CN110204673B - 一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法 - Google Patents

一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法 Download PDF

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CN110204673B
CN110204673B CN201910628797.2A CN201910628797A CN110204673B CN 110204673 B CN110204673 B CN 110204673B CN 201910628797 A CN201910628797 A CN 201910628797A CN 110204673 B CN110204673 B CN 110204673B
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宋红玮
战振生
李庆钊
傅恺凡
王建刚
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Abstract

本发明属于聚氨酯弹性体制备技术领域，尤其涉及一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法。本发明采用特殊结构的三蝶烯衍生物作为扩链剂，该衍生物结构上具有与N原子相连的H，且具有与O原子相连的C，这有助于分子链之间形成氢键，有助于硬段的快速有序排列，最终使产品具有较好的结晶能力；另外，由于三蝶烯衍生物的空间位阻较大，在一定程度上破坏了结晶，且采用较低分子量的多醇作软段，使得最终产品‑‑热塑性聚氨酯弹性体具有较低的硬度、较好的成型性和很好的透明度。

Description

一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法
技术领域
本发明属于聚氨酯弹性体制备技术领域，尤其涉及一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是一类加热可以塑化、化学结构上没有或很少有化学交联的聚氨酯，在宽广的硬度范围内具有高强度、高模量、优良的耐磨性和良好的耐油性。随着TPU的发展，越来越多行业对于硬度在60A-75A的TPU需求越来越高，对其性能要求也不再是简单的低硬度或具备一定使用强度等低端要求，对其成型以及透明性的要求越来越高。从配方角度讲，由于低硬度产品的硬段含量偏低，因此要想使其满足加工的要求，一般大分子二元醇的分子量更倾向于选择3000-4000，这就使得低硬度产品往往满足不了加工要求，又很难获得比较好的透明度，这就限制了低硬度产品的应用。
发明内容
本发明针对上述现有技术存在的不足，提供一种透明成型快的低硬度热塑性聚氨酯弹性体及其制备方法。
本发明解决上述技术问题的技术方案如下：一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：大分子二元醇70-85份、扩链剂3-15份和二异氰酸酯15-35份；
其中，所述扩链剂为三蝶烯衍生物，其结构式如下：
Figure BDA0002128027520000021
R1、R2各自独立的为OH或NH2。
其中，所述的大分子二元醇为聚酯多元醇、聚醚多元醇或聚己内酯多元醇，分子量为1000-2000；
所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或两种以上。
本发明的第二个目的在于提供上述透明成型快的低硬度热塑性聚氨酯弹性体的制备方法，方法如下：将大分子二元醇、扩链剂和二异氰酸酯加入到双螺杆挤出机中，采用一步法双螺杆反应性挤出工艺，出模头后造粒，置于除湿、干燥料斗中干燥得到热塑性聚氨酯弹性体颗粒；
其中，双螺杆挤出机的温度为120-250℃，造粒水温为30-60℃，干燥温度为40-80℃，干燥时间为30mi n-2h。
本发明的特点和有益效果在于：
本发明采用特殊结构的三蝶烯衍生物作为扩链剂，该衍生物结构上具有与N原子相连的H，且具有与O原子相连的C，这有助于分子链之间形成氢键，有助于硬段的快速有序排列，最终使产品具有较好的结晶能力；另外，由于三蝶烯衍生物的空间位阻较大，在一定程度上破坏了结晶，且采用较低分子量的多醇作软段，使得最终产品--热塑性聚氨酯弹性体具有较低的硬度、较好的成型性和很好的透明度。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本发明实施例中使用的发泡珠粒均为市售常规聚合物发泡珠粒。
实施例1
一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：PBA聚酯多元醇(分子量为1500)70份、扩链剂(R1、R2均为OH)10份和甲苯二异氰酸酯20份。
将所得热塑性聚氨酯弹性体进行性能测试，见表1。
实施例2
一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：PEA聚酯多元醇(分子量为2000)75份、扩链剂(R1为OH、R2为NH2)8份和二苯基甲烷二异氰酸酯17份。
将所得热塑性聚氨酯弹性体进行性能测试，见表1。
实施例3
一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：PEBA聚酯多元醇(分子量为1000)75份、扩链剂(R1为OH、R2为NH2)6份和二环己基甲烷二异氰酸酯19份。
将所得热塑性聚氨酯弹性体进行性能测试，见表1。
实施例4
一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：聚醚多元醇(分子量为1000)80份、扩链剂(R1、R2均为NH2)4份和二环己基甲烷二异氰酸酯16份。
将所得热塑性聚氨酯弹性体进行性能测试，见表1。
实施例5
一种透明成型快的低硬度热塑性聚氨酯弹性体，其组分按重量份数计包括：聚己内酯多元醇(分子量为2000)85份、扩链剂(R1、R2均为NH2)5份和二苯基甲烷二异氰酸酯10份。
将所得热塑性聚氨酯弹性体进行性能测试，见表1。
对比例1
一种低硬度热塑性聚氨酯弹性体,其组分按重量份数计包括：聚己内酯多元醇(分子量为2000)85份、扩链剂1,4-丁二醇5份和二苯基甲烷二异氰酸酯10份
将实施例1-5和对比例1所得热塑性聚氨酯弹性体进行性能测试，硬度按ASTMD2240标准进行测试；拉伸强度按ASTM D412标准进行测试；透明度采用2mm试片进行浊度测试；结晶温度采用DSC测试。
表1
Figure BDA0002128027520000041
Figure BDA0002128027520000051
由表1的物性数据可以看出，本发明产品的浊度均较低，且结晶温度相对对比例1明显较高，最终产品在加工时的成型较快。从原理上讲，由于低硬度的TPU其硬段含量较低，能够形成氢键的只能依靠低含量的异氰酸酯上的NH，这个比例是相对较低的，所以此类产品的结晶温度一般较低。采用本发明的扩链剂，其结构上具有与N原子相连的H，且具有与O原子相连的C，这有助于分子链之间形成氢键，进一步提高氢键的比例，有助于硬段的快速有序排列，最终使产品具有较好的结晶能力，在实际生产时成型较快。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种透明成型快的低硬度热塑性聚氨酯弹性体，其特征在于，其组分按重量份数计包括：大分子二元醇70-85份、扩链剂3-15份和二异氰酸酯15-35份；
其中，所述扩链剂为三蝶烯衍生物，其结构式如下：
Figure FDA0002899657610000011
R1、R2同时选自OH或NH2。
2.根据权利要求1所述的透明成型快的低硬度热塑性聚氨酯弹性体，其特征在于，所述的大分子二元醇为聚酯多元醇、聚醚多元醇或聚己内酯多元醇，分子量为1000-2000。
3.根据权利要求1所述的透明成型快的低硬度热塑性聚氨酯弹性体，其特征在于，所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的一种或两种以上。
4.一种权利要求1-3任一项所述透明成型快的低硬度热塑性聚氨酯弹性体的制备方法，其特征在于，方法如下：将大分子二元醇、扩链剂和二异氰酸酯加入到双螺杆挤出机中，采用一步法双螺杆反应性挤出工艺，出模头后造粒，置于除湿、干燥料斗中干燥得到热塑性聚氨酯弹性体颗粒；
其中，双螺杆挤出机的温度为120-250℃，造粒水温为30-60℃，干燥温度为40-80℃，干燥时间为30min-2h。
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