CN101492524B - 低雾度和加工性良好的透明热塑性聚氨酯及其制法和用途 - Google Patents
低雾度和加工性良好的透明热塑性聚氨酯及其制法和用途 Download PDFInfo
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- CN101492524B CN101492524B CN2009100099389A CN200910009938A CN101492524B CN 101492524 B CN101492524 B CN 101492524B CN 2009100099389 A CN2009100099389 A CN 2009100099389A CN 200910009938 A CN200910009938 A CN 200910009938A CN 101492524 B CN101492524 B CN 101492524B
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Abstract
本发明涉及低雾度和加工性良好的透明热塑性聚氨酯及其制法和用途。ASTM D 1003雾度小于10％的光稳定热塑性聚氨酯通过使下列组分反应制备：(a)包括二异氰酸1，6-己二醇酯的二异氰酸酯组分；(b)扩链剂组分，由(b1)1，4-二(β-羟乙基)氢醌和(b2)至少一种选自在两个OH基团间有2或3个碳原子的二醇的扩链剂；以10∶1-1∶4的(b1)与(b2)的摩尔比组成，和(c)至少一种数均分子量为450-10000g/mol和Zerewitinoff-活性氢原子平均数为1.8-3.0的多元醇组分，(a)中异氰酸酯基团与(b)和(c)中异氰酸酯反应性基团的比为0.9∶1-1.1∶1。
Description
技术领域
本发明一般性涉及热塑性聚氨酯及其制法和用途。更具体地涉及具有低雾度和良好加工性的透明热塑性聚氨酯及其制法和用途。
背景技术
热塑性聚氨酯(TPUs)由于其良好的弹性体性能和热塑性加工性而具有重大的工艺重要性。例如Kunststoff Handbuch[G.Becker，D.Braun]，卷7″Polyurethane″，Munich，Vienna，Carl Hanser Verlag，1983给出了TPUs的制备、性能和应用的综述。
TPUs主要由线性多元醇(大分子二醇)，例如聚酯二醇、聚醚二醇或聚碳酸酯二醇，有机二异氰酸酯和短链，主要是二官能醇(扩链剂)组成。它们可以连续或间歇制备。最公知的制备方法是带式方法(例如British Patent Pub.No.GB 1057018)和挤塑方法(例如German Patent Pub.No.DE 1964834)，其各自的全部内容在此引入作为参考。
可热塑性加工的聚氨酯弹性体可以分步(预聚物计量方法)或通过使所有组分在一个阶段同时反应(一步计量方法)制备。
在脂族光稳定性透明材料的应用中，最多使用的却是基于H12-MDI的具有固化行为不佳之缺点的材料。因此需要基于其它材料例如HDI(二异氰酸己二醇酯)的脂族光稳定性透明TPUs作为二异氰酸酯，但是这些TPUs对于这种应用太浑浊。
国际专利公开WO 02/050151(其全部内容在此引入作为参考)描述了基于环氧乙烷多元醇或环氧乙烷-环氧丙烷多元醇与混合扩链剂的透明TPUs，其中扩链剂组分之一选自环氧乙烷、二甘醇或1，3-丙二醇。在实施例中，仅记载了非光稳定性的基于芳族异氰酸酯的TPUs。
发明内容
本发明一般性涉及基于二异氰酸1，6-己二醇酯的光稳定性透明的热塑性聚氨酯模塑组合物，其具有根据ASTM D 1003小于10％的雾度，具有良好的工艺加工性，以及涉及其用途。
根据本发明各种实施方案的基于二异氰酸1，6-己二醇酯的热塑性光稳定性聚氨酯(TPUs)显示出根据ASTM D 1003小于10％的雾度值，同时显示出良好的工艺加工性。
因此本发明包括具有根据ASTM D 1003小于10％的雾度的光稳定性热塑性聚氨酯，其可从下列组分获得：a)二异氰酸1，6-己二醇酯(1，6-HDI)和不同于1，6-HDI的任选的其它脂族二异氰酸酯，b)扩链剂组分，由以下组分组成：b1)1，4-二(β-羟乙基)氢醌，和b2)至少一种扩链剂，其由在两个OH基团之间的链中具有2或3个碳原子的二醇组成，其中扩链剂b1)与扩链剂b2)的摩尔比为10∶1-1∶4，c)至少一种具有450-10000g/mol数均分子量和平均至少1.8个至最多3.0个Zerewitinoff-活性氢原子的多元醇组分，其中组分a)中异氰酸酯基团数与组分b)、c)和任选的g)中异氰酸酯反应性基团数的比值为0.9∶1-1.1∶1，任选在下列组分存在下：d)催化剂，加入下列组分：e)基于热塑性聚氨酯，0.1-10wt％的光稳定剂，f)任选的添加剂和/或辅助物质，g)任选的链终止剂。
本发明的一个实施方案包括具有小于10％的ASTM D 1003雾度值的光稳定性热塑性聚氨酯，该聚氨酯通过包括使下列组分反应的方法制备：(a)包括二异氰酸1，6-己二醇酯的二异氰酸酯组分；(b)扩链剂组分，其由(b1)和(b2)以10∶1-1∶4的扩链剂(b1)与扩链剂(b2)的摩尔比组成，(b1)1，4-二(β-羟乙基)氢醌，和(b2)至少一种选自在两个OH基团之间的链中具有2或3个碳原子的二醇的扩链剂；和(c)至少一种具有450-10000g/mol数均分子量和至少1.8个至最多3.0个Zerewitinoff-活性氢原子平均数的多元醇组分，其中组分(a)中异氰酸酯基团与组分(b)和(c)中异氰酸酯反应性基团的比值为0.9∶1-1.1∶1。
本发明的另一个实施方案包括包含本发明的聚氨酯的光稳定性的透明模塑制品。
本发明的其它实施方案包括制备光稳定性的透明模塑制品的方法，该方法包括：(i)提供根据权利要求1的聚氨酯；和(ii)使该聚氨酯经历注塑和/或挤塑。
具体实施方式
如本文所用的，单数术语“一种”和“该”是同义的并且可以与“一种或多种”及“至少一种”互换使用，除非措辞和/或上下文清楚地作出另外表示。因此，例如，文中或所附权利要求中提到“扩链组分”可以指单一扩链组分或多于一种的扩链组分。另外，除非另外具体注明，所有数值应理解为被用语“约”修饰。
除了二异氰酸1，6-己二醇酯作为主要组分，可以使用作为次要组分(最多30mol％)的下列脂族二异氰酸酯作为有机二异氰酸酯a)：二异氰酸乙二醇酯、二异氰酸1，4-丁二醇酯、二异氰酸1，12-十二烷二醇酯；脂环族二异氰酸酯，例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。优选使用1，4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯。所述二异氰酸酯可以单独使用或以彼此混合物的形式使用。它们也可以与至多15mol％(基于总异氰酸酯组分)的多异氰酸酯一起使用，但是可以加入的多异氰酸酯的最大量产生仍是可热塑性加工的产品。
在两个OH基团之间具有2或3个碳原子的二醇
其中R’和R”彼此独立地是具有1-6个碳原子的烷基]用作扩链剂b2)，优选来自1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、2，2-二甲基-1，3-丙二醇、2-甲基-1，3-丙二醇、2-乙基-2-丁基-1，3-丙二醇或其混合物，其中扩链剂b 1)与扩链剂b2)的摩尔比为10∶1-1∶4。
使用具有平均至少1.8个至最多3.0个Zerewitinoff-活性氢原子和450-10000数均分子量Mn的组分作为组分c)。
特别地，具有2-3个，优选两个羟基基团的化合物是优选的，特别是具有450-6000数均分子量Mn的那些，特别优选具有600-4500数均分子量Mn的那些；具有羟基基团的聚酯、聚醚和聚碳酸酯是特别优选的。作为制备的结果，多元醇经常含有少量非线性化合物。因此经常使用表述“基本线性的多元醇”。
合适的聚醚二醇可以通过使一种或多种在亚烷基基团中具有2-4个碳原子的环氧烷烃与含有所连接的两个活性氢原子的起始分子反应制备。可以提及下列化合物作为环氧烷烃：环氧乙烷、1，2-环氧丙烷、环氧氯丙烷及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。环氧烷烃可以单独使用，或者连续使用或以混合物形式使用。考虑例如以下化合物作为起始分子：水，氨基醇，例如N-烷基-二乙醇胺，例如N-甲基二乙醇胺，和二醇，例如乙二醇、1，3-丙二醇、1，4-丁二醇和1，6-己二醇。任选地还可以使用起始分子的混合物。合适的聚醚多元醇另外是四氢呋喃的含羟基基团的聚合产物。也可以使用数量为0-30wt％的三官能聚醚，基于二官能聚醚，但是最大量为使制备的产品仍是可热塑性加工的。基本线性的聚醚二醇优选具有450-6000的数均分子量Mn。它们可以单独使用或者以彼此的混合物形式使用。
合适的聚酯二醇可以例如由具有2-12个碳原子，优选4-6个碳原子的二羧酸与多价醇制备。考虑例如以下酸作为二羧酸：脂族二羧酸，例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸，或芳族二羧酸，例如邻苯二甲酸、间苯二甲酸和对苯二甲酸。二羧酸可以单独使用或者作为混合物使用，例如以琥珀酸、戊二酸和己二酸混合物的形式使用。任选可能有利的是使用相应的二羧酸衍生物代替二羧酸来制备聚酯二醇，所述衍生物为例如醇基团中具有1-4个碳原子的羧酸二酯、羧酸酐或羧酰氯。多价醇的实例为具有2-10个，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、2，2-二甲基-1，3-丙二醇、1，3-丙二醇或二丙二醇。根据所需性能，多价醇可以单独使用或以彼此混合物的形式使用。另外合适的是碳酸与所述二醇的酯，所述二醇特别为具有4-6个碳原子的那些，例如1，4-丁二醇或1，6-己二醇，ω-羟基羧酸，例如ω-羟基己酸的缩合产物，或内酯，例如任选取代的ω-己内酯的聚合产物。聚己二酸乙二醇酯、聚己二酸1，4-丁二醇酯、聚己二酸乙二醇-1，4-丁二醇酯、聚己二酸1，6-己二醇-新戊二醇酯、聚己二酸1，6-己二醇-1，4-丁二醇酯和聚己内酯优选用作聚酯二醇。聚酯二醇具有450-10000的数均分子量Mn，并且可以单独使用或者以彼此的混合物形式使用。
与异氰酸酯反应的单官能化合物可以用作所谓的链终止剂g)，用量为至多2wt％，基于TPU。例如，单胺，例如丁基胺和二丁基胺、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，例如丁醇、2-乙基己醇、辛醇、十二烷醇、硬脂醇、各种戊基醇、环己醇和乙二醇单甲醚是合适的。
Zerewitinoff-活性化合物的相对量优选选择使得异氰酸酯基团总数与Zerewitinorr-活性氢原子总数的比值为0.9∶1至1.1∶1。
根据本发明的热塑性聚氨酯可以包含优选至多10wt％(基于TPU总量)的常规辅助物质和添加剂作为辅助物质和添加剂f)。典型的辅助物质和添加剂为润滑剂和脱模剂，例如脂肪酸酯、其金属皂、脂肪酸酰胺、脂肪酸酯酰胺和硅氧烷化合物、防粘连剂、抑制剂、抗水解、热和变色的稳定剂、染料、颜料、无机和/或有机填料、增塑剂、具有抑制真菌和抑制细菌作用的物质及其混合物。
关于所述辅助物质和添加剂的进一步信息可见专门文献，例如J.H.Saunders和K.C.Frisch的专著″High Polymers″，卷XVI，Polyurethane，第1和2部分，Verlag Interscience Publishers 1962和1964，the Taschenbuch für Kunststoff-Additive，R.
和H.Müller(HanserVerlag Munich 1990)或DE-A 2901774。
可以掺入到TPU中的其它添加剂是热塑性塑料，例如乙烯/乙酸乙烯酯共聚物、苯乙烯/丁二烯共聚物和其它TPUs。
UV稳定剂、抗氧剂和/或HALS化合物优选用作光稳定剂e)。进一步的信息可见专门文献，并且记载于例如Plastics AdditivesHandbook，2001第5版，Carl Hanser Verlag，Munich中。
合适的催化剂d)是现有技术已知的常规叔胺，例如三乙胺、二甲基环己基胺、N-甲基吗啉、N，N’-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂二环[2.2.2.]辛烷等，并且特别是有机金属化合物，例如钛酸酯，铋化合物，铁化合物或锡化合物，例如二乙酸锡、二辛酸锡、二月桂酸锡或脂族羧酸的锡二烷基盐，例如二乙酸二丁基锡或二月桂酸二丁基锡等。优选的催化剂是有机金属化合物，特别是钛酸酯、铁化合物、锡化合物、锆化合物和铋化合物。在根据本发明的TPUs中催化剂的总量通常优选为0-5wt％，更优选0-2wt％，基于TPU的总量。
可以在制备过程期间和/或向TPU另外配混期间加入辅助物质和添加剂。
根据本发明的TPUs优选用于注塑方法或挤塑方法，例如薄膜挤塑。
根据本发明的TPUs优选用于生产光稳定性的透明模塑制品。
现在参考以下非限制性实施例更详细地描述本发明。
实施例
使用以下缩写：PE 225B 分子量Mn＝2250g/mol的聚酯二醇；BayerMaterialScience AG的产品A 2220N
2220N；分子量Mn＝2250g/mol的聚醚二醇(C3和C2亚烷基单元的混合醚)；BayerMaterialScience AG的产品T2000
2000；分子量Mn为2000g/mol的聚四氢呋喃；Invista Inc.的产品T 10001000；分子量Mn为1000g/mol的聚四氢呋喃；Invista Inc.的产品De C2201
C2201；基于1，6-己二醇的分子量Mn为2000g/mol的聚碳酸酯；BayerMaterialScience AG的产品AD 2055
AD 2055；分子量Mn为2000g/mol的聚(新戊二醇-1，6-己二醇)己酸酯；BayerMaterialScience AG的产品HDI 二异氰酸1，6-己二醇酯HDO 1，6-己二醇BDO 1，4-丁二醇PDO 1，3-丙二醇1，2-PDO 1，2-丙二醇HQEE 1，4-二(β-羟乙基)氢醌EG 乙二醇NPG 新戊二醇
1010抗氧剂，Ciba Specialty Chemicals GmbH234基于苯并三唑的光稳定剂，Ciba Specialty ChemicalsGmbHDBTL 二月桂酸二丁基锡
实施例(本发明和参考例/对比例)：制备TPU的一般性描述：
将1mol多元醇(c)与x mol扩链剂(b1)和y mol扩链剂(b2)及0.5wt％1010(基于总TPU)和60ppm DBTL(基于多元醇的量)的混合物加热到130℃，同时采用叶片式搅拌器以500转每分钟(rpm)的速度搅拌；然后加入(1+x+y)mol的HDI。随后搅拌至最大可能的粘度增长，然后将TPU倒出。在80℃再热处理所述材料30分钟并随后造粒。精确的配方(关于(b1)、x、(b2)和y的信息)在表1中给出。
根据ASTM D 1003在采用抛光模具制备的2mm厚注塑片材上测定雾度。数值也在表1中给出。
在注塑片材上定性评价加工性，所述片材在注塑机上制备。由此记录注塑片材的脱模性和表面性质。
在参考例1-4中使用1，6-己二醇、1，4-丁二醇或其混合物。实际上获得良好的加工性，但雾度值明显高于10％。
在参考例5-7中使用1，3-丙二醇、1，2-乙二醇或其混合物，其中实际上获得低雾度值，但加工性非常差或甚至不可能。
在参考例8-10中单独使用HQEE或少量HQEE与PDO。在实施例8中，实际上加工性良好，但雾度为11％。在实施例9和10中，相对高含量的PDO得到可加工性非常差的材料，作为其结果，不能测定雾度。
在根据本发明的实施例11-16中使用HQEE与PDO、EG、NPG或1，2-PDO的组合。雾度低于10％，并获得良好的加工性。
参考例17描述了使用HQEE与BDO的组合作为扩链剂。获得良好的加工性，但15％的雾度值显然太高了。
根据本发明的实施例18和19描述了使用HQEE和PDO与聚碳酸酯二醇或C-3/C-2醚的组合作为多元醇。获得了良好的加工性以及所需的低雾度值两者。
参考例20对应于申请WO 02/050151，并且描述了使用HQEE与EG和C-3/C-2醚作为多元醇，MDI作为二异氰酸酯。实际上加工性良好，但67％的雾度值显然太高了。
本领域技术人员应该理解，在不背离其宽泛的发明构思的情况下，可以对上述实施方案作出变化。因此，应该理解，本发明不限于所公开的具体实施方案，而是拟覆盖由所附权利要求限定的本发明的主旨和范围内的各种修改。
Claims (13)
1.光稳定性热塑性聚氨酯，其具有小于10％的ASTM D1003雾度值和良好的加工性，该聚氨酯通过包括使下列组分反应的方法制备：
(a)包括二异氰酸1，6-己二醇酯的二异氰酸酯组分；
(b)扩链剂组分，其由(b1)和(b2)以10∶1-1∶4的扩链剂(b1)与扩链剂(b2)的摩尔比组成，(b1)1，4-二(β-羟乙基)氢醌，和(b2)至少一种选自在两个OH基团之间具有2或3个碳原子链长的二醇的扩链剂；和
(c)至少一种具有450-10000g/mol数均分子量和至少1.8个至最多3.0个Zerewitinoff-活性氢原子平均数的多元醇组分，
其中组分(a)中异氰酸酯基团与组分(b)和(c)中异氰酸酯反应性基团的比值为0.9∶1-1.1∶1。
2.根据权利要求1的光稳定性热塑性聚氨酯，其中所述方法包括：使(a)、(b)和(c)在一种或多种选自(d)催化剂；(e)光稳定剂，基于聚氨酯数量为0.1-10wt％；(f)添加剂和辅助物质；和(g)链终止剂的另外组分的存在下反应。
3.根据权利要求1的光稳定性热塑性聚氨酯，其中所述至少一种多元醇组分具有450-6000g/mol的数均分子量。
4.根据权利要求1的光稳定性热塑性聚氨酯，其中所述至少一种多元醇组分具有600-4500g/mol的数均分子量。
5.根据权利要求1的光稳定性热塑性聚氨酯，其中所述二异氰酸酯组分进一步包含至多30mol％的第二种脂族二异氰酸酯。
6.根据权利要求1的光稳定性热塑性聚氨酯，其中所述至少一种扩链剂(b2)包含一种或多种选自1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、2，2-二甲基-1，3-丙二醇、2-甲基-1，3-丙二醇、2-乙基-2-丁基-1，3-丙二醇及其混合物的二醇。
7.光稳定性热塑性聚氨酯，其具有小于10％的ASTM D1003雾度值，该聚氨酯通过包括使下列组分反应的方法制备：
(a)包括二异氰酸1，6-己二醇酯和至多30mol％的第二种脂族二异氰酸酯的二异氰酸酯组分；
(b)扩链剂组分，其由(b1)和(b2)以10∶1-1∶4的扩链剂(b1)与扩链剂(b2)的摩尔比组成，(b1)1，4-二(β-羟乙基)氢醌，和(b2)至少一种选自1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、2，2-二甲基-1，3-丙二醇、2-甲基-1，3-丙二醇、2-乙基-2-丁基-1，3-丙二醇及其混合物的扩链剂；和
(c)至少一种具有600-4500g/mol数均分子量和至少1.8个至最多3.0个Zerewitinoff-活性氢原子平均数的多元醇组分，
其中组分(a)中异氰酸酯基团与组分(b)和(c)中异氰酸酯反应性基团的比值为0.9∶1-1.1∶1。
8.光稳定性透明模塑制品，其包含根据权利要求1的聚氨酯。
9.光稳定性透明模塑制品，其包含根据权利要求7的聚氨酯。
10.制备光稳定性透明模塑制品的方法，该方法包括：
(i)提供根据权利要求1的聚氨酯；和
(ii)使该聚氨酯经历注塑。
11.制备光稳定性透明模塑制品的方法，该方法包括：
(i)提供根据权利要求1的聚氨酯；和
(ii)使该聚氨酯经历挤塑。
12.制备光稳定性透明模塑制品的方法，该方法包括：
(i)提供根据权利要求7的聚氨酯；和
(ii)使该聚氨酯经历注塑。
13.制备光稳定性透明模塑制品的方法，该方法包括：
(i)提供根据权利要求7的聚氨酯；和
(ii)使该聚氨酯经历挤塑。
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| DE102008018967A1 (de) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Oxymethylenpolymere, Verfahren zu deren Herstellung und deren Verwendung |
| US8840976B2 (en) | 2010-10-14 | 2014-09-23 | Ticona Llc | VOC or compressed gas containment device made from a polyoxymethylene polymer |
| EP2505609B1 (en) | 2011-04-01 | 2015-01-21 | Ticona GmbH | High impact resistant polyoxymethylene for extrusion blow molding |
| KR20140040240A (ko) * | 2011-06-17 | 2014-04-02 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 바이오-기반 글리콜로부터의 감소된 블룸에 대한 경향을 갖는 열가소성 폴리우레탄 |
| EP2760902B1 (de) | 2011-09-30 | 2018-08-08 | Covestro Deutschland AG | Homogene extrudierte artikel aus thermoplastisch verarbeitbaren polyurethanen auf basis von polyesterdiolen aus bernsteinsäure und 1,3 -propandiol |
| WO2013101624A1 (en) | 2011-12-30 | 2013-07-04 | Ticona Llc | Printable molded articles made from a polyoxymethylene polymer composition |
| US9745467B2 (en) | 2012-12-27 | 2017-08-29 | Ticona, Llc | Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light |
| EP2918618A1 (de) * | 2014-03-10 | 2015-09-16 | Bayer MaterialScience AG | Aliphatische thermoplastische Polyurethane, ihre Herstellung und Verwendung |
| EP3122795B1 (de) * | 2014-03-25 | 2022-06-15 | Basf Se | Tpu pneumatikschlauch |
| TWI730948B (zh) * | 2014-12-08 | 2021-06-21 | 芬蘭商拜耳股份有限公司 | 新穎的熱塑性聚胺甲酸酯，彼等材料於製造子宮內系統之ｔ-框架之用途及由此等材料製成之ｔ-框架 |
| BR112018004019A2 (pt) * | 2015-09-24 | 2018-12-11 | Basf Se | ?poliuretano termoplástico, processo para a preparação de um poliuretano termoplástico, utilização de um poliuretano termoplástico e mangueira? |
| EP3147303A1 (en) * | 2015-09-25 | 2017-03-29 | Ernesto Monton Martin | Solid surface product comprising aliphatic isocyanate and process for manufacturing thereof |
| CN107383325B (zh) * | 2017-06-28 | 2020-02-07 | 苏州奥斯汀新材料科技有限公司 | 一种高透明热塑性聚氨酯弹性体的制备方法 |
| CN108047415A (zh) * | 2018-01-10 | 2018-05-18 | 中国航发北京航空材料研究院 | 一种光学级热塑性聚氨酯弹性体及其制备方法 |
| CN109679070B (zh) * | 2018-12-29 | 2021-10-12 | 上海优玥新材料科技有限公司 | 一种耐黄变高透光阻尼材料及其制备方法 |
| KR102339304B1 (ko) * | 2019-04-16 | 2021-12-16 | 주식회사 동성케미컬 | 자동차 내장 표피재용 열가소성 폴리우레탄 조성물 및 이의 제조 방법 |
| CN111995729B (zh) * | 2020-08-31 | 2022-04-19 | 山东一诺威聚氨酯股份有限公司 | 软段交联的热塑性聚氨酯弹性体及其制备方法 |
| CN113563554B (zh) * | 2021-07-15 | 2022-03-08 | 盛鼎高新材料有限公司 | 安全玻璃的中间层光学材料的制备方法 |
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| CN1796430A (zh) * | 2004-12-17 | 2006-07-05 | 拜尔材料科学股份公司 | 热塑性聚氨酯及其应用 |
| CN1793193A (zh) * | 2004-12-24 | 2006-06-28 | 拜尔材料科学股份公司 | 脂族可烧结热塑性聚氨酯及其用途 |
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| BRPI0900135A2 (pt) | 2009-09-15 |
| KR20090082156A (ko) | 2009-07-29 |
| AU2009200208A1 (en) | 2009-08-13 |
| EP2083028B1 (de) | 2010-08-25 |
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| US20090189314A1 (en) | 2009-07-30 |
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