CN1281474A - 制备热塑性聚氨酯弹性体的方法 - Google Patents
制备热塑性聚氨酯弹性体的方法 Download PDFInfo
- Publication number
- CN1281474A CN1281474A CN98812082A CN98812082A CN1281474A CN 1281474 A CN1281474 A CN 1281474A CN 98812082 A CN98812082 A CN 98812082A CN 98812082 A CN98812082 A CN 98812082A CN 1281474 A CN1281474 A CN 1281474A
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- reactor
- active hydrogen
- mixture
- thermoplastic elastomer
- temperature
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Classifications
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及连续制备具有改进的均匀性和熔融性能的热塑性聚氨酯弹性体的方法,其中在反应器中在最多5秒的时间内将一种或几种多异氰酸酯(A)和含有Zerewitinoff活性氢原子的混合物(B)以及(相对TPU总量)0-20wt.%的其它助剂及添加剂(C)均匀地混合,其中混合物(B)由B1)和B2)组成,B1)是1-85当量%(相对(A)中异氰酸酯基团)的一种或几种化合物,平均含有至少1.8个Zerewitinoff活性氢原子并且平均分子量Mn为450-10000;B2)是15-99当量%(相对(A)中异氰酸酯基团)的一种或几种增链剂,平均含有至少1.8个Zerewitinoff活性氢原子并且分子量为60-400,其中在进入反应器之前组分(A)和(B)之间的温度差<20℃。
Description
本发明涉及制备热塑性聚氨酯弹性体的方法、由其得到的产品及其应用。
热塑性聚氨酯(TPU)由于其具有良好的弹性且易于加工而被广泛使用。通过适当选择组成成分可得到范围广阔的机械性能。关于TPUs、其性能及应用的综述见例如Kunststoffe 68(1978)819,Kautschuk,Gummi,Kunststoffe 35(1982)569;G.Becker,D.Braun:Kunststoff-Handbuch,vol.7“聚氨酯”Munich,Vienna,Carl Hanser Verlag 1983。关于制备方法的综述见Plastikverarbeiter 40(1989)。
TPUs一般是由线性多元醇如聚酯多元醇或聚醚多元醇、有机二异氰酸酯和短链(一般是双官能团的)醇(增链剂)构成的。它们可分批或连续制备。
连续挤塑法已问世有日。在该方法中将起始原料计量加入到螺杆反应器,在其中缩聚并随后转化成均匀的颗粒形式(US-A 3 642 964,DE-C 23 02 564,DE-C 25 49 371,DE-A 32 30 009,EP-A 31 142)。
挤塑法相对而言简单,但其缺点是起始原料只在反应器中且只在广泛发生聚加成的条件下被混合,这意谓着可能产生不均一性并因此发生不希望且不可控的次级反应。
EP-A 554 718和EP-A 554 719提出了通过将起始原料加入到喷嘴中并在进入挤出机之前进行混合的改进的挤塑法。因为虽然聚加成反应只发生在挤出机中,但由该方法得到的产物也具有不均匀性,这在挤塑产品如薄膜中表现得尤为明显。
在现有技术中首先将起始原料在混合区于不发生聚加成反应的温度进行混合并随后在具有所要求温度的反应区彼此反应的制备方法也是已知的。混合区和反应区优选被设计为静态混合机(DE-A 28 23762,EP-A 747 409,EP-A 747 408)。
现在已经发现当在混合过程进行前用于制备聚氨酯的起始原料间的温度差别尽可能小时可以得到具有改进的均一性和改进的熔融特性的TPUs。
因此本发明提供了连续制备热塑性聚氨酯弹性体的方法,其中在反应器中在最多5秒的时间内将一种或多种有机异氰酸酯(A)和含有Zerewitinoff活性氢原子的混合物(B)和相对TPU总量0-20wt.%的其它助剂和添加剂(C)均匀地预混合,其中混合物(B)包括
B1)相对(A)中异氰酸酯基团1-85当量%的一种或多种化合物,其平均含有至少1.8个Zerewitinoff活性氢原子并且平均分子量
Mn为450-10000,
B2)(相对(A)中异氰酸酯基团)15-99当量%的一种或多种增链剂,其平均含有至少1.8个Zerewitinoff活性氢原子并且分子量为60-400,
其中在进入反应器之前组分(A)和(B)之间的温度差<20℃。
可使用的有机异氰酸酯(A)包括脂族、环脂族、芳脂族、芳族和杂环多异氰酸酯或这些多异氰酸酯的任意混合物(见HOUBEN-WEYL的“有机化学方法”vol.E20,“Makromol ekul are Stoffe”,GeorgThieme Verlag,Stuttgart,New York 1987,1587-1593页或JustusLiebigs Annalen der Chemie,562,75-136页)。
下面是可分别例举的化合物:脂族二异氰酸酯如亚乙基二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、1,12-十二烷基二异氰酸酯,环脂族二异氰酸酯如异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、1-甲基-2,4-环己烷二异氰酸酯和1-甲基-2,6-环己烷二异氰酸酯及相应的异构体混合物、4,4’-二环己基甲烷二异氰酸酯、2,4’-二环己基甲烷二异氰酸酯和2,2’-二环己基甲烷二异氰酸酯及相应的异构体混合物,以及芳族二异氰酸酯如2,4-甲代亚苯基二异氰酸酯、2,4-甲代亚苯基二异氰酸酯和2,6-甲代亚苯基二异氰酸酯的混合物、4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯和2,2’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯和4,4'一苯基甲烷二异氰酸酯的混合物、氨基甲酸酯改性的液态4,4’-二苯基甲烷二异氰酸酯或2,4’-二苯基甲烷二异氰酸酯、4,4’-二异氰酸根合二苯基乙烷-(1,2)和1,5-亚萘基二异氰酸酯。1,6-六亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯含量大于96wt.%的二苯基甲烷二异氰酸酯异构体混合物是优选使用的,特别优选使用4,4’-二苯基甲烷二异氰酸酯和1,5-亚萘基二异氰酸酯。所提到的二异氰酸酯可分别使用或作为彼此的混合物使用。它们也可与最多15mol.%(由总二异氰酸酯含量计算)的多异氰酸酯共同使用,但是多异氰酸酯的最大加入量应足以能够产生仍可热塑性加工的产品。多异氰酸酯的实例为三苯基甲烷-4,4’,4”-三异氰酸酯和多苯基-多亚甲基-多异氰酸酯。
用于本发明方法的Zerewitinoff活性化合物(B1)为含有平均至少1.8-3.0个Zerewitinoff活性氢原子且平均分子量
Mn为450-10000者。
除了含有氨基、硫醇或羧基基团的化合物外,此处所包括的化合物还为含有2-3个,优选2个羟基的化合物,特别是平均分子量
Mn为450-6000者,尤其特别是平均分子量
Mn为600-4500者,例如含有羟基的聚酯、聚醚、聚碳酸酯和聚酯酰胺。
适宜的聚醚二醇可通过使一种或多种烯基中含有2-4个碳原子的氧化烯烃与含有两个键合的活性氢原子的启动分子反应而制备。下面提到的化合物可作为氧化烯烃:例如环氧乙烷、1,2-环氧丙烷、表氯醇及1,2-环氧丁烷和2,3-环氧丁烷。优选使用环氧乙烷、环氧丙烷及1,2-环氧丙烷和环氧乙烷的混合物。氧化烯烃可分别使用、彼此交替使用或作为混合物使用。下列例举的化合物可作为启动分子:水、氨基醇如N-烷基二乙醇胺,例如N-甲基二乙醇胺及二醇如乙二醇、1,3-丙二醇、1,4-丁二醇和1,6-己二醇。或者也可使用启动分子的混合物。适宜的聚醚醇还为含羟基的四氢呋喃的聚合产物。三官能团聚醚可以以相对双官能团聚醚0-30wt.%的比例使用,但其用量最多为所产生的产品仍是可热塑加工的量。基本上为线性的聚醚二醇优选平均分子量
Mn为450-6000。它们可分别使用或以彼此的混合物形式使用。
适宜的聚酯二醇例如可由含有2-12个碳原子,优选4-6个碳原子的二元羧酸和多羟基醇制备。例如下列化合物适于作为二元羧酸:脂族二元羧酸如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸,或芳族二元羧酸如邻苯二甲酸、间苯二甲酸和对苯二甲酸。二元羧酸可分别使用或作为混合物例如以琥珀酸、戊二酸和己二酸的混合物形式使用。为了制备聚酯二醇,可任选有利地使用相应的二元羧酸衍生物如醇基团中含有1-4个碳原子的羧酸二酯、羧酸酸酐或羧酸酰氯来代替二元羧酸。多羟基醇的实例为含有2-10,优选2-6个碳原子的二醇,例如乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-甲基-1,3-丙二醇、1,3-丙二醇或一缩二丙二醇。根据所要求的性能,多羟基醇可分别使用或以彼此混合物的形式使用。同样适宜的是含有上述二醇、特别是含4-6个碳原子醇如1,4-丁二醇或1,6-己二醇的碳酸酯;ω-羟基羧酸如ω-羟基辛酸的缩合产物或者内酯如任选取代的ω-己内酯的聚合产物。下面为优选用作聚酯二醇的化合物:乙二醇聚己二酸酯、1,4-丁二醇-聚己二酸酯、乙二醇-1,4-丁二醇-聚己二酸酯、1,6-己二醇-新戊基二醇-聚己二酸酯、1,6-己二醇-1,4-丁二醇-聚己二酸酯和聚己内酯。聚酯二醇的平均分子量
Mn优选为450-6000并且可分别使用或以彼此混合物的形式使用。
Zerewitinoff活性化合物(B2)即是所谓的增链剂并且含有平均1.8-3.0个Zerewitinoff活性氢原子,分子量为60-400。应理解为这些化合物除包括带有氨基、硫醇或羧基基团的化合物外还包括带有二至三个,优选两个羟基基团的化合物。
含有2-14个碳原子的二醇优选用作增链剂,例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、1,6-己二醇、二甘醇和一缩二丙二醇。但同样适宜的是对苯二甲酸与含有2-4个碳原子的二醇的二酯,例如对苯二甲酸-二-乙二醇或对苯二甲酸-二-1,4-丁二醇;氢醌的羟基亚烷基醚,例如1,4-二-(β-羟基乙基)-氢醌;乙氧基化的二酚,例如1,4-二(β-羟乙基)-双酚A;(环)脂族二胺如异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基-1,3-丙二胺、N,N’-二甲基乙二胺和芳胺如2,4-甲苯二胺、2,6-甲苯二胺、3,5-二乙基-2,4-甲苯二胺或3,5-二乙基-2,6-甲苯二胺或者一级单、二、三或四烷基取代的4,4’-二氨基二苯基甲烷。特别优选乙二醇、1,4-丁二醇、1,6-己二醇、1,4-二-(β-羟基乙基)-氢醌或1,4-二-(β-羟基乙基)-双酚A用作增链剂。也可使用上述增链剂的混合物。此外也可使用少量的三醇。
相对异氰酸酯为单官能团的化合物可以以最多2wt.%(相对TPU)的量使用,它被称作链终止剂。适宜的化合物为例如单胺如丁基和二丁基胺、辛基胺、硬脂基胺、N-甲基硬脂基胺、吡咯烷、哌啶或环己基胺;单醇如丁醇、2-乙基己醇、辛醇、十二醇、十八醇、各种戊基醇、环己醇和乙二醇单甲醚。
如果要制备可热塑加工的聚氨酯弹性体则必须挑选与异氰酸酯反应的物质以使其平均官能度不超过2。如果使用更高官能度的化合物,则必须通过单官能团化合物来降低整体官能度。
优选选择(B)中化合物(B1)和(B2)的相对量以使(A)中异氰酸酯化合物的和与(B)中Zerewitinoff活性氢原子的和之比为0.9∶1-1.2∶1,优选0.95∶1-1.1∶1。
本发明的热塑性聚氨酯弹性体可包括最多20wt.%(相对TPU总量)的常规助剂和添加剂作为助剂和添加剂(C)。典型的助剂和添加剂为催化剂、颜料、着色剂、阻燃剂、防止老化和气候影响的稳定剂、增塑剂、润滑剂和脱模剂、抵御真菌和细菌的物质和填料及其混合物。
根据本发明适宜的催化剂为现有技术中已知的常规叔胺如三乙胺、二甲基环己胺、N-甲基吗啉、N,N’-二甲基哌嗪、2-(二甲基氨基-乙氧基)-乙醇、二氮杂双环[2.2.2]辛烷等,特别是还有有机金属化合物如钛酸盐、铁化合物或锡化合物如二乙酸锡、二辛酸锡、二月桂酸锡或脂肪羧酸的锡二烷基盐如二丁基二乙酸锡或二丁基二月桂酸锡等。优选的催化剂为有机金属化合物,特别是钛酸盐、铁和锡化合物。根据本发明在TPUs中催化剂总量一般占TPU总量的约0-5wt.%,优选0-2wt.%。
其它添加剂的实例为润滑剂,如脂肪酸酯、脂肪酸金属皂、脂肪酸酰胺、脂肪酸酯酰胺和硅化合物,抗结块剂,抑制剂,防止水解、光、热和褪色的稳定剂,阻燃剂,着色剂,颜料,无机和/或有机填料及增强剂。增强剂特别为纤维增强剂如根据现有技术制备且还可在其上涂胶的无机纤维。关于所提到的助剂和添加剂的更详细资料可由专业文献获得,例如J.H.Saunders和K.C.Frisch的专著“高级聚合物”XVI卷,聚氨酯,第1和2部分,Verlag IntersciencePublishers 1962和1964;R.Gchter和H.Müller的“Taschenbuchfür Kunststoff--添加剂”(Hanser Verlag Munich1990)或DE-A29 01 774。
将组分(A)和(B)在反应器中于最多5秒内混合均匀。彻底混合优选只有少量回混发生。在本发明的上下文中均匀的彻底混合意谓着在混合物中组分(A)和(B)及反应产物的浓度分布的相对标准偏差小于5%。在本发明的上下文中少量回混意谓着在反应器中的保留时间符合在≥10个理想搅拌釜系列(阶式搅拌釜)中的保留时间。
在将组分(A)和(B)连续引入到反应器中之前,必须将其分别加热,优选在热交换器中加热到最高60-220℃,优选90-190℃。根据本发明,在将组分(A)和(B)引入反应器之前其温度差别小于20℃是必要的。组分流(A)和(B)的温度差别优选<10℃,特别<5℃。
然后在任意类型的反应器中,优选在挤出机或反应管中将以这种方式获得的混合物转化为TPU。
根据本发明聚加成优选在绝缘且优选是可加热的静态混合器中进行。这样的优点是没有可移动部分,基本无回混的均匀彻底的混合可在尽可能短的时间内进行。根据本发明可使用的静态混合器描述于Chem.-Ing.Techn.52,No.4 285-291页和“Mischen yonKunststoff und Kautschukprodukten”,VDI-Verlag,Düsseldorf1993中。
优选使用根据DE-C 23 28 795的静态混合器。静态混合器的长径比优选为8∶1-16∶1,特别为10∶1-14∶1。在静态混合器中的保留时间<5秒,优选<2.5秒。静态混合器优选是用不锈钢,特别是由V4A制成的。
在另一个优选的实施方案中,本发明的方法是在双轴挤出机中进行的,挤出机的两个轴优选以相同的方向旋转。在这种情况下,挤出机的第一部分也可用来加热异氰酸酯组分(A)。
根据本发明方法制备的TPUs可任选被进一步加工,例如以板材或块材的形式退火,在撕碎机或研磨机中压碎或造粒,熔融脱气和造粒。优选将聚合物送入连续脱气并挤塑生产的体系。该单元可以是例如多螺杆机器,如果可能则不装配捏合元件,或者只有很少的捏合元件。
本发明还提供了使用本发明方法获得的热塑性聚氨酯弹性体。必须承认令人惊讶的是根据本发明制备的模塑组合物具有高度的均匀性和改进的熔融特性。
根据本发明获得的热塑性聚氨酯弹性体优选用于制备薄膜和易熔共挤塑产品,例如层压板、压延产品、热熔粘合剂及用于粉料搪塑共挤塑的产品。
实施例
实施例1
将1630 g/h MDI和2685 g/h重量比为6.9∶1的聚丁二醇己二酸酯
和丁二醇的混合物彼此分离地计量加入到静态混合器中,混合物中包含200 ppm的二辛酸锡。MDI和多元醇/丁二醇混合物各自的温度均为140±10℃。对组分的预混合在带有全能加热系统(SMX型,Sulzer AG)并且直径为6mm、长度为6cm且剪切速率为500 s-1的静态混合器中进行;反应在末端带有混合元件的反应管中进行。
利用该方法,可在超过90min的时间制备出TPU而在静态混合器中未观察到压力升高。
实施例2
试验以与实施例1相同的方式进行,差别在于反应物流的温度为160±5℃。即使是在这样的条件下,也可在超过90min的时间制备出TPU而在静态混合器中未观察到压力升高。
实施例3(对比例)
在ZSK 83型反应挤出机设备中预设下列温度分布:1-4室:120℃,5-9室:无温度标准,10-13室:120℃,头部:200℃。使用与实施例1相同的配方,旋转速率为300 rpm,产量为600kg/h。将MDI计量加入到室1中。MDI在室5入口处的温度为约90℃。将温度为140℃的多元醇/丁二醇混合物计量加入到室5中。
实施例1和2及对比例3的结果在表1中给出。使用Perkin ElmerDSC 7型量热仪通过DSC测定重结晶温度。在DSC测定中由对比例获得的产物在较高的温度出现最大峰。
虽然根据本发明实施例制备的TPUs的熔体流动指数MFI随温度由190℃升高到200℃只增加了2倍,但在对比例中该值则增加了5倍。根据本发明制备的TPUs的熔体流动指数MFI对温度的低依赖性(200℃时的MFI对190℃时的MFI的比值)以及较高的MFI值表明改进了熔融特性。
表1
实施例1 | 实施例2 | 实施例3(对比例) | |
重结晶温度Tc[℃] | 85 | 87 | 102 |
熔体流动指数MFI**(190℃)[g/10min] | 27 | 25 | 4.7 |
熔体流动指数MFI**(200℃)[g/10min] | 55 | 52 | 20.3 |
**根据ASTM D 1238测定。
实施例4(对比例)
试验以与实施例1相同的方式进行,但在入口处MDI的温度为60℃而多元醇/丁二醇混合物的温度为140℃。约10-15分钟后,静态混合器中的压力已升高到>50巴,此时必须终止实验。
在起始组分间使用工业上常见的80℃大温度差,由于不充分搅拌而观察到了严重的不均匀形象。这会在静态混合器中由于交联反应而导致粘连或晶体的过早沉积。
实施例5
将1194 g/h HDI及3800 g/h重量比为11.5∶1的聚四氢呋喃(平均
Mn=1000)和丁二醇的混合物彼此分离地计量加入到静态混合器中。HDI和多元醇/丁二醇混合物的温度各为90±10℃。用带有全能加热系统(SMX型,Sulzer AG)并且直径为6mm、长度为6cm且剪切速率为500 s-1的静态混合器进行混合;反应在末端挤出机中进行。
实施例6(对比例)
试验以与实施例5相同的方式进行,但HDI是在23℃被引入反应器的而多元醇混合物是在80℃被引入反应器的。
实施例5和对比例6的结果在表2中给出。该结果显示根据本发明方法制备的TPU具有改进的熔融特性。在对根据本发明制备的产物进行的测量中各熔体流动指数MFI值的低分散性表明了高度的均匀性。
表2
实施例5 | 实施例6(对比例) | |
重结晶温度Tc[℃] | 68 | 78 |
熔点(℃) | 180 | 190 |
熔体流动指数MFI*(190℃)[g/10min] | 49.6±2 | 55(分散在32-60间) |
*根据ASTM D 1238测定。
实施例7-10
TPU配方:
1.0 mol 聚己二酸丁二酯,
Mn=840 g/mol
1.3 mol 1,4-丁二醇
2.3 mol MDI
200 ppm 二辛酸锡(相对聚己二酸丁二酯)
0.2 wt.% Loxamide(相对TPU总量)
将各组分计量加入到ZSK 83型挤出机中,挤出机以300 rpm的速率运行并且产量为600 kg/h.表3给出了挤出机各室的温度分布。在实施例7-9中,MDI被计量加入到挤出机的第1室中而由聚己二酸丁二酯和1,4-丁二醇组成的多元醇混合物被计量加入到第5室中。在实施例7中MDI的温度为约60℃,在实施例8中为约120℃,在实施例9中为约130℃。在实施例10中,将MDI加热到130℃,将多元醇混合物加热到140℃,然后将两种反应物流都加入到第1室中。每次都将催化剂加入到多元醇混合物中,将loxamide与异氰酸酯混合。
表3:预置的各螺杆室温度
实施例 | 7 | 8 | 9 | 10 |
第1室 | 80℃ | 140℃ | 140℃ | 无 |
2 | 80℃ | 140℃ | 140℃ | 无 |
3 | 80℃ | 140℃ | 140℃ | 无 |
4 | 无 | 140℃ | 140℃ | 无 |
5 | 无 | 无 | 无 | 无 |
6 | 无 | 无 | 无 | 无 |
7 | 无 | 无 | 无 | 无 |
8 | 无 | 无 | 无 | 无 |
9 | 无 | 无 | 无 | 无 |
10 | 无 | 100℃ | 100℃ | 100℃ |
11 | 无 | 100℃ | 100℃ | 100℃ |
12 | 150℃ | 120℃ | 120℃ | 100℃ |
13 | 100℃ | 120℃ | 120℃ | 100℃ |
机头 | 200℃ | 200℃ | 200℃ | 200℃ |
薄膜是使用挤出机吹塑设备由所得产物制备的。将TPU粒料在30/25D Plasticorder PL 2000-6(Brabender Co.)型单轴挤出机(加料速度3 kg/h,温度185-205℃)中熔融并由薄膜吹塑头挤出得到管状薄膜。根据DIN 53504/NSI测定产物的100%模量。结果在表4中给出。
表4
实施例 | 多元醇混合物温度 | MDI温度 | 薄膜性能:斑点/结构 | 100%模量 |
7* | 150℃ | 50℃ | 许多/非常明显 | 12 |
8* | 140℃ | 120℃ | 一些/明显 | 11 |
9 | 140℃ | 130℃ | 非常少/很少 | 11 |
10 | 140℃ | 130℃ | 没有/没有 | 11 |
*对比例,非根据本发明
Claims (8)
1.连续制备热塑性聚氨酯弹性体的方法,其中在反应器中在最多5秒的时间内将一种或多种多异氰酸酯(A)和含有Zerewitinoff活性氢原子的混合物(B)和相对TPU总量0-20wt.%的其它助剂和添加剂(C)均匀地预混合,其中混合物(B)包括
B1)相对(A)中异氰酸酯基团1-85当量%的一种或多种化合物,平均含有至少1.8个Zerewitinoff活性氢原子并且平均分子量Mn为450-10000,
B2)(相对(A)中异氰酸酯基团)15-99当量%的一种或多种增链剂,平均含有至少1.8个Zerewitinoff活性氢原子并且分子量为60-400,
其中在进入反应器之前组分(A)和(B)之间的温度差<20℃。
2.根据权利要求1的方法,其中在进入反应器之前组分(A)和(B)的温度为60-220℃。
3.根据权利要求1的方法,其中反应器为静态混合器。
4.根据权利要求3的方法,其特征在于静态混合器的长径比为8∶1-16∶1。
5.根据权利要求1的方法,其中反应器为双轴挤出机。
6.根据权利要求1的方法,其中所得混合物在挤出机或管状反应器中进行反应以得到热塑性聚氨酯弹性体。
7.由权利要求1的方法制备的热塑性聚氨酯弹性体。
8.由权利要求1的方法制备的热塑性聚氨酯弹性体在制备薄膜、层压板、压延产品、热熔粘合剂和粉料搪塑共挤塑产品方面的应用。
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CN106939071A (zh) * | 2017-04-11 | 2017-07-11 | 东莞市雄林新材料科技股份有限公司 | 一种汽车按摩用tpu复合材料及其制备方法 |
CN108097194A (zh) * | 2017-12-28 | 2018-06-01 | 万华化学(宁波)有限公司 | 一种制备水性聚氨酯分散体的连续生产系统、水性聚氨酯分散体的连续生产工艺和应用 |
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CA2313456A1 (en) | 1999-06-24 |
CA2313456C (en) | 2008-10-28 |
ES2196646T3 (es) | 2003-12-16 |
WO1999031158A1 (de) | 1999-06-24 |
KR100522984B1 (ko) | 2005-10-24 |
JP2008260960A (ja) | 2008-10-30 |
CN1135246C (zh) | 2004-01-21 |
JP2002508416A (ja) | 2002-03-19 |
DE19755545A1 (de) | 1999-06-17 |
EP1068250B1 (de) | 2003-03-19 |
JP5185010B2 (ja) | 2013-04-17 |
TW406099B (en) | 2000-09-21 |
KR20010033041A (ko) | 2001-04-25 |
DE59807593D1 (de) | 2003-04-24 |
AU1965899A (en) | 1999-07-05 |
HK1033145A1 (en) | 2001-08-17 |
EP1068250A1 (de) | 2001-01-17 |
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