CN103154065B - 可固化组合物和催化化学反应的方法 - Google Patents
可固化组合物和催化化学反应的方法 Download PDFInfo
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- CN103154065B CN103154065B CN201180048588.2A CN201180048588A CN103154065B CN 103154065 B CN103154065 B CN 103154065B CN 201180048588 A CN201180048588 A CN 201180048588A CN 103154065 B CN103154065 B CN 103154065B
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- reaction mixture
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- phosphine
- reaction
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Classifications
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- 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
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Abstract
提供了催化化学反应的方法。将具有至少一种取代基(其是烷基)的三取代的膦加入作为反应混合物的催化剂。反应混合物包含异氰酸酯二聚体、酸酐或者异氰酸酯官能物质(包括异氰脲酸酯)与羟基、硫醇和/或胺官能物质的不同组合。还提供了包含这些催化剂和反应混合物的可固化组合物。
Description
发明领域
本发明涉及催化化学反应的方法和可固化组合物。
发明背景
催化是由于被称作催化剂的物质参与而导致的化学反应速率的变化。加速反应的催化剂被称作正催化剂。减慢反应的催化剂被称作负催化剂或者抑制剂。不同于反应物,催化剂不通过反应本身消耗。
催化剂是通过提供获得反应产物的另外的反应路径来起作用的。当这种另外的路线具有比非催化剂调节的反应路线更低的活化能时,反应速率提高。催化剂也能够使本来通过动力学势垒被封闭或者减慢的反应得以进行。催化剂可以提高反应速率或者选择性,或者使反应能够在低温进行。因此,催化剂在工业过程中会是非常有价值的工具。
使用催化剂会存在缺点。例如高碱性胺例如1,8-二氮杂双环-十一碳-7-烯(DBU)和巴顿碱最有效是用于异氰酸酯二聚体/多元醇催化。但是,它们是昂贵的,并且会导致反应产物不期望的黄变。在另一例子中,锡化合物被广泛用于工业产品例如涂料中,作为用于异氰酸酯/羟基反应的催化剂。因为对于一些有机锡化合物的水生毒性(aquatictoxicity)的关注,已经提出了法规来禁止将有机锡化合物用于所有涂料应用。
使用克服现有技术缺点的方法和催化剂来催化化学反应是令人期望的。
发明内容
根据本发明,提供了催化化学反应的方法。在一种实施方案中,一种方法包括将催化剂加入反应混合物中。该催化剂包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基,和该反应混合物包含:
i)a)异氰酸酯官能物质和b)硫醇官能和/或胺官能物质;
ii)a)异氰酸酯二聚体和b)羟基官能、硫醇官能和/或胺官能物质;或者
iii)a)酸酐和b)羟基官能物质。
在本发明的另一实施方案中,提供了催化化学反应的方法,其包括将催化剂加入反应混合物中,其中该催化剂包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基,和其中该反应混合物基本上没有迈克尔受体和该反应混合物包含:
i)异氰酸酯官能物质,其基本上没有噁二嗪三酮环;和
ii)羟基官能物质。
另一实施方案包括将催化剂加入反应混合物中,其中该催化剂基本上没有锡化合物,并且包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基,和该反应混合物基本上没有迈克尔受体和锡化合物,和该反应混合物包含:
i)异氰酸酯官能物质;和
ii)羟基官能物质。
本发明还提供可固化组合物。例子包括a)一种反应混合物,其包含:
i)a)多异氰酸酯和b)聚硫醇和/或多胺;
ii)a)异氰酸酯二聚体和b)多元醇、聚硫醇和/或多胺;或者
iii)a)酸酐和b)多元醇;和
b)催化剂,其包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基。
在一种另外的实施方案中,该可固化组合物包含a)一种反应混合物,其包含:
i)多异氰酸酯;和
ii)多元醇;和
b)催化剂,其包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基;其中该多异氰酸酯基本上没有噁二嗪三酮环,和该反应混合物基本上没有迈克尔受体。
在另一实施方案中,该可固化组合物包含a)反应混合物,其包含:
i)多异氰酸酯;和
ii)多元醇;和
b)催化剂,其中该催化剂基本上没有锡化合物,并且包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基,和该反应混合物基本上没有迈克尔受体和锡化合物。
具体实施方式
不同于操作实施例或者另有指示之处,在说明书和权利要求中所用的表示成分、反应条件等的量的全部数字被理解为在全部的情况中是用术语“大约”来修正的,即使该术语没有明确出现。因此,除非有相反的指示,否则在下面的说明书和附属的权利要求中所阐明的数字参数是近似的,其可以根据本发明所寻求获得的期望的性能来变化。最起码的,并且并非打算应用等价原则来限制权利要求的范围,每个数字参数应当至少根据所报告的有效数字和应用通常的四舍五入技术来解释。
虽然阐明本发明宽的范围的数字范围和参数是近似的,但是在具体实施例中所述的数值是尽可能精确来报告的。但是任何数值本质上包含了在它们各自的测试测量中存在的标准偏差所必然形成的误差。
此处所述的数字范围目的是包括其中所包含的全部子范围。例如,“1-10”的范围目的是包括在所述的最小值1和所述的最大值10之间的全部子范围,并且包括所述的值,即,具有等于或者大于1的最小值和等于或者小于10的最大值。
复数包括了单数,反之亦然;例如,单数形式“一个”、“一种”和“该”包括了复数指示物,除非明确和不含糊的限制到一种指示物。例如在以术语“一个”多异氰酸酯来描述本发明之处,可以使用多个,包括这样的化合物的混合物。
本文使用的术语“聚合物”表示指代预聚物、低聚物、和均聚物和共聚物二者;前缀“聚合”表示两个或者更多个。
本发明的方法包括将催化剂加入反应混合物中,当反应物是多官能时,形成可固化组合物。本发明还涉及可固化组合物。该催化剂包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基。膦上的其他取代基可以是芳基和/或烷基的任意组合。例如膦上的两个取代基可以是具有4或者更多个碳原子、经常是6或者更多个碳原子的烷基,并且一个取代基可以是芳基。可选择地,全部的三个取代基可以是烷基,例如具有6或者更多个碳原子的烷基。在本发明具体的实施方案中,将三辛基膦用作催化剂。
在某些条件下,令人期望的是可在将三取代的膦加入反应混合物中之前使它与酸反应,典型的是有机酸。膦的这种“封闭”使得它在空气中更稳定,并且允许更精确地控制催化反应。任何酸可以是合适的,但是具有1-8个碳原子的挥发性有机酸例如乙酸和丙酸是最经常使用的。
在本发明的方法中,加入催化剂到反应混合物中会引起反应在比不使用该催化剂时所需的温度低的温度进行。而且,该反应可以在给定的温度比在特定的反应物之间原本所观察到的更快地发生。反应可以在环境温度或者在升高的温度例如大于30℃进行,这取决于所涉及的化学。
催化剂以足以使得反应混合物中的任何反应性官能团进行反应或者加速反应的量使用。该量可以基于参与的反应物的化学而变化,但是在本发明方法中使用的三取代的膦的典型量是0.1-10重量%,基于反应混合物中树脂固体的总重量。
本发明的方法用于催化多种化学反应。许多反应混合物适于本发明的方法。反应混合物的组分典型地以分开的包装来提供,并且在即将反应之前混合在一起,这经常用于可固化组合物。另外,在某些实施方案中,该反应混合物可以是粉末或者液体的可固化组合物,并且可以作为涂料或者层合膜来流延、挤出、辊涂或者施涂到基材上。该反应混合物还可以产生透明的反应产物,适于用作游离薄膜、显示器屏幕、窗户(玻璃窗)、挡风玻璃、透镜等。
在本发明的某些实施方案中,该反应混合物可以包含i)a)异氰酸酯官能物质和b)硫醇官能和/或胺官能物质。在这样的实施方案中,异氰酸酯官能物质i)a)可以是任何的异氰酸酯官能物质,例如单异氰酸酯和/或多异氰酸酯,例如二异氰酸酯和三异氰酸酯,包括缩二脲和异氰脲酸酯。任何合适的二异氰酸酯(包括1,4-四亚甲基二异氰酸酯和1,6-六亚甲基二异氰酸酯)的缩二脲可以用作本发明方法中的反应物i)a)。而且,可以使用环脂族二异氰酸酯例如异佛尔酮二异氰酸酯和4,4′-亚甲基-双-(环己基异氰酸酯)。可制备缩二脲合适的芳烷基二异氰酸酯(由其能够制备缩二脲)的例子是间亚二甲苯基二异氰酸酯和α,α,α’,α’-四甲基间亚二甲苯基二异氰酸酯。二异氰酸酯本身也可以用作本发明方法中的反应物i)a)。
三官能异氰酸酯也可以用作反应物i)a),例如异佛尔酮二异氰酸酯的三聚体,三异氰酸酯壬烷,三苯基甲烷三异氰酸酯,1,3,5-苯三异氰酸酯,2,4,6-甲苯三异氰酸酯,以商品名CYTHANE3160由CYTECIndustries销售的三羟甲基丙烷和四甲基二甲苯二异氰酸酯的加合物,和DESMODUR N3300,其是六亚甲基二异氰酸酯的异氰脲酸酯,获自Bayer Corporation。经常用于可固化组合物中的多异氰酸酯包括环异氰酸酯,特别是二异氰酸酯(例如六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯)的异氰脲酸酯。
用作反应物i)a)的异氰酸酯官能物质也可以是上面所公开的那些之一,使用本领域技术人员已知的合适的材料和技术,用一种或多种多胺和/或多元醇来扩链。
用于反应混合物中合适的硫醇官能物质包括具有伯和/或仲硫醇基团的任何材料。该材料可以是单体的、低聚物的或者聚合物的,并且可以是单或者多官能的。这样的反应混合物将产生硫代氨基甲酸酯。同样,用于反应混合物中的合适的胺官能物质也包括任何单体的、低聚物的或者聚合物材料,其具有伯和/或仲胺基。当在三取代的膦存在下与异氰酸酯反应时,形成了脲。硫醇官能和胺官能物质的组合也可以用于该反应混合物中,并且将催化形成根据本发明的硫脲。
在本发明的另外的实施方案中,反应混合物可以包含ii)a)异氰酸酯二聚体和b)羟基官能、硫醇官能和/或胺官能物质。异氰酸酯二聚体可以由可以彼此相同或者不同的任何两种异氰酸酯官能物质(最经常的是单异氰酸酯,但也可以使用多官能异氰酸酯;剩余的游离异氰酸酯基团可以用例如醇来封端)来制备。在本发明的这种实施方案中,据信三取代的膦首先与异氰酸酯二聚体反应来形成中间体,然后该中间体与反应混合物中的其他反应物上的活性氢基团反应(羟基、硫醇和/或胺)。硫醇和胺可以是上面公开的那些中任何一种。用于反应混合物中的合适的羟基官能物质包括任何单体的、低聚物的或者聚合物材料,其具有伯和/或仲羟基,例如单醇、乙二醇、丙二醇、三羟甲基丙烷,和较大的分子,例如低聚物型和/或聚合物型单醇和多元醇,包括丙烯酸系多元醇、聚醚多元醇、聚酯多元醇、聚氨酯多元醇等。
在本发明的其他实施方案中,该反应混合物可以包含iii)a)酸酐和b)羟基官能物质,例如上面公开的那些中任何一种。酸酐可以包括邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、氯菌酸酐(chlorendic anhydride)等。聚酸酐也适用于本发明的方法。
在本发明另外的实施方案中,该反应混合物基本上没有迈克尔受体和可以包含i)基本上没有噁二嗪三酮环的异氰酸酯官能物质,例如多异氰酸酯;和ii)羟基官能物质,例如多元醇。合适的异氰酸酯和醇包括上面公开的那些。在这样的实施方案中,催化剂可以进一步包含锡化合物。合适的锡化合物的例子包括氧化二丁基锡、辛酸锡、二月桂酸二丁基锡、二乙酸二丁基锡、硫醇二丁基锡、二马来酸二丁基锡、二乙酸二甲基锡和/或二月桂酸二甲基锡。可选择的,催化剂和反应混合物二者都可以基本没有锡化合物。作为本申请文件(包括权利要求)整个中所用的,用“基本上没有”表示如果化合物存在于组合物中,则它伴随的存在量小于0.1重量%,通常小于痕量。
其他具体实施方案包括催化化学反应的方法,其包括将催化剂加入反应混合物中,其中该催化剂基本上没有锡化合物,并且包含三取代的膦,该三取代的膦具有至少一个为烷基的取代基,和该反应混合物基本上没有迈克尔受体和锡化合物。在这样的实施方案中,该反应混合物典型地包含i)任何异氰酸酯官能物质,例如上面公开的那些;和ii)羟基官能物质;同样是例如上面公开的那些。
本发明将进一步参考下面的实施例来描述。实施例仅仅是本发明的示例,并非打算限制。除非另有指示,否则全部的份数是重量的。
实施例
实施例1
这个实施例展示了用三辛基膦催化羟基/酸酐涂料。
1.树脂1的合成
羟基官能树脂通过以下方式合成:在100g醋酸正丁酯中混合45.9g的甲基丙烯酸甲酯、15.19g的甲基丙烯酸月桂酯、14.1g苯乙烯、10g的丙烯酸2-羟乙酯、14.81g的羟基聚酯丙烯酸酯(ToneM-100单体,Dow Chemical Company,Midland,密歇根州)。将3.64g的VAZO67(DuPont Chemical Company)用作该聚合的引发剂。
2.树脂2的合成
酸酐官能树脂通过以下方式合成:混合22.01g的马来酸酐、15.6g的甲基丙烯酸甲酯、46.79g的苯乙烯、在9.52g的矿物精油中15.6g丙烯酸正丁酯、35.51g醋酸正丁酯和54.97g的3-乙氧基丙酸乙酯(Eastman Chemical Company,Kingsport,田纳西州)。将7.83g的过氧化-2-乙基己酸叔丁酯用作该聚合的引发剂。
制备了一系列的配制剂,来评价不同的催化剂的性能。表1列出了所述配制剂。
表1:实施例1的涂料配方
1获自Rohm and Haas Company,Dow Chemical Company的全资子公司
2获自Akzo Nobel Surface Chemistry AB,Stenungsund,瑞典
3获自Cytec Industries Inc.,Woodland Park,新泽西州
制备了涂料1-6,使用4密尔刮涂棒刮涂到冷轧钢上,并且监控棉花时间和凝胶时间。棉花时间是涂层达到一定的干燥水平所需的时间量,在该干燥水平下施加棉球时,在将所施涂的涂层反转时该棉球会从施涂的涂层上落下。凝胶时间是涂料凝胶化到以下程度所需的时间量,即当涂料容器从常态旋转90o时涂料不流动。柯尼希硬度测量是在涂料施涂后24、144和312小时进行的。表2列出了获自这个试验的数据。
表2
表2给出的数据表明,三辛基膦是适于羟基/酸酐反应的催化剂。棉花时间和硬度值与所评价的其他催化剂相当,而凝胶时间平均较长。较长的凝胶时间对于涂层是实际上有益的,因为它赋予操作者更多的时间来在涂料凝胶化之前对它进行操作。
实施例2
这个实施例展示了三辛基膦在硫醇/异氰酸酯反应中的封闭。
如下来制备了三种涂料:将6g的SIKKENS AUTOCLEAR UV(获自Akzo Nobel Car Refinishes,荷兰阿姆斯特丹,其包含了季戊四醇四(3-巯基丙酸酯))与5g的66%DESMODUR N3600(来自Bayer MaterialsScience,宾夕法尼亚州匹兹堡)的醋酸正丁酯溶液混合。向该第一涂料中加入0.6g的含有20%的1:1摩尔比的丙酸与三辛基膦的二甲苯溶液。向该第二溶液中加入1.2g的含有20%的5:1摩尔比的丙酸与三辛基膦的二甲苯溶液。向该第三涂料中加入1.8g的含有20%的10:1摩尔比的丙酸与三辛基膦的二甲苯溶液。含有1:1摩尔比的丙酸与三辛基膦的涂料的凝胶时间是15s。含有5:1摩尔比的丙酸与三辛基膦的涂料的凝胶时间是60s。含有10:1摩尔比的丙酸与三辛基膦的涂料的凝胶时间是120s。这些数据表明将酸加入三辛基膦中延缓了三辛基膦的催化能力。
实施例3
这个实施例展示了使用三辛基膦催化了胺和异氰酸酯之间的反应。
使用Cowles刀片混合含有334.8g的JEFFAMINET-5000(Huntsman Corporation,The Woodlands,德克萨斯州)、248.3g的丙烯酸系/天冬氨酸胺固化剂(参见US2008/0141903A1的实施例A)、317.6g的CLEARLINK1000(Dorf Ketal Chemicals LLC,Stafford,德克萨斯州)、11.8g Byk9077(Byk-Chemie GmbH,Wesel,德国)、26.1g的TINUVIN292(Ciba Specialty Chemicals,28.8g VULCAN XC72(CabotCorporation,Billerica,密歇根州)、16.3g的CAB-O-SIL M-5(CabotCorporation,Billerica,密歇根州)、16.3g的CLAYTONE546(SouthernClay Products,Inc.,Gonzales,德克萨斯州)的研磨糊料,然后引入到装有TZP plus 1.0mm研磨介质的Eiger研磨机中。将该研磨糊料研磨到达到7.5Hegman为止,然后从研磨机中除去该混合物。表3包含了使用前述研磨糊料制备的4个配制剂。
表3:使用三辛基膦来催化胺/异氰酸酯反应的配制剂和数据
1CAT133是一种用于DURABED的基于异氰酸酯的催化剂,并且获自宾夕法尼亚洲匹兹堡的PPG Industries,Inc.。
使用刮涂棒刮涂膜,由含有三辛基膦的配制剂A、B和C所制备的膜的不发粘时间分别是25、22和20秒,而含有二月桂酸二丁基锡的配方D的发粘时间是29秒。
实施例4
这个实施例说明了对于羟基和异氰酸酯之间的反应的催化。
丙烯酸系多元醇(丙烯酸系多元醇1)是通过以下物质进行反应来制造:90.6g的丙烯酸单体(其是通过将395.3g的CARDURAE-10P(Hexion Specialty Chemicals,俄亥俄州哥伦布)与115.6g的冰丙烯酸(抑制的)在1.21g的2-乙基己酸锌溶液(8%的矿物精油溶液,获自Dura Chemicals Inc.,Emeryville,加利福尼亚州)和0.09g对甲氧基酚存在下反应来制造的)、372.3g的甲基丙烯酸正丁酯(抑制的)、455g的甲基丙烯酸甲酯、328.6g的苯乙烯、542.4g的甲基丙烯酸羟丙酯、18g的冰丙烯酸(抑制的)在222.4g的甲戊酮和767g的二甲苯中,使用9.1g的月桂基硫醇作为链转移剂和108g的二叔戊基过氧化物和9g的亚磷酸三苯酯作为引发剂。使用表4所列出的基础配方来评价羟基/异氰酸酯反应的催化。
表4:基础配方A
组分 | 基础配方A |
丙烯酸系多元醇1 | 34.09 |
BYK3001 | 0.49 |
EVERSORB742 | 1.27 |
SANOL LS-2923 | 1.74 |
甲基异丁基酮 | 13.76 |
甲戊酮 | 11.75 |
1Byk-Chemie GmbH,Wesel,德国
2Everlight Chemical Industrial Corporation,台湾台北
3Sankyo Lifetech Co.,Ltd.,日本东京
表5所列的配制剂是使用表4的基础配制剂A来制备的。
表5:涂料配制剂和性能
组分 | 涂料A | 涂料B | 涂料C | 涂料D |
基础配制剂A | 25.34 | 24.4 | 24.82 | 25.27 |
10%二月桂酸二丁基锡溶液 | 0 | 0 | 0.26 | 0.53 |
三辛基膦1 | 0 | 0.51 | 0.26 | 0 |
DCX612 | 6.98 | 6.72 | 6.84 | 6.96 |
棉花时间(分钟) | 51 | 48 | 21 | 20 |
凝胶时间(分钟) | >6000 | 317 | 160 | 189 |
柯尼希硬度(24小时)3 | 19 | 39 | 31 | 28 |
1获自Cytec Industries Inc.,Woodland Park,新泽西州
2异氰酸酯硬化剂,获自PPG Refinish Products,Strongsville,俄亥俄州
3ASTM D4366
制备涂料,并且使用常规的供料喷枪来喷涂。含有三辛基膦和二月桂酸二丁基锡的涂料C和含有二月桂酸二丁基锡的涂料D的棉花时间分别是21和20分钟,而含有三辛基膦的涂料B和不含催化剂的涂料A的棉花时间分别是48和51分钟。涂料B、C和D的凝胶时间是317、160和189分钟,而涂料A(无催化剂)的凝胶时间大于6000分钟。在施涂后24小时,涂料A、B、C和D的柯尼希硬度值是19、39、31和28。表5中给出的数据表明三辛基膦本身可以充当催化剂,或者为二月桂酸二丁基锡充当助催化剂,并且发粘时间、凝胶时间和柯尼希硬度值优于没有催化的对照涂料A。
实施例5
这个实施例展示了三辛基膦作为催化剂对于异氰酸酯二聚体与多元醇反应的效力。制备了异氰酸酯二聚体/多元醇配制剂的三个样品,每个包含下面组分的混合物:
1.丙烯酸系多元醇(55.1g),如下来制备:
向装备有搅拌器、热电偶、冷凝器和带泵的加料漏斗的反应容器中装入269.2克(g)的3-乙氧基丙酸乙酯(EktaPro EEP,来自EastmanChemical Products)、15.2g的醋酸正丁酯和5.5g的亚磷酸三苯酯,并且在大约160℃加热回流。接着分别在3和4小时内将两种供料(在此表示为A和B)逐渐加入该容器中,同时将容器的内容物保持在回流条件下。供料A是由548.6g的Tone M-201(己内酯甲基丙烯酸酯,获自Dow Chemical Co.)、274.4g的甲基丙烯酸甲酯和274.4g的苯乙烯的混合物组成。供料B是由65.8g的Luperox DTA(自由基引发剂,来自Atochem)和24.3g的醋酸正丁酯的混合物组成。在两种供料A和B加入完成后,将加料漏斗用每个30.0g的醋酸正丁酯冲洗,并且使得容器的内容物回流1小时。其后,停止加热,使容器的内容物冷却,并且加入150.0g的醋酸正丁酯。
所形成的丙烯酸系多元醇的总固含量在110℃测量1小时为65.8重量%;通过凝胶渗透色谱法,利用聚苯乙烯标准物所测量的峰值分子量是6600,重均分子量是10200和数均分子量是2016;Gardner-Holt粘度为Z;酸值1.1;APHA颜色为20;重量/加仑是8.80;和羟基值是83.3。
2.TP30多元醇(10.0g,乙氧基化的三官能三羟甲基丙烷,来自Perstorp AB,瑞典)。
3.BYK 300(0.20g,聚醚改性的二甲基聚硅氧烷共聚物,来自BYKChemie,Wesel Germany)。
4.CRELAN XP2459(46.8g,环脂族聚异氰酸酯二聚体,来自BayerMaterialScience Inc.,宾夕法尼亚州匹兹堡)。
5.47.1g的试验聚异氰酸酯二聚体,来自BayerMaterialScience,Inc.(由DESMODUR N3400、2-乙基己醇和2-乙基-1,3-己二醇制备;在醋酸正丁酯中的固含量是50%;原样的异氰酸酯二聚体当量是1341)。
6.醋酸丁酯(14.0g)。
向一个样品中加入1.28g的三辛基膦(Cytec Industries Inc.,Woodland Park New Jersey),向另一个样品中加入1.28g的质子海绵(N,N,N’,N’-四甲基-1,8-萘二胺,Sigma-Aldrich Co.,St.LouisMissouri)。第三个是没有催化剂的对照物。在5小时后,通过三辛基膦催化的配制剂已经凝胶化。在24小时后,对照物和具有质子海绵的配制剂没有凝胶化。
虽然在上面已经描述了本发明具体的实施方案来用于说明的目的,但是对本领域技术人员来说,很显然可以对本发明的细节进行诸多的改变,而不脱离附加的权利要求所定义的本发明。
Claims (12)
1.一种催化化学反应的方法,其包括将催化剂加入反应混合物中,其中该催化剂包含三取代的膦,该三取代的膦是用酸封闭的并具有至少一个为烷基的取代基,和其中该反应混合物包含小于0.1重量%的迈克尔受体并且该反应混合物包含:
i)包含小于0.1重量%的噁二嗪三酮环的异氰酸酯官能物质;和
ii)羟基官能物质。
2.权利要求1的方法,其中该三取代的膦是三辛基膦。
3.权利要求1的方法,其中该催化剂进一步包含锡化合物。
4.权利要求1的方法,其中该催化剂和反应混合物包含小于0.1重量%的锡化合物。
5.权利要求1的方法,其中该反应混合物是粉末或者液体的可固化组合物,其可以作为涂料或者层合膜来流延、挤出、辊涂或者施涂到基材上。
6.权利要求5的方法,其中该反应混合物产生透明的反应产物。
7.一种催化化学反应的方法,其包括将催化剂加入反应混合物中,其中该催化剂包含小于0.1重量%的锡化合物并且包含三取代的膦,该三取代的膦是用酸封闭的并具有至少一个为烷基的取代基,并且该反应混合物包含小于0.1重量%的迈克尔受体和锡化合物,并且该反应混合物包含:
i)异氰酸酯官能物质;和
ii)羟基官能物质。
8.权利要求7的方法,其中该三取代的膦是三辛基膦。
9.权利要求7的方法,其中该反应混合物是粉末或者液体的可固化组合物,其可以作为涂料或者层合膜来流延、挤出、辊涂或者施涂到基材上。
10.权利要求9的方法,其中该反应混合物产生透明的反应产物。
11.一种可固化组合物,其包含:
a)反应混合物,其包含:
i)多异氰酸酯;和
ii)多元醇;和
b)催化剂,其包含三取代的膦,该三取代的膦是用酸封闭的并具有至少一个为烷基的取代基;其中该多异氰酸酯包含小于0.1重量%的噁二嗪三酮环,并且该反应混合物包含小于0.1重量%的迈克尔受体。
12.一种可固化组合物,其包含:
a)反应混合物,其包含:
i)多异氰酸酯;和
ii)多元醇;和
b)催化剂,其中该催化剂包含小于0.1重量%的锡化合物,并且包含三取代的膦,该三取代的膦是用酸封闭的并具有至少一个为烷基的取代基,并且该反应混合物包含小于0.1重量%的迈克尔受体和锡化合物。
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CA (1) | CA2813578C (zh) |
HK (1) | HK1186485A1 (zh) |
MX (1) | MX2013003922A (zh) |
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US20130079485A1 (en) * | 2011-09-22 | 2013-03-28 | Prc-Desoto International, Inc. | Sulfur-containing polyureas and methods of use |
US9328275B2 (en) | 2014-03-07 | 2016-05-03 | Prc Desoto International, Inc. | Phosphine-catalyzed, michael addition-curable sulfur-containing polymer compositions |
JP5895109B1 (ja) * | 2014-07-08 | 2016-03-30 | 三井化学株式会社 | 光学材料用重合性組成物およびその用途 |
US10633477B2 (en) | 2018-03-23 | 2020-04-28 | Covestro Llc | Extended pot-life for low temperature curing polyuretdione resins |
US11292864B2 (en) | 2018-03-23 | 2022-04-05 | Covestro Llc | Compositions using polyuretdione resins |
US10731051B2 (en) | 2018-03-23 | 2020-08-04 | Covestro Llc | Basecoat acid neutralization through inorganic salts |
US11312881B2 (en) | 2018-03-23 | 2022-04-26 | Covestro Llc | One component polyurethane/allophanate formulations with reactive reducer |
US11440988B2 (en) | 2018-03-23 | 2022-09-13 | Covestro Llc | Polyuretdione-containing resin blend compositions |
US10696775B2 (en) | 2018-03-23 | 2020-06-30 | Covestro Llc | Curing for polyallophanate compositions through undercoat acid neutralization |
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CA2813578C (en) | 2015-03-17 |
MX2013003922A (es) | 2013-06-28 |
JP5834084B2 (ja) | 2015-12-16 |
SG189207A1 (en) | 2013-06-28 |
CA2813578A1 (en) | 2012-04-12 |
NZ608733A (en) | 2014-11-28 |
EP2625214A1 (en) | 2013-08-14 |
JP2013541616A (ja) | 2013-11-14 |
BR112013008192A2 (pt) | 2020-08-25 |
CN103154065A (zh) | 2013-06-12 |
KR20130064135A (ko) | 2013-06-17 |
US8791223B2 (en) | 2014-07-29 |
US20120088895A1 (en) | 2012-04-12 |
AU2011311800B2 (en) | 2014-10-09 |
AU2011311800A1 (en) | 2013-05-02 |
HK1186485A1 (zh) | 2014-03-14 |
KR101493180B1 (ko) | 2015-02-12 |
WO2012048245A1 (en) | 2012-04-12 |
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