CN1192221A - 官能化苯乙烯聚合物及共聚物 - Google Patents
官能化苯乙烯聚合物及共聚物 Download PDFInfo
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- CN1192221A CN1192221A CN96196014.0A CN96196014A CN1192221A CN 1192221 A CN1192221 A CN 1192221A CN 96196014 A CN96196014 A CN 96196014A CN 1192221 A CN1192221 A CN 1192221A
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- polymkeric substance
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- 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
- C08F8/00—Chemical modification by after-treatment
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/02—Alkylation
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供了一种官能化的苯乙烯聚合物或共聚物,含有如式(Ⅰ)的官能化苯乙烯部分,其中R1为氢、烷基、伯或仲卤代烷基;R2为式(Ⅱ),其中n为2—10的一个整数,R3任意地为氢或烷基,X为NH、O或S。本发明的新型共聚物在制备聚合物共混物中有特别的用途。例如:通过与含羧酸的聚合物或类似物反应可将胺和醇官能化聚合物用作相容剂。
Description
本发明涉及苯乙烯和一种异烯烃的官能化共聚物。
含有苯乙烯的聚合物,尤其是对烷基苯乙烯和一种带有约4-7个碳原子的异烯烃的共聚物在本技术领域已为人们所熟知。实际上,对烷基苯乙烯和异丁烯的共聚物是低Tg的弹性体,它具有低的透气率、单向阻尼特性、优良的耐环境老化性和低的表面能,这使得它们在许多应用中尤其理想。不幸的是,这些聚合物的反应活性低及与大多数其它聚合物的相容性差。因此需要将含苯乙烯的聚合物和共聚物,尤其是异烯烃和对烷基苯乙烯的共聚物用较相容的单元进行官能化以共混。
因此本发明的目的在于通过接枝技术将含苯乙烯的聚合物用反应活性基团官能化,这将使得官能化的聚合物与其它聚合物共反应或相容。
因此,本发明提供了一种官能化的苯乙烯聚合物或共聚物,它含有具有下式的官能化苯乙烯部分:其中,R1为氢、烷基、伯或仲卤代烷基基团,R2为:其中,n为从2到10的整数,R3任意地为氢或1至10个碳原子的烷基基团,X为NH、O或S。
本发明的新型共聚物在制备聚合物共混物中具有特别的用途。例如,胺和醇官能化的聚合物通过与含羧酸的聚合物或类似物反应可以用作相容剂。
含有苯乙烯单元的聚合物可以按照本发明的方法官能化。进行官能作用的特别适合的含苯乙烯的聚合物是具有约4-7个碳原子的异烯烃和苯乙烯或由下式所表示的对烷基苯乙烯部分的共聚物。其中R1为氢、烷基、伯或仲卤代烷基,该烷基和卤代烷基具有大约1-6个碳原子。然而在本发明的实际应用中,特别优选使用异丁烯和对甲基苯乙烯的共聚物。
在路易斯酸存在的条件下,将含苯乙烯的聚合物或共聚物与下式的化合物反应使上述聚合物官能化,
在上述通式中,R3任意地为氢或具有1-约10个碳原子的烷基,A为NH、O、S和CO3,Y是2-10的整数。
当A为NH的情况下,R3优选为烷基。该化合物一个具体例子是甲基氮丙啶。当A为CO3的情况下,碳酸丙二酯尤其适合。当A为O时,环氧类,如环氧丁烷很适合。最后,当A为S时,则使用硫化乙烯。
在制备官能化含苯乙烯的聚合物时任何路易斯酸催化剂都可使用。然而,优选的路易斯酸催化剂是基于金属的,诸如:硼、铝、镓、铟、钛、锆、锡、砷、锑和铋。特别优选的是上述金属的含卤化合物诸如三氟化硼、三氯化铝、二氯化铝及类似物。
一般地,在烃稀释剂如脂族烃存在的条件下或在极性溶剂如硝基苯、二氯甲烷、1,2-二氯乙烷及类似物存在的条件下进行官能化。在本发明的实际应用中特别优选在溶剂存在的条件下实施本方法。
聚合物的官能化一般在大约-50℃至100℃的温度下进行足够时间以便在含苯乙烯的聚合物的芳环上加上官能团,即:烷基胺或烷基醇。
氮丙啶、烯化氧或碳酸烷二酯与含苯乙烯的聚合物中苯乙烯单元的比率可以在很大范围变化。然而,通常使用的是每1摩尔的含苯乙烯的聚合物中的苯乙烯部分用大约0.01-10摩尔的氮丙啶、烯化氧或碳酸烷二酯。
下列实施例证明了本发明。
实施例1:
本实施例中所用的对甲基苯乙烯和异丁烯的共聚物含有7.5%重量的对甲基苯乙烯。该共聚物的门尼粘度为50。将3.00g共聚物在一个装有冷凝器、氮扩散器(bubblier)和滴液漏斗的三颈烧瓶中溶解于30ml二氯甲烷中。在上述溶液中加入0.5g甲基氮丙啶,接着加入0.22g AlCl3。将混合物在室温下搅拌18小时。在溶液中加入100ml 50∶50的丙酮/水的混合物以分离产物。将产物用丙酮冲洗并干燥。产物含有0.17%的N,并且红外光谱图在3396cm-1处具有一吸收峰,显示胺官能度的特性。
实施例2:
用于本实施例的异丁烯和对甲基苯乙烯的共聚物含有6.0%重量的对甲基苯乙烯。该共聚物的重均分子量(Mw)为5400,数均分子量(Mm)为2000,多分散性为2.7。
将2.10g此共聚物在一带有冷凝器、氮扩散器和滴液漏斗的三颈烧瓶中溶解于30ml无水二氯甲烷中。在上述溶液中加入1.0g 1,2-环氧丁烷,然后加入1.2g AlCl3。用氮汽提法除去溶剂二氯甲烷并将产物用100ml 1N的HCl搅拌1小时以溶解铝盐。滗去液相后,再将固体产物用丙酮冲洗并真空干燥。
产物的FTIR在3452cm-1处显示出羟基的特性吸收。
Claims (11)
2.权利要求1的官能化聚合物,其中苯乙烯聚合物是苯乙烯和一种具有大约4-7个碳原子的异烯烃的共聚物。
3.权利要求2的官能化共聚物,其中苯乙烯聚合物是对烷基苯乙烯和一种具有大约4-7个碳原子的异烯烃的共聚物。
4.权利要求3的聚合物,其中R1为甲基。
5.权利要求3的聚合物,其中X为NH。
6.权利要求3的聚合物,其中X为O。
7.权利要求5或6聚合物,其中R3为大约1-10个碳原子的烷基。
9.权利要求8的方法,其中在溶剂存在的条件下进行接触,化合物与聚合物或共聚物中苯乙烯部分的摩尔比率范围为大约0.01∶1至10∶1。
10.权利要求9的方法,其中A为NH。
11.权利要求9的方法,其中A为O。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/508,640 | 1995-07-28 | ||
US08/508,640 US5741864A (en) | 1995-07-28 | 1995-07-28 | Functionalized styrene polymers and copolymers |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1192221A true CN1192221A (zh) | 1998-09-02 |
Family
ID=24023495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96196014.0A Pending CN1192221A (zh) | 1995-07-28 | 1996-07-12 | 官能化苯乙烯聚合物及共聚物 |
Country Status (13)
Country | Link |
---|---|
US (2) | US5741864A (zh) |
EP (1) | EP0842202B1 (zh) |
JP (1) | JPH11510533A (zh) |
CN (1) | CN1192221A (zh) |
BR (1) | BR9610030A (zh) |
CA (1) | CA2223859A1 (zh) |
DE (1) | DE69621619T2 (zh) |
ES (1) | ES2175110T3 (zh) |
MX (1) | MX9800636A (zh) |
PL (1) | PL185031B1 (zh) |
RU (1) | RU2192433C2 (zh) |
TW (1) | TW429263B (zh) |
WO (1) | WO1997005175A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998004598A1 (fr) | 1996-07-31 | 1998-02-05 | Mitsubishi Chemical Corporation | Echangeurs de cations ou agents chelateurs et leur procede de preparation |
CA2223114A1 (en) * | 1997-11-28 | 1999-05-28 | Brent R. Stranix | Functional polymers with carbon-linked functional groups |
CA2222833A1 (en) * | 1997-11-28 | 1999-05-28 | Brent R. Stranix | Functional polymers bearing non-metal oxyacid derivatives on dimethylene spacers |
WO2000046258A1 (en) * | 1999-02-04 | 2000-08-10 | The Dow Chemical Company | Functionalized ethylene/vinyl or vinylidene aromatic interpolymers |
US20040081829A1 (en) * | 2001-07-26 | 2004-04-29 | John Klier | Sulfonated substantiallly random interpolymer-based absorbent materials |
US9914817B2 (en) | 2015-09-30 | 2018-03-13 | Exxonmobil Chemical Patents Inc. | Polycyclic aromatic hydrocarbon functionalized isobutylene copolymers for dispersing graphene and graphite |
JP2018532846A (ja) | 2015-09-30 | 2018-11-08 | エクソンモービル ケミカル パテンツ インコーポレイテッド | 機能性ポリマーコームアームを有するイソブチレンコポリマー主鎖のコーム−ブロックコポリマー |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2915512A (en) * | 1956-11-27 | 1959-12-01 | Monsanto Chemicals | Aminated polystyrenes |
US3070579A (en) * | 1958-09-15 | 1962-12-25 | Dow Chemical Co | Vinyl aromatic polymers having reactive end groups and process for making the same |
US3175997A (en) * | 1959-10-23 | 1965-03-30 | Phillips Petroleum Co | Method of preparing polymers containing hydroxy end groups |
US3111361A (en) * | 1960-05-11 | 1963-11-19 | Rohm & Haas | Synthetic fibers and fabrics thereof, polymers therefor, and methods of producing them |
DE1144007B (de) * | 1961-07-27 | 1963-02-21 | Wolfen Filmfab Veb | Verfahren zur Herstellung von polyfunktionellen Anionenaustauscherharzen |
DE2211134C3 (de) * | 1972-03-08 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von vernetzten, unlöslichen, aromatische Kerne enthaltenden organischen Polymeren mit Aminoalkylgruppen und mit anionenaustauschenden Eigenschaften |
US3900451A (en) * | 1973-08-24 | 1975-08-19 | Dow Chemical Co | Method of making sulfhydryl-containing polymers |
US4471079A (en) * | 1982-03-04 | 1984-09-11 | Pilot Man-Nen Hitsu Kabushiki Kaisha | Aqueous ink |
US4684667A (en) * | 1986-04-21 | 1987-08-04 | The Dow Chemical Company | Tertiary amine resins and use thereof |
DE3720322A1 (de) * | 1987-06-19 | 1988-12-29 | Basf Ag | Verfahren zur herstellung von mercapto-endgruppen aufweisenden homo- oder copolymerisaten und deren verwendung |
JPH04202203A (ja) * | 1990-11-29 | 1992-07-23 | Mitsui Toatsu Chem Inc | イオン交換樹脂の製造方法 |
US5466758A (en) * | 1994-04-13 | 1995-11-14 | Yoon-Sik; Lee | Process for preparing polystyrenes having β hydroxy group and polyglycol-grafted polystyrenes thereof |
-
1995
- 1995-07-28 US US08/508,640 patent/US5741864A/en not_active Expired - Fee Related
-
1996
- 1996-07-12 EP EP96924451A patent/EP0842202B1/en not_active Expired - Lifetime
- 1996-07-12 PL PL96324650A patent/PL185031B1/pl unknown
- 1996-07-12 CN CN96196014.0A patent/CN1192221A/zh active Pending
- 1996-07-12 RU RU98103459/04A patent/RU2192433C2/ru not_active IP Right Cessation
- 1996-07-12 CA CA002223859A patent/CA2223859A1/en not_active Abandoned
- 1996-07-12 WO PCT/US1996/011602 patent/WO1997005175A1/en active IP Right Grant
- 1996-07-12 ES ES96924451T patent/ES2175110T3/es not_active Expired - Lifetime
- 1996-07-12 BR BR9610030A patent/BR9610030A/pt not_active IP Right Cessation
- 1996-07-12 DE DE69621619T patent/DE69621619T2/de not_active Expired - Fee Related
- 1996-07-12 MX MX9800636A patent/MX9800636A/es not_active IP Right Cessation
- 1996-07-12 JP JP9507614A patent/JPH11510533A/ja active Pending
- 1996-07-30 TW TW085109297A patent/TW429263B/zh active
-
1998
- 1998-02-10 US US09/021,479 patent/US6103832A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2223859A1 (en) | 1997-02-13 |
DE69621619D1 (de) | 2002-07-11 |
EP0842202A1 (en) | 1998-05-20 |
EP0842202A4 (en) | 1999-04-28 |
BR9610030A (pt) | 1999-07-06 |
JPH11510533A (ja) | 1999-09-14 |
EP0842202B1 (en) | 2002-06-05 |
US5741864A (en) | 1998-04-21 |
US6103832A (en) | 2000-08-15 |
TW429263B (en) | 2001-04-11 |
PL324650A1 (en) | 1998-06-08 |
ES2175110T3 (es) | 2002-11-16 |
DE69621619T2 (de) | 2003-02-06 |
RU2192433C2 (ru) | 2002-11-10 |
WO1997005175A1 (en) | 1997-02-13 |
PL185031B1 (pl) | 2003-02-28 |
MX9800636A (es) | 1998-04-30 |
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