CN1137195C - 乙烯共聚物材料的加工和增韧 - Google Patents
乙烯共聚物材料的加工和增韧 Download PDFInfo
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- CN1137195C CN1137195C CNB961953462A CN96195346A CN1137195C CN 1137195 C CN1137195 C CN 1137195C CN B961953462 A CNB961953462 A CN B961953462A CN 96195346 A CN96195346 A CN 96195346A CN 1137195 C CN1137195 C CN 1137195C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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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乙烯/α-烯烃共聚物和少量低分子量离聚物的组合物。
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度和可加工性的方法。
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:在共聚物中加入有效量的低分子量离子 共聚物,可以提高在单活性中心催化剂存在下制备的乙烯/α-烯烃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乙烯/α-烯烃共聚物和少量低分子量离子聚合物的组合物。
根据本发明的一个方面,提供了一种具有改进的韧性的聚合物组合物,它含有:(a)主要量的第IVB族金属的环戊二烯基衍生物的单活性中心催化剂制得的乙烯/C3-C12 α-烯烃共聚物;以及(b)低于20%重量的第二种聚合物或共聚物,其重均分子量为11000-20000,并每100g聚合物具有0.1-200毫当量选自羧酸根、磷酸根和磺酸根的离子侧基,该组合物比乙烯/C3-C12 α-烯烃共聚物具有更高的韧性。
其中基于组合物的总重量计,所述第二种聚合物或共聚物的存在量为0.5%-10%重量,优选为乙烯-丙烯酸共聚物且其中离子基团优选是羧酸根基团,更优选被金属中和的。
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.5391629(这里通过引用并入本文)公开的催化剂制得的乙烯/α-烯烃共聚物。一般情况下,可用于本发明中的共聚物的重均分子量为约10000-约2000000,优选约50000-约300000。这些乙烯/α-烯烃聚合物一般含有30%-90%的乙烯和余量的具有约3-12个碳原子的α-烯烃。优选的α-烯烃具有3或4个碳原子。
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磺化聚苯乙烯、磺化叔丁基聚苯乙烯、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。优选的羧酸根型离聚物是乙烯-丙烯酸共聚物。
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。
下列实施例举例说明本发明。
实施例1-5
将使用单活性中心催化剂制备的、熔体指数为4.5、密度为0.873g/cc和多分散度指数为约2.2的乙烯-丁烯共聚物与不同量的重均分子量为2000g/mol、分别被钠和锌中和的乙烯-丙烯酸共聚物熔融共混。熔混操作在于193℃加热的布来本登混合机中进行。物料在100RPM下混合5分钟。冷却到室温,切粒,随后压塑(193℃)成拉伸试样。
采用下述条件通过压塑最终成型为2”×2”×0.02”的片:在193℃预热2分钟,随后在29美吨下压3分钟(193℃),最后经4分钟冷却至室温(仍保持29美吨的压力)。从这些片上切下用于测量拉伸性能试验的适宜大小的试样。
在英斯特朗拉伸试验仪(InstronTensile Tester)在拉伸速度为0.2cm/分钟下测量力学性能。
下表1给出了掺混有不同量的低分子量离聚物(钠盐和锌盐)的共聚物的典型力学性能值。表中还给出了作为对比的未掺混的聚合物的力学性能值。
表1力学性能和扭矩减少率的测量
离聚物添加剂(%) | 模 量(PSI) | 断裂能(in ibs) | 扭 矩减少率(%) | 断裂伸长(%) | 拉伸强度(PSI) | ||
比较例1 | 钠盐 | 0.0 | 301.0 | 12.70 | 0.0 | 1059.0 | 1905.0 |
实施例2 | 钠盐 | 1.0 | 680.0 | 13.50 | 20.0 | 1074.0 | 1657.0 |
实施例3 | 钠盐 | 5.0 | 1091.0 | 11.50 | 18.0 | 1018.0 | 1396.0 |
实施例4 | 锌盐 | 1.0 | 701.0 | 18.0 | 14.0 | 1099.0 | 1776.0 |
实施例5 | 锌盐 | 3.0 | 918.0 | 17.9 | 17.0 | 1099.0 | 1728.0 |
实施例6 | 锌盐 | 5.0 | 1078.0 | 15.8 | 16.0 | 1069.0 | 1677.0 |
表中数据证明,向乙烯共聚物产品中加入低分子量离聚物显著降低了扭矩,可见提高了可加工性。此外,固态物质表现出改进的力学性能、即韧性。
Claims (6)
1.一种具有改进的韧性的聚合物组合物,它含有:(a)主要量的第IVB族金属的环戊二烯基衍生物的单活性中心催化剂制得的乙烯/C3-C12α-烯烃共聚物;以及(b)低于20%重量的第二种聚合物或共聚物,其重均分子量为11000-20000,并每100g聚合物具有0.1-200毫当量选自羧酸根、磷酸根和磺酸根的离子侧基,该组合物比乙烯/C3-C12α-烯烃共聚物具有更高的韧性。
2.根据权利要求1的组合物,其中,基于组合物的总重量计,所述第二种聚合物或共聚物的存在量为0.5%-10%重量。
3.根据权利要求2的组合物,其中,所述离子基团是羧酸根基团。
4.根据权利要求3的组合物,其中,所述离子基团是被金属中和的。
5.根据权利要求1的组合物,其中,所述第二种聚合物是乙烯-丙烯酸共聚物。
6.根据权利要求1的组合物,其中所述离子侧基被50%金属、胺或氨中和。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49926495A | 1995-07-07 | 1995-07-07 | |
US08/499,264 | 1995-07-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1190415A CN1190415A (zh) | 1998-08-12 |
CN1137195C true CN1137195C (zh) | 2004-02-04 |
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Application Number | Title | Priority Date | Filing Date |
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CNB961953462A Expired - Fee Related CN1137195C (zh) | 1995-07-07 | 1996-07-05 | 乙烯共聚物材料的加工和增韧 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0837906B1 (zh) |
JP (1) | JP3878673B2 (zh) |
CN (1) | CN1137195C (zh) |
CA (1) | CA2222454C (zh) |
DE (1) | DE69612202T2 (zh) |
ES (1) | ES2157450T3 (zh) |
WO (1) | WO1997003126A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US6414082B1 (en) | 1995-01-24 | 2002-07-02 | Acushnet Company | Golf ball compositions formed of grafted metallocene-catalyzed polymer blends |
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 |
US7173088B2 (en) | 1997-05-27 | 2007-02-06 | Acushnet Company | Multi-layer golf ball with a thin, castable outer layer |
JP4704547B2 (ja) * | 2000-06-05 | 2011-06-15 | 三井・デュポンポリケミカル株式会社 | 易引き裂き性のあるフィルム乃至シート |
KR100777363B1 (ko) * | 2001-05-15 | 2007-11-19 | (주)바이오니아 | 일체형 격리벽을 갖는 전기 영동판 및 이를 사용하는 핵산염기 서열 분석 장치 |
CN101452755B (zh) * | 2007-11-30 | 2012-02-15 | 北京市电力公司 | 适用于电磁斥力推斥机构的大电流脉冲电源 |
CN117552059B (zh) * | 2024-01-11 | 2024-03-15 | 深圳市协成达科技有限公司 | 一种镀锌电镀液及其制备方法和应用 |
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GB1171085A (en) * | 1967-05-22 | 1969-11-19 | Du Pont | Polymer Composition |
JPS5415692B2 (zh) * | 1971-11-04 | 1979-06-16 | ||
US5071916A (en) * | 1989-04-17 | 1991-12-10 | Shell Oil Company | Blends of linear alternating polyketones and partially neutralized acidic polymers |
KR100330612B1 (ko) * | 1993-11-12 | 2002-11-16 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 열밀봉성필름및그로부터제조된제품 |
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1996
- 1996-07-05 JP JP50590397A patent/JP3878673B2/ja not_active Expired - Fee Related
- 1996-07-05 DE DE69612202T patent/DE69612202T2/de not_active Expired - Fee Related
- 1996-07-05 ES ES96923656T patent/ES2157450T3/es not_active Expired - Lifetime
- 1996-07-05 CN CNB961953462A patent/CN1137195C/zh not_active Expired - Fee Related
- 1996-07-05 EP EP96923656A patent/EP0837906B1/en not_active Expired - Lifetime
- 1996-07-05 CA CA002222454A patent/CA2222454C/en not_active Expired - Fee Related
- 1996-07-05 WO PCT/US1996/011309 patent/WO1997003126A1/en active IP Right Grant
Also Published As
Publication number | Publication date |
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MX9800098A (es) | 1998-03-29 |
EP0837906B1 (en) | 2001-03-21 |
DE69612202T2 (de) | 2001-10-11 |
JPH11508952A (ja) | 1999-08-03 |
ES2157450T3 (es) | 2001-08-16 |
JP3878673B2 (ja) | 2007-02-07 |
CA2222454C (en) | 2005-01-25 |
CN1190415A (zh) | 1998-08-12 |
EP0837906A1 (en) | 1998-04-29 |
WO1997003126A1 (en) | 1997-01-30 |
CA2222454A1 (en) | 1997-01-30 |
DE69612202D1 (de) | 2001-04-26 |
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