WO1997006200A1 - Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom - Google Patents
Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom Download PDFInfo
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- WO1997006200A1 WO1997006200A1 PCT/US1996/012453 US9612453W WO9706200A1 WO 1997006200 A1 WO1997006200 A1 WO 1997006200A1 US 9612453 W US9612453 W US 9612453W WO 9706200 A1 WO9706200 A1 WO 9706200A1
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- 0 CC(*)(CCC1C(N[Al]C)=O)CCC1C(O)=O Chemical compound CC(*)(CCC1C(N[Al]C)=O)CCC1C(O)=O 0.000 description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N C#Cc1ccccc1 Chemical compound C#Cc1ccccc1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- JFARFFOVGOTPSH-UHFFFAOYSA-N CC(C=C1Oc(cc(C)c(C)c2)c2OC1=C1)C1=C Chemical compound CC(C=C1Oc(cc(C)c(C)c2)c2OC1=C1)C1=C JFARFFOVGOTPSH-UHFFFAOYSA-N 0.000 description 1
- RACZTHZYCZONKM-UHFFFAOYSA-N CC(CC=O)C(CC(C1)[N+]([O-])=O)CC1[N+]([O-])=O Chemical compound CC(CC=O)C(CC(C1)[N+]([O-])=O)CC1[N+]([O-])=O RACZTHZYCZONKM-UHFFFAOYSA-N 0.000 description 1
- UOQRFXVMBIURAK-UHFFFAOYSA-N Cc1cc(Oc2cc(N(C(c(c3c4)ccc4C(c(cc4)cc(C(N5[IH]c6cccc(Oc(cc7)ccc7N(C(c(c7c8)ccc8C#Cc8ccccc8)=O)C7=O)c6)=O)c4C5=O)=O)OC)C3=O)ccc2)ccc1 Chemical compound Cc1cc(Oc2cc(N(C(c(c3c4)ccc4C(c(cc4)cc(C(N5[IH]c6cccc(Oc(cc7)ccc7N(C(c(c7c8)ccc8C#Cc8ccccc8)=O)C7=O)c6)=O)c4C5=O)=O)OC)C3=O)ccc2)ccc1 UOQRFXVMBIURAK-UHFFFAOYSA-N 0.000 description 1
- PMMIVUMGFKTIDV-UHFFFAOYSA-N [O-][N+](C(CC(C1)C(Br)=O)CC1N=O)=O Chemical compound [O-][N+](C(CC(C1)C(Br)=O)CC1N=O)=O PMMIVUMGFKTIDV-UHFFFAOYSA-N 0.000 description 1
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- 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
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/935—Hot melt adhesive
-
- 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]
-
- 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
Definitions
- Polyimides are heterocyclic polymers commonly prepared by the condensation reaction of an aromatic diamine with an aromatic dianhydride or derivative thereof and having a repeat unit of the general structure
- Ar is a tetravalent aromatic radical such as 1 ,2,4,5-tetrasubstituted benzene.
- Ar may also be a bis(o-diphenylene) having the general structure
- Ar' is a divalent aromatic radical which may be 1 ,3-phenylene, 1 ,4-phenyiene, 4,4'-biphenylene, 4,.4'-oxydiphenylene, 4,4'-sulfonyldiphenylene, or any other appropriate divalent radical.
- ethynyl and substituted ethynyl containing materials Good processability by either solution casting and/or compression molding have been observed for the ethynyl and substituted ethynyl containing materials.
- thermally cured ethynyl and substituted ethynyl containing materials exhibit a favorable combination of physical and mechanical properties.
- Some ethynyl endcapped materials such as the Thermid ® resins are commercially available (National Starch and Chemical Co., Bridgewater, NJ 08807).
- Phenylethynyl containing amines have been used to terminate imide oligomers [F.W. Harris, A. Pamidimuhkala, R. Gupta, S. Das, T. Wu, and G. Mock, Poly. Prep.. 24 (2), 325. 1983; F.W. Harris, A. Pamidimuhkala, R. Gupta, S. Das, T. Wu, and G. Mock, J. Macromol. Sci.-Chem.. A21 (8 & 9). 1117 (1984); C.W. Paul, R.A. Schultz, and S.P.
- This present invention constitutes new composition of matter. It concerns novel diamines containing phenylethynyl groups and new imide oligomers and co-oliogmers containing pendent phenylethynyl groups.
- the polymers and copolymers prepared from these materials exhibit a unique and
- Another object of the present invention is to provide materials that are useful as adhesives, coatings, films, moldings and composite matrices.
- Another object of the present invention is the composition of several new diamines containing pendent phenylethynyl groups.
- the foregoing and additional objects were obtained by synthesizing controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups and endcapped with phenylethynyl groups or nonreactive groups by different methods.
- PEPAAs pendent phenylethynyl groups
- PEPAAs were prepared by the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and endcapped with a 3-aminophenoxy-4'phenylethynylbenzophenone under a nitrogen atmosphere at room temperature in NMP.
- the imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPI) were prepared by cyclodehydration of the precursor PEPAA oligomers in NMP by azeotropic distillation with toluene.
- the direct preparation of PEPIs has been performed in m-cresol containing isoquinoline at elevated temperature.
- Amide acid oligomers and co-oligomers containing pendent phenylethynyl groups can be prepared by the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and endcapped with a
- Imide oligomers and co-oligomers containing pendent phenylethynyl groups can be prepared by the reaction of the half alkyl ester of aromatic tetracarboxylic acids with aromatic diamines and diamine containing pendent phenylethynyl group(s) and endcapped with the half alkyl ester of
- PEPIs prepared by the alkyl ester route can also be prepared by heating neat or in solvents such as m-cresol.
- Imide oligomers and co-oligomers containing pendent phenylethynyl groups can be prepared by the polymerization of monomeric reactants (PMR) approach by heating a mixture of a diamine and diamine containing pendent phenylethynyl group(s) and the ethyl ester derivatives of dianhydride(s) and endcapped with phenylethynylphthalic anhydride, monofunctional anhydride, phenylethynyl amine, or
- the amine terminated PEPAA oligomer or co-oligomer or the anhydride terminated PEPAA oligomer or co-oligomer can be
- the inherent viscosities ( ⁇ inh ) of the PEPAA oligomers and co-oligomers ranged from 0.21 to 0.65 dL/g and the ⁇ inh of high molecular weight
- unendcapped PEPAA was 0.85 dL/g.
- the glass transition temperatures (T g ) of the uncured as-isolated PEPIs ranged from 209-269°C. In some cases, a crystalline melt temperature was observed for the uncured PEPIs.
- the temperature of onset and peak exotherm due to reaction of the phenylethynyl group was ⁇ 350°C and ⁇ 411 °C, respectively. After curing at 350°C for 1 h in a sealed DSC pan the T g of the cured polymers ranged from 255-313°C.
- Thermogravimetric analysis (TGA) at a heating rate of 2.5°C/min of the uncured as-isolated PEPI powders showed no weight loss occurring below 300°C in air or nitrogen with a 5% weight loss occurring ⁇ 475°C in air and ⁇ 517°C in nitrogen.
- TGA at a heating rate of 2.5°C/min of the cured polymers showed no weight loss occurring below 300°C in air or nitrogen with a 5% weight loss occurring ⁇ 495°C in air and ⁇ 510°C in nitrogen.
- the tensile strength, tensile modulus, and break elongation for unoriented thin films ranged from 18.9-21.8 ksi, 457-600 ksi, and 4-20% at 23°C; and 10.1-14.0 ksi, 290-411 ksi, and 5-34% at 177°C; and 9.2-12.2 ksi, 267-372 ksi, and 6-30% at 200°C, respectively.
- the polymers prepared from these materials exhibit higher glass transition temperatures with no apparent reduction in melt flow behavior as compared to similar materials.
- compression molded samples of PEPIs ranged from 2.9 in lb/in 2 to 10.3 in lb/in 2 .
- the titanium (Ti) to Ti tensile shear properties performed on PASA Jell 107 surface treated adherends were 3900 at 23°C and 4100 at 177°C.
- the Ti to Ti tensile shear properties performed on chromic acid anodized (5V) surface treated adherends were 4300 at 23°C and 4100 at 177°C.
- the diamines containing pendent phenylethynyl group(s) were prepared by the palladium catalyzed reaction of phenylacetylene with bromo
- the polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing, higher tensile moduli and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204 °C when wet without sacrificing melt flow behavior and processability as compared to similar materials.
- FIG. 1 is a schematic of the synthesis of diamines containing pendent phenylethynyl groups according to the present invention
- FIG. 2 is a schematic of the synthesis of controlled molecular weight amide acid and imide co-oligomers containing pendent phenylethynyl groups chain terminated with nonreactive or reactive phthalic anhydride based encapping agents according to the present invention
- FIG. 3 is a schematic of the synthesis of controlled molecular weight amide acid and imide co-oligomers containing pendent phenylethynyl groups chain terminated with nonreactive or reactive aniline based encapping agents according to the present invention
- FIG. 4 is a schematic of the synthesis of controlled molecular weight amide acid and imide oligomers containing pendent phenylethynyl groups chain terminated with nonreactive or reactive phthalic anhydride based encapping agents according to the present invention
- FIG. 5 is a schematic of the synthesis controlled molecular weight amide acid and imide oligomers containing pendent phenylethynyl groups chain terminated with nonreactive or reactive aniline based encapping agents according to the present invention.
- FIG. 6 is the reaction sequence for preparation of uncontrolled molecular weight polyimide containing pendent phenylethynyl groups where R is a 4-benzoyl group and Ar is 3,3'4,4'-diphenylether.
- Novel diamines containing pendent phenylethynyl groups were prepared according to FIG. 1 having the following chemical structure:
- R is a radical selected from the group consisting of:
- Controlled molecular weight amide acid and imide co-oligomers containing pendent phenylethynyl groups and chain terminated with either nonreactive or reactive phthalic anhydride based endcapping agents were prepared according to FIG. 2.
- the chemical structures of these oligomers are indicated below:
- Ar is a member selected from the group consisting of:
- Y is a bond or Y is a radical selected from the group consisting of: O, CO, SO 2 , C(CF 3 ) 2 , isophthalpyl, terephthaloyl, 1 ,3-diphenoxy and 1 ,4-diphenoxy.
- Ar' is a member selected from the group consisting of:
- catenation is selected from the group consisting of 2,2'; 2,3'; 2,4'; 3,3'; 3,4'; and 4,4' and X is a bond or X is a radical selected from the group consisting of:
- W is a radical selected from the group consisting of: H, ,
- R is a radical selected from the group consisting of: ,
- Controlled molecular weight amide acid and imide co-oligomers containing pendent phenylethynyl groups and chain terminated with either nonreactive or reactive aniline based endcapping agents were prepared according to FIG. 3. The chemical structures of these oligomers are indicated below:
- Ar is a member selected from the group consisting of:
- Y is a bond or Y is a radical selected from the group consisting of:
- Ar' is a member selected from the group consisting of:
- catenation is selected from the group consisting of 2,2'; 2,3'; 2,4'; 3,3'; 3,4'; and 4,4' and X is a bond or X is a radical selected from the group consisting of:
- Z is a radical selected from the group consisting of: H,
- R is a radical selected from the group consisting of:
- Controlled molecular weight amide acid and imide oligomers containing pendent phenylethynyl groups and chain terminated with either nonreactive or reactive phthalic anhydride based endcapping agents were prepared according to FIG. 4.
- the chemical structures of these oligomers are indicated below: ,
- Ar is a member selected from the group consisting of: ,
- Y is a bond or Y is a radical selected from the group consisting of: O, CO, SO 2 , C(CF 3 ) 2 , isophthalpyl, terephthaloyl, 1 ,3-diphenoxy and 1 ,4-diphenoxy.
- W is a radical selected from the group consisting of: H, ,
- Controlled molecular weight amide acid and imide oligomers containing pendent phenylethynyl groups and chain terminated with either nonreactive or reactive aniline based endcapping agents were prepared according to FIG. 5.
- the chemical structures of these oligomers are indicated below:
- Ar is a member selected from the group consisting of:
- Y is a bond or Y is a radical selected from the group consisting of: O, CO, SO 2 , C(CF 3 ) 2 , isophthalpyl, terephthaloyl, 1 ,3-diphenoxy and 1 ,4-diphenoxy.
- Ar' is a member selected from the group consisting of:
- Z is a radical selected from the group consisting of: H,
- R is a radical selected from the group consisting of:, ,
- Ar is a member selected from the group consisting of:
- Y is a bond or Y is a radical selected from the group consisting of: O, CO, SO 2 , C(CF 3 ) 2 , isophthalpyl, terephthaloyl, 1 ,3-diphenoxy and 1 ,4- diphenoxy.
- R is a radical selected from the group consisting of: ,
- the following example illustrates the reaction sequence in FIG. 1 for the preparation of the diamine, 3,5-diamino-4'-phenylethynylbenzophenone.
- a yellow tacky solid separated from solution and was recovered by vacuum filtration.
- the tacky solid was washed with methanol, recovered by vacuum filtration and dried at 100°C for 2 h in flowing air to afford 107.60 g (71 %) of a yellow solid.
- Example 1 1.0 3,5-Diamino-4'-phenylethynylbenzophenone and 1.0 4,4'-Oxydiphthalic Anhydride with no Endcapping Agent
- the inherent viscosity of the poly(amide acid) solution (0.5% in DMAc at 25°C) was 0.85 dL/g. Approximately 7 g of poly(amide acid) solution was used to cast an unoriented thin film. Toluene (30 mL) was added to the remaining poly(amide acid) solution and the temperature increased and maintained at ⁇ 150°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the polymer precipitated. The polyimide powder was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a tan powder (2.3 g, 43% yield).
- the T g of the uncured as-isolated polymer (DSC, 20°C/min) was 273°C and the exothermic onset and peak occurred at 340°C and 419°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was not detectable by DSC.
- Unoriented thin film cast from the DMAc solution of the poly(amide acid) and cured at 100, 225, and 350°C for 1 h each in flowing air did not exhibit a T g by DSC.
- the Tg by thermomechanical analysis (TMA) at a heating rate of 5°C/min was 300°C. Polymer characterization is presented in Table 1.
- Example 2 0.85:0.15 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 0.9093 3,3',4,4'-Biphenyltetracarboxylic
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar' is 3,4'-diphenylether and R is a 4-benzoyl group and Ar is 3,3'4,4'-biphenyl and W is a hydrogen atom.
- the ratio of diamines [Ar':R] is 0.85:015.
- the stoichiometric imbalance is 9.07 mole % and the endcapping reagent is 18.14 mole % of phthalic anhydride.
- the oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a brown powder (6.9 g, 66% yield).
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 240°C with a very slight T m at 325°C and the exothermic onset and peak occurred at 340°C and 423°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was not detected by DSC.
- Unoriented thin films cast from a NMP solution of the amide acid oligomer cured at 100, 225, and 350°C for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation at 23°C of 21.8 ksi, 600 ksi, and 4% and at 177°C of 14.0 ksi, 411 ksi, and 5% and at 200°C of 12 ksi, 372 ksi, and 6%, respectively.
- the T g of the cured film was 279°C.
- Example 3 0.85:0.15 3, 4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 0.976 3, 3' 4, 4'-Biphenyltetracarboxylic Dianhydride, using 2.4 mole % Stoichiometric offset and 4.8 mole % Phthalic
- NMP (10.0 mL) was used to wash in the solid to afford a 30.0% (w/w) solution.
- the reaction was stirred at room temperature for 24 h under nitrogen.
- the inherent viscosity of the amide acid oligomeric solution (0.5% in NMP at 25°C) was 0.645 dL/g.
- Approximately 7.1 g of amide acid oligomeric solution was used to cast an unoriented thin film.
- the reaction vessel was fitted with a moisture trap and toluene (40 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the oligomer began to precipitate.
- the oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a brown powder (6.0 g, 75% yield).
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 265°C and the exothermic onset and peak occurred at 340°C and 423°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 297°C by DSC.
- Example 4 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 0.9093 3,3',4,4'-Biphenyltetracarboxylic Dianhydride,
- the oligomer began to precipitate.
- the oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a yellow powder (8.91 g, 70% yield).
- the inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.28 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 217°C with a T m at 276°C.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 255°C with a T m at 367°C.
- the T g of the cured film was 259°C with a T m at 367°C.
- Polymer characterization is presented in Table 1 .
- Example 5 0.70:0.30 3,4'-Oxydianiline and 3.5-Diamino-4'-phenylethynylbenzophenone, and 0.9093 3,3', 4,4'-Biphenyltetracarboxylic
- the reaction vessel was fitted with a moisture trap and toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the oligomer began to precipitate. The oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a brown powder (8.93 g, 71 % yield). The inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.22 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 230°C with T m s at 272 and 286°C
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 293°C
- Unoriented thin films cast from a NMP solution of the amide acid oligomer cured at 100, 225, and 350°C for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation at 23°C of 23.5 ksi, 563 ksi, and 8%; at 177°C of 12.7 ksi, 370 ksi, and 6% and at 200°C of 12.2 ksi, 370 ksi, and 9%, respectively.
- T g of the cured film was 289°C Polymer characterization is presented in Table 1 and thin film mechanical properties are presented in Table 2.
- Example 6 0.85:0.1 5 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 3, 3', 4, 4'-Biphenyltetracarboxylic Dianydride, using 9.07 mole % Stoichiometric offset and 18.14 mole % 3-Aminophenoxy-4'phenylethynylbenzophenone
- the following example illustrates the reaction sequence in FIG. 3 for the preparation of the controlled molecular weight PEPI
- Ar is 3,4'diphenylether and R is a 4-benzoyl group and Ar is 3, 3', 4, 4'-biphenyl and Z is a phenoxy-4'-phenylethynylbenzophenone group located in the 3 position.
- the ratio of diamines [Ar': R] is 0.85:0.1 5.
- the stoichiometric imbalance is 9.07 mole % and the endcapping reagent is 18.14 mole% of 3-aminophenoxy-4'phenylethynylbenzophenone.
- Example 7 0.75:0.15:0.10 3,4'-Oxydianiline, 1 ,3-bis(3- aminophenoxy)benzene
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar'(1 ) is 3,4'-diphenylether and Ar'(2) is 1 ,3-phenoxyphenyl and R is a 4-benzoyl group and Ar is 3, 3', 4, 4'-biphenyl and W is a phenylethynyl group located in the 4 position.
- the ration of diamines [Ar' (1 ): Ar' (2): R] is 0.75.0.1 5:0.10.
- the stoichiometric imbalance is 9.22 mole % and the endcapping reagent is 18.44 mole% of 4-phenylethynylphthalic anhydride.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 286°C Unoriented thin films cast from a m-cresol solution of the amide acid oligomer cured at 100, 225, and 350°C for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation at 23°C of 18.9 ksi, 495 ksi, and 12 %; at 177°C of 10.8 ksi, 301 ksi, and 34 %; and at 200°C of 9.2 ksi, 276 ksi, and 25 %, respectively.
- the T g of the cured film was 290 °C A sample
- Example 8 0.85:0.15 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 3,3',4,4'-Biphenyltetracarboxylic Dianhydride, Using 9.07 mole % Stoichiometric offset and
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar' is 3,4'-diphenylether and R is a 4-benzoyl group and Ar is 3, 3', 4,4'-biphenyl and W is a phenylethynyl group located in the 4 position.
- the ratio of diamines [Ar' :R] is 0.85:0.15.
- the stoichiometric imbalance is 9.07 mole % and the endcapping reagent is 18.14 mole % of 4-phenylethynylphthalic anhydride.
- amide acid oligomeric solution Approximately 10 g was used to cast an unoriented thin film. Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, a precipitate formed. The mixture was cooled, the oligomer was washed in hot water, warm methanol, and dried under vacuum at 220°C for 1.5 h to provide a tan powder (7.94 g, 74% yield).
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 226°C with a T m at 283°C and the exothermic onset and peak occurred at 348°C and 406°C, respectively.
- the inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.28 dL/g.
- the T g of the cured polymer (cure conditions: 350° C/1 h/sealed pan) was 313°C.
- Example 9 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 3,3',4,4'-Biphenyltetracarboxylic Dianhydride, Using 8.97 mole % Stoichiometric offset and
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar is 3,4'-diphenylether and R is a 4-benzoyl group and Ar is 3, 3', 4,4'-biphenyl and W is a phenylethynyl group located in the 4 position.
- the ratio of diamines [Ar' (1 ):Ar' (2)] is 0.90:0.10.
- the stoichiometric imbalance is 8.97 mole % and the endcapping reagent is 17.94 mole % of 4-phenylethynylphthalic anhydride.
- Toluene 60 mL was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, a precipitate formed. The mixture was cooled, the oligomer was washed in hot water, warm methanol, and dried under vacuum at 220°C for 1 .5 h to provide a tan powder (7.00 g, 66% yield). The inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.41 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 223°C with a T m at 274°C and the exothermic onset and peak occurred at 350°C and 412°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 310°C.
- NMP solution of the amide acid oligomer cured at 100, 225, and 350c for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation as 23 °C of 20.5 kst, 495 ksi, and 20%; at 1 17°C of 12.1 ksi, 296 ksi, and 27% and at 200°C of 10.7 ksi, 299 ksi, and 30%, respectively.
- the T g of the cured film was 306°C Polymer characterization is presented in Table 1 and thin film mechanical properties are presented in Table 2.
- Example 10 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'phenylethynylbenzophenone, and 3,3'4,4'-Benzophenonetetracarboxylic
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI where Ar 1 is 3,3',4,4'-benzophenone and W is a phenylethynyl group located in the 4 position.
- the ratio of diamines [Ar 1 : R] is 0.90:0.10.
- the stoichiometric imbalance is 9.48 mole % and the endcapping reagent is 18.96 mole % of 4 phenylethynylphthalic anhydride.
- amide acid oligomeric solution Approximately 10.5 g of amide acid oligomeric solution was used to cast an unoriented thin film. Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, a precipitate formed. The mixture was cooled, the oligomer was washed in hot water, warm methanol, and dried under vacuum at 220°C for 1.5 h to provide a tan powder (7.43 g, 66% yield).
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 269°C and the exothermic onset and peak occurred at 352°C and 399°C, respectively.
- the T g of the cured polymer (cure conditions: 350° C/1 h/sealed pan) was 296° C.
- An unoriented thin films cast from a NMP solution of the amide acid oligomer cured at 100, 225, and 350° C for 1 h each in flowing air was brittle and broke on the plate.
- the T g of the cured film was 296°C Polymer characterization is presented in Table 1.
- Example 1 1 : 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and Pyromellitic Dianhydride, Using 7.57 mole % Stoichiometric offset and 15.14 mole % 4-Phenylethynylphthalic Anhydride
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar' is 3,4'-diphenylether and R is a 4-benzoyl group and Ar is 1 ,2,4,5-tetrasubstituted benzene
- W is a phenylethynyl group located in the 4 position.
- the ration of diamines [Ar':R] is 0.90:0.10.
- the stoichiometric imbalance is 9.48 mole % and the endcapping reagent is 18.96 mole % of 4-phenylethynylphthalic anhydride.
- Example 12 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 4,4'-Oxydiphthalic Dianhydride,
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar' is 3,4'-diphenylether and R is a 4-benzoyl group and Ar is 3, 3', 4,4'- diphenylether and W is a phenylethynyl group located in the 4 position.
- the ratio of diamines [Ar': R] is 0.90:0.10.
- the stoichiometric imbalance is 9.3 mole % and the endcapping reagent is 18.6 mole % of 4-phenylethynylphthalic anhydride.
- the oligomer began to precipitate.
- the oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a brown powder
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was ⁇ 240°C by DSC and the exothermic onset and peak occurred at 340°C and 423°C, respectively.
- the T g of the cured polymer (cure conditions: 350° C/1 h/sealed pan) was 260°C by DSC. Polymer characterization is presented in
- Example 1 3: 0.70:0.15:0.1 5 3,4'-Oxydianiline, 1 ,3-bis(3-aminophenoxy)benzene and 3,5-Diamino-4'-phenylethynylbenzophenone, and 3, 3', 4,4'- Biphenyltetracarboxylic Dianhydride Using 9.33 mole % Stoichiometric offset and
- the following example illustrates the reaction sequence in FIG. 2 for the preparation of the controlled molecular weight PEPI
- Ar'(1 ) is 3,4'-diphenylether and Ar'(2) is 1 ,3-diphenoxyphenyl and R is a 4-benzoyl group and Ar is 3,3',4,4'-biphenyl and W is a phenylethynyl group located in the 4 position.
- the ration of diamines [Ar'( 1 ): Ar'(2):R] is 0.70:0.1 5:0.1 5.
- the stoichiometric imbalance is 9.33 mole % and the endcapping reagent is 18.66 mole % of 4-phenylethynylphthalic anhydride.
- amide acid oligomeric solution Approximately 12.6 g of amide acid oligomeric solution was used to cast an unoriented thin film. Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the oligomer precipitated in solution. The oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 2 h to provide a brown powder (8.07 g, 66% yield). The inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.32 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 224°C with a T m at 284°C and the exothermic onset and peak occurred at 363°C and 416°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 289°C Unoriented thin films cast from a NMP solution of the amide acid oligomer cured at 100, 225, and 350°C for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation at 23°C of 20.4 ksi, 492 ksi, and 15 %; at 177°C of 11.2 ksi, 307 ksi, and 24 % and at 200°C of 9.9 ksi, 285 ksi, and 28 %, respectively.
- the T g of the cured film was 301 °C.
- Example 14 0.90:0.10 3,4'-Oxydianiline and 3,5-Diamino-4'-phenylethynylbenzophenone, and 0.85:0.1 5 3,3',4,4'-Benzophenonetetracarboxylic Dianhydride and 4,4'-Benzophenonetetracarboxylic
- endcapping reagent is 18.04 mole % of 4-phenylethynylphthalic anhydride
- the inherent viscosity of the amide acid oligomeric solution (0.5% in NMP at 25°C) was 0.35 dL/g. Approximately 10.6 g of amide acid oligomeric solution was used to cast an unoriented thin film. Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the oligomer remained in solution. As the mixture was cooled, a precipitate formed. The oligomer was washed in hot water, warm methanol, and dried under vacuum at 220°C for 1.5 h to provide a brown powder (9.47 g, 76% yield).
- the inherent viscosity of the imide oligomer (0.5% in m- cresol at 25°C) was 0.26 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was not detected with T m s at 243 and 262°C and the exothermic onset and peak occurred at 320° C and 391°C , respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 310°C.
- the T g of the cured film was 294°C.
- Polymer characterization is presented in Table 1 and thin film mechanical properties are presented in Table 2.
- Example 1 5: 0.90:0.10 3,4'-Oxydianiline and 3,5 Diamino-4'-phenylethynylbenzophenone, and 0.70:0.30 3, 3', 4,4'- Benzophenonetetracarboxylic Dianhydride and 4,4'-Oxydiphthalic Anhydride, Using
- the inherent viscosity of the amide acid oligomeric solution (0.5% in NMP at 25°C) was 0.33 dL/g. Approximately 10.9 g of amide acid oligomeric solution was used to cast an unoriented thin film. Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, the oligomer remained in solution. As the mixture was cooled, a precipitate formed. The oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a brown powder (7.98 g, 63% yield).
- the inherent viscosity of the imide oligomer (0.5% in m-cresol at 25°C) was 0.31 dL/g.
- the T g of the uncured as-isolated oligomer (DSC, 20°C/min) was 227°C with a T m at 260°C and the exothermic onset and peak occurred at 340°C and 419°C, respectively.
- the T g of the cured polymer (cure conditions: 350°C/1 h/sealed pan) was 299°C
- Unoriented thin films cast from a NMP solution of the amide acid oligomer cured at 100, 225, and 350°C for 1 h each in flowing air gave tensile strength, tensile modulus, and elongation at 23°C of 19.5 ksi, 457 ksi, and 16 %; at 177°C of 10.1 ksi, 291 ksi, and 20 % and at 200°C of 9.2 ksi, 299 ksi, and 12 %, respectively.
- T g of the cured film was 296°C Polymer characterization is presented in Table 1 and thin film mechanical properties are presented in Table 2.
- Example 16 3,5-Diamino-4'-phenylethynylbenzopheone and 3, 3', 4,4'- Biphenyltetracarboxylic Dianhydride, Using 10.80 mole % Stoichiometric offset and
- the following example illustrates the reaction sequence in FIG. 5 for the preparation of the controlled molecular weight PEPI where Ar is 1 ,3-diphenylene, R is a 4-benzoyl group and Ar is 3,3',4,4'-biphenyl and Z is a phenoxy-4'-phenylethynylbenzophenone group located in the 3 position.
- the stoichiometric imbalance is 10.80 mole % and the endcapping reagent is 21 .60 mole % of 3-aminophenoxy-4'phenylethynylbenzophenone.
- Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, a precipitate formed.
- the mixture was cooled, the Toluene (60 mL) was added to the remaining amide acid oligomeric solution and the temperature increased and maintained at ⁇ 180°C for ⁇ 16 h under a nitrogen atmosphere. As cyclodehydration to the imide occurred, a precipitate formed.
- the mixture was cooled, the oligomer was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a tan powder (2.27 g, 40% yield).
- the T g of the uncured as- isolated oligomer (DSC, 20°C/min) was not detected by DSC and the exothermic onset and peak was washed in hot water, warm methanol, and dried under vacuum at 230°C for 4 h to provide a tan powder (2.27 g, 40%) yield).
- the T g of the uncured as-isolated oligomer (DSC,
- the following example illustrates the reaction sequence in equation 4 for the preparation of the controlled molecular weight PEPI where R is a 4-benzoyl group and Ar is 3,3',4,4'-biphenyl and W is a phenylethynyl group located in the 4 position.
- the stoichiometric imbalance is 10.80 mole % and the endcapping reagent is 21.60 mole % of 4-phenylethynylphthalic anhydride.
- NMP N-methyl-2-pyrrolidinone
- Polymer characterization is presented in Table 1. Oligomer and polymer characterization is presented in Table 1 , unoriented thin film properties are presented in Table 2, preliminary titanium (Ti) to Ti tensile shear adhesive properties are presented in Table 3, and preliminary composite properties are presented in Table 4.
Abstract
Description
Claims
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EP96928021A EP0842212B1 (en) | 1995-08-04 | 1996-08-02 | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
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CA002230047A CA2230047C (en) | 1995-08-04 | 1996-08-02 | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
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US4045409A (en) * | 1976-04-19 | 1977-08-30 | The United States Of America As Represented By The Secretary Of The Air Force | Thermally stable, highly fused imide compositions |
US5412066A (en) * | 1994-03-03 | 1995-05-02 | Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Phenylethynyl terminated imide oligomers |
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1995
- 1995-08-04 US US08/511,422 patent/US5606014A/en not_active Expired - Lifetime
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Patent Citations (3)
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US4837300A (en) * | 1985-06-20 | 1989-06-06 | The United States Of America As Represented By The Administration Of The National Aeronautics And Space Administration | Copolyimide with a combination of flexibilizing groups |
US5138028A (en) * | 1990-02-20 | 1992-08-11 | National Starch And Chemical Investment Holding Corporation | Polyimides end-capped with diaryl substituted acetylene |
US5138028B1 (en) * | 1990-02-20 | 1996-12-24 | Nat Starch Chem Invest | Polyimides end-capped with diaryl substituted acetylene |
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KR100503918B1 (en) * | 2004-01-20 | 2005-08-17 | (주) 뉴텍 | Fixed type fishing boat salvage device |
Also Published As
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JP3810800B2 (en) | 2006-08-16 |
EP0842212A4 (en) | 1998-10-14 |
DE69634359T2 (en) | 2005-12-15 |
JP2000505119A (en) | 2000-04-25 |
US5689004A (en) | 1997-11-18 |
EP0842212B1 (en) | 2005-02-16 |
DE69634359D1 (en) | 2005-03-24 |
EP0842212A1 (en) | 1998-05-20 |
CA2230047A1 (en) | 1997-02-20 |
CA2230047C (en) | 2009-10-13 |
KR19990036090A (en) | 1999-05-25 |
US5606014A (en) | 1997-02-25 |
KR100515284B1 (en) | 2006-01-27 |
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