CN103347920A - 具有低总燃烧热的聚氨酯粘合剂以及由该粘合剂组装的保温板 - Google Patents
具有低总燃烧热的聚氨酯粘合剂以及由该粘合剂组装的保温板 Download PDFInfo
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- CN103347920A CN103347920A CN2011800669284A CN201180066928A CN103347920A CN 103347920 A CN103347920 A CN 103347920A CN 2011800669284 A CN2011800669284 A CN 2011800669284A CN 201180066928 A CN201180066928 A CN 201180066928A CN 103347920 A CN103347920 A CN 103347920A
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
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Abstract
具有低总燃烧热的聚氨酯粘合剂用来组装保温板如矿棉保温板。该聚氨酯粘合剂含有多异氰酸酯边和多元醇边。该多元醇边包括特定的聚醚醚多元醇和芳族聚酯二醇。这些多元醇的混合物提供极好的粘合以及,合适的低粘度(即使在高填料水平的情况下也是如此),以及提供具有低总燃烧热的固化粘合剂。
Description
本申请要求于2010年12月26日提交的美国临时专利申请No.61/427193的优先权。
本申请涉及具有低总燃烧热的聚氨酯粘合剂,以及由该粘合剂组装的层压体,例如保温板。
保温板广泛用于提供住宅、建筑物、冷藏设备、船和其他建筑构造的热保温。一类保温板是陶瓷纤维保温板。这些保温板含有纤维状的陶瓷层,例如玻璃纤维、矿棉等,其粘结在面层的一边或两边。纤维状的陶瓷层通常通过含有矿物颗粒填料的聚氨酯粘合剂粘结到面层上。这样的聚氨酯粘合剂的实例描述在美国公开专利申请No.2005-0080218中。这些粘合剂通常是包含多异氰酸酯组分和多元醇组分的两组分粘合剂体系。商业上成功的配方已经有基于蓖麻油的。基于蓖麻油的粘合剂趋向于具有非常优良的粘合性能。
由于防火安全是一个重点关注,许多管辖区域已经颁布了关于保温板的防火性能的标准。一个这样的标准是Euroclass A2标准。这个标准对特定建筑材料和它们的组成元件设定了总燃烧热的极限。用于那些建筑材料的粘合剂层必须显示不大于4.0兆焦耳/m2的燃烧热(根据EN ISO1716测量)。
这个限制对能施加的粘合剂层的厚度设定了一个实际极限。基于蓖麻油的粘合剂趋向于具有比想要的稍高的燃烧热。如果粘合剂的燃烧热变得太高,只能施加非常薄层的粘合剂,而其可能不能提供必须的粘结。同时非常薄的层更难以施加和精准计量。因此,从制造和产品强度的观点来看,最好粘合剂层足够厚,以便能容易制造产品以及在纤维层和面层之间形成优良的粘结。为了达到这个目的,每单位重量粘合剂的燃烧热必须尽可能的低,同时在制造过程中保持足够的粘结强度和加工性能。
主要的加工限制是形成聚氨酯粘合剂的活性组分的粘度。多元醇组分的粘度是最关注的,特别是在它含有填料颗粒的情况下(这是通常的情况)。如果这些粘度变得太高,用于施加粘合剂的抽吸、混合以及分配装置不能容易地处理该组分。这导致不良的或不一致的混合和计量,其随后导致产品的不一致和高次品率。因此,对粘合剂体系的改变来减少它的总燃烧热不能导致粘度的大量增加。
一种减少粘度的方式是通过填料的粒径。较大填料颗粒趋向于减少粘合剂粘度。但是,这个方法受限于较大填料颗粒有较大倾向从粘合剂(或它的组分)中沉淀出来并阻塞混合和分配装置。
另一种减少粘度的方法是在粘合剂配方中包含稀释剂或溶剂。这个方法不是有利的,因为这些稀释剂或溶剂在制造条件下通常多少具有挥发性,因此可能导致气味或工人曝露的问题。
渴望的是一种具有低总燃烧热的聚氨酯粘合剂,其由低粘度组分制备,并且其在纤维状陶瓷层和面层之间形成强粘结。该聚氨酯粘合剂优选含有很少的或不含稀释剂或溶剂。
本发明是两组分聚氨酯粘合剂体系,包括
A)多异氰酸酯组分,其含有芳族多异氰酸酯,以及
B)多元醇组分,其含有B-1)20-75%重量的聚醚多元醇或聚醚多元醇混合物,基于组分B-1)和B-2)的总重量,其中该聚醚多元醇或聚醚多元醇混合物每分子平均具有2-4个羟基,并且在25℃具有至多500mPa·s的粘度,B-2)25-80%重量的芳族聚酯二醇,基于组分B-1)和B-2)的总重量,B-3)0.1-3%重量的水,B-4)0-15%重量的不同于B-1)、B-2)和B-3)的异氰酸酯反应性组分,进一步条件在于
i)组分A)、组分B)或两者含有至少一种用于异氰酸酯基团和羟基反应的催化剂;
ii)芳族聚酯二醇是芳族二羧酸、芳族二酰卤或芳族二羧酸酐与一缩二乙二醇和聚乙二醇的反应产物,具有约150-约250的羟基当量,并且在25℃具有不大于2000mPa·s的粘度;以及
iii)组分A)、组分B)或两者可以组分A)和B)总重量的至多65%的量含有颗粒矿物填料。
通过混合和固化这种两组分粘合剂组合物的组分而制造的固化粘合剂具有低总燃烧热。未填充(即不含颗粒矿物填料的)的粘合剂可具有不超过30兆焦耳(MJoules)每千克以及更典型地不超过28兆焦耳每千克的总燃烧热。对本发明来说,总燃烧热是根据EN ISO1716在弹式量热器中测量,或者等效的方法。根据本发明的填充粘合剂具有明显较低的总燃烧热。在填料水平高达约25-40%重量时,固化的粘合剂经常具有22兆焦耳每千克以下并且经常在18兆焦耳每千克以下或者甚至在17兆焦耳每千克以下的总燃烧热。在更高的填料水平下,可以达到更低的总燃烧热。当填料水平接近50-65%重量时,填料的总燃烧热可以是15兆焦耳每千克以下。
组分A)和B)每一种的布氏粘度在20℃时通常不大于40000mPa·s,甚至在不存在稀释剂或溶剂的情况下也是如此。典型地,填料引入多元醇组分B)中,结果是多元醇组分B)的粘度典型地大大高于多异氰酸酯组分A)的粘度。当多元醇组分含有40-55%重量的填料颗粒时,粘度典型地是20000mPa·s以下。当多元醇组分含有更大量的填料颗粒时,例如55-65%重量的填料,粘度趋向于为20000-35000mPa·s。
固化后的粘结性能与可商购的基于蓖麻油的粘合剂体系(在相当的填料水平下)非常相当,而后者具有明显较高的总燃烧热。本发明的粘合剂趋向于在纤维撕裂方式下失效,而不是通过内聚失效(即在粘合剂层内部破裂)或通过脱胶(即从面层分层)失效。
在另一方面,本发明是层压体,包括纤维状陶瓷层、面层和插入在纤维状陶瓷层和面层之间并在纤维状陶瓷层和面层之间形成粘结的粘合剂层,其中粘合剂层是固化的聚氨酯,通过混合本发明的两组分粘合剂体系的多异氰酸酯组分A)和多元醇组分B),将得到的混合物施加在纤维状陶瓷层和面层之间,和固化该混合物而制备。
由于固化粘合剂的低总燃烧热,在保持在诸如Euroclass A2标准的限制内的同时可以施加更厚层的粘合剂,其中Euroclass A2标准设定了每单位表面积燃烧热的上限。使用更厚粘合剂层的能力导致更容易的加工和保温板层之间更好的粘结。
粘合剂体系的多异氰酸酯组分A)包含至少一种芳族多异氰酸酯。芳族多异氰酸酯的实例包含甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯或其混合物、2,4’-甲烷二苯基二异氰酸酯、4,4’-甲烷二苯基二异氰酸酯、聚亚甲基聚苯基异氰酸酯等。前述的任意物质可用脲基甲酸酯(allophonate)、碳化二亚胺、脲酮亚胺、氨基甲酸酯、脲或缩二脲连接基改性。优选的多异氰酸酯是聚合MDI。“聚合MDI”是指MDI与含有至少三个苯基异氰酸酯基团的聚亚甲基聚苯基异氰酸酯的混合物。包含在多异氰酸酯组分A)中的芳族多异氰酸酯或其混合物合适地每分子含有2-3.5,更优选2.2-3.2个异氰酸酯基团,并且每个异氰酸酯基团的当量为125-250,优选125-140。芳族多异氰酸酯或其混合物优选在25℃具有不大于500mPa·s的粘度,并且更优选在25℃具有不大于200mPa·s的粘度。这些粘度,与本文提到的其他所有一样,是所述温度下的布氏粘度。
芳族多异氰酸酯可以是多异氰酸酯组分A)的唯一组分。可以存在于多异氰酸酯组分A)中的其他组分包括一种或多种催化剂、颗粒填料或其他任选的不与异氰酸酯基团反应的添加剂,如下面更全面的描述。
多元醇组分B)包括聚醚多元醇或聚醚多元醇混合物(B-1),其中聚醚多元醇或聚醚多元醇混合物每分子平均具有2-4个羟基,并且在25℃具有至多500mPa·s的粘度。聚醚多元醇或聚醚多元醇混合物优选含有一种或多种聚(氧化丙烯)聚合物或70-99.5%重量的氧化丙烯和0.5-30%重量的氧化乙烯的共聚物。这样的共聚物可以是无规或嵌段共聚物。如果是嵌段共聚物,优选氧化乙烯聚合在链的末端来引入伯羟基。聚醚多元醇或混合物优选具有约800-1500,更优选约800-1200的平均分子量。每分子优选平均含有2-3个,更优选2.5-3个羟基。
多元醇组分B)还包括芳族聚酯二醇(B-2)。这个聚酯二醇是芳族二羧酸、芳族二酰卤或芳族二羧酸酐与一缩二乙二醇和聚乙二醇的反应产物。该反应可以多步骤实施,并且可能涉及一种或多种环状中间体的形成。芳族二羧酸优选带有一缩二乙二醇和聚乙二醇的邻苯二甲酸(或它的酰卤或酸酐)或对苯二甲酸(或它的酰卤或酸酐)。这种多元醇的芳族含量优选约10-25%,更优选12-20%,以及仍然更优选14-18%。芳族含量是指由芳环(包含环上的氢原子)构成的芳族聚酯多元醇的重量比例。芳族聚酯二醇具有约150-约250、优选约160-240以及更优选160-220的羟基当量。它的粘度优选在25℃不大于1200mPa·s,更优选不大于1000mPa·s。
组分B-1和B-2以20:80-75:25的重量比率存在。组分B-1和B-2的优选比率是30:70-45:55。
颗粒矿物填料可以是,例如,任何各种类型的粘土、碳酸钙、氧化钙、滑石、二氧化钛、氧化铁、氢氧化镁、氢氧化铝、炭黑、石墨等,或陶瓷材料,比如玻璃、氮化硼、氮化硅、氮化铝、碳化硅、碳化硼、碳化铝等。
颗粒矿物填料的平均粒径(d(50%))优选在0.5-50微米、更优选在0.75-10微米以及仍然更优选在1-5微米的范围内。颗粒矿物填料优选占全部粘合剂的30-45%重量。增加颗粒矿物填料的量能提供减少粘合剂总燃烧热的优点,但是同时增加多元醇组分的粘度并且可能减少形成的粘结的强度。
在多元醇组分B)中存在的水(组分B-3)在与多异氰酸酯反应时产生气体并且在组合物固化时使该组合物轻微膨胀。这导致固化时的粘合剂更好地渗透进入纤维状陶瓷材料的纤维之间并且在之间形成强的粘结。优选的水量是0.15-1.0%重量以及更优选的量是0.2-0.8%重量。
除了已经描述的那些,多元醇组分B)可含有其他异氰酸酯反应性材料(组分B-4)。但是,如果存在这些材料,它们应该是少量,例如不大于组分B-1、B-2、B-3和B-4总重量的15%。如果存在,组分B-4可占组分B-1、B-2、B-3和B-4的总重量的至多6%或至多3%。多元醇组分B)优选不含组分B-4材料。
用于异氰酸酯基团与羟基(包括水)反应的催化剂存在于多异氰酸酯组分A)、多元醇组分B)或两者中。催化剂优选包括在多元醇组分B)中。合适的催化剂包括叔胺化合物和有机金属化合物,特别是羧酸锡和四价锡化合物。代表性的叔胺催化剂包括三甲胺、三乙胺、二甲基乙醇胺、N-甲基吗啉、N-乙基吗啉、N,N-二甲基苯胺、N,N-二甲基乙醇胺、Ν,Ν,Ν,Ν-四甲基-l,4-丁二胺、Ν,Ν-二甲基哌嗪、l,4-重氮双环-2,2,2-辛烷、双(二甲基氨基乙基)醚、双(2-二甲基氨基乙基)醚、吗啉、4,4'-(氧二-2,l-乙二基)双(4,4'-(oxydi-2,l-ethanediyl)bis)、三亚乙基二胺、五甲基二亚乙基三胺、二甲基环己基胺、N-鲸蜡基-二甲胺、N-椰油基-4-吗啉、Ν,Ν-二甲基氨甲基-N-甲基乙醇胺、N,N,N'-三甲基-N'-羟乙基双(氨乙基)醚、N,N-双(3-二甲基氨丙基)N-异丙醇胺、(N,N-二甲基)氨基-乙氧基乙醇、N,N,N,N'-四甲基己二胺、1,8-重氮双环-5,4,0-十一碳烯-7、N,N-二吗啉二乙基醚、N-甲基咪唑、二甲基氨丙基二丙醇胺、双(二甲基氨丙基)氨基-2-丙醇、四甲基氨基双(丙胺)、(二甲基(氨基乙氧基乙基))((二甲胺)乙基)醚、三(二甲基氨丙基)胺、二环己基甲胺、双(N,N-二甲基-3-氨丙基)胺、1,2-亚乙基哌啶(1,2-ethylenepiperidine)以及甲基羟乙基哌嗪。有用的锡催化剂的实例包括辛酸亚锡,二丁基锡双醋酸盐,二月桂酸二丁锡,二丁基锡二硫醇,二烃基锡二烷基硫酸,氧化二丁锡,二甲基锡二硫醇,二甲基锡二异辛基硫酸乙酯等。
粘合剂组合物的多异氰酸酯和/或多元醇组分可含有其他任选的组分,例如表面活性剂、润湿剂、着色剂、杀菌剂、防腐剂等。任何或所有的这些可略去。粘合剂组合物优选含有最小量(不超过5%重量,优选不超过2%重量、仍然更优选不超过0.5%重量)的具有小于1000分子量的非反应性有机化合物。“非反应性”是指该材料既不与羟基也不与异氰酸酯基团在固化反应的条件下起反应。
本发明的粘合剂组合物用于粘结基材,通过混合多元醇和异氰酸酯组分,在基材之间施加该混合物,然后固化该混合物。常规的用于混合、施加和固化两组分聚氨酯粘合剂的方法全部合适地用于本发明,并且不需要特殊装置或固化条件。粘合剂组合物将在室温下固化;但是,可以施加高温来加速固化。多元醇和异氰酸酯组分应该以使异氰酸酯指数为70-200,优选90-130以及更优选约100-125的比率混合。异氰酸酯指数等于多元醇组分中的羟基与异氰酸酯组分中的异氰酸酯基团的比例的100倍。
本发明的粘合剂组合物用于制造保温板。这些板是包括纤维状陶瓷层、面层以及插入在纤维状陶瓷层和面层之间并且在它们之间形成粘结的粘合剂层的层压体。在大多数情况下,板具有三明治结构,其中纤维状陶瓷层形成芯,位于两个面层之间,每个面层通过粘合剂层附在纤维状陶瓷层之上。根据本发明的固化的粘合剂组合物构成使面层附在纤维状陶瓷层之上的粘合剂层。
纤维状陶瓷层由无机材料的纤维来组成。纤维可以是无规、缠结、编织或形成层或垫。纤维可由,例如,玻璃、硼、碳、石棉、铝硅酸盐材料或其他无机材料制成。优选的纤维状陶瓷层是所谓的矿棉或岩棉(有时称作渣棉)的层。纤维可具有约0.5-50μm,更优选1-约25μm的直径。可存在粘结剂来保持纤维在一起形成整体。通过其含有的明显的空体积,陶瓷纤维层给保温板提供热保温特性,该空体积中通常充满空气但也可充满其他气体。优选的纤维状陶瓷层具有至少50%和至少90%的空体积。纤维状陶瓷层合适地具有2-约8磅每立方尺(32-148kg/m3)的密度。
纤维状陶瓷层的厚度典型地是约6-300mm,更典型地是20-约300mm以及仍然更典型地是100-200mm。
各式各样的结构、功能或装饰材料可用作保温板的面层。可以使用诸如钢,镀锌钢,铝等的金属。箔、纸、各种各样的聚合材料、木头和其他材料也是有用的。在保温板相对的两侧的面层可由不同的材料制成。
与具有更高总燃烧热的粘合剂相比,固化的粘合剂的低总燃烧热允许稍微更厚一些的粘合剂层施加在这些保温板中。通过使用本发明的粘合剂组合物,粘合剂层厚度通常可以增加10-20%。含有220-300、优选235-260克每平方米的根据本发明的固化的粘合剂的保温板通常会符合Euroclass A2对于非楼板结构材料的标准。
当然,如果能获得良好的粘结,可以使用更少量的粘合剂,而如果它的总燃烧热特别低,或者如果没必要符合Euroclass A2标准,可以使用更大量的粘合剂。
提供下述实施例来阐明本发明而不是想限制它的范围。除非另有说明,所有的份和百分比是重量。
实施例1和对比样品A-D
由含有32%的蓖麻油,7%的分子量为450的聚(氧化丙烯)三醇,5%的分子量为400的聚(氧化丙烯)二醇,1%的二缩三丙二醇,1.2%的叔胺催化剂溶液(Dabco KTM60,来自Air Products and Chemicals),53.55份的具有2.7μm平均粒径(d50%)的碳酸钙(Millicarb OG,来自Omya UK,Ltd.)和0.25%的水的多元醇组分制备对比样品A。该配制的多元醇组分具有133的羟基数和在20℃具有3480mPa·s的粘度。多异氰酸酯组分是聚合MDI材料,具有31.1%的异氰酸酯含量、2.7的异氰酸酯官能度和190mPa·s的粘度。
以100:35(异氰酸酯指数110)的重量比率混合多元醇的各个部分和异氰酸酯组分并固化。固化的粘合剂样品的总燃烧热根据EN ISO1716在弹式量热器中评估;发现填充粘合剂的总燃烧热约为18.9兆焦耳/千克。与此相关联的未填充的粘合剂的总燃烧热约为31.1兆焦耳/千克。
以类似的方式制造和测试实施例1和对比样品B、C和D。这些每个的配方列在下述表1中。表1还报道了每种情况下多元醇组分的粘度,和固化的粘合剂的总燃烧热,和未填充的固化的粘合剂的总燃烧热。
表1
12.7官能度、160当量的芳族聚酯多元醇。这种多元醇在25℃具有16000mPa·s的粘度。22.0官能度、180当量的芳族聚酯。这种多元醇是对苯二甲酸、一缩二乙二醇和聚乙二醇的反应产物,在25℃具有600mPa·s的粘度。3Stepan公司销售的双官能邻苯二甲酸酐/一缩二乙二醇聚酯PS-3152,具有178的当量,在25℃具有2700mPa·s的粘度。4Dabco KTM60催化剂,来自Air Products and Chemicals。5Millcarb OG碳酸钙颗粒,来自Omya UK,Ltd.6固化的粘合剂的最大涂层重量将产生4.0兆焦耳/m2(Euroclass A2标准)的总燃烧热。7最大涂层重量的厚度增加将产生4.0兆焦耳/m2的总燃烧热,与对比样品A相比。
从表1的数据可以看出,用聚醚多元醇和聚酯多元醇取代蓖麻油导致粘合剂非常明显的总燃烧热的降低。此外,配方中的多元醇组分的粘度非常实质地依赖于多元醇组成的选择。聚酯多元醇的选择对多元醇组分的粘度具有特别大的影响。对比样品C和D的多元醇组分的粘度太高以致于不能容易地加工。基于低粘度和低总燃烧热的结合,对比样品B和实施例1,和对比样品A一起,接受粘性试验。
粘性试验如下实施:
将多元醇和异氰酸酯组分预热到约40℃并且以使异氰酸酯指数为110的比率混合。将得到的混合物以珠状施加到0.7mm厚的金属板(面层)上并且使用凹口铲涂布,得到250g/m2的涂层重量。在粘合剂层的顶上放置6cm×6cm×4cm的矿棉厚块。施加100g/m2的压力到矿棉上,并且在40-60℃下固化粘合剂层。当粘合剂固化后,人工从面层上分离矿棉层。通过目测检查分层材料的表面来评价粘合剂的失效方式。失效方式如下表征:
在粘合剂和面层之间脱胶(失败);
在粘合剂和矿棉层之间脱胶(失败);
粘合剂的内聚失效(粘合剂层分离)(失败);
纤维撕裂方式(矿棉层分离)(通过)。
前述测试在如下的各种温度条件下实施:
A.面层和粘合剂层都是20℃;
B.面层38℃,粘合剂层20℃;
C.面层20℃,粘合剂层38℃;以及
D.面层和粘合剂层都是38℃。
除了失效类型1(在粘合剂层和面层之间脱胶)之外,通过使用钝头工具试图从面层上分离粘合剂来评价与面层的粘结的粘合剂。在这个测试中,粘合剂的剥离指示的是差的粘结(-);以这种方式不能剥离粘合剂时指示的是优良的粘结(+++)。在这个测试中,中间等级(+,++)表示观察到一些不完全的剥离。
结果示于表2。
表2
ND-由于内聚破坏方式无法测量。
从表2的数据可以看出,对比样品B尽管其具有低粘度和低总燃烧热,但是在粘性试验中表现非常差。另一方面,实施例1表现得非常类似于商业产品(对比样品A),并且具有明显较低的总燃烧热的优点。
实施例2
由多元醇组分和与实施例1中相同的多异氰酸酯来制备粘合剂,该多元醇组分含有:
1000MW的聚(氧化丙烯)三醇:14份
芳族聚酯二醇(与实施例1中的一样):19.7份
催化剂(与实施例1中的一样):0.4份
黑浆:0.1份
填料颗粒(碳酸钙和碳酸镁):65份
水:0.8份
这种多元醇组分在25℃具有22800mPa·s的粘度。当这个多元醇组分以120的指数与多异氰酸酯组分混合并固化时,固化的粘合剂具有约14.4兆焦耳/kg的总燃烧热。未填充的粘合剂具有约26.9兆焦耳/kg的总燃烧热。
Claims (13)
1.一种两组分聚氨酯粘合剂体系,其包括:
A)多异氰酸酯组分,其含有芳族多异氰酸酯,以及
B)多元醇组分,其含有B-1)20-75%重量的聚醚多元醇或聚醚多元醇混合物,基于组分B-1)和B-2)的总重量,其中该聚醚多元醇或聚醚多元醇混合物每分子平均具有2-4个羟基,并且在25℃具有至多500mPa·s的粘度,B-2)25-80%重量的芳族聚酯二醇,基于组分B-1)和B-2)的总重量,B-3)0.1-3%重量的水,和B-4)0-15%重量的不同于B-1)、B-2)和B-3)的异氰酸酯反应性组分,进一步条件在于
i)组分A)、组分B)或两者含有至少一种用于异氰酸酯基团和羟基反应的催化剂;
ii)所述芳族聚酯二醇是芳族二羧酸、芳族二酰卤或芳族二羧酸酐与一缩二乙二醇和聚乙二醇的反应产物,具有约150-约250的羟基当量,并且在25℃具有不大于2000mPa·s的粘度;以及
iii)组分A)、组分B)或两者可以含有颗粒矿物填料,其量为组分A)和B)总重量的至多65%。
2.权利要求1的两组分粘合剂体系,其中所述多元醇组分含有40-55%重量的颗粒矿物填料,并且具有至多20000mPa·s的粘度。
3.权利要求1的两组分粘合剂体系,其中所述多元醇组分含有55-65%重量的颗粒矿物填料,并且具有20000-35000mPa·s的粘度。
4.前述权利要求中任一项的两组分粘合剂体系,其中所述多元醇组分含有0.15-1%重量的水。
5.前述权利要求中任一项的两组分粘合剂体系,其含有不超过3%的组分B-4,基于组分B-1、B-2、B-3和B-4的总重量。
6.前述权利要求中任一项的两组分粘合剂体系,其中组分B-1含有一种或多种聚(氧化丙烯)聚合物或70-99.5%重量的氧化丙烯和0.5-30%重量的氧化乙烯的共聚物,并且组分B-1具有约800-1500的平均分子量且每分子平均含有2-3个羟基。
7.前述权利要求中任一项的两组分粘合剂体系,其中组分B-2具有12-20%的芳族含量和约160-240的羟基当量。
8.前述权利要求中任一项的两组分粘合剂体系,其中组分A是聚合MDI,其每分子具有2.2-3.2个异氰酸酯基团并且每异氰酸酯基团的当量为125-250。
9.一种层压体,包括纤维状陶瓷层、面层和插入在纤维状陶瓷层和面层之间并在纤维状陶瓷层和面层之间形成粘结的粘合剂层,其中所述粘合剂层是通过如下步骤制备的固化的聚氨酯:混合前述权利要求中任一项的两组分粘合剂体系的多异氰酸酯组分A)和多元醇组分B),将得到的混合物施加在纤维状陶瓷层和面层之间,和固化该混合物。
10.权利要求9的层压体,其中所述纤维状陶瓷层是矿棉。
11.权利要求9或10的层压体,其中所述面层是金属。
12.权利要求9-11中任一项的层压体,其中所述粘合剂层具有220-260克每平方米的重量并且具有不超过4.0兆焦耳每平方米的总燃烧热。
13.权利要求9-11中任一项的层压体,其中所述粘合剂层具有235-260克每平方米的重量并且具有不超过4.0兆焦耳每平方米的总燃烧热。
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CN103347920B (zh) | 2015-04-08 |
WO2012091927A1 (en) | 2012-07-05 |
RU2013134993A (ru) | 2015-02-10 |
BR112013015899A2 (pt) | 2018-06-05 |
US20140329084A1 (en) | 2014-11-06 |
PL2655465T3 (pl) | 2015-07-31 |
EP2655465B1 (en) | 2015-01-21 |
US9279072B2 (en) | 2016-03-08 |
ES2531860T3 (es) | 2015-03-20 |
EP2655465A1 (en) | 2013-10-30 |
BR112013015899B1 (pt) | 2020-03-17 |
PT2655465E (pt) | 2015-03-26 |
RU2585286C2 (ru) | 2016-05-27 |
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