CN113861372A - 一种透明热塑性聚氨酯弹性体 - Google Patents

一种透明热塑性聚氨酯弹性体 Download PDF

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CN113861372A
CN113861372A CN202111202881.1A CN202111202881A CN113861372A CN 113861372 A CN113861372 A CN 113861372A CN 202111202881 A CN202111202881 A CN 202111202881A CN 113861372 A CN113861372 A CN 113861372A
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王超
申治华
贾桓
马晓峰
罗艳龙
罗振扬
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Abstract

本发明公开了一种透明热塑性聚氨酯弹性体，属于热塑性弹性体领域。本发明的弹性体采用一种新型的扩链剂，以二甘醇胺与1,1,3,3‑四甲基二硅烷为原料而合成，其中，二甘醇胺与1,1,3,3‑四甲基二硅烷的摩尔比为2:1。该扩链剂的结构中同时含有硅氧烷、氨基和醚键，这个结构的扩链剂，既能够打乱聚氨酯硬段的规整性，保证弹性体的透明性，又能够以氢键的形式提高材料的力学性能，从而得到综合性能优越的高透明热塑性聚氨酯弹性体。

Description

一种透明热塑性聚氨酯弹性体
技术领域
本发明属于热塑性弹性体领域，具体地说，涉及一种透明热塑性聚氨酯弹性体。
背景技术
光学透明高分子材料是指光线透过率在80%以上的高分子材料。光学透明高分子材料应用广泛，最常见的透明高分子有聚碳酸酯、聚苯乙烯和聚甲基丙烯酸甲酯。这几种材料透明度高，但在其他性能方面均有不足。如聚碳酸酯硬度低，耐磨性、耐老化性较差；聚苯乙烯抗冲击性差，低温脆性明显，耐候性差；聚甲基丙烯酸甲酯力学性能一般，抗冲击性差。随着对高透明高分子材料应用的拓展，透明聚氨酯材料进入了人们的视野。
聚氨酯弹性体是由二异氰酸酯、低聚物多元醇和小分子二元醇或二元胺为扩链剂组成的一种嵌段共聚物。异氰酸酯与小分子二元醇或二元胺形成硬段，低聚物多元醇构成软段，硬段和软段在热力学上不相容性，使聚氨酯产生了微相分离结构。聚氨酯弹性体的这种结构特点赋予了其具有拉伸强度高、断裂伸长率大、耐磨、耐撕裂、抗刺穿、与金属的黏结性能好、玻璃化温度低等特点，综合性能优异。聚氨酯的产品形式丰富多样，可以制成胶黏剂、涂料、弹性体甚至是塑料，在汽车工业、医用设备、航空航天、国防建设、安全防护等领域得到了广泛应用。
在高分子材料中，大分子的结晶现象是影响材料透明性的重要因素。根据高聚物理论，非晶聚合物是透明的；在结晶聚合物中，如果晶相和非晶相的密度非常接近或晶粒尺寸小于可见光波长时，结晶聚合物也是透明的。聚氨酯弹性体软段聚集态柔软，结晶倾向不强，硬段在强极性的氨基甲酸酯基团、氢键以及分子间作用力的作用下，容易产生有序排列而结晶，具有明显的微相分离结构，因此，为保证聚氨酯弹性体的高透明性，要尽可能地使硬段和软段具有一定相容性或控制结晶相晶粒尺寸小于可见光波长度。
聚硅氧烷是典型的无定型结构，不结晶。如果用含硅氧烷结构的二元醇或二元胺作为聚氨酯弹性体的扩链剂，可以有效打乱硬段的规整性，有利于提高聚氨酯弹性体的透明性。1,1,3,3-四甲基-1,3-二硅氧烷二醇和1,1,3,3-四甲基-1,3-二硅氧烷二胺均可作为聚氨酯弹性体的扩链剂，但这两种化学品作为扩链剂时，在热塑性聚氨酯弹性体（TPU）反应型挤出加工时，因为和多元醇、二异氰酸酯相容性差距较大，反应型挤出加工性能不佳。而且，由于1,1,3,3-四甲基-1,3-二硅氧烷二胺高的反应活性，也很难适用于反应型挤出。
为了相对提高各种原料之间的相容性，可以选择1,3-双(4-羟基丁基)四甲基硅氧烷这类现成的二硅氧烷二醇做扩链剂。但扩链剂结构中没有和聚氨酯形成氢键的基团，难以在保证弹性体透明的情况下提高材料的力学性能。
发明内容
针对现有技术存在的上述问题，本发明的目的在于提供一种透明热塑性聚氨酯弹性体，它采用了一种同时含有硅氧烷结构和氨基、醚键的二元醇作为扩链剂，在保证弹性体透明的情况下提高材料力学性能。
为了解决上述问题，本发明所采用的技术方案如下：
一种透明热塑性聚氨酯弹性体，由多元醇、二异氰酸酯和扩链剂聚合而成，所述的 扩链剂的结构式为
Figure 841061DEST_PATH_IMAGE001
，将其命名为1,3- 双[2-(2-羟基乙氧基)-乙基氨基]四甲基二硅氧烷。
所述的扩链剂的制备方法为：以二甘醇胺与1,1,3,3-四甲基二硅烷为原料，合成所述的扩链剂，其中，二甘醇胺与1,1,3,3-四甲基二硅烷的摩尔比为2:1。
将二甘醇胺置于反应器中，通入保护气，然后在-20~20℃条件下，1~3小时内滴加1,1,3,3-四甲基二硅烷，滴加完成后，维持原温度反应0.5小时，然后升温至50~80℃，继续反应1小时，得到所述的扩链剂。
所述的多元醇为聚四氢呋喃聚醚二醇、聚己二酸二醇酯或聚碳酸酯二醇。
所述的二异氰酸酯为二苯基甲烷二异氰酸酯（MDI）、4,4'-二环己基甲烷二异氰酸酯（HMDI）、苯二亚甲基二异氰酸酯（XDI）或六亚甲基二异氰酸酯（HDI）。
采用双螺杆反应型挤出的方式制备所述的热塑性聚氨酯弹性体。
多元醇、扩链剂和二异氰酸酯的摩尔比为1:(3~6):(4~8)。
螺杆的加料段、熔融段、混合段和均化段的温度分别设置为(140~145):(160~170):(165~170):(145~155)。
相比于现有技术，本发明的热塑性聚氨酯弹性体采用一种新型的扩链剂，该扩链剂的结构中同时含有硅氧烷、氨基和醚键，这个结构的扩链剂，既能够打乱聚氨酯硬段的规整性，保证弹性体的透明性，又能够以氢键的形式提高材料的力学性能，从而得到综合性能优越的高透明热塑性聚氨酯弹性体。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
将105.1g二甘醇胺置于三颈烧瓶中，接入保护氮气于液面以下。在10℃条件下，1.0小时内缓慢滴入67.1g 1,1,3,3-四甲基二硅烷。滴加完成后，在10℃下继续反应0.5小时，然后升温至70℃，继续搅拌反应1小时，得到170.2g 1,3-双[2-(2-羟基乙氧基)-乙基氨基]四甲基二硅氧烷。
实施例2
将147.2g二甘醇胺置于三颈烧瓶中，接入保护氮气于液面以下。在5℃条件下，2.5小时内缓慢滴加94.0g 1,1,3,3-四甲基二硅烷。滴加完成后，在5℃下继续反应0.5小时，然后升温至73℃，继续搅拌反应1小时，得到238.4g 1,3-双[2-(2-羟基乙氧基)-乙基氨基]四甲基二硅氧烷。
实施例3
将210.3g二甘醇胺置于三颈烧瓶中，接入保护氮气于液面以下。在-15℃条件下，2.8小时内缓慢滴加134.3g的1,1,3,3-四甲基二硅烷。滴加完成后，在-15℃下继续反应0.5小时，然后升温至65℃，继续搅拌反应1小时，得到340.6g 1,3-双[2-(2-羟基乙氧基)-乙基氨基]四甲基二硅氧烷。
以制备的成品1,3-双[2-(2-羟基乙氧基)-乙基氨基]四甲基二硅氧烷为扩链剂（标注为B），采用双螺杆反应型挤出工艺制备热塑性弹性体，螺杆长径比为40:1。以1,3-双(4-羟基丁基)四甲基硅氧烷为扩链剂制备热塑性弹性体作为对比例。具体配方、挤出工艺和产物的性能见表1，可以看出，本发明制备的弹性体的透光性和力学性能均较好。
表1 工艺及弹性体性能
Figure 430305DEST_PATH_IMAGE003

Claims (8)

1.一种透明热塑性聚氨酯弹性体，由多元醇、二异氰酸酯和扩链剂聚合而成，其特征在于，所述的扩链剂的结构式为
Figure DEST_PATH_IMAGE001
。
2.根据权利要求1所述的透明热塑性聚氨酯弹性体，其特征在于，所述的扩链剂的制备方法为：以二甘醇胺与1,1,3,3-四甲基二硅烷为原料，合成所述的扩链剂，其中，二甘醇胺与1,1,3,3-四甲基二硅烷的摩尔比为2:1。
3.根据权利要求2所述的透明热塑性聚氨酯弹性体，其特征在于，将二甘醇胺置于反应器中，通入保护气，然后在-20~20℃条件下，1~3小时内滴加1,1,3,3-四甲基二硅烷，滴加完成后，维持原温度反应0.5小时，然后升温至50~80℃，继续反应1小时，得到所述的扩链剂。
4.根据权利要求1所述的透明热塑性聚氨酯弹性体，其特征在于，所述的多元醇为聚四氢呋喃聚醚二醇、聚己二酸二醇酯或聚碳酸酯二醇。
5.根据权利要求1所述的透明热塑性聚氨酯弹性体，其特征在于，所述的二异氰酸酯为二苯基甲烷二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯或六亚甲基二异氰酸酯。
6.根据权利要求1所述的透明热塑性聚氨酯弹性体，其特征在于，采用双螺杆反应型挤出的方式制备所述的热塑性聚氨酯弹性体。
7.根据权利要求6所述的透明热塑性聚氨酯弹性体，其特征在于，多元醇、扩链剂和二异氰酸酯的摩尔比为1:(3~6):(4~8)。
8.根据权利要求6所述的透明热塑性聚氨酯弹性体，其特征在于，螺杆的加料段、熔融段、混合段和均化段的温度分别设置为(140~145):(160~170):(165~170):(145~155)。
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