CN1061995C - 高压制备聚丙烯的方法 - Google Patents
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Abstract
一种制备丙烯均聚物或丙烯与其它烯烃或烯烃混合物共聚物的方法，其中，聚合反应在(100～3000)×105Pa和100～330℃下进行，所用催化剂为茂金属催化剂体系。
Description
本发明涉及丙烯均聚物或丙烯与其它烯烃或其混合物的共聚物的制备方法。
采用Ziegler催化剂体系低压制备丙烯均聚物和/或共聚物的方法公开于例如EP-A351392和EP-A321852中。但是，过程中出现非均相，其生产率并不令人满意，而且单体的选择受到限制。
本发明目的之一是提供一种不具有所述缺点的丙烯均聚物和/或共聚物的制备方法。
我们发现采用下述方法可达到该目标，即制备丙烯均聚物或丙烯与其它烯烃或烯烃混合物的共聚物时，聚合反应在(100～3000)×105Pa和100～330℃下进行，所用催化剂为茂金属催化剂体系。
该方法可制得线型丙烯均聚物或具有短支链的线型共聚物。
3～12(最好为4～8)个碳原子的环烯烃、二烯，尤其是4～10个碳原子的α，ω-二烯，例如已-1，5-二烯，和2～10个碳原子的烯烃(优选乙烯、丁烯和已烯)被认为是适合于与丙烯共聚的烯烃，其中α-烯烃特别优选。这些烯烃也可以具有芳基或杂原子取代基，例如苯乙烯或不饱和的取代硅烷。
通常，这些共聚单休的用量以丙烯用量为基准计是0.1～99.9％(重量)，优选1～99％(重量)。
所用催化剂是茂金属催化剂体系，它包含作为活性成份之一的周期表Ⅳ和Ⅴ副族金属元素的络合物，尤其是钛、锆、铪、钒、铌或钡的络合物。优选的络合物是那些金属原子通过π键与不饱和环烃原子键合的络合物，所述环烃的例子有：环戊二烯基、芴基或茚基。此外，在优选的络合物中，金属原子还可以与其它配位体键合，尤其是氟、氯、溴、碘或C1-C10烷基例如甲基、乙基、丙基或丁基配合体。特别适宜的络合物特别含有氯。
优选的茂金属催化剂体系包含下列活性成份：a)通式Ⅰ茂金属络合物式中M是钛、锆、铪、钒、铌或钽，X是氟、氯、溴、碘、氢、C1-C10烷基，C6-C15芳基或-OR6，R6是C1-C10烷基、C6-C15芳基、烷基芳基、芳基烷基、氟代烷基或氟代芳基，上述基团中烷基均含1～10个碳原子；芳基均含6～20个碳原子；R4至R5各自是氢，C1-C10烷基，5～7元环烷基，该环烷基本身又可带有一个C1-C6烷基作为取代基，C6-C15芳基或芳烷基，其中相邻的两个基团还可以进一步形成4～15个碳原子的不饱和环，或Si(R7)3R7是C1-C10烷基，C6-C15芳基或C3-C10环烷基；Z是X或
R8至R12各自是氢，C1-C10烷基，5～7元环烷基，该环烷基本身又可带有一个C1-C10烷基作为取代基，C6-C15芳基或芳烷基，其中相邻的两个基团还可以进一步形成4～15个碳原子的不饱和环，或Si(R13)3R13是C1-C10烷基，C6-C15芳基或C3-C10环烷基；或者R4和Z一起形成基团-[Y(R14)2]n-E-，Y是硅、锗、锡或碳，R14是C1-C10烷基、C3-C10环烷基或C6-C10环烷基，n是1，2，3或4R15是C1-C10烷基，C6-C15芳基、C3-C10环烷基、烷基芳基或Si(R15)3并且R16是C1-C10烷基、C6-C15芳基、C3-C10环烷基、或烷基芳基，和b)通式Ⅱ或Ⅲ的开链或环状铝氧烷(alumoxane)化合物 
式中R17是C1-C4烷基，m是一个5～30的整数。
在通式Ⅰ的茂金属络合物中，优选： 
特别优选的式Ⅰa化合物是那些其中M是钛、锆或铪，X是氯和R1至R5各自是氢或C1-C4烷基的化合物。
特别优选的式Ⅰb化合物是那些其中M是锆、或铪，X是氯，R1至R5各自是氢、C1-C4烷基或Si(R7)3和R6至R10各自是氢、C1-C4烷基或Si(R13)3的化合物
特别合适的式Ⅰb化合物是那些其中环戊二烯基相同的化合物，优选未取代的环戊二烯基。
特别合适的式Ⅰc化合物是那些其中R1和R8相同且各自为氢或C1-C10烷基，R5和R12相同且各自为氢、甲基、乙基、异丙基或叔丁基，R3和R10是C1-C4烷基，R2和R9各自是氢，或者两个相邻基团R2和R3、R9和R10一起形成4～12个碳原子的不饱和环状基团，R14是C1-C8烷基，M是锆或铪，Y是硅、锗、锡或碳和X是氯的化合物。
特别合适的络合物的实例包括二甲基硅烷二基双-(3-叔丁基-丁基-5-甲基环戊二烯基)锆二氯化物二乙基硅烷二基双-(3-叔丁基-丁基-5-甲基环戊二烯基)锆二氯化物甲基乙基硅烷二基双-(3-叔丁基-丁基-5-甲基环戊二烯基)锆二氯化物二甲基硅烷二基双-(3-叔丁基-丁基-5-乙基环戊二烯基)锆二氯化物二甲基硅烷二基双-(3-叔丁基-丁基-5-甲基环戊二烯基)二甲基锆二甲基硅烷二基双-(2-甲基茚基)锆二氯化物二乙基硅烷二基双-(2-甲基茚基)锆二氯化物二甲基硅烷二基双-(2-乙基茚基)锆二氯化物二甲基硅烷二基双-(2-异丙基茚基)锆二氯化物二甲基硅烷二基双-(2-叔丁基茚基)锆二氯化物二乙基硅烷二基双-(2-甲基茚基)锆二溴化物二甲基硫化双-(2-甲基茚基)锆二氯化物二甲基硅烷二基双-(2-甲基-5-甲基环戊二烯基)锆二氯化物二甲基硅烷二基双-(2-甲基-5-乙基环戊二烯基)锆二氯化物二甲基硅烷二基双-(2-乙基-5-异丙基环戊二烯基)锆二氯化物二甲基硅烷二基双-(2-甲基苯并茚基)锆二氯化物二甲基硅烷二基双-(2-甲基茚基)铪二氯化物
在通式Ⅰd化合物中，特别合适的是那些取代基如下定义的化合物：M是锆或铪，X是氯或C1-C10烷基，当n是1时Y是硅或碳，当n是2时Y是碳，R14是C1-C8烷基、C5或C6环烷基或C6-C10芳基，A是-O-，-S-或
NR15和R1至R3和R5各自是氢、C1-C10烷基、C3-C10环烷基、C6-C15芳基或Si(R7)3。
这种络合物可通过常规方法合成，最好是由相应的取代的环状烃阴离子与钛、锆、铪、钒、铌或钽的囟化物反应合成，相应制备方法的例子尤其可参见：Journal of Organometallic Chemistry 369(1989)，359-370。
茂金属络合物也可以阳离子的形式存在，参见EP-A 277003和EP-A 277004。
除了述络合物外，茂金属催化剂体系通常还包含通式Ⅱ或Ⅲ的低聚铝氧烷化合物，其中优选的R17是甲基或乙基和m是10～25。
通常，将三烷基铝的溶液与水反应制备上述低聚铝氧烷化合物，尤其可参见Ep-A 284708和US-A 4794096。
通常，得到的低聚铝氧烷化合物是不同长度的线型和环状链分子的混合物形式，因此m被认为是一个平均值。铝氧烷化合物也可以与其它烷基金属化物(优选烷基铝)的混合物形式存在。
在该新方法中，已经证明下述作法是有利的：即周期表第Ⅳ和Ⅴ族副族金属络合物和低聚铝氧烷化合物的用量应当使低聚铝氧烷化合物中的铝，与周期表第Ⅳ和Ⅴ族副族金属络合物中的过渡金属的原子数比为10∶1至106∶1，特别是10∶1到104∶1。对于该新方法，催化剂的用量通常是每升10-1～10-9mol金属，优选每升10-2～10-5mol金属。
该过程可在通常用于高压聚合的反应器中，例如，在搅拌的高压釜中进行。
也已证明，聚合前首先将周期表第Ⅳ和Ⅴ族副族金属络合物与低聚铝氧烷化合物混合是有利的，结果生成活化的催化剂体系。活化步骤的时间通常是1至120分钟，最好是10至100分钟。混合应最好使络合物与低聚铝氧烷化合物的惰性溶剂溶液在0～50℃充分接触。所述惰性溶剂的例子有：苯、甲苯、己烷、庚烷或其混合物。
该新方法可如下进行：将络合物溶液与低聚铝氧烷溶液逆流进入反应器混合和/或通过多个进料点送入反应器混合。聚合反应可分批或连续进行。采用的压力为(100～3500)×105Pa，优选(500～3000)×105Pa，特别是(1000-3000)×105Pa，采用的温度是100～330℃，优选是120～300℃，特别是120～250℃。停留时间为20～240秒，优选30～120秒。
本新方法的实质性进步是能达到高的生产率，共聚单体的选择范围宽，并且在较短的停留时间内和高分子量的同时能达到高的转化率。
实施例1聚丙烯均聚物(PP)的制备
将400mg(约1mmol)
溶于50ml(36g，0.5mol)三乙胺和290g 1.53M的甲基铝氧烷(0.5mol)的甲苯(10l)溶液的混合液中。在无水和隔绝空气的条件下，将10m3丙烯/h和上述溶液计置送入连续的高压搅拌釜中。
表1给出实验条件和结果。重均分子量MW用凝胶渗透色谱测定
表1
| 温度[℃] | 压力[Pa] | g Ic′/h | 停留时间[min] | 生产率：[g PP/gIc′·h] | Mw |
| 149 | 1,510·105 | 0.17 | 1.5 | 8,380 | 2,000 |
实施例2丙烯/乙烯共聚物的制备
按实施例1所述的方法，不同之处仅在于将丙烯和乙烯的混合物聚合。
表2给出实验条件和结果。
表2
| 温度[℃] | 压力[Pa] | g Ic′/h | 气体混合物中丙烯与乙烯重量酯数之比 | 生产率[g polu,/g Ic′·h] | Mw |
| 190 | 1,508·105 | 0.078 | 77/23 | 24,358 | 10,000 |
Claims (1)
1．一种制备丙烯均聚物或丙烯与其它烯烃或烯烃混合物共聚物的方法，其中，聚合反应在(100～3000)×105Pa和100～330℃下进行，所用催化剂为茂金属催化剂体系，催化剂用量是10-1-10-9mol金属/1，并且在聚合前，首先将周期表第Ⅳ和Ⅴ副族的金属的茂金属络合物与低聚铝氧烷化合物混合，结果生成活化的催化剂体系，a)茂金属铬合物具有通式Ⅰ
式中M是钛、锆、铪、钒、铌或钽，X是氟、氯、溴、碘、氢、C1-C10-烷基，C6-C15芳基或-OR6，R6是C1-C10烷基、C6-C15芳基、烷基芳基、芳基烷基、氟代烷基或氟代芳基，上述基团中烷基均含1～10个碳原子；芳基均含6～20个碳原子；R1至R5各自是氢，C1-C10烷基，5～7元环烷基，该环烷基本身又可带有一个C1-C10烷基作为取代基，C6-C15芳基或芳烷基，其中相邻的两个基团还可以进一步形成4～15个碳原子的不饱和环，或Si(R7)3R7是C1-C10烷基，C6-C15基或C3-C10环烷基；Z是X或
R8至R12各自是氢，C1-C10烷基，5～7元环烷基，该环烷基本身又可带有一个C1-C10烷基作为取代基，C6-C15芳基或芳烷基，其中相邻的两个基团还可以进一步形成4～15个碳原子的不饱和环，或Si(R13)3R13是C1-C10烷基，C6-C15芳基或C3-C10环烷基；或者R4和Z一起形成基团-[Y(R14)2]n-E-，Y是硅、锗、锡或碳，R14是C1-C10烷基、C3-C10环烷基或C6-C15环烷基，n是1，2，3或4R15是C1-C10烷基，C6-C15芳基、C3-C10环烷基、烷基芳基或Si(R16)3并且R16是C1-C10烷基、C6-C15芳基、C3-C10环烷基、或烷基芳基，和b)铝氧烷化合物为通式Ⅱ或Ⅲ的开链或环状铝氧烷化合物
式中R17是C1-C4烷基，m是一个5～30的整数。
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| DEP4130299.0 | 1991-09-12 | ||
| DE4130299A DE4130299A1 (de) | 1991-09-12 | 1991-09-12 | Verfahren zur herstellung von polypropylen unter hochdruck |
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| CN1061995C true CN1061995C (zh) | 2001-02-14 |
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| EP (1) | EP0603232B1 (zh) |
| JP (1) | JPH06510808A (zh) |
| CN (1) | CN1061995C (zh) |
| AR (1) | AR248032A1 (zh) |
| CA (1) | CA2118711A1 (zh) |
| DE (2) | DE4130299A1 (zh) |
| ES (1) | ES2085033T3 (zh) |
| FI (1) | FI941139A (zh) |
| HU (1) | HUT66545A (zh) |
| NO (1) | NO302075B1 (zh) |
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| ZA (1) | ZA926925B (zh) |
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| US5384299A (en) * | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
| US5408017A (en) * | 1987-01-30 | 1995-04-18 | Exxon Chemical Patents Inc. | High temperature polymerization process using ionic catalysts to produce polyolefins |
| WO1994000500A1 (en) * | 1992-06-26 | 1994-01-06 | Exxon Chemical Patents Inc. | Solution phase polymerization process utilizing metallocene catalyst with production of olefin polymers |
| FI105820B (fi) * | 1995-10-10 | 2000-10-13 | Borealis Tech Oy | Prosessi propeenin homo- tai kopolymeerien valmistamiseksi |
| JP3421053B2 (ja) | 1995-10-10 | 2003-06-30 | ボレアリス、アクティーゼルスカブ | プロピレンホモポリマーもしくはコポリマーを製造する方法 |
| DE19653079A1 (de) * | 1996-12-19 | 1998-06-25 | Basf Ag | Verfahren zur Gasphasenpolymerisation von C¶2¶-C¶8¶-Alk-1-enen mittels Ziegler -Natta- oder Metallocen-Katalysatorsystemen |
| CN1246127A (zh) | 1997-02-07 | 2000-03-01 | 埃克森化学专利公司 | 含乙烯基的大分子单体的制备 |
| BR9807672A (pt) | 1997-02-07 | 2000-02-15 | Exxon Chemical Patents Inc | Composições elastoméricas termoplásticas a partir de copolìmeros olefìnicos |
| US6153702A (en) * | 1997-09-12 | 2000-11-28 | Eastman Chemical Company | Polymers, and novel compositions and films therefrom |
| US6117962A (en) * | 1997-12-10 | 2000-09-12 | Exxon Chemical Patents Inc. | Vinyl-containing stereospecific polypropylene macromers |
| DE19903783A1 (de) * | 1999-02-01 | 2000-08-03 | Elenac Gmbh | Verfahren zur Herstellung von Polyolefinen mit breiter Molekulargewichtsverteilung |
| WO2002038628A2 (en) | 2000-11-07 | 2002-05-16 | Symyx Technologies, Inc. | Substituted pyridyl amine ligands, complexes and catalysts therefrom; processes for producing polyolefins therewith |
| GB0111020D0 (en) * | 2001-05-04 | 2001-06-27 | Borealis Tech Oy | Process |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| CN101041701B (zh) | 2002-09-20 | 2013-02-27 | 埃克森美孚化学专利公司 | 包括丙烯的聚合物及其应用 |
| US7807769B2 (en) | 2002-09-20 | 2010-10-05 | Exxonmobil Chemical Patents Inc. | Isotactic polypropylene produced from supercritical polymerization process |
| CN101124235B (zh) | 2004-07-08 | 2010-12-15 | 埃克森美孚化学专利公司 | 烯烃聚合催化剂体系及其使用方法 |
| US7741420B2 (en) | 2004-07-14 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US8022142B2 (en) | 2008-12-15 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Thermoplastic olefin compositions |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| WO2008150572A1 (en) * | 2007-06-04 | 2008-12-11 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US7910637B2 (en) | 2007-09-13 | 2011-03-22 | Exxonmobil Research And Engineering Company | In-line blending of plasticizers with a base polymer |
| CN101855249B (zh) | 2007-09-13 | 2013-02-13 | 埃克森美孚研究工程公司 | 在线生产增塑聚合物和增塑聚合物共混物的方法 |
| US7910679B2 (en) | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
| US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| CN101945942B (zh) | 2007-12-20 | 2012-08-08 | 埃克森美孚研究工程公司 | 生产粒料稳定的聚烯烃的在线方法 |
| US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
| CH710441A2 (de) | 2014-12-02 | 2016-06-15 | Rowak Ag | Pulverförmige Zusammensetzungen aus thermoplastischen Kunststoffen und Verwendung der Zusammensetzungen. |
| CA3159497A1 (en) * | 2019-12-03 | 2021-06-10 | Dongcheol Shin | Transition metal compound, catalyst composition comprising same, and method for producing olefin polymer using catalyst composition |
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| DE3150270A1 (de) * | 1981-12-18 | 1983-06-30 | EC Erdölchemie GmbH, 5000 Köln | Hochdruckpolymerisation von ethylen |
| US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
| DE3743320A1 (de) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-olefinstereoblockpolymerwachs und verfahren zu seiner herstellung |
| DE3929693A1 (de) * | 1989-09-07 | 1991-03-14 | Hoechst Ag | Verfahren zur herstellung eines polyolefinwachses |
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- 1992-09-02 ES ES92918593T patent/ES2085033T3/es not_active Expired - Lifetime
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| Publication number | Publication date |
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| NO940873D0 (no) | 1994-03-11 |
| FI941139A0 (fi) | 1994-03-10 |
| DE4130299A1 (de) | 1993-03-18 |
| CN1070654A (zh) | 1993-04-07 |
| HU9400744D0 (en) | 1994-06-28 |
| ES2085033T3 (es) | 1996-05-16 |
| JPH06510808A (ja) | 1994-12-01 |
| EP0603232B1 (de) | 1996-04-10 |
| DE59205977D1 (de) | 1996-05-15 |
| ZA926925B (en) | 1994-03-11 |
| FI941139A (fi) | 1994-03-10 |
| NO940873L (no) | 1994-03-11 |
| WO1993005082A1 (de) | 1993-03-18 |
| EP0603232A1 (de) | 1994-06-29 |
| AR248032A1 (es) | 1995-05-31 |
| HUT66545A (en) | 1994-12-28 |
| CA2118711A1 (en) | 1993-03-18 |
| NO302075B1 (no) | 1998-01-19 |
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