505.
The aryl or polyaryl "sulfone" dlamines prevlously descrlbed are preferred, slnce these dlamlnes provlde hlgh thermal stablllty to the resultlng ollgomers and composltes.
Mlxtures of dlamlnes mlght be used.
The dlalcohol ls generally a polyaryl compound and preferably ls selected from the group conslstlng of HO - Ar - OH;
HO - Ar - L - Ar' - L - Ar - OH;
HO - Ar' - L - Ar - L - Ar' - OH;
whereln L = -CH2-~ -(CF3)2C-~ -(CH3)2C-~ ~ 2 -CO-;
Ar' = ~ L ~ Tl)q ~ ~ ~,,(Tl)k, ( T ) k T ( T ) 5~}_ ( T l ) j ( l)k (T)k ( l)k .~
;~,~( T 1 ) q ~_ _~T 1 ) q T and Tl = lower alkyl, lower alkoxy, aryl, aryloxy, substituted aryl, halogen, or mixtures thereof;
q = O - 4 k = O - 3; and j = O, 1, or 2;
hydroquinone;
bisphenol A;
p' p' - bisphenol 4' 4' - dihydroxydiphenylsulfide;
4' 4' - dihydroxydiphenylether;
4' 4' - dihydroxydiphenylisopropane;
4' 4' - dihydroxydiphenylhexafluoropropane;
a dialcohol having a Schiff base segment, the radical being selected from the group consisting of:
~N= CH~ CH=~N- R- N= CH~ CH--N~
~H=N- R-N=CH~ , or ~CH=N- R-N--CH~CH=N- R-N--CH~ ' wherein R is selected from the group consisting of:
phenyl;
biphenyl;
naphthyl; or a radical of the general formula:
~W~
-wherein W = -CH2- or -S02-; or a dialcohol selected from the group:
~ HO ~ O ~ 0 30H
HO ~ L ~L ~OH
HO ~ L ~0 ~OH
HO~ O _~0 ~0 ~O~j, HO~ O ~L ~0 ~0~, HO~ L ~ O -~ L ~OH, HO~ S02 ~2~52~
HO ~ CH~ ~` SO ~ ~[~\ ~OH" or CH3 CH~
HO ~ D ~ ~ D ~ ~ D
wherein L is as defined above;
Me = CH3-;
m = an integer, generally less than 5, and preferably O or 1; and D = any of -CO-, -S02-, or -(CF3)2C-.
While bisphenol A is preferred (because of cost and avallablllty)~ the other dlalcohols can be used to add rlgldlty to the ollgomer wlthout slgnlflcantly lncreaslng the average formula welght, and, therefore, can lncrease the solvent reslstance. Random or block copolymers are posslble.
Furthermore, the dlalcohols may be selected from the dlhydrlc phenol lmlde sulfone reslns descrlbed ln Unlted States Patent 4,584,364, or those dlhydrlc phenols descrlbed ln Unlted States Patents 3,262,914 or 4,611,048. In fact, the hydroxy-termlnated etherlmldes of U.S. Patent 4,611,048 can be reacted wlth A-NO2 to provlde crossllnklng etherlmldes of the present lnventlon.
Dlalcohols of thls nature are commerclally avallable.
Some may be easlly syntheslzed by reactlng hallde lntermedlates wlth bls-phenates, such as by the reactlon of 4,4'-chlorophenyl-sulfone wlth bls(dlsodlum blphenolate).
The ollgomers can be syntheslzed ln a homogeneous reaction scheme whereln all the reactants are mlxed at one tlme (and thls scheme ls preferred), or ln a stepwlse reactlon. The dlamlne and dlalcohols can be mlxed, for example, followed by addltlon of the nltrophthallc anhydrlde to lnltlate the poly-merlzatlon and thereafter the end caps to quench lt. Those skilled in the art will recognize the varlant methods that mlght be used. To the extent posslble, undeslrable competltlve reactlons should be mlnimized by controlling the reactlon steps (l.e., addltlon of reactants) and the reactlon condltlons.
'~.
20a 13 3 5 89 3 66239-1364 Instead of Schiff base linkages in the dialcohols, these compounds might include oxazole, thlazole, or lmldazole llnkages. All of these llnkages present the potentlal for creatlng conductlve or semlconductlve composltes, lf sultably doped.
.
Dopants for creating semiconductive or conductive composites are preferably selected from compounds commonly used to dope other polymers, namely (l) dispersions of alkali metals (for high activity) or (2) strong chemical oxidizers, particularly alkali perchlorates (for lower activity). Arsenic compounds and elemental halogens, while active dopants, are too dangerous for general usage, and are not recommended.
The dopants react with the polymers to form charge transfer complexes. N-type semiconductors result from doping with alkali metal dispersions. P-type semiconductive result from doping with elemental iodine or perchlorates.
While research into conductive or semiconductive polymers has been intense, the resulting compounds (mainly polyacetylenes, polyphenelenes, and polyvinylacetylenes) are unsatisfactory for aerospace applications because the polymers are:
(a) unstable in air;
(b) unstable at high temperatures;
(c) brittle after doping;
(d) toxic because of the dopants; or (e) intractable.
These problems may be overcome or significantly reduced with the conductive oligomers of the present invention.
While conventional theory holds that semiconductive polymers should have (l) low ionization potentials, (2) long conjugation lengths, and (3) planar backbones, there is an inherent trade-off between conductivity and toughness or processibility, if these constraints are followed. To overcome the processing and toughness shortcomings common with Schiff base, oxazole, imidazole, or thiazole oligomers, the oligomers of the present invention, include "sulfone" linkages interspersed along the backbone providing a mechanical swivel for the rigid, conductive segments of the arms.
Since it is difficult to include the oxazole, imidazole, or thiazole linkages in the reactants, Schiff base compounds are preferred. The principle focus of the invention is toward improved etherimide, thioetherimides, or sulfoneimides, and the conductive or semiconductive composites are not the preferred compounds of the present invention. They are but a small subset of the compounds that comprise the present invention.
Solubility of the oligomers becomes an increasing problem as the length of the backbones increases. Therefore, shorter backbones are preferred, so long as the resulting oligomers remain processible.
That is, the backbones should be long enough to keep the oligomers soluble to the reaction sequence.
Blends of the crosslinkable oligomers and noncrosslinking, compatible polymers can also be made.
These blends generally comprise substantially equimolar mixtures of the oligomer and polymer. The polymer should have a backbone substantially identical with the oligomer, and may be made in accordance with a process described in U.S. Patent 4,297,474 or 3,847,869.
Impact resistance of the cured composites formed from prepregs of the oligomers can be increased without deleterious loss of solvent resistance by forming the prepregs with such a blend. Generally, the blend includes capped oligomers to provide crosslinking upon curing and noncrosslinking polymers of a corresponding backbone to provide compatibility of the oligomer and polymer. A 50-50 blend on a molar basis of oligomers and polymer may be formed by (a) dissolving the capped oligomer in a suitable first solvent, (b) dissolving the capped polymer in a separate portion of the same solvent or in a solvent miscible with the first solvent, (c) 23 133~893 mixing the two solvent solutions to form a lacquer, and (d) applying the lacquer to fabric in a conventional prepregging process.
Although the polymer in the blend usually has the same backbone (structure and formula weight) as the oligomer, the properties of the composite formed from the blend can be adjusted by altering the ratio of formula weight for the polymer and oligomer.
The terminal groups of the polymer are unimportant so long as the polymer's terminal groups do not react with or impede the crosslinking of the oligomer end caps. Also, it is probably nonessential that the oligomer and polymer have identical repeating units (structure), but that the oligomer and polymer merely be compatible in the solution prior to sweeping out as a prepreg. Of course, if the polymer and oligomer have identical backbones, compatibility in the blend is more likely.
The noncrosslinking polymer can be made by the same synthetic method as the oligomer with the substitution of a quenching cap for the crosslinking end cap. For example, phenol can replace end caps of the formula A-OH; benzamine can replace end caps of the formula A-NH2; and, nitrobenzene can replace end caps of the formula A-NO2.
While the best blends are probably those in which the backbones are essentially identical and of modest formula weight and those in which the oligomer and polymer are in equimolar proportions, other variant blends may be prepared, as will be recognized by those of ordinary skills in the art.
Anhydrides of the formula:
1l A X R ~ > O
lcl wherein X = -O- or -S-;
R = a trivalent C(6-13) aromatic organic radical;
A = (Z
n = 1 or 2;
Z = 1 ~ ~\N (Rl)j ~C\N--( R ~ ~ ( R ~
O Me O
(Rl)j~ N--R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = O, 1, or 2; and G = -CH2-, -O-, -S-, or -S02-, are useful in the synthesis of the etherimides of the present invention, and are prepared by the condensation of the corresponding end cap phenol or thiol (-XH) with a nitro- or halo- anhydride that contains the R moiety.
In at least one synthesis of the etherimides of the present invention, a compound of the formula:
~\
A - N < ~ R - Y
~. ~
is an intermediate or reactant, wherein:
R = a trivalent C(6-13) aromatic organic radical' A = Zn n = l or 2;
(R~ /\N - , (R~ \ N - , ~1 0 ~? ~[~
HC_~b/ E
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
This intermediate if formed by reacting A-NH2 with a substituted phthalic anhydride of the formula:
o wherein Y = halo- or nitro-. These substituted anhydrides are described in United States Patents 4,297,474 and 3,847,869.
Polysulfoneimide oligomers can be prepared by reacting about m+1 moles of a dianhydride with about m moles of a diamine and about 2 moles of an amine end cap (A-NH2). The resulting oligomer has the general formula:
A--~1~C~S02 R--SO~z ~ NR' A
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms. R and R' may include halogenated aromatic C(6-20) hydrocarbon derivatives;
alkylene radicals and cycloakylene radicals having from 2-20 carbon atoms; C(2-8) alkylene terminated - polydiorganosiloxanes; and radicals of the formula:
~q~
wherein q = -CyH2y~l -CO-, -SO2-, -O-, or -S-; and y = 1 to 5.
Comparable polymers, usable in blends of the sulfoneimides, are described in United States Patent 4,107,147. - Other aromatic dithio dianhydrides are described in United S~ates Patent 3,933,862.
~ he oligomers of the present invention can be combined with reinforcing materials, such as fibers, chopped fibers, whiskers, or fabrics, and cured to composite materials using heat or chemicals to activate crosslinking between end caps. Prepregs can be prepared by conventional prepregging technigues. Curing generally is conducted in conventional vacuum bagging te~hn~ques at elevated temperatures. The curing temperature varies with the choice of end cap. If desired, mixtures of end caps might be used.
While ~- isomerism has generally been described, other isomers may be used. The phenyl or aryl moieties in the backbones can also include substituents so long as the substituents do not interfere with the crosslinking or synthesis. While polyaryl compounds are described, aliphatic moieties can be included in the backbones, in some cases, although the ultimate use temperatures of these oligomers or composites may bè lower than with entirely polyaryl backbones.
While preferred embodiments have been described, those skilled in the art will readily recognize alterations, variations or modifications which might be made to the embodiments without departing from the inventive concept. Therefore, the claims should be interpreted liberally with the support of the full range of equivalents known to those or ordinary skill based upon this description. The claims should be limited only as is necessary in view of the pertinent prior art.
Claims (20)
1. Polyetherimide oligomers, comprising the product of the process of reacting:
(I);
(II);
(III); and H2N-R'XH (IV) in about the stoichiometric ratio of I:II:III:IV =
1:1:m:m, wherein m is an integer greater than or equal to one, the reaction product having the general formula:
wherein X = -O- or -S-;
A = n = 1 or 2;
Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R = a trivalent C(6-13) aromatic organic radical;
R1 - any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j - 0, 1, or 2,; and G = -CH2-, -O-, -S-, or -SO2-.
(I);
(II);
(III); and H2N-R'XH (IV) in about the stoichiometric ratio of I:II:III:IV =
1:1:m:m, wherein m is an integer greater than or equal to one, the reaction product having the general formula:
wherein X = -O- or -S-;
A = n = 1 or 2;
Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R = a trivalent C(6-13) aromatic organic radical;
R1 - any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j - 0, 1, or 2,; and G = -CH2-, -O-, -S-, or -SO2-.
2. A blend of polyetherimide oligomers and polyetherimide polymers, comprising substantially equimolar amounts of an oligomer of claim 1 and a polymer having a compatible backbone absent the crosslinking end cap radicals (A) of the oligomer, the polymer including repeating units of the formula:
wherein X, R, and R' are as defined in claim 1.
wherein X, R, and R' are as defined in claim 1.
3. A prepreg comprising a suitable reinforcement and the oligomer of claim 1.
4. A prepreg comprising a suitable reinforcement and the blend of claim 2.
5. A cured composite formed by curing the prepreg of claim 3.
6. A cured composite formed by curing the prepreg of claim 4.
7. A cured composite formed by curing the oligomer of claim 1.
8. A cured composite formed by curing the blend of claim 2.
9. A method of synthesizing a polyetherimide oligomer, comprising the step of reacting:
(I);
(II);
(III); and H2NR'XH (IV) in about the ratio of about I:II:III:IV = 1:1:m:m, wherein m is an integer greater than or equal to one, the reaction product having the general formula:
wherein R = a trivalent C(6-13) aromatic organic radical;
X = -O- or -S-;
A = ;
n = 1 or 2;
Z =
' , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R1 = any of lower alkyl, lower alkoxy, aryl,.or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the reaction occurring in a suitable solvent under an inert atmosphere.
(I);
(II);
(III); and H2NR'XH (IV) in about the ratio of about I:II:III:IV = 1:1:m:m, wherein m is an integer greater than or equal to one, the reaction product having the general formula:
wherein R = a trivalent C(6-13) aromatic organic radical;
X = -O- or -S-;
A = ;
n = 1 or 2;
Z =
' , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R1 = any of lower alkyl, lower alkoxy, aryl,.or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the reaction occurring in a suitable solvent under an inert atmosphere.
10. An anhydride of the formula:
wherein X = -O- or -S-;
R = a trivalent C(6-13) aromatic organic radical;
A = ;
n = 1 or 2;
z = , , , , , or ;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the anhydride being formed by reacting A-XH with a substituted phthalic anhydride of the formula:
wherein Y = halo- or nitro-.
wherein X = -O- or -S-;
R = a trivalent C(6-13) aromatic organic radical;
A = ;
n = 1 or 2;
z = , , , , , or ;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the anhydride being formed by reacting A-XH with a substituted phthalic anhydride of the formula:
wherein Y = halo- or nitro-.
11. A compound of the formula:
wherein R = a trivalent C(6-13) aromatic organic radical;
A = ;
n = 1 or 2;
, , , , , or ;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the compound being formed by reacting A-NH2 with a substituted phthalic anhydride of the formula:
wherein Y - halo- or nitro-.
wherein R = a trivalent C(6-13) aromatic organic radical;
A = ;
n = 1 or 2;
, , , , , or ;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-, the compound being formed by reacting A-NH2 with a substituted phthalic anhydride of the formula:
wherein Y - halo- or nitro-.
12. Polyetherimide oligomers of the general formula:
wherein X = -O- or -S-;
A = ;
n = 1 or 2;
Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-;
R2 = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
wherein X = -O- or -S-;
A = ;
n = 1 or 2;
Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-;
R2 = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
13. Polyetherimide oligomers prepared by the process of reacting a polyetherimide polymer made by the self-condensation of a phthalimide salt of the formula:
with crosslinking end cap moieties of the formulae:
and wherein X = -O- or -S-;
A = ;
n = 1 or 2 Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2;
G = -CH2-, -O-, -S-, or -SO2-; and M = an alkali metal ion, ammonium salt, or hydrogen.
with crosslinking end cap moieties of the formulae:
and wherein X = -O- or -S-;
A = ;
n = 1 or 2 Z =
, , , , , or ;
E = allyl or methallyl;
Y = halo- or nitro-R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
R' = a divalent C(6-30) aromatic organic radical;
j = 0, 1, or 2;
G = -CH2-, -O-, -S-, or -SO2-; and M = an alkali metal ion, ammonium salt, or hydrogen.
14. A method of making polyetherimide oligomers comprising the step of:
condensing a mixture of about 2m + 2 moles of nitrophthalic anhydride of the formula:
with about m + 1 moles of diamine, about m moles of dialcohol, and about 2 moles of A-OH, wherein A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , , , or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
condensing a mixture of about 2m + 2 moles of nitrophthalic anhydride of the formula:
with about m + 1 moles of diamine, about m moles of dialcohol, and about 2 moles of A-OH, wherein A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R = a trivalent C(6-13) aromatic organic radical;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , , , or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
15. The polyetherimide oligomer that is the product of the process of claim 14.
16. A method for making polyetherimide oligomers comprising the step of:
condensing about 2 m + 2 moles of nitrophthalic anhydride with about m+1 moles of dialcohol, about m moles of diamine, and about 2 moles of A-NH2, wherein:
A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , ;
, or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
condensing about 2 m + 2 moles of nitrophthalic anhydride with about m+1 moles of dialcohol, about m moles of diamine, and about 2 moles of A-NH2, wherein:
A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , ;
, or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
17. The polyetherimide oligomer that is the product of the process of claim 16.
18. A method for making polyetherimide oligomers comprising the steps of:
condensing about 2m moles of nitrophthalic anhydride with about m+1 moles of dialcohol, about m moles of diamine, and about 2 moles of A-NO2, wherein:
A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , , , or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
condensing about 2m moles of nitrophthalic anhydride with about m+1 moles of dialcohol, about m moles of diamine, and about 2 moles of A-NO2, wherein:
A = ;
n = 1 or 2;
m = an integer greater than or equal to 1;
E = allyl or methallyl;
R1 = any of lower alkyl, lower alkoxy, aryl, or substituted aryl;
Z =
, , , , , or ;
j = 0, 1, or 2; and G = -CH2-, -O-, -S-, or -SO2-.
19. The polyetherimide oligomers that is the product of the process of claim 18.
20. The polysulfoneimide oligomers comprising the product of the process of reacting:
m+1 moles of a dianhydride;
m moles of a diamine; and 2 moles of an amine end cap, the oligomer having the general formula:
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms, these radicals including halogenated aromatic C(6-20) hydrocarbon derivatives; alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms; C(2-8) alkylene terminated polydiorganosiloxanes; and radicals of the formula:
wherein q = -CyH2y-, -CO-, -SO2, -O-, or -S-; and y = 1 to 5.
m+1 moles of a dianhydride;
m moles of a diamine; and 2 moles of an amine end cap, the oligomer having the general formula:
wherein R and R' are divalent aromatic organic radicals having from 2-20 carbon atoms, these radicals including halogenated aromatic C(6-20) hydrocarbon derivatives; alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms; C(2-8) alkylene terminated polydiorganosiloxanes; and radicals of the formula:
wherein q = -CyH2y-, -CO-, -SO2, -O-, or -S-; and y = 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US016,703 | 1987-02-20 | ||
| US07/016,703 US4851495A (en) | 1987-02-20 | 1987-02-20 | Polyetherimide oligomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335893C true CA1335893C (en) | 1995-06-13 |
Family
ID=21778499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 555820 Expired - Fee Related CA1335893C (en) | 1987-02-20 | 1988-01-05 | Polyetherimide oligomers and blends |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US4851495A (en) |
| EP (1) | EP0283636A3 (en) |
| JP (1) | JPS63264569A (en) |
| KR (1) | KR880010021A (en) |
| CA (1) | CA1335893C (en) |
| IL (1) | IL85016A (en) |
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| US5645925A (en) * | 1988-03-14 | 1997-07-08 | Boeing Company | Advanced composite blends |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5367083A (en) * | 1987-09-03 | 1994-11-22 | The Boeing Company | Extended acid halide capping monomers |
| US5516876A (en) * | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5344894A (en) * | 1983-09-27 | 1994-09-06 | The Boeing Company | Polyimide oligomers and blends |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5216117A (en) * | 1987-09-03 | 1993-06-01 | The Boeing Company | Amideimide blends |
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5521014A (en) | 1981-11-13 | 1996-05-28 | The Boeing Company | Extended multidimensional ether or ester oligomers |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5144000A (en) * | 1987-02-20 | 1992-09-01 | The Boeing Company | Method for forming crosslinking polyetherimide oligomers |
| US5109105A (en) * | 1987-06-12 | 1992-04-28 | The Boeing Company | Polyamide oligomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| US4996101A (en) * | 1988-08-08 | 1991-02-26 | Lockheed Corporation | Processible polyimide blends |
| JPH02152962A (en) * | 1988-12-06 | 1990-06-12 | Mitsubishi Gas Chem Co Inc | Diimidodicarboxylic acid |
| US5098961A (en) * | 1989-01-26 | 1992-03-24 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Semi-interpenetrating polymer network for tougher and more microcracking resistant high temperature polymers |
| EP0449117A3 (en) * | 1990-03-23 | 1992-05-06 | Matsushita Electric Industrial Co., Ltd. | Organic polymer and preparation and use thereof |
| US5114612A (en) * | 1990-04-04 | 1992-05-19 | The United States Of America As Represented By The Department Of Energy | Liquid crystal polyester thermosets |
| US5152863A (en) * | 1990-10-31 | 1992-10-06 | E. I. Du Pont De Nemours And Company | Reactive-oligoimide adhesives, laminates, and methods of making the laminates |
| US5096998A (en) * | 1990-10-31 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Reactive-oligoimide adhesives, laminates, and methods of making the laminates |
| CA2055919A1 (en) * | 1990-11-26 | 1992-05-27 | Philip Manos | Chemically etchable adhesives |
| US5272245A (en) * | 1990-11-26 | 1993-12-21 | E. I. Du Pont De Nemours And Company | Chemically etchable adhesives |
| US5084345A (en) * | 1990-11-26 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Laminates utilizing chemically etchable adhesives |
| US5243023A (en) * | 1991-08-28 | 1993-09-07 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyimides containing amide and perfluoroisopropylidene connecting groups |
| US5288835A (en) * | 1993-05-21 | 1994-02-22 | E. I. Du Pont De Nemours And Company | Melt processable polyesters and poly(imide-esters) |
| US9586699B1 (en) | 1999-08-16 | 2017-03-07 | Smart Drilling And Completion, Inc. | Methods and apparatus for monitoring and fixing holes in composite aircraft |
| JP2004509072A (en) * | 2000-06-28 | 2004-03-25 | ブリストル−マイヤーズ スクイブ カンパニー | Selective androgen receptor modulators and methods for their identification, design and use |
| US20040077605A1 (en) * | 2001-06-20 | 2004-04-22 | Salvati Mark E. | Fused heterocyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function |
| US7001911B2 (en) | 2000-06-28 | 2006-02-21 | Bristol-Myers Squibb Company | Fused cyclic modulators of nuclear hormone receptor function |
| US6939940B2 (en) | 2000-09-13 | 2005-09-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers |
| US6953679B2 (en) | 2000-09-19 | 2005-10-11 | Bristol-Myers Squibb Company | Method for the preparation of fused heterocyclic succinimide compounds and analogs thereof |
| EP1854798A3 (en) * | 2000-09-19 | 2007-11-28 | Bristol-Myers Squibb Company | Fused heterocyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function |
| KR100700749B1 (en) * | 2000-11-02 | 2007-03-27 | 한학수 | Imide oligomer, method for preparing the same and polyimide thin layer prepared from crosslinking reaction of the imide oligomer |
| US20040087548A1 (en) | 2001-02-27 | 2004-05-06 | Salvati Mark E. | Fused cyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function |
| US9625361B1 (en) | 2001-08-19 | 2017-04-18 | Smart Drilling And Completion, Inc. | Methods and apparatus to prevent failures of fiber-reinforced composite materials under compressive stresses caused by fluids and gases invading microfractures in the materials |
| ATE404544T1 (en) * | 2001-12-19 | 2008-08-15 | Bristol Myers Squibb Co | CONDENSED HETEROCYCLIC COMPOUNDS AND ANALOGUES THEREOF; MODULATORS OF THE FUNCTION OF NUCLEAR HORMONE RECEPTORS |
| KR100667967B1 (en) | 2005-04-06 | 2007-01-11 | 주식회사 잉크테크 | ?-Sulfone imides and preparation thereof |
| KR100782932B1 (en) | 2006-09-19 | 2007-12-07 | 삼성전기주식회사 | Method for making polyetherimide precursor |
| US20080300374A1 (en) * | 2007-05-31 | 2008-12-04 | The Boeing Company | Dinadic phenyl amine reactive endcaps |
| US8309663B2 (en) | 2007-05-31 | 2012-11-13 | The Boeing Company | Water-entrained-polyimide chemical compositions for use in high-performance composite fabrication |
| US7825211B2 (en) * | 2007-06-22 | 2010-11-02 | The Boeing Company | Single-step-processable polyimides |
| US8524854B2 (en) * | 2009-12-31 | 2013-09-03 | Sabic Innovative Plastics Ip B.V. | Chloro-substituted polyetherimides having improved relative thermal index |
| US8853342B2 (en) | 2012-09-24 | 2014-10-07 | Ticona Llc | Crosslinkable liquid crystalline polymer |
| US8822628B2 (en) | 2012-09-24 | 2014-09-02 | Ticona Llc | Crosslinkable liquid crystalline polymer |
| US9145519B2 (en) | 2012-09-24 | 2015-09-29 | Ticona Llc | Crosslinkable aromatic polyester |
| US10377860B2 (en) | 2013-09-13 | 2019-08-13 | Sabic Global Technologies B.V. | Polyetherimides, methods of manufacture, and articles formed therefrom |
| US9382382B2 (en) | 2013-09-13 | 2016-07-05 | Sabic Global Technologies B.V. | Polyetherimides, methods of manufacture, and articles formed therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3998786A (en) * | 1973-05-25 | 1976-12-21 | University Of Notre Dame Du Lac | Process for preparing aromatic polyimides, polyimides prepared thereby |
| US3847869A (en) * | 1973-09-28 | 1974-11-12 | Gen Electric | Method for preparing polyetherimides |
| US3933862A (en) * | 1974-08-23 | 1976-01-20 | General Electric Company | Aromatic dithio dianhydrides |
| FR2400014A1 (en) * | 1977-08-09 | 1979-03-09 | Rhone Poulenc Ind | PREPARATION OF OLIGOIMIDES |
| US4107147A (en) * | 1977-09-02 | 1978-08-15 | General Electric Company | Polysulfoneimides |
| US4302575A (en) * | 1979-12-26 | 1981-11-24 | General Electric Company | Heat curable polyimides |
| US4297474A (en) * | 1980-02-29 | 1981-10-27 | General Electric Company | Polyetherimides prepared by self-condensation of hydroxyaryl phthalimide salts |
| US4418181A (en) * | 1981-05-26 | 1983-11-29 | Plastics Engineering Company | Polyimides having bis-maleimide terminal groups |
| US4536559A (en) * | 1983-06-17 | 1985-08-20 | The Boeing Company | Thermally stable polyimide polysulfone compositions for composite structures |
| US4684714A (en) * | 1983-09-27 | 1987-08-04 | The Boeing Company | Method for making polyimide oligomers |
| US4604437A (en) * | 1984-01-31 | 1986-08-05 | Ciba-Geigy Corporation | Polymer from substituted, unsaturated, bicyclic imide |
| US4556705A (en) * | 1984-10-26 | 1985-12-03 | General Electric Company | Thermoplastic polyetherimide ester elastomers |
| US4611048A (en) * | 1985-10-04 | 1986-09-09 | General Electric Company | Hydroxy terminated polyetherimide oligomers |
-
1987
- 1987-02-20 US US07/016,703 patent/US4851495A/en not_active Expired - Fee Related
- 1987-12-31 KR KR870015790A patent/KR880010021A/en not_active Application Discontinuation
-
1988
- 1988-01-01 IL IL8501688A patent/IL85016A/en unknown
- 1988-01-05 JP JP63000594A patent/JPS63264569A/en active Pending
- 1988-01-05 EP EP19880100074 patent/EP0283636A3/en not_active Withdrawn
- 1988-01-05 CA CA 555820 patent/CA1335893C/en not_active Expired - Fee Related
- 1988-09-06 US US07/241,997 patent/US5530089A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4851495A (en) | 1989-07-25 |
| EP0283636A3 (en) | 1988-11-17 |
| JPS63264569A (en) | 1988-11-01 |
| US5530089A (en) | 1996-06-25 |
| KR880010021A (en) | 1988-10-06 |
| IL85016A0 (en) | 1988-06-30 |
| IL85016A (en) | 1992-09-06 |
| EP0283636A2 (en) | 1988-09-28 |
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