JP4940130B2 - ブロックコポリマーの調製の改良方法及びそれから調製されるブロックコポリマー - Google Patents
ブロックコポリマーの調製の改良方法及びそれから調製されるブロックコポリマー Download PDFInfo
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- JP4940130B2 JP4940130B2 JP2007505666A JP2007505666A JP4940130B2 JP 4940130 B2 JP4940130 B2 JP 4940130B2 JP 2007505666 A JP2007505666 A JP 2007505666A JP 2007505666 A JP2007505666 A JP 2007505666A JP 4940130 B2 JP4940130 B2 JP 4940130B2
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- Prior art keywords
- block copolymer
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- homoblock
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- 238000000034 method Methods 0.000 title claims description 80
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- 238000006243 chemical reaction Methods 0.000 claims description 80
- 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 claims description 69
- 239000000178 monomer Substances 0.000 claims description 45
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- -1 aromatic diol Chemical class 0.000 claims description 20
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- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
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- 125000005843 halogen group Chemical group 0.000 claims description 9
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- 239000003513 alkali Substances 0.000 claims description 6
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
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- 125000001174 sulfone group Chemical group 0.000 claims description 2
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- 229920005649 polyetherethersulfone Polymers 0.000 claims 4
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- 229920006030 multiblock copolymer Polymers 0.000 description 9
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
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- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 5
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/005—Modified block copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/906—Polysulfone
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyethers (AREA)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN400/MUM/2004 | 2004-04-01 | ||
| US10/897,405 | 2004-07-23 | ||
| US10/897,405 US7312282B2 (en) | 2004-04-01 | 2004-07-23 | Process of preparation of block copolymers and the block copolymers prepared therefrom |
| IN400MU2004 IN213584B (https=) | 2004-04-01 | 2005-03-29 | |
| PCT/IB2005/000864 WO2005095491A1 (en) | 2004-04-01 | 2005-03-29 | An improved process of preparation of block copolymers and the block copolymers prepared therefrom |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2007530763A JP2007530763A (ja) | 2007-11-01 |
| JP2007530763A5 JP2007530763A5 (https=) | 2008-05-15 |
| JP4940130B2 true JP4940130B2 (ja) | 2012-05-30 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007505666A Expired - Fee Related JP4940130B2 (ja) | 2004-04-01 | 2005-03-29 | ブロックコポリマーの調製の改良方法及びそれから調製されるブロックコポリマー |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7312282B2 (https=) |
| JP (1) | JP4940130B2 (https=) |
| KR (1) | KR101414909B1 (https=) |
| CN (1) | CN1942506B (https=) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7382873B2 (en) * | 2003-06-27 | 2008-06-03 | General Motors Corporation | Method and system for automatic calling unit replenishment |
| US20070117962A1 (en) * | 2005-11-21 | 2007-05-24 | General Electric Company | High heat polyethersulfone compositions |
| KR20110138266A (ko) | 2009-04-03 | 2011-12-26 | 바스프 에스이 | 염소 저함유 폴리비페닐 술폰 중합체의 제조 방법 |
| ES2436367T3 (es) * | 2009-06-08 | 2013-12-30 | Basf Se | Procedimiento para la preparación de copolímeros de bloque de poliarilenéter |
| MY162228A (en) | 2009-08-20 | 2017-05-31 | Basf Se | Method for producing low-halogen polybiphenylsulfone polymers |
| JP5703645B2 (ja) | 2009-09-29 | 2015-04-22 | 住友化学株式会社 | 芳香族ポリスルホン樹脂及びその膜 |
| CN103012796B (zh) * | 2011-09-23 | 2014-07-16 | 北京师范大学 | 一种制备聚砜的方法 |
| EP2662399B1 (de) * | 2012-05-11 | 2014-07-16 | Ems-Patent Ag | Verfahren zur Herstellung von Polysulfonen |
| EP2662398B1 (de) * | 2012-05-11 | 2014-07-16 | Ems-Patent Ag | Verfahren zur Herstellung von Polysulfonen und Polysulfone |
| WO2014057042A1 (en) | 2012-10-12 | 2014-04-17 | Solvay Specialty Polymers Usa, Llc | High temperature sulfone (hts) foam meterials |
| EP2738219A1 (en) | 2012-11-28 | 2014-06-04 | Solvay Specialty Polymers USA, LLC. | PAEK/PAES compositions |
| EP3082706B1 (en) | 2013-12-16 | 2018-05-30 | Pride Mobility Products Corporation | Elevated height wheelchair |
| KR101704475B1 (ko) * | 2014-08-25 | 2017-02-10 | 주식회사 삼양사 | 내열성 및 내화학성이 우수한 폴리술폰 공중합체 및 그 제조방법 |
| US20180298192A1 (en) | 2015-10-14 | 2018-10-18 | Sabic Global Technologies B.V. | Methods of manufacture of thermoplastic polymers |
| EP3383935B1 (en) | 2015-12-01 | 2022-04-27 | Solvay Specialty Polymers USA, LLC. | Polymer compositions including a poly(ether sulfone) blend and articles made therefrom |
| US20200384681A1 (en) * | 2017-04-24 | 2020-12-10 | Solvay Specialty Polymers Usa, Llc | Method of making a three-dimensional object using ppsu |
| WO2019219870A1 (en) * | 2018-05-17 | 2019-11-21 | Solvay Specialty Polymers Usa, Llc | Process for preparing a poly(biphenyl ether sulfone) (ppsu) polymer |
| FR3085040B1 (fr) * | 2018-08-20 | 2020-10-23 | Roquette Freres | Procede de preparation de polyethersulfones aromatiques a base d'isohexide |
| KR102889828B1 (ko) * | 2019-03-18 | 2025-11-24 | 사이언스코 스페셜티 폴리머즈 유에스에이, 엘엘씨 | 관능화된 폴리(아릴 에테르 설폰) 공중합체 |
| CN110452383A (zh) * | 2019-08-28 | 2019-11-15 | 江西金海新能源科技有限公司 | 一种高热稳定性封端砜聚合物、制备方法及其在餐具上的应用 |
| EP3822302A1 (en) * | 2019-11-13 | 2021-05-19 | Solvay Specialty Polymers USA, LLC. | Functionalized poly(aryl ether sulfones) copolymers and polymer adducts obtained therefrom |
| JP2022546718A (ja) | 2019-09-09 | 2022-11-07 | ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー | 官能化ポリ（アリールエーテルスルホン）コポリマー及びそれから得られるポリマー付加物 |
| CN112159526B (zh) * | 2020-09-08 | 2023-04-25 | 威海金泓管材有限公司 | 降低ppsu管材吸水率的工业化制备方法 |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446120A (en) * | 1985-10-07 | 1995-08-29 | The Boeing Company | Polyethersulfone oligomers and blends |
| US4476184A (en) * | 1983-08-09 | 1984-10-09 | The Boeing Company | Thermally stable polysulfone compositions for composite structures |
| US4533721A (en) * | 1983-08-23 | 1985-08-06 | Showa Denko Kabushiki Kaisha | Chlorine containing polyether sulfone polymers and preparation thereof |
| DE3614594A1 (de) | 1986-04-30 | 1988-01-07 | Basf Ag | Hochtemperaturbestaendige formmassen |
| JPH0737525B2 (ja) * | 1986-07-23 | 1995-04-26 | 旭化成工業株式会社 | ブロツク共重合体の製造方法 |
| DE3785421T2 (de) * | 1986-11-20 | 1993-10-14 | Dainippon Ink & Chemicals | Harz auf der Basis eines Polyphenylensulfid-Polyphenylensulfonblockkopolymerisats, Verfahren zur Herstellung des Kopolymers und geformter Gegenstand. |
| JPS63256653A (ja) * | 1987-04-14 | 1988-10-24 | Asahi Glass Co Ltd | 耐熱性樹脂組成物 |
| CA1334469C (en) * | 1988-03-03 | 1995-02-14 | Marvin Edward Sauers | Poly(aryl ether sulfones) with improved environmental stress-crack resistance and medical devices made therefrom |
| US5180750A (en) * | 1988-07-29 | 1993-01-19 | Asahi Glass Company Ltd. | Anion exchanger |
| JPH0813326B2 (ja) * | 1988-09-06 | 1996-02-14 | 旭硝子株式会社 | 酸の新規な回収方法 |
| JP2522356B2 (ja) * | 1988-09-01 | 1996-08-07 | 旭硝子株式会社 | 新規な架橋構造を有する陰イオン交換体 |
| JPH0722710B2 (ja) * | 1988-07-29 | 1995-03-15 | 旭硝子株式会社 | 陰イオン交換体 |
| DE3900675A1 (de) * | 1989-01-12 | 1990-07-19 | Basf Ag | Hochtemperaturbestaendige polysulfon-polyimid-blockcopolykondensate, verfahren zu ihrer herstellung durch schmelzkondensation und ihre verwendung |
| US5077351A (en) * | 1989-04-03 | 1991-12-31 | Amoco Corporation | Process for the preparation of polycarbonate and/or polyarylate block copolymers with poly(aryl ethers) |
| JP2875550B2 (ja) * | 1989-07-07 | 1999-03-31 | ダイセル化学工業株式会社 | 芳香族ポリスルホン共重合体の製造方法 |
| US5204400A (en) * | 1990-06-22 | 1993-04-20 | Amoco Corporation | Poly(biphenyl ether sulfone)compositions |
| JPH0680799A (ja) * | 1992-08-28 | 1994-03-22 | Asahi Glass Co Ltd | 耐蝕性陰イオン交換膜 |
| US5378763A (en) * | 1992-10-30 | 1995-01-03 | Enichem S.P.A. | Miscible blends of polysulfones and aromatic alkyl methacrylate polymers |
| US5500479A (en) * | 1994-09-23 | 1996-03-19 | Bayer Corporation | Polyethersulfone/polyester block copolymers and a process for their preparation |
| US5700902A (en) * | 1995-07-27 | 1997-12-23 | Circe Biomedical, Inc. | Block copolymers |
| US5633331A (en) * | 1996-05-02 | 1997-05-27 | The Dow Chemical Company | Blends of polysulfone with diaryl fluorene carbonate polymer |
| US5798437A (en) * | 1996-07-29 | 1998-08-25 | Circe Biomedical, Inc. | Thermoplastic block copolymers |
| US6172180B1 (en) * | 1998-08-25 | 2001-01-09 | Circe Biomedical, Inc. | Highly branched block copolymers |
| JP2003522266A (ja) * | 2000-02-09 | 2003-07-22 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | ハイパーブランチ両親媒性ポリマー添加剤及び増加された表面エネルギーを有するポリマー組成物 |
| DE10007272B4 (de) * | 2000-02-17 | 2005-04-07 | Membrana Gmbh | Blockcopolymere mit sulfonierten Polyethersulfoneinheiten |
| JP4032749B2 (ja) * | 2002-01-11 | 2008-01-16 | 宇部興産株式会社 | 芳香族ポリエーテルスルホンブロック共重合体の製造法 |
-
2004
- 2004-07-23 US US10/897,405 patent/US7312282B2/en not_active Expired - Lifetime
-
2005
- 2005-03-29 CN CN2005800120498A patent/CN1942506B/zh not_active Expired - Fee Related
- 2005-03-29 JP JP2007505666A patent/JP4940130B2/ja not_active Expired - Fee Related
- 2005-03-29 KR KR1020127012131A patent/KR101414909B1/ko not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120066074A (ko) | 2012-06-21 |
| CN1942506A (zh) | 2007-04-04 |
| US20050228149A1 (en) | 2005-10-13 |
| JP2007530763A (ja) | 2007-11-01 |
| US7312282B2 (en) | 2007-12-25 |
| CN1942506B (zh) | 2011-03-23 |
| KR101414909B1 (ko) | 2014-07-04 |
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