CN104861153A - 具有高的玻璃化转变温度Tg的透明聚氨酯 - Google Patents
具有高的玻璃化转变温度Tg的透明聚氨酯 Download PDFInfo
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Abstract
本发明涉及一种聚氨酯，其仅由多异氰酸酯组分和多元醇组分组成，其中所述多异氰酸酯组分由一种或多种多异氰酸酯组成，且该多异氰酸酯组分每分子的平均NCO官能度≥3，和所述多元醇组分由一种或多种多元醇组成，且该多元醇组分每分子的平均OH官能度≥3且其OH含量为≥25wt％。本发明进一步涉及一种生产本发明聚氨酯的方法，涉及一种包含本发明的聚氨酯或由本发明的聚氨酯组成的光学元件，还涉及本发明的聚氨酯用于传导光，散射光及/或偏转光的用途。
Description
本发明涉及具有高的玻璃化转变温度Tg的透明聚氨酯。
光学元件，例如光导体、光扩散器(optical diffuser)或透镜的生产需要透明材料，即所述材料对电磁波特别是在人类可见的400至800纳米的光谱范围内具有最大可能的透过性。由于许多光源如白炽灯和LED，在它们发光的同时产生热，因此，相当重要的是光学元件以及用于生产它们的材料各自具有高的热稳定性和机械稳定性。具体地，这意味着，例如甚至在材料经受明显加热时也不允许其发生变形，因为否则例如透镜将变得无用。同时，它们在常温下还必须具有足够的硬度，以抵抗机械负荷。
此外，日益增长的LED作为光源的用途已对新材料产生了相当大的需求，其中该材料一方面要符合现行需要，另一方面要适合于LED封装，或封装LED的铸造工艺。
因此，本发明的目的是提供一种透明的，具有高的热稳定性和机械稳定性，此外还适用于光源如LED的封装的材料。
根据本发明，所述目的可通过这样的聚氨酯实现，该聚氨酯仅由多异氰酸酯组分和多元醇组分构成，其中该多异氰酸酯组分由一种或多种多异氰酸酯组成，且该多异氰酸酯组分每分子的平均NCO官能度≥3，和该多元醇组分由一种或多种多元醇组成，且该多元醇组分每分子的平均OH官能度≥3且其OH含量为≥25wt％。
令人惊讶地，已经发现这种类型的聚氨酯具有高的透明度：按照在实验部分中描述的方法进行测量，它们显示出80％以上的透光率。此外，本发明的聚氨酯还具有非常高的热稳定性。按照在实验部分所述的方法，确定的本发明的聚氨酯的玻璃化转变温度为高于80℃。因此，它们非常适于生产预定用于暴露在高温下的光学元件，例如光导体，光扩散器或透镜。此外，根据在实验部分中所描述的方法，确定本发明聚氨酯的肖氏D硬度大于70，而且这证明了该聚合物的好地机械稳定性。本发明的聚氨酯还能容易地用于如LED的光源的封装。
对于本发明的方法而言，被认为是聚氨酯的化合物是具有氨基甲酸酯基团-NH-CO-O-的有机化合物。
多异氰酸酯是具有NCO基团的有机化合物。
多异氰酸酯组分的NCO官能度可通过组成该多异氰酸酯组分的多异氰酸酯的NCO基团的总数除以多异氰酸酯组分的分子总数来计算。
出现的术语多元醇是指具有OH基团的有机化合物。
多元醇组分的OH官能度可通过组成该多元醇组分的多元醇的OH基团总数除以多元醇组分的分子总数来计算。
OH含量是，以重量百分比表示的，基于所述多元醇组分的总分子量计由OH基团提供的分子量的大小。
第一优选具体实施方式提供了多异氰酸酯组分的NCO官能度是≤4和/或多元醇组分的OH官能度是≤6。
根据本发明合适的多异氰酸酯的实例是本领域技术人员已知的任意有机脂族、脂环族、芳族或杂环多异氰酸酯。特别优选的是所有多异氰酸酯的NCO官能度≥2。
也优选的是，所述多异氰酸酯是脂族化合物。同样优选的是，该多异氰酸酯组分仅由脂族多异氰酸酯组成。
合适的多异氰酸酯的实例是脂族二-或三异氰酸酯的低聚物，例如己烷二异氰酸酯(六亚甲基二异氰酸酯，HDI)、戊烷二异氰酸酯、丁烷二异氰酸酯、亚甲基双(环己基-4，4′-二异氰酸酯)、3，5，5-三甲基1-异氰酸根合-3-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯，IPDI)、4-异氰酸根合甲基辛烷-1，8-二异氰酸酯、1，3-双(异氰酸根合甲基)苯(XDI)、氢化苯二亚甲基二异氰酸酯，以及氢化甲苯二异氰酸酯。
上述二-和/或三异氰酸酯的加合物被称为低聚物。这些都可以从异氰酸酯基团之间的加成反应来制备以得到脲二酮和/或异氰脲酸酯，和/或从异氰酸酯基团与水和胺，或与醇的反应产物及其下游产物来制备，其中低聚物的每分子反应的二-或三异氰酸酯的数为至少2。该低聚物进一步包含反应性异氰酸酯基团。此外，为了本发明的目的，将该低聚物定义为每分子中具有小于40wt％，优选小于25wt％的具有多于11个反应的二-或三异氰酸酯的成分的化合物。
多异氰酸酯组分的NCO含量特别地可为≥15wt％且≤55wt％，优选≥18wt％且≤50wt％，并特别优选≥20wt％且≤30wt％。该NCO含量为，以重量百分比表示的，基于所述多异氰酸酯组分的总分子量计由NCO基团所提供的分子量的大小。
根据另一个优选的具体实施方式，至少一种多异氰酸酯是缩二脲类化合物，脲二酮或二-或三异氰酸酯的异氰脲酸酯。此处优选的二-或三异氰酸酯选自己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(环己基-4，4’-二异氰酸酯)、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、氢化甲苯二异氰酸酯、戊烷二异氰酸酯和4-异氰酸根合甲基辛烷-1，8-二异氰酸酯。
非常特别优选的是使用二-或三异氰酸酯的异氰脲酸酯作为多异氰酸酯。还更优选的是使用己烷二异氰酸酯或异佛尔酮二异氰酸酯的异氰脲酸酯或它们的异氰脲酸酯的混合物作为多异氰酸酯。
根据本发明合适的多元醇的实例是本领域技术人员已知的任意有机脂族、环脂族、芳族或杂环的多元醇。特别优选的是所有多元醇的羟基官能度≥2。
合适的多元醇的实例是1，2，10-癸三醇、1，2，8-辛三醇、1，2，3-三羟基苯、甘油、1，1，1-三羟甲基丙烷、1，1，1-三羟甲基乙烷、季戊四醇或糖醇。
特别优选的多元醇是纯脂族的化合物甘油、1，1，1-三羟甲基丙烷、1，1，1-三羟甲基乙烷、季戊四醇和糖醇。
本发明的一个具体实施方式提供了多元醇组分的OH含量是≥25wt％且≤60wt％，优选≥30wt％且≤60wt％，特别优选≥35wt％且≤60wt％。
多异氰酸酯与多元醇的分子比率可以以这样的方式调节，以使NCO基团与OH基团的比率在0.95∶1.00至1.20∶1.00的范围，优选1.05∶1.00，特别优选1.00∶1.00。
本发明进一步提供通过混合所述多异氰酸酯组分和所述多元醇组分，并任选加入催化剂和/或添加剂，并任选加热该混合物来生产本发明的聚氨酯的方法。
所述多异氰酸酯组分和所述多元醇组分可例如在本领域技术人员已知的多种静态或动态混合组件的帮助下混合。
本发明方法的一个优选的具体实施方式提供，在混合过程之前，将所述多异氰酸酯组分和所述多元醇组分加热到30到90℃，优选35到80℃，特别优选40到60℃的温度。
同样优选的是催化剂的加入量为0.001到0.100wt％，优选为0.002到0.050wt％，特别优选为0.005到0.030wt％，基于所述多异氰酸酯组分和多元醇组分的质量总和计。
合适的催化剂的实例是例如在Becker/Braun，Kunststoffhandbuch Band 7，Polyurethane，第3.4章中列出的典型的氨基甲酸酯化的催化剂。可以使用的一种特别的催化剂是选自胺和有机金属化合物，优选选自有机锡化合物和有机铋化合物的化合物，特别优选二月桂酸二丁基锡。
该催化剂可以以用合适的溶剂稀释的形式或未稀释的形式加入到两种组分中的一种中。优选的是将该催化剂与一种组分进行预混合，不加入溶剂，在该组分与其它组分混合之前。
可以添加多种添加剂作为另外的组分，实例为阻燃剂、染料、荧光剂、透明填料、光稳定剂、抗氧化剂、具有触变效果的试剂、脱模剂、增粘剂、光散射剂、和任选的其它助剂和添加物质。
为了防止不希望的副反应和气泡形成，在混合之前，任选使用合适的方法将起始材料干燥和脱气。
由于少量的水分会导致气泡形成，因此，在本发明的方法中有利的是，在无水条件下混合所述多异氰酸酯组分和多元醇组分，以及任选的其它成份。因此，混合物中残留的水含量应保持足够小，以避免出现任何不期望的效果。该混合物中的水含量可优选为＜0.5wt％。
本发明的方法也可使用最高40wt％的有机溶剂进行，但是优选不使用或仅使用少量溶剂
本发明还进一步提供包含本发明的聚氨酯或由其组成的光学元件。
本发明的光学元件可以通过多种生产方法生产，例如浇铸，快速注射成型(RIM)，浸涂或其它涂布方法，或其它合适的工艺。
该光学元件可以优选是光导体，光扩散器，或透镜。
本发明的光学元件的实例可以是在汽车前灯中的透镜，光学校正透镜，光导体，具有任选混合了荧光增白剂(在业内通常称为“荧光体”)的LED封装体系，或其它透明组件。本发明同样提供了任意本发明的聚氨酯用于传导光、散射光和/或偏转光的用途。
在下文中，根据实施例更详细地说明本发明。
基本信息：
除非另有说明，所有的百分比都是指重量百分比(重量％)。
将实验进行时的环境温度，23℃，描述为RT(室温)。
通过计算，确定多种原材料在每种情况下的NCO或OH官能度。
测试方法：
以下所列的确定相应的参数的方法用于这些实例的实施和评价，也是用于确定本发明相关参数的一般方法。
测定透光率：
根据ASTM标准D1003，使用Byk-Gardner haze-gard plus装置测定固化的聚氨酯体系的透光率。该测量在厚度为1cm的样品上进行。
测定玻璃化转变温度：
通过使用DMA方法，在自由膜上以1赫兹的激发频率来确定玻璃化转变温度(Tg)。
测定肖氏硬度：
根据DIN 53505，在由固化聚氨酯体系制成的厚度为2mm的膜上检测肖氏硬度。
起始材料
Desmodur N 3600是来自Bayer MaterialScience的NCO含量为23.0wt％的HDI三聚体(NCO官能度＞3)。粘度是1200mPas(DIN EN ISO 3219/A.3)。
Desmodur N 3200是来自于Bayer MaterialScience的NCO含量为23wt％的低粘度HDI缩二脲(NCO官能度＞3)，其。粘度是2500mPas(DIN EN ISO3219/A.3)。
Desmodur N 3400是来自于Bayer MaterialScience的NCO含量为21.8wt％的HDI脲二酮(NCO官能度＜3)。粘度是175mPas(DIN EN ISO 3219/A.3)。
Desmodur N 3900是来自于Bayer MaterialScience的NCO含量为23.5wt％的基于六亚甲基二异氰酸酯的低粘度脂族多异氰酸酯树脂(NCO官能度＞3)。粘度为730mPas(DIN EN ISO 3219/A.3)。
Desmodur XP 2489是来自于Bayer MaterialScience的NCO含量为21.0wt％的HDI/IPDI三聚体(NCO官能度＞3)。粘度为22500mPas(DIN EN ISO3219/A.3)。
甘油(1，2，3-丙三醇)购自Calbiochem，纯度为99.0％。
1，1，1-三羟甲基丙烷(TMP)购自Aldrich，纯度为97.0％。
Desmophen VP LS 2249/1是来自Bayer MaterialScience的羟基含量为15.5％的支化(2-＜F＜3)短链聚酯多元醇。
Desmophen XP 2488是来自Bayer MaterialScience的羟基含量为16％的支化(2＜F＜3)聚酯多元醇。
Desmophen VP LS 2328是来自Bayer MaterialScience的羟基含量为7.95％的线性(F＝2)短链聚酯多元醇。
二月桂酸二丁基锡(DBTL)作为Tinstab BL277购自Acros Chemicals。
除了催化剂，所有的原材料在使用之前均在真空中进行脱气，且也将多元醇进行干燥。
制备聚氨酯
除非另有说明，该聚氨酯通过以下方式生产，即将两种组分(多异氰酸酯和多元醇)加热到50℃，并将它们以1.0∶1.0的NCO∶OH比率混合，加入给定量的催化剂，然后在来自Hauschild的Speedmixer DAC 150.1FVZ中，将整个组合物以2750rpm混合60秒。
然后，将混合物浇铸到合适的模具中并在烘箱中固化。此处所用的加热程序如下：50℃下2小时+100℃下16小时+150℃下2小时。这样得到清澈透明的模制件。
表1：本发明实施例
表1中所列的本发明的聚氨酯具有高的机械稳定性。肖氏D硬度值提供了这方面的证据，在每种情况下均在高于70。然而，它们此外还具有高的热稳定性，这可以从所确定的玻璃化转变温度＞80℃看出。最后，透光率的测定也表明，所生产的聚氨酯是透明的，因此特别好的适合于光学应用。
表2：比较例
从表2显示的比较例中很明显看出，当多异氰酸酯组分的NCO官能度＜3或多元醇组分的OH官能度＜3或其OH的含量＜25wt％时，不可能获得同时具有高机械稳定性(肖氏D)、高热稳定性(Tg)和高透明度(透光率)的聚氨酯。
Claims (15)
1.聚氨酯，其仅由多异氰酸酯组分和多元醇组分组成，其中所述多异氰酸酯组分由一种或多种多异氰酸酯组成，且所述多异氰酸酯组分每分子的平均NCO官能度≥3，和所述多元醇组分由一种或多种多元醇组成，且所述多元醇组分每分子的平均OH官能度≥3和其OH含量为≥25wt％。
2.根据权利要求1的聚氨酯，其特征在于所述多异氰酸酯组分每分子的平均NCO官能度是≤4和/或所述多元醇组分每分子的平均OH官能度是≤6。
3.根据权利要求1或2的聚氨酯，其特征在于所述多异氰酸酯组分仅由脂族多异氰酸酯组成。
4.根据权利要求1至3任意一项的聚氨酯，其特征在于所述多异氰酸酯组分的NCO含量为≥15wt％且≤55wt％，优选≥18wt％且≤50wt％，且特别优选≥20wt％且≤30wt％。
5.根据权利要求1至4任意一项的聚氨酯，其特征在于至少一种多异氰酸酯是缩二脲类化合物、脲二酮或者二-或三异氰酸酯的三聚体。
6.根据权利要求5的聚氨酯，其特征在于所述二-或三异氰酸酯选自己烷二异氰酸酯、异佛尔酮二异氰酸酯、二异氰酸根合二环己基甲烷、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、三甲基己烷二异氰酸酯、氢化苯二亚甲基二异氰酸酯、氢化甲苯二异氰酸酯、戊烷二异氰酸酯和4-异氰酸根合甲基辛烷-1，8-二异氰酸酯。
7.根据权利要求1至6任意一项的聚氨酯，其特征在于所述多元醇组分的OH含量是≥25wt％且≤60wt％，优选≥30wt％且≤60wt％，特别优选≥35wt％且≤60wt％。
8.根据权利要求1至7任意一项的聚氨酯，其特征在于以这样的方式调节多异氰酸酯与多元醇的分子比率，以致NCO基团与OH基团的比率在0.95∶1.00至1.20∶1.00的范围，优选在1.05∶1.00，特别优选1.00∶1.00的范围。
9.根据权利要求1至8任意一项的聚氨酯的生产方法，其特征在于混合所述多异氰酸酯组分和所述多元醇组分，任选地加入催化剂，和任选地加热该混合物。
10.根据权利要求9的方法，其特征在于在混合过程之前，将所述多异氰酸酯组分和所述多元醇组分加热到30到90℃，优选35到80℃，特别优选40到60℃的温度。
11.根据权利要求9或10的方法，其特征在于所加入的催化剂的量为0.001到0.100wt％，优选为0.002到0.050wt％，特别优选为0.005到0.030wt％，基于所述多异氰酸酯组分和所述多元醇组分的质量总和计。
12.根据权利要求9至11任意一项的方法，其特征在于使用选自胺和有机金属化合物，优选选自有机锡化合物和有机铋化合物的化合物，和特别优选二月桂酸二丁基锡作为催化剂。
13.包含根据本发明权利要求1至8中任意一项的聚氨酯或由其组成的光学元件。
14.根据权利要求13的光学元件，其特征在于其是光导体、光扩散器或透镜。
15.根据权利要求1至8中任意一项的聚氨酯用于传导光、散射光和/或偏转光的用途。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676349A (zh) * | 2018-07-28 | 2018-10-19 | 望江县天长光学仪器有限公司 | 一种高透光率光学透镜材料 |
| CN109293865A (zh) * | 2017-10-18 | 2019-02-01 | Skc株式会社 | 用于塑料镜片的可聚合组合物 |
| CN112375202A (zh) * | 2020-11-30 | 2021-02-19 | 山东一诺威聚氨酯股份有限公司 | 用于导光条的热塑性聚氨酯弹性体及其制备方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017010422A1 (ja) * | 2015-07-10 | 2017-01-19 | 三井化学株式会社 | ポリウレタンゲルおよびその製造方法 |
| WO2017032620A1 (de) * | 2015-08-21 | 2017-03-02 | Covestro Deutschland Ag | Polyurethan-kompositwerkstoff |
| DE102019133078A1 (de) | 2019-12-04 | 2021-06-10 | resintec GmbH | Polyurethan Gießharz mit hoher UV Transparenz und hoher Temperaturstabilität |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0978523A1 (de) * | 1998-08-04 | 2000-02-09 | Basf Aktiengesellschaft | Verfahren zur Herstellung von kompakten, transparenten Polyisocyanat-Polyadditionsprodukten |
| US20070155936A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
| CN102292370A (zh) * | 2009-01-22 | 2011-12-21 | 拜尔材料科学股份公司 | 聚氨酯浇注材料 |
| CN103003322A (zh) * | 2010-07-13 | 2013-03-27 | 巴斯夫欧洲公司 | 具有氨基甲酸酯基团的高官能度多异氰酸酯 |
| CN103140530A (zh) * | 2010-07-30 | 2013-06-05 | 巴斯夫欧洲公司 | 包含氨基甲酸酯基的高官能度多异氰酸酯 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994009048A1 (en) * | 1992-10-13 | 1994-04-28 | Rijksuniversiteit Te Groningen | Polyurethane network for biomedical use |
-
2014
- 2014-10-27 EP EP14190394.8A patent/EP2910586A1/de not_active Withdrawn
-
2015
- 2015-02-18 US US14/624,761 patent/US20150246998A1/en not_active Abandoned
- 2015-02-18 CN CN201510130114.2A patent/CN104861153A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0978523A1 (de) * | 1998-08-04 | 2000-02-09 | Basf Aktiengesellschaft | Verfahren zur Herstellung von kompakten, transparenten Polyisocyanat-Polyadditionsprodukten |
| US20070155936A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
| CN102292370A (zh) * | 2009-01-22 | 2011-12-21 | 拜尔材料科学股份公司 | 聚氨酯浇注材料 |
| CN103003322A (zh) * | 2010-07-13 | 2013-03-27 | 巴斯夫欧洲公司 | 具有氨基甲酸酯基团的高官能度多异氰酸酯 |
| CN103140530A (zh) * | 2010-07-30 | 2013-06-05 | 巴斯夫欧洲公司 | 包含氨基甲酸酯基的高官能度多异氰酸酯 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293865A (zh) * | 2017-10-18 | 2019-02-01 | Skc株式会社 | 用于塑料镜片的可聚合组合物 |
| CN108676349A (zh) * | 2018-07-28 | 2018-10-19 | 望江县天长光学仪器有限公司 | 一种高透光率光学透镜材料 |
| CN112375202A (zh) * | 2020-11-30 | 2021-02-19 | 山东一诺威聚氨酯股份有限公司 | 用于导光条的热塑性聚氨酯弹性体及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2910586A1 (de) | 2015-08-26 |
| US20150246998A1 (en) | 2015-09-03 |
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