CN1058602A - 丙烯的间规结晶共聚物 - Google Patents
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Abstract
丙烯和少量丁烯-1的基本上是间规结晶共聚
物，它具有良好的机械性能，较低熔点和在25℃下于
二甲苯中有有限的溶解度，以及采用由立体刚性和手
性锆和铪化合物和从聚甲基铝氧烷化合物制得的催
化剂聚合丙烯和丁烯-1混合物制备上述共聚物的方
法。
Description
本发明涉及基本上间规结构的新的丙烯结晶共聚物及其制备方法。
已经知道在聚合期间导入少量的共聚单体，主要是乙烯和丁烯-1来改性等规聚丙烯，是为了制得的聚合物具有足够低的熔点，适合于生产改善的可焊性性能的薄膜。
从J.A.C.S.，1988，110，6255中已知如何用催化剂体系来聚合丙烯，此催化剂体系是从立体刚质锆或铪的金属茂化物如Zr或Hf的异丙基（环戊二烯基-1-芴基）的二氯化物，和聚甲基铝氧烷制成的，因此，制得间规聚丙烯。
公开欧洲申请318049叙述了制备带有等规结构的丙烯与少量的乙烯、丁烯-1或4-甲基戊烯-1的结晶共聚物，它具有良好的机械性能，并在二甲苯（25℃）中有低的溶解度，此共聚物是用由立体刚质和手性锆化合物，如乙烯-双-（4，5，6-四氢茚基）锆二氯化物和聚甲基铝氧烷化合物所制成催化剂聚合烯烃而制成的。
现根据本发明，所采用的催化剂体系是从：
a异丙基（环戊二烯-1-芴基）锆或铪二氯化物，
b下式的铝氧烷 
式中n是2到25，或 
式中n是1到25，
有可能制得基本上是带有少量丁烯-1的丙烯间规共聚物，它具有高结晶度和良好的机械性能（非常像间规丙烯均聚物）、其熔点为110℃至140℃，并在室温下于二甲苯中有有限的溶解度（在25℃可溶于二甲苯中的聚合物部分小于10%（重量））。上述共聚物是在生成共聚物的组成类似于气相中存在的单体混合物的组成的条件下，聚合单体而制得。
业已发现这就构成本发明完全意外的方面，即当所述混合物中的丁烯-1含量为2到10%摩尔时，共聚物的组成类似于各单体在气相中的组成。在上述指明条件下进行操作，所得的共聚物具有均匀的共聚单体的分布，这可由13C-NMR方法来测定：不存在多个丁烯单元链区的典型信号。基本上是间规共聚物是意味着共聚物具有rrrr五价物含量大于85%。
所得本发明共聚物的可能性完全是意外的，这是由于丙烯与共聚单体的聚合是与丁烯-1不同的，例如乙烯和甲基戊烯-1，所得共聚物在25℃下于二甲苯中有很高的可溶性。
本发明共聚物的制备是采用上述催化剂于液相中（于惰性烃溶剂或液体丙烯中）进行接触聚合，并加入恒定组分的单体气相混合物，聚合温度为-30到70℃，优选为20到30℃。
在上述条件下所制得的共聚物特性粘度（在135℃于四氢萘中）大于0.2分升/克。正如已述的，此共聚物主要用于薄膜领域中，这是由于所制得的薄膜具有良好的可热合密封特性。
用下面例子加以说明本发明，但不是对本发明的限制。
实施例
例1：聚甲基铝氧烷的合成
于一个500毫升装有热电偶、泡型冷凝器（与气量计连接）、一个100毫升的滴液漏斗、一个氮气阀和一个电磁搅拌器的烧瓶中，在氮气下从滴液漏斗加入39.4克Al2（SO4）3·16H2O，250毫升甲苯和50毫升AlMe3。当气表打开时关闭氮气阀，在室温下和保持强力搅拌下将三甲基铝于5～10分钟内滴入硫酸铝悬浮液中。
将温度升至55℃，然后让其升到70℃并用热浴保持恒定，反应在4小时内完成。过滤悬浮液并干燥此溶液，得到15.8克产物，其产率为44%。
平均冰点分子量为1200和平均齐聚度为21。
锆化合物的合成
根据J.A.C.S.，1988，110，6255所述已对异丙基（环戊二烯-1-芴基）锆二氯化物进行合成，如下所述：所有操作都在惰性气体下进行的。
将4.93克异丙基（环戊二烯-1-芴）的配位体溶于约150毫升的四氢呋喃中，通过滴液漏斗，在搅拌下向此溶液中加入23毫升正-丁基锂（在己烷中16M等于36.8摩尔）。在真空下蒸发此溶剂，分离得红色固体的二价阴离子盐，然后用戊烷洗涤几次来净化。4.62克ZrCl4悬浮在200毫升CH2Cl2中并冷却到-78℃，含有二价阴离子物的容器也冷却到-78℃。将此ZrCl4悬浮液迅速倒入此固体二价阴离子物，在-78℃下保持搅拌2小时，然后让其温度降到室温，将此混合物一直在搅拌下过夜。过滤出LiCl和再用CH2Cl2反复洗涤，在-78℃下结晶制得产物。
聚合
在一个装有连接到真空/氮气管线的阀门，电磁搅拌器和25℃的恒温槽的100毫升玻璃聚合釜中，在氮气流下加入含有77.1毫克聚甲基铝氧烷的50毫升甲苯溶液。除去氮气相后，在2个大气压下连续地加入丙烯/丁烯-1混合物（流率为30升/时）。如上所述制备含有0.7毫克锆化合物的溶液，然后再加入含有21.2毫克甲基铝氧烷的10毫升甲苯。气体混合物的压力升到3个大气压。90分钟后注入1毫升甲醇，停止聚合，制得3克聚合物。
用于例2和比较例1、2和3的催化剂组分是与例1一样的。
例2
按照例1同样的程序进行丙烯/丁烯-1的共聚，并采用下述配方的量。0.2毫克锆化合物、26.0毫克聚甲基铝氧烷，55毫升甲苯。将含有1.65摩尔丁烯的混合物，在3个大气压力和流率为30升/时下导入，在25℃下30分钟后得到0.8克聚合物。
比较例1
在一个装有外加热套、连接到真空/氮气管线的阀和一个机械搅拌器的1升玻璃聚合斧中，在丙烯流下加入350毫升甲苯，然后在15℃下用气体丙烯饱和，加热夹套的恒温器设定在25℃，加入含有1.85毫克锆化合物和0.87克聚甲基铝氧烷的10毫升甲苯溶液。然后在4个大气压，25℃下聚合80分钟，采用排气和注入1毫升甲醇来停止聚合，制得100克聚合物。
比较例2
按照例1的方法来进行丙烯/乙烯的共聚，并采用下列配方的量：0.9毫克锆化合物、183毫克聚甲基铝氧烷、45毫升甲苯。含有25%摩尔乙烯混合物在3个大气压下加入，其流率为30升/时，在26℃下20分钟后，制得6.3克聚合物。
比较例3
在例1的100毫升的聚合釜中进行丙烯/4-甲基-1-戊烯的共聚。
在氮气流下向装有25℃的恒温槽的聚合釜中加入69.4毫克聚甲基铝氧烷和60毫升甲苯。然后除去氮气并在氮气下加入1毫升4-甲基-1戊烯，然后注入含有114.1毫克聚甲基铝氧烷和1.8毫克锆化合物的5毫升甲苯溶液。在压力升到3个大气压，1小时后注入1毫升甲醇停止聚合，制得7.3克聚合物。
Claims (2)
1、基本上是间规结构的丙烯和丁烯-1结晶共聚物，含有2到10摩尔%丁烯-1单元，其熔点为120到140℃和在25℃下于二甲苯中可溶分数小于10%(重量)。
2、制备权利要求1的共聚物的方法，包括用催化剂进行丙烯和丁烯-1的气体混合物的聚合，所述催化剂是（环戊二烯-1-芴基）铪或锆的二氯化物和聚甲基铝氧烷的下列的环状或线型化合物而制得
式中n是1到25，操作是进料气体混合物中丁烯-1摩尔含量是从2到10%条件下，和聚合温度是小于20℃下进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20778A/90 | 1990-06-27 | ||
| IT02077890A IT1249008B (it) | 1990-06-27 | 1990-06-27 | Copolimeri cristallini sindiotattici del propilene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1058602A true CN1058602A (zh) | 1992-02-12 |
Family
ID=11171934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91105308A Pending CN1058602A (zh) | 1990-06-27 | 1991-06-27 | 丙烯的间规结晶共聚物 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5196496A (zh) |
| EP (1) | EP0464684B1 (zh) |
| JP (1) | JP3320751B2 (zh) |
| KR (1) | KR920000804A (zh) |
| CN (1) | CN1058602A (zh) |
| AU (1) | AU7935091A (zh) |
| BR (1) | BR9102708A (zh) |
| CA (1) | CA2045728A1 (zh) |
| DE (1) | DE69110355T2 (zh) |
| FI (1) | FI913135A (zh) |
| IT (1) | IT1249008B (zh) |
| MX (1) | MX26389A (zh) |
| ZA (1) | ZA914893B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106408C (zh) * | 1997-12-10 | 2003-04-23 | 埃克森美孚化学专利公司 | 结合大分子单体的丙烯聚合物 |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620760A (en) * | 1992-06-30 | 1997-04-15 | Montell Technology Company Bv | Shaped articles for biomedical use |
| US5420220A (en) * | 1993-03-25 | 1995-05-30 | Mobil Oil Corporation | LLDPE films |
| US5602067A (en) * | 1992-12-28 | 1997-02-11 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
| US5332706A (en) * | 1992-12-28 | 1994-07-26 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
| US5608019A (en) * | 1992-12-28 | 1997-03-04 | Mobil Oil Corporation | Temperature control of MW in olefin polymerization using supported metallocene catalyst |
| US5338790A (en) * | 1993-07-14 | 1994-08-16 | Shell Oil Company | Polymer compositions |
| US5455741A (en) * | 1993-10-26 | 1995-10-03 | Pulse Engineering, Inc. | Wire-lead through hole interconnect device |
| US5614456A (en) * | 1993-11-15 | 1997-03-25 | Mobil Oil Corporation | Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers |
| DE69502851T2 (de) | 1994-02-25 | 1998-11-12 | Sumitomo Chemical Co | Statistisches Propylencopolymer und Filmlaminat davon |
| JPH07330829A (ja) | 1994-06-09 | 1995-12-19 | Sumitomo Chem Co Ltd | シンジオタクチック構造を有する結晶性プロピレン／１−ブテン共重合体 |
| IT1274606B (it) * | 1994-08-09 | 1997-07-18 | Spherilene Srl | Miscele di polipropilene atattico e polipropilene sindiotattico |
| US5525678A (en) * | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
| US5882750A (en) * | 1995-07-03 | 1999-03-16 | Mobil Oil Corporation | Single reactor bimodal HMW-HDPE film resin with improved bubble stability |
| DE19533337A1 (de) * | 1995-09-11 | 1997-03-13 | Basf Ag | Propen/But-1-en-Copolymere |
| US6486089B1 (en) | 1995-11-09 | 2002-11-26 | Exxonmobil Oil Corporation | Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution |
| US6417130B1 (en) | 1996-03-25 | 2002-07-09 | Exxonmobil Oil Corporation | One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization |
| CA2259999A1 (en) * | 1996-07-15 | 1998-01-22 | Mobil Oil Corporation | Comonomer pretreated bimetallic catalyst for blow molding and film applications |
| US6005463A (en) * | 1997-01-30 | 1999-12-21 | Pulse Engineering | Through-hole interconnect device with isolated wire-leads and component barriers |
| US6051525A (en) * | 1997-07-14 | 2000-04-18 | Mobil Corporation | Catalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distribution |
| US6153551A (en) | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
| US5990232A (en) * | 1997-08-25 | 1999-11-23 | Arco Chemical Technology, L.P. | Stabilizers for polymer polyols |
| US7101939B2 (en) * | 2001-11-30 | 2006-09-05 | Exxonmobil Chemical Patents Inc. | Ethylene/α-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and use |
| US7053163B1 (en) * | 2005-02-22 | 2006-05-30 | Fina Technology, Inc. | Controlled comonomer distribution along a reactor for copolymer production |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1193760B (it) * | 1978-06-14 | 1988-08-24 | Sumitomo Chemical Co | Procedimento per produrre copolimeri di propilene e pellicola di polipropilene a piu' strati con esso ottenuta |
| IT1221653B (it) * | 1987-11-27 | 1990-07-12 | Ausimonti Spa | Copolimeri cristallini del propilene |
| KR100197327B1 (ko) * | 1988-07-15 | 1999-06-15 | 치어즈 엠. 노우드 | 신디오택틱 폴리프로필렌 |
| US4892851A (en) * | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
| PT93853A (pt) * | 1989-04-28 | 1990-11-20 | Mitsui Toatsu Chemicals | Processo para a preparacao de um copolimero de polipropileno sindiotatico |
-
1990
- 1990-06-27 IT IT02077890A patent/IT1249008B/it active IP Right Grant
-
1991
- 1991-06-25 ZA ZA914893A patent/ZA914893B/xx unknown
- 1991-06-26 CA CA002045728A patent/CA2045728A1/en not_active Abandoned
- 1991-06-26 AU AU79350/91A patent/AU7935091A/en not_active Abandoned
- 1991-06-26 MX MX2638991A patent/MX26389A/es unknown
- 1991-06-26 US US07/721,049 patent/US5196496A/en not_active Expired - Fee Related
- 1991-06-27 BR BR919102708A patent/BR9102708A/pt unknown
- 1991-06-27 FI FI913135A patent/FI913135A/fi not_active Application Discontinuation
- 1991-06-27 JP JP18326891A patent/JP3320751B2/ja not_active Expired - Fee Related
- 1991-06-27 EP EP91110681A patent/EP0464684B1/en not_active Expired - Lifetime
- 1991-06-27 DE DE69110355T patent/DE69110355T2/de not_active Expired - Fee Related
- 1991-06-27 CN CN91105308A patent/CN1058602A/zh active Pending
- 1991-06-27 KR KR1019910010822A patent/KR920000804A/ko not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106408C (zh) * | 1997-12-10 | 2003-04-23 | 埃克森美孚化学专利公司 | 结合大分子单体的丙烯聚合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0464684B1 (en) | 1995-06-14 |
| DE69110355D1 (de) | 1995-07-20 |
| MX26389A (es) | 1993-12-01 |
| IT9020778A1 (it) | 1991-12-27 |
| JP3320751B2 (ja) | 2002-09-03 |
| US5196496A (en) | 1993-03-23 |
| EP0464684A2 (en) | 1992-01-08 |
| KR920000804A (ko) | 1992-01-29 |
| BR9102708A (pt) | 1992-02-04 |
| ZA914893B (en) | 1992-04-29 |
| CA2045728A1 (en) | 1991-12-28 |
| IT1249008B (it) | 1995-02-11 |
| JPH0687930A (ja) | 1994-03-29 |
| AU7935091A (en) | 1992-01-02 |
| IT9020778A0 (zh) | 1990-06-27 |
| FI913135A (fi) | 1991-12-28 |
| FI913135A0 (fi) | 1991-06-27 |
| EP0464684A3 (en) | 1992-11-19 |
| DE69110355T2 (de) | 1996-01-18 |
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