CN106751043A - 一种高强度、高热稳定性的聚4‑甲基‑1‑戊烯微孔膜及其制备方法 - Google Patents

一种高强度、高热稳定性的聚4‑甲基‑1‑戊烯微孔膜及其制备方法 Download PDF

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CN106751043A
CN106751043A CN201611207747.XA CN201611207747A CN106751043A CN 106751043 A CN106751043 A CN 106751043A CN 201611207747 A CN201611207747 A CN 201611207747A CN 106751043 A CN106751043 A CN 106751043A
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张龙
王郗
高东波
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Hefei Xingyuan New Energy Materials Co Ltd
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Abstract

本发明公开了一种高强度、高热稳定性的聚（4‑甲基‑1‑戊烯）微孔膜及其制备方法。该隔膜由聚（4‑甲基‑1‑戊烯）、抗氧剂和稀释剂组成。其中，聚（4‑甲基‑1‑戊烯）树脂：25～50份；抗氧剂：0.05～1份；稀释剂：50～75份；通过混炼熔融、挤出成型、双向拉伸、萃取干燥、热处理定型等工序制得聚（4‑甲基‑1‑戊烯）微孔膜，本发明的优点在于，相比于聚烯烃隔膜，具有高耐热性、高机械强度及高吸液保液率等优点。用本发明所制备的聚（4‑甲基‑1‑戊烯）微孔膜在105℃/1h时MD方向上热收缩率不大于3.0，TD方向上的热收缩率不大于2.0，MD拉伸强度大于200MPa，TD拉伸强度大于170MPa，透气率范围150±50 sec/100mL。

Description

一种高强度、高热稳定性的聚4-甲基-1-戊烯微孔膜及其制备 方法
技术领域
本发明涉及锂离子隔膜材料，具体为一种高强度、高热稳定性的聚(4-甲基-1-戊烯)微孔膜及其制备方法,本发明属于锂离子二次电池制造技术领域。
背景技术
目前，以热致相分离法制备的锂离子电池的隔膜以PE(聚乙烯)为主，其具有良好的化学稳定性和优异的物理性能，但是，商品化的PE隔膜熔点在150℃以下，高温下，热收缩性能差，在锂离子电池使用的过程中，由于一些原因，造成隔膜被刺穿而穿孔，或者因内部或外部的作用下电池温度升高，隔膜发生热收缩或者融化，锂电池正负极直接接触，从而造成锂电池短路甚至爆炸，致使锂电池的安全使用受到局限。
从锂离子电池使用的安全性考虑，隔膜企业纷纷开始研发高强度、高热稳定性的锂电池隔膜，从而保证锂电池能在较高温度下的安全使用。
聚(4-甲基-1-戊烯)(以下简称TPX)，TPX是其商品名，TPX具有耐高温、维卡软化点195℃左右、熔点高达240℃、较高的机械强度、高温下耐蠕变性等优良特性，耐环境和耐化学性能好，受到了锂电池行业的注意。
发明内容
本发明旨在克服上述缺点，提供一种高强度、高热稳定性的TPX微孔膜及其制备方法。
本发明的目的是通过以下技术措施实现的：
一种高强度、高热稳定性的TPX微孔膜，由聚(4-甲基-1-戊烯)树脂以及稀释剂和抗氧剂组成，其重量份数为：
聚(4-甲基-1-戊烯)树脂：25～50份；
抗氧剂：0.05～1份；
稀释剂：50～75份。
所述TPX分子量为1×104～1×107；
所述TPX结晶度为30-60％；
所述抗氧剂为受阻酚、抗氧剂168、抗氧剂1010、抗氧剂CA、胺类抗氧剂或有机硫化物的一种或两种以上的混合物；
所述稀释剂为十氢萘、矿物油、石蜡油中的至少一种；
一种高强度、高热稳定性TPX微孔膜的制备方法，包括如下步骤：
(1)将TPX粒料、抗氧剂及稀释剂按一定的重量比加入到挤出机，挤出机工作温度为200～350℃；挤出机螺杆转速为50～300rpm/min；输出压力为10～60MPa，；塑化混炼得到混合物I；
(2)步骤(1)所述混合物I经过计量泵和过滤器过滤后输送到模头并挤出，模头温度240～400℃；然后通过冷却辊将熔体冷却制得前驱体膜，冷却辊工作温度为20～90℃；
(3)将前驱体膜进行双向拉伸，双向拉伸倍率为3～15×5～20；
(4)在室温下利用清洗剂对前驱体膜萃取除去稀释剂并干燥，所述清洗剂为醇或卤代烷烃；
(5)将步骤(4)中干燥后的膜经过热处理定型，定型温度为80～140℃，定型时间1～5分钟。
本发明的有益效果在于：
本发明具有连续生产、工艺流程操作简单等优点，本发明所述微孔膜在105℃/1h时MD方向上热收缩率不大于3.0，TD方向上的热收缩率不大于2.0，MD拉伸强度大于200MPa，TD拉伸强度大于170MPa，透气率范围150±50sec/100mL。本发明所生产的微孔膜具有高耐热性、高机械强度及高吸液保液率等优点。
具体实施方式
以下结合具体的实施例来对本发明的内容进一步说明，但是本发明的保护范围并不仅仅局限于实施例所描述的内容。
实施例1
称量50份TPX(分子量为1×105，结晶度为30％)，0.05份抗氧剂(抗氧剂1010)，50份的石蜡油，将TPX和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成TPX混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到TPX微孔膜，其中挤出机工作温度240℃，模头温度280℃，螺杆转速50rpm/min，输出压力为15Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
实施例2
称量25份TPX(分子量为5×106，结晶度为60％)，1份抗氧剂(抗氧剂168)，75份的石蜡油，将TPX和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成TPX混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到TPX微孔膜，其中挤出机工作温度280℃，模头温度300℃，螺杆转速150rpm/min，输出压力为45Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
实施例3
称量30份TPX(分子量为2×105，结晶度为35％)，0.1份抗氧剂(抗氧剂1010)，69.5份的石蜡油，将TPX和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成TPX混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到TPX微孔膜，其中挤出机工作温度240℃，模头温度280℃，螺杆转速50rpm/min，输出压力为25Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
实施例4
称量40份TPX(分子量为2×105，结晶度为35％)，0.5份抗氧剂(抗氧剂1010)，59.5份的矿物油，将TPX和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成TPX混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到TPX微孔膜，其中挤出机工作温度240℃，模头温度280℃，螺杆转速50rpm/min，输出压力为25Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
实施例5
称量30份TPX(分子量为5×106，结晶度为50％)，0.5份抗氧剂(抗氧剂168)，69.5份的矿物油，将TPX和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成TPX混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到TPX微孔膜，其中挤出机工作温度260℃，模头温度300℃，螺杆转速120rpm/min，输出压力为40Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
对比例
称量35份PE，0.1份抗氧剂(抗氧剂1010)，64.9份的石蜡油，将PE和抗氧剂按比例输送到挤出机，再将石蜡油由辅机输送到挤出机，由挤出机塑化混溶形成PE混合熔体，通过冷却辊铸片成片材，经双向拉伸、萃取干燥、热处理定型后得到PE微孔膜，其中挤出机工作温度240℃，模头温度280℃，螺杆转速50rpm/min，输出压力为15Mpa，冷却辊温度60℃，双向拉伸倍率为8×10倍，定型温度120℃，定型时间1min，产品性能见表1。
表1
由表1可以看出,以TPX为原料所制备的微孔膜,其机械强度、热稳定性都较PE微孔膜有很大的提高，且其吸液保液性能也较PE膜好，其中TPX结晶度高，其透气性能较好。
以上是对本发明一种高强度、高热稳定性的聚(4-甲基-1戊烯)微孔膜及其制备方法进行了阐述，用于帮助理解本发明，但本发明的实施方式并不受上述实施例的限制，凡以本发明所述特征或原理做的等效修改或替换，均应包含在本发明的保护范围之内。

Claims (6)

1.一种高强度、高热稳定性的聚（4-甲基-1-戊烯）微孔膜，其特征在于，由以下组分按重量份制备而成：
聚（4-甲基-1-戊烯）树脂：25～50份；
抗氧剂：0.05～1份；
稀释剂：50～75份。
2.根据权利要求1所述的聚（4-甲基-1-戊烯）微孔膜，其特征在于，所述聚（4-甲基-1-戊烯）树脂的分子量为1×104～1×107。
3.根据权利要求1所述的聚（4-甲基-1-戊烯）微孔膜，其特征在于，所述聚（4-甲基-1-戊烯）树脂的结晶度为30-60%。
4.根据权利要求1所述的聚（4-甲基-1-戊烯）微孔膜，其特征在于，所述抗氧剂为受阻酚、抗氧剂168、抗氧剂1010、抗氧剂CA、胺类抗氧剂或有机硫化物的一种或两种以上的混合物。
5.根据权利要求1所述的聚（4-甲基-1-戊烯）微孔膜，其特征在于，所述稀释剂为十氢萘、矿物油、石蜡油中的至少一种。
6.一种制备权利要求1～7任一所述高强度、高热稳定性聚（4-甲基-1-戊烯）微孔膜的方法，其特征在于，包括如下步骤：
（1）将聚（4-甲基-1-戊烯）树脂粒料、抗氧剂及稀释剂按一定的重量比加入到挤出机，挤出机工作温度为200～350℃；挤出机螺杆转速为50～300rpm/min；输出压力为10～60MPa，塑化混炼得到混合物I；
（2）步骤（1）所述混合物I经过计量泵和过滤器过滤后输送到模头并挤出，模头温度240～400℃；然后通过冷却辊将熔体冷却制得前驱体膜，冷却辊工作温度为20～90℃；
（3）将前驱体膜进行双向拉伸，双向拉伸倍率为3～15×5～20；
（4）在室温下利用清洗剂对前驱体膜萃取除去稀释剂并干燥，所述清洗剂为醇或卤代烷烃；
（5）将步骤（4）中干燥后的膜经过热处理定型，定型温度为80～140 ℃，定型时间1～5分钟。
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CN108269957A (zh) * 2018-01-22 2018-07-10 四川大学 具有高浸润性、高热稳定性的锂电池隔膜及其制备方法
CN108269957B (zh) * 2018-01-22 2020-07-31 四川大学 具有高浸润性、高热稳定性的锂电池隔膜及其制备方法
CN112778679A (zh) * 2020-12-31 2021-05-11 苏州市新广益电子有限公司 一种高强度、高热稳定性的聚4-甲基-1-戊烯微孔膜及其制备方法
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