CN87106011A - 生产稳定无腐蚀性的无定形聚α-烯烃的工艺方法 - Google Patents
生产稳定无腐蚀性的无定形聚α-烯烃的工艺方法 Download PDFInfo
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Abstract
通过使聚合物在熔融状态与足够的水相接触，水/铝摩尔比至少为3∶1，来去除生产无定形聚α-烯烃中残留的催化剂的活性，然后用一种受阻酚抗氧剂稳定该聚合物。
Description
本发明涉及无定形聚α-烯烃，如无定形丙烯均聚物及其共聚物中残留催化剂的去活方法。具体地说，涉及一种新颖的在采用高活性载体氯化钛催化剂和烷基铝共催化剂直接生产实际上无定形的聚α-烯烃本体聚合过程中的去活方法。无定形聚合物是此生产过程的唯一产物，在分离未反应的单体和去除聚合物中残留催化剂的活性后，将此聚合物在足够高的温度下贮存起来，以防止其在加工设备中发生不希望有的硬化。通常，用于产品贮存和将产品运输到用户的设备也要加热，以便于熔融态无规聚合物的卸料。为了防止热引起的降解，该聚合物必须按惯例用受阻酚抗氧剂加以稳定化。
然而，人们意外地发现，当采用其它传统而成功的应用于生产诸如全同立构丙烯聚合物这类高分子量高结晶性α-烯烃聚合物的那些去活和稳定化技术时，所得到的无定形产物却极不稳定。特别是，当将C3-C8的醇，如异丙醇，注入热的止汽化产品物料，来去除残留催化剂的活性，并接着加入一种市售的受阻酚抗氧剂时，分析此予期被稳定化的产品，所能够发现的受阻酚抗氧剂含量却是微不足道的。
用这类醇来去除聚合物中含氯化物的残留催化剂的活性，还将引起氯化氢的释放，随之带来的是管道和容器的腐蚀问题。解决这一问题的办法是将一中和剂加入该聚合物，如羟基碳酸铝镁。可是，这显著地增加了最终产品的成本。
所附的图是本发明工艺方法一具体实施方案的示意图。
逐渐导致本发明的调研工作表明，醇处理确实使催化剂失活了，因为物料从反应釜排出后，没有发生进一步的聚合。可是，出人意外地发现，与稳定化问题相关联的仍然是聚合物去活的方法，而不是如何选择用以稳定聚合物的抗氧剂。虽然不希望被任何特定的理论所束缚，本发明者还是相信，这个问题要归因于在醇去活剂和有机铝共催化剂之间形成了醇化铝反应产物，此反应产物进一步与受阻酚抗氧剂反应，产生一不能防止氧化降解的化合物。本发明者发现这个问题可利用少量水作为去活剂加以解决。
本发明者还发现，水去活导致了聚合物腐蚀性引人注目的下降。本发明者相信，在使用传统醇去活方法的情况下，聚合物腐蚀性问题是由于形成了醇化铝而引起的，这种醇铝不能中和去活化过程中释放的氯化氢。可以认为，使用水作为残留催化剂的去活剂，导致形成了氢氧化铝，它是一种优异的氯化氢中和剂。
因而，根据本发明，提供了一种生产稳定的无腐蚀性的无规聚α-烯烃的工艺方法，它包括：
（1）从聚合反应区排出反应釜物料，该物料包括a未反应的单体和b含有残留催化剂的无定形聚α-烯烃，此残留催化剂由残余烷基铝催化剂组成;
（2）加热此反应釜流出物料;
（3）从该物料中分离熔融的无定形聚α-烯烃;
（4）使步骤（3）的熔融无定形聚α-烯烃与水紧密接触，水与上述聚α-烯烃中铝的摩尔比至少为3∶1。
（5）用一受阻酚抗氧剂稳定步骤（4）的产物。
优选的水/铝摩尔比，大约应在5∶1至15∶1之间。应给去活过程提供充分的接触时间，一般至少0.5分钟，最好至少1分钟。时间超过3-4分钟也不会再有进一步的收益了。
选择什么样的聚合条件及催化体系制备无定形聚α-烯烃，对于本发明的成败是无关紧要的，聚合物是均聚物还是共聚物也无关紧要。不过，在美国专利申请号S·N·880，456中（1986年6月30日提交）公布了一种特别方便的制备这种无定形聚α-烯烃的工艺方法，这里作为参考且并入本发明。
本发明工艺方法的聚合物产品具有优异的性能，使其适于各种应用，如用于胶粘剂，嵌缝胶，密封接合，屋顶材料成份等等。
为更好地理解本发明，可参考所附的示意图，它描述了本发明所申请工艺方法的一具体实施例。一主要部分为丙烯，其余为乙烯的无定形共聚物，如约85%（重量）的丙烯和15%（重量）乙烯的共聚物，可自闪蒸区（未标出）来的管线10获得，其中聚合区流出物料中的大部分未反应的乙烯和丙烯单体，氢和丙烷稀释剂都在闪蒸区从共聚物中除掉。经过闪蒸的物料温度约为350°F，表压约为60磅/吋2，除了熔融的聚合物外还含有少量的乙烯，丙烯和丙烷。
聚合物本身含有少量由烷基铝残余物组成的残留催化剂，在本实施例中是50/50（重量%）氯化二乙基铝和三乙基铝的混合物。物料液流10被加到带有蒸汽加热套和搅拌并装有再循环回路12和再循环泵13的两个产品贮存罐11中的一个（只标出一个），水以足够的量被不断地沿管线14泵入罐内（泵未标出），以保证在循环产品液流中，提供约为5∶1的水/铝摩尔比。在搅拌容器16中，抗氧剂被溶于异丙醇，由过滤器17过滤，当容器16被充满时，由泵（未标出）送至循环回路12。含有乙烯、丙烯、丙烷、水和异丙醇的蒸汽流，通过管线18被间歇地排出。第一个贮罐11装到预定容量后，关闭管线10和14中的物料液流，往罐中加入稳定剂，经稳定的产品通过管线19泵出贮存起来。与此同时，第二个贮罐11（未标出）投入使用。
下面的实施例进一步说明本发明。
实施例1和2
在对比实施例1中，按金属计算含有约400PPM铝的熔融无定形丙烯均聚物，在400°F温度下，以65克/分的流速，流经一个带搅拌的容器及其后的输送管线（总长20呎，内径0.43吋）。然后往聚合物里混入1097PPM的一种为人们所熟知的高效受阻酚抗氧剂Isonox
129，并分析抗氧剂含量。如表1数据所示，在不用水去活的情况下，仅可获得10%的抗氧剂回收率。
实施例2是以同样的方式进行的，不同之处仅在于将0.08克/分的水引入该容器，这相当于大约5∶1的水/铝摩尔比。水-聚合物接触时间约为6.5分钟。分析此被稳定的聚合物表明，用水去活处理方法的抗氧剂回收率差不多是100%。
表1
实施例3、4和5
在对比实施例3中，按金属计算含有约400PPM铝的熔融无定形乙烯-丙烯共聚物，流经与对比实施例1相同的搅拌容器和输送管线，并加以改进以便在360°F到380°F的聚合物温度下能既引入去活剂又引入抗氧剂溶液。当1000PPM的Isonox
129作为10%正己烷溶液被加入聚合物，而不加去活剂时，如表2所示，仅可回收约40%的抗氧剂，且聚合物是高度腐蚀性的。
实施例4是以同样的方式进行的，不同之处仅在于异丙醇按5∶1的异丙醇/铝摩尔比，以0.222克/分的流速被引入该容器。异丙醇/聚合物的接触时间约为8.7分钟。分析此物料再一次显示了40%的抗氧剂回收率，且聚合物有高腐蚀性。
实施例5也是类似进行的，不同之处在于水以0.134克/分的流速，按5∶1的水/聚合物摩尔比被引入流容器。水-聚合物接触时间约为4.4分钟。分析此经水处理的物料表明，得到了大约100%抗氧剂的回收率和无腐蚀性的聚合物。
表2
（1）腐蚀指数
0-无腐蚀
1-轻度腐蚀
2-中度腐蚀
3-一般腐蚀
4-高度腐蚀
5-极度腐蚀
实施例6
进行下述连续中试装置实验，用4.5克/小时的水，在约390°F至400°F温度下，处理约60磅/小时（含0.28摩尔铝/小时）熔融止汽无定形乙烯-丙烯共聚物液流，接触时间12.9分钟。
水在51呎长的将聚合物送到贮存罐的输送管道（内径1吋）始端加入，抗氧剂Isonox
129在上述管道的终端刚好进入该贮存罐前的地方加入。这个实验连续地进行了一周，每天用气相色谱法分析经稳定的聚合物的抗氧剂含量，结果列在下面的表3中，这个处理方法导致了接近90%的抗氧剂回收率。
表3
当然，本发明的工艺方法可以进行许多变更和改进。所有这些变化都被认为属于由说明书和所附权力要求书所限定的本发明范围。
Claims (5)
1、一种制备稳定无腐蚀性的无定形聚α-烯烃的工艺方法，它包括：
①从聚合物反应区排出反应釜物料，该物料包括(a)未反应的单体和(b)含有残留催化剂的无定形聚α-烯烃，此残留催化剂由残余烷基铝催化剂组成；
②加热该反应釜流出物料；
③从该物料中分离熔融的无定形聚α-烯烃；
④使步骤③的熔融无定形聚α-烯烃与水紧密接触，水与上述聚α-烯烃中铝的摩尔比至少为3∶1；
⑤用一受阻酚抗氧剂稳定步骤④的产物。
2、权力要求1的工艺方法，其中水/铝摩尔比保持在约5∶1到15∶1之间。
3、权力要求1的工艺方法，其中步骤④的接触时间至少延续0.5分钟。
4、权力要求3的工艺方法，其中接触时间至少延续1.0分钟。
5、权力要求1的工艺方法，其中无定形聚α-烯烃是一类以丙烯为主的聚合物，这类可选择的聚合物包括无定形丙烯均聚物，丙烯和乙烯的无定形共聚物以及丙烯、乙烯和另一种每个分子带4到8个碳原子的α-烯烃的共聚物。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US904,579 | 1986-09-08 | ||
| US06/904,579 US4701489A (en) | 1986-09-08 | 1986-09-08 | Process for the production of stable noncorrosive amorphous polyalphaolefins |
| US904579 | 1986-09-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87106011A true CN87106011A (zh) | 1988-07-06 |
| CN1039016C CN1039016C (zh) | 1998-07-08 |
Family
ID=25419384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87106011A Expired - Fee Related CN1039016C (zh) | 1986-09-08 | 1987-08-29 | 生产稳定无腐蚀性的无定形聚α－烯烃的工艺方法 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4701489A (zh) |
| EP (1) | EP0259965B1 (zh) |
| JP (1) | JPH07110887B2 (zh) |
| KR (1) | KR950006124B1 (zh) |
| CN (1) | CN1039016C (zh) |
| AT (1) | ATE91288T1 (zh) |
| AU (1) | AU603583B2 (zh) |
| CA (1) | CA1312406C (zh) |
| DE (1) | DE3786433T2 (zh) |
| ES (1) | ES2056823T3 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360571C (zh) * | 2002-06-24 | 2008-01-09 | 巴塞尔聚烯烃意大利有限公司 | α-烯烃聚合的液相法 |
| CN114901705A (zh) * | 2020-01-02 | 2022-08-12 | 博里利斯股份公司 | 用于在溶液中聚合烯烃的过程包括通过热量使聚合催化剂去活化 |
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| US5041492A (en) * | 1990-02-21 | 1991-08-20 | Findley Adhesives, Inc. | Hot melt adhesive |
| GB9103527D0 (en) * | 1991-02-20 | 1991-04-10 | Exxon Chemical Patents Inc | Hp catalyst killer |
| US5371053A (en) * | 1993-05-18 | 1994-12-06 | Exxon Chemical Patents Inc. | Process for deactivating Ziegler-Natta and metallocene catalysts |
| US6143842A (en) * | 1993-08-05 | 2000-11-07 | Huntsman Polymers Corporation | Elastomeric polyolefins production and recovery |
| US5948447A (en) * | 1993-08-05 | 1999-09-07 | Huntsman Polymers Corporation | Apparatus for product recovery of polyolefings |
| US5807976A (en) * | 1993-08-05 | 1998-09-15 | Mchaney; Stephen | Method for product recovery of polyolefins |
| DE4442166A1 (de) * | 1994-11-26 | 1996-05-30 | Basf Ag | Verfahren zur Herstellung von Polyolefinen mit geringen extrahierbaren Anteilen |
| EP0723977B1 (en) * | 1995-01-26 | 2000-06-21 | Huntsman Polymers Corporation | Method for product recovery of polyolefins |
| AU684579B2 (en) * | 1995-01-30 | 1997-12-18 | Rexene Corporation | Method for product recovery of polyolefins |
| BR9914982A (pt) * | 1998-11-02 | 2001-08-14 | Ciba Sc Holding Ag | Estabilização de produtos de cuidados do corpo e domésticos |
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| US6858684B2 (en) * | 2002-12-30 | 2005-02-22 | Univation Technologies, Llc | Processes for transitioning between various polymerization catalysts |
| US6949612B2 (en) * | 2002-12-31 | 2005-09-27 | Univation Technologies, Llc | Processes for transitioning between metallocene and Ziegler-Natta polymerization catalysts |
| KR20060127404A (ko) * | 2003-12-11 | 2006-12-12 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | 올레핀의 액상 중합 방법 |
| US7989670B2 (en) * | 2005-07-19 | 2011-08-02 | Exxonmobil Chemical Patents Inc. | Process to produce high viscosity fluids |
| WO2007011462A1 (en) | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Lubricants from mixed alpha-olefin feeds |
| US8748361B2 (en) * | 2005-07-19 | 2014-06-10 | Exxonmobil Chemical Patents Inc. | Polyalpha-olefin compositions and processes to produce the same |
| US20090234083A1 (en) * | 2005-07-27 | 2009-09-17 | Basell Poliolefine Italia S.R.L. | Polymerization Process for Preparing Polyolefins |
| EP1748039B1 (en) * | 2005-07-29 | 2013-01-23 | Linde AG | Method for deactivation of an organometallic catalyst |
| US7446167B2 (en) * | 2006-04-13 | 2008-11-04 | Fina Technology, Inc. | Catalyst deactivation agents and methods for use of same |
| US8921290B2 (en) | 2006-06-06 | 2014-12-30 | Exxonmobil Research And Engineering Company | Gear oil compositions |
| US8834705B2 (en) | 2006-06-06 | 2014-09-16 | Exxonmobil Research And Engineering Company | Gear oil compositions |
| US8501675B2 (en) | 2006-06-06 | 2013-08-06 | Exxonmobil Research And Engineering Company | High viscosity novel base stock lubricant viscosity blends |
| US8535514B2 (en) | 2006-06-06 | 2013-09-17 | Exxonmobil Research And Engineering Company | High viscosity metallocene catalyst PAO novel base stock lubricant blends |
| US8299007B2 (en) * | 2006-06-06 | 2012-10-30 | Exxonmobil Research And Engineering Company | Base stock lubricant blends |
| JP5555490B2 (ja) * | 2006-07-19 | 2014-07-23 | エクソンモービル・ケミカル・パテンツ・インク | メタロセン触媒を用いたポリオレフィンの製造方法 |
| US20100069687A1 (en) | 2006-09-06 | 2010-03-18 | Chemtura Corporation | Process for synthesis of polyalphaolefin and removal of residual catalyst components |
| US7601255B2 (en) * | 2006-09-06 | 2009-10-13 | Chemtura Corporation | Process for removal of residual catalyst components |
| US8513478B2 (en) * | 2007-08-01 | 2013-08-20 | Exxonmobil Chemical Patents Inc. | Process to produce polyalphaolefins |
| CA2710926C (en) * | 2008-01-31 | 2012-10-30 | Exxonmobil Chemical Patents Inc. | Improved utilization of linear alpha olefins in the production of metallocene catalyzed poly-alpha olefins |
| US8865959B2 (en) * | 2008-03-18 | 2014-10-21 | Exxonmobil Chemical Patents Inc. | Process for synthetic lubricant production |
| JP5633976B2 (ja) | 2008-03-31 | 2014-12-03 | エクソンモービル・ケミカル・パテンツ・インク | 剪断安定性の高粘度ｐａｏの製造 |
| US8394746B2 (en) | 2008-08-22 | 2013-03-12 | Exxonmobil Research And Engineering Company | Low sulfur and low metal additive formulations for high performance industrial oils |
| US8247358B2 (en) | 2008-10-03 | 2012-08-21 | Exxonmobil Research And Engineering Company | HVI-PAO bi-modal lubricant compositions |
| US8716201B2 (en) | 2009-10-02 | 2014-05-06 | Exxonmobil Research And Engineering Company | Alkylated naphtylene base stock lubricant formulations |
| US8530712B2 (en) | 2009-12-24 | 2013-09-10 | Exxonmobil Chemical Patents Inc. | Process for producing novel synthetic basestocks |
| US8728999B2 (en) | 2010-02-01 | 2014-05-20 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
| US8748362B2 (en) * | 2010-02-01 | 2014-06-10 | Exxonmobile Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient |
| US8759267B2 (en) | 2010-02-01 | 2014-06-24 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
| US8598103B2 (en) | 2010-02-01 | 2013-12-03 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient |
| US8642523B2 (en) | 2010-02-01 | 2014-02-04 | Exxonmobil Research And Engineering Company | Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient |
| US9815915B2 (en) | 2010-09-03 | 2017-11-14 | Exxonmobil Chemical Patents Inc. | Production of liquid polyolefins |
| US9399746B2 (en) | 2011-10-10 | 2016-07-26 | Exxonmobil Chemical Patents Inc. | Poly alpha olefin compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE617696A (zh) * | 1961-05-16 | |||
| US3773743A (en) * | 1969-02-03 | 1973-11-20 | Dow Chemical Co | Process for improving the color of ziegler olefin polymers |
| JPS5415313B2 (zh) * | 1974-04-30 | 1979-06-13 | ||
| US4137387A (en) * | 1976-09-30 | 1979-01-30 | The Badger Company, Inc. | Equipment for handling spent-aqueous Ziegler type catalyst in the polymerization of olefins |
| DE2716910C3 (de) * | 1977-04-16 | 1981-03-12 | Dr.-Ing. Reiner Foerst Gmbh, 5270 Gummersbach | Einrichtung zum Stimmen von Musikinstrumenten |
| US4504615A (en) * | 1979-12-21 | 1985-03-12 | Phillips Petroleum Company | Treating polymers of ethylene |
| AU548257B2 (en) * | 1981-06-09 | 1985-12-05 | Du Pont Canada Inc. | Deactivation of alpha olefin catalyst |
-
1986
- 1986-09-08 US US06/904,579 patent/US4701489A/en not_active Expired - Fee Related
-
1987
- 1987-06-03 CA CA000538696A patent/CA1312406C/en not_active Expired - Fee Related
- 1987-06-12 AU AU74170/87A patent/AU603583B2/en not_active Ceased
- 1987-07-30 EP EP87306762A patent/EP0259965B1/en not_active Expired - Lifetime
- 1987-07-30 DE DE87306762T patent/DE3786433T2/de not_active Expired - Fee Related
- 1987-07-30 AT AT87306762T patent/ATE91288T1/de active
- 1987-07-30 ES ES87306762T patent/ES2056823T3/es not_active Expired - Lifetime
- 1987-08-25 JP JP62209409A patent/JPH07110887B2/ja not_active Expired - Lifetime
- 1987-08-29 CN CN87106011A patent/CN1039016C/zh not_active Expired - Fee Related
- 1987-09-07 KR KR1019870009874A patent/KR950006124B1/ko not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360571C (zh) * | 2002-06-24 | 2008-01-09 | 巴塞尔聚烯烃意大利有限公司 | α-烯烃聚合的液相法 |
| CN114901705A (zh) * | 2020-01-02 | 2022-08-12 | 博里利斯股份公司 | 用于在溶液中聚合烯烃的过程包括通过热量使聚合催化剂去活化 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE91288T1 (de) | 1993-07-15 |
| DE3786433D1 (de) | 1993-08-12 |
| KR950006124B1 (ko) | 1995-06-09 |
| DE3786433T2 (de) | 1993-10-28 |
| EP0259965A2 (en) | 1988-03-16 |
| JPH07110887B2 (ja) | 1995-11-29 |
| US4701489A (en) | 1987-10-20 |
| KR880003978A (ko) | 1988-06-01 |
| AU603583B2 (en) | 1990-11-22 |
| ES2056823T3 (es) | 1994-10-16 |
| AU7417087A (en) | 1988-03-10 |
| EP0259965B1 (en) | 1993-07-07 |
| EP0259965A3 (en) | 1989-09-13 |
| CA1312406C (en) | 1993-01-05 |
| CN1039016C (zh) | 1998-07-08 |
| JPS6369802A (ja) | 1988-03-29 |
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