CN1312145C - Process for preparation of 4-phenylacetylene phthalic anhydride - Google Patents
Process for preparation of 4-phenylacetylene phthalic anhydride Download PDFInfo
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- CN1312145C CN1312145C CNB2004100533784A CN200410053378A CN1312145C CN 1312145 C CN1312145 C CN 1312145C CN B2004100533784 A CNB2004100533784 A CN B2004100533784A CN 200410053378 A CN200410053378 A CN 200410053378A CN 1312145 C CN1312145 C CN 1312145C
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- Prior art keywords
- phenylacetylene
- anhydride
- preparation
- mol ratio
- acid anhydride
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 48
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 46
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 11
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- -1 4-bromobenzene acid anhydride Chemical class 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract 2
- PPKPKFIWDXDAGC-IHWYPQMZSA-N (z)-1,2-dichloroprop-1-ene Chemical compound C\C(Cl)=C\Cl PPKPKFIWDXDAGC-IHWYPQMZSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AQBFKBMMIDHCFS-UHFFFAOYSA-N 4-bromo-2-benzofuran-1,3-dione Chemical compound BrC1=CC=CC2=C1C(=O)OC2=O AQBFKBMMIDHCFS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SFAZBJLFDAGITE-UHFFFAOYSA-N C1(C=2C(C(=O)O1)=CC=CC2)=O.C2(=CC=CC=C2)C#C Chemical class C1(C=2C(C(=O)O1)=CC=CC2)=O.C2(=CC=CC=C2)C#C SFAZBJLFDAGITE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method for 4-phenylacetylene benzene anhydride, which comprises the steps that (1) when catalysts, cuprous iodide and dichlor double triphenyl phosphor, are matched with platinum, 4-phenylacetylene benzene anhydride and phenylacetylene make a refluxing reaction in triethylamine solvent for 19 to 21 hours under the atmosphere of nitrogen, and the reaction temperature is from 75 to 85 DEG C; (2) the triethylamine is separated; solid precipitate is mixed with acetic anhydride; the molar ratio of the acetic anhydride to the 4-phenylacetylene benzene anhydride is 1.5 to 6.0: 1; the heating and the refluxing are carried out for 30 minutes; acetic acid and the acetic anhydride are steamed to be removed; the recrystallization is carried out by mixing solvent of toluene and normal hexane having the same volume to obtain the 4-phenylacetylene benzene anhydride; the melting point is from 151.6 to 152.3 DEG C, and the yield rate is from 90 to 91%.
Description
Technical field
The present invention relates to the preparation method of 4-phenylacetylene phthalic anhydride, relate to method or rather by 4-bromobenzene acid anhydride and phenylacetylene prepared in reaction 4-phenylacetylene phthalic anhydride.
Background technology
4-phenylacetylene phthalic anhydride and derivative thereof are with the necessary cementability of polyimide, thermotolerance and physical strength, its utility value is high, it is the raw materials of aerospace with the matrix material parent resin, the matrix material made of polyimide precursor resins by its preparation, higher more than 30 ℃ than epoxy resin composite material use temperature, be the desired configuration material of subsonic aircraft.Prior art spy opens flat JP11-180970,6jul.1999 by phenylacetylene or its derivative and bromo phthalic anhydride, reaction in the presence of cuprous iodide and divalence or zeroth order palladium complex, then use the alkaline solution hydrolysis, with excessive equivalent aqueous hydrochloric acid precipitation product, filtration drying obtains 4-phenylacetylene phthalic anhydride with chemical closed loopization or hot closed loopization, fusing point is 151.8～152.8 ℃, the 4-phenylacetylene phthalic anhydride of omnidistance yield 92.3～92.5%.
In the prior art in order to prepare highly purified 4-phenylacetylene phthalic anhydride, the reactor product of 4-bromobenzene acid anhydride and phenylacetylene is become 4-phenylacetylene phosphorus benzene bis-acid potassium with the aqueous hydrolysis of sodium hydroxide, and then become 4-phenylacetylene phthalic anhydride with aceticanhydride chemistry closed loop, this basic hydrolysis, hydrochloric acid water precipitation and organic acid carry out the method for chemical closed loopization, step is many, and separate complex is need be improved on industrial production.
Summary of the invention
Preparation method of the present invention only in the triethylamine solvent, and does not have 4-bromobenzene acid anhydride and phenylacetylene under the existence of benzene, uses dichlorobis triphenylphosphine palladium PdCl
2[P (C
6H
5)
3]
2Cuprous iodide and triphenylphosphine are made catalyzer, the solid precipitation that back flow reaction makes directly mixes with aceticanhydride, reflux makes that issuable 4-phenylacetylene phthalic acid all changes into 4-phenylacetylene phthalic anhydride in the reaction, has got rid of in the background technology solid precipitation and has used earlier the aqueous sodium hydroxide solution hydrolysis, precipitate this step with excessive equivalent aqueous hydrochloric acid again, simplified production technique, separated simply, and suitable suitability for industrialized production.
The preparation method's of 4-phenylacetylene phthalic anhydride of the present invention step comprises:
(1) under nitrogen atmosphere, at the catalyzer cuprous iodide, divalence palladium complex and triphenylphosphine exist down, with 4-bromobenzene acid anhydride and phenylacetylene back flow reaction 19～21 hours in organic bases triethylamine solvent, temperature of reaction is 75～85 ℃, and the mol ratio of phenylacetylene and 4-bromobenzene acid anhydride is 1.06～1.10: 1.
(2) separate triethylamine, suction filtration, solid precipitation mixed stirring, reflux 20～40 minutes with aceticanhydride, made that issuable 4-phenylacetylene phthalic acid all changes into 4-phenylacetylene phthalic anhydride in the reaction.Add equal-volume toluene then and normal hexane mixed solvent recrystallization makes 4-phenylacetylene phthalic anhydride, fusing point: 151.6～152.3 ℃, yield 90～91%.
Among the preparation method of the present invention, the add-on of catalyzer is 0.8～2.4 weight % of 4-bromobenzene acid anhydride add-on, and catalyzer divalence palladium complex is a dichlorobis triphenylphosphine palladium, and its molecular formula is: PdCl
2[P (C
6H
5)
3]
2, dichloro bi triphenyl phosphorus cooperates the mol ratio of palladium and cuprous iodide to be: 1: 3～4.8, and the mol ratio of triphenyl phosphorus and cuprous iodide is 1.6～2.0: 1.
Among the preparation method of the present invention, the mol ratio of used triethylamine solvent and raw material 4-bromobenzene acid anhydride is 50～70: 1.
The amount of adding aceticanhydride and the mol ratio of raw material 4-bromobenzene acid anhydride are among the preparation method of the present invention: 1.5～6.0: 1.
The present inventor by analysis, think in the process of 4-bromobenzene acid anhydride and phenylacetylene prepared in reaction 4-phenylacetylene phthalic anhydride, under the sour water condition, partly acid anhydride may hydrolysis, if but add organic acid such as acetic acid, aceticanhydride carries out chemical ring-closure reaction and just can make highly purified 4-phenylacetylene phthalic anhydride.
In the prior art, when making solvent with organic bases such as triethylamine, add benzene or toluene etc. simultaneously, purpose is to remove the contained moisture content of triethylamine.The present invention does not use these solvents, and the triethylamine of use is water content not on substantially, and it obtains through pre-treatment, as distillation or molecular sieve dehydration etc.
The present invention is applicable to that 4-bromobenzene acid anhydride and derivative thereof and phenylacetylene and derivatives reaction thereof prepare phenylacetylene phthalic anhydride derivative.
The present invention except that adding the organic bases triethylamine, no longer adds other dewatering agent in reactive system, got rid of NaOH aqueous hydrolysis operation of the prior art, and the manufacturing operation process is simple.The inventive method can prepare high quality, high yield product 4-phenylacetylene phthalic anhydride, and its yield is 90～91%, fusing point is 151.6～152.3 ℃
Embodiment
In order to implement the present invention better, especially exemplified by following embodiment, but embodiment is not a limitation of the present invention.
Embodiment 1
Be equipped with the 500ml flask of nitrogen ingress pipe, spherical condensation tube, drying tube, dropping funnel and magnetic stirring apparatus, vacuumize earlier, with nitrogen replacement air three times, and always under nitrogen atmosphere, in there-necked flask, add 27.24g (0.12 mole) 4 monobromo phthalic anhydrides, (0.1g 0.52 mmole) cuprous iodide, (0.1g 0.15 mmole) dichlorobis triphenylphosphine palladium, (0.24g 0.92 mmole) triphenylphosphine and 380ml exsiccant triethylamine, stirring, heating, at 85 ℃ down with dripping 13.5g (0.13 mole) phenylacetylene that is dissolved in the 10ml triethylamine in 1 hour.After dripping, continued heated and stirred 20 hours, decantation goes out triethylamine, and suction filtration, merges all solids, aceticanhydride mixes for solid and 70ml (0.74 mole), stirring, reflux 30 minutes, boil off acetic acid, aceticanhydride, add 70ml toluene then and equal-volume normal hexane recrystallization gets 4-phenylacetylene phthalic anhydride, dry weight 26.8 grams, productive rate 90.1%, 151.8 ℃ of fusing points.
1HNMR (CDCl
3, 300Hz), δ: 7.39 (1H), 7.41 (2H), 7.57 (dd, J=8.4Hz, 2H).
13CNMR (CDCl
3, 300Hz), δ: 86.9,96.0,121.5,125.6,128.1,128.6,129.5,129.7,131.7,131.9,138.6,162.1.IR (KBr) v:2210.4 (vs, C ≡ C), 1844.6[vs, (CO)
2O], 1775.0 (vs, CO) cm
-1. ultimate analysis C
16H
8O
3Calculated value: C, 77.42; H, 3.25. measured value: C, 77.20; H, 3.39.
Embodiment 2
Remove and add phenylacetylene 13.7 grams (0.132 mole), 80 ℃ of reactions 19 hours, and adding cuprous iodide 0.138 gram (0.72 mmole), outside the aceticanhydride 45ml (0.48 mole), all the other prescriptions and operation steps and embodiment 1 are just the same, the result removes 4-phenylacetylene phthalic anhydride yield 90%, 151.6 ℃ of fusing points, and other analytical results is the same with embodiment 1.
Embodiment 3
Remove and add phenylacetylene 13.19 grams (0.127 mole), 85 ℃ of reactions 20 hours, and adding cuprous iodide 0.087 gram (0.45 mmole), outside the aceticanhydride 18ml (0.19 mole), other operation is fully the same with embodiment 1 with prescription, the yield that the result removes 4-phenylacetylene phthalic anhydride is 91%, and outside 152 ℃ of the fusing points, other analytical results is the same with embodiment 1.
Claims (4)
1, a kind of preparation method of 4-phenylacetylene phthalic anhydride is characterized in that step comprises:
(1) under nitrogen institute atmosphere, in the presence of catalyzer cuprous iodide, divalence palladium complex and triphenylphosphine, with 4-bromobenzene acid anhydride and phenylacetylene back flow reaction 19～20 hours in organic bases triethylamine solvent, temperature of reaction is 75～85 ℃, and the mol ratio of phenylacetylene and 4-bromobenzene acid anhydride is 1.10: 1;
(2) separate triethylamine, suction filtration, solid precipitation mixes with aceticanhydride, stirring, reflux 20～40 minutes, boils off acetic acid and aceticanhydride, add equal-volume toluene then and normal hexane mixed solvent recrystallization makes 4-phenylacetylene phthalic anhydride, fusing point: 151.6～152.3 ℃.
2, preparation method according to claim 1 is characterized in that: the add-on of catalyzer is 0.8～2.4 weight % of 4-bromobenzene acid anhydride add-on, and described catalyzer divalence palladium complex is a dichlorobis triphenylphosphine palladium, and its molecular formula is PdCl
2[P (C
6H
5)
3]
2, the mol ratio of dichlorobis triphenylphosphine palladium and cuprous iodide is 1: 3～4.8, the mol ratio of triphenylphosphine and cuprous iodide is 1.6～2.0: 1.
3, preparation method according to claim 1 is characterized in that: the mol ratio of used triethylamine solvent and 4-bromobenzene acid anhydride is 50～70: 1.
4, preparation method according to claim 1 is characterized in that: adding the amount of aceticanhydride and the mol ratio of 4-bromobenzene acid anhydride is 1.5～6.0: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100533784A CN1312145C (en) | 2004-08-03 | 2004-08-03 | Process for preparation of 4-phenylacetylene phthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100533784A CN1312145C (en) | 2004-08-03 | 2004-08-03 | Process for preparation of 4-phenylacetylene phthalic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1603317A CN1603317A (en) | 2005-04-06 |
| CN1312145C true CN1312145C (en) | 2007-04-25 |
Family
ID=34666099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100533784A Expired - Lifetime CN1312145C (en) | 2004-08-03 | 2004-08-03 | Process for preparation of 4-phenylacetylene phthalic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1312145C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550122B (en) * | 2008-04-01 | 2012-01-04 | 四川大学 | Method for preparing 4-phenylethynylphthalic anhydride by taking water as solvent |
| WO2010013620A1 (en) * | 2008-07-31 | 2010-02-04 | マナック株式会社 | Process for producing phthalic anhydride derivative |
| ES2523824T3 (en) * | 2012-04-20 | 2014-12-01 | Nexam Chemical Ab | Process for the production of (etino-1,2-diyl) bis (isobenzofuran-1,3-dione) |
| CN103641806A (en) * | 2013-11-19 | 2014-03-19 | 常州市天华制药有限公司 | Preparation method of 4-phenylethynylphthalic anhydride |
| CN113024496A (en) * | 2021-03-24 | 2021-06-25 | 天津市泰合利华材料科技有限公司 | Method for preparing 4-p-trifluoromethyl phenyl alkynyl phthalic anhydride |
| CN113603662B (en) * | 2021-06-15 | 2023-06-06 | 陕西泰合利华工业有限公司 | Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride |
| CN117304149B (en) * | 2023-09-28 | 2025-12-12 | 常州市尚科新材料有限公司 | Synthesis of 4-phenylacetylene phthalic anhydride |
| CN117777076B (en) * | 2023-12-26 | 2025-12-05 | 中国科学院过程工程研究所 | A method for preparing 4-phenylethynyl phthalic anhydride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
| CN1324794A (en) * | 2000-05-19 | 2001-12-05 | 黑龙江省石油化学研究院 | Prepn. of diphenyl ether tetraformic dianhydride |
-
2004
- 2004-08-03 CN CNB2004100533784A patent/CN1312145C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
| CN1324794A (en) * | 2000-05-19 | 2001-12-05 | 黑龙江省石油化学研究院 | Prepn. of diphenyl ether tetraformic dianhydride |
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| Publication number | Publication date |
|---|---|
| CN1603317A (en) | 2005-04-06 |
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Effective date of registration: 20210128 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE Co.,Ltd. Address before: 200235 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070425 |