CN105778038B - 聚氨酯拉挤成型制品 - Google Patents

聚氨酯拉挤成型制品 Download PDF

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CN105778038B
CN105778038B CN201410854460.0A CN201410854460A CN105778038B CN 105778038 B CN105778038 B CN 105778038B CN 201410854460 A CN201410854460 A CN 201410854460A CN 105778038 B CN105778038 B CN 105778038B
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coating
polyurethane
fibers
isocyanate
pultruded
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CN105778038A (zh
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张晨曦
陈湛
李志江
吴非
赵辉
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Covestro Deutschland AG
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Priority to CN201410854460.0A priority Critical patent/CN105778038B/zh
Priority to EP15819819.2A priority patent/EP3237481B1/en
Priority to TR2018/19319T priority patent/TR201819319T4/tr
Priority to DK15819819.2T priority patent/DK3237481T3/en
Priority to PCT/EP2015/080840 priority patent/WO2016102496A1/en
Priority to US15/539,415 priority patent/US10442905B2/en
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Abstract

本发明提供了一种聚氨酯拉挤成型制品，聚氨酯拉挤成型制品包含聚氨酯拉挤成型复合材料和施用在复合材料上的涂层，聚氨酯拉挤成型复合材料包含聚氨酯树脂基体和增强材料并且通过聚氨酯拉挤成型工艺制备，聚氨酯树脂基体通过包含如下组分的聚氨酯组合物制备：A)异氰酸酯组分，其包含一种或多种多异氰酸酯；B)异氰酸酯反应性组分，其包含：b1)第一聚醚多元醇，第一聚醚多元醇的官能度为2‑3，羟值为10‑120mgKOH/g；b2)第二聚醚多元醇，第二聚醚多元醇的官能度为3‑8，羟值为810‑1900mgKOH/g；b4)一种或多种异氰酸酯反应性阻燃剂。本发明提供的聚氨酯拉挤成型制品即具有良好的阻燃性，而且涂层与复合材料之间也具有良好的粘附力。

Description

聚氨酯拉挤成型制品
技术领域
本发明涉及一种聚氨酯拉挤成型制品，所述聚氨酯拉挤成型制品包括聚氨酯拉挤成型复合材料和施用在所述复合材料上的涂层，其不但具有良好的阻燃性能，并且涂层与聚氨酯拉挤成型复合材料也具有良好的粘附力。
背景技术
聚氨酯拉挤成型材料具有玻纤含量高、物理性能良好的特点，因此广泛应用于工业界。然而在在户外长期使用时，特别是在海岛或沙漠等极端气候条件下，仍需进行外涂涂料进行防护。
然而现有的涂料，特别是具有耐候性的氟碳涂料，对聚氨酯拉挤成型复合材料的粘附力较差，在户外长期使用时涂层会脱落，从而造成复合材料暴露和粉化。
因此本领域中一直期望提供一种具有良好涂装性能的聚氨酯拉挤成型复合材料。
发明概述
本发明提供了一种聚氨酯拉挤成型制品，所述聚氨酯拉挤成型制品包含聚氨酯拉挤成型复合材料和施用在所述复合材料上的涂层，所述聚氨酯拉挤成型复合材料包含聚氨酯树脂基体和增强材料并且通过聚氨酯拉挤成型工艺制备，所述聚氨酯树脂基体通过包含如下组分的聚氨酯组合物制备：
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)第一聚醚多元醇，所述第一聚醚多元醇的官能度为2-3，羟值为10-120mgKOH/g；
b2)第二聚醚多元醇，所述第二聚醚多元醇的官能度为3-8，羟值为810-1900mgKOH/g；
b4)一种或多种异氰酸酯反应性阻燃剂。
在本发明一些实施例中，所述异氰酸酯反应性阻燃剂包含卤素和/或磷，优选地，所述反应性阻燃剂选自下列的一种或多种：芳香族或脂肪族溴化醇、二醇或三醇、卤化的脂肪族聚醚二醇和三醇。
在本发明另一些实施例中，所述涂层通过氟烯烃-乙烯基醚(FEVE)涂料和/或聚偏氟乙烯(PVDF)涂料制备。
在本发明又一些实施例中，所述增强材料选自：玻璃纤维、碳纳米管、碳纤维、聚酯纤维、天然纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合，优选地，所述增强材料的含量为60-85wt.％，基于所述聚氨酯拉挤成型复合材料的总重量按100wt.％计。
在本发明还一些实施例中，所述异氰酸酯反应性组分B)还包含：
b3)第三聚醚多元醇，所述第三聚醚多元醇的官能度为3-8，羟值为150-800mgKOH/g。
在本发明还一些实施例中，所述涂层通过旋涂法、刀涂法、微凹版涂布法、直接凹版涂布法、胶印凹版法、反转凹版法、逆转辊涂布法、棒涂法、模具涂布法、喷涂法或浸涂法制备。
具体实施方式
本发明提供一种聚氨酯拉挤成型制品，所述聚氨酯拉挤成型制品包含聚氨酯拉挤成型复合材料和施用在所述聚氨酯复合材料上的涂层，其中涂层与聚氨酯拉挤成型复合材料具有良好的亲和力，因此本发明提供的聚氨酯拉挤成型制品具有良好的耐候性，并且由于聚氨酯拉挤成型复合材料的树脂基体中含有反应性阻燃剂，因此本发明提供的聚氨酯拉挤成型制品也具有良好的阻燃性。
本发明提供的聚氨酯拉挤成型制品可通过将涂料组合物施用在聚氨酯拉挤成型复合材料的表面而制备，其中所述涂料组合物可以是本领域中常用的涂料组合物，其包括但不限于：聚氨酯涂料、氟碳涂料、过氯乙烯涂料、氯化橡胶涂料、环氧树脂涂料，在本发明优选的实施例中，所述涂料组合物选自氟碳涂料，更优选地选自：氟烯烃-乙烯基醚(FEVE)涂料、聚偏氟乙烯(PVDF)涂料。所述涂料组合物可以采用本领域中常用的方式施用于聚氨酯拉挤成型复合材料上，例如旋涂法、刀涂法、微凹版涂布法、直接凹版涂布法、胶印凹版法、反转凹版法、逆转辊涂布法、棒涂法、模具涂布法、喷涂法或浸涂法。
在本发明一些实施例中，先在聚氨酯拉挤成型复合材料上施用一层或多层底漆后，再施用上述涂料组合物。在本发明一些实施例中，可以根据实际需要，在聚氨酯拉挤成型复合材料上形成一层或多层涂层。
可用于本发明的聚氨酯拉挤成型复合材料包含聚氨酯树脂基体和增强材料并且通过聚氨酯拉挤成型工艺制备。美国专利US 3960629和US 4935279公开了聚氨酯拉挤成型工艺，将这两篇专利的全部内容以引用的方式合并入本文。在聚氨酯拉挤成型工艺中，通常将玻璃纤维从纱架上引出，穿过导纱板，进入注胶盒，穿过模腔。将穿过模腔的玻璃纤维纱用牵引装置牵引拉顺；开启模具加温系统及模口冷却系统。启动注胶机，将树脂泵送至注胶盒，使纤维纱充分浸透。被注胶盒树脂浸透的纤维纱经牵引装置连续地拉过模具，经过加热的模具时，树脂纤维逐步固化后被继续地拉出模具，经切割获得的聚氨酯拉挤成型复合材料。
可用于本发明的增强材料可以选自：玻璃纤维、碳纳米管、碳纤维、聚酯纤维、天然纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合。在本发明一些优选的实施例中，所述增强材料选自玻璃纤维，所述增强材料的含量为60-85wt.％，基于所述聚氨酯拉挤成型复合材料的总重量按100wt.％计。
聚氨酯树脂基体可以通过包含如下组分的聚氨酯组合物制备：
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)第一聚醚多元醇，所述第一聚醚多元醇的官能度为2-3，羟值为10-120mgKOH/g；
b2)第二聚醚多元醇，所述第二聚醚多元醇的官能度为3-8，羟值为810-1900mgKOH/g；
b4)一种或多种异氰酸酯反应性阻燃剂。
在本发明一些优选的实施例中，所述聚氨酯组合物是不混溶的体系。
可用作异氰酸酯组分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pMDI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DIN 53019-1-3测定。
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)。将该文献的全部内容以引用的方式合并入本文。
异氰酸酯反应性组分B)包含第一聚醚多元醇b1)和第二聚醚多元醇b2)，在本发明一个优选的实施例中，异氰酸酯反应性组分B)包含第一聚醚多元醇b1)、第二聚醚多元醇b2)和第三聚醚多元醇b3)。
聚醚多元醇可以通过已知的工艺过程制备，例如，在催化剂存在下，由烯烃氧化物与起始剂反应制得。所述的催化剂，优选但不限于碱性氢氧化物、碱性醇盐、五氯化锑、氟化硼合乙醚、或它们的混合物。所述的烯烃氧化物，优选但不限于四氢呋喃、环氧乙烷、环氧丙烷、1，2-环氧丁烷、2，3-环氧丁烷、氧化苯乙烯、或它们的混合物，特别优选环氧乙烷和/或环氧丙烷。所述的起始剂，优选但不限于多羟基化合物或多胺基化合物，所述多羟基化合物，优选但不限于水、乙二醇、1，2-丙二醇、1，3-丙二醇、二甘醇、三羟甲基丙烷、甘油、双酚A、双酚S或它们的混合物，所述多胺基化合物，优选但不限于乙二胺、丙二胺、丁二胺、己二胺、二亚乙基三胺、甲苯二胺或它们的混合物。
在本发明优选的实施例中，第一聚醚多元醇的官能度为2-3，羟值为10-120mgKOH/g，优选为20-80mgKOH/g，特别优选为25-35mgKOH/g。第一聚醚多元醇的含量为5-40wt％，优选为10-30wt％，特别优选为10-25wt％，以异氰酸酯反应性组分B)中所有聚醚多元醇的总重量为100wt％计。第二聚醚多元醇的官能度为3-8，羟值为810-1900mgKOH/g；优选官能度为3-5，羟值为900-1500mgKOH/g的聚醚多元醇；特别优选的官能度为3，羟值为1000-1300mgKOH/g的聚醚多元醇。第二聚醚多元醇的含量为5-40wt％，优选为8-30wt％，特别优选为10-25wt％，以异氰酸酯反应性组分B)中所有聚醚多元醇的总重量为100wt％计。
在本发明还优选的实施例中，异氰酸酯反应性组分B)还包含第三聚醚多元醇b3)，所述第三聚醚多元醇的官能度为3-8，羟值为150-800mgKOH/g优选官能度为3-6，羟值为200-750mgKOH/g的聚醚多元醇；特别优选的官能度为3，羟值为250-700mgKOH/g的聚醚多元醇。第三聚醚多元醇的含量为15-80wt％，优选为20-70wt％，特别优选为30-60wt％，以异氰酸酯反应性组分B)中所有聚醚多元醇的总重量为100wt％计。
异氰酸酯反应性组分B)还可以包含一种或多种异氰酸酯反应性阻燃剂B2)。当用于本发明时，术语“异氰酸酯反应性阻燃剂”是指含有异氰酸酯基反应性基团的阻燃剂，所述异氰酸酯基反应性基团例如羟基和氨基。这些阻燃剂可以与多异氰酸酯反应，因而结合到聚氨酯树脂基体中。
在本发明优选的实施例中，所述异氰酸酯反应性阻燃剂包含卤素和/或磷。可用于本发明的包含卤素的异氰酸酯反应性阻燃剂包括芳香族或脂肪族溴化醇、二醇或三醇，卤化的脂肪族聚醚二醇和三醇，所述芳香族或脂肪族溴化醇、二醇或三醇的实例包括但不限于四溴邻苯二甲酸酐二醇、二溴新戊二醇和三溴新戊醇(TBNPA)，卤化的脂肪族聚醚二醇和三醇的实例包括但不限于可从Solvay Fluor获得的IXOL M125和IXOL B251，四溴邻苯二甲酸酐二醇的实例包括但不限于从Albemarle and Great Lakes购得的Saytex RB 79和PHT-4。
可用于本发明的包含磷的异氰酸酯反应性阻燃剂包括二醇双(2-氯乙基)磷酸酯、三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、三(一缩二丙二醇)亚磷酸酯。
异氰酸酯反应性组分B)还可以包含添加型阻燃剂、交联剂、催化剂等组分。
添加型阻燃剂可以是有机阻燃剂也可以是无机阻燃剂，包括但不限于三(2-氯乙基)磷酸酯(TCEP)、磷酸三(2-氯丙基)酯(TCPP)、三氯丙基磷酸酯(TDCPP)、甲基膦酸二甲酯(DMMP)、磷酸三苯酯、正磷酸三聚氰胺(MPP)等或它们的混合；无机阻燃剂，包括但不限于水合氢氧化铝、水合氢氧化镁、磷酸一铵、磷酸二铵、氯化铵、硼酸、水合硼酸锌(FB)等或它们的混合。
交联剂通常选用分子量小于800的含活泼氢原子化合物，优选分子量为18-400的含活泼氢原子化合物。含活泼氢原子化合物，优选但不限于，烷基二醇、二亚烃基二元醇、聚烷基多元醇、它们的混合物，例如：乙二醇、1，4-丁二醇、1，6-己二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，10-癸二醇、二甘醇、二丙二醇、聚亚氧烷基乙二醇、它们的混合物。所述含活泼氢原子化合物，也可以包括其它接枝或不饱和的烷基二醇、它们的混合物，例如：1，2-丙二醇、2-甲基-1，3-丙二醇、2，2-二甲基-1，3-丙二醇、2-丁基-2-乙基-1，3-丙二醇、2-丁烯-1，4-二醇、2-丁炔-1，4-二醇、它们的混合物。交联剂用量通常为0-10wt％，以异氰酸酯反应性组分的总重量为100wt％计。
催化剂，优选但不限于，胺类催化剂、有机金属催化剂、它们的混合物。胺类催化剂，优选但不限于，三乙基胺、三丁基胺、三亚乙基二胺、N-乙基吗啉、N，N，N’，N’-四甲基-乙二胺、五甲基二亚乙基-三胺、N，N-甲基苯胺、N，N-二甲基苯胺、它们的混合物。有机金属催化剂，优选但不限于有机锡类化合物，例如：乙酸锡(II)、辛酸锡(II)、乙基己酸锡、月桂酸锡、二丁基氧化锡、二丁基二氯化锡、二丁基二乙酸锡、二丁基马来酸锡、二辛基二乙酸锡、它们的混合物。催化剂的用量为B组分的用量的0.001-10重量％。
在本发明下文中，结合实施例对本发明作进一步说明。本发明所公开的具体实施例和方法，其描述是示例性而非限制性的。
实施例
本发明文中提及的原料及设备说明如下：
聚醚多元醇A：以甘油为起始剂的聚醚多元醇，官能度为3，羟值为1050mg KOH/g；
聚醚多元醇B：以甘油为起始剂的聚醚多元醇，官能度为3，羟值为475mg KOH/g；
聚醚多元醇C：以甘油为起始剂的聚醚多元醇，官能度为3，羟值为235mg KOH/g；
聚醚多元醇C：以丙二醇为起始剂的聚醚多元醇，官能度为2，羟值为28mg KOH/g；
Ixol M125：阻燃剂，可购自苏威公司；
Formerz UL 29：有机锡类催化剂，可购自Momentive公司；
Baydur18BD101：内脱模剂，可购自拜耳材料科技有限公司；
多异氰酸酯1：NCO为30.5-32.5，官能度为2.8；
FEVE FT氟碳漆：购自Nippon Paint公司；
实施例1-8：聚氨酯拉挤成型复合材料的制备
将表1中除多异氰酸酯组分外的组分按比例混合，然后将混合物与多异氰酸酯组分分别加入聚氨酯低压双组分静态混合机储料罐中。
将276根玻璃纤维纱从纱架上引出，穿过三级导纱板，进入注胶盒，穿过模腔。将穿过模腔的玻璃纤维纱用牵引绳绑牢再开启履带牵引装置向前牵引至纱全部拉顺；开启模具加温系统加热模具同时开启模口冷却系统，模温从入口到出口控制为：20℃/60℃/190℃/170℃。启动注胶机，将上述组分按照表1所示的用量连续泵送至静态混合头，经混合头混合后将注胶盒注满同时使纤维纱被充分浸透。被注胶盒浸透的纤维纱被履带牵引装置连续地拉过模具，经加热的模具固化后成为平板被连续地拉出模具，再经切割获得100mm*50mm的试验样板进行涂装试验。
复合材料阻燃性基于标准GB8624-2006标准测试，测试结果列于表1中。
表1：用于制备复合材料的聚氨酯组合物
Figure BSA0000112632580000081
实施例9-16：聚氨酯拉挤成型制品的制备
将实施例1-8的样板清洁、干燥、无尘处理，将不需要施用底漆的样品喷涂FEVE涂料，涂料用200目滤网过滤，面漆湿膜厚度约90μm，然后置于烘箱中，将温度在30分钟内从40℃梯度升温至100℃，冷却后取出即可获得制品。将需要施用底漆的样板手工喷涂底漆，然后将样品置于烘箱中，将温度在30分钟内从40℃梯度升温至100℃，冷却后取出，再安装上述方式喷涂面漆，即可获得制品。
将获得的制品根据GBT9286-1998测试涂料粘附力，以百格法测试涂层与复合材料的粘附力，测试结果列于表2中，其中0-5的数值代表意义如表3所示。在该方法中，以百格刀在样板上形成10*10的100格的正方形，然后将透明力敏胶带粘附于正方形上，再以瞬间的力道将胶带撕起，记录脱落的面积并按照表3所示标准给予等级。
表2：聚氨酯拉挤成型制品及测试结果
Figure BSA0000112632580000091
表3：百格法测试结果意义
Figure BSA0000112632580000092
上述结果表明本发明的聚氨酯拉挤成型制品不但具有良好的阻燃性，同时表明涂层与复合材料之间也具有良好的粘附力。

Claims (5)

1.一种聚氨酯拉挤成型制品，所述聚氨酯拉挤成型制品包含聚氨酯拉挤成型复合材料和施用在所述复合材料上的涂层，所述聚氨酯拉挤成型复合材料包含聚氨酯树脂基体和增强材料并且通过聚氨酯拉挤成型工艺制备，所述聚氨酯树脂基体通过包含如下组分的聚氨酯组合物制备：
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)第一聚醚多元醇，所述第一聚醚多元醇的官能度为2-3，羟值为10-120mgKOH/g；
b2)第二聚醚多元醇，所述第二聚醚多元醇的官能度为3-8，羟值为810-1900mgKOH/g；
b3)第三聚醚多元醇，所述第三聚醚多元醇的官能度为3-8，羟值为150-800mgKOH/g；
b4)一种或多种异氰酸酯反应性阻燃剂；
其中，所述异氰酸酯反应性阻燃剂包含卤素和/或磷；
所述聚氨酯拉挤成型制品通过将涂料组合物施用在聚氨酯拉挤成型复合材料的表面而制备，所述涂料组合物选自氟碳涂料；
所述异氰酸酯反应性阻燃剂选自下列的一种或多种：芳香族或脂肪族溴化醇、二醇或三醇；
所述涂层通过FEVE涂料和/或聚偏氟乙烯(PVDF)涂料制备；
所述增强材料选自：玻璃纤维、碳纳米管、碳纤维、聚酯纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合。
2.根据权利要求1所述的聚氨酯拉挤成型制品，其中所述增强材料的含量为60-85wt.％，基于所述聚氨酯拉挤成型复合材料的总重量按100wt.％计。
3.根据权利要求1所述的聚氨酯拉挤成型制品，其中所述二醇或三醇选自卤化的脂肪族聚醚二醇和三醇。
4.根据权利要求1所述的聚氨酯拉挤成型制品，其中所述涂层通过旋涂法、刀涂法、微凹版涂布法、直接凹版涂布法、胶印凹版法、反转凹版法、逆转辊涂布法、棒涂法、模具涂布法、喷涂法或浸涂法制备。
5.根据权利要求1所述的聚氨酯拉挤成型制品，其中所述增强材料选自天然纤维。
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