CN1190416A - 乙烯共聚物－单官能基离聚物的组合物 - Google Patents

乙烯共聚物－单官能基离聚物的组合物 Download PDF

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CN1190416A
CN1190416A CN96195347A CN96195347A CN1190416A CN 1190416 A CN1190416 A CN 1190416A CN 96195347 A CN96195347 A CN 96195347A CN 96195347 A CN96195347 A CN 96195347A CN 1190416 A CN1190416 A CN 1190416A
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composition
molecular weight
alpha
olefin
ethylene
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CN1145668C (zh
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D·G·派弗
J·J·克鲁德辛斯基
C－T·卢
T·C·厄德利
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ExxonMobil Technology and Engineering Co
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
    • C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

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乙烯/α－烯烃共聚物或中和的磺化乙烯/α－烯烃共聚物的组合物。

Description

乙烯共聚物-单官能基离聚物的组合物
发明领域
本发明涉及乙烯/α-烯烃共聚物的组合物。更具体地说，本发明涉及改进用单活性中心催化剂制得的乙烯/α-烯烃共聚物的可加工性的方法。
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)]，与传统齐格勒-纳塔型催化剂相比，用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该聚合物材料比用传统齐格勒-纳塔型催化剂得到的聚合物材料具有更好的物理性能。但是，由于这些材料的分子量分布窄，它们更难于加工。因此，需要一种提高用单活性中心催化剂制得的乙烯/α-烯烃共聚物的可加工性的方法。
本发明概述
本发明是基于如下发现完成的：在单活性中心催化剂存在下制得的重均分子量大于约30000的乙烯/α-烯烃共聚物的性能和可加工性，可通过向该共聚物中加入有效量的低分子量乙烯/α-烯烃共聚物或中和的磺化乙烯/α-烯烃共聚物而提高。
因此，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乙烯/α-烯烃共聚物或中和的磺化乙烯/α-烯烃共聚物的组合物。
阅读了随后的本发明详细描述之后，将更清楚本发明的上述及其它实施方案。
本发明的详细描述
构成本发明组合物的主要成分的聚合物包括使用单活性中心催化剂、特别是US No.5391629、US No.4 668 834和EP-B128046和129368(它们的公开内容通过引用被并入本文)公开的催化剂制备的乙烯与具有约3-12个碳原子的α-烯烃的共聚物。一般情况下，可用于本发明中的共聚物的重均分子量为约30000-约1000000，优选约30000-约300000。
本发明组合物还包含少量低分子量乙烯/α-烯烃或中和的磺化乙烯/α-烯烃共聚物，它们的重均分子量为约600-50000、最优选800-20000，α-烯烃具有3-12个碳原子。乙烯/α-烯烃共聚物使用上述美国和欧洲专利中公开的单活性中心催化剂制备。中和的磺化聚合物的制备公开在US No.5389271(通过引用将其并入本文)中。由于这些低分子量中和的磺化乙烯/α-烯烃共聚物是由具有大量不饱和端基的聚合物制备的，所以所引入的官能基主要位于聚合物的链端。
一般情况下，该离聚物每100g聚合物具有约0.5-约200毫当量、优选约1.0-100毫当量被中和的磺酸根侧基。优选磺酸根基团约50％被第IA、IIA、IB或IIB族金属(见前述元素周期表)、胺或氨中和。
在本发明组合物中，低分子量共聚物中的α-烯烃优选与高分子量共聚物中的α-烯烃相同。
本发明组合物可用任意常规方法制备。例如，可通过在适宜混合机如布来本登(Brabender)混合机中混合来制备该组合物。
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，组合物均在于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25℃、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。
实施例1
使用单活性中心催化剂制备一种乙烯/1-丁烯共聚物，它含有82.3％wt(重量)的乙烯，重均分子量为7400g/mol，用它来制备被中和的磺化共聚物。
磺化过程如下进行：在装有氮气进管、温度计、气动搅拌器、冷凝器、加热套的1升四颈烧瓶中加入300ml庚烷。随后将30g乙烯/丁烯(EB)共聚物溶解。为确保半结晶EB的完全溶解，将溶液的温度升至约90℃(即，89-95℃)。达到热平衡时，溶解2.3ml乙酸酐，随后慢慢加入0.9ml的硫酸。滴加硫酸所用的时间约为15-20分钟。连续搅拌30分钟之后，用溶于6ml水和3ml甲醇中的2.58g乙酸钠将得到的官能化的EB共聚物中和，此间使温度降至室温。
用汽提法将中和的共聚物分离，将其回收、风干，然后在60℃的真空烘箱中更彻底地干燥24小时。进行硫量分析，用含硫量计算磺化度。在此特定试验中，硫量分析值为0.43wt，对应于含硫量为13.5meq/100g聚合物。最终产物是钠中和的(单官能基)磺化EB共聚物。
实施例2
重复实施例1的操作，不同之处在于，使用乙酸锌、即溶于8ml水和3ml甲醇中的5.78g乙酸锌进行中和。
含硫量为0.58％wt，对应于18.2meq/100g聚合物。最终产物是锌中和的(单官能基)磺化EB共聚物。
实施例3
重复实施例1的操作，不同之处在于，使用乙酸钙、即溶于16ml水和3ml甲醇中的4.99g乙酸钙进行中和。
含硫量为0.64％wt，对应于20.0meq/100g聚合物。最终产物是钙中和的(单官能基)磺化EB共聚物。
实施例4-11
将上述磺化EB半结晶、单官能基离聚物以不同的量与用单活性中心催化剂制备的熔体指数为4.5、密度为0.873g/cm3的乙烯-丁烯共聚物熔融共混。
测量上述共混物的拉伸性能和扭矩的减小率，结果列于下表。
实施例12-14
使用未官能化的低分子量EB共聚物(7400g/mol)和熔体指数为4.5、密度为0.8739/cm3的EB共聚物制备共混物。下表中也给出了这些共混物的拉伸性能和扭矩的减少率。
比较例1
测量未共混的EB共聚物的拉伸性能，结果列于下表。
                                                          表
                                              力学性能和扭矩减少率的测量
  金属抗衡离子    添加剂(％)     模量(PSI)   扭矩减少率(％)     断裂能(IN-LBS)    断裂伸长(％))    拉伸强度(PSI)
    对比例     无     0.0     301.0     0.0     12.7     1059.0     1905.0
    Ex 4     钠     1.0     667.0     10.0     13.6     1055.0     1736.0
    Ex 5     钠     3.0     708.0     30.0     12.7     1013.0     1723.0
    Ex 6     钠     5.0     695.0     27.0     11.9     1037.0     1802.0
    时比例     无     0.0     301.0     0.0     12.7     1059.0     1905.0
    Ex 7     锌     1.0     738.0     10.0     13.0     1043.0     1711.0
    Ex 8     锌     3.0     1028.0     22.0     10.3     966.0     1520.0
    Ex 9     锌     5.0     1041.0     18.0     12.2     995.0     1602.0
    时比例     无     0.0     301.0     0.0     12.7     1059.0     1905.0
Ex 10 钙 1.0 610.0 15.0 12.8 1041.0 1695.0
    Ex 11     钙     5.0     864.0     22.0     11.2     970.0     1693.0
    对比例     无     0.0     301.0     0.0     12.7     1059.0     1905.0
    Ex 12     无     1.0     743.0     28.0     16.0     1097.0     1739.0
    Ex 13     无     3.0     904.0     27.0     12.6     1018.0     1726.0
Ex 14 无 5.0 1194.0 27.0 11.3 935.0 1572.0

Claims (7)

1.一种组合物，它包含：
(a)主要量的使用第VIB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乙烯/α-烯烃共聚物，其重均分子量大于约30000；和
(b)少量的使用第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乙烯/α-烯烃共聚物或其磺化衍生物，其分子量小于第一种共聚物的分子量、为约600-约50000，磺化衍生物的约50％被金属、胺或氨中和。
2.根据权利要求1的组合物，其中，所述低分子量共聚物的重均分子量为约600-约50000。
3.根据权利要求2的组合物，其中，两种共聚物中的α-烯烃具有约3-约12个碳原子。
4.根据权利要求3的组合物，其中，两种共聚物中的α-烯烃是相同的。
5.根据权利要求4的组合物，其中，所述离子聚合物每100g聚合物具有约10-约200毫当量离子基团，约50％的离子基团被金属、胺或氨中和。
6.根据权利要求5的组合物，其中，所述离子基团是磺酸根基团。
7.根据权利要求6的组合物，其中，所述离子基团是被金属中和的。
CNB961953470A 1995-07-07 1996-07-05 乙烯共聚物-单官能基离聚物的组合物 Expired - Fee Related CN1145668C (zh)

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US08/499,262 US5677381A (en) 1995-07-07 1995-07-07 Ethylene copolymer-monofunctional ionomer compositions

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US3642728A (en) * 1968-10-07 1972-02-15 Exxon Research Engineering Co Sulfonated polymers
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JP3157163B2 (ja) * 1991-12-30 2001-04-16 ザ・ダウ・ケミカル・カンパニー エチレンインターポリマーの重合
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ES2155095T5 (es) * 1993-10-21 2006-04-16 Exxonmobil Oil Corporation Mezclas de poliolefinas con distribucion bimodal de pesos moleculares.
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CA2222458A1 (en) 1997-01-30
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US5677381A (en) 1997-10-14
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DE69612096D1 (de) 2001-04-19
DE69612096T2 (de) 2001-08-02
MX9800099A (es) 1998-03-31
EP0837907B1 (en) 2001-03-14
WO1997003125A1 (en) 1997-01-30
CN1145668C (zh) 2004-04-14
EP0837907A1 (en) 1998-04-29

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