CN101041722A - 由超高分子量聚烯烃混合体制造的膜 - Google Patents
由超高分子量聚烯烃混合体制造的膜 Download PDFInfo
- Publication number
- CN101041722A CN101041722A CNA2007100868724A CN200710086872A CN101041722A CN 101041722 A CN101041722 A CN 101041722A CN A2007100868724 A CNA2007100868724 A CN A2007100868724A CN 200710086872 A CN200710086872 A CN 200710086872A CN 101041722 A CN101041722 A CN 101041722A
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- China
- Prior art keywords
- molecular weight
- uhmwpe
- film
- weight polyethylene
- ultrahigh molecular
- Prior art date
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- 239000012528 membrane Substances 0.000 title abstract description 4
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- 239000003921 oil Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/002—Organic membrane manufacture from melts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
一种为微孔薄片的膜,由第一超高分子量聚烯烃和第二超高分子量聚烯烃的混合体制成。各聚烯烃具有一分子量,那些分子量均大于1百万,且一种分子量大于另一种。此外,膜的本征粘度(IV)可大于等于6.3。
Description
发明领域
本发明涉及由超高分子量(UHMW)聚烯烃混合体制造的微孔膜。
发明背景
微孔膜用于各种用途,包括:用于电化学装置(例如电池、燃料电池和电容器)的隔板、分离装置(例如传质装置和过滤装置)、医疗设备(例如血液氧化和透析)、压力调节器、合成纸等等。
制造微孔聚烯烃膜的工艺可大致分为干法工艺(或CELGARD工艺)和湿法工艺。
CELGARD工艺包括使晶状聚烯烃树脂熔融,将熔融物挤压成薄膜,使薄膜退火,以及将薄膜定向(或拉伸)以形成微孔。CELGARD工艺不包括抽提步骤(即溶剂处理),因而其本身比湿法工艺简单。
湿法工艺包括将聚烯烃树脂与液态烃或一些其它低分子量物质混合,使混合体加热并熔融,将熔融物挤压成薄片,定向(或拉伸)薄片,以及用挥发性溶剂将液体从薄片中抽提出来。湿法工艺用于制造包含超高分子量聚乙烯(UHMWPE)的微孔膜。
湿法工艺通常包括下述相分离过程中的一种:(1)液-液相分离;或(2)固-液相分离。液-液相分离,也称TIPS,是指形成富聚合物液相基体和分散的贫聚合物液相,并伴有随后的聚合物凝固。固-液相分离,也称GEL工艺,是指聚合物由熔融混合体结晶。
从KY的Daramic of Owensboro、日本的Tonen Chemical ofTokyo和日本的Asahi Chemical of Tokyo可以购得由填充或未填充颗粒的UHMWPE制备的微孔膜。这些种类的膜也公开于,例如,美国专利US6,824,865、US6,666,969、US6,566,012、US6,245,272、US6,153,133、US6,096,213、US5,993,954、US5,922,492、US5,853,633、US5,830,554、US5,786,396、US5,741,848、US5,281,491、US5,051,183、US4,873,034、US4,734,196、US4,650,730、US4,620,955、US4,600,633、US4,588,633、US4,539,256、和日本专利JP3497569(平成年JP08-064194)、JP3258737(平成年JP06-212006)中。
在一种最终用途——用于二次锂离子电池的电池隔板中,存在着保持或增加其强度(即击穿强度)的同时而减小隔板厚度的持续要求。
因此,需要新的膜来满足这些和其它要求。
发明概述
一种膜,是由第一超高分子量聚乙烯和第二超高分子量聚乙烯混合体制成的微孔薄片。每种聚乙烯具有一分子量,那些分子量均大于1百万,且一种分子量大于另一种。另外,膜的本征粘度(IV)大于等于6.3。
附图说明
为了说明本发明,在附图中显示了一种目前优选的形式;但要理解的是,本发明不限于所示的精确排列和方法。
图1是拉伸前残留在前体中的工艺油百分比与平均孔径间关系的图解说明。
图2是膜的孔隙率与平均孔径间关系的图解说明。
发明说明
一种膜,是指由至少两种超高分子量聚烯烃混合体制成的微孔薄片。下文将更详细地讨论这些混合体。该膜或微孔薄片可以用下列参数中的一种或多种表征:厚度、孔隙率、平均孔径、击穿强度、MacMullin数、Gurley数、本征粘度(IV)和断路温度。下面将讨论这些参数中的每一种。
膜的厚度可小于5mil(125微米)。在另一实施方案中,厚度可在10微米至50微米范围内变化。在又一实施方案中,厚度可在10微米至25微米范围内变化。
膜的孔隙率可在25和85%之间。在一个实施方案中,孔隙率在32-58%范围内变化。在又一实施方案中,孔隙率在43-57%范围内变化。
膜的平均孔径可在0.01-0.5微米之间。在一个实施方案中,平均孔径在0.025-0.09微米范围内变化。在又一实施方案中,平均孔径在0.027-0.054微米范围内变化。
击穿强度可大于等于300gr-force/mil。通过使用Midtech StevensLFRA组织分析仪和直径为1.65mm的针和0.5mm半径,以6mm的最大偏移在2mm/sec速率下记录数据,对分布在成品宽度内的10次测量取平均而测得击穿强度。
MacMullin数(Nmac)可在6-15的范围内。MacMullin数是对离子运动阻力的度量。MacMullin数是电解质饱和的隔板的阻力(r)与当量体积电解质阻力(r0)之比。(Nmac=r/r0)。还可参见通过引用包含于本文的美国专利US4,464,238。
Gurley数(归一化至1mil的厚度)可小于60sec/10cc/mil厚。在一个实施方案中,Gurley数在12至56sec/10cc/mil范围内变化。Gurley数是依据ASTM D-726(B.)由Gurley透气度测定仪(如4120型)测得的在12.2英寸水柱压力下使10cc空气通过一平方英寸薄膜所需的以秒计的时间。
膜的本征粘度(IV)可大于等于6.3dl/g。在另一个实施方案中,IV可大于等于7.7dl/g。由于在挤压过程中聚合物发生断裂和分子量因而降低,薄膜的IV不是构成膜的挤压前的树脂的加权平均。本文所用的本征粘度是指用以提高溶液粘度的溶液中聚合物容量的度量。本征粘度值定义为具体粘度/浓度在零浓度下的极限值。因此,就需要得到不同浓度下的粘度,然后外推至零浓度。粘度值随浓度的变化取决于分子以及溶剂的种类。一般地,线性大分子物质的本征粘度与重均分子量或聚合度有关。对于线性大分子,当已经确定了分子量和粘度之间的关系时,粘度值测量可提供一种快速确定分子量的方法。通过首先在150℃下将0.02g膜溶解于100ml萘烷中1小时,然后用Ubbelohd粘度计在135℃下确定其本征粘度而测量IV。这依据的是ASTM D4020(本文报告为RSV值)。
断路温度可小于140℃。在一个实施方案中,断路温度可小于135℃。在又一实施方案中,断路温度可小于130℃。
膜可以是具有不同分子量的超高分子量聚烯烃的混合体。在一个实施方案中,这些超高分子量聚烯烃可以是超高分子量聚乙烯(UHMWPE)。在另一实施方案中,膜是具有第一分子量的第一超高分子量聚乙烯和具有第二分子量的第二超高分子量聚乙烯的混合体,第一分子量和第二分子量大于1百万且彼此不同。在另一实施方案中,膜是具有第一分子量的第一超高分子量聚乙烯、具有第二分子量的第二超高分子量聚乙烯和具有第三分子量的第三聚烯烃的混合体,第一分子量和第二分子量大于1百万且彼此不同,第三分子量小于1百万。在又一实施方案中,膜可具有大于等于6.3dl/g的IV。在另一实施方案中,膜可具有大于等于7.7dl/g的IV。
第一超高分子量聚乙烯可具有7<IV<15范围内的IV。例如,这种材料可从KY的Ticona of Florence以GUR 4012(IV=10)购得。
第二超高分子量聚乙烯可具有大于等于15的IV。例如,这种材料可从KY的Ticona of Florence以GUR 4120(4022)(IV=21)和4130(4032)(IV=24)以及荷兰的DSM of Beek以STAMYLAN UH 034(IV=15)购得。
第三聚烯烃可为任何“可熔化处理”的聚烯烃。本文所用的“可熔化处理”是指当在其熔点熔融时,聚合物会流动。这种可熔化处理的聚合物可具有小于1.0×106的分子量,也可具有小于等于0.5×106的分子量。这样的聚合物包括,例如,聚乙烯、聚丙烯、聚丁烯、聚戊烯。在一个实施方案中,聚烯烃是聚乙烯,例如高密度聚乙烯(HDPE)。举例来说,这样的HDPE’s可以从KY的Ticona of Florence以GHR 8020(MW=0.35×106)和2110(MW=0.5×106)购得。这种组分的作用之一是,当膜用作电池隔板时允许断路。
在形成微孔薄片后测量膜的IV值。由于在挤压机中的混合和胶凝过程中聚合物发生断链,因此膜的IV值不只是原料IV的加权平均。因此,断链导致比起始组分加权平均低的IV。
在仅有第一和第二UHMWPE组分的膜的那些实施方案中,混合体可包括两种组分的任意重量百分比,例如各组分为1%-99%。在一个实施方案中,混合体可包括20~80重量%的第一组分树脂和80~20重量%的第二组分。在仅有第一和第二组分的另一实施方案中,混合体可包括40~60%的第一组分和60~40%的第二组分。
在具有第一UHMWPE、第二UHMWPE和第三聚烯烃的膜的那些实施方案中,混合体可构成1-6∶1-6∶1-6的第一∶第二∶第三组分的重量比。在这种膜的另一实施方案中,组分比可在1-6∶1-3∶1-6的范围内。在又一实施方案中,混合体可构成1-5.5∶1-2∶1-5.5的重量比。
可通过湿法工艺制造膜。通过使起始树脂组分与将在下文讨论的约10%的工艺油相混合,可将起始树脂组分制成一种干混合体。这种干混合体可装入双螺杆挤压机,与在挤压机中捏合所有组分之前注入挤压机的其余工艺油相混合。通过一狭口模具可将此混合物挤压成无孔薄片。任选地,可通过在定向(拉伸)前抽提(常规的)而将任意比例或全部的工艺油从薄片中除去。可使薄片定向,例如,双轴定向。之后,如果需要,抽提出任何残留的工艺油(即常规抽提技术)。或者,可在挤压机的捏合段之前将起始聚合物组分直接装入挤压机并将全部油注入挤压机中,然后按上面所说的处理。在任一上述实施方案中,也可在第一捏合段之前向挤压机中注入一部分油,然后在第一捏合段后注入其余的油。尽管不是必需的,但已经发现加入将在下文讨论的VEL(粘弹性润滑剂)有益于上述工艺。在挤压时,树脂可构成总混合物的约10-55重量%,其余为工艺油或工艺油和VEL。在另一实施方案中,在挤压时,树脂可构成总混合物的约10-40%。
工艺油在较低温度下(如60℃)对UHMWPE几乎没有溶剂效应,但在高温(如200℃)下则有显著的溶剂效应。这样的油包括石蜡油、环烃油、芳香油和其它材料,包括邻苯二甲酸酯增塑剂,如邻苯二甲酸二丁酯、邻苯二甲酸双(2-亚乙基)酯、邻苯二甲酸二异癸酯、邻苯二甲酸二环己酯、邻苯二甲酸丁苄酯和邻苯二甲酸二(十三)酯。在美国专利US3,351,495、US4,588,633、US4,833,172、US5,248,461和US5,948,557中提到了另外的油、增塑剂和/或溶剂,仅将上述专利中涉及这样的油、增塑剂和/或溶剂的相关部分通过引用包含于本文。
VEL是当加入上述树脂混合物中时改善混合物加工性的组分。改善的加工性是指熔融时间(聚合物体系熔融(或溶化)成流动溶体所需的时间)减少。改善的加工性也被视为挤压机马达耗能减少和当比较加入或不加入润滑剂体系时混合温度的降低。此现象产生的结果包括,但不限于,能耗降低、聚合物的热和机械降解减少、聚合物强度增加、机械磨损减少和聚合物处理量增加。
这样的VEL选自以下物质:脂肪酸酯、乙氧基脂肪酸酯、乙二醇酯、聚乙二醇酯、甘油酯、乙氧基酯、山梨醇酯、乙氧基山梨醇酯、芳香乙氧基酯、醇乙氧基酯、硫醇乙氧基酯、改性乙氧基酯、酰胺表面活性剂、磷酸酯、膦酸酯、亚磷酸酯、烷基硫酸盐、脂肪酸醚、烷基醚硫酸盐、烷芳基醚硫酸盐、磺酸酯、萘磺酸酯、磺基琥珀酸酯、磺化酯、磺化酰胺、烷基醚羧酸酯、烷芳基醚羧酸酯、季铵类、氨基季铵类、乙氧化胺、咪唑啉衍生物、甜菜碱、磺基甜菜碱、氨基丙酸酯、邻苯二酚衍生物、饱和脂肪酸、不饱和脂肪酸、及其混合物。举例来说,可从市场上购得这样的润滑剂。下表给出了示例性目录。
表
商品名或缩写 | 表面活性剂的通常类别 | 具体化学制剂 | 公司 |
RhodasurfLA-12 | 醇乙氧基酯 | 混合直链醇乙氧基酯 | Rhodia HPCII |
RhodasurfLA-3 | 醇乙氧基酯 | 混合直链醇乙氧基酯 | Rhodia HPCII |
RhodapexCD-128 | 烷基(和烷芳基)醚硫酸盐 | 氨直链醇醚硫酸盐 | Rhodia HPCII |
RhodaponBOS | 烷基硫酸盐 | 2-乙基己基硫酸钠 | Rhodia HPCII |
RhodaponUB | 烷基硫酸盐 | 十二烷基硫酸钠 | Rhodia HPCII |
AlkamideSTEDA/B | 酰胺表面活性剂 | 亚乙基双硬脂酰胺 | Rhodia HPCII |
IgepalCO-210 | 芳香乙氧基酯 | 壬基苯酚乙氧基化物 | Rhodia HPCII |
IgepalCO-630 | 芳香乙氧基酯 | 壬基苯酚乙氧基化物 | Rhodia HPCII |
IgepalRC-630 | 芳香乙氧基酯 | 十二烷基酚乙氧基化物 | Rhodia HPCII |
MirataineCBS | 甜菜碱、磺基甜菜碱和氨基丙酸酯 | 椰油/油酰胺丙基甜菜碱 | Rhodia HPCII |
MirataineCOB | 甜菜碱、磺基甜菜碱和氨基丙酸酯 | 椰油酰胺丙基羟基磺基甜菜碱 | Rhodia HPCII |
MiranateLEC-80 | 醚羧酸酯 | 月桂基醚13羧酸钠 | Rhodia HPCII |
RhodameenPN-430 | 乙氧基脂肪胺 | 乙氧基(5摩尔)牛油脂肪胺 | Rhodia HPCII |
RhodameenT-50 | 乙氧基脂肪胺 | 乙氧基(50摩尔)牛油脂肪胺 | Rhodia HPCII |
Calcium Stearate | 脂肪酸,饱和的 | 硬脂酸钙 | |
Linseed Oil | 脂肪酸,不饱和的 | 亚油酸和亚麻酸 | HardwareStore |
Tung Oil | 脂肪酸,不饱和的 | 桐酸 | HardwareStore |
AlkamulsGMS | 甘油酯 | 甘油硬脂酸酯 | Rhodia HPCII |
Kemester1000 | 甘油三油酸酯 | 甘油三油酸酯 | CromptonCorp. |
AlkamulsEGDS | 乙二醇酯 | 乙二醇二硬脂酸酯 | Rhodia HPCII |
AlkamulsJK | 格尔伯特酯(Guerbet ester) | 格伯特二酯 | Rhodia HPCII |
Neustrene059 | 氢化牛脂甘油 | (30%棕榈酸,60%硬脂酸) | CromptonCorp. |
Neustrene064 | 氢化牛脂甘油 | (88%硬脂酸,10%棕榈酸) | CromptonCorp. |
MiranolC2M-SF | 咪唑啉衍生物 | 两性椰油二丙酸二钠 | Rhodia HPCII |
MiranolJEM | 咪唑啉衍生物 | 混合C8两性羧酸钠 | Rhodia HPCII |
Antarox724/P | 乙氧基化物 | Rhodia HPCII | |
RhodacalN | 萘甲醛磺酸盐 | 萘甲醛磺酸盐 | Rhodia HPCII |
SupragilTMWP | 萘磺酸盐 | 二异丙基萘磺酸钠 | Rhodia HPCII |
AlkamulsEL-620 | 聚乙二醇酯 | PEG-30蓖麻油(蓖麻油酸+油酸+棕榈酸) | Rhodia HPCII |
Duraphos2EHAP04 | 磷酸酯 | 磷酸,单&二(2-乙基己基)酯 | Rhodia HPCII |
DEHPAextractant | 磷酸酯 | 磷酸,双(2-乙基己基)酯 | Rhodia HPCII |
RhodafacLO-11ALA | 磷酸酯 | 磷酸,混合直链辛基/癸基醇酯 | Rhodia HPCII |
AmgardTOF | 磷酸酯 | 磷酸,三(2-乙基己基)酯 | Rhodia HPCII |
AlbriteB(2EH)2EHP | 磷酸酯 | 膦酸(2-乙基己基)-双(2-乙基己基)酯 | Rhodia HPCII |
Octylphosphonic Acid | 磷酸酯 | 辛基膦酸酯 | Rhodia HPCII |
RhodaquatDAET-90 | 季胺 | 复合二牛油基硫酸季胺 | Rhodia HPCII |
AlkamulsSML | 脱水山梨醇酯 | 失水山梨糖醇单月桂酸酯 | Rhodia HPCII |
AlkamulsSMO | 脱水山梨醇酯 | 失水山梨糖醇单油酸酯 | Rhodia HPCII |
AlkamulsSTO | 脱水山梨醇酯,乙氧基化 | 失水山梨糖醇三油酸酯 | Rhodia HPCII |
OT-75,OT-100 | 磺基丁二酸酯 | 二辛基磺基琥珀酸钠 | Cytec |
本发明的另一方面涉及通过在定向前预抽提一部分工艺油(或工艺油和VEL)而控制膜的物理性能的方法。已经确定,前体的工艺油含量在定向过程中显著影响膜的物理性能。因此,可通过在定向前从膜中除去的油的量来控制膜的物理性能。
例如,平均孔径和孔隙率明显受定向前前体中油含量的影响。参见图1,证明了拉伸过程中残留在前体中的油(或油和VEL)%(x-轴)与平均孔径(y-轴)之间的关系。曲线1说明当初始(挤出的)混合物在油中包含约24%树脂时的关系。曲线2说明当初始(挤出的)混合物在油中包含约30%树脂时的关系。可以看出,通过在定向前抽提油,可增加平均孔径。参见图2,说明了膜的孔隙率和平均孔径(由拉伸过程中前体中残留的油(或油和VEL)%确定,如图1所示)之间的关系。在图2中,孔隙率是由图1所示的膜样品确定的。可以看出,通过在拉伸前抽提油,空隙率将增加。
实施例
通过以下非限制性实施例进一步说明本发明。表中所列的性能值是在所述条件下单个实验的汇总。在以下所有实施例中,通过双螺杆挤压机,使初始工艺油(或工艺油和VEL,如所指出的那样)和树脂溶液通过一个狭口模具挤压,然后,或者1)抽提(部分或全部)工艺油,之后拉伸(双轴向地),和最后,如果需要,将任何残留的工艺油完全抽提出来;或者2)进行无预拉伸的抽提,然后拉伸(双轴向地),和最后将工艺油完全抽提出来。实验工作包括加入和不加入粘弹性润滑剂(VEL)的配方。百分组成意味着总混合体的重量%。比例表达为重量比。
在一初始实验中,按下述配方制备微孔薄膜:33%HDPE、33%第一UHMWPE(IV=10)和33%第二UHMWPE(IV=24),油与树脂之比为3∶1,无VEL。由此实验确定,在挤压过程中,当与挤压前树脂混合体的加权平均IV相比时,树脂混合物的IV损失在20-30%之间。因此,即使不使用VEL也可制成微孔膜,但使用VEL是优选的。在随后的实验中,由表1所列的配方制备微孔薄膜。
表1
配方 | 油∶VEL | HDPE | UHMWPEIV=10 | UHMWPEIV=15 | UHMWPEIV=21 | UHMWPEIV=24 |
A | 10∶1 | - | 50 | - | - | 50 |
B | 3∶1 | 33 | 33 | - | 33 | - |
C | 3∶1 | 33 | 33 | - | 33 | - |
D | 3∶1 | 33 | 33 | - | - | 33 |
E | 3∶1 | 40 | 20 | - | - | 40 |
F | 3∶1 | 33 | 33 | 33 | - | - |
G | 3∶1 | 55 | 10 | - | - | 35 |
加工参数和薄膜性能列于表2(具有第一UHMWPE和第二UHMWPE混合体的配方)和表3(具有HDPE、第一UHMWPE和第二UHMWPE混合体的配方)。
表2
聚合物(X) | 挤压时聚合物% | 拉伸温度℃ | 拉伸比例(Y) | 厚度微米 | Gurlev数Sec/mil | 击穿强度gr-force | 孔隙率 | 孔径微米 |
A | 24 | 122 | 4×4 | 24-28 | 36-38 | 416 | 38 | 0.029 |
A | 24 | 122 | 5×5 | 16-19 | 36-42 | 406-437 | 40-43 | 0.024-0.028 |
A | 24 | 120 | 4×4 | 13-23 | 9-31 | 184-271 | 48-51 | 0.037-0.049 |
A | 24 | 125 | 4×4 | 11-19 | 23-49 | 131-178 | 46-57 | 0.030-0.050 |
A | 24 | 125 | 5×5 | 11-18 | 26-35 | 166-205 | 47-53 | 0.026-0.043 |
A | 30 | 122 | 4×4 | 14-22 | 26-41 | 333-395 | 40-45 | 0.037-0.037 |
A | 30 | 125 | 4×4 | 12-28 | 21-56 | 226 | 43 | 0.039 |
A | 25 | 115,120 | 3.6-4.4 | 12.4-19.1 | 24.3-35.5 |
表3
聚合物(X) | 挤出时聚合物% | 拉伸温度℃ | 拉伸比例(Y) | 薄膜IV | 厚度微米 | GurleySec/mil | 击穿强度gr-force | MacMullin | 孔隙率 | 孔径微米 | 弯扭系数 | 断路温度℃ |
B | 30 | 120 | 4×4 | 7.7 | 28 | 9-12 | 367 | 51 | 0.041 | |||
B | 30 | 120 | 5×5 | 7.7 | 14-17 | 22-32 | 321-340 | 10.9 | 46-48 | 0.027-0.041 | 2.3 | |
B | 30 | 122 | 4×4 | 7.7 | 21 | 10-11 | 254 | 6.1 | 55 | 0.047 | 1.8 | |
B | 30 | 122 | 5×5 | 7.7 | 12-17 | 19-27 | 256-342 | 9.5 | 50-53 | 0.040-0.055 | 2.2 | |
B | 30 | 122 | 6×6 | 7.7 | 14-18 | 27-33 | 383-393 | 9.1-11.9 | 47-49 | 0.029-0.032 | 2.1-2.4 | |
B | 30 | 125 | 4×4 | 7.7 | 19-20 | 7-23 | 213 | 49 | 0.041 | |||
B | 30 | 125 | 5×5 | 7.7 | 13-17 | 16-21 | 173-249 | 47-48 | 0.051-0.060 | |||
B | 30 | 125 | 6×6 | 7.7 | 12-13 | 13 | 219 | 54 | 0.044 | |||
C | 25 | 115,120 | 3.9-4.8 | 9.0 | 11.2-18.0 | 25.7-44.7 | 254-407 | 7-15 | 47-50 | 0.033-0.038 | 1.9 | 146 |
D | 25 | 115,120 | 3.6-4.8 | 9.2 | 11.4-21.6 | 16.3-53.0 | 260-353 | 7-12 | 43 | 0.029 | 151 | |
D | 25 | 115,120 | 3.5-4.6 | 9.5 | 11.7-20.8 | 14.8-54.9 | 313-322 | 8-12 | 49-54 | 0.031-0.041 | 2 | |
E | 25 | 115,120 | 3.4-4.9 | 8.9 | 12.2-21.1 | 28.4-52.4 | 358-383 | 10 | 48 | 0.033-0.038 | 2.2 | 145 |
F | 25 | 115,120 | 3.7-4.5 | 7.6 | 10.9-17.5 | 12.8-53.5 | 235-387 | 6-8 | 51-57 | 0.037-0.054 | 1.8 | 145 |
G | 25-35 | 115,120 | 3.4-5.5 | 11.2-22.4 | 25.6-52.3 | 133 |
本发明可以不背离其精神和本质特征的其它形式体现,因此,本发明指明的保护范围,应当参考所附的权利要求书,而非上述说明书。
Claims (30)
1、一种包括微孔薄片的膜,由具有第一分子量的第一超高分子量聚乙烯和具有第二分子量的第二超高分子量聚乙烯的混合体制成,所述第一分子量和所述第二分子量大于1百万且彼此不同。
2、如权利要求1所述的膜,其中,该膜具有大于等于6.3的本征粘度。
3、如权利要求2所述的膜,其中,所述本征粘度大于等于7.7。
4、如权利要求1所述的膜,其中,所述第一分子量为7<IV<15。
5、如权利要求1所述的膜,其中,所述第二分子量为IV≥15。
6、如权利要求1所述的膜,具有选自以下集合的性质,该集合的组成有:小于5mil(125微米)的厚度;25和85%之间的孔隙率;0.01-0.5微米之间的平均孔径;大于300gr-force/mil(25微米)的击穿强度;6-15之间的MacMullin数;小于60sec/l0cc/mil的Gurley数;和上述性质的组合。
7、如权利要求1所述的膜,为电池隔板。
8、如权利要求1所述的膜,为锂电池用电池隔板。
9、一种包括微孔薄片的膜,由具有第一分子量的第一超高分子量聚乙烯、具有第二分子量的第二超高分子量聚乙烯、和具有第三分子量的第三聚烯烃的混合体制成,所述第一分子量和所述第二分子量大于1百万且彼此不同,所述第三分子量小于1百万。
10、如权利要求9所述的膜,其中,该膜具有大于等于6.3的本征粘度。
11、如权利要求10所述的膜,其中,所述本征粘度大于等于7.7。
12、如机利要求9所述的膜,其中,所述第一分子量为7≤IV≤15。
13、如权利要求9所述的膜,其中,所述第二分子量为IV≥15。
14、如权利要求9所述的膜,其中,所述第三分子量为IV≤7。
15、如权利要求9所述的膜,具有选自以下如下集合的性质,该集合的组成有:小于5mil(125微米)的厚度;25和85%之间的孔隙率;0.01-0.5微米之间的平均孔径;大于300gr-force/mil(25微米)的击穿强度;6-15之间的MacMullin数;小于60sec/l0cc/mil的Gurley数;和上述性质的组合。
16、如权利要求9所述的膜,为电池隔板。
17、如权利要求9所述的膜,为锂电池用电池隔板。
18、一种制造膜的方法,该膜包括微孔薄片,由具有第一分子量的第一超高分子量聚乙烯和具有第二分子量的第二超高分子量聚乙烯的混合体制成,所述第一分子量和所述第二分子量大于1百万且彼此不同,且具有选自以下集合的性质,该集合的组成有:小于5mil(125微米)的厚度;25和85%之间的孔隙率;0.01-0.5微米之间的平均孔径;大于300gr-force/mil(25微米)的击穿强度;6-15之间的MacMullin数;小于60sec/l0cc/mil的Gurley数;和上述性质的组合,该方法包括步骤:
在挤压机中将第一超高分子量聚乙烯、第二超高分子量聚乙烯和工艺油混合;
挤压出一无孔薄片;
将该无孔薄片定向;和
从定向的无孔薄片中抽提工艺油,从而形成所述膜。
19、如权利要求18所述的方法,其中,混合进一步包括将第一超高分子量聚乙烯、第二超高分子量聚乙烯、工艺油、和粘弹性润滑剂混合。
20、如权利要求18所述的方法,其中,混合进一步包括将第一超高分子量聚乙烯、第二超高分子量聚乙烯、具有小于1百万分子量的聚烯烃、和工艺油混合。
21、如权利要求20所述的方法,其中,混合进一步包括将第一超高分子量聚乙烯、第二超高分子量聚乙烯、具有小于1百万分子量的聚烯烃、工艺油、和粘弹性润滑剂混合。
22、如权利要求18所述的方法,其中,所述工艺油在定向前被部分抽提。
23、如权利要求18所述的方法,其中,在工艺油中第一超高分子量聚乙烯和第二超高分子量聚乙烯占第一超高分子量聚乙烯和第二超高分子量聚乙烯的混合物的10-55重量%。
24、如权利要求18所述的方法,其中,在工艺油中第一超高分子量聚乙烯和第二超高分子量聚乙烯占第一超高分子量聚乙烯、第二超高分子量聚乙烯、和分子量小于1百万的聚烯烃的混合物的10-55重量%。
25、一种用于控制微孔膜物理性质的方法,其包括下列步骤:
将聚合物树脂和工艺油的混合物挤压出模具,以形成无孔前体;
从无孔前体中抽提部分工艺油;和
在部分抽提后拉伸前体,其中,未经部分抽提的微孔膜的物理性质不同于经过部分抽提的微孔膜的物理性质。
26、如权利要求25所述的方法,其中,物理性质选自以孔径和孔隙率构成的集合。
27、如权利要求25所述的方法,其中,该聚合物树脂包括超高分子量聚乙烯。
28、如权利要求25所述的方法,其中,该聚合物树脂包括具有第一分子量的第一超高分子量聚乙烯和具有第二分子量的第二超高分子量聚乙烯,所述第一分子量和所述第二分子量大于1百万且彼此不同。
29、如权利要求25所述的方法,其中,该聚合物树脂包括具有第一分子量的第一超高分子量聚乙烯、具有第二分子量的第二超高分子量聚乙烯、和具有第三分子量的第三聚烯烃的混合体,所述第一分子量和所述第二分子量大于1百万且彼此不同,所述第三分子量小于1百万。
30.如权利要求25所述的方法,其中,从无孔前体中抽提的工艺油部分在40%至100%范围内。
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US20160043372A1 (en) | 2016-02-11 |
US10615388B2 (en) | 2020-04-07 |
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JP5174364B2 (ja) | 2013-04-03 |
US20210013477A1 (en) | 2021-01-14 |
JP2007314764A (ja) | 2007-12-06 |
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