CN114206970A - 含有聚硅氧烷己内酯多元醇的热塑性聚氨基甲酸酯 - Google Patents

含有聚硅氧烷己内酯多元醇的热塑性聚氨基甲酸酯 Download PDF

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CN114206970A
CN114206970A CN202080055667.5A CN202080055667A CN114206970A CN 114206970 A CN114206970 A CN 114206970A CN 202080055667 A CN202080055667 A CN 202080055667A CN 114206970 A CN114206970 A CN 114206970A
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T·皮埃德拉克莱门特
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Abstract

耐热性热塑性聚氨基甲酸酯组合物是通过包含多元醇组分的反应制得，所述多元醇组分包括聚硅氧烷与ε‑己内酯的反应产物。

Description

含有聚硅氧烷己内酯多元醇的热塑性聚氨基甲酸酯
背景技术
热塑性聚氨基甲酸酯材料在各种应用中的效用在许多新兴行业中为我们所了解。然而，热塑性聚氨基甲酸酯材料通常可见的一个缺点为暴露于高温时性能损失。
因此，需要在高温应用中保持良好物理特性的热塑性聚氨基甲酸酯组合物。
发明内容
本发明为一种包括多元醇组分与聚异氰酸酯组分的反应产物的热塑性聚氨基甲酸酯组合物，其中所述多元醇组分包括聚硅氧烷与ε-己内酯的反应产物，其中聚硅氧烷与ε-己内酯以1:12到1:25，例如1:12到1:15的摩尔比反应。
在一个实施例中，多元醇组分包括
Figure BDA0003495288820000011
其中n与m可相同或不同，n或m可为0到15，条件为n+m为至少12，例如12-15；y可为25到33；R1与R2可相同或不同且为直链或支链C1到C10基团。使此多元醇组分与二异氰酸酯和任选的扩链剂反应以形成热塑性聚氨基甲酸酯组合物。
具体实施方式
热塑性聚氨基甲酸酯组合物通常由多元醇组分、二异氰酸酯组分和任选的扩链剂组分的反应产物形成。如本文所描述，数均分子量是通过分析末端官能团确定。
多元醇组分
在本发明中，用于制备本发明的热塑性聚氨基甲酸酯组合物的多元醇组分包括ε-己内酯与聚硅氧烷多元醇引发的反应产物。
ε-己内酯或简称为己内酯为具有七元环的内酯(环酯)。ε-己内酯是本领域中众所周知的单体。
适合的聚硅氧烷多元醇包含经α-ω-羟基或胺或羧酸或硫醇或环氧基封端的聚硅氧烷。实例包含用羟基或胺或羧酸或硫醇或环氧基封端的聚(二甲基硅氧烷)。在一些实施例中，聚硅氧烷多元醇为经羟基封端的聚硅氧烷。在一些实施例中，聚硅氧烷多元醇的数均分子量在300到5,000或400到3,000范围内。
聚硅氧烷多元醇可通过聚硅氧烷氢化物与脂肪族多元醇或聚氧化烯醇之间的脱氢反应获得以将醇羟基引入聚硅氧烷主链上。
在一些实施例中，聚硅氧烷可由一种或多种具有下式的化合物表示：
Figure BDA0003495288820000021
其中：各R1和R2独立地为氢、1到4个碳原子烷基、苯甲基或苯基；各E为OH或NHR3，其中R3为氢、1到6个碳原子烷基或5到8个碳原子环烷基；a和b各自独立地为2到8的整数；c为3到50的整数。在含氨基聚硅氧烷中，E基团中的至少一者为NHR3。在含羟基聚硅氧烷中，E基团中的至少一者为OH。在一些实施例中，R1和R2均为甲基。
可用于本发明中的聚硅氧烷材料的实例包含二羟基聚二甲基硅氧烷、经α,ω-羟丙基封端的聚(二甲基硅氧烷)和经α,ω-氨基丙基封端的聚(二甲基硅氧烷)，其均为可商购的材料。其它实例包含聚(二甲基硅氧烷)材料与聚(环氧烷)的共聚物。
在一个实施例中，本发明的多元醇组分包括聚二甲基硅氧烷与ε-己内酯的反应产物，其中聚二甲基硅氧烷与ε-己内酯以1:12到1:25或1:12到15的摩尔比反应
在一个实施例中，多元醇组分适用于本发明，所述多元醇组分为
Figure BDA0003495288820000022
其中n与m可相同或不同，n或m可为0到15，条件为n+m为至少12，例如12-15，进一步例如12、13、14或15；y可为25到33，例如25、26、27、28、29、30、31、32或33；R1与R2可相同或不同且为直链或支链C1到C10基团，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、苯基、环己基、甲氧基乙基或3,3'-氧基二丙基。在一个实施例中，R1和R2为CH2-CH2-CH2。
在一个实施例中，本发明的多元醇组分基本上由以下组成或由以下组成：
Figure BDA0003495288820000023
其中n或m可为0到15，条件为n+m为至少12，例如12到25，或甚至12到15，进一步例如12、13、14或15，且y为25到33，例如25、26、27、28、29、30、31、32或33；R1与R2可相同或不同且为直链或支链C1到C10基团，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、苯基、环己基、甲氧基乙基或3,3'-氧基二丙基。在一个实施例中，R1和R2为CH2-CH2-CH2。
多元醇组分可具有约2000到4000，例如约3000到4000，进一步例如约3500的数均分子量。
聚异氰酸酯组分
适用于制备本发明的热塑性聚氨基甲酸酯组合物的聚异氰酸酯包含一种或多种二异氰酸酯，通常选自芳香族聚异氰酸酯或脂肪族聚异氰酸酯或其组合。适用的聚异氰酸酯的实例包含芳香族二异氰酸酯，如4,4'-亚甲基双(异氰酸苯酯)(MDI)、间二甲苯二异氰酸酯(XDI)、3,3'-二甲氧基-4,4'-亚联苯基二异氰酸酯、亚苯基-1,4-二异氰酸酯(PDI)、亚苯基-1,3-二异氰酸酯、萘-1,5-二异氰酸酯、3,3'-二甲基-4,4'-亚联苯基二异氰酸酯(TODI)、1,5-萘二异氰酸酯(NDI)和二异氰酸甲苯酯(TDI)；以及脂肪族二异氰酸酯，如异佛尔酮二异氰酸酯(IPDI)、二异氰酸1,4-环己酯(CHDI)、癸烷-1,10-二异氰酸酯、赖氨酸二异氰酸酯(LDI)、1,4-丁烷二异氰酸酯(BDI)、二异氰酸己二酯(HDI)、1,4-双(异氰酸酯基甲基)环己烷(1,4-H6XDI)和二环己基甲烷-4,4'-二异氰酸酯(H12MDI)。可使用两种或更多种聚异氰酸酯的混合物。
在一个实施例中，聚异氰酸酯组分基本上由4,4'-亚甲基双(异氰酸苯酯)组成或由其组成。在另一个实施例中，聚异氰酸酯基本上由二异氰酸己二酯组成或由其组成。
扩链剂组分
本文所描述的热塑性聚氨基甲酸酯组合物任选地包含扩链剂组分。扩链剂包含二醇、二胺和其组合。
适合的扩链剂包含相对较小的聚羟基化合物，例如具有2到20个、或2到12个、或2到10个碳原子的低碳数脂肪族或短链二醇。适合的实例包含乙二醇、二乙二醇、三乙二醇、四乙二醇、丙二醇、二丙二醇、1,4-丁二醇(BDO)、1,6-己二醇(HDO)、1,3-丁二醇、1,5-戊二醇、新戊二醇、1,4-环己烷二甲醇(CHDM)、2,2-双[4-(2-羟乙氧基)苯基]丙烷(HEPP)、庚二醇、壬二醇、十二烷二醇、3-甲基-1,5-戊二醇和羟乙基间苯二酚(HER)、五螺环乙二醇(PSG)、氢醌双(2-羟乙基)醚氢醌(HQEE)、二丙二醇(DPG)、2-甲基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇(BEPD)等，以及其混合物。在本发明的一个实施例中，扩链剂基本上由1,4-丁二醇组成或由其组成。在另一个实施例中，扩链剂组分基本上由氢醌双(2-羟乙基)醚氢醌组成或由其组成。在另一个实施例中，扩链剂组分基本上由五螺环乙二醇组成或由其组成。如本文所用，“五螺环乙二醇”或PSG是指如美国专利第2,945,008号中所描述的多元醇，例如由下式表示的3,9-双(1,1-二甲基-2-羟乙基)-2,4,8,10-四氧杂螺[5.5]十一烷：
Figure BDA0003495288820000041
为了制备根据本发明的热塑性聚氨基甲酸酯组合物，组分(多元醇、二异氰酸酯和任选的扩链剂)可一起反应以形成本发明的热塑性聚氨基甲酸酯组合物。使组分反应的任何已知方法可用于制备本发明的热塑性聚氨基甲酸酯组合物。在一个实施例中，所述方法为所谓的“一次性”方法，其中将所有三种组分添加到挤出机反应器中且反应。
本发明的热塑性聚氨基甲酸酯组合物也可利用预聚物方法制备。在预聚物途径中，使多元醇中间物与通常当量过量的一种或多种二异氰酸酯反应以形成其中具有游离或未反应的二异氰酸酯的预聚合物溶液。随后，如上文所指出，以通常等于异氰酸酯端基以及任何游离或未反应的二异氰酸酯化合物的当量添加扩链剂。通常，预聚物途径可在包含挤出机的任何常规装置中进行。在此类实施例中，多元醇中间物在挤出机的第一部分中与当量过量的二异氰酸酯反应以形成预聚物溶液，且扩链剂随后在下游部分处添加且与预聚物溶液反应。
在一个实施例中，在单螺杆或双螺杆挤出机上混合成分，在其进料端与其模具端之间具有多个加热区和多个进料口。可在一个或多个进料口处添加成分，且可粒化离开挤出机的模具端的所得热塑性聚氨基甲酸酯组合物。
本发明的热塑性聚氨基甲酸酯组合物的制备可通过任何已知常规程序和方法或以后开发的程序和方法来进行。本领域的技术人员将理解其特定组分的量、各种反应物比率、处理温度、其催化剂的量、如各种类型的挤出机的聚合设备等。
在聚合反应期间可存在一种或多种聚合催化剂。通常，可利用任何常规催化剂使二异氰酸酯与多元醇中间物或扩链剂反应。特别是可促进二异氰酸酯的NCO基团与多元醇的羟基和扩链剂之间的反应的适合的催化剂的实例为从现有技术已知的常规叔胺，例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N'-二甲基哌嗪、2-(二甲氨基乙氧基)乙醇、二氮杂二环[2.2.2]辛烷等，以及特别是有机金属化合物，如钛酯；铁化合物，例如乙酰基丙酮酸铁；锡化合物例如二乙酸亚锡、二辛酸亚锡、二月桂酸亚锡或脂肪族羧酸的二烷基锡盐，例如二乙酸二丁基锡、二月桂酸二丁基锡等；丙酸苯汞；辛酸铅；乙酰基丙酮酸铁；乙酰基丙酮酸镁或铋化合物，如辛酸铋、月桂酸铋等。
本发明的热塑性聚氨基甲酸酯组合物可具有95A或更小的肖氏A硬度(Shore Ahardness)，例如35A到95A，进一步例如50A到95A。
其它任选的组分可在聚合反应期间存在，和/或并入到上文所描述的热塑性聚氨基甲酸酯组合物中以改良处理和其它特性。这些添加剂包含(但不限于)抗氧化剂，如酚类、有机亚磷酸酯、膦和亚膦酸二酯、受阻胺、有机胺、有机硫化合物、内酯和羟胺化合物；杀生物剂；杀真菌剂；抗微生物剂；增容剂；电耗散剂或抗静电添加剂；填充剂和增强剂，如二氧化钛、氧化铝、粘土和碳黑；阻燃剂，如磷酸盐、卤化材料和烷基苯磺酸盐的金属盐；抗冲击改性剂，如甲基丙烯酸脂-丁二烯-苯乙烯(“MBS”)和甲基丙烯酸甲酯丙烯酸丁酯(“MBA”)；脱模剂，如蜡、脂肪和油；颜料和着色剂；增塑剂；聚合物；流变改性剂，如单胺、聚酰胺蜡、硅酮和聚硅氧烷；助滑添加剂，如石蜡、烃类聚烯烃和/或氟化聚烯烃；和UV稳定剂，其可具有受阻胺光稳定剂(HALS)和/或UV光吸收剂(UVA)类型。其它添加剂可用于增强热塑性聚氨基甲酸酯组合物或掺合产物的性能。上文所描述的所有添加剂可以这些物质的惯用有效量使用。
这些额外添加剂可并入到热塑性聚氨基甲酸酯组合物的组分中或并入到用于制备热塑性聚氨基甲酸酯组合物的反应混合物中或在制备热塑性聚氨基甲酸酯组合物之后并入。在另一方法中，所有材料均可与热塑性聚氨基甲酸酯组合物混合且随后熔融，或其可直接并入到热塑性聚氨基甲酸酯组合物的熔融物中。
本发明的热塑性聚氨基甲酸酯组合物或其任何掺合物也可用于使用如挤出或模制的已知技术制备各种制品。挤出或模制方法为本领域的技术人员所熟知，且包含(但不限于)浇铸模制、冷成型对模模制、压缩模制、发泡模制、射出模制、气体辅助射出模制、型面共挤出、型面挤出、旋转模制、薄片挤出、凝塑模制、喷涂技术、热成型、转移模制、真空成型、湿式叠层或接触模制、吹塑、挤出吹塑、射出吹塑和射出拉伸吹塑或其组合。
本发明的热塑性聚氨基甲酸酯组合物可用于制备用于期望耐热性的热塑性聚氨基甲酸酯的应用的制品。热塑性聚氨基甲酸酯组合物可用于汽车、电子设备、便携式电子设备、电子配件、电气、通信、电气设备和医学应用的零件或组件中。举例来说，其可用于生产电缆绝缘体、汽车零件、电子设备和电气设备的组件。
其它应用可包含(但不限于)：保护盖；液体管线组件和空气管道；建筑密封件；瓶封闭件；家具组件；用于手持式装置的耐磨和感觉柔软的手柄；封装组件，如密封件、瓶子、罐、杯子；医学和卫生装置；炊具零件和配件；体育和休闲用品，如球拍、自行车零件；鞋类鞋底、玩具和一般橡胶零件；医学装置；体育用品；穿戴式装置(表带、健身追踪器、眼镜鼻托)；以及一般橡胶零件。
通过以下实例进一步说明本发明。在实例中，PCL-BDO(2000)是指由0.84摩尔ε-己内酯与0.052摩尔1,4-丁二醇引发的反应制得的多元醇组分。PCL-PDMS(3500)是指由0.35摩尔ε-己内酯与0.029摩尔直链聚二甲基硅氧烷丙基羟基共聚物引发的反应制得的多元醇组分，BDO是指1,4-丁二醇，HQEE是指氢醌双(2-羟乙基)醚，MDI是指4,4'-亚甲基双(异氰酸苯酯)，HDI是指二异氰酸己二酯。摩尔计算是基于制备100g聚己内酯多元醇。
通过使表1中所指出的组分反应形成一系列比较热塑性聚氨基甲酸酯组合物。
表1
Figure BDA0003495288820000061
1热机械分析：在Mettler TMA/SDTA 2+单元上，在-25℃到250℃的温度范围内记录热分析图。在10℃/分钟的加热速率下进行分析。将板用作测试穿透类型中的样本。所施加的力为0.02N。
通过使表2中所指出的组分反应来形成一系列本发明的热塑性聚氨基甲酸酯组合物。
-------------------
表2
Figure BDA0003495288820000071
如上表所示，本发明的热塑性聚氨基甲酸酯组合物提供了优于单独的硅酮橡胶材料和其它基于聚己内酯的热塑性聚氨基甲酸酯的优良结果，特别在耐热性方面。

Claims (18)

1.一种热塑性聚氨基甲酸酯组合物，其包括以下各者的反应产物：
(a)由ε-己内酯和聚二甲基硅氧烷的反应产物制得的多元醇组分，其中所述聚二甲基硅氧烷与ε-己内酯以1:12到1:25的摩尔比存在；
(b)二异氰酸酯。
2.根据权利要求1所述的热塑性聚氨基甲酸酯组合物，其进一步包括扩链剂组分。
3.根据权利要求2所述的热塑性聚氨基甲酸酯组合物，其中所述扩链剂包括1,4-丁二醇。
4.根据权利要求2所述的热塑性聚氨基甲酸酯，其中所述扩链剂包括氢醌双(2-羟乙基)醚。
5.根据权利要求1到4中任一项所述的热塑性聚氨基甲酸酯组合物，其中所述二异氰酸酯包括4,4'-亚甲基双(异氰酸苯酯)。
6.根据权利要求1到4中任一项所述的热塑性聚氨基甲酸酯组合物，其中所述二异氰酸酯包括二异氰酸己二酯。
7.根据权利要求1到6中任一项所述的热塑性聚氨基甲酸酯，其中所述ε-己内酯与聚二甲基硅氧烷以1:12到1:15的摩尔比存在。
8.一种热塑性聚氨基甲酸酯组合物，其包括以下各者的反应产物：
(a)多元醇组分，其包括
Figure FDA0003495288810000011
其中n和m个别地为0到15，条件为n+m为至少12，y为25到33，且R1与R2相同或不同且选自直链或支链C1到C10基团；以及
(b)二异氰酸酯。
9.根据权利要求8所述的热塑性聚氨基甲酸酯组合物，其中n和m个别地为0到15，条件为n+m为12到15。
10.根据权利要求8或9所述的热塑性聚氨基甲酸酯组合物，其中R1与R2相同或不同且选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、苯基、环己基、甲氧基乙基或3,3'-氧基二丙基。
11.根据权利要求8到10中任一项所述的热塑性聚氨基甲酸酯组合物，其进一步包括扩链剂组分。
12.根据权利要求10所述的热塑性聚氨基甲酸酯组合物，其中所述扩链剂由1,4-丁二醇组成。
13.根据权利要求10所述的热塑性聚氨基甲酸酯组合物，其中所述扩链剂由氢醌双(2-羟乙基)醚组成。
14.根据权利要求8到13中任一项所述的热塑性聚氨基甲酸酯组合物，其中所述二异氰酸酯由4,4'-亚甲基双(异氰酸苯酯)组成。
15.根据权利要求8到13中任一项所述的热塑性聚氨基甲酸酯组合物，其中所述二异氰酸酯由二异氰酸己二酯组成。
16.一种由根据权利要求1到15中任一项所述的热塑性聚氨基甲酸酯组合物制得的制品。
17.一种提高制品的耐热性的方法，其包括以下步骤：
(i)使(a)多元醇组分，所述多元醇组分包括
Figure FDA0003495288810000021
其中n和m个别地为0到15，条件为n+m为至少12，y为25到33，且R1与R2相同或不同且选自直链或支链C1到C10基团；与
(b)二异氰酸酯反应；
(ii)通过挤出或模制形成制品。
18.根据权利要求17所述的方法，其中R1与R2相同或不同且选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、苯基、环己基、甲氧基乙基或3,3'-氧基二丙基。
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US20220289898A1 (en) 2022-09-15

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