CN105143298B - 喷雾聚氨酯弹性体的制备方法和由该方法制备的弹性体 - Google Patents

喷雾聚氨酯弹性体的制备方法和由该方法制备的弹性体 Download PDF

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CN105143298B
CN105143298B CN201480015313.2A CN201480015313A CN105143298B CN 105143298 B CN105143298 B CN 105143298B CN 201480015313 A CN201480015313 A CN 201480015313A CN 105143298 B CN105143298 B CN 105143298B
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J·W·詹妮
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Abstract

固体含量大于40重量％的聚氨酯弹性体由可喷雾的聚氨酯形成体系制备，所述聚氨酯形成体系由异氰酸酯组分和异氰酸酯反应性组分组成。异氰酸酯组分的固体含量为40至80重量％，基于异氰酸酯组分的总重量计，且其由至少一种NCO含量为24至33％且官能度为2至3的芳族多异氰酸酯和至少一种固体填料组成。异氰酸酯反应性组分的固体含量为40至80重量％，基于异氰酸酯反应性组分的总重量计，且其由至少一种羟值为25至40且官能度为2至4的聚醚多元醇和至少一种固体填料组成。

Description

喷雾聚氨酯弹性体的制备方法和由该方法制备的弹性体
背景技术
本发明涉及喷雾弹性体和制备这些喷雾弹性体的方法。在本发明方法中，将固体填料分别纳入至异氰酸酯组分和异氰酸酯反应性组分中。该喷雾方法使得制备具有比以前可能的固体含量更高的固体含量的弹性体成为可能。由本发明方法制备的弹性体可特别地用作汽车应用的声学部件，如仪表盘绝缘体和地毯背衬。
聚氨酯弹性体中包含固体使得降低这种弹性体的成本同时不牺牲弹性体的物理性能成为可能。因此，将聚氨酯弹性体的固体含量提高至最大可能的水平是商业上期望的。
然而，固体的量不能增加至太高的水平，以致聚氨酯形成组分的加工变得很难使得在商业上难以实现。
美国专利6,432,543公开了用于制备特别适合汽车行业的部件的特定的可喷雾的弹性体组合物。这些部件具有模制弹性外层和聚氨酯泡沫内层。所述弹性体为芳族多异氰酸酯、含固体的多元醇、第二多元醇和其他添加剂的反应产物。除多异氰酸酯外的所有组分的总固体含量最高达40重量％。含有这种数量的固体的弹性体的硬度通常限制在70至85肖氏A范围内。然而，美国专利6,432,543没有教导所公开的弹性体可具有大于40％的固体含量。
在现有的聚氨酯喷雾弹性体体系中，固体仅被纳入至异氰酸酯反应性组分中，如在美国专利6,432,543中所教导。然而，具有高固体含量(即，固体含量大于40％)的弹性体的制备受该方法限制，这是因为可纳入至异氰酸酯反应性组分中的固体材料的量不能太大，以致异氰酸酯反应性组分的粘度对喷雾来说太高。因此，为了获得更高的固体含量，需要调节与含固体的异氰酸酯反应性组分相结合的异氰酸酯组分的体积比。目前已知的喷雾聚氨酯弹性体体系中使用的体积比(即，异氰酸酯反应性组分的体积:异氰酸酯组分的体积)通常为11:1至14:1。这种体积比需要使用专用的设备。
因此，有利的是开发一种用于制备固体含量大于40％的聚氨酯弹性体的喷雾方法，该方法可使用常规的喷雾设备来进行。
发明内容
本发明的目的是提供固体含量大于40重量％、优选大于50重量％的喷雾聚氨酯弹性体。
本发明的另一目的是提供一种用于制备固体含量大于40％的喷雾聚氨酯弹性体的喷雾方法，该方法可使用常规的喷雾设备来进行。
这些目的和对本领域技术人员来说显而易见的其他目的通过将填料纳入至待喷雾的聚氨酯形成体系(polyurethane-forming system)的异氰酸酯组分和异氰酸酯反应性组分二者中来实现。
具体实施方式
本发明涉及通过喷雾制备聚氨酯弹性体的聚氨酯形成体系，其总固体含量为40至80重量％，基于聚氨酯形成体系的总重量计。为了确保聚氨酯形成体系为可喷雾的，异氰酸酯组分和异氰酸酯反应性组分在25℃下的粘度通常均小于4,000mPa·s，优选小于2,000mPa·s，最优选小于1,000mPa·s。聚氨酯形成体系的异氰酸酯组分可具有40至80重量％的固体含量，并包括：(i)至少一种芳族多异氰酸酯，其NCO含量为24％至33％且官能度为2至3，以及(ii)至少一种固体填料，其以足够获得固体含量为40至80重量％的异氰酸酯组分的量存在。本发明的聚氨酯形成体系的异氰酸酯反应性组分可具有40至80重量％的固体含量，并包括：(i)至少一种聚醚多元醇，所述聚醚多元醇的羟值为25至40且官能度为2至4，以及(ii)至少一种固体填料，所述固体填料以足够获得固体含量为40至80重量％的异氰酸酯反应性组分的量存在。然而，异氰酸酯组分和异氰酸酯反应性组分的总的结合固体含量必须在40重量％和80重量％之间，基于聚氨酯形成体系的总重量计。
用于本发明的异氰酸酯组分的合适的多异氰酸酯和/或其预聚物的NCO基团含量必须为约24％至约33％，优选为约28％至约33％，最优选为约30％至约32％。
优选的多异氰酸酯及其预聚物的实例包括基于二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯、NCO基团含量在24％至33％的要求范围内的那些。
合适的多异氰酸酯在25℃下的粘度通常为至少约15mPa·s，更优选至少约20mPa·s且最优选至少约23mPa·s。这些多异氰酸酯的粘度通常为小于或等于50mPa·s，优选小于或等于40mPa·s且最优选小于或等于35mPa·s。所述多异氰酸酯的粘度可在这些上限值和下限值的任意组合之间，包括端值。
当异氰酸酯组分包含异氰酸酯预聚物时，所述异氰酸酯预聚物通常通过将合适的多异氰酸酯与异氰酸酯反应性材料反应来制备，使得所得的预聚物的NCO基团含量在24和33％之间。这些预聚物在25℃下的粘度通常为至少约30mPa·s，更优选至少约35mPa·s且最优选至少约40mPa·s。这些预聚物的粘度通常小于或等于70mPa·s，优选小于或等于60mPa·s且最优选小于或等于50mPa·s。所述预聚物的粘度可在这些上限值和下限值的任意组合之间，包括端值。
以前描述的可用作异氰酸酯组分的任何多异氰酸酯可用于制备满足在本发明的实施中有用的％NCO含量和粘度要求的预聚物。
适于制备用作本发明体系的异氰酸酯组分的异氰酸酯预聚物的异氰酸酯反应性材料包括含有2至4、优选2至3、最优选约3个官能团的有机化合物，所述官能团能够与异氰酸酯基团反应。合适的异氰酸酯反应性基团包括OH基团、NH基团和SH基团，其中OH基团是特别优选的。
用于制备预聚物的这些异氰酸酯反应性化合物的合适的分子量范围为至少约200，优选至少约500，且最优选至少约1,000。这些化合物的分子量还通常小于或等于约7000，优选小于或等于约6500且最优选小于或等于约6000。异氰酸酯反应性组分的分子量可在这些上限值和下限值的任何组合之间。
用作用于制备预聚物的异氰酸酯反应性材料的合适的化合物的实例包括：聚醚多元醇、聚酯多元醇、聚碳酸酯二醇、多羟基聚硫醚、聚缩醛和脂族硫醇。优选聚醚多元醇。
在本发明的喷雾体系中用作异氰酸酯组分的特别优选的异氰酸酯为低官能度的聚合的二苯基甲烷二异氰酸酯(pMDI)。
本发明的喷雾体系的异氰酸酯反应性组分必须包括至少一种聚醚多元醇，其羟值为约25至约40，优选约28至约36且官能度为约2至约4，优选约3且在25℃下的粘度小于4,000mPa·s，优选小于2,000mPa·s，最优选小于1,000mPa·s。
除了聚醚多元醇之外的羟值为约25至约40且官能度为2至4的异氰酸酯反应性材料也可任选地包括在本发明体系的异氰酸酯反应性组分中。这些任选的异氰酸酯反应性化合物可包含能够与NCO基团反应的几乎任意类型的反应基团，条件是它们不会使异氰酸酯反应性组分在25℃下的粘度增加至4000mPa·s以上。
适于用作本发明中的异氰酸酯反应性组分的聚醚多元醇可通过本领域技术人员已知的任何技术来制备。合适的聚醚多元醇以下列商品名购得：Hyperlite E-824、Multranol 9111、Multranol 4012、Multranol4050和Arcol Polyol LHT-240。
本发明的聚氨酯形成体系的异氰酸酯反应性组分可任选地包括含羟基的聚酯。合适的含羟基的聚酯包括多羟基醇(优选二元醇)——任选地加入三元醇——和多元(优选二元)羧酸的反应产物。合适的聚缩醛包括通过二醇(如二乙二醇、三乙二醇、4,4'-二羟基二苯基甲烷和己二醇)与甲醛的缩合或通过环状缩醛(如三氧杂环己烷(trioxane))的聚合而获得的化合物。
可包括在本发明的异氰酸酯反应性组分中的其他任选的异氰酸酯反应性材料包括：聚醚多元醇、聚酯多元醇、聚碳酸酯二醇、多羟基聚硫醚、聚缩醛和脂族硫醇。
可任选包括在本发明体系的异氰酸酯反应性组分中的代表性含羟基化合物的一般性讨论可见于例如由Saunders和Frisch著的Polyurethanes Chemistry andTechnology,Interscience Publishers,纽约，伦敦，第I卷，1962，第32-42页和第44-54页，以及第II卷，1964，第5-6页和第198-199页；以及Kunststoff-Handbuch，第VII卷，Vieweg-Hochtlen，Carl-Hanser-Verlag，慕尼黑，1966，第45至71页。
包括在本发明的异氰酸酯反应性组分中的其他合适的添加剂和助剂包括例如催化剂、表面活性剂、扩链剂、交联剂和发泡剂。
固体填料必须以40重量％至80重量％、优选45重量％至75重量％、最优选50重量％至70重量％的量包括在本发明的聚氨酯形成体系的异氰酸酯组分和异氰酸酯反应性组分中，基于纳入了填料的组分计，且总固体含量(由于填料的纳入)必须为40至80重量％，优选45至75重量％，最优选50至70重量％，基于聚氨酯形成体系的总重量计。
合适的固体填料包括：硫酸钡、碳酸钙、实心微球、中空微球和水合氧化铝。特别优选硫酸钡。填料的粒径必须是使得其中分散有填料的反应性组分可用常规的喷雾设备来喷雾。合适的粒径的确定是本领域技术人员所熟知的。
尽管通常将相同的填料纳入至本发明的聚氨酯形成体系的异氰酸酯组分和异氰酸酯反应性组分中，但是在异氰酸酯组分和异氰酸酯反应性组分中还可以使用不同的填料。
当将固体填料加入到异氰酸酯组分和异氰酸酯反应性组分中后，这些组分可在1:4至1:1、优选5:16至3:4、最优选3:8至5:8的体积比下以本领域技术人员已知的任何方式来结合。在含有填料的组分的结合存在延迟的情况下，可能需要搅拌这些组分中的一者或两者，以确保填料的均匀分布。
在其中分散有固体填料的异氰酸酯组分和异氰酸酯反应性组分结合之后，可使用常规的喷雾设备将所得的聚氨酯形成体系喷雾至表面上。
可利用常规的喷雾设备以用于形成复合材料的任何已知的方法来使用本发明的可喷雾的聚氨酯形成体系。例如，美国专利6,294,248、6,432,543和6,649,107公开了这种方法。
本发明的聚氨酯弹性体的特征在于固体含量大于40重量％，优选40至80重量％，且最优选50至70重量％。
以下实施例进一步阐述了制备和使用本发明组合物的细节。在前文的公开内容中提出的本发明不受这些实施例的精神或范围的限制。本领域技术人员易于理解，以下制备步骤的条件和方法的已知变型可用于制备这些组合物。除非另有说明，所有的温度为摄氏温度且所有的份数和百分数分别为重量份数和重量百分数。
实施例
实施例1-6：粘度测试
向四个不同的异氰酸酯组分中填充50％、60％和70％水平的硫酸钡或碳酸钙。然后，混合后立即、6小时后且在测定前混合2分钟、以及24小时后且在测定前混合2分钟，测定这些填充的异氰酸酯组分的粘度。测定的粘度记录于表1中。不可接受的高粘度用星号(*)标记。
用于该研究的异氰酸酯如下：
ISO A：改性的单体4,4’-二苯基甲烷二异氰酸酯，其NCO含量为29.9％，官能度为且在25℃下的粘度为50mPa·s，其以Mondur CD的商品名购自Bayer MaterialScienceLLC。
ISO B：二苯基甲烷二异氰酸酯，其NCO含量为32.5％，官能度为2.3且在25℃下的粘度为29mPa·s，其以Mondur 1488的商品名购自Bayer MaterialScience。
ISO C：50份ISO A和50份ISO B的混合物，其NCO含量为31.2％，官能度为2.24且在25℃下的粘度为40mPa·s。
ISO D：聚合的二苯基甲烷二异氰酸酯，其NCO含量为31.5％，官能度为2.8且在25℃下的粘度为200mPa·s，其以Mondur MR的商品名购自Bayer MaterialScience LLC。
表1
实施例/填料 ISO/％填料 时间 温度(℃) 粘度(mPa·s)
1/BaSO4 A/50％ 0 22.1 108
A/60％ 0 23.7 293.9
A/70％ 0 26.5 1092
A/50％ 6小时 22.1 389.9
A/60％ 6小时 22.5 1548
A/70％ 6小时 23.2 11,362*
A/50％ 2天 22.3 1044
A/60％ 2天 23.3 2387
A/70％ 2天 24.1 16466*
2/BaSO4 B/50％ 0 25 156
B/60％ 0 24.8 305.9
B/70％ 0 28.4 1818
B/50％ 6小时 21.2 234
B/60％ 6小时 21.4 888
B/70％ 6小时 22.5 58384*
B/50％ 2天 21.7 359.9
B/60％ 2天 22.8 2190
B/70％ 2天 23.8 Max*
3/BaSO4 C/60％ 0 23.4 395.9
C/60％ 6小时 22.5 653.9
C/60％ 2天 23.8 2657
4/CaCO3 D/50％ 0 29.8 1512
D/60％ 0 34.5 6020*
D/70％ 0 47.5 76,184*
D/50％ 6小时 26.6 3155
D/60％ 6小时 26.7 270,000*
D/50％ 2天 25.3 63,811*
实施例5-6：喷雾弹性体的制备
根据本发明，用于制备固体含量大于40％的喷雾弹性体的异氰酸酯反应性组分中包括以下材料：
多元醇A：羟值为36mg KOH/g且官能度为约3的多元醇，其以Hyperlite E-824的商品名购自Bayer MaterialScience LLC。
多元醇B：羟值为370mg KOH/g的聚环氧丙烷系三醇，其以Multranol 4012的商品名购自Bayer MaterialScience LLC。
多元醇C：羟值为238mg KOH/g的聚环氧丙烷系三醇，其以Arcol Polyol LHT-240的商品名购自Bayer MaterialScience LLC。
多元醇D：特别地用环氧乙烷改性的羟值为28mg KOH/g的聚环氧丙烷系二醇，其以Multranol 9111的商品名购自Bayer MaterialScience LLC。
多元醇E：羟值为630mg KOH/g的胺系四官能聚醚多元醇，其以Multranol 4050的商品名购自Bayer MaterialScience LLC。
颜料：含有炭黑颜料的着色剂，被称为Colormatch DR-0217(黑色)。
Baytec 505二乙基甲苯二胺(DETDA)，其为芳族二胺，以Baytec 505的商品名购自Bayer MaterialScience LLC。
Dabco T-12用作聚氨酯催化剂的高沸点有机锡化合物(二月桂酸二丁基锡)，其购自Air Products and Chemicals,Inc。
Dytek A甲基支化的5碳链二胺(2-甲基五亚甲基二胺)，其购自Invista。
填料1：加入到异氰酸酯反应性组分中的硫酸钡。
填料2：加入到异氰酸酯组分中的硫酸钡。
将用于制备异氰酸酯反应性组分的材料以列于表2的量进行结合。然后，将166g硫酸钡加入到异氰酸酯反应性组分中以获得固体含量为60％的异氰酸酯反应性组分。
将83g硫酸钡加入到列于表2中的异氰酸酯中以获得固体含量为60％的异氰酸酯组分。
然后，将异氰酸酯组分和异氰酸酯反应性组分以等于1:2(异氰酸酯组:异氰酸酯反应性组分)的体积比进行结合。异氰酸酯反应性组分由多元醇A、多元醇B、多元醇C、多元醇D或多元醇E、颜料、Baytec505、Dabco T-12、Dytek A和填料1组成。异氰酸酯组分由ISO B或ISO C和填料2组成。
通过将异氰酸酯组分和异氰酸酯反应性组分结合而形成的聚氨酯形成体系的总固体含量和聚氨酯形成体系的各组分的粘度都记录在表2中。然后将该聚氨酯形成体系喷雾至加热的铝表面上以产生测试样品。
表2
尽管在前文中为了说明的目的对本发明已作详细描述，应理解的是这种详述仅仅为了说明的目的，并且除非受到权利要求书的限制，否则本领域技术人员在不脱离本发明的精神和范围的情况下，可以对其进行变化。

Claims (14)

1.聚氨酯形成体系，适合于通过喷雾来制备聚氨酯弹性体，所述聚氨酯形成体系包含：
a)基于异氰酸酯组分的总重量计，固体含量为40至80重量％且在25℃下的粘度小于4,000mPa·s的异氰酸酯组分，所述异氰酸酯组分包含：
(i)至少一种芳族多异氰酸酯，其NCO含量为24至33％，官能度为2至3，以及
(ii)至少一种固体填料，所述填料以足够获得a)的固体含量的量存在
以及
b)基于异氰酸酯反应性组分的总重量计，固体含量为40至80重量％且在25℃下的粘度小于4,000mPa·s的异氰酸酯反应性组分，所述异氰酸酯反应性组分包含：
(i)至少一种聚醚多元醇，所述聚醚多元醇的羟值为25至40且官能度为2至4，以及
(ii)至少一种固体填料，所述填料以足够获得b)的固体含量的量存在
其中，组分b)还包括羟值为600至660mg KOH/g的胺系聚醚多元醇，并且
a)加b)的总固体含量为40至80重量％，基于聚氨酯形成体系的总重量计。
2.权利要求1的体系，其中所述多异氰酸酯为聚合的MDI、改性的MDI或其混合物。
3.权利要求1的体系，其中组分a)和b)中的固体填料均选自硫酸钡和碳酸钙。
4.权利要求1的体系，其中在组分a)和b)中使用相同的填料。
5.权利要求4的体系，其中所述填料为硫酸钡。
6.权利要求1的体系，其中所述固体填料以50至70重量％的量存在于异氰酸酯组分中。
7.权利要求1的体系，其中所述固体填料以50至70重量％的量存在于异氰酸酯反应性组分中。
8.权利要求1的体系，其中所述总固体含量为50至70重量％。
9.权利要求1的体系，其中所述异氰酸酯组分和所述异氰酸酯反应性组分的粘度均小于3000mPa·s。
10.权利要求1的体系，其中所述异氰酸酯组分和所述异氰酸酯反应性组分以60至160的NCO/OH比例进行反应。
11.权利要求1的体系，其中组分b)还包括羟值为220至260mg KOH/g的环氧丙烷系三醇。
12.弹性体，其通过喷雾权利要求1的聚氨酯形成体系而制备。
13.弹性体，其通过喷雾权利要求5的聚氨酯形成体系而制备。
14.制备聚氨酯弹性体的方法，其包括喷雾权利要求1的体系。
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EP2970560A1 (en) 2016-01-20
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KR101817845B1 (ko) 2018-01-11

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