CN1215741A - Potassium titanate crystal whisker reinforced polyimide composite material - Google Patents
Potassium titanate crystal whisker reinforced polyimide composite material Download PDFInfo
- Publication number
- CN1215741A CN1215741A CN 97106672 CN97106672A CN1215741A CN 1215741 A CN1215741 A CN 1215741A CN 97106672 CN97106672 CN 97106672 CN 97106672 A CN97106672 A CN 97106672A CN 1215741 A CN1215741 A CN 1215741A
- Authority
- CN
- China
- Prior art keywords
- potassium titanate
- crystal whisker
- titanate crystal
- composite
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A potassium titanate whisker reinforced polyimide compound material is prepared through wet mixing of the acidic solution of polyamide as mother material of polyimide and its copolymer with potassium titanate whisker (K2O-6TiO2), graphite powder as filler and MoS2, imination reaction under the action of acetic oxide as dewatering agent and triethylamine as catalyst, heat treating at 200-240 deg.C to obtain powdered polyimide compound material, and moulding at 360-400 deg.C and 60-80 MPa. Obtained product has excellent mechanical and heat resisting performance.
Description
The present invention relates to a kind of composite polyimide material and its preparation method, specifically, relate to a kind of potassium titanate crystal whisker reinforced polyimide composite material and preparation method thereof.
Matrix material of the present invention is formed and is comprised that the polymer repeat unit structure is
Polyimide or its multipolymer 45~90% (weight), potassium titanate crystal whisker (K
2O-6TiO
2) 5~50% (weight), filler 5~20% (weight).This matrix material be with can change into the dicarboxylic anhydride of above-mentioned polymer repeat unit structure and diamines by etc. the homopolymerization that aggregates into of mol ratio or copolyamide acid solution and potassium titanate crystal whisker and filler through mix, dewater, filtration, drying and thermal treatment and make.
1988, Japan was big
KCC has reported the composition and method of making the same that contains potassium titanate crystal whisker, for example a day disclosure is speciallyyed permit among the flat 1-313558 and is reported, after the 6-potassium titanate crystal whisker handled with organo-silicon coupling agent, and polyetherimide (Ultem1010-1000) adds twin screw extruder from main hopper and side hopper respectively, at 340 ℃ of melting mixings, extrude granulating, injection molding prepares test piece.Its objective is the intensity, rigidity and the thermotolerance that improve polyetherimide, viscosity is with low uncertainty when making fusion, is suitable for production management and mass-produced needs.Provide and be suitable for small-sized, thin-walled polyetherimide formed product composition processed especially.And for example in world patent WO88/09356, disclose and a kind of thermoplastic resin, potassium titanate crystal whisker, heat resistant fibre and pulverulent solids lubricant have been metered in the drum-type blending machine behind the uniform mixing by prescription, by the forcing machine melting mixing, be extruded into the method for granulated product.This relatively poor through screw extrusion press fusion, interface cohesive force mixing, that blending obtains polyimide compositions by the solid materials dry mixed, the product of making can be seen demixing phenomenon with scanning electron microscopic observation, it is the separated attitude of polyimide and potassium titanate crystal whisker, therefore, the mechanical property of this matrix material and thermotolerance are relatively poor.
The purpose of this invention is to provide a kind of potassium titanate crystal whisker enhanced composite polyimide material that makes through the liquid phase wet-mixed.Mechanics such as its tensile strength, flexural strength, tensile modulus and resistance toheat all are better than the potassium titanate crystal whisker polyimide material that dry mixed makes.The present invention is by the liquid phase wet-mixed of polyamic acid, pass through chemical imidization again, make polyimide resin be deposited on the surface of potassium titanate crystal whisker, strengthened the interface cohesive force of polyimide and whisker, whisker is covered by in the resin, overcome the separation phenomenon of resin and whisker, made this matrix material have excellent physical and mechanical properties.
The present invention forms and comprises: the polymer repeat unit structure is
Polyimide (YS-20) or its multipolymer 45~90% (weight), potassium titanate crystal whisker (K
2O-6TiO
2) 5~50% (weight), filler 5~20% (weight).
Multipolymer of the present invention can be chosen any one kind of them from pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, dihydroxyphenyl propane dianhydride or two or more mixture and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride and choosing any one kind of them from 4,4 '-diaminodiphenyl-methane, mphenylenediamine, phenyl ether diamines or multipolymer that two or more mixture copolymerization obtains.
Potassium titanate crystal whisker of the present invention is a white, needle-shaped crystals, and its length is 10~50 μ m, and diameter is 0.2~0.8 μ m, and relative density is 3.1~3.3.
Filler of the present invention can be chosen any one kind of them from molybdenumdisulphide, graphite, tetrafluoroethylene, glass fiber powder or be two or more.
The step of preparation process of potassium titanate crystal whisker reinforced polyimide composite material of the present invention is as follows:
(1) under 0~10 ℃ of temperature, with the dicarboxylic anhydride in above-mentioned polyimide YS-20 or its copolymer component and diamines by etc. the homopolymerization of mol ratio polymeric or copolyamide acid solution and potassium titanate crystal whisker and filler under agitation carry out wet-mixed,
(2) under 0~10 ℃ of temperature, will carry out the chemical imidization reaction in dewatering agent, the catalyzer adding mixture,
(3) with after reaction product filtration, the drying,, heat-treat, make imidization complete, obtain Powdered composite polyimide material at 200~240 ℃.
Described dewatering agent can be chosen any one kind of them from aceticanhydride, propionic anhydride, butyryl oxide and benzoyl oxide or two or more mixtures.
Described catalyzer can be chosen any one kind of them or two or more mixtures from pyridine, lutidine, N-methylmorpholine, 3-picoline, 4-picoline, Trimethylamine 99, triethylamine and isoquinoline 99.9.
Adopt polyamic acid solution of the present invention and potassium titanate crystal whisker and filler under agitation to carry out wet-mixed, again through the chemical imidization reaction, make polyimide resin be deposited on the potassium titanate crystal whisker surface, whisker is coated in the middle of the resin, the interlayer bonding force of resin and whisker is very big, has overcome the separation phenomenon of resin and whisker.Thereby make the every physical and mechanical properties of whisker strongthener of wet-mixed all obviously be better than dry mixed matrix material.
We adopt wet method and dry method to prepare the polyimide metal whisker composite respectively, and their performance is measured and compared, and its result is as shown in the table:
The polyimide metal whisker composite performance comparison of wet method and dried preparation
Material property | Dry method polyimide metal whisker composite YS20WH/D | Wet method polyimide metal whisker composite YS20WH/W |
Density (g/m 3)??????? | ????1.63 | ????1.66 |
Tensile strength (MPa) | ????97.2 | ????129 |
Tensile modulus (GPa) | ????1.23 | ????2.77 |
Flexural strength (MPa) | ????151 | ????186 |
Shock strength (KJ/m 2) | ????24.0 | ????33.1 |
Mechanical property such as tensile strength, tensile modulus, flexural strength and the shock strength of the potassium titanate crystal whisker matrix material of producing from wet method shown in the above form obviously are better than the matrix material that dry method makes.Overcome the interfacial separation phenomenon of resin and whisker in the dried preparation, improved surface flatness and the hardness of material.Make matrix material of the present invention can be used for the spiral case lap tool of screw type compressor and the base material of transmission shaft.Matrix material of the present invention also has good thermotolerance, can be used to prepare the matrix material that uses more than 250 ℃.Matrix material of the present invention has also reduced frictional coefficient, and frictional coefficient is 0.25, has improved Drawing abillity.
In order to implement the present invention better, the present invention is further illustrated now to enumerate following embodiment, but embodiment is not a limitation of the present invention.
Embodiment 1
4,4 '-diaminodiphenyl oxide (ODA), 200 grams (1mol) and 3200mL dimethylacetamide solvent add in the reactor, add 3 down at 5 ℃ then, 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 310 grams (1mol), 0~10 ℃ of scope internal reaction 0.5 hour, make polyamic acid solution, then add potassium titanate crystal whisker 200 grams, filler Graphite Powder 99 40 grams, mixed 0.5 hour, add dewatering agent aceticanhydride 1700mL and catalyst of triethylamine 170mL, be stirred to and separate out powder, finish chemical imidization, filter, washing with acetone 2 times of powder after the filtration, room temperature is dried, and 240 ℃ of thermal treatments 2 hours, obtains the powdery composite polyimide material then.
This powdery composite polyimide material is contained in the mould, 360~400 ℃ of heating 5 minutes, applied 60~80MPa pressure then and carry out mold pressing, pressurize made the polyimide molding material in 2~3 minutes.Its performance is: density 1.66 gram/cm
3, hardness 264MPa, tensile strength 129MPa, flexural strength 167MPa, shock strength 33.1KJ/m
2, tensile modulus 2.8GPa, frictional coefficient 0.25.
Embodiment 2
Except polyamic acid solution by 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 155 grams (0.5mol) and pyromellitic acid anhydride (PMDA) 109 grams (0.5mol) prepare with 4,4 '-diaminodiphenyl oxide (ODA), 200 gram (1mol) reactions, potassium titanate crystal whisker 420 grams, filler molybdenumdisulphide 40 restrain, all the other prescriptions, reaction conditions and step are with embodiment 1.The moulded plastics part performance that makes is: heat-drawn wire is 260 ℃, and tensile strength is 90MPa, shock strength 25KJ/m
2, frictional coefficient 0.20~0.22.
Embodiment 3
Except polyamic acid solution by 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 217 grams (0.7mol) and bisphenol A-type dianhydride 155 grams (0.3mol) prepare with 200 gram (1mol) reactions of 4,4 '-diaminodiphenyl oxide, potassium titanate crystal whisker 40 grams, filler tetrafluoroethylene powder 70 restrain, all the other prescriptions, reaction conditions and step are with embodiment 1.The moulded plastics part performance that makes is: tensile strength 120MPa, 220 ℃ of heat-drawn wires, shock strength 40KJ/m
2, frictional coefficient 0.24~0.25.
Embodiment 4
Except polyamic acid solution by 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 155 grams (0.5mol) and benzophenone tetracarboxylic dianhydride (BTDA) 161 grams (0.5mol) prepare with 200 gram (1mol) reactions of 4,4 '-diaminodiphenyl oxide, potassium titanate crystal whisker 74 grams, filler glass fiber powder 150 restrain, all the other prescriptions, reaction conditions and step are with embodiment 1.The moulded plastics part performance that makes is: 260 ℃ of heat-drawn wires, tensile strength 100MPa, tensile modulus 2.9GPa, frictional coefficient 0.24~0.25.
Claims (7)
1, a kind of potassium titanate crystal whisker reinforced polyimide composite material is characterized in that: composition comprises: the polymer repeat unit structure is:
Polyimide or its multipolymer 45~90% (weight), potassium titanate crystal whisker (K
2O-6TiO
2) 5~50% (weight), filler 5~20% (weight).
2, composite polyimide material according to claim 1 is characterized in that: described multipolymer can be chosen any one kind of them from pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, bisphenol A-type dianhydride or two or more mixture and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride and choosing any one kind of them from 4,4 '-diaminodiphenyl-methane, mphenylenediamine, phenyl ether diamines or multipolymer that two or more mixture copolymerization obtains.
3, composite polyimide material according to claim 1 is characterized in that: described potassium titanate crystal whisker is a white, needle-shaped crystals, and its length is 10~50 μ m, and diameter is 0.2~0.8 μ m, and relative density is 3.1~3.3.
4, composite polyimide material according to claim 1 is characterized in that: described filler can be chosen any one kind of them from molybdenumdisulphide, graphite, tetrafluoroethylene, glass fiber powder or be two or more.
5, a kind of preparation method of potassium titanate crystal whisker reinforced polyimide composite material is characterized in that comprising following processing step:
(1) under 0~10 ℃ of temperature, with the dicarboxylic anhydride described in the claim 2 and diamines by etc. the homopolymerization of mol ratio polymeric or copolyamide acid solution and potassium titanate crystal whisker and filler under agitation carry out wet-mixed,
(2) under 0~10 ℃ of temperature, will carry out the chemical imidization reaction in dewatering agent, the catalyzer adding mixture,
(3) with after reaction product filtration, the drying,, heat-treat, make imidization complete, obtain Powdered composite polyimide material at 200~240 ℃.
6, the preparation method of composite polyimide material according to claim 5 is characterized in that: described dewatering agent can be chosen any one kind of them from aceticanhydride, propionic anhydride, butyryl oxide and benzoyl oxide or two or more mixtures.
7, the preparation method of composite polyimide material according to claim 5 is characterized in that: described catalyzer can be chosen any one kind of them or two or more mixtures from pyridine, lutidine, N-methylmorpholine, 3-picoline, 4-picoline, Trimethylamine 99, triethylamine and isoquinoline 99.9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97106672A CN1085707C (en) | 1997-10-23 | 1997-10-23 | Potassium titanate crystal whisker reinforced polyimide composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97106672A CN1085707C (en) | 1997-10-23 | 1997-10-23 | Potassium titanate crystal whisker reinforced polyimide composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1215741A true CN1215741A (en) | 1999-05-05 |
CN1085707C CN1085707C (en) | 2002-05-29 |
Family
ID=5168890
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97106672A Expired - Lifetime CN1085707C (en) | 1997-10-23 | 1997-10-23 | Potassium titanate crystal whisker reinforced polyimide composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1085707C (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1318499C (en) * | 2003-06-10 | 2007-05-30 | 上海英泰塑胶有限公司 | Composite polypropylene material containing potassium titanate whisker and glass fiber |
CN102356116A (en) * | 2009-03-17 | 2012-02-15 | 纳幕尔杜邦公司 | Co-polymer based polyimide articles and their uses in an aircraft |
US8319299B2 (en) | 2009-11-20 | 2012-11-27 | Auman Brian C | Thin film transistor compositions, and methods relating thereto |
US8653512B2 (en) | 2009-11-20 | 2014-02-18 | E. I. Du Pont De Nemours And Company | Thin film transistor compositions, and methods relating thereto |
CN103725001A (en) * | 2013-12-27 | 2014-04-16 | 上海市合成树脂研究所 | Preparation method of aerospace low-resistivity polyimide composite material |
CN104446142A (en) * | 2014-11-12 | 2015-03-25 | 广东中旗新材料科技有限公司 | Potassium titanate crystal whisker composite quartz plate product and preparation method of composite quartz plate product |
CN105980722A (en) * | 2013-12-31 | 2016-09-28 | 美国圣戈班性能塑料公司 | Composite bearings having a polyimide matrix |
CN106015766A (en) * | 2016-08-01 | 2016-10-12 | 扬州赛尔达尼龙制造有限公司 | Nylon composite steel pipe changing color under pressure |
CN106479099A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of potassium titanate crystal whisker modified acroleic acid esters microsphere composite and preparation method thereof |
CN108117749A (en) * | 2017-12-24 | 2018-06-05 | 桂林理工大学 | The preparation method of polyimides/sisal cellulose crystallite composite material of shape memory |
CN108264766A (en) * | 2018-01-25 | 2018-07-10 | 无锡创彩光学材料有限公司 | A kind of preparation method of Kapton |
CN111286194A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Wear-resistant self-lubricating polyimide resin and preparation method thereof |
CN111995774A (en) * | 2020-08-20 | 2020-11-27 | 株洲时代新材料科技股份有限公司 | Preparation method of wear-resistant polyamide-imide molding powder |
CN113327775A (en) * | 2021-05-28 | 2021-08-31 | 河北工业大学 | Preparation method of potassium ion micro hybrid capacitor and electrode material |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2761563B2 (en) * | 1988-06-10 | 1998-06-04 | 大▲塚▼化学株式会社 | Polyetherimide resin composition |
JP2744067B2 (en) * | 1989-06-02 | 1998-04-28 | 三井東圧化学株式会社 | Tooth wheel |
JP2999835B2 (en) * | 1991-03-07 | 2000-01-17 | 三井化学株式会社 | Polyimide resin composition |
JP3258466B2 (en) * | 1993-10-20 | 2002-02-18 | 三井化学株式会社 | Polyimide resin composition and injection molded article excellent in fatigue characteristics |
US5508377A (en) * | 1993-12-21 | 1996-04-16 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
JP3377859B2 (en) * | 1994-05-11 | 2003-02-17 | 三井化学株式会社 | Polyimide resin composition and injection molded article excellent in fatigue characteristics |
JP3403498B2 (en) * | 1994-05-26 | 2003-05-06 | 三井化学株式会社 | Oil-containing polyimide resin composition for sliding materials |
JPH0977870A (en) * | 1995-09-14 | 1997-03-25 | Mitsui Toatsu Chem Inc | Polyimide copolymer and its production |
-
1997
- 1997-10-23 CN CN97106672A patent/CN1085707C/en not_active Expired - Lifetime
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1318499C (en) * | 2003-06-10 | 2007-05-30 | 上海英泰塑胶有限公司 | Composite polypropylene material containing potassium titanate whisker and glass fiber |
CN102356116A (en) * | 2009-03-17 | 2012-02-15 | 纳幕尔杜邦公司 | Co-polymer based polyimide articles and their uses in an aircraft |
US8319299B2 (en) | 2009-11-20 | 2012-11-27 | Auman Brian C | Thin film transistor compositions, and methods relating thereto |
US8653512B2 (en) | 2009-11-20 | 2014-02-18 | E. I. Du Pont De Nemours And Company | Thin film transistor compositions, and methods relating thereto |
CN103725001B (en) * | 2013-12-27 | 2016-08-17 | 上海市合成树脂研究所 | A kind of preparation method of aerospace low-resistivity polyimide composite material |
CN103725001A (en) * | 2013-12-27 | 2014-04-16 | 上海市合成树脂研究所 | Preparation method of aerospace low-resistivity polyimide composite material |
US10266722B2 (en) | 2013-12-31 | 2019-04-23 | Saint-Gobain Performance Plastics Corporation | Composite bearings having a polyimide matrix |
CN105980722A (en) * | 2013-12-31 | 2016-09-28 | 美国圣戈班性能塑料公司 | Composite bearings having a polyimide matrix |
CN104446142A (en) * | 2014-11-12 | 2015-03-25 | 广东中旗新材料科技有限公司 | Potassium titanate crystal whisker composite quartz plate product and preparation method of composite quartz plate product |
CN106479099A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of potassium titanate crystal whisker modified acroleic acid esters microsphere composite and preparation method thereof |
CN106015766A (en) * | 2016-08-01 | 2016-10-12 | 扬州赛尔达尼龙制造有限公司 | Nylon composite steel pipe changing color under pressure |
CN108117749A (en) * | 2017-12-24 | 2018-06-05 | 桂林理工大学 | The preparation method of polyimides/sisal cellulose crystallite composite material of shape memory |
CN108264766A (en) * | 2018-01-25 | 2018-07-10 | 无锡创彩光学材料有限公司 | A kind of preparation method of Kapton |
CN111286194A (en) * | 2019-12-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Wear-resistant self-lubricating polyimide resin and preparation method thereof |
CN111995774A (en) * | 2020-08-20 | 2020-11-27 | 株洲时代新材料科技股份有限公司 | Preparation method of wear-resistant polyamide-imide molding powder |
CN111995774B (en) * | 2020-08-20 | 2023-02-07 | 株洲时代新材料科技股份有限公司 | Preparation method of wear-resistant polyamide-imide molding powder |
CN113327775A (en) * | 2021-05-28 | 2021-08-31 | 河北工业大学 | Preparation method of potassium ion micro hybrid capacitor and electrode material |
CN113327775B (en) * | 2021-05-28 | 2022-04-29 | 河北工业大学 | Preparation method of potassium ion micro hybrid capacitor and electrode material |
Also Published As
Publication number | Publication date |
---|---|
CN1085707C (en) | 2002-05-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1085707C (en) | Potassium titanate crystal whisker reinforced polyimide composite material | |
JP2838406B2 (en) | Self-reinforcing polymer composite and method for producing the same | |
CN107501928B (en) | Hydrolysis-resistant nylon material and preparation method thereof | |
EP0423311B1 (en) | Wholly aromatic polyester fiber-reinforced high performance thermoplastic and process for preparing same | |
CN101717580B (en) | High-performance polyphenylene sulfide insulating composite material and preparation method thereof | |
CN103012794B (en) | Preparation method of polyamide-imide copolymer | |
EP0361636B1 (en) | Polyamide-polyarylene sulfide blends | |
CN109749373B (en) | Modified liquid crystal polyester resin compound and preparation method thereof | |
CN112646333B (en) | Modified PET material and preparation method thereof | |
CN1036787C (en) | Toughening mother particle for polyolefine plastics and producing process thereof | |
CN1197902C (en) | Polyimide material filled with nano zinc oxide | |
CN114891320B (en) | Epoxy resin/chopped glass fiber composite material and preparation method thereof | |
JPH0317156A (en) | Highly heat-resistant crystalpolyphthalamide compounds | |
US5021226A (en) | Method of producing fibrous magnesium oxysulfate of granular form | |
CN112694751B (en) | Polyamide-imide composite material and preparation method and application thereof | |
CN1277983A (en) | Liquid crystal polyester resin composition, and moulding products therefrom | |
JPH05194847A (en) | Polymer composition for producing in-situ composite molding | |
JPH10158510A (en) | Production of injection-moldable polyimide resin composition and production of molded product | |
JPS63251461A (en) | Nylon composite material and production thereof | |
CN115746542B (en) | High-performance long glass fiber reinforced thermoplastic composite material and preparation method thereof | |
CN112111136A (en) | Preparation method of reinforced and toughened calcium sulfate whisker composite material | |
JPH0286628A (en) | Manufacture of clay mineral/nylon composite | |
CN109762306B (en) | High-strength, high-toughness and low-shrinkage PBT (polybutylene terephthalate) composite material and preparation method thereof | |
CN1884375A (en) | Low water absorption polyamide resin composition | |
JPH10147710A (en) | Polyamide resin composition, production thereof and automobile parts produced therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS CO Free format text: FORMER NAME: SHANGHAI INST. OF SYNTHETIC RESIN |
|
CP03 | Change of name, title or address |
Address after: 200235 No. 36, Shanghai, Caobao Road Patentee after: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS CO., LTD. Address before: 200233 No. 36, Shanghai, Caobao Road Patentee before: Shanghai Inst. of Synthetic Resin |
|
CX01 | Expiry of patent term |
Granted publication date: 20020529 |
|
CX01 | Expiry of patent term |