CN1103347C - 用低分子量添加剂提高聚烯烃和聚烯烃共聚物的韧性和可加工性 - Google Patents
用低分子量添加剂提高聚烯烃和聚烯烃共聚物的韧性和可加工性 Download PDFInfo
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Abstract
在本发明的一个实施方案中，本发明提供一种包含主要量的聚烯烃或聚烯烃共聚物和少量低分子量离聚物和阴离子表面活性剂的组合物。
Description
技术领域
本发明涉及聚烯烃和聚烯烃共聚物的组合物。更具体地说，本发明涉及提高使用单活性中心催化剂制得的聚烯烃聚合物和共聚物的韧性和可加工性的方法。
发明背景
近年来，通过使用所谓的单活性中心催化剂已开发出一类新的聚烯烃和聚烯烃共聚物。这些催化剂是元素周期表第IVB族金属的环戊二烯基衍生物的有机金属配合物[《物化手册(Handbook of Chemistry andPhysics)》，第56版，CRC出版社(1975)]，与传统的齐格勒-纳塔型催化剂相比，由它们制得的聚烯烃具有更窄的分子量分布。这种窄的分子量分布使得该聚合物材料比常规齐格勒-纳塔型催化剂得到的聚合物材料具有更好的物理性能。
虽然具有这些改进的物理性能，但由单活性中心催化剂制得的聚合物仍需进一步增韧。此外，由于这些材料的分子量分布窄，它们更难于加工。因此，也需要一种提高用单活性中心催化剂制得的聚烯烃和聚烯烃共聚物的可加工性的方法。
本发明的概述
本发明是基于如下发现而完成的：在聚合物或共聚物中加入有效量的低分子量离子共聚物和阴离子表面活性剂，可以提高在单活性中心催化剂存在下制备的共聚物的韧性和可加工性。
因此，在本发明的一个实施方案中，提供一种包含主要量的聚烯烃共聚物和少量低分子量离子聚合物和阴离子表面活性剂的组合物。
在阅读了随后的本发明详细描述之后，将会更清楚本发明的这些和其它实施方案。
本发明的详细描述
可用于本发明中的聚合物包括使用单活性中心催化剂、特别是美国专利No.5 391 629(这里通过引用并入本文)公开的催化剂制得的聚烯烃和聚烯烃共聚物，例如乙烯/α-烯烃共聚物。一般情况下，可用于本发明中的聚合物和共聚物的重均分子量为约30000-约1000000，优选约50000-约200000。
本发明组合物还含有少量的低分子量离子聚合物或共聚物，即，它的重均分子量为约1000-20000，最优选2000-10000。
一般情况下，离子聚合物每100g聚合物具有约0.1-约200、优选约1.0-100毫当量离子侧基。可用的离子基团的示例有羧酸根、磷酸根和磺酸根。优选的离子基团是约有50％被第IA、IIA、IB或IIB族(见先前引用的元素周期表)金属、胺或氨中和的。
基于组合物的总重量，离子聚合物或共聚物的用量低于约20％wt(重量)，一般为约0.5％-约10.0％wt。
特别适用于本发明中的离子聚合物和共聚物包括乙烯/甲基丙烯酸共聚物、磺化聚苯乙烯、磺化叔丁基苯乙烯、磺化乙烯共聚物、磺化丙烯共聚物、磺化苯乙烯/丙烯腈共聚物、磺化苯乙烯/甲基丙烯酸甲酯共聚物、磺化聚异丁烯、磺化乙烯/丙烯三元共聚物、磺化聚异戊二烯以及磺化的弹性体及它们的共聚物。
用于本发明组合物中的阴离子表面活性剂包括，具有约6-20个碳原子的烷基磺酸和羧酸的碱金属盐以及在链烯基中具有约6-约20个碳原子的链烯基硫酸的碱金属盐。在本发明组合物中，阴离子表面活性剂以少量使用。一般情况下，基于组合物的总重量，阴离子表面活性剂的用量为约1％wt，优选的范围为约0.1％-约10.0％wt。
本发明组合物可用任意方便方法制备。例如，可以通过在适宜共混机如布来本登(Brabender)混合机中混合来制备组合物。
实施例
下列实施例将证明，本发明的聚烯烃组合物具有改进的韧性和可加工性。在全部实施例中，基础聚合物或共聚物均使用单活性中心催化剂制备，组合物约在于193℃加热的布来本登混合机中熔融加工。将物料在100RPM下混合5分钟。混合后，将物料冷却至室温，切粒，在193℃压塑成拉伸试样。试样在29美吨压力下压塑成型为约2”×2”×0.02”的片，从这些片上切下用于拉伸试验测量的适当尺寸的试样。
在拉伸速率为0.2cm/分钟下，在英斯特朗(Instron)拉伸试验仪上测量力学性能。
用于实施例中的离聚物是被金属中和的、重均分子量为2000g/mol的乙烯/甲基丙烯酸聚合物。
使用的表面活性剂是具有的碳原子数为约12、端基为钠中和的磺酸根基团的被钠中和的α-烯烃磺酸。
直接在布来本登熔融混合机上测量扭矩减少率。扭矩减少率是将含添加剂的熔体与不含添加剂的熔体的扭矩值比较得到的。
实施例1
将使用单活性中心催化剂制备的、密度为0.873g/cc并且熔体指数为4.5的乙烯/丁烯共聚物与不同量的离子表面活性剂和其中的金属为锌的离聚物熔融共混。测量各共混物的拉伸性能和扭矩减少率，结果列于下表1中。表1中还给出了没有添加表面活性剂和离聚物的对比样的结果。
表中数据证明，向弹性体乙烯共聚物产品中加入表面活性剂和低分子量共聚物离聚物，可以减小扭矩，即改进可加工性。此外，固态物质表现出改进的力学性能。
实施例2
表2列出了如实施例1所述与0.5％wt α-烯烃磺酸盐表面活性剂和不同量的被钠中和的低分子量离聚物熔融共混的乙烯/丁烯共聚物(见实施例1)的力学性能。表中给出了共混物的拉伸强度以及断裂能和扭矩减少率(100RPM)，还给出了没有添加表面活性剂的共混物的结果。
表中数据再次证明，使用低分子量共聚物离聚物和表面活性剂的混合物大大改善了力学性能和可加工性。
实施例3
在此实施例中，使用结晶度为40％-50％的线型低密度聚乙烯和锌中和的离聚物进行试验。操作方法如实施例1中所述，结果列于下表3中。
实施例4
同样使用实施例3中的线型低密度聚乙烯和实施例1的操作方法，但在此实施例中使用共聚物离聚物的钠盐。结果列于下表4中。
表1
力学性能和扭矩减少率的测量
| 表面活性剂(％) | 离聚物，(％) | 模量(psi) | 拉伸强度(psi) | 断裂伸长(％) | 断裂能(In.Lbs.) | 扭矩减少率(％) |
| 0.0 | 0.0 | 301.0 | 1905.0 | 1059.0 | 12.7 | 0.0 |
| 0.5 | 0.25 | 419.0 | 1932.0 | 1196.0 | 23.0 | 12.0 |
| 0.5 | 0.5 | 434.0 | 1962.0 | 1208.0 | 23.8 | 17.0 |
| 0.5 | 1.0 | 500.0 | 2015.0 | 1224.0 | 24.1 | 15.0 |
| 0.5 | 3.0 | 542.0 | 2037.0 | 1257.0 | 28.6 | 13.0 |
| 0.0 | 0.0 | 301.0 | 1905.0 | 1059.0 | 12.7 | 0.0 |
| 0.0 | 1.0 | 701.0 | 1776.0 | 1099.0 | 18.0 | 14.0 |
| 0.0 | 3.0 | 918.0 | 1728.0 | 1099.0 | 17.9 | 17.0 |
| 0.0 | 5.0 | 1078.0 | 1677.0 | 1069.0 | 15.8 | 16.0 |
表2
力学性能和扭矩减少率的测量
| 表面活性剂，％ | 离聚物，(％) | 模量(psi) | 拉伸强度(psi) | 断裂伸长(％) | 断裂能(In.Lbs.) | 扭矩减少率(％) |
| 0.0 | 0.0 | 301.0 | 1905.0 | 1059.0 | 12.7 | 0.0 |
| 0.5 | 0.25 | 460.0 | 1932.0 | 1214.0 | 22.5 | 16.0 |
| 0.5 | 0.5 | 793.0 | 1775.0 | 1204.0 | 21.7 | 11.0 |
| 0.5 | 1.0 | 781.0 | 1782.0 | 1202.0 | 22.0 | 19.0 |
| 0.5 | 3.0 | 954.0 | 1701.0 | 1176.0 | 22.6 | 17.0 |
| 0.0 | 0.0 | 301.0 | 1905.0 | 1059.0 | 12.7 | 0.0 |
| 0.0 | 1.0 | 680.0 | 1657.0 | 1074.0 | 13.5 | 20.0 |
| 0.0 | 3.0 | 992.0 | 1508.0 | 1061.0 | 12.5 | 25.0 |
| 0.0 | 5.0 | 1091.0 | 1396.0 | 1018.0 | 11.5 | 18.0 |
表3
力学性能和扭矩减少率的测量
| 表面活性剂，(％) | 离聚物(％) | 模量(psi) | 拉伸强度(psi) | 断裂伸长(％) | 断裂能(In.Lbs.) | 扭矩减少率(％) |
| 0.0 | 0.0 | 35108.0 | 3834.0 | 693.0 | 25.3 | 0.0 |
| 0.5 | 0.25 | 34421.0 | 4177.0 | 784.0 | 39.8 | 20.0 |
| 0.5 | 0.5 | 35427.0 | 5182.0 | 887.0 | 47.9 | 20.0 |
| 0.5 | 1.0 | 32438.0 | 4842.0 | 862.0 | 42.7 | 20.0 |
| 0.5 | 3.0 | 33701.0 | 7443.0 | 849.0 | 40.9 | 21.0 |
| 0.0 | 0.0 | 35108.0 | 3834.0 | 693.0 | 25.3 | 0.0 |
| 0.0 | 1.0 | 32594.0 | 4478.0 | 783.0 | 38.4 | 10.0 |
| 0.0 | 3.0 | 34046.0 | 3943.0 | 721.0 | 33.3 | 14.0 |
| 0.0 | 5.0 | 33366.0 | 4497.0 | 821.0 | 38.7 | 14.0 |
表4
力学性能和扭矩减少率的测量
| 表面活性剂，(％) | 离聚物，(％) | 模量(psi) | 拉伸强度(psi) | 断裂伸长(％) | 断裂能(In.Lbs.) | 扭矩减少率(％) |
| 0.0 | 0.0 | 35108.0 | 3834.0 | 693.0 | 25.3 | 0.0 |
| 0.5 | 0.25 | 33461.0 | 4567.0 | 824.0 | 41.8 | 19.0 |
| 0.5 | 0.5 | 33521.0 | 4898.0 | 892.0 | 48.8 | 19.0 |
| 0.5 | 1.0 | 34304.0 | 4994.0 | 897.0 | 46.4 | 15.0 |
| 0.5 | 3.0 | 33934.0 | 4718.0 | 869.0 | 46.0 | 19.0 |
| 0.0 | 0.0 | 35108.0 | 3834.0 | 693.0 | 25.3 | 0.0 |
| 0.0 | 1.0 | 33947.0 | 4599.0 | 816.0 | 39.8 | 17.0 |
| 0.0 | 3.0 | 33069.0 | 4540.0 | 838.0 | 42.2 | 14.0 |
| 0.0 | 5.0 | 33351.0 | 4564.0 | 838.0 | 41.8 | 15.0 |
Claims (6)
1.一种组合物，它包含：
(a)使用第IVB族金属的环戊二烯基衍生物的单活性中心催化剂制备的第一种聚烯烃或聚烯烃共聚物，其重均分子量为30000-1000000；和
(b)基于组合物的总重量计，0.5％-20％重量的(i)重均分子量为1000-20000的第二种聚合物，该聚合物选自乙烯/甲基丙烯酸共聚物、磺化聚苯乙烯、碘化叔丁基苯乙烯、磺化乙烯共聚物、磺化丙烯共聚物、磺化苯乙烯/丙烯腈共聚物、磺化苯乙烯/甲基丙烯酸甲酯共聚物、磺化聚异丁烯、磺化乙烯/丙烯三元共聚物、磺化聚异戊二烯以及磺化的弹性体及它们的共聚物，并且该聚合物每100克聚合物具有0.1-200毫当量离子侧基，离子侧基选自羧酸根、磷酸根和磺酸根基团，它们中的50％被金属、胺或氨中和，和(ii)基于组合物的总重量计，0.1％-10％重量的阴离子表面活性剂，所述阴离子表面活性剂选自具有6-20个碳原子的烷基磺酸和羧酸的碱金属盐和具有6-20个碳原子的链烯基硫酸的碱金属盐及其混合物。
2.根据权利要求1的组合物，其中，基于组合物的总重量计，第二种聚合物的存在量为0.5％-10％重量。
3.根据权利要求1或2的组合物，其中，基于组合物的总重量计，所述表面活性剂的存在量为0.5％重量。
4.根据权利要求3的组合物，其中，第二种聚合物中的50％是被金属中和的。
5.根据权利要求4的组合物，其中，所述金属为锌。
6.根据权利要求5的组合物，其中，所述金属为钠。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49926695A | 1995-07-07 | 1995-07-07 | |
| US08/499,266 | 1995-07-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1190414A CN1190414A (zh) | 1998-08-12 |
| CN1103347C true CN1103347C (zh) | 2003-03-19 |
Family
ID=23984558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96195334A Expired - Fee Related CN1103347C (zh) | 1995-07-07 | 1996-07-03 | 用低分子量添加剂提高聚烯烃和聚烯烃共聚物的韧性和可加工性 |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0837904B1 (zh) |
| JP (1) | JP3904232B2 (zh) |
| CN (1) | CN1103347C (zh) |
| CA (1) | CA2222098C (zh) |
| DE (1) | DE69607167T2 (zh) |
| ES (1) | ES2144758T3 (zh) |
| WO (1) | WO1997003123A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6677401B2 (en) | 1995-01-24 | 2004-01-13 | Acushnet Company | Multi-layer golf ball with a thin, castable outer layer |
| US6653403B2 (en) | 1995-01-24 | 2003-11-25 | Acushnet Company | Golf balls having a cover layer formed from an ionomer and metallocene-catalyzed polyolefin blend and methods of making same |
| US6414082B1 (en) | 1995-01-24 | 2002-07-02 | Acushnet Company | Golf ball compositions formed of grafted metallocene-catalyzed polymer blends |
| US7173088B2 (en) | 1997-05-27 | 2007-02-06 | Acushnet Company | Multi-layer golf ball with a thin, castable outer layer |
| JP5669573B2 (ja) * | 2010-12-28 | 2015-02-12 | ダンロップスポーツ株式会社 | ゴルフボール用樹脂組成物およびゴルフボール |
| CN107841018A (zh) * | 2017-10-31 | 2018-03-27 | 格林美（武汉）城市矿产循环产业园开发有限公司 | 一种用于塑料托盘的改性再生高抗冲pe及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0541869A1 (en) * | 1990-08-08 | 1993-05-19 | Exxon Research And Engineering Company | Polyethylene reinforced elastomeric blend compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974240A (en) * | 1974-11-18 | 1976-08-10 | Exxon Research And Engineering Company | Thermoplastic elastomer compositions |
-
1996
- 1996-07-03 DE DE69607167T patent/DE69607167T2/de not_active Expired - Fee Related
- 1996-07-03 ES ES96923634T patent/ES2144758T3/es not_active Expired - Lifetime
- 1996-07-03 WO PCT/US1996/011264 patent/WO1997003123A1/en active IP Right Grant
- 1996-07-03 EP EP96923634A patent/EP0837904B1/en not_active Expired - Lifetime
- 1996-07-03 CN CN96195334A patent/CN1103347C/zh not_active Expired - Fee Related
- 1996-07-03 JP JP50588897A patent/JP3904232B2/ja not_active Expired - Fee Related
- 1996-07-03 CA CA002222098A patent/CA2222098C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0541869A1 (en) * | 1990-08-08 | 1993-05-19 | Exxon Research And Engineering Company | Polyethylene reinforced elastomeric blend compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11508950A (ja) | 1999-08-03 |
| CA2222098A1 (en) | 1997-01-30 |
| ES2144758T3 (es) | 2000-06-16 |
| JP3904232B2 (ja) | 2007-04-11 |
| WO1997003123A1 (en) | 1997-01-30 |
| EP0837904A1 (en) | 1998-04-29 |
| DE69607167D1 (de) | 2000-04-20 |
| CA2222098C (en) | 2003-12-30 |
| DE69607167T2 (de) | 2000-08-10 |
| EP0837904B1 (en) | 2000-03-15 |
| MX9800094A (es) | 1998-03-31 |
| CN1190414A (zh) | 1998-08-12 |
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