CN109414902A - 聚氨酯层压模制品及其制备方法 - Google Patents

聚氨酯层压模制品及其制备方法 Download PDF

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Publication number
CN109414902A
CN109414902A CN201780037601.1A CN201780037601A CN109414902A CN 109414902 A CN109414902 A CN 109414902A CN 201780037601 A CN201780037601 A CN 201780037601A CN 109414902 A CN109414902 A CN 109414902A
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CN
China
Prior art keywords
layer
polyurethane
moulded product
polyalcohol
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201780037601.1A
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English (en)
Inventor
E.朱
J.李
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
A Polymer (china) Cosmos Co Ltd
Covestro Deutschland AG
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A Polymer (china) Cosmos Co Ltd
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Application filed by A Polymer (china) Cosmos Co Ltd filed Critical A Polymer (china) Cosmos Co Ltd
Publication of CN109414902A publication Critical patent/CN109414902A/zh
Pending legal-status Critical Current

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Abstract

本发明涉及聚氨酯层压模制品，所述聚氨酯层压模制品包括芯层和置于所述芯层的至少一面上的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施加到一层或多层增强纤维毡或增强纤维织物上和使所述聚氨酯树脂固化来形成。通过本发明提供的聚氨酯层压模制品具有良好的脱模性能并实现高生产率。

Description

聚氨酯层压模制品及其制备方法
技术领域
本发明涉及聚氨酯层压模制品，所述聚氨酯层压模制品包括芯层和置于所述芯层的至少一面上的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施加到一层或多层增强纤维毡或增强纤维织物上和使所述聚氨酯树脂固化来形成。本发明还涉及制备所述聚氨酯层压模制品的方法。
背景
聚氨酯层压模制品是本领域技术人员已公知的。所述聚氨酯层压模制品可以通过将增强纤维毡或增强纤维织物置于芯层（例如纸蜂窝、铝蜂窝、泡沫芯材等）的一面或两面上、将聚氨酯反应混合物施加到该增强纤维毡或增强纤维织物上、然后将用聚氨酯反应混合物覆盖的部件放置到模具中、所述部件在特定温度下层压以使该聚氨酯反应混合物固化并形成三维结构、并脱模来获得。
工业领域已在寻找一种能够有效提高生产率并由此降低成本的方法。现有的聚氨酯层压产品需要约每10次脱模喷涂外部脱模剂。此外，由于差的脱模效果，产品会容易粘附在模具上，以致模具表面必须每几小时进行清洁。所有这些操作会暂停正常生产，由此降低生产率和增加成本。因此，本领域一直希望提供具有良好脱模性能的聚氨酯层压模制品。
简述
本发明提供聚氨酯层压模制品，所述聚氨酯层压模制品包括芯层和置于所述芯层的至少一面上的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施加到一层或多层增强纤维毡或增强纤维织物上和使所述聚氨酯树脂固化来形成，其中所述聚氨酯树脂组合物包含：
A) 包含一种或多种多异氰酸酯的异氰酸酯组分；和
B) 异氰酸酯反应性组分，其包含
b1) 第一多元醇，其选自基于植物油的多元醇或其衍生物和改性产物，其含量为5-50重量%，基于所述异氰酸酯反应性组分重量作为100重量%计，
b2) OH值为300-700 mgKOH/g且官能度为2-6的第二多元醇；
b3) 一种或多种三聚催化剂；和
b4) 内部脱模剂，其含量为0.1-5重量%，基于所述异氰酸酯反应性组分重量作为100重量%计。
在本发明的一个实施方案中，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产物。
在本发明的另一个实施方案中，所述聚氨酯树脂组合物的异氰酸酯指数是130-300。
在本发明的又一个实施方案中，所述三聚催化剂选自胺或金属盐三聚催化剂。
在本发明的另一个实施方案中，所述芯层选自：可热成型的聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
在本发明的另一个实施方案中，所述增强纤维网或增强纤维织物由玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
本发明还提供了制备聚氨酯层压模制品的方法，其包括：
i) 提供要层压的部件，其包括芯层和置于所述芯层的至少一面上的一层或多层增强纤维毡或增强纤维织物；
ii) 将聚氨酯树脂组合物施加到所述（一个或多个）增强纤维毡层或（一个或多个）增强纤维织物层上，
iii) 将获自步骤ii)的部件放置到模具中、层压所述部件以获得三维形状，并且使所述聚氨酯树脂组合物固化；并
iv) 脱模以获得所述聚氨酯层压模制品，
其中所述聚氨酯树脂组合物包含：
A) 包含一种或多种多异氰酸酯的异氰酸酯组分；和
B) 异氰酸酯反应性组分，其包含：
b1) 第一多元醇，其选自基于植物油的多元醇或其衍生物和改性产物，其含量为5-50重量%，基于所述异氰酸酯反应性组分重量作为100重量%计，
b2) OH值为300-700 mgKOH/g且官能度为2-6的第二多元醇；
b3) 一种或多种三聚催化剂；和
b4) 内部脱模剂，其含量为0.1-5重量%，基于所述异氰酸酯反应性组分重量作为100重量%计。
在本发明的一个实施方案中，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产物。
在本发明的另一个实施方案中，所述聚氨酯树脂组合物的异氰酸酯指数是130-300。
在本发明的又一个实施方案中，所述三聚催化剂选自胺或金属盐三聚催化剂。
在本发明的又一个实施方案中，所述芯层选自：可热成型的聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
在本发明的又一个实施方案中，所述增强纤维网或增强纤维织物由玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
详述
I. 聚氨酯层压模制品
一方面，本发明涉及聚氨酯层压模制品，所述聚氨酯层压模制品包含芯层和置于所述芯层的至少一面上的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施加到一层或多层增强纤维毡或增强纤维织物上和使所述聚氨酯树脂固化来形成。
本发明的聚氨酯层压模制品不仅具有良好的机械性能，而且具有优异的脱模性能和良好的可操作性。
当在本发明中使用时，术语“聚氨酯层压模制品”具有本领域技术人员公知的定义。例如，CN1321816C和CN101641384都详细描述了这一结构。
本发明提供的聚氨酯层压模制品的芯层可以是本领域常见的芯层，其包括但不限于可热成型的聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。在本发明的一个优选实施方案中，所述芯层选自纸蜂窝。
在所述芯层的一面或两面上，安置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由玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。在本发明的一个优选实施方案中，所述增强纤维毡或增强纤维织物由玻璃纤维制备。
在获得上述部件后，可以将聚氨酯组合物施加到所述增强纤维毡或增强纤维织物上，并且该聚氨酯组合物会渗透所述增强纤维毡或织物的网状结构，然后在特定温度和模具压力下在模具中固化，以形成聚氨酯-增强纤维复合结构，即聚氨酯层压模制品。
可用于本发明的聚氨酯树脂组合物包含：
A) 包含一种或多种多异氰酸酯的异氰酸酯组分；和
B) 异氰酸酯反应性组分，其包含
b1) 第一多元醇，其选自基于植物油的多元醇或其衍生物和改性产物，其含量为5-50重量%，基于所述异氰酸酯反应性组分重量作为100重量%计，
b2) OH值为300-700 mgKOH/g且官能度为2-6的第二多元醇；
b3) 一种或多种三聚催化剂；和
b4) 内部脱模剂，其含量为0.1-5重量%，基于所述异氰酸酯反应性组分重量作为100重量%计。
所述聚氨酯树脂组合物中的内部脱模剂的量小于本领域中目前用于聚氨酯树脂组合物的量，但该组合物仍具有良好的脱模时间和性能。
可用于所述聚氨酯组合物的组分A)的有机多异氰酸酯包括有机二异氰酸酯，其可以是已知可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（聚合MDI）的混合物；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，例如甲苯-2,4-或2,6-二异氰酸酯，或其混合物；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。
在本发明的实施方案中，有机多异氰酸酯包含基于二苯基甲烷二异氰酸酯的异氰酸酯，特别是含有聚合MDI的那些。所述有机多异氰酸酯优选具有1.9至3.5，特别优选2.0至2.8的官能度。所述有机多异氰酸酯的粘度优选为5至600mPas，特别优选10至300mPas，根据DIN 53019-1-3在25℃下测量。所述异氰酸酯组分的含量可以为40-80重量％，基于该聚氨酯组合物总重量作为100重量%计。
所述有机多异氰酸酯也可以以多异氰酸酯预聚物的形式使用。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基团的化合物在例如30至100℃，优选约80℃下反应来获得。本发明的多异氰酸酯预聚物的NCO含量优选为20-33重量％，特别优选25-32重量％。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“Plastic Handbook”, 第3.1章 (“Kunststoff-handbuch, 7,Polyurethanes”, Carl Hanser-Verlag, 第3版, 1993所述的那些）。
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产物。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，或从植物的果实、种子或胚芽中提取的油，其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多种植物油起始的多元醇。用于合成植物油多元醇的原料包括但不限于大豆油和蓖麻油。植物油多元醇的原料可以通过诸如裂解、氧化或酯交换之类的方法引入羟基，然后通过本领域技术人员公知的制备有机多元醇的方法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产物具有1.9至6，优选2至4的官能度和30至350 mgKOH/g，优选50至200 mgKOH/g的OH值。在本发明的一些优选实施方案中，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OH值为300至700 mgKOH/g，官能度为2至6。在本发明的一个优选实施方案中，所述第二多元醇选自可根据本领域常用方法制备的聚醚多元醇。
可用于本发明的三聚催化剂具有本领域技术人员公知的含义，即它是指可将异氰酸酯转化为三聚结构的催化剂。在本发明的一个优选实施方案中，所述三聚催化剂选自胺或金属盐三聚催化剂。可用于本发明的三聚催化剂的实例包括但不限于乙酸钾或异辛酸钾。
在本发明的一个实施方案中，所述聚氨酯组合物的异氰酸酯指数是130至300。通过使用这一类型的聚氨酯组合物，可以实现更好的脱模性能。
当在本发明中使用时，异氰酸酯指数X定义如下：
。
可用于本发明的内部脱模剂可以是本领域常用的那些。其实例包括但不限于脂肪酸酯和多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个碳原子的饱和和/或不饱和脂(环)族羧酸和叔胺形成的盐，特别是通过下列物质的酯化或酰胺化而制备的内部脱模剂，例如羧酸酯和/或羧酰胺：如EP153639中公开的由褐煤酸和至少一种具有至少10个碳原子的脂族羧酸与分子量为60至400g/mol的至少双官能的烷醇酰胺、多元醇和/或多胺形成的混合物；如DE-A-3 607447中公开的由有机胺、硬脂酸、和有机一元羧酸和/或二元羧酸的金属盐或它们的酸酐形成的混合物；或如US4764537中所公开的由亚胺化合物、羧酸金属盐和（如果合适的话）羧酸形成的混合物。在本发明中，内部脱模剂的用量为0.1-5重量％，优选0.1-3重量％，基于所述异氰酸酯反应性基团重量作为100重量％计。
上述聚氨酯组合物可进一步包含本领域的常用助剂，其包括但不限于触变剂、填料、抗氧化剂、染料、颜料、荧光增白剂和对于热、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制组合物还可包含置于所述增强纤维层或芯层上的装饰层。所述装饰层可以通过在模具闭合前用于半成品部件中并然后通过闭模层压来形成，从而在模制组合物的表面上形成一个或多个装饰层。所述（一个或多个）装饰层也可以在脱模后通过粘附而置于模制组合物上。
本发明提供的聚氨酯层压模制品可以是汽车备胎盖、行李架板、天窗板、汽车地板和其它汽车内饰件。
II. 制备聚氨酯层压模制组合物的方法
另一方面，本发明还提供了制备聚氨酯层压模制组合物的方法，其包括：
i) 提供要层压的部件，其包括芯层和置于所述芯层的至少一面上的一层或多层增强纤维毡或增强纤维织物；
ii) 将聚氨酯树脂组合物施加到所述（一个或多个）增强纤维毡层或（一个或多个）增强纤维织物层上，
iii) 将获自步骤ii)的部件放置到模具中、层压所述部件以获得三维形状，并且使所述聚氨酯树脂组合物固化；并
iv) 脱模以获得所述聚氨酯层压模制品。
本发明提供的方法可以降低使用外部脱模剂的频率，因此提高生产率，即提供更好的脱模效果。
实施例
本发明文中提到的原料和设备描述如下：
NJ303：OH值为475 mgKOH/g的聚醚多元醇，购自Jurong Ningwu New MaterialCompany；
DC380：OH值为380 mgKOH/g的聚醚多元醇，购自Dongchang Company；
4050E：OH值为630 mgKOH/g的聚醚多元醇，购自Covestro Polymers (China) Co.,Ltd；
PU1748：改性胺助剂，购自Covestro Polymers (China) Co., Ltd；
DETDA：3,5-二乙基甲苯二胺，购自Albemarle Corporation；
G71S：内部脱模剂，购自Henkel AG；
B8870：硅油，购自Evonik；
Dabco K-15：三聚催化剂，购自Air Product Corporation；
PERMAUQRE® EX-GP-77-263：颜料，购自ISL-Chemie Corporation；
Desmodur 44V20：多异氰酸酯，购自Covestro Polymers (China) Co., Ltd。
实施例 1-3
将表1中包含的实施例中除了异氰酸酯之外的组分混合，以通过高压喷射系统与异氰酸酯混合，并喷涂到“夹层半成品”上。所谓的夹层半成品是蜂窝状纸板，其在两面上覆盖着玻璃纤维毡。所用玻璃纤维毡的克重为250 g/m2。所述聚氨酯树脂组合物的喷涂量为250g/m2。在完成喷涂之后，机械臂将经喷涂的产品输送到压机中，以在120℃的模具温度下固化和模制。在涂有相同量外部脱模剂的模具上测试产品的自脱模次数。脱模后得到聚氨酯层压模制品。对于所有，脱模时间为90秒。
为了准确地测量脱模效果，在每种情况下用相同克的外部脱模剂喷涂模具。使用拉拔器进行脱模，并且如果拉拔器中显示的拉力超过100 N，则脱模被定义为失败。
表1：聚氨酯组合物配方及其脱模性能
实施例 1 (对比) 2 3
NJ303 61.5 42.5 40
DC380 8 9.5 9.5
4050E 4 4 6
甘油 6 9 9
DETDA 2 1.5 1.5
PU1748 10 10.2 10.2
G71S 4 2 2
蓖麻油 0 19 17
B8870 0.4 0.2 0.2
Dabco K-15 0 0 0.25
水 0.3 0.3 0.3
PERMAUQRE® EX-GP-77-263 3.8 1.8 4.05
总计 100 100 100
Desmodur 44V20 130 126 155
异氰酸酯指数 110 110 140
脱模次数 5 5 6
本发明中用于测量脱模次数的方法是实验室方法，其不同于工业中使用的方法。通常，如果通过实验室方法测量的脱模次数为5，相应地，在实际工业应用中脱模次数可为约15；如果通过实验室方法测量的脱模次数为6，在实际工业应用中脱模次数可为约20。
通过比较实施例1和实施例2，将蓖麻油加入到实施例2的配方中，因此在减少内部脱模剂量的条件下，实施例2可以达到相同的脱模次数。通过比较实施例2和实施例3，实施例3使用了三聚催化剂，因此脱模次数进一步提高且生产率提高。

Claims (12)

1.聚氨酯层压模制品，所述聚氨酯层压模制品包括芯层和置于所述芯层的至少一面上的增强纤维层，所述增强纤维层通过将聚氨酯树脂组合物施加到一层或多层增强纤维毡或增强纤维织物上和使所述聚氨酯树脂固化来形成，其中所述聚氨酯树脂组合物包含：
A) 包含一种或多种多异氰酸酯的异氰酸酯组分；和
B) 异氰酸酯反应性组分，其包含
b1) 第一多元醇，其选自基于植物油的多元醇或其衍生物和改性产物，其含量为5-50重量%，基于所述异氰酸酯反应性组分重量作为100重量%计，
b2) OH值为300-700 mgKOH/g且官能度为2-6的第二多元醇；
b3) 一种或多种三聚催化剂；和
b4) 内部脱模剂，其含量为0.1-5重量%，基于所述异氰酸酯反应性组分重量作为100重量%计。
2.根据权利要求1所述的聚氨酯层压模制品，其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产物。
3.根据权利要求1所述的聚氨酯层压模制品，其中所述聚氨酯树脂组合物的异氰酸酯指数是130-300。
4.根据权利要求1所述的聚氨酯层压模制品，其中所述三聚催化剂选自胺或金属盐三聚催化剂。
5.根据权利要求1所述的聚氨酯层压模制品，其中所述芯层选自：可热成型的聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
6.根据权利要求1所述的聚氨酯层压模制品，其中所述增强纤维网或增强纤维织物由玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
7.制备聚氨酯层压模制品的方法，其包括：
i) 提供要层压的部件，其包括芯层和置于所述芯层的至少一面上的一层或多层增强纤维毡或增强纤维织物；
ii) 将聚氨酯树脂组合物施加到所述（一个或多个）增强纤维毡层或（一个或多个）增强纤维织物层上，
iii) 将获自步骤ii)的部件放置到模具中、层压所述部件以获得三维形状，并且使所述聚氨酯树脂组合物固化；并
iv) 脱模以获得所述聚氨酯层压模制品，其中所述聚氨酯树脂组合物包含：
A) 包含一种或多种多异氰酸酯的异氰酸酯组分；和
B) 异氰酸酯反应性组分，其包含：
b1) 第一多元醇，其选自基于植物油的多元醇或其衍生物和改性产物，其含量为5-50重量%，基于所述异氰酸酯反应性组分重量作为100重量%计，
b2) OH值为300-700 mgKOH/g且官能度为2-6的第二多元醇；
b3) 一种或多种三聚催化剂；和
b4) 内部脱模剂，其含量为0.1-5重量%，基于所述异氰酸酯反应性组分重量作为100重量%计。
8.根据权利要求7所述的制备聚氨酯层压模制品的方法，其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产物。
9.根据权利要求7所述的制备聚氨酯层压模制品的方法，其中所述聚氨酯树脂组合物的异氰酸酯指数是130-300。
10.根据权利要求7所述的制备聚氨酯层压模制品的方法，其中所述三聚催化剂选自胺或金属盐三聚催化剂。
11.根据权利要求7所述的制备聚氨酯层压模制品的方法，其中所述芯层选自：可热成型的聚氨酯泡沫、纸蜂窝、金属蜂窝、塑料蜂窝或其组合。
12.根据权利要求7所述的制备聚氨酯层压模制品的方法，其中所述增强纤维网或增强纤维织物由玻璃纤维、天然纤维、碳纤维、芳族聚酰胺纤维或其组合制备。
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