CN104558510A - 一种用于高回弹性热塑性聚氨酯的组合物及制备方法 - Google Patents
一种用于高回弹性热塑性聚氨酯的组合物及制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于高回弹性热塑性聚氨酯的组合物及制备方法,该组合物由包括下列重量份的组分制成:二苯基甲烷二异氰酸酯30~40份;聚己内酯二元醇40~50份;1,4-丁二醇4~10份;间苯二酚-双(2-羟乙基)醚4~10份;阿克苏诺贝尔Expancel微球0.2~4份;填料0.2~4份;抗氧化剂13301~2份;消泡剂0.5~1份;催化剂0.01~0.05份。发明的高回弹性热塑性聚氨酯弹性体材料使用最尖端的弹性体生产技术,对配方进行精密的涉及和调节,将微球成功应用到密封件材料中,生产出回弹性好、永久压缩变形小、耐磨性好、强度高的热塑性聚氨酯弹性体材料,能使用于各种高端密封件,尤其是对材料回弹性和永久压缩变形率有特殊要求的应用。
Description
发明领域
本发明涉及密封件材料领域,特别涉及一种密封件用的高回弹性热塑性聚氨酯组合物及其制备方法。
背景技术
TPU即热塑性聚氨脂(Thermoplastic polyyrethane),是一种新型的有机高分子合成材料,属于化合物,是一种各项性能优异,可以代替橡胶rubber,软性聚氯乙烯材料pvc,优异的物理性能,例如耐磨性,回弹力都好过普通聚氨酯,PVC,耐老化性好过橡胶,可以说是替代PVC和PU的最理想的材料。被国际上称为新型聚合物材料。热塑性聚氨酯弹性体(TPU)是由线性多元醇、有机二异氰酸酯和小分子扩链剂构成。可以通过选择聚氨酯各组成成分并调节它们的比例使得TPU的性能有很宽的变化范围,使其既有橡胶的柔性,又有塑料的刚性,即具有高强度、高伸长性和高弹性等特性。热塑性聚氨酯弹性体(TPU)一般分为聚酯型TPU和聚醚型TPU。
目前密封件市场多数用的是国产的聚酯型弹性体和聚醚型弹性体以及进口的聚己内酯型弹性体。聚酯型弹性体强度高,耐热性好,但弹性差,永久压缩变形差;聚醚型弹性体弹性好,永久压缩变形好,但强度和耐热性差。
发明内容
本发明目的在于提供一种高回弹性热塑性聚氨酯弹性体材料,以解决现有技术中热塑性聚氨酯弹性体回弹性和永久压缩变形差的缺点,特别是特殊应用比如高频率往复装置中对回弹性的超高要求。具体技术方案如下:
一种用于高回弹性热塑性聚氨酯的组合物,包括以下重量份的组分:
一种高回弹性热塑性聚氨酯的制备方法,包括如下步骤:
在反应釜中加入40~50重量份聚己内酯二元醇,缓慢升温至80~100℃,然后加入0.2~4重量份阿克苏诺贝尔Expancel微球,用纳米分散机分散1~2分钟;
然后,加入0.5~1重量份消泡剂,继续分散2~4分钟,再依次加入0.2~4重量份填料、1~2重量份抗氧化剂1330,缓慢升温至110℃后,加入30~40重量份二苯基甲烷二异氰酸酯,在-0.5~-0.2Mpa下脱水2~3小时,得到中间产物;
将4~10重量份1,4-丁二醇、4~10重量份间苯二酚-双(2-羟乙基)醚、0.01~0.05重量份催化剂混合均匀得到混合物,然后所述中间产物与所述混合物在115~135℃下混合后倒入涂有脱模剂的不锈钢钢盘,再放入80℃的鼓风烘箱中硫化20~24小时,继续放置5~7天后取出破碎造粒,即得到所述高回弹性热塑性聚氨酯。
与现有技术相比,本发明有以下有益效果:
本发明的高回弹性热塑性聚氨酯弹性体材料使用最尖端的弹性体生产技术,对配方进行精密的设计和调节,将微球成功应用到密封件材料中,生产出回弹性好、永久压缩变形小、耐磨性好、强度高的热塑性聚氨酯弹性体材料,能使用于各种高端密封件,尤其是对材料回弹性和永久压缩变形率有特殊要求的应用。
附图说明
图1是实施例1的分散效果图;
图2是实施例1的分散效果图。
具体实施方式
下面结合具体实施例来进一步描述本发明,本发明的优点和特点将会随着描述而更为清楚。但这些实施例仅是范例性的,并不对本发明的范围构成任何限制。本领域技术人员应该理解的是,在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换,但这些修改和替换均落入本发明的保护范围内。
实施例1
聚酯型弹性体强度高,耐热性好,但弹性差,永久压缩变形差;聚醚型弹性体弹性好,永久压缩变形好,但强度和耐热性差。本配方使用的聚己内酯二醇兼顾聚酯和聚醚的优点,既具有优秀的强度和耐热性,也有出色的弹性、永久压缩变形率,极大的提升了密封件材料的实用性。
使用分散机和消泡剂完美地分散了微球,微球在注塑加工中高温受热体积会大幅度膨胀,同时微球膨胀为微孔,由此产生的微孔可以为材料提供更好的弹性和永久压缩变形率。微球在体系中的分散效果如图1和图2所示。
扩链剂HER的结构能带给材料更高的耐热性和回弹性,扩链剂HER和BDO的混用提高了材料的回弹性和永久压缩变形率。
表1 聚己内酯的使用
单位 | 聚酯 | 聚醚 | 聚己内酯 | |
硬度 | ShA | 95 | 95 | 95 |
拉伸强度 | Mpa | 52 | 44 | 56 |
断裂伸长 | % | 452 | 528 | 552 |
永久压缩变形率,70℃/24h | % | 36 | 31 | 28 |
回弹性 | % | 30 | 46 | 44 |
由实验数据可以看出,聚己内酯二元醇能提供更好的回弹性和永久压缩变形率。以上试验多元醇(聚酯、聚醚、聚己内酯二醇)48份,二异氰酸酯二苯基甲烷二异氰酸酯37份,扩链剂1,4-丁二醇8份,扩链剂间苯二酚-双(2-羟乙基)醚4.3份。其余为填料、抗氧化剂、消泡剂、催化剂。
表2 加入微球的效果
由实验数据可以看出,选择合适比例的微球,使用分散机和消泡剂能有效的提高材料的回弹性和永久压缩变形率。以上试验多元醇聚己内酯二醇48份,二异氰酸酯二苯基甲烷二异氰酸酯37份,扩链剂1,4-丁二醇8份,扩链剂间苯二酚-双(2-羟乙基)醚4.3份。微球分别为1份和2份。其余为填料、抗氧化剂、消泡剂、催化剂。
表3 扩链剂HER和BDO的混用
单位 | HER | BDO | HER与BDO为1:1 | |
硬度 | ShA | 95 | 95 | 95 |
拉伸强度 | Mpa | 38 | 52 | 48 |
断裂伸长 | % | 529 | 478 | 451 |
永久压缩变形率,70℃/24h | % | 32 | 41 | 28 |
回弹性 | % | 36 | 33 | 38 |
由实验数据可以看出,HER和BDO的混合,能有效的提高材料的回弹性和永久压缩变形率。
扩链剂HER的结构能带给材料更高的耐热性和回弹性,扩链剂HER和BDO的混用提高了材料的回弹性和永久压缩变形率。
表3中的配方(重量份)依次如下:
1、聚己内酯二醇54份,二异氰酸酯二苯基甲烷二异氰酸酯29份,扩链剂间苯二酚-双(2-羟乙基)醚16份。其余为填料、抗氧化剂、消泡剂、催化剂。
2、聚己内酯二醇50份,二异氰酸酯二苯基甲烷二异氰酸酯38份,扩链剂1,4-丁二醇10份。其余为填料、抗氧化剂、消泡剂、催化剂。
3、聚己内酯二醇48份,二异氰酸酯二苯基甲烷二异氰酸酯37份,扩链剂1,4-丁二醇8份,扩链剂间苯二酚-双(2-羟乙基)醚4.3份。其余为填料、抗氧化剂、消泡剂、催化剂。
Claims (2)
1.一种用于高回弹性热塑性聚氨酯的组合物,其特征在于,包括以下重量份的组分:
2.一种高回弹性热塑性聚氨酯的制备方法,其特征在于,包括如下步骤:
在反应釜中加入40~50重量份聚己内酯二元醇,缓慢升温至80~100℃,然后加入0.2~4重量份阿克苏诺贝尔Expancel微球,用纳米分散机分散1~2分钟;
然后,加入0.5~1重量份消泡剂,继续分散2~4分钟,再依次加入0.2~4重量份填料、1~2重量份抗氧化剂1330,缓慢升温至110℃后,加入30~40重量份二苯基甲烷二异氰酸酯,在-0.5~-0.2Mpa下脱水2~3小时,得到中间产物;
将4~10重量份1,4-丁二醇、4~10重量份间苯二酚-双(2-羟乙基)醚、0.01~0.05重量份催化剂混合均匀得到混合物,然后所述中间产物与所述混合物在115~135℃下混合后倒入涂有脱模剂的不锈钢钢盘,再放入80℃的鼓风烘箱中硫化20~24小时,继续放置5~7天后取出破碎造粒,即得到所述高回弹性热塑性聚氨酯。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106243321A (zh) * | 2016-08-02 | 2016-12-21 | 四川航科新材料科技有限公司 | 一种功能性聚氨酯弹性体材料及其制备方法 |
CN109438644A (zh) * | 2018-09-29 | 2019-03-08 | 张海军 | 一种高弹力聚氨酯的制备方法 |
CN111234171A (zh) * | 2020-01-15 | 2020-06-05 | 中国科学院长春应用化学研究所 | 一种用于液力端总成的聚氨酯凡尔胶皮材料 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1663976A (zh) * | 2004-03-05 | 2005-09-07 | 拜尔材料科学股份公司 | 发泡聚氨酯挠性模塑件及其应用 |
CN103130981A (zh) * | 2013-03-20 | 2013-06-05 | 黎明化工研究设计院有限责任公司 | 一种高硬度热塑性聚氨酯弹性体及其制备方法 |
CN104193956A (zh) * | 2014-09-12 | 2014-12-10 | 上海东方雨虹防水技术有限责任公司 | 硬质聚氨酯浇注材料 |
-
2015
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1663976A (zh) * | 2004-03-05 | 2005-09-07 | 拜尔材料科学股份公司 | 发泡聚氨酯挠性模塑件及其应用 |
CN103130981A (zh) * | 2013-03-20 | 2013-06-05 | 黎明化工研究设计院有限责任公司 | 一种高硬度热塑性聚氨酯弹性体及其制备方法 |
CN104193956A (zh) * | 2014-09-12 | 2014-12-10 | 上海东方雨虹防水技术有限责任公司 | 硬质聚氨酯浇注材料 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106243321A (zh) * | 2016-08-02 | 2016-12-21 | 四川航科新材料科技有限公司 | 一种功能性聚氨酯弹性体材料及其制备方法 |
CN106243321B (zh) * | 2016-08-02 | 2019-03-19 | 四川航科新材料科技有限公司 | 一种功能性聚氨酯弹性体材料及其制备方法 |
CN109438644A (zh) * | 2018-09-29 | 2019-03-08 | 张海军 | 一种高弹力聚氨酯的制备方法 |
CN111234171A (zh) * | 2020-01-15 | 2020-06-05 | 中国科学院长春应用化学研究所 | 一种用于液力端总成的聚氨酯凡尔胶皮材料 |
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