CN1563150A - Method for preparing polyetherimide through continuous extrusion reaction - Google Patents
Method for preparing polyetherimide through continuous extrusion reaction Download PDFInfo
- Publication number
- CN1563150A CN1563150A CN 200410017711 CN200410017711A CN1563150A CN 1563150 A CN1563150 A CN 1563150A CN 200410017711 CN200410017711 CN 200410017711 CN 200410017711 A CN200410017711 A CN 200410017711A CN 1563150 A CN1563150 A CN 1563150A
- Authority
- CN
- China
- Prior art keywords
- polyetherimide
- reactor
- screw
- double
- temperature
- 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
- 239000004697 Polyetherimide Substances 0.000 title claims abstract description 33
- 229920001601 polyetherimide Polymers 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 20
- 238000001125 extrusion Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000012745 toughening agent Substances 0.000 claims description 11
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
In the preparation method, bisphenol A diether anhydride, aromatic diamine and chain stopper are added into feeding section of reactor; the added material is passed through melting section and mass transfering section then mixed with reinforcing agent of glass fibre at polymerizing section; polyether imide and water formed by reaction are separated out at reactor after high speed cutting and strong mixing are applied.
Description
Technical field
The present invention relates to prepare the method for polyetherimide, relate to or rather with double-screw reactor and extrude the method for preparing polyetherimide based on the reaction mass of dihydroxyphenyl propane diether acid anhydride and aromatic diamine continuously with the continuous extrusion reaction thing of double-screw reactor.
Background technology
The polyetherimide production cost is relatively low, is mass-produced thermoplastic polyimide.Its process operation performance can be comparable with high-performance thermoplastics polyethersulfone and polysulfones.This amorphous thermoplastic polyetherimide characteristic performance is high strength, high-modulus, moderate electrical property, the transparent color of amber, intrinsic flame retardant resistance, moderate chemical proofing, good thermotolerance, heat-drawn wire is more than 200 ℃, use temperature is 170 ℃ continuously, is widely used in the world.Since nineteen eighty-two, General Electric Apparatus Co.(U.S.A.) has obtained 100 multinomial patents.Estimate that its world consumption amount will be with annual 10% speed increase from now on.
Because the performance and the purposes of polyetherimide are noticeable, so, also in the ascendant to its preparation method's research.Prior art USP 4,421,907, and Dec.20.1983 has introduced a method of polyetherimide successive polymerization.This method is done blending earlier with organic dianhydride, organic diamine and chain terminator, then blend is added in the reactor, through 50～300 ℃ of melt kneading, be transported to the mass transfer section of 200～350 ℃ of temperature, the water row that reaction generates is in atmosphere, then to be transferred to temperature be 300～400 ℃ polymeric segment to material, through high speed shear and intense mixing, extrudes to stable state polyetherimide and branch is dried up under 1～25 normal atmosphere.This method feed rate 227g/hr, the limiting viscosity of polymkeric substance in chloroform is 0.44dl/g, the plastic sample mechanical property is tensile yield strength 100Mpa, compressive ultimate strength 98Mpa, elongation 96%, cantilever beam impact strength 28.3J/m, Gardner's shock strength 36Nm.This method prepares polyetherimide continuously with double-screw reactor comes via two step method synthesizing polyether imide in solvent compared with traditional method, and its advantage is apparent.Also need improved aspect if mention, that be exactly runtime greater than 5 hours, polymer property viscosity has only 0.44dl/g, feed rate also has only 227g/hr, be difficult to adapt to mass production.And length will cause polymer degradation runtime, and polymer viscosity is low also to its system of being of limited application.
Summary of the invention
The purpose of this invention is to provide a method for preparing polyetherimide continuously, this method feed rate is fast, 2～5kg/hr, the limiting viscosity scope 0.45～0.65dl/g of product, material residence time in reactor is short, have only 1.5～5 minutes, plastics exemplar good mechanical performance, cantilever beam impact strength 50～150KJ/m
2, can be described as an ideal method.
The process that the continuous extrusion reaction of the present invention prepares polyetherimide comprises:
(1) high-speed mixing finely powdered dihydroxyphenyl propane diether acid anhydride, aromatic diamine and chain terminator;
(2) mixture of step (1) being added to temperature is that double-screw reactor is formed and comprised feeding section, melt zone, mass transfer section and polymeric segment in 150 ℃～275 ℃ the feeding section of double-screw reactor;
(3) carrying mixture is 275 ℃～300 ℃ melt zone to temperature, and material is melt into liquid through heating by kneading, and the water of generation is discharged in the atmosphere;
(4) liquid being transported to temperature is 300 ℃～310 ℃ mass transfer section, and the water that reaction generates is discharged in the atmosphere;
(5) be provided with the toughener admission port between mass transfer section and polymeric segment, toughener is introduced the reactor from admission port;
(6) melts and toughener being transported to temperature is 310 ℃～330 ℃ polymeric segment, generates water and is discharged in the atmosphere, and material bears 10～30 normal atmosphere, stands high speed shear and enhancing mixed;
(7) polyetherimide and generation water are separated from double-screw reactor.
The dihydroxyphenyl propane diether acid anhydride and the aromatic diamine of mol ratios such as employing of the present invention.The amount of chain terminator phthalic anhydride is 1～10% of a dihydroxyphenyl propane diether acid anhydride weight.
Be applicable to that aromatic diamine kind of the present invention is a lot, as: mphenylenediamine, Ursol D, 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl-methane, 4,4 '-the diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide etc., be preferably from 4 and 3,4 '-choose any one kind of them in the diaminodiphenyl oxide.
Toughener of the present invention can be from E type glass fibre, S type glass fibre, and carbon fiber, glass powder is chosen any one kind of them in the fine powder of carbon or several, and add-on is 0～40% of dihydroxyphenyl propane diether acid anhydride and an aromatic diamine gross weight.
Double-screw reactor of the present invention is a self design.It is that screw rod rotates intermeshing reactor in the same way, screw diameter 35mm, and length-to-diameter ratio is 48, and feeding section length is 530mm, and melting length is 450mm, and the mass transfer segment length is 270mm, polymeric segment length is 400mm, screw speed 250～550r/min.
The speed that is added to feeding section through the mixture of high-speed mixing is 2～5kg/hr, and the residence time of material in double-screw reactor is 1.5～5min.
The limiting viscosity of polyetherimide N-Methyl pyrrolidone of separating from polymeric segment is 0.45～0.65dl/g.
According to the plastics exemplar of the polyetherimide of the present invention preparation, its tensile strength 100～200Mpa, compressive strength 150～220Mpa, elongation 2～8%, shock strength 50～150KJ/m
2
The polymer repeat unit structure that the polyetherimide that the present invention relates to has is as follows:
Embodiment
In order to implement the present invention better,, but not limitation of the present invention especially exemplified by the example explanation.
Embodiment 1
3640g (7 moles) dihydroxyphenyl propane diether acid anhydride, 1400g (7 moles) 4,4 '-diaminodiphenyl oxide and 218g phthalic anhydride mix in high-speed mixer, be added to by the speed of 4kg/hr and rotate in the same way in the intermeshing double-screw reactor feeding section, screw speed is 400r/min, controlling this section temperature is 200 ℃, then to be sent to temperature be 290 ℃ melt zone to material, material is melt into liquid by kneading, the water that generates is sucked and is discharged in the atmosphere, to be transported to temperature be that the water of generation is sucked and is discharged in the atmosphere in 305 ℃ the mass transfer section to liquid then.The 800g glass fibre is introduced the reactor from the toughener admission port, being transported to temperature together with original material is 320 ℃ polymeric segment, material bears 20 normal atmosphere in this section, through high speed shear and intense mixing, the polyetherimide and the water that generate is separated from reactor together.Material is residence time 4min in screw rod, and water sepn is discharged in the atmosphere, and glass enhanced polyetherimide is through tie rod, cooling, granulation.Glass fibre reinforced polyetherimide dissolves through N-Methyl pyrrolidone, filters, and recording limiting viscosity is 0.47dl/g.Plastics exemplar mechanical property is: tensile strength 115Mpa, compressive strength 170Mpa, elongation 3%, shock strength 100KJ/m
2
Embodiment 2
With 3,4 '-diaminodiphenyl oxide replacement 4, chain terminator phthalic anhydride add-on is 182g, feed rate 5kg/hr, 150 ℃ of control feeding section temperature, 300 ℃ of melt zone temperature, 310 ℃ of mass transfer section temperature, replace glass fibre with carbon fiber, add-on is 1300g, and screw speed is 300r/min, 310 ℃ of polymeric segment temperature, pressure 10 normal atmosphere, material lagging time 4.8min, other operation stepss are the same with embodiment 1 with proportioning, as a result gained polyetherimide limiting viscosity 0.55dl/g, tensile strength 145Mpa, compressive strength 210Mpa, elongation 5%, shock strength 70KJ/m
2
Embodiment 3
Removing chain terminator phthalic anhydride add-on is 356g, feed rate 3kg/hr, 272 ℃ of control feeding section temperature, 277 ℃ of melt zone temperature, 302 ℃ of mass transfer section temperature, screw speed is 550r/min, and toughener is the mixture of glass powder 1000g and carbon fiber powder 900g, 330 ℃ of polymeric segment temperature, pressure 30 normal atmosphere, material lagging time 1.6min, other prescription operation stepss are the same with embodiment 1 with proportioning, as a result gained polyetherimide limiting viscosity 0.52dl/g, tensile strength 195Mpa, compressive strength 215Mpa, elongation 3%, shock strength 55KJ/m
2
Embodiment 4
Except that not adding toughener, chain terminator phthalic anhydride add-on is 54.6 grams, and all the other prescriptions are identical with embodiment 1 with operation, gained polyetherimide limiting viscosity 0.64dl/g as a result, tensile strength 105Mpa, compressive strength 154Mpa, elongation 7.5%, shock strength 148KJ/m
2
Claims (7)
1, continuous extrusion reaction prepares the mode of polyetherimide, it is characterized in that its step comprises:
(1) high-speed mixing finely powdered dihydroxyphenyl propane diether acid anhydride, aromatic diamine and chain terminator;
(2) mixture of step (1) being added to temperature is that double-screw reactor is formed and comprised feeding section, melt zone, mass transfer section and polymeric segment in 150 ℃～275 ℃ the feeding section of double-screw reactor;
(3) carrying mixture is 275 ℃～300 ℃ melt zone to temperature, and material is melt into liquid through heating by kneading, and the water of generation is discharged in the atmosphere;
(4) liquid being transported to temperature is 300 ℃～310 ℃ mass transfer section, and the water that reaction generates is discharged in the atmosphere;
(5) be provided with the toughener admission port between mass transfer section and polymeric segment, toughener is introduced the reactor from admission port;
(6) melts and toughener being transported to temperature is 310 ℃～330 ℃ polymeric segment, generates water and is discharged in the atmosphere, and material bears 10～30 normal atmosphere, stands high speed shear and enhancing mixed;
(7) polyetherimide and generation water are separated from double-screw reactor.
Mol ratios such as 2, the method for preparing polyetherimide according to claim 1, the ratio of components that it is characterized in that described dihydroxyphenyl propane diether acid anhydride and aromatic diamine are, the amount of chain terminator phthalic anhydride is 1～10% of a dihydroxyphenyl propane diether acid anhydride weight.
3, the method for preparing polyetherimide according to claim 1 is characterized in that described aromatic diamine is from 4,3,4 '-select for a post in the diaminodiphenyl oxide a kind of.
4, the method for preparing polyetherimide according to claim 1 is characterized in that described toughener is from E type glass fibre, S type glass fibre, carbon fiber, glass powder, choose any one kind of them in the fine powder of carbon or several, add-on is 0～40% of dihydroxyphenyl propane diether acid anhydride and an aromatic diamine gross weight.
5, the method for preparing polyetherimide according to claim 1, it is characterized in that described double-screw reactor is that screw rod rotates in the same way, the intermeshing reactor of screw rod, screw diameter 35mm, length-to-diameter ratio is 48, feeding section length is 530mm, melting length is 450mm, the mass transfer segment length is 270mm, and polymeric segment length is 400mm, screw speed 250～550r/min.
6, the method for preparing polyetherimide according to claim 1 is characterized in that the speed that mixture is added to feeding section is 2～5kg/hr, and the residence time of material in double-screw reactor is 1.5～5min.
7, the method for preparing polyetherimide according to claim 1 is characterized in that the limiting viscosity of polyetherimide in N-Methyl pyrrolidone of separating is 0.45～0.65dl/g from double-screw reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410017711 CN1252137C (en) | 2004-04-15 | 2004-04-15 | Method for preparing polyetherimide through continuous extrusion reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410017711 CN1252137C (en) | 2004-04-15 | 2004-04-15 | Method for preparing polyetherimide through continuous extrusion reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563150A true CN1563150A (en) | 2005-01-12 |
| CN1252137C CN1252137C (en) | 2006-04-19 |
Family
ID=34479120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410017711 Expired - Lifetime CN1252137C (en) | 2004-04-15 | 2004-04-15 | Method for preparing polyetherimide through continuous extrusion reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1252137C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010596A (en) * | 2010-12-27 | 2011-04-13 | 南京立汉化学有限公司 | Glass fibre reinforced polyetherimide and preparation method thereof |
| CN102675639A (en) * | 2012-06-12 | 2012-09-19 | 辛庆生 | Polyetherimide product and method for preparing same |
| CN103325497A (en) * | 2013-06-25 | 2013-09-25 | 江苏凯诺电缆集团有限公司 | Covering method of class 1E category K1 cables for nuclear power station |
| CN103992477A (en) * | 2014-05-07 | 2014-08-20 | 江苏凯诺电缆集团有限公司 | Method for preparation of polyimide siloxane/carbon fiber composite material by reactive extrusion |
| US9777118B2 (en) | 2014-04-15 | 2017-10-03 | Sabic Global Technologies B.V. | Methods of manufacture of salts of hydroxy-substituted aromatic compounds and polyetherimides |
| US10457778B2 (en) | 2014-04-15 | 2019-10-29 | Sabic Global Technologies B.V. | Methods of manufacture of polyetherimides |
-
2004
- 2004-04-15 CN CN 200410017711 patent/CN1252137C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010596A (en) * | 2010-12-27 | 2011-04-13 | 南京立汉化学有限公司 | Glass fibre reinforced polyetherimide and preparation method thereof |
| CN102010596B (en) * | 2010-12-27 | 2012-07-25 | 南京立汉化学有限公司 | Glass fibre reinforced polyetherimide and preparation method thereof |
| CN102675639A (en) * | 2012-06-12 | 2012-09-19 | 辛庆生 | Polyetherimide product and method for preparing same |
| CN103325497A (en) * | 2013-06-25 | 2013-09-25 | 江苏凯诺电缆集团有限公司 | Covering method of class 1E category K1 cables for nuclear power station |
| US9777118B2 (en) | 2014-04-15 | 2017-10-03 | Sabic Global Technologies B.V. | Methods of manufacture of salts of hydroxy-substituted aromatic compounds and polyetherimides |
| US10457778B2 (en) | 2014-04-15 | 2019-10-29 | Sabic Global Technologies B.V. | Methods of manufacture of polyetherimides |
| US11130843B2 (en) | 2014-04-15 | 2021-09-28 | Shpp Global Technologies B.V. | Methods of manufacture of polyetherimides |
| CN103992477A (en) * | 2014-05-07 | 2014-08-20 | 江苏凯诺电缆集团有限公司 | Method for preparation of polyimide siloxane/carbon fiber composite material by reactive extrusion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1252137C (en) | 2006-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012794B (en) | Preparation method of polyamide-imide copolymer | |
| EP1401911A1 (en) | Modified postcondensed polyester | |
| WO1992019676A1 (en) | Mixing process for generating in-situ reinforced thermoplastics | |
| CN109054311A (en) | A kind of high temperature resistance polyester film and preparation method thereof | |
| CN1252137C (en) | Method for preparing polyetherimide through continuous extrusion reaction | |
| CN100465231C (en) | Heat resistant nylon material containing thormotropic liquid crystal polymer and its preparation method | |
| CN111138815A (en) | Low-dielectric-constant liquid crystal polymer and preparation method thereof | |
| US5981007A (en) | Extruded thermoplastic, liquid crystalline polymers and blends thereof having a planar morphology | |
| CN106750258A (en) | Film stage polyetheretherketoneresin resin PP Pipe Compound, preparation method and the application in polyether-ether-ketone/PEI alloy firm is prepared | |
| CN112745493B (en) | Heat-resistant polyester resin and preparation method thereof | |
| CN107698754B (en) | Preparation method of graphene oxide modified polyamide-6 | |
| KR20220124195A (en) | Chain cleavage to make improved polymers for 3D printing | |
| CN109627684B (en) | Ternary alloy containing aromatic polyamide and preparation method thereof | |
| CN103709681B (en) | A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof | |
| DE10136911A1 (en) | Process for preparation of a modified polyester of improved mechanical and rheological properties containing a hyperbranched polymer | |
| EP0361636A2 (en) | Polyamide-polyarylene sulfide blends | |
| WO1992017545A1 (en) | Extruded blends of thermoplastic and liquid crystalline polymers | |
| CN102942783A (en) | Composite material of polyamide (PA)6/recycled polyethylene glycol terephthalate (PET) bottle slices and preparation method thereof | |
| CN110804303B (en) | Regenerated carbon fiber reinforced PA6 material and preparation method thereof | |
| CN1055710C (en) | Composite containing carbon fibre and liquid crystal polymer | |
| CN114605633B (en) | Bulk flame-retardant nylon and preparation method and application thereof | |
| CN114989605B (en) | Polyimide resin with low thermal expansion coefficient and preparation method and application thereof | |
| CN102675639B (en) | Polyetherimide product and method for preparing same | |
| CN1073601C (en) | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer | |
| CN114149586B (en) | Chain-extended polysulfate and preparation method thereof |
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: 200235 Xuhui District, Caobao Road, No. 36, Patentee before: SHANGHAI Research Institute OF SYNTHETIC RESINS |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210203 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. |
|
| TR01 | Transfer of patent right | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060419 |
|
| CX01 | Expiry of patent term |