CN1775825B - 聚天冬酰亚胺 - Google Patents

聚天冬酰亚胺 Download PDF

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CN1775825B
CN1775825B CN2005101250452A CN200510125045A CN1775825B CN 1775825 B CN1775825 B CN 1775825B CN 2005101250452 A CN2005101250452 A CN 2005101250452A CN 200510125045 A CN200510125045 A CN 200510125045A CN 1775825 B CN1775825 B CN 1775825B
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K·丹尼尔梅尔
C·A·甘比诺
R·格特兹曼
R·R·罗斯勒
T·D·韦特
E·P·斯奎勒
M·E·洪口
K·M·亨德森
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Abstract

本发明涉及一种新型的聚天冬酰亚胺及其制备方法和这些聚天冬酰亚胺作为两组分聚氨酯涂料组合物中的多异氰酸酯的活性组分的应用。该聚天冬酰亚胺由聚醚胺与马来酰亚胺反应来制备。

Description

聚天冬酰亚胺
技术领域
本发明涉及一种新型的聚天冬酰亚胺(polyaspartimide)、一种由具体的伯胺和马来酰亚胺制备它们的方法、以及它们作为两组分聚氨酯涂料组合物中的聚异氰酸酯的活性组分的应用。
背景技术
含有作为粘合剂的多异氰酸酯组分与一种或多种异氰酸酯-活性组分相结合的两组分涂料组合物是已知的。它们适合用于制备坚硬、有弹性、耐磨、耐溶剂和耐侯的高质量涂层。
含有酯基团的聚仲胺已在两组分的表面涂料工业中得到了公认。它们特别适合与漆料多异氰酸酯相结合用作溶剂含量低或不含溶剂、高固体含量的涂料组合物的粘合剂,因为它们提供低温下涂层的快速固化。
这些聚仲胺是聚天冬氨酸酯,在例如美国专利5126170、5214086、5236741、5243012、5364955、5412056、5623045、5736604、6183870、6355829、6458293、6482333和欧洲专利申请公开667362中有描述。另外,含有醛亚胺基团的天冬氨酸酯也是已知的(参见美国专利5489704、5559204和5847195)。仲天冬酸酰胺酯(secondary aspartic acid amide ester)也是已知的(参见美国专利6005062)。它们在两组分涂料组合物中单独用作异氰酸酯-活性组分或与其它异氰酸酯-活性组分混合使用,也描述在上述专利中。制备这些聚天冬氨酸酯的方法是相应的聚伯胺与马来酸酯或延胡索酸酯反应,导致聚仲胺的形成。因为空间效应、结构效应和电子效应,这些聚仲胺基团对于异氰酸酯基团活性有了充足的下降,可以可靠又简易的方法与多异氰酸酯相混合。
如同现有技术中已知的,用于制备聚天冬氨酸酯的反应是伯胺与烯键式羰基化合物中的活性C-C双键的加成反应。但是,已发现该反应在实际的合成工艺过程(例如,60℃下搅拌24小时)中不能进行完全。实际的反应程度取决于伯胺的类型。因此,使用1,6-环己烷二胺在反应1天后的转化度(通过测量游离的、未转化的马来酸酯和延胡索酸酯的浓度来确定,在碱性催化剂存在下,马来酸酯重排成延胡索酸酯)约为90%至93%。而使用具有空间位阻伯胺基团的脂环族多胺,即4,4’-二氨基-3,3’-二甲基二环己基甲烷,在1天后的转化度仅为77%。完全转化或基本上完全转化只能在若干天后才能实现,若是4,4’-二氨基-3,3’-二甲基二环己基甲烷的话,则需要几个月的时间才能完全转化。
在通常的商业生产中,反应进行16个小时,取决于所使用的胺,转化度在75%至95%之间。“未完成的”材料装桶且存储直到反应完全。这通常需要二个星期至六个月不等。美国专利5821326中描述了某种五元芳香环化合物作为催化剂在加快天冬氨酸酯的制备速度中的应用。
常规的天冬氨酸酯能够进一步转化(用异氰酸酯固化后),形成乙内酰脲环结构。乙内酰脲的形成可导致涂层的收缩和不利的醇的形成。期望制备出一种天冬氨酸酯,其形成乙内酰脲的趋势较小。
于2004年1月21日提交的美国申请序列号10/761643描述了通过将过量的伯胺与马来酸酯或延胡索酸酯反应,然后将所得的产物与马来酰亚胺反应形成一种同时具有天冬氨酸酯基团和天冬酰亚胺基团的产物来制备天冬氨酸酯。
发明内容
本发明涉及一种新型的聚天冬酰亚胺,其通式为:
Figure A20051012504500061
其中,X代表n价的通过从对应于通式X-(NH2)n的的聚醚胺中除去n个氨基基团得到的聚醚基,其中所述的聚醚胺的数均分子量约为200至6000,并含有其它或者对异氰酸酯基团有反应活性、或者在最高为100℃的温度下对异氰酸酯基团呈惰性的官能团,
R2和R3可等同或不同,代表选自i)、ii)、iii)和iv)的部分:i)氢;ii)直链或支链的C1至C8烷基基团,其最多可被三个含有6至10个碳原子的芳基基团取代;iii)C6至C10芳基基团,其最多可被三个含有1至3个碳原子的烷基基团取代;iv)R2和R3一起形成五元或六元环烷基基团,所述环烷基基团被0到3个含有1至3个碳原子的烷基基团取代;
R1代表选自i)、ii)和iii)的部分:i)氢;ii)直链或支链的C1至C8烷基基团,其最多可被三个含有6至10个碳原子的芳基基团取代;iii)C6至C10芳基基团,其最多可被三个含有1至3个碳原子的烷基基团取代,以及
n代表2至4的整数。
本发明的产物与多异氰酸酯组合时,会具有较长的贮存期,并比现有技术中基于聚醚的天冬氨酸酯提供更为坚硬的涂层,产物形成乙内酰脲环的趋势较小。
本发明还涉及一种制备上述通式的聚天冬酰亚胺的方法,其包括在约室温至约100℃的温度下,在溶液中或在无溶剂的情况下,对应于通式x[-NH2]n的二胺或多胺与马来酰亚胺以马来酰亚胺对氨基基团的当量比为约0.95∶1至约1.05∶1的比例反应,其中X和n如上文所定义。最优的比例为1∶1。
本发明还涉及一种两组分涂料组合物,其含有作为粘合剂的
a)多异氰酸酯组分,和
b)异氰酸酯-活性组分,其含有
b1)对应于本发明的聚天冬酰亚胺的化合物,和
b2)任选的其它异氰酸酯-活性化合物,
其中,异氰酸酯基团对异氰酸酯-活性基团的当量比为约0.8∶1至约2∶1,以及任选的表面涂料技术中已知的添加剂。
具体实施方式
分子量为数均分子量(Mn),并且由端基分析来确定(NH值)。
合适的多胺对应于现有技术中已知并用于制备异氰酸酯封端预聚物的聚醚多元醇,除了链端的羟基基团转化成了氨基基团,该转化或者是通过氨基化作用,或者是将羟基基团与二异氰酸酯反应、且随后将链端的异氰酸酯基团水解为氨基基团来实现。优选的多胺为氨基封端的聚醚,诸如可从Huntsman公司购得的Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00011
树脂。
聚醚胺组分包括任何能实现本发明目的的聚醚胺。合适的聚醚胺通常包括具有聚环氧丙烷基团的二官能胺和多官能胺。这些胺是众所周知的,可通过如德国专利公开1193671、美国专利3236895和法国专利1466708中描述的方法来制备,其内容通过引用包括于此。合适的二官能胺的实例为可从Hunstman公司购得的聚环氧丙烷二胺,诸如Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00012
D-230、Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00013
D-400、Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00014
D-2000。合适的三官能聚环氧丙烷胺包括聚氧化丙三胺、(Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00015
T-403)、JeffamineT-3000和Jeffamine
Figure DEST_PATH_GA20173269200510125045201D00017
T-5000,它们也从Huntsman公司购得。据信也可以使用多官能聚醚胺如四官能聚环氧丙烷胺。
有用的马来酰亚胺是那些具有以下结构的马来酰亚胺:
Figure DEST_PATH_GA20173269200510125045201D00018
其中,R1、R2和R3如上文所定义。具体有用的马来酰亚胺包括N-甲基马来酰亚胺、N-乙基马来酰亚胺、N-丙基马来酰亚胺、N-异丙基马来酰亚胺、N-异丁基马来酰亚胺、N-丁基马来酰亚胺、N-戊基马来酰亚胺、N-乙基戊基马来酰亚胺、N-甲基异戊基马来酰亚胺、N-甲基己基马来酰亚胺、N-苯基马来酰亚胺、N-乙基-2-甲基马来酰亚胺、N-2,3-三甲基甲基马来酰亚胺、3-甲基-N-苯基马来酰亚胺、N-苯基-3,4,5,6-四氢邻苯二甲酰亚胺和3-苯基-N苯基马来酰亚胺。
反应通常在约50至约100℃的温度下进行约1小时至4小时。马来酰亚胺对胺基基团的当量比为约0.95∶1至约1.05∶1,1∶1的比率为佳。然后可除去任何过量的马来酰亚胺以提供100%树脂产品,或者过量的马来酰亚胺也可以留在产品中并作为增塑剂起作用。如果使用过量的胺,通常是可容许的,但是此类的产品会具有较高的活性,从而缩短了总体系的贮存时间。
制备本发明的聚天冬酰亚胺的方法可在溶液中或无溶剂的情况下实施。溶剂也可在合成过程之后加入,例如,用来降低粘度。合适的溶剂包括任何有机溶剂,优选那些根据表面涂料技术已知不与任何反应参与物反应的溶剂。实例包括乙酸正丁酯、乙酸羟甲基丙酯、甲苯、二甲苯和高级芳香族溶剂(诸如Exxon的Solvesso溶剂)。
依据本发明制备的聚天冬酰亚胺可在合成过程结束后直接用作多异氰酸酯的活性组分。
本发明的聚天冬酰亚胺的一种用途是由两组分涂料组合物制备涂层,该涂料组合物包括作为粘合剂的以下组合
a)多异氰酸酯组分,和
b)异氰酸酯-活性组分,其含有
b1)一种或多种本发明的聚天冬酰亚胺,和
b2)任选的其它已知的异氰酸酯-活性组分。
合适的多异氰酸酯组分a)是已知的且包括聚氨酯化学中已知的多异氰酸酯,例如,低分子量的多异氰酸酯和由这些低分子量的多异氰酸酯制得的漆料多异氰酸酯(lacquer polyisocyanate)。优选的是表面涂料技术中已知的漆料多异氰酸酯。这些漆料多异氰酸酯可含有缩二脲基团、异氰尿酸酯基团、脲基甲酸酯基团、脲二酮基团、碳二亚胺基团和/或氨基甲酸乙酯基团,并优选由脂环族多异氰酸酯制备得到。
适用于本发明的、或用于制备漆料多异氰酸酯的低分子量多异氰酸酯是那些分子量为140至300的多异氰酸酯,诸如1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)、2,2,4-和/或2,4,4-三甲基-六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、2-甲基-1,5-二异氰酸基戊烷、1,4-二异氰酸基环己烷、1-异氰酸基-3,3,5-三甲基-5-异氰酸基-甲基环己烷(IPDI)、2,4-和/或4,4’-二异氰酸基-二环己基甲烷、1-异氰酸基-1-甲基-3(4)-异氰酸基甲基环己烷(IMIC)、2,4-和/或2,6-六氢甲代亚苯基二异氰酸酯(H6TDI)、2,4-和/或4,4’-二异氰酸基二苯基甲烷或这些同分异构体与它们的高级同系物(可通过已知的方法由苯胺/甲醛的缩合产物的光气化作用得到)的混合物、2,4-和/或2,6-二异氰酸基甲苯、和它们的混合物。使用低分子量的多异氰酸酯本身不是首选。同样,使用由芳族多异氰酸酯如2,4-和/或2,6-二异氰酸基甲苯制得的漆料多异氰酸酯也不怎么好。含有氨基甲酸乙酯基团的漆料多异氰酸酯最好是基于分子量为62至300的低分子量多元醇化合物,诸如乙二醇、丙二醇和/或三羟甲基丙烷。
优选的用作组分a)的漆料多异氰酸酯是那些基于1,6-六亚甲基二异氰酸酯、NCO含量为16重量%至24重量%、23℃下最大粘度为10000毫帕秒-较优的为3000毫帕秒的多异氰酸酯。优选的还有那些基于TPDI的异氰酸酯。
任选的原料组分b2)是已知的含有至少两个异氰酸酯-活性基团的化合物,异氰酸酯-活性基团包括在受潮或/和受热的效应下可与异氰酸酯基团反应的基团。实例包括羟基官能聚丙烯酸酯、聚酯多元醇和聚醚多元醇和现有技术中已知类型的天冬氨酸酯和醛亚胺。也可以使用这些化合物的混合物。
依据本发明,对在粘合剂中使用的组分a)、b1)和(任选的)b2)的量加以选择以使异氰酸酯基团对异氰酸酯-活性基团的当量比为约0.8∶1至约2.0∶1,较优的约0.8∶1至约1.2∶1。
依据本发明,粘合剂的制备方法是在没有溶剂的情况下、或者是在聚氨酯表面涂料技术中常用的溶剂存在下,将各个组分混合。合适的溶剂包括乙酸乙酯、乙酸丁酯、乙酸甲氧基丙酯、甲基异丁基酮、甲基乙基酮、二甲苯、N-甲基吡咯烷酮、石油溶剂油、氯苯、Solvesso溶剂或它们的混合物。
优选地,根据本发明,粘合剂组分a)和b)对涂料组合物中的溶剂的重量比为约40∶60至约100∶0,约60∶40至约100∶0更佳。
涂料组合物还可以含有表面涂料技术中已知的添加剂。这些添加剂包括颜料、填充物、流动控制剂、催化剂和防沉降剂。
由依据本发明的涂料组合物制得的涂层性质可通过适当选择原料组分a)、b1)和b2)的类型和比率来调节。
涂料组合物可通过任何已知的方法以单层或多层的形式施涂到任何基材上,例如,通过喷涂、涂漆、浸渍、浮涂(flood)或使用辊或涂布机来施涂。依据本发明的涂料组合物适用于在基材上制备涂层,诸如在金属、塑料、木材或玻璃上。涂料组合物特别适用于涂敷用来生产车身、机器、外挂板、桶和容器的不锈钢板材。在施涂本发明的涂料组合物之前,可先给基材上合适的底漆。涂层的干燥可在约0至160℃的温度下进行。
本发明的聚天冬酰亚胺可在合成过程完成后直接使用,因为与现有技术的天冬氨酸酯相比,可以达到几乎百分之百的转化度。产物对异氰酸酯表现出合理的而不是剧烈的活性。因为它们粘度低,所以,作为活性稀释剂,它们远不只是以前使用的污染环境的有机溶剂的合适的替代品,因此使用在高质量、低溶剂或甚至不含溶剂的、高固体的两组分涂料组合中。
马来酰亚胺的反应比马来酸二烷基酯要快得多,这是因为在马来酰亚胺中不可能发生顺反异构化,而顺反异构化出现在马来酸酯异构化为延胡索酸酯时,且使反应缓慢。这是一个优势,因为减少了合成时间且消除了老化过程。另一个优势在于琥珀酰亚胺部分不能象天冬氨酸酯一样进一步转化(在用异氰酸酯固化后)形成乙内酰脲环结构。此类乙内酰脲环的形成伴随着醇的脱去,这会导致涂层的收缩。而本技术的另一个优势在于可能形成基于如Jeffamine多胺之类的慢胺(slow amine)天冬酰亚胺。令人惊喜的是,与Jeffamine
Figure 200510125045210000210003_8
多胺和马来酸二乙酯的反应相比,基于Jeffamine
Figure 200510125045210000210003_9
多胺和马来酰亚胺的产物可在短时间内完全形成。与马来酸二乙酯和Jeffamine
Figure 200510125045210000210003_10
多胺的反应相比,马来酰亚胺与Jeffamine
Figure 200510125045210000210003_11
多胺的反应可在数个小时内反应完全,而马来酸二乙酯和Jeffamine
Figure 200510125045210000210003_12
多胺的反应如此之慢以致于6个月内只有50%转化为天冬氨酸酯。这给更为灵活地合成天冬氨酸酯类共反应物提供了可能性。
如无相反指示,以下实施例中所有的份数和百分数都以重量计。
                          实施例
胺1是Jeffamine
Figure 200510125045210000210003_13
T-3000。
胺2-给一圆底烧瓶配置搅拌器、加热罩、氮气进口、热电偶和加料漏斗。在室温下向烧瓶中加入1170份(1.0当量)的Jeffamine
Figure 200510125045210000210003_14
T-3000。然后加入125.13份(1.0当量)的N-乙基马来酰亚胺。烧瓶的温度上升到60℃。然后将反应在60℃保持24小时,此时碘量滴定表明反应进行完全。反应混合物冷却至室温。透明的近无色的最终产物的粘度为1420厘泊,胺值为46.9:(理论胺值:43.3)。
对比例-给一圆底烧瓶配置搅拌器、加热罩、氮气进口、热电偶和加料漏斗。在室温下向烧瓶中加入500份(0.5当量)的Jeffamine
Figure 200510125045210000210003_15
T-3000。然后加入62.6份(0.5当量)的马来酸二乙酯。烧瓶的温度上升到60℃。然后将反应在60℃保持24小时,此时碘量滴定表明反应只完成了24%。将反应混合物冷却并在室温下保持2个月,此时碘量滴定表明向天冬氨酸酯的转化只完成了50%。
将实施例1中的样品与Desmodur N-3300(NCO含量为21.8重量%、当量重量为192的三聚己烷二异氰酸酯)以(NCO∶NH)比率为1的指数手工混合。在Brookfield粘度计上测量粘度。样品干燥时间通过对混合样品在玻璃上进行刮涂来测量。样品以10密耳湿进行刮涂。每隔2分钟,将一棉球压在刮涂面上以测试膜的固化。当棉球不留下印迹时,样品膜即完全固化。Shore D硬度通过将混合样品倒入铝杯中并在3天后用D-2型Shore硬度计按ASTM D2240来测量。
Figure G051C5045220051129D000081
虽然在前文中为了举例说明的目的对本发明进行了详细的描述,但应理解,这些详细描写仅仅是为了该目的,本领域一般技术人员可对其进行修改,而不背离本发明的精神和范围,除由权利要求书所限制者。

Claims (5)

1.一种如下式所示的聚天冬酰亚胺:
Figure FSB00000090553900011
其中,X代表n价的聚醚基,所述聚醚基为通过从对应于通式X-(NH2)n的聚醚胺中除去n个氨基基团所得,其中所述聚醚胺的数均分子量为200至6000,选自聚环氧丙烷二胺、聚环氧丙烷三胺和聚环氧丙烷四胺,并任选含有其它官能团,所述的官能团或者对异氰酸酯基团有反应活性、或者在最高为100℃的温度下对异氰酸酯基团呈惰性,
R2和R3任选等同或不同,并代表选自下组的部分:i)氢;ii)直链或支链的C1至C8烷基基团,所述烷基基团可最多被三个含有6至10个碳原子的芳基基团所取代;iii)C6至C10芳基基团,所述芳基基团可最多被三个含有1至3个碳原子的烷基基团所取代;和iv)R2和R3一起形成五元或六元的环烷基基团,所述环烷基基团被0到3个含有1至3个碳原子的烷基基团所取代,
R1代表选自下组的部分:i)氢;ii)直链或支链的C1至C8烷基基团,所述烷基基团可最多被三个含有6至10个碳原子的芳基基团取代;iii)C6至C10芳基基团,所述芳基基团可最多被三个含有1至3个碳原子的烷基基团所取代,以及
n代表2至4的整数。
2.一种制备如下式所示的聚天冬酰亚胺的方法:
Figure FSB00000090553900012
其中,X代表n价的聚醚基,所述聚醚基为通过从对应于通式X-(NH2)n的聚醚胺中除去n个氨基基团所得,其中所述聚醚胺的数均分子量为200至6000,选自聚环氧丙烷二胺、聚环氧丙烷三胺和聚环氧丙烷四胺,并任选含有其它官能团,所述的官能团或者对异氰酸酯基团有反应活性、或者在最高为100℃的温度下对异氰酸酯基团呈惰性,
R2和R3任选等同或不同,并代表选自下组的部分:i)氢;ii)直链或支链的C1至C8烷基基团,所述烷基基团可最多被三个含有6至10个碳原子的芳基基团所取代;iii)C6至C10芳基基团,所述芳基基团可最多被三个含有1至3个碳原子的烷基基团所取代;和iv)R2和R3一起形成五元或六元的环烷基基团,所述环烷基基团被0到3个含有1至3个碳原子的烷基基团所取代,
R1代表选自下组的部分:i)氢;ii)直链或支链的C1至C8烷基基团,所述烷基基团可最多被三个含有6至10个碳原子的芳基基团取代;iii)C6至C10芳基基团,所述芳基基团可最多被三个含有1至3个碳原子的烷基基团所取代,以及
n代表2至4的整数,所述方法包括:在50℃至100℃的温度下,在溶液中或在无溶剂的情况下,使式X[-NH2]n所示的胺与马来酰亚胺以马来酰亚胺对氨基基团的当量比为0.95∶1至1.05∶1的比例发生反应,其中X和n如上文所定义,所述溶剂包括不与任意反应参与物反应的任何有机溶剂。
3.如权利要求2所述的方法,其特征在于,所述马来酰亚胺如下式所示:
Figure FSB00000090553900021
其中,R1、R2和R3如上所定义。
4.如权利要求2所述的方法,其特征在于,所述马来酰亚胺对氨基基团的当量比为1∶1。
5.一种两组分涂料组合物,所述组合物含有作为粘合剂的以下组合:
a)多异氰酸酯组分,和
b)异氰酸酯-活性组分,所述异氰酸酯-活性组分含有
b1)权利要求1所述的聚天冬酰亚胺,
b2)任选的其它异氰酸酯-活性化合物,其包含至少两个异氰酸酯活性基团,
其中,异氰酸酯基团对异氰酸酯-活性基团的当量比为0.8∶1至2.0∶1。
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