CN1597734A - Synthesis of biphenyl type polyimide resin with phenyl ethyne dead-end - Google Patents
Synthesis of biphenyl type polyimide resin with phenyl ethyne dead-end Download PDFInfo
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- CN1597734A CN1597734A CN 200410011062 CN200410011062A CN1597734A CN 1597734 A CN1597734 A CN 1597734A CN 200410011062 CN200410011062 CN 200410011062 CN 200410011062 A CN200410011062 A CN 200410011062A CN 1597734 A CN1597734 A CN 1597734A
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- phenylacetylene
- polyimide resin
- biphenyl dianhydride
- diamino
- diaminodiphenyl
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Abstract
A process for synthesizing the phenylacetylene dead-end biphenylpolyimide resin with high thermal stability and mechanical performance and low viscosity of molten body includes such steps as proportionally adding diphenyldianhydride, bibasic amine and phenylacetylene phenylanhydride to polar solvent, stirring while reacting, adding acetic anhydride and triethylamine, stirring while reacting, depositing, washing the deposit and drying.
Description
Technical field
The invention belongs to the synthetic method of phenylacetylene-capped biphenyl polyimide resin.
Background technology
Thermocurable polyimide is a class advanced composite material matrix resin, has very high heatproof oxidation performance, mechanical property and high second-order transition temperature, in the aerospace material field very important use is arranged.The end capped polyimide resin of phenylacetylene phthalic anhydride has low-down melt viscosity, is expected to be used for resin transfer molding (RTM) contour machining procedure, and this technology has the characteristics of high efficiency, low cost, and can process the composite product of various complexity.U.S. NASA progressively is applied to RTM with on the polyimide resin with it in recent years, the polyimide resin of xenyl has very high second-order transition temperature and high mechanical property, have very wide purposes, performance is also obviously owing to the polyimide resin based on ketone acid anhydride or ether type dianhydride.Therefore very fast based on the phenylacetylene-capped developer resin of biphenyl in recent years, mainly also be to study it as the application on the resin transfer moulding technology (United States Patent (USP), 5493002; 5567800; 6133401; 6350817, document, journal of compositematerials, 2002,36 (19), 2255), wherein having related to 3 of the not commercial as yet comparatively costliness of a large amount of employings, the 4-biphenyl dianhydride makes that also the final cost of resin is higher.
Summary of the invention
The purpose of this invention is to provide the synthetic of a kind of phenylacetylene-capped biphenyl polyimide resin.
Institute's synthetic polymkeric substance has low-down melt viscosity, also have simultaneously good thermostability and mechanical property, and owing to adopt copolymerization, reduced by 3, the usage quantity of 4-biphenyl dianhydride, have very low cost, therefore be well suited for the novel resin transfer molding process planning polyimide resin of development.The present invention adopts the polyimide resin of phenylacetylene phthalic anhydride as reaction end-capping reagent synthetic biphenyl type in all kinds of SOLVENTS with isomery biphenyl two tinctures and various diamine polymerization.
Preparation process is as follows:
With biphenyl dianhydride, diamine and phenylacetylene phthalic anhydride according to n: (n+1): 2 ratio joins in the polar solvent, the stirring at room reaction is after 2-10 hour, add dewatering agent diacetyl oxide and dehydration catalyst triethylamine, again in stirring at room reaction 4-12 hour, it is sunk in the water, obtain throw out, behind the thorough washing, dry sediment promptly gets polyimide resin.
Synthetic route is:
Wherein the position of S can be 3 or 4 of phenyl ring; Dicarboxylic anhydride is 4,4 '-biphenyl dianhydride, 3,4 '-biphenyl dianhydride or 3,3 '-biphenyl dianhydride one or more blend wherein, and three's consumption can not be zero simultaneously, three's molar percentage is 1-100%: 0-100%: 0-100%.
N is the polymerization degree of resinous polymer, 10 〉=n 〉=1;
Diamine is H
2N-Ar-NH
2Be mphenylenediamine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-hexichol Oxy-1 "; 4 "-benzene, 4,4 '-diamino-hexichol Oxy-1 ", 3 "-benzene, 3,3 '-diamino-hexichol Oxy-1 "; 3 "-benzene or 4,4 '-diamino-two phenoxy group-4 ", wherein one or more of the different propane of 4 -phenylbenzene; this consumption can not be zero simultaneously, and nine molar percentage is 0-100%: 0-100%: 0-100%: 0-100%: 0-100%: 0-100%0-100%: 0-100%: 0-100%.
Solvent of the present invention is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO) or cresols.
Dewatering agent of the present invention is a diacetyl oxide, and consumption is 2-4 a times of diamine mole number.
Dehydration catalyst of the present invention is triethylamine or pyridine, and consumption is 0.1-1 a times of diacetyl oxide mole number.
Characteristics of the present invention are that institute's synthetic polyimide is to have low melt viscosity, may be used in the RTM moulding process.
Embodiment
Embodiment 1 is with 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 1,6-hexanediamine (23.2g, 0.2mol) and phenylacetylene phthalic anhydride 0.1mol (24.8g) join N, among the N '-dimethyl formamide (3000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 0.4mol (40g) and catalyst of triethylamine 0.04mol (4g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out faint yellow precipitation, filter collecting precipitation, and use the ethanol thorough washing, get the phenylacetylene-capped polyimide resin of 73g after the drying.
Embodiment 2
With 3,4 '-biphenyl dianhydride 0.2mol (65.2g), Ursol D 0.3mol (32.4g) and phenylacetylene phthalic anhydride 0.2mol (49.6g) join N, among the N '-dimethyl formamide (300mL), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 1.5mol (153g) and catalyst of triethylamine 1mol (101g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 3
With 3,3 '-biphenyl dianhydride 0.1mol (32.6g), mphenylenediamine 0.11mol (11.9g) and phenylacetylene phthalic anhydride 0.02mol (5g) join N, among the N '-dimethyl formamide (110ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 0.44mol (44g) and catalyst of triethylamine 0.44mol (44g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 4
With 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-diamines yl diphenyl ether 0.3mol (60g) and phenylacetylene phthalic anhydride 0.2mol (49.6g) join in the N-N-methyl-2-2-pyrrolidone N-(700ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 1.2mol (122g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 5
With 4,4 '-biphenyl dianhydride 0.01mol (3.26g), 3,4 '-biphenyl dianhydride 0.99mol (323g), 4,4 '-diaminodiphenyl-methane 2mol (397g) and phenylacetylene phthalic anhydride 1mol (248g) join in the N-N-methyl-2-2-pyrrolidone N-(1500ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 5mol (510g) and catalyst of triethylamine 1mol (101g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 6
With 3,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane 0.3mol (68g) and phenylacetylene phthalic anhydride 0.2mol (50g) join in the dimethyl sulfoxide (DMSO) (600ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.4mol (245g) and catalyst of triethylamine 2mol (202g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 7
With 4,4 '-biphenyl dianhydride 0.3mol (97.8g), 3,4 '-biphenyl dianhydride 0.3mol (97.8g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-diamino-hexichol Oxy-1 "; 4 "-benzene 0.8mol (234g) and phenylacetylene phthalic anhydride 0.2mol (50g) join in the cresols (400ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 3.2mol (326g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 12h, with in a large amount of ethanol of its impouring, separate out precipitation then, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 8
With 4,4 '-biphenyl dianhydride 0.2mol (65.2g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.4mol (117g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (3L), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 1.2mol (122g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 9
With 4,4 '-biphenyl dianhydride 0.2mol (65.2g), 3,3 '-biphenyl dianhydride 0.5mol (163g), 3,3 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.8mol (234g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (2000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 3.2mol (326g) and catalyst of triethylamine 3mol (303g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 10
With 3,3 '-biphenyl dianhydride 0.2mol (65.2g), 4,4 '-biphenyl dianhydride 0.5mol (163g), 3,3 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.8mol (234g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (2000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 3.2mol (326g) and catalyst of triethylamine 3mol (303g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 11
With 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-biphenyl dianhydride 0.2mol (65.2g), 4,4 '-diamino-two phenoxy group-4 "; different propane 0.4mol of 4 -phenylbenzene (164g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N; among the N '-N,N-DIMETHYLACETAMIDE (600ml); under the room temperature behind the stirring reaction 6h; add dewatering agent diacetyl oxide 6mol (612g) and catalyst of triethylamine 0.6mol (60g) continuation stirring reaction 20h; with in a large amount of ethanol of its impouring, separate out precipitation, collecting precipitation then, and use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 12
With 4,4 '-biphenyl dianhydride 0.2mol (65.2g), 3,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-diamino-hexichol Oxy-1 "; 4 "-benzene 0.3mol (87.7g), Ursol D 0.2mol (21.6g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-N,N-DIMETHYLACETAMIDE (700ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide (2mol204g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 12h, then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 13
With 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 4,4 '-diaminodiphenyl oxide 0.1mol (20g), 4,4 '-diamino-two phenoxy group-4 "; the different propane 0.1mol of 4 -phenylbenzene (41g); 1; 6-hexanediamine 0.1mol (11.6g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N; among the N '-dimethyl formamide (400ml); under the room temperature behind the stirring reaction 10h, add dewatering agent diacetyl oxide 1mol (102g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 9h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 14
With 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-diaminodiphenyl oxide 0.16mol (32g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.04mol (11.7g) and phenylacetylene phthalic anhydride 0.1mol (24.8g) join N, among the N '-dimethyl formamide (300ml), under the room temperature behind the stirring reaction 7h, add dewatering agent diacetyl oxide 0.8mol (81.6g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 8h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 15
With 3,4 '-biphenyl dianhydride 0.8mol (261g), 4,4 '-diaminodiphenyl oxide 0.7mol (140g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.2mol (58.4g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (1000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 3mol (306g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 6h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 16
With 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-biphenyl dianhydride 0.2mol (65.2g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-diaminodiphenyl oxide 0.4mol (80g), 4,4 '-diaminodiphenyl-methane 0.05mol (9.9g), 3,3 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.05mol (14.6g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-N,N-DIMETHYLACETAMIDE (500ml), behind the stirring reaction 12h, add dewatering agent diacetyl oxide 5mol (510g) and catalyst of triethylamine 0.5mol (50g) and continue stirring reaction 12h, under the room temperature then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, and use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 17
With 4,4 '-biphenyl dianhydride 0.4mol (130g), 3,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-diaminodiphenyl oxide 0.4mol (80g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.1mol (29.2g), mphenylenediamine 0.1mol (10.8g), 4,4 '-diaminodiphenyl-methane 0.1mol (19.8g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (1000ml), behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.1mol (214g) and catalyst of triethylamine 0.7mol (71g) and continue stirring reaction 12h, under the room temperature then with in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, promptly get phenylacetylene-capped polyimide resin after the drying.
Embodiment 18
With 3,4 '-biphenyl dianhydride 0.4mol (130g), 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-diaminodiphenyl oxide 0.4mol (80g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.1mol (29.2g), mphenylenediamine 0.01mol (1.08g), 4,4 '-diaminodiphenyl-methane 0.19mol (37.7g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (1000ml), behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.1mol (214g) and catalyst of triethylamine 0.7mol (71g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring under the room temperature, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 19
With 3,4 '-biphenyl dianhydride 0.4mol (130g), 4,4 '-biphenyl dianhydride 0.2mol (65.2g), 3,4 '-diaminodiphenyl oxide 0.4mol (80g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.1mol (29.2g), mphenylenediamine 0.01mol (1.08g), 4,4 '-diaminodiphenyl-methane 0.19mol (37.7g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-dimethyl formamide (1000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.1mol (214g) and catalyst of triethylamine 0.7mol (71g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 20
With 3,4 '-biphenyl dianhydride 0.6mol (195.6g), 3,4 '-diaminodiphenyl oxide 0.4mol (80g), 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene 0.1mol (29.2g), mphenylenediamine 0.01mol (1.08g), 4,4 '-diaminodiphenyl-methane 0.19mol (37.7g) and phenylacetylene phthalic anhydride 0.2mol (50g) join in the N-N-methyl-2-2-pyrrolidone N-(1000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.1mol (214g) and catalyst of triethylamine 0.7mol (71g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Embodiment 21
With 3,4 '-biphenyl dianhydride 0.4mol (130g), 4,4 '-biphenyl dianhydride 0.1mol (32.6g), 3,3 '-biphenyl dianhydride 0.1mol (32.6g), 3,4 '-diaminodiphenyl oxide 0.7mol (140g) and phenylacetylene phthalic anhydride 0.2mol (50g) join N, among the N '-N,N-DIMETHYLACETAMIDE (1000ml), under the room temperature behind the stirring reaction 12h, add dewatering agent diacetyl oxide 2.1mol (214g) and catalyst of triethylamine 0.7mol (71g) and continue stirring reaction 12h, in a large amount of ethanol of its impouring, separate out precipitation, filter collecting precipitation, use the ethanol thorough washing, get phenylacetylene-capped polyimide resin after the drying.
Claims (1)
1. a phenylacetylene-capped biphenyl polyimide resin is synthetic, its preparation process is for to join dicarboxylic anhydride, diamine and phenylacetylene phthalic anhydride in the polar solvent, the stirring at room reaction is after 2-10 hour, add dewatering agent diacetyl oxide and dehydration catalyst triethylamine, in stirring at room reaction 4-12 hour, it is sunk in the water again, obtain throw out, behind the thorough washing, dry sediment promptly gets polyimide resin, and reaction process is as follows:
N is the polymerization degree of resinous polymer, 10 〉=n 〉=1; Diamine is H
2N-Ar-NH
2,
It is characterized in that the dicarboxylic anhydride that adopts is 4,4 '-biphenyl dianhydride, 3,4 '-biphenyl dianhydride or 3,3 '-biphenyl dianhydride one or more blend wherein, three's consumption can not be zero simultaneously, and three's molar percentage is 0-100%: 0-100%: 0-100%; The diamine that is adopted is a Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-hexichol Oxy-1 "; 4 "-benzene, 4,4 '-diamino-hexichol Oxy-1 "; 3 "-benzene, 3,3 '-diamino-hexichol Oxy-1 ", 3 "-benzene or 4,4 '-diamino-two phenoxy group-4 "; the different propane of 4 -phenylbenzene one or more blend wherein, this consumption can not be zero simultaneously, nine weight percent is 0-100%: 0-100%: 0-100%: 0-100%: 0-100%: 0-100%: 0-100%: 0-100%; Wherein any one molar percentage that accounts for the diamine blend is 0-100%; Solvent is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), cresols or phenol; Dewatering agent is a diacetyl oxide, and consumption is 2-4 a times of diamine mole number; Dehydration catalyst is triethylamine or pyridine, and consumption is 0.1-1 a times of diacetyl oxide mole number.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011062 CN1597734A (en) | 2004-08-27 | 2004-08-27 | Synthesis of biphenyl type polyimide resin with phenyl ethyne dead-end |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410011062 CN1597734A (en) | 2004-08-27 | 2004-08-27 | Synthesis of biphenyl type polyimide resin with phenyl ethyne dead-end |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586931C (en) * | 2008-04-25 | 2010-02-03 | 中国科学院长春应用化学研究所 | Method for synthesizing 2,4-diamino[4'-(4-phenylacetylenylphthalimido)]diphenyl ether |
| CN102206344A (en) * | 2010-11-04 | 2011-10-05 | 浙江吉利汽车研究院有限公司 | Formable polyimide resin for automobile and preparation method thereof |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
| CN104151549A (en) * | 2014-08-04 | 2014-11-19 | 哈尔滨工程大学 | Polyimide resin adopting thermosetting comb type structure and preparation method thereof |
| CN108085769A (en) * | 2017-12-14 | 2018-05-29 | 东华大学 | A kind of preparation method of Cross-linkable polyimides fibrid |
| CN108586403A (en) * | 2018-04-19 | 2018-09-28 | 吉林大学 | A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
| CN117186765A (en) * | 2023-11-08 | 2023-12-08 | 成都石大力盾科技有限公司 | Solid self-lubricating coating and preparation method thereof |
-
2004
- 2004-08-27 CN CN 200410011062 patent/CN1597734A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586931C (en) * | 2008-04-25 | 2010-02-03 | 中国科学院长春应用化学研究所 | Method for synthesizing 2,4-diamino[4'-(4-phenylacetylenylphthalimido)]diphenyl ether |
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
| CN102206344A (en) * | 2010-11-04 | 2011-10-05 | 浙江吉利汽车研究院有限公司 | Formable polyimide resin for automobile and preparation method thereof |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| CN104151549A (en) * | 2014-08-04 | 2014-11-19 | 哈尔滨工程大学 | Polyimide resin adopting thermosetting comb type structure and preparation method thereof |
| CN108085769A (en) * | 2017-12-14 | 2018-05-29 | 东华大学 | A kind of preparation method of Cross-linkable polyimides fibrid |
| CN108586403A (en) * | 2018-04-19 | 2018-09-28 | 吉林大学 | A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
| CN117186765A (en) * | 2023-11-08 | 2023-12-08 | 成都石大力盾科技有限公司 | Solid self-lubricating coating and preparation method thereof |
| CN117186765B (en) * | 2023-11-08 | 2024-01-30 | 成都石大力盾科技有限公司 | Solid self-lubricating coating and preparation method thereof |
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