CN1424348A - 扩散膜 - Google Patents

扩散膜 Download PDF

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CN1424348A
CN1424348A CN02152444A CN02152444A CN1424348A CN 1424348 A CN1424348 A CN 1424348A CN 02152444 A CN02152444 A CN 02152444A CN 02152444 A CN02152444 A CN 02152444A CN 1424348 A CN1424348 A CN 1424348A
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blend
ethylene
propylene
rubber
film
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CN1263795C (zh
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K·V·尼盖恩
D·K·西蒙斯
R·W·考尔
S·E·赫克斯
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SIKAD CO
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

一种扩散膜为包括脂族聚烯烃和热塑性烯烃(TPO)弹性体的共混物的微孔片材。该共混物包括低于10wt％的弹性体。优选的聚烯烃选自聚乙烯、聚丙烯、其共聚物和其共混物。优选的TPO弹性体选自乙烯－丙烯橡胶(EPR)、乙烯－丙烯－二烯烃三元聚合物橡胶(EPDM)和其混合物。

Description

扩散膜
发明领域
一种扩散膜由脂族聚烯烃和热塑性烯烃弹性体的共混物制备。
发明背景
膜为在两个不同相之间起到边界作用并更大或更低程度地阻止分子在这两相之间运动的结构。这种运动又称为扩散。膜可为实心即无孔的，或半渗透性即微孔的。这些微孔结构起到扩散阻挡物，以及在分子尺寸范围内的高效过滤器的作用，它使离子、水和其它非常小分子的溶剂通过，但几乎不使大分子如蛋白质和胶体颗粒渗透过。这些膜被用于工艺操作，如废液回收、脱盐、电解、渗透和渗析中，和工业应用中如打火机中的流动调节器、氧合器中的膜、电荷储存装置(如电池和燃料电池)中的隔板。
一种这样的膜称为“Celgard”膜。这种Celgard膜具有独特的物理性能并由独特的干燥拉伸工艺制备，其中将半结晶聚合物挤出、退火，然后拉伸形成微孔薄膜。参见：Kesting，R.E.，Syntheticpolymeric Membranes，第二版，John Wiley & Sons，Inc.，NewYork，NY，1985，pp.290-297，和Bierenbaum，H.S.等人，“Microporous Polymeric Films，”Ind.Eng.Chem.，Prod.Res.Develop.，Vol.13，No.1，1974，pp.2-9，这里都作为参考引入。这些膜已成型为中空纤维和平片材。这些薄膜已可用作血液氧合器和打火机的膜，并作为电池隔膜。
尽管这些膜已获得巨大的商业成功，但仍然需要不仅增强其在已有应用中的性能，而且要扩展其在要求更大机械强度同时保持这些膜的独特微孔结构的其它领域中的用途。因此需要在不损害这些膜的微孔结构下提高此类微孔膜的机械强度。
这些膜通常由聚烯烃如聚丙烯和聚乙烯制备。薄膜领域中已知：可通过加入聚异丁烯橡胶和填料提高无孔聚丙烯薄膜的机械强度，参见US4,911,985；可通过加入弹性体改进无孔包装膜，参见US5,071,686；和可通过加入弹性体改进无孔高密度聚乙烯薄膜，参见US5,635,262。然而，这些现有技术无一教导或建议如何改进微孔膜的性能，同时保持膜的孔隙率。欧洲专利公开1,153,967公开了由包括丙烯酸类化合物和选自聚烯烃、热塑性弹性体和接枝聚合物的树脂的树脂组合物构成的微孔膜。
因此，本领域需要一种改进微孔膜的机械强度同时保持膜的孔隙率的方法。
发明概述
一种扩散膜为包括脂族聚烯烃和热塑性烯烃(TPO)弹性体的微孔片材。该共混物包括低于10wt％的弹性体。优选的聚烯烃选自聚乙烯、聚丙烯、其共聚物和其共混物。优选的TPO弹性体选自乙烯-丙烯橡胶(EPR)、乙烯-丙烯-二烯烃三元聚合物橡胶(EPDM)和其混合物。
本发明详细描述
这里公开的膜为微孔膜，参见Kesting，Ibid.，这里作为参考引入。该膜具有厚度低于2mil(50μm)，优选低于1mil(25μm)，最优选厚度0.35至0.9mil(8至23μm)。该膜将具有纵向(MD)拉伸强度(TS ASTMD638)大于1,500kg/cm2和穿刺强度(PS，测试方法在下面描述)大于400g/mil。该微孔膜具有Gurley(ASTM-D726B)低于35sec/10cc，优选低于25sec/10cc。除此之外，这些膜可用作电池隔膜。这些膜可由转相法或干燥拉伸法制备(Kesting，Ibid.，p237-297，和Bierenbaum，Ibid.，都作为参考引入)，但后一方法是优选的。
该微孔膜将由脂族聚烯烃和热塑性烯烃(TPO)弹性体的共混物构成。该共混物将由按共混物计低于10wt％、优选2至10wt％和最优选3至7wt％的弹性体构成。
这里使用的脂族聚烯烃涉及衍生自单一烯烃的并具有构成碳原子的直链-或支化链排列特征的热塑性聚合物的类或组名。重要的聚烯烃包括聚乙烯、聚丙烯、聚丁烯、聚异戊二烯、聚甲基戊烯和其共聚物。它们优选选自聚乙烯、聚丙烯、其共聚物和其共混物。聚乙烯优选指具有密度(ASTM D792)0.95至0.96g/cm2的高密度聚乙烯，和熔体流动指数(MFI，ASTM D1238，190℃/2.16kg)0.38至0.42dg/min。聚丙烯优选指具有密度(ASTM D1505)约0.905和MFI(ASTM1238，230℃/2.16kg)1.5的等规均聚物。
TPO弹性体为基于聚烯烃单体的共聚物或三元聚合物。例如，乙烯-丙烯橡胶(EPR)为一种共聚物，乙烯-丙烯-二烯烃(EPDM)橡胶是指三元聚合物。EPR优选具有门尼粘度(ASTM D1646)约51、以及乙烯单体含量(ASTM D3900)约61wt％和窄分子量分布。EPDM优选具有门尼粘度45至52，乙烯含量69至70wt％和二烯烃含量0.5至3.4wt％，并且分子量分布可以宽或窄。
本发明将参考下面的实施例更充分理解。
实施例
实施例1、3、5和7为无孔前体(即引入孔隙率的拉伸前)薄膜。实施例2、4、6和8为微孔薄膜。将所有物质通过常规熔体共混工艺掺混。实施例1和2为聚乙烯(HDPE，密度-0.959，MFI-0.42，中等分子量，窄分子量分布)与EPDM橡胶(门尼粘度-45，乙烯％-69，二烯烃％-0.5，窄分子量分布)的共混物。实施例3和4为聚丙烯(等规均聚物，密度-0.905，MFI-1.5)与EPDM橡胶(与实施例1和2相同)的共混物。实施例5和6为聚丙烯(与实施例3和4相同)与EPR橡胶(门尼粘度-51，乙烯％-61，窄分子量分布)的共混物。实施例7和8为聚乙烯(HDPE，密度-0.961，MFI-0.38)与EPDM橡胶(门尼粘度-52，乙烯％-70，二烯烃％-3.4，宽分子量分布)的共混物。将这些膜按常规方式通过干拉伸法制备，其中将共混物挤出、退火，然后拉伸形成微孔膜。
测试方法
所有测试方法都是常规的。Gurley(sec/10cc或sec)按照ASTM-D726(B)测量。穿刺强度(PS)按照如下测量。这些测量沿拉伸产品的宽度进行并平均。使用MiTech Stevens LFRA纺织品分析器。针具有直径1.65mm和半径0.5mm。下降速度速率为2mm/sec，和偏离量为6mm。将该膜在具有中心孔11.3mm的夹持装置中夹紧。记录针刺穿了的薄膜相对薄膜产生的耐受力(克力)而形成的位移(毫米)。穿透能量(穿刺强度)定义为抵抗力与最大点的位移之间的乘积。在纵向的拉伸强度(TS)按照ASTM D638用2英寸x0.5英寸样品测量。将5个测量值平均，并记录平均值。
表1
实施例 共混物％弹性体 厚度(密耳) 拉伸强度(TS)kg/cm2 穿刺(PS)kg/mil  Gurleysec/10cc
 1  0  0.56  928  293  NA
 5  0.61  1184  329  NA
 10  0.45  1250  378  NA
 2  0  0.44  1173  373  22
 5  0.48  1837  468  23
 10  0.40  1828  510  29
 3  0  0.84  972  275  NA
 5  0.84  1049  310  NA
 10  0.60  1120  352  NA
 4  0  0.75  1446  353  19
 5  0.69  1580  426  22
 10  0.49  1669  494  123
 5  0  0.83  1040  311  NA
 5  0.70  1137  350  NA
 10  0.59  1420  408  NA
 6  0  0.75  -  386  26
 5  0.65  -  482  20
 10  0.59  -  462  68
 7  0  0.88  -  199  NA
 5  0.86  -  263  NA
 10  0.88  -  299  NA
 8  0  0.74  -  288  25
 5  0.70  -  327  32
 10  0.70  -  355  88
本发明在不离开其精神和中心特征下可具有其它形式的实施方案，因此，应参考所附权利要求，而不是上面的说明书，作为描述本
发明的范围。

Claims (11)

1.一种改进膜的方法，包括如下步骤：
提供一种包括脂族聚烯烃和按共混物计低于10wt％选自乙烯-丙烯橡胶、乙烯-丙烯-二烯烃三元聚合物橡胶和其组合的热塑性烯烃弹性体的共混物的微孔片材。
2.权利要求1的方法，其中弹性体占共混物的约2至10wt％。
3.权利要求2的方法，其中弹性体占共混物的约3至7wt％。
4.权利要求1的方法，其中微孔片材具有Gurley值低于35sec。
5.权利要求4的方法，其中微孔片材具有Gurley值低于25sec。
6.权利要求1的方法，其中聚烯烃选自聚乙烯、聚丙烯、其共聚物和其共混物。
7.权利要求1的方法，其中热塑性烯烃弹性体选自乙烯-丙烯橡胶、乙烯-丙烯-二烯烃三元聚合物橡胶和其组合。
8.一种改进膜的方法，包括如下步骤：
提供一种包括脂族聚烯烃和热塑性烯烃弹性体的一种共混物的具有Gurley值低于35sec的微孔片材，所述脂族聚烯烃选自聚乙烯、聚丙烯、其共聚物和其共混物，所述热塑性烯烃弹性体选自乙烯-丙烯橡胶、乙烯-丙烯-二烯烃三元聚合物橡胶和其组合，该弹性体占共混物的约3至7wt％。
9.一种扩散膜，包括；
一种包括脂族聚烯烃和热塑性烯烃弹性体的一种共混物的微孔片材，该共混物包括低于共混物重量10wt％的弹性体，所述脂族聚烯烃选自聚乙烯、聚丙烯、其共聚物和其共混物，热塑性烯烃弹性体选自乙烯-丙烯橡胶、乙烯-丙烯-二烯烃三元聚合物橡胶和其组合。
10.权利要求9的膜，其中所述共混物占2至10wt％。
11.权利要求10的膜，其中所述共混物占3至7wt％。
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