CN101568566A - 用于反应注塑成型以及用于喷涂系统的配方 - Google Patents
用于反应注塑成型以及用于喷涂系统的配方 Download PDFInfo
- Publication number
- CN101568566A CN101568566A CNA2008800012980A CN200880001298A CN101568566A CN 101568566 A CN101568566 A CN 101568566A CN A2008800012980 A CNA2008800012980 A CN A2008800012980A CN 200880001298 A CN200880001298 A CN 200880001298A CN 101568566 A CN101568566 A CN 101568566A
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- China
- Prior art keywords
- mixture
- phenylenediamine
- diethyl
- isophthalic acid
- methyl isophthalic
- Prior art date
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- 239000007921 spray Substances 0.000 title description 5
- 238000009472 formulation Methods 0.000 title 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 66
- 125000003118 aryl group Chemical group 0.000 claims abstract description 60
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims abstract description 44
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Abstract
本发明提供通过反应注塑制造的制品和喷涂层,以及用于形成这样的制品和涂层的方法。该涂层和制品是聚脲或聚脲氨酯。用于形成涂层和制品的成分包括至少(A)芳族多异氰酸酯和(B)由以下组分形成的混合物,该组分包括(i)至少一种多元醇和/或至少一种聚醚胺,(ii)芳族伯二胺和(iii)具有约12到约40个碳原子的脂肪族仲二胺,并且该脂肪族仲二胺中具有的氨基的烃基基团是仲或叔烃基基团。
Description
技术领域
本发明涉及经反应注塑或者经喷涂系统制造聚脲和聚脲氨酯的配方。
背景技术
在聚脲和聚氨酯-脲聚合物的制备中,有许多已表明可用作增链剂的多官能化合物,包括二醇和芳族二胺。这些化合物中没有具有足以使其普遍适用的反应性,并且对于通过利用它们制造的产品,部分化合物无法提供令人满意的性能。因而,仍然有必要寻求能够充当增链剂或固化剂的化合物。美国专利号4,806,616教导了在制备聚氨酯和聚脲时某些N,N′-二烷基苯二胺作为增链剂的应用。就此而论,还参见例如U.S.4,528,363,其教导了脂肪族仲二胺用作树脂粘合剂的一部分,以及U.S.6,218,480B1,其公开了芳族二胺用作用于聚氨酯-脲的固化剂。
聚氨酯、聚脲和聚氨酯-脲聚合物被用于喷涂层和反应注塑。喷涂层在混凝土涂层、建筑涂层、二次密封涂层、停放甲板涂层、防水涂层、减波涂层、屋顶涂层、桥梁涂层、隧道衬里、管道衬里、检修孔衬里、卡车厢衬等方面得到应用。反应注塑在制造用于汽车、娱乐车和农业设备的主体部分方面获得应用。就此而论,需要一种结合增链剂混合物的喷涂系统,其借助于具有适当胶凝时间的配方提供具有可接受的物理性能的涂层。类似地,需要一种结合增链剂混合物的反应注塑方法,提供具有适当的胶凝时间、具有适合的脱模性能以及具有可接受的物理性能的反应注射混合物。
发明概述
本发明提供喷涂层和通过反应注塑制造的制品,以及采用增链剂混合物用于喷涂层和用于反应注塑的方法。已经发现利用某些增链剂混合物提供具有希望的物理性能的聚脲和聚脲氨酯。因而,本发明的特征在于通过适当选择增链剂,可以根据希望的具体特性,定制涂层的反应性和物理性能。
本发明的实施方式是由包括至少(A)芳族多异氰酸酯;和(B)的成分形成的喷涂层,其中(B)是包含以下物质的组分形成的混合物:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
本发明的另一个实施方式是用于形成喷涂层的方法,该方法包括将至少(A)芳族多异氰酸酯和(B)包含以下物质的组分形成的混合物汇集在一起,
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
本发明的还有另一个实施方式是通过反应注塑形成的制品,由包括至少以下的成分形成该制品:(A)芳族多异氰酸酯和(B)由包含以下物质的组分形成的混合物:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
本发明的又一个实施方式是用于制备反应注塑产品的方法。该方法包括I)将至少(A)芳族多异氰酸酯和(B)包含以下(i)、(ii)和(iii)的组分形成的混合物汇集在一起。以形成成型混合物;II)将I)中形成的成型混合物注入模具形成模制产品;和III)打开模具并移除II)中形成的产品。在混合物(B)中,用于形成该混合物的(i)、(ii)和(iii)为:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
由随后的描述以及所附的权利要求书,本发明的这些和其它实施方案以及特征将更明显。
发明的进一步详述
在本发明中,涂层或制品是聚合物,其为聚脲或聚脲氨酯(有时被称为聚脲-聚氨酯(polyurea-polyurethanes))。类似地,本发明的方法生产聚合物,该聚合物为聚脲或聚脲氨酯。
为了形成聚氨酯-脲,使多异氰酸酯(通常并且优选二异氰酸酯)与二元醇反应。为了形成聚脲,使多异氰酸酯(通常并且优选二异氰酸酯)与聚醚胺反应。
I.成分
A.芳族多异氰酸酯
在本发明的涂层、制品和方法中的芳族多异氰酸酯(A)是具有至少两个异氰酸酯基团的有机多异氰酸酯。通常,该异氰酸酯具有至少约0.1wt.%的游离-NCO含量。优选该异氰酸酯具有约10wt.%到约35wt.%的游离-NCO含量。可用于本发明实践的芳族多异氰酸酯包括亚苯基二异氰酸酯、甲苯二异氰酸酯(TDI)、二甲苯二异氰酸盐、1,5-萘二异氰酸酯、氯亚苯基2,4-二异氰酸酯、联甲苯二异氰酸酯(bitoluene diisocyanate)、联茴香胺二异氰酸酯、联甲苯胺二异氰酸酯、烷基化苯二异氰酸酯、亚甲基间隔的芳族二异氰酸酯例如亚甲基联苯二异氰酸酯、特别是4,4-亚甲基联苯二异氰酸酯和2,4-亚甲基联苯二异氰酸酯(MDI)、亚甲基间隔的芳族二异氰酸酯的烷基化类似物(例如3,3′-二甲基-4,4′-联苯甲烷二异氰酸酯)以及聚合的亚甲基联苯二异氰酸酯。在本发明的实践中可以采用两种以上芳族多异氰酸酯的混合物。优选的芳族多异氰酸酯包括2,4-亚甲基联苯二异氰酸酯(MDI)、4,4-亚甲基联苯二异氰酸酯及其混合物。在例如US 4,595,742中也教导了可以采用的异氰酸酯的例子。
B.多元醇和聚醚胺
典型地用于制造聚脲氨酯的异氰酸酯反应性多元醇和典型地用于制造聚脲和聚脲氨酯的聚醚胺(有时被称作胺封端的多元醇)分子量从约60到超过6,000变化。多元醇可以是二羟基、三羟基或多羟基的多元醇,但通常是二羟基的。适宜的多元醇的例子包括聚(氧乙烯)二醇(poly(ethyleneoxy)glycols)、二丙二醇、聚(氧丙烯)二醇、二丁二醇、聚(氧丁烯)二醇以及通常被称为聚己酸内酯的由己内酯聚合的二醇。在本发明的实践中可以采用两种以上多元醇的混合物。用于制造聚脲的聚醚胺是单端胺基多元醇(amine-cappedpolyols),其是多元醇和带有烯化氧的胺以及含有单端胺基羟基(amine-cappedhydroxyl)的聚酯的反应产物。在本发明的实践中可以采用两种以上聚醚胺的混合物。聚醚胺典型地具有约200到约6000的分子量。可从亨斯迈化学公司(Huntsman Chemical Company)获得的被称为的几种市场上可买到的聚醚胺,包括T-5000,分子量约5000的聚氧丙烯三胺,XTJ-509,分子量约3000的聚氧丙烯三胺,XTJ-510,分子量约4000的聚氧丙烯二胺,以及D-2000,分子量约2000的聚氧丙烯二胺。在本发明的实践中T-5000和D-2000是优选的聚醚胺。
C.增链剂
本文件始终将组分(ii)和(iii)一起称作增链剂。本发明中采用的增链剂是由芳族伯二胺和脂肪族仲二胺形成的,其中脂肪族仲二胺具有约12到约40个碳原子,并且其中该氨基的烃基基团是仲或叔烃基基团。该组分可以按各种比例存在于增链剂组合物中;优选的比率随用于形成涂层或制品所希望的反应性而改变。
1.组分(ii)
芳族伯二胺是用于本发明的增链剂的组分(ii)。
可用于本发明的一类芳族伯二胺是这样的芳族伯二胺,其中邻接每个氨基的至少一个位置具有作为取代基的氢原子,并且芳族伯二胺或者是环上有两个氨基基团的一个苯环的形式,或者通过亚烷基桥连接并在每个环上有一个氨基基团的两个苯环的形式。苯环可以有但不是必须有一个或更多在苯环上的烃基基团。当在苯环上存在烃基基团时,烃基基团可以相同或不同。当氨基基团都在一个苯环上时,氨基基团可以处于环上相对于彼此的任意位置;优选氨基基团是相对于彼此的间位或对位。当氨基基团在通过亚烷基桥连接的两个苯环上时,它们可以处于环上的任意位置;优选氨基基团是相对于亚烷基桥的间位或对位。双环二胺的亚烷基桥具有从一个到约六个碳原子;优选亚烷基桥具有从一个到约三个碳原子。更优选亚烷基桥具有一个或两个碳原子;非常优选的是具有一个碳原子的亚烷基桥。当在苯环上存在烃基基团时,烃基基团可以相同或不同。在芳环上适宜的烃基基团的例子包括甲基、乙基、丙基、异丙基、正丁基、仲丁基、叔丁基、戊基、环戊基、己基、甲基环己基、庚基、辛基、环辛基、壬基、癸基、十二烷基、苯基、苄基等。在芳族二亚胺的苯环上优选的烃基基团(邻接亚氨基基团)是具有从1到约6个碳原子的直链或支链烷基基团;特别优选的烃基基团是甲基、乙基、异丙基、丁基以及这些基团中两种或更多的混合物。这里,对于丁基基团优选包括正丁基、仲丁基和叔丁基基团。当在苯环上存在一个或更多烃基基团时,该烃基基团可以具有从1到约20个碳原子;优选烃基基团具有从1到约6个碳原子。
在一个苯环上具有两个氨基的这类适宜的芳族伯二胺包括但不局限于1,2-苯二胺、1,3-苯二胺、1,4-苯二胺、4-乙基-1,2-苯二胺、2-异丙基-1,3-苯二胺、4-叔丁基-1,3-苯二胺、2-戊基-1,4-苯二胺、4,5-二己基-1,2-苯二胺、4-甲基-5-庚基-1,3-苯二胺、4,6-二正丙基-1,3-苯二胺、2,5-二辛基-1,4-苯二胺、2,3-二乙基-1,4-苯二胺和4,5,6-三己基-1,3-苯二胺。
适宜的这类芳族伯二胺(其中在两个苯环的每一个上有一个氨基基团)的例子包括2,2′-亚甲基双(苯胺)、2,3′-亚甲基双(苯胺)、2,4′-亚甲基双(苯胺)、3,3′-亚甲基双(苯胺)、3,4′-亚甲基双(苯胺)、4,4′-亚甲基双(苯胺)、4,4′-(1,2-乙二基)双(苯胺)、3,4′-(1,3-丙二基)双(苯胺)、2,2′-亚甲基双(5-叔丁基苯胺)、3,3′-亚甲基双(2-甲基苯胺)、3,3′-亚甲基双(5-戊基苯胺)、3,3′-亚甲基双(6-异丙基苯胺)、4,4′-亚甲基双(2-甲基苯胺)、4,4′-亚甲基双(3-仲丁基苯胺)、4,4′-(1,2-乙二基)双(2-甲基苯胺)、3,3′-亚甲基双(2,4-二戊基苯胺)、3,3′-亚甲基双(5,6-二异丙基苯胺)、4,4′-亚甲基双(2,3-二仲丁基苯胺)、4,4′-亚甲基双(3,5-二叔丁基苯胺)等。
可用于本发明的另一种芳族伯二胺,优选的芳族伯二胺类型是这样的芳族伯二胺,其中每个邻接(直接地相邻)氨基基团的位置均带有烃基基团,并且该芳族伯二胺或者为环上具有两个氨基基团的一个苯环的形式,该氨基基团相对于彼此间位或对位,或者是通过亚烷基桥连接并在每个环上具有一个氨基基团的两个苯环的形式。在苯环上的烃基基团(邻接氨基基团)通常具有最高约20个碳原子,并且烃基基团可以相同或不同。双环伯二胺的亚烷基桥具有从1到约6个碳原子;优选该桥具有从1到约3个碳原子。更优选亚烷基桥具有1或2个碳原子;尤其优选作为亚烷基桥的是亚甲基基团。特别优选的在一个以上苯环上的烃基基团是甲基、乙基、异丙基、丁基以及两种以上这些基团的混合物。这里,丁基基团包括正丁基、仲丁基和叔丁基基团。
更优选的在一个苯环上有两个氨基基团的芳族伯二胺具有相对于彼此间位的氨基基团。非常优选的烃基基团是甲基、乙基、异丙基、丁基及其混合物,对于丁基基团优选包括正丁基、仲丁基和叔丁基基团。特别优选的是其中在两个间位氨基基团之间的烃基基团是甲基基团而剩余的两个烃基基团是乙基基团的芳族伯二胺,以及其中在两个间位氨基基团之间的烃基基团是乙基基团而剩余两个烃基基团中一个是甲基基团另一个是乙基基团的芳族伯二胺,及它们的混合物。更优选的芳族伯二胺还是那些,其中在两个苯环中的每一个上有一个氨基基团,两个苯环经亚烷基桥连接,并具有相对于亚烷基桥对位的两个氨基基团。尤其优选的这类芳族伯二胺是一种化合物,其中邻接氨基基团的每个烃基基团是乙基基团,并且亚烷基桥是亚甲基基团。
优选的芳族伯二胺是这样一种,其中每个邻接氨基基团的位置均带有烃基基团,并且该芳族伯二胺为环上具有两个氨基基团的一个苯环的形式,该氨基基团相对于彼此间位或对位,或者其中该芳族伯二胺具有相对于彼此间位的氨基基团,和/或邻位烃基基团是甲基、乙基、异丙基、丁基或它们的混合物。
更优选的芳族伯二胺的例子包括3,6-二正丁基-1,2-苯二胺、2,4,6-三乙基-1,3-苯二胺、2,4-二乙基-6-甲基-1,3-苯二胺、4,6-二乙基-2-甲基-1,3-苯二胺、2,4-二异丙基-6-甲基-1,3-苯二胺、2-甲基-4,6-二仲丁基-1,3-苯二胺、2-乙基-4-异丙基-6-甲基-1,3-苯二胺、2,3,5-三正丙基-1,4-苯二胺、2,3-二乙基-5-仲丁基-1,4-苯二胺、3,4-二甲基-5,6-二庚基-1,2-苯二胺、2,4,5,6-四正丙基-1,3-苯二胺、2,3,5,6-四乙基-1,4-苯二胺、2,2′-亚甲基双(6-正丙基苯胺)、2,2′-亚甲基双(3,6-二正丙基苯胺)、3,3′-亚甲基双(2,6-二正丁基苯胺)、4,4′-亚甲基双(2,6-二乙基苯胺)、4,4′-亚甲基双(2,6-二异丙基苯胺)、4,4′-亚甲基双(2-异丙基-6-甲基苯胺)、4,4′-(1,2-乙二基)双(2,6-二乙基苯胺)、4,4′-(1,2-乙二基)双(2,6-二异丙基苯胺)、2,2′-亚甲基双(3,4,6-三戊基苯胺)、3,3′-亚甲基双(2,5,6-三己基苯胺)、4,4′-亚甲基双(2,3,6-三甲基苯胺)、4,4′-亚甲基双(2,3,4,6-四甲基苯胺)等。在这些更优选的芳族伯二胺类型中,特别优选的是4,4′-亚甲基双(2,6-二乙基苯胺)、4,4′-亚甲基双(2,6-二异丙苯胺)以及2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺(DETDA,100)的混合物。
本领域技术人员将认可这里有几种命名用于本发明的芳族伯二胺的方式。例如,结构
其代表本发明中特别优选的芳族伯二胺,能够被称为包括2,4-二乙基-6-甲基-1,3-苯二胺(benzenediamine)、2,4-二乙基-6-甲基-1,3-亚苯基二胺(phenylenediamine)、3,5-二乙基-2,4-二氨基甲苯或3,5-二乙基-甲苯-2,4-二胺。类似地,结构
其代表本发明中另一特别优选的芳族伯二胺,能够被称为4,4′-亚甲基双(2,6-二乙基苯胺)、4,4′-亚甲基双(2,6-二乙苯胺)或3,3′,5,5′-四乙基-4,4′-二氨基二苯基甲烷。
2.组分(iii)
组分(iii)是具有氨基烃基基团的脂肪族仲二胺,该氨基烃基基团的烃基基团是仲或叔烃基基团。该脂肪族仲二胺的氨基烃基基团的烃基基团可以是环状或枝状。优选氨基烃基基团的烃基基团是具有从3个到约12个碳原子的支链烷基基团。适合的氨基烃基基团的烃基基团的例子包括异丙基、仲丁基、叔丁基、3,3-二甲基-2-丁基、3-戊基、环戊基、4-己基、环己基、甲基环己基、环辛基、5-壬基等。
脂肪族仲二胺是烃基仲二胺,其中该二胺的烃基部分是脂肪族的,“烃基部分”指连接两个氨基基团的部分。脂肪族二胺的烃基部分可以是环状、枝状或直链。优选环状或直链作为该脂肪族仲二胺的烃基部分。当该二胺的烃基部分是环状时,环状部分可以是稠环、双环或三环体系(三环体系可以包含稠环和/或双环)。氨基基团可以直接连接到环上,或者一个或两个氨基基团可以连接到该环的取代基基团上;优选至少一个氨基基团连接到该环上。脂肪族仲二胺典型地具有约12到约40个碳原子;优选该脂肪族仲二胺具有约15到约25个碳原子。基于当量基准,增链剂组合物中芳族伯二胺比脂肪族仲二胺的相对比例优选为约9∶1到约1∶9;更优选基于当量基准该相对比例为约3∶1到约2∶3。基于重量,增链剂组合物中芳族伯二胺比脂肪族仲二胺的相对比例优选为约6∶1到约1∶6;更优选基于重量该相对比例为约2∶1到约1∶3。
可用于本发明的脂肪族仲二胺包括但不局限于N,N′-二(1-环丙基乙基)-1,5-二氨基戊烷、N,N′-二(3,3-二甲基-2-丁基)-1,5-二氨基-2-甲基戊烷、N,N′-二仲丁基-1,6-二氨基己烷、N,N′-二环己基-1,6-二氨基己烷、N,N′-二(3-戊基)-2,5-二甲基-2,5-己二胺、N,N′-二(2,4-二甲基-3-戊基)-1,3-环己烷双(甲胺)、N,N′-二异丙基-1,7-二氨基庚烷、N,N′-二仲丁基-1,8-二氨基辛烷、N,N′-二(2-戊基)-1,10-二氨基癸烷、N,N′-二(3-己基)-1,12-二氨基十二烷、N,N′-二(3-甲基-2-环己烯基)-1,2-二氨基丙烷、N,N′-二(2,5-二甲基环戊基)-1,4-二氨基-丁烷、N,N′-二(3,3,5-三甲基环己基)-1,5-二氨基戊烷(N,N′-di(isophoryl)-1,5-diaminopentane)、N,N′-二(薄荷基)-2,5-二甲基-2,5-己二胺和N,N′-二(3,3-二甲基-2-丁基)-3(4),8(9)-双(氨甲基)-三环[5.2.1.0(2,6)]癸烷(也被称为N,N′-二(3,3-二甲基-2-丁基)-TCD二胺)。优选的脂肪族仲二胺包括N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷、N,N′-二环己基-1,6-二氨基己烷和N,N′-二(3,3-二甲基-2-丁基)-TCD二胺。
基于当量基准,芳族伯二胺比脂肪族仲二胺的相对比例可以是约5∶1到约1∶5。基于当量基准,优选芳族伯二胺比脂肪族仲二胺的相对比例是约3∶1到约1∶3。
多元醇和/或聚醚胺比增链剂的相对比例通常在约1∶1到约1∶4的范围内,并且优选在约1∶1.5到约1∶3的范围内。
D.其它成分
可以任选地使用的其它成分包括但不局限于阻燃剂或燃烧抑制剂、催化剂、溶剂、稀释剂、水分净化剂、促进剂、抗氧化剂、偶联剂、稳定剂、润滑剂、表面活性剂、乳化剂、粘度控制剂、增塑剂、杀菌剂、抗静电剂、填料、纤维补强剂例如切碎的玻璃纤维、颜料、染料、起泡剂、发泡剂、触变剂、泡孔调节剂(cell regulators)以及聚合物和树脂添加剂。当通过反应注塑形成聚脲或聚氨酯-脲聚合物时,该任选的成分还包括内和/或外脱模剂。
II.本发明的方法
在本发明的方法中,“A方”反应物包括多异氰酸酯,以及“B方”反应物包括与二胺增链剂连同任何任选的成分一起混合的多元醇和/或聚醚胺。在本发明的一些方法中,多异氰酸酯与多元醇和/或聚醚胺混合形成准预聚物。当采用准预聚物时,该准预聚物至少是部分A方反应物;B方反应物还包括与二胺增链剂混合的多元醇和/或聚醚胺。在本发明的实践中,采用准预聚物是生产聚脲的优选方法。
A.喷涂层
通过采用为混合并喷涂双组分液体化学体系设计的高压冲击喷涂装置制备本发明的涂层。该液体体系由多异氰酸酯(A方)与多元醇和/或聚醚胺以及增链剂(B方)组成,在该装置中于高压下将A方及B方组分混合并喷涂到基质上,以便在该基质上形成聚脲或聚脲氨酯涂层。能够获得低到约0.03英寸(0.08cm)的涂层厚度。通常,本发明的涂层具有在约0.05英寸到约0.125英寸(0.32cm)范围内的厚度,不过不是这些厚度的涂层也在本发明的范围内。能够获得具有希望的胶凝时间的涂层而不会不利地影响涂层的性能,例如打磨性能(sandability)、持久性、固化温度、涂层外观以及涂覆参数如喷涂性。可以将反应物喷涂以在各种物质上产生涂层,该物质包括玻璃或合成纤维、纺织品或无纺基材、木材、混凝土、石料以及金属,包括金属箔和钢。如果希望,在涂覆反应物之前和/或期间可以将基材加热。
在喷涂层中,通常将多异氰酸酯(A方)和多元醇和/或聚醚胺以及增链剂(B方)置于分离的容器中,然后通过可变的或固定的喷嘴同时喷在基材上。通常并且优选A方反应物和B方反应物以大体上相等的体积(例如,1∶1体积比)喷涂。其它体积比例如大体上2∶1(A方比B方)是可能的,并且也在本发明的范围内。
应强调在一个或者两个物流中不能发生不合逻辑的改变。未实质上影响实施该方法的中断包括在本发明的范围内。为了避免超过技术的法律措词的解释,在描述本发明过程中确实已经谨慎采用术语“大体上相等”和“大体上2∶1”。但无论使用什么术语,应当如同本领域技术人员在彻底、无偏见地阅读了本公开的全部内容,并由这样的阅读获得的本发明的精神之后,再执行该方法那样实施该方法。
希望的胶凝时间随具体的基材和涂覆所形成的涂层而变化,但约2秒到约50秒的胶凝时间是代表性的。优选胶凝时间也可以变化,但常常在约6秒到约15秒的范围内。如上所述,改变增链剂的组分和/或它们的相对比例能够改变涂层的胶凝时间。
B.反应注塑
通过反应注塑制备本发明的制品。在反应注塑中,将多异氰酸酯(A方反应物)和多元醇和/或聚醚胺连同增链剂(B方反应物)汇集在一起,注入模具,并暴露于条件下以便制备固化制品。其后从模具中移出该固化制品。
更具体地说,反应注塑方法包括将A方和B方反应物汇集在一起,通常在注入之前。可以在混料头中进行汇集,由该混料头将混合物注入模具。推荐和优选供给反应物使它们按希望的重量比汇集。反应物在混合后迅速反应,形成聚脲或聚氨酯/聚脲聚合物;在反应注塑中,希望使聚合物主要在模具中成型以形成模制品。在模制之前通常将反应物保存在分离的容器中。
希望的胶凝时间随形成的制品的具体应用而变化,但约1秒到约20秒的胶凝时间是代表性的。优选胶凝时间也可以变化,但常常在约2秒到约6秒的范围内。如上所述,改变增链剂的组分和/或它们的相对比例能够改变用于形成制品的胶凝时间。
为了说明,给出下列实施例,并不是试图限制本发明的范围。
在下列实施例中,用装有2.5加仑(9.5L)进料槽、60英尺(18m)的0.25英寸(6.35mm)内径高压软管和内部机械多进料混合喷枪(固瑞克公司(Graco,Inc.),Fusion MP)的双部件比例喷涂机(Graco,Inc.,型号#E-XP2)喷涂反应物。使用直接撞冲混合模块(Graco,Inc.,型号#XF1818),喷嘴是金属合金(Graco,Inc.,商标CeramTip#424)。该装置被设计为输送1∶1体积比的A方和B方。
实施例1(比较)
通过将两种聚醚胺D-2000和T-5000(亨斯迈聚氨酯(Huntsman Polyurethanes))、2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺(100,雅宝公司(Albemarle Corporation))以及N,N′-二(仲丁基)-4,4′-亚甲基双(苯胺)(4200,Dorf Ketal公司)的混合物混合在一起制造B方反应物。在每次运行中变化B方的比例;参见表1。称量每种成分精确到0.1克,放入装有罐盖的加衬里的5加仑(~22L)罐中。制造每批12公斤。在所有成分已放入5加仓的罐后,封闭该罐并放置在水平的鼓形滚筒上,在环境温度下翻滚4小时直到混合物内部均匀。
将B方反应物装载入喷涂机的槽内,并在该槽内设置氮气衬垫(55psi)。将A方反应物装载入喷涂机的另一槽内,并在该槽内设置氮气衬垫(55psi,3.79×105Pa)。用氮气清扫软管中的空气,4~5升材料冲过软管,除去所用系统以前的任何残留物。将槽内的反应物加热到50℃并将混合/喷涂压力设定在2100psi(1.45×107Pa)。
通过将一定量液体反应混合物喷涂到立式面板上,同时测量从喷涂冲击直到涂层不再移动的时间,测量得到胶凝时间。
通过采用具有抛光面的金属面板制造面板模具,该面板装有4个0.125英寸(3.18mm)厚的条以在四边设置障碍。用硅酮材料(Chesterton 983,脱模剂)预处理该模具以促进涂层的移除。当面板模具处于水平位置,以多次的方式将反应物的混合物喷涂在面板模具上,生产样品面板。使涂层于室温下在面板模具中固化直到能够将它们移除而不使得到的面板变形(~1~2hr)。24小时后,根据每种适用于ASTM测试的尺寸从面板上切割测试部分。测试前将测试部分在75°F(+/-5°F)(~24℃+/-2.8℃)下老化两个星期。
结果总结在表1中。所示每个样品是三次运行的平均结果,每次运行采用四个样品。样品1喷涂过快。超出两个标准偏差的结果不用于确定表1中所示的值。
表1
实施例2
表2
应了解无论在本文中用化学名称或化学式提及的反应物和组分,不论以单数或复数提及,被确定为如同在与用化学名称或化学类型提及的另一种物质(例如,另一种反应物、溶剂等)接触之前它们存在的一样。无论在所得混合物或溶液或反应介质中发生什么初级化学变化、转化和/或反应(如果有),这些变化、转化和/或反应是在按照本公开要求的条件下将特定的反应物和/或组分汇集到一起的正常结果。因而反应物和组分被确定为与执行希望的化学操作或反应或者在形成用于实施希望的操作或反应的混合物中有关的汇集到一起的成分。此外,即使实施方案可能以现在时态(“由…组成”、“包括”、“是”等)提到物质、组分和/或成分,涵义是物质、组分和/或成分如同它按照本公开与一种或更多其它物质、组分和/或成分最初接触、掺合或混合之前存在的状态。
除非另外清楚地指明,如果以及如本文所用的冠词“a”或“an”不是试图限制并且也不应当被解释为将权利要求限制或描述成该冠词涉及的单个要素。更合适地,除非文中另外清楚地表明,如果以及如本文所用的冠词“a”或“an”试图覆盖一种或更多这种要素。
此外,即使权利要求可能以现在时态(例如,“包括”、“是”等)提到物质、组分和/或成分,涵义是物质按照本公开与一种或更多其它物质最初接触、掺合或混合之前存在的状态。
本说明书任何部分提及的每个专利或其它出版物或公开的文献通过引用并入本公开,就像本文完全地阐述的那样。
在所附权利要求的精神和范围内容易对本发明作出相当大的改变。
Claims (23)
1.一种喷涂层,由包括至少(A)芳族多异氰酸酯和以下(B)混合物的成分形成,其中该(B)混合物是由包含以下物质的组分形成的:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
2.如权利要求1中所述的涂层,其中,
(ii)是芳族伯二胺,其中邻接氨基基团的每个位置均带有烃基基团,并且该芳族伯二胺为环上具有两个氨基基团的一个苯环的形式,该两个氨基基团相对于彼此是间位或对位,和/或
该脂肪族仲二胺的烃基部分是直链。
3.如权利要求1中所述的涂层,其中
(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,和/或
(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
4.如权利要求3中所述的涂层,其中(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,并且其中(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
5.如权利要求1-4中任一项所述的涂层,其中所述多异氰酸酯是4,4-亚甲基联苯二异氰酸酯、2,4-亚甲基联苯二异氰酸酯或其混合物。
6.一种用于形成喷涂层的方法,该方法包括将至少以下物质汇集在一起:
(A)至少一种芳族多异氰酸酯;和
(B)由包含以下物质的组分形成的混合物:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团;
以及,将混合物喷涂在表面上。
7.如权利要求6中所述的方法,其中
(ii)是芳族伯二胺,其中邻接氨基基团的每个位置均带有烃基基团,并且该芳族伯二胺为环上具有两个氨基基团的一个苯环的形式,该两个氨基基团相对于彼此是间位或对位,和/或
该脂肪族仲二胺的烃基部分是直链。
8.如权利要求6中所述的方法,其中
(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,和/或
(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
9.如权利要求8中所述的方法,其中(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,并且其中(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
10.如权利要求6-9中任一项所述的方法,其中所述多异氰酸酯是4,4-亚甲基联苯二异氰酸酯、2,4-亚甲基联苯二异氰酸酯或其混合物。
11.如权利要求6-10中任一项所述的方法,其中至少部分(i)是准预聚物。
12.一种通过反应注塑成型形成的制品,该制品由包括至少(A)芳族多异氰酸酯和以下(B)混合物的成分形成,其中该(B)混合物是由包含以下物质的组分形成的:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团。
13.如权利要求12所述的制品,其中
(ii)是芳族伯二胺,其中邻接氨基基团的每个位置均带有烃基基团,并且该芳族伯二胺为环上具有两个氨基基团的一个苯环的形式,该两个氨基基团相对于彼此是间位或对位,和/或
该脂肪族仲二胺的烃基部分是直链。
14.如权利要求12所述的制品,其中
(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,和/或
(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
15.如权利要求14所述的制品,其中(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,并且其中(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
16.如权利要求12-15中任一项所述的制品,其中所述多异氰酸酯是4,4-亚甲基联苯二异氰酸酯、2,4-亚甲基联苯二异氰酸酯或其混合物。
17.一种用于制备反应注塑成型产品的方法,该方法包括
I)将至少(A)芳族多异氰酸酯和(B)以下混合物汇集在一起形成成型混合物,该(B)混合物是由包含以下物质的组分形成的:
(i)至少一种多元醇和/或至少一种聚醚胺,
(ii)芳族伯二胺,和
(iii)脂肪族仲二胺,它具有约12到约40个碳原子,并且其中所具有的氨基的烃基基团是仲或叔烃基基团;
II)将I)中形成的所述成型混合物注入模具,形成模制产品;和
III)打开模具,移出在II)中形成的产品。
18.如权利要求17所述的方法,其中
(ii)是芳族伯二胺,其中邻接氨基基团的每个位置均带有烃基基团,并且该芳族伯二胺为环上具有两个氨基基团的一个苯环的形式,该两个氨基基团相对于彼此是间位或对位,和/或
该脂肪族仲二胺的烃基部分是直链。
19.如权利要求17所述的方法,其中
(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物,和/或
(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷。
20.如权利要求19所述的方法,其中(iii)是N,N′-二(3,3-二甲基-2-丁基)-1,6-二氨基己烷或N,N′-二环己基-1,6-二氨基己烷,并且其中(ii)是2,4-二乙基-6-甲基-1,3-苯二胺和4,6-二乙基-2-甲基-1,3-苯二胺的混合物。
21.如权利要求17-20中任一项所述的方法,其中(i)是至少一种聚醚胺。
22.如权利要求17-21中任一项所述的方法,其中所述多异氰酸酯是4,4-亚甲基联苯二异氰酸酯、2,4-亚甲基联苯二异氰酸酯或其混合物。
23.如权利要求17-22中任一项所述的方法,其中至少部分(i)是准预聚物。
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2466501B (en) * | 2008-12-23 | 2012-11-28 | Isothane Ltd | Method for preparing a composite material |
JP5427296B2 (ja) * | 2010-08-06 | 2014-02-26 | 川崎重工業株式会社 | ガス用調圧弁 |
CN106795316B (zh) * | 2014-06-11 | 2020-02-18 | 巴斯夫欧洲公司 | 用于制备集成绝热部件的聚氨酯化合物 |
GB201622030D0 (en) * | 2016-12-22 | 2017-02-08 | Hardshell Uk Ltd | Reinforced polymer coating |
NL2018902B1 (nl) * | 2017-05-11 | 2018-11-15 | Cleopatra B V | Werkwijze voor het vervaardigen van een zelfdragend product |
DE102019113433A1 (de) * | 2019-05-21 | 2020-11-26 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Bauteil mit einer Beschichtung und Verfahren zum Beschichten |
US11358169B2 (en) * | 2019-08-26 | 2022-06-14 | Raymond Micucci, JR. | Automated system for applying coating to a surface |
Family Cites Families (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2380420A (en) * | 1940-12-16 | 1945-07-31 | William S Emerson | Production of secondary and tertiary amines from nitrogen compounds |
US2497292A (en) * | 1946-05-07 | 1950-02-14 | Du Pont | Preparation of n-isobutyl hexamethylenediamines |
US2582128A (en) * | 1950-02-11 | 1952-01-08 | Rohm & Haas | Aldimines |
US2953579A (en) * | 1958-05-07 | 1960-09-20 | Shell Oil Co | Epoxy aldimines |
US2965605A (en) * | 1958-06-23 | 1960-12-20 | Shell Oil Co | Nu, nu'-dialkyl aromatic diamines |
US3209030A (en) * | 1962-07-09 | 1965-09-28 | Universal Oil Prod Co | Reductive alkylation of amines |
NL127232C (zh) * | 1963-03-12 | 1900-01-01 | ||
US3275567A (en) * | 1963-06-27 | 1966-09-27 | Engelhard Ind Inc | Method of preparing a sulfided platinum on carbon catalyst |
US3350450A (en) * | 1963-08-12 | 1967-10-31 | Uniroyal Inc | Process of preparing aromatic amines by the catalytic hydrogenation of aromatic nitro compounds |
GB1070759A (en) | 1964-02-13 | 1967-06-01 | Goodyear Tire & Rubber | Polyurethanes and method of making |
DE1518021C2 (de) * | 1964-05-25 | 1978-10-05 | Monsanto Co, St. Louis, Mo. (V-StA.) | Verfahren zur Herstellung von sekundären Aminen durch reduktive Alkylierung über die entsprechenden Imine |
CH481963A (de) * | 1967-06-08 | 1969-11-30 | Ciba Geigy | Neue härtbare Mischungen aus Diepoxydverbindungen, disekundären Aminen sowie mindestens 3 Aminwasserstoffatome enthaltenden Polyaminen |
US3538161A (en) * | 1967-10-20 | 1970-11-03 | Uniroyal Inc | Reductive alkylation of aromatic amino compounds utilizing platinum metal selendies and tellurides as catalysts |
US3625710A (en) * | 1969-06-25 | 1971-12-07 | Procter & Gamble | Aldimines as chocolate-like flavors |
NL7011639A (zh) * | 1969-08-11 | 1971-02-15 | ||
US3943158A (en) * | 1970-07-01 | 1976-03-09 | Bayer Aktiengesellschaft | Urea diisocyanate compositions |
US3761425A (en) * | 1971-02-19 | 1973-09-25 | Hoechst Ag | Process for preparing sulfided platinum on carbon catalysts |
US3952056A (en) * | 1972-02-07 | 1976-04-20 | Ciba-Geigy Corporation | Plant growth regulating agent |
US3937730A (en) * | 1972-06-06 | 1976-02-10 | Ciba-Geigy Corporation | Plant growth regulating agent |
US3994975A (en) * | 1974-10-07 | 1976-11-30 | Petrolite Corporation | Cyclohexylamines |
US4161492A (en) * | 1975-01-24 | 1979-07-17 | Bayer Aktiengesellschaft | Cycloaliphatic amines and process for preparing same |
DE2503261C2 (de) | 1975-01-28 | 1976-12-30 | Ruhrchemie Ag | Verfahren zur sulfidierung von platin-auf-kohlenstoff-katalysatoren |
DE2525295C3 (de) * | 1975-06-06 | 1980-02-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Azomethinen |
US4140718A (en) * | 1976-10-14 | 1979-02-20 | Uop Inc. | Preparation of N,N'-dialkylphenylenediamines |
US4317916A (en) * | 1979-04-16 | 1982-03-02 | Ciba-Geigy Corporation | Process for producing N-substituted-N-acetyl-2,6-dialkyl-anilines |
JPS6033423B2 (ja) * | 1980-08-13 | 1985-08-02 | 宇部興産株式会社 | N−アルキルアルキレンジアミンの製法 |
DE3126435A1 (de) | 1981-07-04 | 1983-01-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von gegebenenfalls zelligen polyurethan-polyharnstoff-formkoerpern und alkylsubstituierte phenylendiamine hierzu |
US4900868A (en) * | 1982-01-18 | 1990-02-13 | Monsanto Company | Process for producing N,N'-disubstituted paraphenylene diamine mixtures by sequential reductive alkylation |
DE3232736A1 (de) * | 1982-09-03 | 1984-03-08 | Bayer Ag, 5090 Leverkusen | Aromatische uretdion-di-harnstoff-diamine, verfahren zu ihrer herstellung und ihre verwendung bei der polyurethansynthese |
JPS59155470A (ja) * | 1983-02-23 | 1984-09-04 | Kansai Paint Co Ltd | 熱硬化性塗料用樹脂組成物 |
US4521624A (en) * | 1984-04-16 | 1985-06-04 | Ethyl Corporation | Process for making cyclic amines |
US4714512A (en) * | 1985-03-25 | 1987-12-22 | Uop Inc. | Polyurethane coatings and adhesives |
DE3528262A1 (de) * | 1985-08-07 | 1987-02-12 | Hoechst Ag | Verfahren zur herstellung aromatischer dialkylamine |
US4631298A (en) * | 1985-12-16 | 1986-12-23 | Ethyl Corporation | Mixed diamine chain extender |
US4663201A (en) * | 1986-04-25 | 1987-05-05 | Uop Inc. | Polyurea coatings for objects of metal glass wood or plastic |
MX170643B (es) * | 1986-08-01 | 1993-04-12 | Ici America Inc | Poliureas preparadas a partir de una mezcla de poliaminas y un poliisocianato |
DE3710432A1 (de) * | 1987-03-28 | 1988-10-06 | Basf Ag | Polyamid- und polyharnstoffgruppen gebunden enthaltende elastomere sowie verfahren zur herstellung von elastischen, kompakten oder zelligen formkoerpern hieraus |
WO1988008009A1 (en) * | 1987-04-07 | 1988-10-20 | The Dow Chemical Company | Flexible polyurea or polyurea-polyurethane foams prepared from high equivalent weight amine-terminated compounds and process for preparing the same |
EP0288067A1 (en) | 1987-04-24 | 1988-10-26 | Asahi Glass Company Ltd. | Process for producing polyurethane elastomer and compositon as starting material therefor |
EP0309980A1 (en) | 1987-10-02 | 1989-04-05 | The B.F. Goodrich Company | Alkylated polyalkylene polyamines and process for selective alkylation |
DE3739480A1 (de) * | 1987-11-21 | 1989-06-01 | Huels Chemische Werke Ag | Verfahren zur herstellung von blockierten harnstoffgruppenhaltigen polyisocyanaten sowie die danach hergestellten produkte |
US4806616A (en) * | 1987-12-09 | 1989-02-21 | Uop Inc. | N-N'-dialkylphenylenediamines as curing agents in polyurethane and polyurea manufacture by reaction injection molding |
US5001267A (en) * | 1987-12-21 | 1991-03-19 | Texaco Chemical Company | Secondary alkyl amine derivatives of ethylenediamine |
US5008453A (en) * | 1989-04-14 | 1991-04-16 | Ethyl Corporation | Aromatic diimines |
US5041668A (en) * | 1989-04-14 | 1991-08-20 | Ethyl Corporation | Secondary diamines |
EP0420426A3 (en) * | 1989-09-29 | 1991-09-04 | Texaco Chemical Company | Sprayable and pourable polyurea elastomer |
US5002806A (en) * | 1990-01-11 | 1991-03-26 | Ashland Oil, Inc. | Curative for structural urethane adhesive |
US5059672A (en) * | 1990-06-25 | 1991-10-22 | Thare Coat, Inc. | Elastomeric reaction products of aromatic isocyanate, aliphatic isocyanate and aromatic diamine components |
US5087661A (en) | 1990-07-20 | 1992-02-11 | Mitsui Toatsu Chemicals, Inc. | Moisture curable polyurethane composition comprising polyaldimine |
US5145825A (en) * | 1991-04-08 | 1992-09-08 | Engelhard Corporation | Oxidation catalyst resistant to sulfation |
US5198524A (en) | 1991-04-22 | 1993-03-30 | W.R. Grace & Co.-Conn. | Moisture-curing acrylate/epoxy hybrid adhesives |
MY109091A (en) * | 1992-12-29 | 1996-11-30 | Syngenta Participations Ag | Process for the preparation of 2-alkyl-6-methyl-n-(1''''''''- methoxy-2''''''''-propyl)-aniline and a process for the preparation of their chloracetanilides. |
TW322432B (zh) * | 1993-06-14 | 1997-12-11 | Degussa | |
US5312886A (en) * | 1993-09-20 | 1994-05-17 | Uop | Bis(N-alkylaminocyclohexyl)methanes as curing agents for polyurethanes and polyureas |
DE4406949A1 (de) * | 1994-03-03 | 1995-09-07 | Bayer Ag | Verfahren zur Herstellung von aliphatischen Iminen |
DE4413618A1 (de) * | 1994-04-19 | 1995-10-26 | Hoechst Ag | Verfahren zur Herstellung von Glykoloylaniliden |
US5470890A (en) * | 1994-06-17 | 1995-11-28 | Uop | Bis-(N-alkylaminocyclohexyl)methanes as curing agents in polyurethane and polyurea flexible foam manufacture |
CA2151672C (en) | 1994-06-24 | 2007-05-29 | Dudley Joseph Ii Primeaux | Preparation of sprayable aliphatic polyurea elastomers having improved properties |
ES2164773T3 (es) * | 1994-07-14 | 2002-03-01 | Gates Corp | Elastomeros de poliuretano/urea de alta temperatura. |
US5646235A (en) * | 1995-03-27 | 1997-07-08 | Huntsman Petrochemical Corporation | Reductive alkylation of polyamines |
JPH09100260A (ja) | 1995-04-13 | 1997-04-15 | Nippon Kayaku Co Ltd | 4,4′−ジ(n−アルキルアニリン)類の製造方法 |
US5591807A (en) * | 1995-05-23 | 1997-01-07 | The Sherwin-Williams Company | Polyimine/polyisocyanate coating composition containing polymeric anhydride |
KR19990028421A (ko) | 1995-06-28 | 1999-04-15 | 스프레이그 로버트 월터 | 케트이민 경화제 및 케트이민으로 제조된 신속하게 경화되는 자기 기록 매체 및 필름 |
DE19546750A1 (de) | 1995-12-14 | 1997-06-19 | Huels Chemische Werke Ag | Uretdiongruppenhaltige Polyadditionsprodukte sowie deren Herstellung |
US5731397A (en) * | 1996-04-16 | 1998-03-24 | Huntman Petrochemical Corporation | Polyurea spray railcar lining systems |
DE19637375A1 (de) * | 1996-09-13 | 1998-03-19 | Huels Chemische Werke Ag | Uretdiongruppenhaltige Polyisocyanate, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
DE19637377A1 (de) * | 1996-09-13 | 1998-03-19 | Huels Chemische Werke Ag | Uretdiongruppenhaltige Polyadditionsverbindungen, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
US6399736B1 (en) * | 1997-03-11 | 2002-06-04 | Huntsman Petrochemical Corporation | Method of preparing spray elastomer systems |
US6013755A (en) * | 1997-03-11 | 2000-01-11 | Huntsman Petrochemical Corporation | Method of preparing an aliphatic polyurea spray elastomer system |
US6218480B1 (en) * | 1997-06-16 | 2001-04-17 | Mmr Technologies, Inc. | Water-compatible urethane-containing amine hardener |
US6103799A (en) * | 1998-01-20 | 2000-08-15 | Air Products And Chemicals, Inc. | Surface tension reduction with N,N'-dialkylalkylenediamines |
US5874619A (en) * | 1998-04-07 | 1999-02-23 | Albemarle Corporation | Reducing the coloration of aromatic diamines |
DE19816547A1 (de) * | 1998-04-15 | 1999-10-21 | Degussa | Harnstoff- und uretdiongruppenhaltige Polyisocyanate |
AUPP991799A0 (en) * | 1999-04-23 | 1999-05-20 | Cardiac Crc Nominees Pty Limited | Siloxane-containing polyurethane-urea compositions |
EP1067116A1 (en) | 1999-07-09 | 2001-01-10 | The Procter & Gamble Company | Process for the production of imines |
EP1229020B1 (en) | 1999-11-11 | 2011-01-19 | Idemitsu Kosan Co., Ltd. | Transition metal compound, olefin polymerization catalyst, and method of polymerizing olefin |
DE10002089A1 (de) * | 2000-01-19 | 2001-07-26 | Basf Ag | Witterungsstabile, strahlungshärtbare Polyurethane |
US6403752B1 (en) * | 2000-07-17 | 2002-06-11 | Uop Llc | Secondary aliphatic diamines as curing agents for polyurethanes and polyureas prepared using high-pressure impingement mixing |
US20030004265A1 (en) * | 2001-05-16 | 2003-01-02 | Gupta Laxmi C. | Polyurea coating composition |
ES2288553T3 (es) * | 2001-06-15 | 2008-01-16 | Huntsman Petrochemical Corporation | Extensores de cadena amina sinergicos en elastomeros en pulverizacion de poliurea. |
US6803445B2 (en) * | 2001-08-08 | 2004-10-12 | The Yokohama Rubber Co., Ltd. | Moisture curable polyurethane and/or epoxy resin composition and storage stabilizer contained therein |
AUPR732601A0 (en) | 2001-08-28 | 2001-09-20 | Polychip Pharmaceuticals Pty Ltd | Methods for the synthesis of amines such as ephedrine and inter mediates |
US6831187B2 (en) * | 2001-12-18 | 2004-12-14 | Univation Technologies, Llc | Multimetallic catalyst compositions for the polymerization of olefins |
US6429338B1 (en) * | 2002-01-17 | 2002-08-06 | Air Products And Chemicals, Inc. | Hydrogenation of single ring aromatic diamines |
US20040015016A1 (en) * | 2002-07-22 | 2004-01-22 | Huntsman Petrochemical Corporation | Preparation of secondary amines |
CA2767153A1 (en) | 2003-02-20 | 2004-09-02 | Encysive Pharmaceuticals Inc. | Phenylenediamine urotensin-ii receptor antagonists and ccr-9 antagonists |
US6939939B2 (en) * | 2003-02-24 | 2005-09-06 | Younger Mfg. | Polyurea/urethane optical material and method for making it |
US7045632B2 (en) * | 2003-03-04 | 2006-05-16 | Chevron Phillips Chemical Company, Lp | Composition and method for a hexadentate ligand and bimetallic complex for polymerization of olefins |
US20040197472A1 (en) * | 2003-04-04 | 2004-10-07 | Scofield Harry J. | Process and apparatus for sealing freezer enclosures from moisture and contamination |
GB0323213D0 (en) | 2003-10-03 | 2003-11-05 | Univ Warwick | Metallo-supramolecular arrays as anti-cancer and anti-viral agent |
US20060068198A1 (en) | 2004-09-02 | 2006-03-30 | Bratys Dan M | Composite films and process for making the same |
US7964695B2 (en) * | 2005-03-28 | 2011-06-21 | Albemarle Corporation | Chain extenders |
US8076518B2 (en) * | 2005-03-28 | 2011-12-13 | Albemarle Corporation | Chain extenders |
KR101264458B1 (ko) * | 2005-03-28 | 2013-05-21 | 알베마를 코포레이션 | 디이민 및 2 차 디아민 |
US20070066786A1 (en) * | 2005-09-22 | 2007-03-22 | The Hanson Group, Llc | Methods of preparing and using polyurea elastomers |
US20070100112A1 (en) | 2005-10-27 | 2007-05-03 | Bayer Materialscience Llc | Polyurethane-urea elastomers |
-
2008
- 2008-01-09 EP EP08705821A patent/EP2102265A1/en not_active Withdrawn
- 2008-01-09 AU AU2008204847A patent/AU2008204847A1/en not_active Abandoned
- 2008-01-09 CA CA002670041A patent/CA2670041A1/en not_active Abandoned
- 2008-01-09 EA EA200970678A patent/EA200970678A1/ru unknown
- 2008-01-09 BR BRPI0809262-1A2A patent/BRPI0809262A2/pt not_active IP Right Cessation
- 2008-01-09 JP JP2009545665A patent/JP2010515811A/ja active Pending
- 2008-01-09 CN CN2008800012980A patent/CN101568566B/zh not_active Expired - Fee Related
- 2008-01-09 US US12/444,870 patent/US8143365B2/en not_active Expired - Fee Related
- 2008-01-09 WO PCT/US2008/050659 patent/WO2008086437A1/en active Application Filing
- 2008-01-09 KR KR1020097009782A patent/KR20090098961A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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JP2010515811A (ja) | 2010-05-13 |
CA2670041A1 (en) | 2008-07-17 |
US20100160592A1 (en) | 2010-06-24 |
US8143365B2 (en) | 2012-03-27 |
KR20090098961A (ko) | 2009-09-18 |
EA200970678A1 (ru) | 2009-12-30 |
BRPI0809262A2 (pt) | 2014-10-07 |
CN101568566B (zh) | 2012-07-11 |
EP2102265A1 (en) | 2009-09-23 |
WO2008086437A1 (en) | 2008-07-17 |
AU2008204847A1 (en) | 2008-07-17 |
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