CN1120341A - 具有末端甲硅烷基的丁二烯聚合物 - Google Patents
具有末端甲硅烷基的丁二烯聚合物 Download PDFInfo
- Publication number
- CN1120341A CN1120341A CN94191643A CN94191643A CN1120341A CN 1120341 A CN1120341 A CN 1120341A CN 94191643 A CN94191643 A CN 94191643A CN 94191643 A CN94191643 A CN 94191643A CN 1120341 A CN1120341 A CN 1120341A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- butadiene
- polymeric
- silyl
- silyl ether
- 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
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
Abstract
具有末端甲硅烷基的氢化丁二烯聚合物由(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚,作为甲硅烷基醚引发剂或封端剂或两者加到聚合物链中进行制备。然后,将甲硅烷基转化为酚基。该聚合物可用于生产涂料、密封剂、和粘合剂,以及与聚酯、聚酰胺、和聚碳酸酯的嵌段共聚物。
Description
本发明涉及生产具有末端甲硅烷基的氢化丁二烯聚合物以及该聚合物在生产涂料和其它高分子量聚合物方面的应用。
在许多参考文献包括讲述氢化丁二烯聚合物的丁二烯1,2-加成量(35-55%)与玻璃化温度之间关系的美国专利Re.27,145中,已叙述了用锂引发剂例如仲丁基锂进行共轭二烯的阴离子催化聚合以及残余不饱和键的氢化。
在美国专利4,417,029、4,518,753以及4,753,991中叙述了终止活性阴离子聚合物以生成官能端基。其中,可转化为末端酚基的末端甲硅烷基对本发明是特别有意义的。
如美国专利4,518,753和3,652,732中所述,众所周知,对于不饱和的1,3-丁二烯聚合物而言,为了获得低粘度,1,2-加成必须较低。然而,当这些聚合物被氢化时,它们是结晶固体。这种结晶聚合物可以从Mitsubishi买到,并命名为POLYT AIL H,其熔点为72℃。
如美国专利4,020,125中所述,当丁二烯的1,2-加成量超过30%时,氢化丁二烯聚合物是非结晶的。如美国专利4,866,120和4,020,125中所述,非结晶的氢化丁二烯聚合物在低分子量的情况下是粘性液体。Mitsubishi生产的POLYT AIL HA聚合物和Nippon Soda生产的NISSO GI-2000聚合物是低分子量氢化丁二烯聚合物的商品实例,它们具有末端官能团,且其1,2-加成量约为84%。
本发明的一个目的是提供可转化为末端酚基的具有末端甲硅烷基氢化丁二烯聚合物。本发明的另一个目的是提供用以生产无溶剂涂料和生产高分子量聚合物的低粘度聚合物。
具有一个或多个末端甲硅烷基的氢化丁二烯聚合物是通过在活性丁二烯分子的末端聚合(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚而制备的。这些甲硅烷基被转化为酚基。(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚也可以用作产生末端甲硅烷基的聚合引发剂。当采用凝胶渗透色谱法测定,其峰值分子量为1,000-10,000时,本发明的氢化丁二烯聚合物可以在室温下使用而无需溶剂。
如美国专利4,039,593和Re.27,145中所述,采用锂引发剂进行共轭二烯烃的阴离子催化聚合是众所周知的。聚合从单锂、二锂或多锂引发剂开始,它可以在每一锂位上产生活性聚合物骨架。典型的含有聚合共轭二烯烃的活性聚合物结构是:
X-B-Li
X-A-B-Li
X-A-B-A-Li
Li-B-Y-B-Li
Li-A-B-Y-B-A-Li式中B表示一种或多种共轭二烯烃例如丁二烯或异戊二烯的聚合单元,A表示一种或多种芳族乙烯系化合物例如苯乙烯,X表示单锂引发剂的残基例如仲丁基锂,和Y表示二锂引发剂的残基例如仲丁基锂和m-二异丙烯基苯的二加合物。一些包括有关多锂引发剂或苯乙烯和共轭二烯的无规单元的结构,虽然在本技术领域中是已知的,然而其实用性通常有限。
共轭二烯烃的阴离子催化聚合通常采用结构改进剂例如乙醚或甘醇二甲醚(1,2-二乙氧基乙烷)加以控制,以便获得所需的1,4-加成量。如Re 27,145中所述,丁二烯聚合物或共聚物的1,2-加成量在氢化后会显著地影响弹性。
具有末端官能团的1,3-丁二烯聚合物的1,2-加成会影响聚合物的粘度。例如,采用6%(以体积计)乙醚或1000ppm甘醇二甲醚,在50℃下聚合时,1,2-加成量可达40%。
采用仲丁基锂(s-BuLi)和m-二异丙烯基苯的二加合物的二锂引发也需要在非活性的偶合剂例如乙醚、甘醇二甲醚或三乙胺的存在下进行,否则,会得到单锂引发。如上所述,在阴离子催化聚合过程中醚通常是存在的,为了获得特定聚合物结构所需的醚量,通常已足以产生二锂引发。
阴离子催化聚合通常采取加水将锂以氢氧化锂(LiOH)的形式除去或通过加醇(ROH)将锂以醇锂(LiOR)的形式除去而终止。对于具有末端甲硅烷基的聚合物而言,采用具有以下结构代表受护羟基-苯乙烯单体的(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚,首先将常规的聚合物链终止:式中,R是氢或具有至多10个碳原子的烷基,且优选氢或具有1或2个碳原子的烷基,更优选氢或甲基。该末端甲硅烷基以下式表示式中,P表示除去锂之前的聚合物。
当甲硅烷基醚的单体与烷基锂(R1-Li),优选仲丁基锂反应时,也可以形成聚合引发剂。该聚合引发剂具有下式结构:式中,R是氢或具有至多10个碳原子的烷基,和R1是具有2-20个碳原子的烷基。采用常规的聚合方法该引发剂可从共轭二烯产生线性的、支链的、或星形的聚合物。
用甲硅烷醚引发剂制备的活性聚合物可以通过与偶合剂例如四氯化硅、二氯二甲硅烷、或二乙烯苯反应或与封端剂例如环氧乙烷、二氧化碳、或上述产生多端基的甲硅烷基醚单体反应而终止。
优选加热或通过与脱甲硅基试剂例如酸或氟化四丁铵反应除去甲硅烷基,优选通过与用于优选方法的氢化催化步骤中所用的酸反应除去。脱甲硅基的结果产生末端酚基。
如美国专利Re.27,145和4,970,254以及美国专利5,166,277中所述,采用镍催化剂可以使丁二烯聚合物中不饱和度的氢化达到至少90%,优选至少95%。优选的催化剂是下面的实施例1中详细叙述的2-乙基己酸镍和三乙基铝的混合物。
具有两个或多个末端官能团选自羟基、羧基、酚基、环氧基、和胺基的丁二烯聚合物,当其峰值分子量为500-50,000,优选500-20,000时可以使用。这些官能团不呈现明显的原子吸引力,否则,将固化官能化的聚合物。
本发明的聚合物具有常规的实用性例如生产涂料、密封剂、和粘合剂。此外,如美国专利4,994,526中所述,在生产聚碳酸酯、聚酯、和聚酰胺的过程中,这种具有约两个或多个末端酚基的丁二烯聚合物可以与常规的化合物共聚。
根据本发明优选的实施方案,每分子中具有约两个末端甲硅烷基的氢化1,3-丁二烯聚合物优选从式A中R是氢或甲基的(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚生产。在室温下,当采用聚苯乙烯标准通过凝胶渗透色谱法测定,其峰值分子量为1,000-10,000时,这种聚合物是低粘度的液体,且1,2-加成量为40-70%。
以下实施例说明本发明的具体实施方案,然而绝不限制本发明权利要求的范围。
在这些实施例中报道的峰值分子量是采用具有已知峰值分子量的聚苯乙烯标准标定,通过凝胶渗透色谱法测定的。所有用于GPC样品的溶剂均为四氢呋喃。该聚合物的微结构(1,2-加成)通过13C和1H NMR在氯仿溶液中测定。
实施例1
可按下述方法制备每分子中具有约两个末端甲硅烷基的线性氢化丁二烯聚合物;采用聚苯乙烯标准通过凝胶渗透色谱(GPC)测定,其峰值分子量为5,800(Mw/Mn=1.13)且通过核磁共振(NMR)方法测定1,2-加成量为88%。采用聚合1,3-丁二烯的甲硅烷基醚引发剂合成活性丁二烯前体聚合物。采用甲硅烷基醚单体将该活性聚合物链端封端,以提供具有末端的、甲硅烷基官能度的线性前体聚合物。采用Ni/Al催化剂氢化该聚合物,于是,甲硅烷基就转化为末端酚基。
为了合成甲硅烷基醚引发剂,将250毫升环己烷、10.0毫升四氢呋喃、以及0.55克未取代的(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚(SST)(0.002摩尔)在约5℃、惰性氮气气氛下在500毫升的玻璃瓶反应容器中混合。通过用s-BuLi溶液滴定,将可能干扰阴离子催化聚合的杂质除去,直到生成不变的微黄色为止。然后,按存在的每当量SST,用1当量s-BuLi(0.002摩尔)处理净化后的溶液。在5℃下反应10分钟,得到所需的甲硅烷基醚引发剂溶液。
在引发剂生成后,在氮气气氛中于5℃下添加0.183摩尔1,3-丁二烯。聚合的温升通过冷却反应器控制,使反应混合物的温度保持在5℃。1.5小时后,聚合反应基本上结束。
将含活性聚合物的溶液在5℃下与0.55克SST(0.002摩尔)再反应。让反应进行40分钟,然后,用20毫升MeOH终止。通过在过量5倍的异丙醇中沉淀聚合物回收该聚合物。
采用1H NMR对聚合物进行分析,显示出由2摩尔%SST和98摩尔%丁二烯组成的具有约90%1,2-加成的组合物。
将具有末端甲硅烷基的8.95克丁二烯聚合物等分试样与586克环己烷装入1升高压釜中,用镍/铝催化剂进行氢化。该催化剂(190ppm Ni)预先通过2-乙基己酸镍与三乙基铝按其量足以达到2.6摩尔铝与1摩尔镍之比,在环己烷中反应而制备。采用氢在32℃下对该聚合物溶液鼓泡2分钟。然后,引入16.14克催化剂,并在反应器中充入氢气使压力达到50巴(700磅/平方英寸,表压)。接着,就发生放热的氢化反应。
1小时后,反应溶液的温度升高到80℃,让反应持续进行总计2小时17分钟。
通过用HCl酸化将氢化催化剂从聚合物胶泥中除去,然后,用具有甲醇∶盐酸(浓度37%,水中)=5∶1的4份甲醇/酸洗涤液萃取。1H和13C NMR都证实,至少98%的烯属不饱和键被氢化。
在除去氢化催化剂的步骤中,继甲硅烷基暴露在HCl中之后,氢化的丁二烯聚合物中包含了酚基。
实施例2
除了用添加0.006摩尔与乙基·己烯基苯混合的二乙烯苯(55wt%DVB)来代替第二次添加SST之外,按实施例1中所述的方法制备具有末端酚基的活性氢化丁二烯聚合物。所得的聚合物具有星形结构,其中,在甲硅烷基转化为酚基之前,每一分支具有的峰值分子量为约5,800。
实施例3
除了将甲硅烷基醚引发剂与丁二烯单体之比调节到提供峰值分子量为4,000,并添加足够的乙醚将1,2-加成减小到50%之外,按实施例1中所述的方法制备具有末端酚基的氢化后的丁二烯聚合物。
实施例4
除了在环己烷中进行聚合以及将1,2-加成减小到15%之外,按实施例1中所述的方法制备具有末端酚基的氢化后的丁二烯聚合物。
Claims (10)
2.根据权利要求1的聚合物,其中,该末端甲硅烷基是从(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚引发剂、(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚单体,或两者生产的。
3.根据权利要求2的聚合物,其中,该聚合物具有线性结构、每分子中至少两个甲硅烷基、以及1,2-加成量为30-70%。
4.根据权利要求3的聚合物,其中,该聚合的丁二烯具有的峰值分子量为500-20,000。
5.根据权利要求4的聚合物,其中,该聚合的丁二烯至少95%被氢化。
6.根据权利要求5的聚合物,其中,该峰值分子量为1,000-10,000。
7.一种通过将(4-乙烯基亚苯基)二甲基(叔丁基)甲硅烷基醚与聚合的1,3-丁二烯反应且氢化至少90%不饱和键而生产的聚合物组合物。
8.根据权利要求7的聚合组合物,其中该聚合的1,3-丁二烯具有的峰值分子量为1,000-10,000。
9.根据权利要求8的聚合物组合物,其中该聚合的1,3-丁二烯通过将甲硅烷基醚与烷基锂反应,然后添加1,3-丁二烯来生产。
10.根据权利要求9的聚合组合物,其中在氢化后,该聚合物与HCl反应。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/029,866 | 1993-03-11 | ||
US08/029,866 US5336726A (en) | 1993-03-11 | 1993-03-11 | Butadiene polymers having terminal silyl groups |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1120341A true CN1120341A (zh) | 1996-04-10 |
CN1057778C CN1057778C (zh) | 2000-10-25 |
Family
ID=21851324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94191643A Expired - Fee Related CN1057778C (zh) | 1993-03-11 | 1994-03-09 | 具有末端甲硅烷基的丁二烯聚合物 |
Country Status (10)
Country | Link |
---|---|
US (1) | US5336726A (zh) |
EP (1) | EP0688341B1 (zh) |
JP (1) | JP3476823B2 (zh) |
KR (1) | KR100312402B1 (zh) |
CN (1) | CN1057778C (zh) |
BR (1) | BR9405897A (zh) |
DE (1) | DE69403784T2 (zh) |
ES (1) | ES2102850T3 (zh) |
TW (1) | TW264485B (zh) |
WO (1) | WO1994020553A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100562529C (zh) * | 2003-04-04 | 2009-11-25 | 株式会社普利司通 | 可固化的密封胶组合物 |
CN101959903A (zh) * | 2007-12-28 | 2011-01-26 | 株式会社普利司通 | 羟芳基官能聚合物 |
CN102482186A (zh) * | 2009-06-30 | 2012-05-30 | 株式会社普利司通 | 阴离子聚合引发剂和工艺 |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU1922095A (en) * | 1994-02-18 | 1995-09-04 | Fmc Corporation | New functionalized initiators for anionic polymerization |
US6197891B1 (en) | 1994-05-13 | 2001-03-06 | Fmc Corporation | Functionalized chain extended initiators for anionic polymerization |
US5478899A (en) * | 1994-10-27 | 1995-12-26 | Shell Oil Company | Alkoxy silyl capping agents for making terminally functionalized polymers |
US5922810A (en) * | 1995-07-31 | 1999-07-13 | Fmc Corporation | Deprotection of protected functional polymers |
WO1997048731A1 (en) * | 1996-06-18 | 1997-12-24 | Fmc Corporation | Protected functionalized telechelic polymers and processes for making the same |
US5965681A (en) * | 1996-06-18 | 1999-10-12 | Fmc Corporation | Protected functionalized telechelic polymers and processes for making the same |
AU3641897A (en) | 1996-07-17 | 1998-02-09 | Conrad W Kamienski | Protected functionalized heterotelechelic polymers and processes for preparing the same |
US6153706A (en) * | 1997-07-30 | 2000-11-28 | Fmc Corporation | Protected multi-functionalized star polymers and processes for making the same |
CA2342788C (en) | 1998-08-20 | 2008-10-14 | Kaneka Corporation | Resin composition, polymer and process for producing polymer |
US6228947B1 (en) | 1999-02-26 | 2001-05-08 | Shell Oil Company | Deprotection of polymers prepared with silyloxy protected functional initiators by reaction with aqueous fluoroboric acid |
US20030069366A1 (en) * | 2001-09-17 | 2003-04-10 | Letchford Robert J. | Urethane oligomers of heterotelechelic amine functional polyolefins |
US6867264B2 (en) | 2002-08-28 | 2005-03-15 | Kraton Polymers U.S. Llc | Process for removing residual silicon species from hydrocarbon solvents |
US7608664B2 (en) * | 2005-01-18 | 2009-10-27 | Bridgestone Corporation | Curable sealant composition and method for manufacturing same |
BRPI1015573B1 (pt) | 2009-07-01 | 2019-11-12 | Bridgestone Corp | método para fabricação de interpolímero com funcionalidade hidróxi-arila por polimerização iniciada via radical livre |
CN104892975B (zh) * | 2010-02-28 | 2017-07-25 | 株式会社普利司通 | 制备填充的橡胶组合物的方法 |
US8637600B2 (en) | 2010-08-11 | 2014-01-28 | Bridgestone Corporation | Processing of rubber compositions including siliceous fillers |
Family Cites Families (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3415898A (en) * | 1967-02-09 | 1968-12-10 | Phillips Petroleum Co | Polyolefin hydrogenation process |
US3652732A (en) * | 1968-11-05 | 1972-03-28 | Exxon Research Engineering Co | Solventless encapsulating block copolymers |
USRE27145E (en) * | 1969-05-20 | 1971-06-22 | Side-chain | |
JPS5014277B2 (zh) * | 1971-09-14 | 1975-05-26 | ||
US3770698A (en) * | 1971-12-17 | 1973-11-06 | C Riew | Phenol terminated carboxy containing diene elastomers |
BE793660A (en) * | 1973-01-04 | 1973-05-02 | Goodrich Co B F | Phenolic terminated elastomers - from carboxy terminated diene elastomers for impact modifying resins |
US3935342A (en) * | 1973-02-09 | 1976-01-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Hydrophilization of non-polar surfaces |
US4039593A (en) * | 1973-05-18 | 1977-08-02 | Lithium Corporation Of America | Preparation of hydroxy-terminated conjugated diene polymers |
JPS5224559B2 (zh) * | 1973-12-14 | 1977-07-01 | ||
DE2431394C3 (de) * | 1974-06-29 | 1978-10-12 | Th. Goldschmidt Ag, 4300 Essen | Verfahren zur Herstellung von PoIyorganosiloxanblockcopolymeren |
US4028485A (en) * | 1976-01-29 | 1977-06-07 | Mobil Oil Corporation | Non-aqueous removal of soluble hydrogenation catalyst |
DD147247A1 (de) * | 1979-05-17 | 1981-03-25 | Klaus Ruehlmann | Verfahren zur herstellung oxydationsgeschuetzter polymere |
US4417029A (en) * | 1981-08-03 | 1983-11-22 | Atlantic Richfield Company | Derivatization of star-block copolymers |
DD208470A3 (de) * | 1982-04-20 | 1984-05-02 | Klaus Ruehlmann | Verfahren zur herstellung von polymeren kv-stabilisatoren |
US4518753A (en) * | 1982-04-26 | 1985-05-21 | National Research Development Corporation | Anionic polymerization of conjugated dienes in the presence of hindered triaryl boron or aluminum derivatives |
JPS5953515A (ja) * | 1982-09-22 | 1984-03-28 | Tounen Sekiyu Kagaku Kk | 新規リビングブロツク共重合体及びその製造方法 |
JPS5953516A (ja) * | 1982-09-22 | 1984-03-28 | Tounen Sekiyu Kagaku Kk | 新規ブロツク共重合体及びその製造方法 |
FR2536752A1 (fr) * | 1982-11-25 | 1984-06-01 | Brossas Jean | Resines liquides, reticulees, a base de polyolefines, et le procede de leur preparation |
JPS59113016A (ja) * | 1982-12-20 | 1984-06-29 | Hodogaya Chem Co Ltd | 水性ポリウレタン樹脂 |
JPS6052845A (ja) * | 1983-09-02 | 1985-03-26 | Japan Synthetic Rubber Co Ltd | パタ−ン形成材料 |
US4560817A (en) * | 1984-03-02 | 1985-12-24 | Phillips Petroleum Company | Hydrogenation catalyst |
US4595749A (en) * | 1984-11-23 | 1986-06-17 | Shell Oil Company | Direct removal of NI catalysts |
DE3670642D1 (de) * | 1985-01-23 | 1990-05-31 | Nissan Chemical Ind Ltd | Polymere von substituierten 1,3-butadienverbindungen und verfahren zu deren herstellung. |
DD234683A1 (de) * | 1985-02-13 | 1986-04-09 | Univ Dresden Tech | Verfahren zur herstellung von polymeren langzeitstabilisatoren mit hals-gruppen |
DD234682A1 (de) * | 1985-02-13 | 1986-04-09 | Univ Dresden Tech | Verfahren zur herstellung von langzeitstabilisierten polymeren mit hals-gruppen |
NL8502134A (nl) * | 1985-07-26 | 1987-02-16 | Dsm Resins Bv | Gehydrogeneerde koolwaterstofhars en toepassing daarvan in lijmen. |
DE3527909A1 (de) * | 1985-08-03 | 1987-02-12 | Basf Ag | Polymerisate mit aminogruppen, deren herstellung und verwendung |
JPS62225514A (ja) * | 1986-03-26 | 1987-10-03 | Shin Etsu Chem Co Ltd | ブロツク・グラフト共重合体及びその製造法 |
US4855509A (en) * | 1987-01-28 | 1989-08-08 | Manville Corporation | Removal of alkali metals from polyols |
JPS63268703A (ja) * | 1987-04-28 | 1988-11-07 | Mitsubishi Kasei Corp | フエノ−ル性水酸基を有する重合体 |
US4994526A (en) * | 1987-08-10 | 1991-02-19 | General Electric Company | Telechelic polyisobutylene and block copolymer derivatives |
US4906691A (en) * | 1987-10-09 | 1990-03-06 | Minnesota Mining And Manufacturing Company | Adhesive compositions made with condensed phase polymers and sheet materials coated therewith |
US4857615A (en) * | 1987-10-09 | 1989-08-15 | Minnesota Mining And Manufacturing Company | Method of making condensed phase polymers |
US4857618A (en) * | 1987-10-09 | 1989-08-15 | Minnesota Mining And Manufacturing Company | Condensed phase polymers |
US4996266A (en) * | 1987-10-09 | 1991-02-26 | Minnesota Mining And Manufacturing Company | Method of making condensed phase polymers |
CA1338317C (en) * | 1988-02-25 | 1996-05-07 | Akio Imai | Modified diene polymer rubbers |
JP2718059B2 (ja) * | 1988-04-28 | 1998-02-25 | 日本合成ゴム株式会社 | 重合体の水素添加方法および触媒 |
US4866120A (en) * | 1988-06-09 | 1989-09-12 | Mobil Oil Corporation | Elastomeric end difunctional polymers |
US5081191A (en) * | 1989-01-18 | 1992-01-14 | The Dow Chemical Company | Functionalized polymers prepared by anionic polymerization |
US4994532A (en) * | 1989-06-16 | 1991-02-19 | General Electric Company | Polycarbonate-silicone block copolymer compositions |
GB9002804D0 (en) * | 1990-02-08 | 1990-04-04 | Secr Defence | Anionic polymerisation |
US5039755A (en) * | 1990-05-29 | 1991-08-13 | Shell Oil Company | Selective hydrogenation of conjugated diolefin polymers |
US5166277A (en) * | 1991-10-31 | 1992-11-24 | Shell Oil Company | Hydrogenation of unsaturation in low molecular weight diene polymers |
-
1993
- 1993-03-11 US US08/029,866 patent/US5336726A/en not_active Expired - Fee Related
-
1994
- 1994-03-01 TW TW083101745A patent/TW264485B/zh active
- 1994-03-09 WO PCT/EP1994/000810 patent/WO1994020553A1/en active IP Right Grant
- 1994-03-09 EP EP94911174A patent/EP0688341B1/en not_active Expired - Lifetime
- 1994-03-09 JP JP51960994A patent/JP3476823B2/ja not_active Expired - Fee Related
- 1994-03-09 ES ES94911174T patent/ES2102850T3/es not_active Expired - Lifetime
- 1994-03-09 DE DE69403784T patent/DE69403784T2/de not_active Expired - Fee Related
- 1994-03-09 BR BR9405897A patent/BR9405897A/pt not_active IP Right Cessation
- 1994-03-09 KR KR1019950703814A patent/KR100312402B1/ko not_active IP Right Cessation
- 1994-03-09 CN CN94191643A patent/CN1057778C/zh not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100562529C (zh) * | 2003-04-04 | 2009-11-25 | 株式会社普利司通 | 可固化的密封胶组合物 |
CN101959903A (zh) * | 2007-12-28 | 2011-01-26 | 株式会社普利司通 | 羟芳基官能聚合物 |
CN101959903B (zh) * | 2007-12-28 | 2016-02-17 | 株式会社普利司通 | 羟芳基官能聚合物 |
CN102482186A (zh) * | 2009-06-30 | 2012-05-30 | 株式会社普利司通 | 阴离子聚合引发剂和工艺 |
CN102482186B (zh) * | 2009-06-30 | 2015-09-30 | 株式会社普利司通 | 阴离子聚合引发剂和工艺 |
Also Published As
Publication number | Publication date |
---|---|
KR960701105A (ko) | 1996-02-24 |
JPH08507321A (ja) | 1996-08-06 |
TW264485B (zh) | 1995-12-01 |
JP3476823B2 (ja) | 2003-12-10 |
ES2102850T3 (es) | 1997-08-01 |
DE69403784D1 (de) | 1997-07-17 |
US5336726A (en) | 1994-08-09 |
WO1994020553A1 (en) | 1994-09-15 |
KR100312402B1 (ko) | 2001-12-28 |
EP0688341B1 (en) | 1997-06-11 |
BR9405897A (pt) | 1995-12-26 |
EP0688341A1 (en) | 1995-12-27 |
DE69403784T2 (de) | 1997-10-23 |
CN1057778C (zh) | 2000-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1057778C (zh) | 具有末端甲硅烷基的丁二烯聚合物 | |
Auschra et al. | Synthesis of block copolymers with poly (methyl methacrylate): P (Bb-MMA), P (EB-b-MMA), P (SbBb-MMA) and P (Sb-EB-b-MMA) | |
US4089913A (en) | Process for producing transparent block copolymer resin | |
USRE39617E1 (en) | Butadiene polymers having terminal functional groups | |
US5681895A (en) | Coupling of anionic polymers with trialkoxysilanes having silicon-hydrogen bonds | |
TW200307698A (en) | Process for making a coupled block copolymer composition and the resulting composition | |
EP0298667A2 (en) | Block polymers of methacrylates and derivatives thereof | |
US5098959A (en) | Block polymers of methacrylates | |
EP0841347B1 (en) | Synthesis of macrocyclic polymers with group IIA and IIB metal cyclic organometallic initiators | |
US4461874A (en) | Block copolymers of conjugated dienes or vinyl substituted aromatic hydrocarbons and acrylic esters and process for their manufacture | |
US5391637A (en) | Capping of anionic polymers with oxetanes | |
JP2991824B2 (ja) | 共役ジオレフィンポリマーの選択的水素化 | |
US5218053A (en) | Polymers having stable anhydride rings | |
US4079176A (en) | Polymerization process | |
CA1271280A (en) | Transparent, impact-resistant styrene block polymers and their preparation | |
USH1464H (en) | Method for preparing asymmetric radial copolymers having two first arms and two second arms | |
US4238576A (en) | Orthoesters as coupling agents for producing novel polymers | |
US5397841A (en) | Grafted polymers having reactive groups at the base | |
US5338824A (en) | Removal of alkali metal methoxide catalyst residue from hydroxy-terminated conjugated diene polymers | |
EP0738738B1 (en) | Polymer containing saturated cyclic molecular structure units | |
US4297464A (en) | Orthoesters as coupling agents for producing monovinylarene homopolymers | |
EP0986584B1 (en) | Process for making terminally functionalized polymers using protected functional initiator | |
CA2157896A1 (en) | Cyclic conjugated diene polymer | |
CN116472295A (zh) | 具有统计嵌段和两个终端聚乙烯嵌段的富含乙烯的二烯三嵌段聚合物 | |
CN114106273A (zh) | 1,2-二烷氧基丙烷作为合成高乙烯基芳基乙烯-共轭二烯嵌段共聚物极性调节剂的应用 |
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 | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |