CN107512057B - 聚氨酯层压模塑制品及其制备方法 - Google Patents

聚氨酯层压模塑制品及其制备方法 Download PDF

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Publication number
CN107512057B
CN107512057B CN201610463695.6A CN201610463695A CN107512057B CN 107512057 B CN107512057 B CN 107512057B CN 201610463695 A CN201610463695 A CN 201610463695A CN 107512057 B CN107512057 B CN 107512057B
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China
Prior art keywords
polyurethane
reinforcing fiber
molded article
isocyanate
resin composition
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CN201610463695.6A
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English (en)
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CN107512057A (zh
Inventor
朱宏
李军
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority to CN201610463695.6A priority Critical patent/CN107512057B/zh
Priority to PCT/EP2017/064594 priority patent/WO2017216251A1/en
Priority to US16/304,956 priority patent/US20200324529A1/en
Priority to CN201780037601.1A priority patent/CN109414902A/zh
Priority to EP17734255.7A priority patent/EP3471955B1/en
Publication of CN107512057A publication Critical patent/CN107512057A/zh
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Publication of CN107512057B publication Critical patent/CN107512057B/zh
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Abstract

本发明一种聚氨酯层压模塑制品，所述聚氨酯层压模塑制品包含芯层以及设置在所述芯层至少一侧的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施用于一层或多层增强纤维毡或增强纤维织物上并将所述聚氨酯树脂固化后形成。本发明提供的聚氨酯层压模塑制品具有良好的脱模性和生产率。

Description

聚氨酯层压模塑制品及其制备方法
技术领域
本发明涉及一种聚氨酯层压模塑制品，所述聚氨酯层压模塑制品包含芯层以及设置在所述芯层至少一侧的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施用于一层或多层增强纤维毡或增强纤维织物上并将所述聚氨酯树脂固化后形成。本申请另一方面涉及所述聚氨酯层压模塑制品的制备方法。
背景技术
聚氨酯层压模塑制品已为本领域技术人员所熟知，其通过在芯层(例如纸蜂窝、铝蜂窝、泡沫芯材等)一侧或两侧设置增强纤维毡或增强纤维织物，并将聚氨酯反应混合物施用于增强纤维毡或增强纤维织物上，然后将覆有聚氨酯反应混合物的部件置于模具中，在一定的温度下层压所述部件使得聚氨酯反应混合物固化并形成一种三维结构，脱模后便可获得所述聚氨酯层压模塑制品。
工业界一直在寻找一种可以有效提高生产效率从而降低成本的方法。现有的聚氨酯层压产品大概每脱模10次左右就要喷涂一次外脱模剂。并且由于脱模效果不佳，产品容易粘模，所以每隔几个小时就要清理下模具表面。这些操作都会使正常的生产暂停，降低了生产效率，提高了成本。因此本领域一直都在需要提供一种良好脱模性能的聚氨酯层压模塑制品。
发明概述
本发明一个方面提供了一种聚氨酯层压模塑制品，所述聚氨酯层压模塑制品包含芯层以及设置在所述芯层至少一侧的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施用于一层或多层增强纤维毡或增强纤维织物上并将所述聚氨酯树脂固化后形成，其中所述聚氨酯树脂组合物包含：
A)异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B)异氰酸酯反应性组分，所述异氰酸酯组分包含
b1)第一多元醇，所述第一多元醇选自基于植物油的多元醇或其衍生物和改性物，含量为5-50wt％，基于异氰酸酯反应性组分的重量为100wt.％计；
b2)第二多元醇，所述第二多元醇的羟值为300-700mgKOH/g，官能度为2-6；
b3)一种或多种三聚催化剂；
b4)内脱模剂，所述内脱模剂的含量为0.1-5wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
在本发明一个实施例中，所述第一多元醇选自基于蓖麻油或大豆油的多元醇或其衍生物和改性物。
在本发明另一个实施例中，所述聚氨酯树脂组合物的异氰酸酯指数为130-300。
在本发明又一个实施例中，所述三聚催化剂选自胺类或金属盐类三聚催化剂。
在本发明还一个实施例中，所述芯层选自：可热成型聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
在本发明还一个实施例中，所述增强纤维网或增强纤维织物通过玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
本发明另一方面提供了一种聚氨酯层压模塑制品的制备方法，所述制备方法包括步骤：
i)提供一个待层压部件，所述待层压部件包含芯层以及设置在所述芯层至少一侧的一层或多层增强纤维毡或增强纤维织物；
ii)在所述增强纤维毡或增强纤维织物层上施用聚氨酯树脂组合物；
iii)将步骤ii)所得的部件置于模具中，层压该部件以获得一种三维形状，并使所述聚氨酯树脂组合物固化；和
iv)脱模，以获得所述聚氨酯层压模塑制品，
其中所述聚氨酯树脂组合物包含：
A)异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B)异氰酸酯反应性组分，所述异氰酸酯组分包含
b1)第一多元醇，所述第一多元醇选自基于植物油的多元醇或其衍生物和改性物，含量为5-50wt％，基于异氰酸酯反应性组分的重量为100wt.％计；
b2)第二多元醇，所述第二多元醇的羟值为300-700mgKOH/g，官能度为2-6；
b3)一种或多种三聚催化剂；
b4)内脱模剂，所述内脱模剂的含量为0.1-5wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
在本发明一个实施例中，所述第一多元醇选自基于蓖麻油或大豆油的多元醇或其衍生物和改性物。
在本发明另一个实施例中，所述聚氨酯树脂组合物的异氰酸酯指数为130-300。
在本发明又一个实施例中，所述三聚催化剂选自胺类或金属盐类三聚催化剂。
在本发明还一个实施例中，所述芯层选自：可热成型聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
在本发明还一个实施例中，所述增强纤维网或增强纤维织物通过玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
具体实施方式
I.聚氨酯层压模塑制品
本发明一方面涉及一种聚氨酯层压模塑制品，所述聚氨酯层压模塑制品包含芯层以及设置在所述芯层至少一侧的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施用于一层或多层增强纤维毡或增强纤维织物上并将所述聚氨酯树脂固化后形成。
本发明的聚氨酯层压模塑制品不但具有良好的机械性能并且具有很好的脱模性，实际操作性好。
当用于本发明时，术语“聚氨酯层压模塑制品”具有本领域技术人员所熟知的定义，如CN1321816C和CN101641384中均对此结构有详细描述。
本发明提供的聚氨酯层压模塑制品的芯层可以是本领域中常用的芯层，包括但不限于：可热成型聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。在本发明一个优选的实施例中，所述芯层选自纸蜂窝。
在所述芯层的一层或两侧设置有一层或多层增强纤维毡或增强纤维织物。所述增强纤维毡或增强纤维织物可以通过玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。在本发明一个优选的实施例中，所述增强纤维毡或增强纤维织物通过玻璃纤维制备。
在获得上述部件后，可以在所述增强纤维毡或增强纤维织物上施用一种聚氨酯组合物，聚氨酯组合物会渗入增强纤维毡或织物的网孔结构中，之后在模具中一定的温度和模压下固化，形成一种聚氨酯-增强纤维复合结构，即为聚氨酯层压模塑制品。
可用于本发明的聚氨酯树脂组合物包含：
A)异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B)异氰酸酯反应性组分，所述异氰酸酯组分包含
b1)第一多元醇，所述第一多元醇选自基于植物油的多元醇或其衍生物和改性物，含量为5-50wt％，基于异氰酸酯反应性组分的重量为100wt.％计；
b2)第二多元醇，所述第二多元醇的羟值为300-700mgKOH/g，官能度为2-6；
b3)一种或多种三聚催化剂；
b4)内脱模剂，所述内脱模剂的含量为0.1-5wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
所述聚氨酯树脂组合物中内脱模剂用量较现有的用于本领域的聚氨酯树脂组合物少，但是仍然具有良好的脱模时间和性能。
可用于所述聚氨酯组合物组分A)的有机多异氰酸酯包括有机二异氰酸酯，其可以是已知用于制备聚氨酯的任何脂族、脂环族或芳族异氰酸酯。其实例包括但不限于：2，2’-、2，4-和4，4’-二苯基甲烷二异氰酸酯；单体型二苯基甲烷二异氰酸酯和具有更多环的二苯基甲烷二异氰酸酯同系物的混合物(聚合MDI)；异佛尔酮二异氰酸酯(IPDI)或其低聚物；甲苯二异氰酸酯(TDI)，例如甲苯二异氰酸酯异构体如甲苯-2，4-或2，6-二异氰酸酯，或者其混合物；四亚甲基二异氰酸酯或其低聚物；六亚甲基二异氰酸酯(HDI)或其低聚物；萘二异氰酸酯(NDI)或其混合物。
在本发明实施例中，有机多异氰酸酯包括基于二苯基甲烷二异氰酸酯的异氰酸酯，尤其是包含聚合MDI的那些。有机多异氰酸酯的官能度优选为1.9-3.5，特别优选2.0-2.8。有机多异氰酸酯粘度优选为5-600mPas，特别优选10-300mPas，在25℃下根据DIN53019-1-3测定。所述异氰酸酯组分的含量可以为40-80wt.％。基于所述聚氨酯组合物的总重量按100wt.％计。
有机多异氰酸酯还可以以多异氰酸酯预聚物形式使用。这些多异氰酸酯预聚物可以通过使过量的上述有机多异氰酸酯与具有至少两个异氰酸酯反应性的基团的化合物在例如30-100℃，优选约80℃的温度下反应获得。本发明多异氰酸酯预聚物的NCO含量优选为20-33wt.％，特别优选25-32wt.％。本领域技术人员熟知具有至少两个异氰酸酯反应性基团的化合物，例如在《塑料手册》第3.1章中的说明(“Kunststoffhandbuch，7，Polyurethanes”，Carl Hanser-Verlag，第3版，1993)
可用于本发明的第一多元醇组分b1)选自基于植物油的多元醇或其衍生物和改性物。当用于本发明时，基于植物油的多元醇包括植物油、植物油多元醇或其改性产物和衍生物。植物油是由不饱和脂肪酸和甘油制备的化合物或者是从植物的果实、种子、胚芽中提取油脂，优选但不限于大豆油和蓖麻油。所述植物油多元醇，是由一种或几种植物油起始的多元醇。合成植物油多元醇的起始剂包括但不限于大豆油和蓖麻油。植物油多元醇的起始剂可通过裂解、氧化或酯交换等工艺引入羟基，再通过本领域技术人员熟知的制备有机多元醇的工艺制备相应的植物油多元醇。可用于本发明的基于植物油的多元醇或其衍生物和改性物官能度为1.9-6，优选2-4，羟值为30-350mgKOH/g，优选50-200mgKOH/g。在本发明一些优选的是实例中，所述第一多元醇组分b1)选自蓖麻油、大豆油或其组合。
可用于本发明的第二多元醇的羟值为300-700mgKOH/g，官能度为2-6。在本发明一个优选的实施例中，所述第二多元醇选自聚醚多元醇，所述聚醚多元醇可以通过本领域常用的方法制备。
可用于本发明的三聚催化剂具有本领域技术人员所公知的含义，即是指能够将异氰酸酯转换成三聚结构的催化剂。在本发明一个优选的实施例中，所述三聚催化剂选自胺类或金属盐类三聚催化剂。可用于本发明的三聚催化剂的实例包括但不限于醋酸钾或异辛酸钾。
在本发明一个实施例中，所述聚氨酯组合物的异氰酸酯指数为130-300，适用此类聚氨酯组合物可以获得更好的脱模性能。
当用于本发明时，异氰酸酯指数X如下所定义：
Figure BSA0000131454310000061
可用于本发明的内脱模剂可以是本领域中常用的那些，其实例包括但不限于：脂肪酸酯与聚异氰酸酯的反应产物、由脂肪酸和含氨基的聚硅氧烷形成的盐、由具有至少8个碳原子的饱和或不饱和(环状)脂肪族羧酸和叔胺形成的盐，尤其是通过以下物质的酯化或酰胺化而制得的内含脱模剂，例如羧酸酯和/或羧酰胺：由褐煤酸和至少一种具有至少10个碳原子的脂肪族羧酸与分子量为60-400g/mol的至少双官能的烷醇胺、多元醇和/或多胺形成的混合物，例如EP 153 639中所公开；由有机胺、硬脂酸和有机一元羧酸和/或二元羧酸或它们的酸酐的金属盐形成的混合物，如DE-A-3 607447中所公开；或由一种亚胺化合物、羧酸的金属盐以及如果合适一种羧酸形成的混合物，如US 4 764 537中所公开的。在发明中，内脱模剂的用量为0.1-5wt.％，优选为0.1-3wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
上述聚氨酯组合物还可以包含本领域中常用的助剂，包括但不限于：触变剂、填料、抗氧化剂、染料、颜料、荧光增白剂、及针对热、光和/或UV辐射的稳定剂、增塑剂和表面活性剂。
本发明的聚氨酯层压模塑组合物还可包括设置在增强纤维层或芯层上的装饰层，所述装饰层可以通过在合模之前先适用于半成品部件上，然后通过合模层压从而在模塑组合物表面形成一层或多层装饰层，所述装饰层也可以在脱模之后通过粘合等方式设置在模塑组合物上。
本发明提供的聚氨酯层压模塑制品可以为汽车备胎盖板、行李架板、天窗板、汽车地板以及其他汽车内饰件。
II.聚氨酯层压模塑组合物的制备方法
本发明另一方面还提供了一种聚氨酯层压模塑组合物的制备方法，所述制备方法包括步骤：
i)提供一个待层压部件，所述待层压部件包含芯层以及设置在所述芯层至少一侧的一层或多层增强纤维毡或增强纤维织物；
ii)在所述增强纤维毡或增强纤维织物层上施用上述聚氨酯树脂组合物；
iii)将步骤ii)所得的部件置于模具中，层压该部件以获得一种三维形状，并使所述聚氨酯树脂组合物固化；和
iv)脱模，以获得所述聚氨酯层压模塑制品，
本发明提供的方法可以降低外脱模剂的使用频率，提高了生产效率，即提供了更好的脱模效果。
实施例
本发明文中提及的原料及设备说明如下：
NJ303：聚醚多元醇，羟值为475mgKOH/g，从句容宁武新材料公司购得；
DC380：聚醚多元醇，羟值为380mgKOH/g，从东昌公司购购得；
4050E：聚醚多元醇，羟值为630mgKOH/g，从科思创聚合物(中国)有限公司购得；
PU1748：改性胺类助剂，从科思创聚合物(中国)有限公司购得
DETDA：3，5-二乙基甲苯二胺，从雅保化学公司购得；
G71S：内脱模剂，从汉高公司购得；
B8870：硅油，从赢创公司购得；
Dabco K-15：三聚催化剂，从Air product公司购得；
Figure BSA0000131454310000081
EX-GP-77-263：颜料，从ISL-Chemie公司购得；
Desmodur 44V20：多异氰酸酯，从科思创聚合物(中国)有限公司
实施例1-3
将表1中各实施例中除异氰酸酯以外的组分混合，通过一个高压喷涂系统与异氰酸酯进行混合并喷涂在“夹层半成品”上。所谓的夹层半成品为蜂窝状纸板，两面覆盖以玻纤毡。所用玻纤毡克重为250g/m2，聚氨酯树脂组合物的喷涂量为250g/m2。喷涂结束后，机械手臂将喷涂后的物件送至压机中，在120℃的模温下进行固化成型，在涂有同样外脱模剂量的模具上测试其自脱模次数，脱模后即可获得聚氨酯层压模塑制品，脱模时间均为90秒。
为了准确地衡量脱模效果，每次都在模具上喷涂相同克数的外脱模剂，脱模时选用拉拔器进行脱模，如果拉拔器上显示的拉拔力超过100牛，则定义为脱模失败。
表1：聚氨酯组合物配方及其脱模性
Figure BSA0000131454310000091
本发明所用的测量脱模次数的方法为实验室方法，与工业界所用方法不同，通常而言采用实验室方法测得的脱模次数为5次的话，相应地，在实际工业应用中可以脱模约15次。实验方法脱模次数为6次对应于实际工业生产中的约20次。
通过比较实施例1和2，实施例2在配方中加入了蓖麻油，在减少内脱模剂用量的条件下，可以达到相同的脱模次数。通过实施例2与3的比较，实施例3使用了三聚催化剂，进一步提高了脱模次数，提高了生产率。

Claims (10)

1.一种聚氨酯层压模塑制品，所述聚氨酯层压模塑制品包含芯层以及设置在所述芯层至少一侧的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施用于一层或多层增强纤维毡或增强纤维织物上并将所述聚氨酯树脂组合物固化后形成，其中所述聚氨酯树脂组合物包含：
A)异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B)异氰酸酯反应性组分，所述异氰酸酯反应性组分包含：
b1)第一多元醇，所述第一多元醇选自基于蓖麻油的多元醇或其衍生物和改性物，含量为5-50wt.％，基于异氰酸酯反应性组分的重量为100wt.％计；
b2)第二多元醇，所述第二多元醇的羟值为300-700mgKOH/g，官能度为2-6；
b3)一种或多种三聚催化剂；
b4)内脱模剂，所述内脱模剂的含量为0.1-5wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
2.根据权利要求1所述的聚氨酯层压模塑制品，其中所述聚氨酯树脂组合物的异氰酸酯指数为130-300。
3.根据权利要求1所述的聚氨酯层压模塑制品，其中所述三聚催化剂选自胺类或金属盐类三聚催化剂。
4.根据权利要求1所述的聚氨酯层压模塑制品，其中所述芯层选自：可热成型聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
5.根据权利要求1所述的聚氨酯层压模塑制品，其中所述增强纤维毡或增强纤维织物通过玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
6.一种聚氨酯层压模塑制品的制备方法，所述制备方法包括步骤：
i)提供一个待层压部件，所述待层压部件包含芯层以及设置在所述芯层至少一侧的一层或多层增强纤维毡或增强纤维织物；
ii)在所述增强纤维毡或增强纤维织物层上施用聚氨酯树脂组合物；
iii)将步骤ii)所得的部件置于模具中，层压该部件以获得一种三维形状，并使所述聚氨酯树脂组合物固化；和
iv)脱模，以获得所述聚氨酯层压模塑制品，
其中所述聚氨酯树脂组合物包含：
A)异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B)异氰酸酯反应性组分，所述异氰酸酯反应性组分包含：
b1)第一多元醇，所述第一多元醇选自基于蓖麻油的多元醇或其衍生物和改性物，含量为5-50wt.％，基于异氰酸酯反应性组分的重量为100wt.％计；
b2)第二多元醇，所述第二多元醇的羟值为300-700mgKOH/g，官能度为2-6；
b3)一种或多种三聚催化剂；
b4)内脱模剂，所述内脱模剂的含量为0.1-5wt.％，基于所述异氰酸酯反应性组分的重量按100wt.％计。
7.根据权利要求6所述的聚氨酯层压模塑制品的制备方法，其中所述聚氨酯树脂组合物的异氰酸酯指数为130-300。
8.根据权利要求6所述的聚氨酯层压模塑制品的制备方法，其中所述三聚催化剂选自胺类或金属盐类三聚催化剂。
9.根据权利要求6所述的聚氨酯层压模塑制品的制备方法，其中所述芯层选自：可热成型聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
10.根据权利要求6所述的聚氨酯层压模塑制品的制备方法，其中所述增强纤维毡或增强纤维织物通过玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
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