CN101213229B - 喷涂聚脲体系及其制备方法和应用 - Google Patents
喷涂聚脲体系及其制备方法和应用 Download PDFInfo
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- CN101213229B CN101213229B CN2006800244175A CN200680024417A CN101213229B CN 101213229 B CN101213229 B CN 101213229B CN 2006800244175 A CN2006800244175 A CN 2006800244175A CN 200680024417 A CN200680024417 A CN 200680024417A CN 101213229 B CN101213229 B CN 101213229B
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- China
- Prior art keywords
- polyurea system
- chainextender
- polyurea
- acid
- polyaminoamide
- Prior art date
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- 239000012948 isocyanate Substances 0.000 claims description 13
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Abstract
聚脲喷涂体系,含有多异氰酸酯、多元胺和作为扩链剂的含咪唑啉的聚氨基酰胺,适于作为饮用水管线和储罐的内涂层。
Description
本发明涉及一种(杂)聚脲体系以及它主要在涂布饮用水管线或储罐的内表面中的应用。
已发现聚脲弹性体用途广泛,包括用作涂层如喷涂应用,以及用作泡沫。
当用作涂层时,这些材料提供理想的性能平衡,这些性能包括光稳定性;快速固化;相对水不敏感性;无溶剂体系;优异的物理性能,包括拉伸强度、伸长率和耐磨性;着色能力;容易施涂,例如使用商购喷涂设备等;以及由于无需催化剂而具有始终如一的反应性和长期贮存稳定性。
聚脲用于各种泡沫用途,其中包括:诸如汽车内饰品如座椅等之类的模塑泡沫体;通常用作地毯衬垫或用于家具中的块状泡沫塑料;以及其它各种填充或缓冲应用。具有硬、闭孔结构的泡沫体用于绝缘;模拟类似扬声器腔室、相框、门等木质零件;包装泡沫体;震动吸收泡沫体等。这种泡沫体应具有良好的拉伸强度、伸长率、压缩强度、尺寸稳定性以及其它需要的性能以在这些或其它应用中有良好表现。
喷涂弹性体聚脲体系在各种应用中通常视为涂料,如保护二级外壳(containments)和暴露结构如桥梁、钢罐、管道、金属建筑物、以及实际任何存在腐蚀或可能有腐蚀问题的表面。
聚脲涂层也用于翻新已有管道如饮用水管道的内部结构。尤其是它们的快速硬化和对湿度不敏感的固化性能使聚脲非常适合于此种用途。液态涂料组合物由沿着管道移动的装置喷涂到管道的内表面上,从而以高速固化速率形成具有高强度和延性的整体柔软衬里。
与饮用水接触的化学组合物和体系应当仅含有大纲文件许用表中(级别0-4对于饮用水应用是重要的)的天然材料或组分:“报告给欧洲委员会作为能用于制造拟与食品接触的塑料的物质的单体和添加剂的临时清单”(SANCOD3/LR(2003))。
一般通过使异氰酸酯和胺在扩链剂存在下反应制备聚脲弹性体体系。对于管道内涂布而言,快速硬化是需要的因而需要使用快速固化扩链剂。大多数快速固化芳族扩链剂如二乙基甲苯二胺(DETDA),使用最广泛的扩链剂之一,商业可获得的如Ethacure 100或Lonzacure M80,不在批准用于饮用水用途的化学品之列。
4,4’-亚甲基-双(3-氯-2,6-二乙基苯胺)(Lonzacure M-CDEA)属于批准的化学品但所提供的体系太缓慢以至于不能用于管道内涂布。
因此本发明的目标是提供能用于饮用水管道内衬的(杂)聚脲体系,所述聚脲体系不含有任何不在上述许用表中的原材料或组分(如DETDA),以及提供优异并且快速的固化(制备管道内稳定的衬里所需凝胶时间为几秒)。
已发现使用含有咪唑啉基的聚氨基酰胺作为扩链剂,优选与作为额外扩链剂的4,4’-亚甲基-双(3-氯-2,6-二乙基苯胺)或乙酰氨基三甲基环己烷甲胺组合可以制备这样的聚脲体系或杂聚脲(混合的聚脲-聚氨酯)体系。
采用仅仅基于在所述许用表中的组分的聚脲体系就实现了受控固化(不太慢也不太快)。因此所述体系非常适用于饮用水管道和储罐的内部涂层。
本发明的扩链剂是可以通过使聚亚烷基多胺与含有2-40个碳原子的酸反应获得的含有咪唑啉基的聚氨基酰胺。任选地所述化合物能进一步与平均每分子含有至少一个环氧基的环氧化合物反应;然而这通常将使扩链剂的粘度增大。
按已知的方式通过使聚亚烷基多胺与脂肪酸缩合制备含有咪唑啉基的聚氨基酰胺。合适的聚亚烷基多胺包括任何直链或支链聚亚烷基多胺,优选含有至少3个氨基、更优选4-5个氨基如二亚丙基三胺、三亚丙基四胺、四亚丙基五胺。含有5或更多个胺氢原子的聚亚乙基多胺是优选的材料。这样的聚亚乙基多胺的实例包括二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)以及更高阶聚亚乙基多胺。在缩合反应中使用的含有2-40个碳原子的酸可以含有单体、二聚、三聚、饱和或不饱和、直链或支链烃残基。优选的是含有至少8个碳原子的脂肪酸。特别优选的是含有至少14个碳原子的单体不饱和脂肪酸如油酸、妥尔油酸、亚油酸、亚麻酸。其它合适的含有12-36个碳原子的脂肪酸包括月桂酸、棕榈酸、硬脂酸、肉豆蔻酸和褐煤酸。本发明优选使用的扩链剂是二亚乙基三胺与C18-单体脂肪酸的反应产物。
将该酸组分于60℃-100℃加入到聚亚烷基多胺中以制备本发明的扩链剂。加热该反应混合物至180℃-260℃,有时直至300℃,蒸馏除去反应水。在第一缩合步骤中获得酰胺,第二缩合步骤中产生咪唑啉。第二缩合步骤的产率由蒸馏去除的水的量决定,并且可以达到第一缩合步骤获得的聚氨基酰胺的90%。一般获得的反应混合物含有至少10mol%聚氨基酰胺以及高达90mol%的含有咪唑啉的聚氨基酰胺。优选该反应混合物包含至少40mol%、优选至少60mol%的含有咪唑啉的聚氨基酰胺。聚亚烷基多胺/酸的摩尔比优选为1∶1-1∶1.5。
优选本发明扩链剂的咪唑啉含量大于60%,优选大于75%。较低的咪唑啉含量产生较高粘度产物和容易结晶的产物。
任选含有咪唑啉的聚氨基酰胺可以与环氧化合物进一步反应。这些环氧化合物是一般可获得的并且通常每分子含有的环氧基多于一个,衍生自单-或多官能酚,该多官能酚可以含有多于一个环,如双酚A和双酚F二缩水甘油醚。在″Epoxidverbindungen und Epoxidharze″,AM.Paquin,Springer Verlag Berlin,1958中可以发现其它合适的环氧化合物清单。通过加热该含有咪唑啉的聚氨基酰胺至60℃-100℃并且在约60分钟过程中向其中加入已经加热至约50℃的环氧化合物以获得这样的加合物。再持续搅拌60分钟以完成反应。对于1摩尔含有咪唑啉的聚氨基酰胺而言,优选使用0.01-0.5,优选0.05-0.2环氧当量的环氧化合物。
关于此扩链剂的组成及其制备的更多细节可见WO 03/031495,全部引入本发明作为参考。
本发明优选使用的扩链剂是二亚乙基三胺与分子量约357的妥尔油脂肪酸的氨基咪唑啉。
含有咪唑啉的聚氨基酰胺与环氧化合物的这种加合物记载于US 5541338中,作为通过反应注射成型制备的聚氨酯、聚氨酯/脲或聚脲弹性体的交联化合物。
本发明扩链剂一般用量为反应体系总重量的2%-35%,优选10%-25%。
本发明的聚脲体系含有上述扩链剂、多异氰酸酯和能与异氰酸酯反应的多官能组合物。
本发明的聚脲体系第一部分包含一种或多种可以是脂族或芳族的多异氰酸酯。
合适的(环)脂族异氰酸酯包括六亚甲基二异氰酸酯(HDI)、四烷基二甲苯二异氰酸酯、环己烷二异氰酸酯、1,12-十二烷二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,3-和1,4-环己烷二异氰酸酯、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基-环己烷(异佛尔酮二异氰酸酯)、4,4′-、2,2′-和2,4′-二环己基甲烷二异氰酸酯,以及相应的异构体混合物等。
芳族异氰酸酯包括但不必限于间-亚苯基二异氰酸酯、对-亚苯基二异氰酸酯、4,4′-或2,4′-或2,2′-二苯基甲烷二异氰酸酯(MDI)、聚亚甲基聚亚苯基二异氰酸酯(MDI及其低聚物的混合物,在本领域称为″粗品″或异氰酸酯官能度大于2的聚合MDI)、2,4-和2,6-甲苯二异氰酸酯(TDI)、联甲氧基苯胺二异氰酸酯、二甲代亚苯基二异氰酸酯、亚萘基-1,4-二异氰酸酯、二亚苯基4,4′-二异氰酸酯等。
合适的脂族或芳族二异氰酸酯包括但不必限于苯二亚甲基-1,3-二异氰酸酯、双(4-异氰酸根合苯基)甲烷、双(3-甲基-4-异氰酸根合苯基)甲烷和4,4′-二苯基丙烷二异氰酸酯。
前述异氰酸酯可以单独或组合使用。
在本发明的一个实施方案中,芳族异氰酸酯由于提供快速反应体系并且具有比脂族异氰酸酯更低的毒性水平而优选。最优选的多异氰酸酯是二苯基甲烷二异氰酸酯(MDI)的异构体或异构体混合物,优选含有30wt%-95wt%的4,4′-MDI和5wt%-70wt%的2,4′-MDI。由于纯MDI是固体因而不便于使用,优选脲酮亚胺(uretonimine)或碳化二亚胺改性生成的液态MDI产物。
作为选择,可以使用由多异氰酸酯(MDI、改性MDI和/或p-MDI)与多元醇或多元胺(如下所述)反应形成的准预聚物。
合适的多元醇的实例包括聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚己内酯多元醇和其它多元醇。这些多元醇可以单独使用或以两种或更多种组合使用。
给出的聚醚多元醇实例为聚乙二醇、聚丙二醇、聚丙二醇-乙二醇共聚物、聚丁二醇、聚己二醇、聚庚二醇、聚癸二醇以及通过使用官能度为2-8的能与异氰酸酯反应的引发剂开环共聚诸如环氧乙烷和/或环氧丙烷之类的环氧烷烃而得到的聚醚多元醇。
通过使多元醇和多元酸反应而获得的聚酯二元醇是给出的聚酯多元醇的实例。作为多元醇的实例,可以给出乙二醇、聚乙二醇、丁二醇、聚丁二醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,9-壬二醇、2-甲基-1,8-辛二醇等。作为多元酸的实例,可以给出邻苯二甲酸、二聚酸、间苯二甲酸、对苯二甲酸、马来酸、富马酸、己二酸、癸二酸等。
作为聚碳酸酯多元醇的实例,可以给出聚四氢呋喃的聚碳酸酯、聚(己二醇碳酸酯)、聚(壬二醇碳酸酯)、聚(3-甲基-1,5-戊二醇碳酸酯)等。
给出的熔点为0℃或更高的聚己内酯多元醇的实例有通过ε-己内酯和二醇化合物反应得到的聚己内酯二元醇。
本申请给出的二醇化合物实例为乙二醇、聚乙二醇、聚丙二醇、丁二醇、聚丁二醇、1,2-聚丁二醇、1,6-己二醇、壬二醇、1,4-环己烷二甲醇、1,4-丁二醇等。
作为其它多元醇的实例,可以给出乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、环己烷二甲醇、聚氧乙烯双酚A醚、聚氧丙烯双酚A醚、聚氧乙烯双酚F醚、聚氧丙烯双酚F醚等。
对于准预聚物制备而言,多异氰酸酯相对于多元醇或多元胺的用量至少为多异氰酸酯相对多于多元醇或多元胺的化学计量过量。一般每摩尔多元醇或多元胺使用大于1,优选约1.05-约25,最优选约10-约25摩尔当量的多异氰酸酯。
优选的芳族多异氰酸酯一般具有5%-35%,优选10%-25%,最优选15%-20%的异氰酸酯含量。
在本发明聚脲体系中特别优选使用的多异氰酸酯是NCO值为16%-25%,优选16%-20%的由任选脲酮亚胺改性的MDI和聚丙二醇(优选MW 2000)获得的预聚物。
本发明聚脲体系的第二部分包含能与异氰酸酯反应的多官能组合物,优选包含一种或多种任选与一种或多种多元醇共混的多元胺。在后者的情形中获得含有一些聚氨酯基团的杂聚脲体系。多元醇可以是上述任何与准预聚物组合物有关的多元醇。在所述第二部分中优选使用的多羟基化合物是1,4-丁二醇或单乙二醇。如果使用,所述多元醇的用量小于多元胺用量。一般,基于全部多官能的能与异氰酸酯反应的化合物,多元醇含量小于50wt%,优选5wt%-15wt%。加入这种多元醇的好处包括可控的固化曲线和可靠的混合。
多元胺优选是聚氧化烯多元胺。该聚氧化烯多元胺可以是伯和/或仲胺封端的聚醚多元醇,一般重均分子量大于约100以及优选为约200至约5000;官能度为2-6,以及优选为2-3;以及胺重量当量为约750至约4000。聚氧化烯多元胺包括下式表示的化合物:
在此式中的变量具有下述含义。Q’是用作引发剂的含活性氢的化合物的多价残基。Q’的化合价由y’给定,其中y’至少为2,优选2-8,以及最优选2-3。各个R’独立地是氢或低级烷基,如甲基或乙基。R’基团优选是氢和/或甲基,包括它们的混合物。每个胺的氧化烯重复单元的平均数由x’给定,至少为1,优选约1至约40,以及最优选约1至约10。
典型的引发剂中包括以下的一种或多种:多羟基化合物,包括二醇如乙二醇、丙二醇、1,2-或1,4-丁二醇,以及三元醇如三羟甲基丙烷和甘油。优选的引发剂包括乙二醇、丙二醇、三羟甲基丙烷和甘油。典型的氧化烯重复单元包括氧化乙烯、氧化丙烯、氧化丁烯等,包括其混合物。当使用两种或更多种氧化烯时,它们可以诸如无规或嵌段的任何形式存在。优选的聚氧化烯多元胺包括商购自Huntsman的JEFFAMINE聚氧化烯多元胺,如二元胺D-230、D-400、D-2000、D-4000、SD-231、SD-401、XTJ-576以及三元胺T-403、T-3000、T-5000、ST-404。在本聚脲体系用于饮用水管道内涂层时,应避免JEFFAMINE T-5000、T-3000和T-403的存在。
在本发明实践中,可以使用单一的多元胺也可以使用高分子量聚氧化烯多元胺的混合物,如二-和三官能材料和/或不同分子量或不同化学组成材料的混合物。
除了上述含有咪唑啉的聚氨基酰胺扩链剂之外,本聚脲体系还可以含有本领域已知和记载的用于聚脲体系的常规胺封端的扩链剂。
合适的扩链剂包括但不必限于在US 5162388和5480955(在此引入作为参考)中公开的那些脂族和环脂族二元胺扩链剂。也可以使用诸如US 5317076(引入本申请作为参考)中公开的芳族二元胺扩链剂。在本发明的一个实施方案中,优选芳族扩链剂。
合适的额外扩链剂的实例包括1-甲基-3,5-二乙基-2,4-或2,6-二氨基苯(也称为二乙基甲苯二胺或DETDA);1,3,5-三乙基-2,6-二氨基苯;3,5,3′,5′-四乙基-4,4′-二氨基二苯基甲烷;二(甲硫基)-甲苯二胺,包括3,5-二(甲硫基)-2,4和2,6-甲苯二胺;N,N′-双(叔丁基)乙二胺;4,4′-亚甲基双(2-异丙基-6-甲基苯胺);4,4′-亚甲基双(2,6-二异丙基苯胺);异佛尔酮二胺;如WO2004/090009中公开的三聚氰二胺,尤其是2,4-二氨基-6-壬基-1,3,5-三嗪(得自Degussa),Clearlink 1000(得自UOP);Polyclear 135(商购自BASF);4,4′-亚甲基-双(3-氯-2,6-二乙基苯胺)(以LONZACURE M-CDEA商购));乙酰氨基三甲基环己烷甲胺(以JEFFLINK 754商购)。尤其后两者优选为额外扩链剂;在该聚脲体系用于饮用水管道内涂层时,特别优选LONZACURE M-CDEA。
如果LONZACURE M-CDEA用作额外扩链剂,则优选加入1,4-丁二醇以改善固化;如果加入JEFFLINK 754,则为同样目的优选加入单乙二醇。
在本发明的总聚脲弹性体体系中扩链剂的总量可以为约7wt%-约30wt%,优选约10wt%-约25wt%,更优选约10wt%-约17wt%。
有利的是,不借助催化剂,多异氰酸酯和能与异氰酸酯反应的组分包括扩链剂反应以形成本发明的聚脲弹性体体系。然而,如果需要,可以使用催化剂。
诸如叔胺或有机锡化合物之类的催化剂可以合适地为亚锡或锡化合物,如羧酸的亚锡盐、三烷基锡氧化物、二烷基锡二卤化物、二烷基锡氧化物等,其中锡化合物的有机部分的有机基团是含有1-8个碳原子的烃基。例如,可以使用二月桂酸二丁锡、二乙酸二丁锡、二乙酸二乙锡、二乙酸二己锡、二-2-乙基己基锡氧化物、二辛基锡二氧化物、辛酸亚锡、油酸亚锡等,或它们的混合物。叔胺催化剂包括三烷基胺(例如三甲基胺、三乙基胺);杂环胺如N-烷基吗啉(如N-甲基吗啉、N-乙基吗啉等)、2,2′-二吗啉代二乙基醚、1,4-二甲基哌嗪等;以及脂族多元胺如N,N,N′,N′-四甲基-1,3-丁二胺、二甲基二氨基二乙醚、三亚乙基二胺。
在本发明的一个实施方案中(但不是该聚脲体系用于饮用水管道内涂层的情形),本发明的聚脲体系还可以包括有机碳酸亚烷基酯,如US 5442034所定义,引入本申请作为参考。如其中所指出,碳酸亚烷基酯优选选自碳酸乙二酯、碳酸丙二酯、碳酸丁二酯和碳酸二甲酯。使用碳酸亚烷基酯降低体系的粘度。碳酸亚烷基酯还能减缓喷涂聚氨酯弹性体体系的有效反应性、改善性能和表面特性(流动性)以及改善对于弹性体所喷涂的表面的粘合性。它还可以作为两种组分之间的相容剂用以改善组分的混合以及体系的均匀性。
其它合适的添加剂包括如US 5731397所公开的官能化的烷氧基硅烷,用以改善粘合性。
其它常规配方成分可以用于本发明的聚脲弹性体体系,举例说,例如泡沫稳定剂,也称为硅油或乳化剂。该泡沫稳定剂可以是有机硅烷或类似硅氧烷的聚硅氧烷-聚氧化烯嵌段共聚物。颜料或着色剂,如二氧化钛可以加入到弹性体体系中以赋予弹性体颜色性能。一般,这样的颜料随胺树脂加入。如本领域技术人员所知道的,如果需要,增强材料在本发明实施中是有用的。例如切断或研磨玻璃纤维、切断或研磨碳纤维和/或矿物纤维是有用的。
有机和无机填料可以加入以提高弯曲模量并且改善体系的加工性。这些填料可以加入到多异氰酸酯组合物和/或能与多异氰酸酯反应的组合物中。填料的量一般占能与多异氰酸酯反应的组合物的0-40wt%。特别优选的填料是滑石。
多异氰酸酯相对于聚氧化烯多元胺和扩链剂的用量为足以制备聚脲弹性体的任意量。一般,为每摩尔胺提供约0.7-约1.6,优选约0.8-约1.3,以及最优选约1.05-约1.25摩尔异氰酸酯。一般,基于聚氧化烯多元胺的量,提供约30-约80wt%,优选约40-约60wt%的扩链剂。
起始原料组分的重量百分数、摩尔百分数或体积会根据所使用设备、原料组分活性和所需产品的特性而改变。用于制备本发明聚脲弹性体体系而构思的组分A(多异氰酸酯)和组分B(多元胺/多元醇和扩链剂)的一般配方包含约30-70wt%组分A对约70-30wt%组分B,更优选约40-60%组分A对约60-40%组分B,以及最优选50-50wt%组分A和组分B的混合物。
多异氰酸酯、聚氧化烯多元胺和扩链剂连同任何其它任选成分在任何有效的,包括已知用于多元胺与多异氰酸酯反应的条件下反应。一般,在反应中的温度范围可以为约0℃-约90℃,优选约40℃-约90℃,以及最优选约60-约80℃。这些组分可以在环境压力下或高达约3000,优选约1500-约3000,以及最优选约2000-约2500psig的更高压力下结合。
当用于喷涂用途时,可以使用高压喷涂设备将这些组分直接冲击混合。具体地,组分(A)和(B)的第一和第二加压流分别由定量给料器的两个分离腔室传送并且相互高速碰撞或冲击用以均匀混合两种组分以制备弹性体,然后用喷枪或RIM设备将该弹性体输送至所需基材上或内。组分(A)与(B)的体积比可以为任意合适的量,一般为约3∶7到7∶3。这些组分一般施加速率为至少0.5,优选约1-约30,以及最优选约20磅/分钟。
该聚脲弹性体可以任选通过加热进行后固化,如以下建立的程序。一般使用后固化以提高弹体性能,如热熔垂(heat sag)。
所获得的聚脲可以具有少量氨基甲酸酯或其它由反应组分中的异氰酸酯与羟基或其它活性氢基团反应形成的键。
本发明的聚脲用于喷涂、辊压、堵缝或修平类型的用途。通过高或低压喷枪或类似工具能实现本发明的喷涂。通过任何合适的辊如设备辊或手动辊实现本发明的辊压。通过使用填缝枪、填缝机等完成本发明的堵缝。当本发明用于修平类型用途时,考虑修平刀。
本发明的聚脲用于涂层、嵌缝胶、腐蚀预防、磨损预防、封装、防腐蚀、化学防护、结构修复以及其它类似工艺。
本发明比现有聚脲有优势的具体应用应该是饮用水内涂层,其以高固化速率形成显示出高强度和柔软性以及对于已有管壁具有高度粘合性的整体衬里。咪唑啉聚氨基酰胺扩链剂可以取代未被准许用于上述用途的DEDTA,并且仍然提供快速固化体系。而且本发明的聚脲涂层的质量和物理性能与基于DEDTA的聚脲涂层相当。
实施这种管道内涂布时,该体系的第一和第二部分例如通过软管分别供料至本身已知的喷涂装置,能被推进穿过已有待翻新的管道。该装置优选在涂布到管道内部前加热该体系的两部分并且在将该混合物涂布至管道的内表面前立即将两部分混合。在机器和喷头之间的软管通常被加热以保持在为良好混合而需要设定的温度,致使这些组分的粘度较低由此通过撞击较好地混合以及让固化材料的性能优异。两部分的混合物在管道内表面固化形成柔软不渗透的涂层。特别适于所述应用的喷涂设备商购自TWIN INPRES。
本发明的聚脲体系可以用于涂布饮用水管道、储罐、贮槽和灌溉管网的内表面(例如用结构衬里翻新它们或修补它们或临时保护),而且越来越多的污水管网被采用“许可”体系内涂布,该体系仅含有在防止净化装置污染的许用表之列的原料或组分。例如在生产单元中将新管道安装于地下之前,本聚脲体系还能用作新管道的衬里。
通过下述实施例对本发明各个方面进行举例说明,但不受其限制。
在这些实施例中使用下述成分:
ISO 1:基于二-MDI和p-MDI和聚丙二醇的NCO值为19.3%的预聚MDI
ISO 2:基于脲酮亚胺改性的二-MDI和聚丙二醇的NCO值为15%的预聚MDI
ISO 3:基于脲酮亚胺改性的二-MDI和聚丙二醇的NCO值为18%的预聚MDI
ISO 4:基于脲酮亚胺改性的二-MDI和聚丙二醇的NCO值为18.3%的预聚MDI
JEFFAMINE D2000:从Huntsman获得的平均MW为2000的聚亚烷基多胺
JEFFAMINE T5000:从Huntsman获得的平均MW为5000的聚亚烷基多胺
DETDA:从Albemarle获得(如Ethacure 100)或从Lonza获得(如LonzacureM80)
Lonzacure M-CDEA:从Lonza获得
Jefflink 754:从Huntsman获得
BDO:1,4-丁二醇
MEG:单乙二醇
TK2971:二亚乙基三胺和MW 357妥尔油脂肪酸的氨基咪唑啉
滑石:填料
实施例1
将这些成分在约80℃按下表所示量(pbw)混合,然后用冲击混合枪喷涂到混凝土、钢或砖墙之上。
检测该体系的反应性(凝胶时间)。
对所获得的涂层实施微观评价以测定水泡或气泡的存在。
目测该涂层的常规质量。
测量膜性能,如拉伸强度、伸长率、撕裂强度和硬度。
结果列于下表。
这些结果显示,根据本发明的聚脲体系(#4-11)提供了具有可接受的固化特征和膜性能的质量良好的涂层。
表1
体系# | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
ISO 1 | 100 | 57.1 | 95.3 |
ISO 2 | 100 | 67.1 | 75.4 | 125.9 | |||||||
ISO 3 | 100 | 125 | 115 | ||||||||
ISO 4 | 100 | ||||||||||
D2000 | 61.6 | 62.4 | 70 | 59 | 59 | 55 | 55 | 55 | 64.7 | 64.7 | 51.7 |
T5000 | 10.3 | ||||||||||
DETDA | 28.1 | 37.6 | |||||||||
M-CDEA | 30 | 29 | 29 | 18 | 18 | 18 | |||||
Jefflink 754 | 7.3 | 7.3 | 5.9 | ||||||||
BDO | 10 | 10 | 10 | 12 | |||||||
MEG | 12 | 9.6 | |||||||||
TK2971 | 12 | 12 | 17 | 17 | 17 | 16 | 16 | 12.8 | |||
滑石 | 20 | ||||||||||
许用表 | 否 | 否 | 是 | 否 | 是 | 是 | 否 | 是 | 否 | 否 | 否 |
起泡 | 否 | 否 | 否 | 否 | 否 | 否 | 否 | 否 | 否 | 否 | 否 |
质量 | 好 | 差 | 好 | 好 | 好 | 好 | 好 | 好 | 好 | 好 | 好 |
凝胶时间(sec) | 3 | <1 | >15 | 3 | 10 | 6 | 1 | 3 | 2 | 2 | 2 |
拉伸强度(MPa) | 20.6 | 11 | 9 | 13 | 14 | 14 | 12 | ||||
伸长率(%) | 400 | 220 | 320 | 280 | 120 | 250 | 350 | ||||
裤形撕裂强度(N/m) | 32 | 23 | 25 | 28 | 21 | 25 | 20 | ||||
硬度肖氏D | 46 | 47 | 39 | 43 | 48 | 45 | 36 |
Claims (15)
1.含有咪唑啉基的聚氨基酰胺在聚脲体系中作为扩链剂的应用,所述聚脲体系不含二乙基甲苯二胺,其中通过使含有5个或更多个胺氢原子的聚亚乙基多胺与含有2-40个碳原子的酸反应获得含有咪唑啉基的聚氨基酰胺。
2.根据权利要求1的应用,其中聚脲体系是杂聚脲体系。
3.根据权利要求1的应用,其中二亚乙基三胺用作聚亚乙基多胺以及妥尔油脂肪酸用作酸。
4.根据权利要求1或2的应用,其中聚氨基酰胺的咪唑啉含量大于60%。
5.聚脲体系,包含a)多异氰酸酯组合物,b)能与异氰酸酯反应的多官能组合物,该组合物含有如权利要求1-4任一项中所定义的扩链剂,所述聚脲体系不含二乙基甲苯二胺。
6.根据权利要求5的聚脲体系,其中多异氰酸酯为具有5-35wt%NCO值的芳族多异氰酸酯。
7.根据权利要求5或6的聚脲体系,其中能与异氰酸酯反应的多官能组合物包含一种或多种聚氧化烯多胺以及任选的一种或多种多元醇化合物。
8.根据权利要求5或6的聚脲体系,其中含有咪唑啉的聚氨基酰胺扩链剂占总的能与异氰酸酯反应的组合物的5-25wt%。
9.根据权利要求5或6的聚脲体系,其中4,4’-亚甲基-双(3-氯-2,6-二乙基苯胺)用作额外的扩链剂。
10.根据权利要求9的聚脲体系,其中1,4-丁二醇用作多元醇。
11.根据权利要求5或6的聚脲体系,其中乙酰氨基三甲基环己烷甲胺用作额外的扩链剂。
12.根据权利要求11的聚脲体系,其中单乙二醇用作多元醇。
13.根据权利要求5-12任一项的聚脲体系用于喷涂中的应用。
14.在表面形成涂层的方法,该方法包括以下步骤:a)提供权利要求5-12任一项所定义的液态的双-部分的聚脲体系,b)将第一部分和第二部分混合在一起形成混合物,以及c)将该混合物作为涂层涂布在所述表面上。
15.根据权利要求14的方法,其中涂层提供在饮用水管线或储罐的内表面上。
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PCT/EP2006/063676 WO2007006656A1 (en) | 2005-07-07 | 2006-06-29 | Spray polyurea system, process for producing and use thereof |
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KR101250226B1 (ko) * | 2010-09-30 | 2013-04-08 | 주식회사 라이닝시티 | 파이프 라이닝용 속경화성 폴리우레아우레탄 조성물 |
WO2012088395A1 (en) * | 2010-12-22 | 2012-06-28 | Falcon Technologies And Services, Inc. | Anchoring system and method |
WO2012161774A1 (en) | 2011-03-30 | 2012-11-29 | 3M Innovative Properties Company | Composition comprising cyclic secondary amine and methods of coating drinking water pipelines |
EP2861684B1 (en) | 2012-06-15 | 2016-03-30 | 3M Innovative Properties Company | Curable polyurea forming composition, method of making, and composite article |
CN107001591B (zh) | 2014-12-24 | 2020-03-13 | 陶氏环球技术有限责任公司 | 快速凝固的环氧树脂系统和使用所述环氧树脂系统涂布管道的方法 |
WO2018033589A1 (en) * | 2016-08-17 | 2018-02-22 | Ppg Coatings Europe B.V. | Coated conduits and methods of repairing or reinforcing conduits |
GB201616654D0 (en) * | 2016-09-30 | 2016-11-16 | Spencer Coatings Limited | Composition |
WO2019118483A1 (en) * | 2017-12-11 | 2019-06-20 | Innovative Surface Technologies, Inc. | Polyurea copolymer coating compositions and methods |
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US3474056A (en) * | 1962-03-20 | 1969-10-21 | Schering Ag | Curing agents for polyepoxides |
US5541338A (en) * | 1995-03-22 | 1996-07-30 | Air Products And Chemicals, Inc. | Fatty imidazoline crosslinkers for polyurethane, polyurethaneurea and polyurea applications |
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CA2020349C (en) * | 1989-09-05 | 2001-10-09 | Dudley J. Ii Primeaux | Aliphatic spray polyurea elastomers |
US5162388A (en) * | 1991-06-04 | 1992-11-10 | Texaco Chemical Company | Aliphatic polyurea elastomers |
US5317076A (en) * | 1993-04-12 | 1994-05-31 | Texaco Chemical Co. | Polyurea elastomer with reduced moisture vapor transmission |
US5442034A (en) * | 1994-06-01 | 1995-08-15 | Huntsman Corporation | Spray polyurea elastomers containing organic carbonates to improve processing characteristics |
US5731397A (en) * | 1996-04-16 | 1998-03-24 | Huntman Petrochemical Corporation | Polyurea spray railcar lining systems |
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2006
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- 2006-06-29 KR KR1020087003191A patent/KR20080035612A/ko not_active Application Discontinuation
- 2006-06-29 CN CN2006800244175A patent/CN101213229B/zh not_active Expired - Fee Related
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- 2006-06-29 RU RU2008104630/04A patent/RU2008104630A/ru not_active Application Discontinuation
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US3474056A (en) * | 1962-03-20 | 1969-10-21 | Schering Ag | Curing agents for polyepoxides |
US5541338A (en) * | 1995-03-22 | 1996-07-30 | Air Products And Chemicals, Inc. | Fatty imidazoline crosslinkers for polyurethane, polyurethaneurea and polyurea applications |
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US20080200620A1 (en) | 2008-08-21 |
KR20080035612A (ko) | 2008-04-23 |
CA2614053A1 (en) | 2007-01-18 |
EP1913047A1 (en) | 2008-04-23 |
RU2008104630A (ru) | 2009-08-20 |
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JP2009500483A (ja) | 2009-01-08 |
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