CN101027326B - 具有内在光敏引发剂的可辐射固化迈克尔加成树脂 - Google Patents
具有内在光敏引发剂的可辐射固化迈克尔加成树脂 Download PDFInfo
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- CN101027326B CN101027326B CN2005800185878A CN200580018587A CN101027326B CN 101027326 B CN101027326 B CN 101027326B CN 2005800185878 A CN2005800185878 A CN 2005800185878A CN 200580018587 A CN200580018587 A CN 200580018587A CN 101027326 B CN101027326 B CN 101027326B
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- 230000009467 reduction Effects 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明的液体、未交联、可紫外固化的迈克尔加成树脂及其混合物显示出了具有使它们能够非常有效地涂覆材料的表现性能,并且这些性能可以通过依赖于其中的组成而得到显著改性。迈克尔给体和受体可以由I型和/或II型光敏引发剂构成,并且可以将其加入到在此公开的涂覆组分中,从而使得可紫外固化的涂料具有卓越的光化活性和性能。可以形成对金属、塑料、木材、纸张和玻璃具有优良粘合性能的树脂。它们显示出广泛的硬度、刚性、挠性、拉伸强度、抗污性、耐划伤性、耐冲击性、耐溶剂性等等。通过适当选择原料结构单元,几乎可以得到任何期望的涂布性能参数。
Description
技术领域
本发明涉及由丙烯酸酯的单体和低聚物(迈克尔受体)与诸如可以参与迈克尔加成反应的β-酮酸酯、β-二酮和β-酮酰胺等β-二羰基化合物(迈克尔给体)反应形成的多官能丙烯酸酯低聚物(迈克尔加成树脂)。特别地,本发明涉及被改性以含有其它光敏部分,如光敏引发剂和/或光敏剂的具有更佳固化响应的改良迈克尔加成树脂。所述改良迈克尔加成树脂具有由迈克尔加成反应直接形成的、以及由侧挂的I型光敏部分(例如,取代的苯偶姻、苄基缩酮、苯乙酮或者酰基氧膦)或者II型光敏部分(例如,取代的二苯酮、噻吨酮、樟脑醌或者联咪唑)直接形成的多个光敏基团。
背景技术
多官能丙烯酸酯和甲基丙烯酸酯通常用于制备交联薄膜、粘合剂、铸模砂结合剂、复合材料等等。美国专利5,945,489和6,025,410(均为Ashland公司的专利)公开了经β-二羰基化合物与多官能丙烯酸酯进行迈克尔加成反应制备的液体未交联的树脂。本发明包括液体、未交联、可紫外固化的迈克尔加成树脂,所述迈克尔加成树脂利用改性至含有侧挂I型(例如取代的苯偶姻、苄基缩酮、苯乙酮或者酰基氧膦)或者II型(例如取代的二苯酮、噻吨酮、樟脑醌或者联咪唑)光敏部分的β-二羰基迈克尔给体和/或丙烯酸酯受体制备得到。由此,所得低聚物具有在暴露于紫外线时可促进丙烯酸基团加成聚合的I型和II型光敏官能团的一种或两种。除了在迈克尔反应期间形成的光敏取代酮之外,上述结构的改变还提供了引发自由基聚合的补充发色团。
本发明在此公开的内容表明将这些未交联树脂单独用于或者通过与其它物质反应/混合的改性而用于多种基材涂布应用中的有利用途。这些其它物质包含多种丙烯酸和乙烯基的单体与低聚物、伯胺和仲胺、有机硝基化合物、酸官能材料、硅氧烷、弹性体、石蜡以及其它,以改性和改良涂料性能。
如上所述的低聚物可以通过一般用于交联丙烯酸材料的所有方法进行固化,不过最有利的是通过暴露于紫外辐射进行固化。固化或者交联通常通过自由基链式机理得以实现,这会需要一些自由基生成物种,如过氧化物、氢过氧化物、氧化还原络合物等,在加热或在环境温度下,在胺和过渡金属助催化剂的存在下,它们会分解以形成自由基。电子束(EB)辐射是另一种适用于引发丙烯酸部分反应的能源。
相对于常规的多官能丙烯酸单体和低聚物,本发明所述的树脂提供了显著的优点,所述优点在于它们不需要额外的光敏引发剂,仅通过暴露于紫外辐射即可以固化。而常规的多官能丙烯酸酯和/或低聚物暴露于紫外辐射不会发生固化,除非将通常相对较高含量的光敏引发剂加入到涂料配制物中。常规的光敏引发剂(例如,二苯酮)可能难溶、有毒、昂贵,并造成薄膜有色,这会限制所述涂料在白色和浅色基材上的涂覆。此外,一些传统光敏引发剂的分解会形成不利于健康的***产物(例如,苯甲醛)。***的碎片会“浮散”在可能接触皮肤的固化涂层的表面。在此公开的本发明提供了这些常规发色团部分的迅速应用,同时最大的碎片被固着或者“限制”在热固性涂料基体中。
在此公开的新颖树脂和掺混物显示了使得它们成为非常有效的涂布材料的性质。这些性质可以得到取决于其组成的显著改进。由此,可以形成对金属、塑料、木材、纸张和玻璃具有优良粘结性能的树脂。它们显示出宽广范围的硬度、刚性、挠性、拉伸强度、抗污性、耐划伤性、耐冲击性、耐溶剂性等。通过正确选择原料结构单元,几乎可以得到任何期望的涂布性能。
发明内容
在此详述的本发明包括通过丙烯酸酯的单体和低聚物与可以参与迈克尔加成反应、作为迈克尔给体的β-酮酸酯(例如,乙酰乙酸酯)、β-二酮(例如,2,4-戊二酮)、β-酮酰胺(例如,N-乙酰乙酰苯胺、乙酰乙酰胺)和/或其它β-二羰基化合物反应形成的一类新颖的多官能丙烯酸酯低聚物,以及这些树脂在涂料中的应用。本发明的迈克尔加成树脂经改性而含有起光敏引发剂作用的光敏部分。也就是说,所得迈克尔低聚物具有直接源于迈克尔加成反应以及侧挂I型光敏部分(例如,取代的苯偶姻、苄基缩酮、苯乙酮或者酰基氧膦)或者II型光敏部分(例如,取代的二苯酮、噻吨酮、樟脑醌或者联咪唑)的多个光敏酮基,如美国专利5,945,489和6,025,410中所公开。这使得β-二羰基迈克尔给体的加载量要低得多,从而导致所得低聚物与在先公开的低聚物相比有降低的粘度和更好的固化响应。
在标准的紫外-固化条件下,如上所述的新颖低聚物可以在低紫外辐射剂量下固化。为了增强涂覆性能,还可以将活性的(常规聚丙烯酸酯)和非活性的(例如,溶剂)其它物质结合入到该***中。其中,这些添加剂包含多种丙烯酸单体与低聚物和乙烯基单体与低聚物、伯胺和仲胺、有机硝基化合物、酸性官能的单体和低聚物、有机和无机填料、硅氧烷、石蜡和弹性体。当用作包括金属、塑料、木材、纸张和玻璃的多种基材的涂层时,所述树脂显示出了优良的性能。可以通过化学方式、热、或通过暴露于紫外辐射或电子束辐射固化这些涂料。
附图说明
图1:在1,8-二氮杂二环[5.4.0]十一-7-烯(DBU)存在下,三羟甲基丙烷三丙烯酸酯(TMPTA)与乙酰乙酸乙酯(EAA)以2∶1的摩尔比进行反应。所得聚丙烯酸酯低聚物具有双官能。其兼具丙烯酸官能(四个)和可以通过暴露于紫外线而分解从而引发所述低聚物的自由基聚合的取代酮基。
图2:TMPTA与二苯酮进行结合。甲基二乙醇胺作为协合剂被加入其中,以改善聚合的效率。通过暴露于紫外辐射,上述混合物固化成非常脆性的、高度交联的薄膜。
图3:常规的苄基缩酮类光敏引发剂(4-(2-羟基乙氧基)苯基-2-羟基-2-丙基酮)与官能化试剂反应,从而产生如图所示的产物分子。然后,将乙酰乙酰氧基官能的产物分子(A)或者丙烯酸官能的产物分子(B,C)用于图4详述的反应方案中。
图4:由I型α-裂解乙酰乙酸酯迈克尔给体和TMPTA形成的新颖的“混杂发色团”迈克尔加合物。
图5:图解对比了含有常规I型α-裂解光敏引发剂的发色团、自引发低聚物的迈克尔加合物和混杂双发色团(I型光敏部分加上迈克尔反应产物的取代酮)。圆形区域表示化学键均裂形成自由基引发物种的点。
图6:由II型H-夺取型光敏引发剂(羟基二苯酮)、乙酰乙酸缩水甘油酯迈克尔给体和TMPTA形成的新颖的“混杂发色团”迈克尔加合物。
具体实施方式
本发明涉及已经改性而含有I型和/或II型光敏部分的液体、非交联、可紫外固化的迈克尔加成树脂。对于本发明而言,迈克尔加成树脂等同地称为迈克尔聚丙烯酸酯树脂、迈克尔低聚物、迈克尔加合物或者迈克尔加成产物。本发明的迈克尔加成树脂可以在催化剂的存在下进行制备。可以将本领域的其它已知组分加入到所述液体、非交联、可紫外固化的迈克尔加成树脂中,比如胺协合剂、活性稀释剂、硅氧烷和石蜡等。
所述液体、未固化的迈克尔加成树脂是由多官能丙烯酸酯迈克尔受体和β-二羰基迈克尔给体形成的聚丙烯酸酯低聚物。可以将少量单官能丙烯酸酯与多官能丙烯酸酯一起加入,以改性所述产品低聚物,比如,增强粘合性、刚性或者最终迈克尔加合物的其它特性。所述技术描述于受让人均为Ashland Inc.的美国专利5,945,489和6,025,410中,其全部内容通过引用结合在此。
所述β-二羰基迈克尔给体适当地选自β-酮酸酯、β-二酮、β-酮酰胺和β-酮苯胺。所述多官能丙烯酸酯迈克尔受体适当地选自单丙烯酸酯、双丙烯酸酯、三丙烯酸酯和四丙烯酸酯等。所述β-二羰基给体和单或者多官能丙烯酸酯受体的选择范围为组分设计者提供了最终产品性能的宽泛选择性。
单丙烯酸酯包括但不限于:2-苯氧基乙基丙烯酸酯(PEA)和/或更高级的烷氧基化产物、丙烯酸异冰片酯、丙烯酸四氢糠酯(THFFA)、丙烯酸缩水甘油酯、丙烯酸十二烷基酯、苯基硫代乙基丙烯酸酯、丙烯酸酯官能的聚硅氧烷、全氟烷基乙基丙烯酸酯及其混合物。基于迈克尔加成树脂的总重量,单丙烯酸酯的用量可以为至多约20wt%,优选至多约10wt%。
二丙烯酸酯包括但不限于:二丙烯酸乙二醇酯、二丙烯酸丙二醇酯、二丙烯酸二甘醇酯、二丙烯酸二丙二醇酯、二丙烯酸三甘醇酯、二丙烯酸三丙二醇酯、二丙烯酸四甘醇酯、二丙烯酸四丙二醇酯、二丙烯酸聚乙二醇酯、二丙烯酸聚丙二醇酯、乙氧基化双酚A二丙烯酸酯、双酚A二环氧甘油醚二丙烯酸酯、间苯二酚二环氧甘油醚二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、环己烷二甲醇二丙烯酸酯、乙氧基化新戊二醇二丙烯酸酯、丙氧基化新戊二醇二丙烯酸酯、乙氧基化环己烷二甲醇二丙烯酸酯、丙氧基化环己烷二甲醇二丙烯酸酯、硫代二甘醇二丙烯酸酯、丙烯酸酯官能的聚硅氧烷、环氧二丙烯酸酯、芳基氨基甲酸乙酯二丙烯酸酯、脂肪族氨基甲酸乙酯二丙烯酸酯、聚酯二丙烯酸酯及它们的混合物。
三丙烯酸酯包括但不限于:三羟甲基丙烷三丙烯酸酯、甘油三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯、乙氧基化甘油三丙烯酸酯、丙氧基化甘油三丙烯酸酯、季戊四醇三丙烯酸酯、芳基氨基甲酸乙酯三丙烯酸酯、脂族氨基甲酸乙酯三丙烯酸酯、三聚氰胺三丙烯酸酯、酚醛环氧三丙烯酸酯、脂族环氧三丙烯酸酯、聚酯三丙烯酸酯及它们混合物。
四丙烯酸酯包括但不限于:双-三羟甲基丙烷四丙烯酸酯、季戊四醇四丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯、丙氧基化季戊四醇四丙烯酸酯、双季戊四醇四丙烯酸酯、乙氧基化双季戊四醇四丙烯酸酯、丙氧基化双季戊四醇四丙烯酸酯、芳基氨基甲酸乙酯四丙烯酸酯、脂族氨基甲酸乙酯四丙烯酸酯、聚酯四丙烯酸酯、三聚氰胺四丙烯酸酯、酚醛环氧四丙烯酸酯、丙烯酸酯官能的聚硅氧烷及它们的混合物。
根据期望的树脂质量,本发明可以用β-酮酸酯(如乙酰乙酸乙酯)、β-酮苯胺(如N-乙酰乙酰苯胺)、β-酮酰胺(如乙酰乙酰胺)或者迈克尔给体混合物来进行。
具有2个官能度的适宜β-二羰基给体化合物包括但不限于:乙酰乙酸乙酯、乙酰乙酸甲酯、2-乙基己基乙酰乙酸酯、乙酰乙酸月桂酯、乙酰乙酸叔丁酯、N-乙酰乙酰苯胺、N-烷基N-乙酰乙酰苯胺、乙酰乙酰胺、2-乙酰乙酰氧基乙基丙烯酸酯、2-乙酰乙酰氧基乙基甲基丙烯酸酯、乙酰乙酸烯丙酯、乙酰乙酸苄酯、2,4-戊二酮、乙酰乙酸异丁酯和2-甲氧基乙基乙酰乙酸酯。
具有4个官能度的合适的β-二羰基给体化合物包括但不限于:1,4-丁二醇二乙酰乙酸酯、1,6-己二醇二乙酰乙酸酯、新戊二醇二乙酰乙酸酯、环己烷二甲醇二乙酰乙酸酯和乙氧基化双酚A二乙酰乙酸酯。
具有6个官能度的合适的β-二羰基给体化合物包括但不限于:三羟甲基丙烷三乙酰乙酸酯、三乙酰乙酸甘油酯和聚己酸内酯三乙酰乙酸酯。
迈克尔加成反应由强碱催化。优选的碱为二氮杂二环十一烯(DBU),其碱性足够强且容易溶于单体混合物中。其它的环脒如二氮杂二环壬烯(DBN)和胍也都适合催化这种反应。典型的适于促进所需反应的有第I族醇盐碱如叔丁醇钾,只要它们在反应介质中具有足够的溶解度。氢氧化季铵盐和季铵盐醇盐如氢氧化四丁基铵或甲氧基苄基三甲基铵构成另一类促进麦克尔加成反应的优选的碱催化剂。最后,亲有机物质的醇盐强碱可以通过卤化物阴离子(如卤化季盐)和环氧化物部分之间的反应原位生成。转让给Ashland,Inc.的美国专利6,706,414公开了这种原位催化剂,其全部内容通过引用结合在此。
在此公开的迈克尔加成树脂还可以通过加入胺协合剂进行改性,以增强其性能。这种改性的实例包括将伯胺或者仲胺加入未固化的迈克尔加成树脂中。该技术公开于美国专利6,673,851中,其全部教导通过引用结合在此。一般的伯胺包括乙醇胺、甲基-1,6-己二胺、3-氨基丙基三甲氧基硅烷、二氨基丙烷、苄胺、三亚乙基四胺、异氟尔酮二胺及其混合物。一般的仲胺包括二甲胺、二丁胺、二乙醇胺(DEA)、哌啶、吗啉及其混合物。如果用伯胺或仲胺改性液体迈克尔加成树脂,改性胺只与液体的未固化迈克尔加成树脂反应。
在本发明中,对β-二羰基迈克尔给体和/或迈克尔受体进行了改性,从而使其含有侧挂I型(例如,取代的苯偶姻、苄基缩酮、苯乙酮或者酰基氧膦)或者II型(例如,取代的二苯酮、噻吨酮、樟脑醌或者联咪唑)光敏部分。由此所得的液体、未交联的迈克尔加成树脂除了具有源自于迈克尔加成反应的取代酮之外,还具有I型和II型光敏官能团的一种或者两种,在暴露于紫外线时,这些官能团能促进丙烯酸基团的加成聚合。所述改性迈克尔给体的实例包括:含有具有以下混合结构的I型光敏部分的迈克尔给体:
包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基。包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基。包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,R为简单烷基或者芳基。包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基。包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基等。
在以下实施例中描述的树脂产品可以用通常用于喷射涂覆至基材的溶剂进行稀释,或者通过使所述树脂与制品的形状和组成一致,以100%固态对其进行涂覆。除非另有说明,在这些实施例中都是通过“涂层取样(draw down)”技术将树脂涂覆至基材上,从而形成不同厚度的薄膜。通过以特定的剂量暴露于单个600W Fusion“ H”灯泡下而实现固化。耐化学性评估在用磷酸盐处理过的钢板上进行。
树脂表现性能通过多种试验方法进行测定。为了确定本领域熟练技术人员熟知的性能,利用以下试验方法:
动态粘度-在确定温度下,基于恒定剪切的锥板测量的数值,单位为泊。
固化响应-在暴露于500mJ/cm2总辐射量的“基准”剂量后,基于涂层评价的评价值:1(潮湿;未固化)、2(粘性)、3(“油滑表面”,易划伤)、4(无粘性,可以被棉花擦划伤)或者5(无粘性/无划伤)。
达到无粘性/无划伤固化的最小剂量-实现上述等级“5”的总剂量,单位为mJ/cm2。
耐MEK性-穿透或者显著划伤所述涂层所需要的MEK双倍摩擦#。
以下实施例说明了详述于此说明书中的新颖的多官能丙烯酸酯低聚物的组成、应用、固化和表现性能。
材料制备1:Irqacure 2959 乙酰乙酸酯
将224.25g得自于Ciba-Geigy的Irgacure 2959I型光敏引发剂Irgacure 2959加入2升的三口圆底烧瓶中的250ml甲苯中,所述烧瓶装配有高架式搅拌器、热电偶、冷凝器和氮气入口管。将158.2g得自于Eastman Chemical Company的乙酰乙酸叔丁酯加入其中,在室温下搅拌反应器,直至形成均相为止。然后,将该反应器内物质加热到110℃,并将反应器保持此温度30分钟。
总共加热1小时后,给反应器装上蒸馏头,在温和氮气流下除去甲苯/叔丁醇的共沸物,直至容器内温度达到125℃。此时,将反应器内容物倾倒入1升单口圆底烧瓶中,在70℃和微弱氮气鼓泡下,在旋转蒸发器上对此黄色液体进行2小时汽提。回收得到309g粘性黄色液体。
NMR分析表明,Irgacure 2959接近定量地转化为伯酯或者叔酯的混合物。为了便于处理,用三羟甲基丙烷(乙氧基)三丙烯酸酯(TMPEOTA)将所得树脂稀释为52%w/w的活性乙酰乙酸酯。
材料制备2:乙酰乙酸缩水甘油酯
乙酰乙酸缩水甘油酯根据Witzeman和Nottingham(J.Org.Chem,1991,56,1713)的方法进行制备。将296g缩水甘油(Dixie Chemical Company,Pasadena,TX)、632.8g乙酰乙酸叔丁酯和500ml甲苯在装配有机械搅拌器、热电偶、冷凝器和氮气入口管的1升反应器中混合。将该反应器内容物加热到110℃,并保持此温度下30分钟。然后,给该反应器装上蒸馏头,在温和氮气流下,在2小时内从反应器蒸出甲苯/叔丁醇的共沸物。反应器中达到的最高温度为120℃。总共4小时后,将所得反应混合物冷却,并且在旋转蒸发器上在70℃下对其汽提2小时。通过1HNMR对所得黄色液体产物进行分析。经证实,缩水甘油基本上定量转化为乙酰乙酸缩水甘油酯。
材料制备3:2959丙烯酸酯酯
将132g Irgacure 2959I型光敏引发剂加入2升三口圆底烧瓶中的乙酸乙酯中,所述烧瓶装有高架式搅拌器、热电偶、冷凝器以及带氮气入口管的滴加漏斗。将57.9g冷的丙烯酰氯(Aldrich Chemical Company,Milwaukee,WI)加入其中,并且用冰浴将反应器冷却至<5℃。在90分钟的时间内将65g三乙胺滴加到其中,同时保持反应器温度低于10℃。在室温下将此所得的黄色“浆液”搅拌2小时,并用FTIR分析样品。几乎观察不到羟基官能团,由此判定该反应已经完全。在室温下对所得产品进行吸滤,所得滤饼用乙酸乙酯漂洗两次。然后,将所得产品液体倒入500ml的单口烧瓶中,在轻微鼓泡的干燥空气下,在旋转蒸发器中在40℃下将其汽提2小时。回收得到163g粘性黄色液体。NMR和FTIR分析表明,Irgacure 2959接近定量地进行了转化(>97%)。为了便于处理,用二丙烯酸己二酯(HDDA)将所得树脂稀释为75%w/w的活性2959丙烯酸酯。
材料制备4:2959/HEA MDI二丙烯酸酯
在装配有高架式搅拌器、热电偶、冷凝器和空气入口管的2升树脂锅中,对528g亚甲基二苯基二异氰酸酯(Mondur ML,Bayer)和605g二丙烯酸己二酯(HDDA)进行混合。然后,将0.81g二月桂酸二丁基锡(DABCOT-12,Air Products)和448.5g Irgacure 2959加入上述搅拌的混合物中,并将反应器加热至60℃。然后,在30分钟时间内将232.4g 2-HEA缓慢加入,同时保持峰值温度低于65℃。随后通过FTIR对反应进行监控。将上述各组分加热总共25小时,此时,NMR和FTIR监控都认为反应已经进行完全。将另外的605g HDDA加入,从而产生了在单体中浓度为50%w/w的2959氨基甲酸乙酯丙烯酸酯。
实施例1“基准实施例”:无内在的I型或者II型光敏引发剂
根据美国专利6,706,414中所描述的方法,将126.6g二丙烯酸己二酯、9.8g三羟甲基丙烷三丙烯酸酯(TMPTA)、29.6g XZ 92551.00环氧丙烯酸酯(DoWChemical Company,Midland,MI)、21.4g乙酰乙酸乙酯(EAA)、0.96g溴化四丁基铵和3.8g甲基丙烯酸缩水甘油酯混合。将反应器温度设置在95℃,并且保持此温度直至经13C NMR确定达到了100%的迈克尔给体的双取代。4小时之后,将7.9g二乙醇胺加入到所述混合物中,在搅拌下将反应产物冷却至室温。
最终产品为低粘度的澄清液体,其锥板粘度为231cP。将该树脂产品涂覆于磷酸盐处理过的钢板上,用600W/in的中压汞灯(Fusion“H”灯泡)的紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 2.31 |
固化响应(500mJ/cm2) | 3 |
无粘性/无划伤固化的最小剂量 | 1740mJ/cm2 |
耐MEK性 | >200 |
实施例2
根据美国专利6,706,414中所描述的方法,将113.8g二丙烯酸己二酯、8.8g三羟甲基丙烷三丙烯酸酯、26.6g XZ 92551.00环氧丙烯酸酯、16.1g乙酰乙酸乙酯、22.8g材料制备1的基于Irgacure 2959的乙酰乙酸酯的50%w/w溶液、0.96g溴化四丁基铵和3.9g甲基丙烯酸缩水甘油酯混合。将反应器温度设置在95℃,并且保持此温度直至经13C NMR确定达到了100%的迈克尔给体的双取代。4小时后,将7.1g二乙醇胺加入所述述混合物中,在搅拌下冷却反应产物至室温。
最终产品为低粘度的澄清液体,其锥板粘度为320cP。将该树脂产品涂覆于磷酸盐处理过的钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)的紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 3.20 |
固化响应(500mJ/cm2) | 5 |
无粘性/无划伤固化的最小剂量 | 446mJ/cm2 |
耐MEK性 | >200 |
实施例3
根据美国专利6,706,414中所描述的方法,将129.3g二丙烯酸己二酯、10.0g三羟甲基丙烷三丙烯酸酯、30.2g XZ 92551.00环氧丙烯酸酯、17.7g乙酰乙酸缩水甘油酯(GAA)和0.96g溴化四丁基铵混合。将反应器温度设置在95℃,并且保持在此温度下,直至如折光指数测量确定实现了100%的迈克尔给体的双取代。将14.6g 2-(4-氯苯甲酰基)苯甲酸(CBBA)加入上述混合物中,并且保持在此温度下约两小时。此时,所有CBBA都通过与环氧部分的反应被消耗。总共蒸煮6小时后,将8.0g二乙醇胺加入其中,在搅拌下将所得反应混合物冷却至室温。最终产品为低粘度的澄清液体,其锥板粘度为366cP。将该树脂产品涂覆于钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 3.66 |
固化响应(500mJ/cm2) | 5 |
无粘性/无划伤固化的最小剂量 | 185mJ/cm2 |
耐MEK性 | >200 |
实施例4
根据美国专利6,706,414中所描述的方法,将114.8g二丙烯酸己二酯、31.7gActilane 584(Akzo Nobel Resins)、28.5g XZ 92551.00环氧丙烯酸酯、12.5g乙酰乙酸缩水甘油酯(GAA)和0.96g溴化四丁基铵混合。将反应器温度设置在95℃,并且保持在此温度下,直至如折光指数测量确定实现了100%的迈克尔给体的双取代。将10.3g 2-苯甲酰基苯甲酸(BBA)加入上述混合物中,并且保持此温度约两小时。此时,所有BBA都通过与环氧部分的反应而被消耗。总共蒸煮7小时后,将7.6g二乙醇胺加入上述混合物中,在搅拌下将反应产物冷却至室温。
最终产品为低粘度的澄清液体,其锥板粘度为230cP。将该树脂产品涂覆于钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 2.30 |
固化响应(500mJ/cm2) | 5 |
无粘性/无划伤固化的最小剂量 | 243mJ/cm2 |
耐MEK性 | >200 |
实施例5
根据美国专利6,706,414中所描述的方法,将192.3g二丙烯酸己二酯、44.4g三羟甲基丙烷三丙烯酸酯、35.8g乙酰乙酸乙酯、9.3g由材料制备3得到的基于Irgacure 2959的丙烯酸酯的75%w/w HDDA中的溶液、1.45g溴化四丁基铵和5.8g甲基丙烯酸缩水甘油酯混合。将反应器温度设置在95℃,并且保持此温度直至经13C NMR确定达到了100%的迈克尔给体的双取代。总反应时间3小时后,将6.0g二乙醇胺加入上述混合物中,在搅拌下冷却所得反应产物至室温。
最终产品为低粘度的澄清液体,其锥板粘度为111cP。将该树脂产品涂覆于钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 1.11 |
固化响应(500mJ/cm2) | 4 |
无粘性/无划伤固化的最小剂量 | 650mJ/cm2 |
耐MEK性 | >200 |
实施例6
根据美国专利6,706,414中所描述的方法,将192.3g二丙烯酸己二酯、44.4g三羟甲基丙烷三丙烯酸酯、35.8g乙酰乙酸乙酯、19.7g类似于材料制备4的基于Irgacure 2959的氨基甲酸乙酯丙烯酸酯的75%w/w HDDA溶液、1.46g溴化四丁基铵和5.8g甲基丙烯酸缩水甘油酯混合。将反应器温度设置在95℃,并且保持在此温度下,直至如折光指数测量确定实现了100%的迈克尔给体的双取代。总反应时间为4.5小时后,将12.0g二乙醇胺加入上述混合物中,在搅拌下冷却所得反应产物至室温。
最终产品为低粘度的澄清液,其锥板粘度为301cP。将该树脂产品涂覆于钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 3.01 |
固化响应(500mJ/cm2) | 5 |
无粘性/无划伤固化的最小剂量 | 449mJ/cm2 |
耐MEK性 | >200 |
实施例7
根据美国专利6,706,414中所描述的方法,将203.6g二丙烯酸己二酯、45.0gXZ 92551.00环氧丙烯酸酯、25.0g 2,4-戊二酮、14.5g Ebecryl P-36丙烯酸二苯酮酯、1.48g溴化四丁基铵和5.9g甲基丙烯酸缩水甘油酯混合。将反应器温度设置在95℃,并且保持在此温度下,直至如折光指数测量确定实现了100%的迈克尔给体的双取代。总反应时间为5.5小时之后,将4.0g二乙醇胺加入上述混合物中,在搅拌下将所得反应产物冷却至室温。
所得最终产品为低粘度的澄清液,其锥板粘度为180cP。将该树脂产品涂覆于钢板上,并且用600W/in的中压汞灯(Fusion“H”灯泡)的紫外线对其进行辐照。
以下性能是如上制备的树脂的性能列表:
性能 | 数值 |
粘度(泊,25℃) | 1.80 |
固化响应(500mJ/cm2) | 5 |
无粘性/无划伤固化的最小剂量 | 425mJ/cm2 |
耐MEK性 | >200 |
在此公开的新颖树脂和掺混物显示了使得它们成为非常有效的涂布材料的性质。这些性质可以得到取决于其组成的显著改进。由此,可以形成对金属、塑料、木材、纸张和玻璃具有优良粘结性能的树脂。它们显示出宽广范围的硬度、刚性、挠性、拉伸强度、抗污性、耐划伤性、耐冲击性、耐溶剂性等。通过正确选择原料结构单元,几乎可以得到任何期望的涂布性能参数。
Claims (12)
1.一种液体、未交联、可紫外固化的迈克尔加成产物,其包括迈克尔受体和选自以下组中的I型和/或II型光敏引发剂改性的β-二羰基迈克尔给体的反应产物:
a.包含具有以下混合结构的I型光敏部分的迈克尔给体:
b.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,
c.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,
d.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,且R是单一的烷基或芳基,
e.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,和
f.包含具有以下结构、包括异构体的II型光敏部分的改性迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,并且,
其中该迈克尔受体是多官能的丙烯酸酯,或者是多官能丙烯酸酯和单官能丙烯酸酯的混合物。
2.权利要求1的迈克尔加成产物,其中所述迈克尔受体是I型和/或II型光敏引发剂改性的迈克尔受体,并且其中所述I型和/或II型光敏引发剂如权利要求1中所定义的。
3.权利要求1的迈克尔加成产物,其中所述迈克尔受体是二丙烯酸酯、三丙烯酸酯、四丙烯酸酯、或它们的混合物。
4.权利要求1的迈克尔加成产物,其进一步包括胺协合剂。
5.权利要求1的迈克尔加成产物,其进一步包括催化剂。
6.权利要求1的迈克尔加成产物,其进一步包括活性稀释剂。
7.权利要求1的迈克尔加成产物,其中相对于迈克尔给体的当量,迈克尔受体的当量为过量。
8.包括权利要求1的迈克尔加成产物的固化交联的残余物的涂料。
9.权利要求8的涂料,其中所述迈克尔加成产物通过暴露于光辐射而固化。
10.一种制品,其包括:
A.基材,和
B.权利要求1的迈克尔加成产物的固化交联的残余物。
11.权利要求10的制品,其中所述基材为金属、塑料、木材、纸张或玻璃。
12.一种改性的β-二羰基迈克尔给体,其包含选自以下组中的I型和/或II型光敏部分:
a.包含具有以下混合结构的I型光敏部分的迈克尔给体:
b.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,
c.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,
d.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,且R是单一的烷基或芳基,
e.包含具有以下结构、包括异构体的II型光敏部分的迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基,和
f.包含具有以下结构、包括异构体的II型光敏部分的改性迈克尔给体:
其中W、X、Y和/或Z各自独立地为卤素、氢、烷基、烷氧基、芳基、氨基、烷基氨基、腈、硝基、磺基或者二氧磷基。
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US56402604P | 2004-04-21 | 2004-04-21 | |
US60/564,026 | 2004-04-21 | ||
PCT/US2005/013196 WO2005108452A2 (en) | 2004-04-21 | 2005-04-19 | Radiation-curable michael addition resins having built-in photoinitiators |
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CN101027326B true CN101027326B (zh) | 2011-03-23 |
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US (1) | US7524565B2 (zh) |
EP (1) | EP1740621B1 (zh) |
JP (1) | JP2007534800A (zh) |
KR (1) | KR20070042503A (zh) |
CN (1) | CN101027326B (zh) |
AT (1) | ATE470680T1 (zh) |
AU (1) | AU2005241006A1 (zh) |
BR (1) | BRPI0510100B1 (zh) |
CA (1) | CA2563358A1 (zh) |
DE (1) | DE602005021773D1 (zh) |
ES (1) | ES2345157T3 (zh) |
TW (1) | TW200613475A (zh) |
WO (1) | WO2005108452A2 (zh) |
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US7307106B2 (en) * | 2004-12-10 | 2007-12-11 | 3M Innovative Properties Company | Photocurable Michael addition polymers |
AU2006320646B2 (en) * | 2005-11-30 | 2012-02-02 | Ashland Licensing And Intellectual Property Llc | Prepregs and cured in place solid surfaces prepared therefrom |
WO2007079541A1 (en) * | 2006-01-12 | 2007-07-19 | John Lyndon Garnett | Radiation curable system |
EP2121771B2 (en) * | 2006-12-21 | 2016-12-07 | AGFA Graphics NV | Novel radiation curable compositions |
US8110610B2 (en) * | 2006-12-21 | 2012-02-07 | Agfa Graphics N.V. | Amine co-initiators for radiation curable compositions |
EP2065362A1 (en) * | 2007-11-29 | 2009-06-03 | Agfa Graphics N.V. | Preparation method of copolymerizable photoinitiators |
EP2199273B1 (en) | 2008-12-18 | 2018-02-21 | Agfa Nv | Polymerizable photoinitiators and radiation curable compositions |
EP2236541A1 (en) | 2009-03-25 | 2010-10-06 | DSM IP Assets B.V. | Polyesteramide macromolecule and composition comprising such a macromolecule. |
CN102428112B (zh) | 2009-05-18 | 2014-01-08 | 爱克发印艺公司 | 可聚合的聚合物光引发剂和辐射可固化组合物 |
CA2769210A1 (en) | 2009-06-29 | 2011-01-06 | Dic Corporation | Michael addition reaction product and active energy ray-curable composition |
KR101212177B1 (ko) | 2010-04-08 | 2012-12-13 | 한국화학연구원 | 다수의 수산기를 포함하는 마이클 수용체, 이로부터 유도된 마이클 부가 생성물 |
EP2656144B1 (en) * | 2010-12-20 | 2020-06-24 | Agfa Nv | A curable jettable fluid for making a flexographic printing master |
WO2012084786A1 (en) | 2010-12-20 | 2012-06-28 | Agfa Graphics Nv | A curable jettable fluid for making a flexographic printing master |
KR101942698B1 (ko) * | 2015-01-05 | 2019-01-25 | 아이지엠 몰타 리미티드 | Led-경화성 저 이동 광개시제 |
US11079675B2 (en) * | 2016-05-13 | 2021-08-03 | Dic Corporation | Compound, photocurable composition, cured product of same, printing ink, and printed matter curing the printing ink |
EP3345942B1 (en) * | 2017-01-05 | 2020-04-01 | IGM Resins Italia S.r.l. | Composition useful as a pressure sensitive adhesive, its use and adhesive articles comprising it |
EP3788083A1 (en) | 2018-04-30 | 2021-03-10 | Basf Se | High molar mass polymers from a continuous process |
EP4189021A1 (en) | 2020-07-31 | 2023-06-07 | Sun Chemical Corporation | Self-initiated energy curable ink compositions |
CN115260857A (zh) * | 2022-07-13 | 2022-11-01 | 广东希贵光固化材料有限公司 | 一种uv肤感涂料 |
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AU2005241006A1 (en) | 2005-11-17 |
CN101027326A (zh) | 2007-08-29 |
DE602005021773D1 (de) | 2010-07-22 |
WO2005108452A2 (en) | 2005-11-17 |
BRPI0510100A (pt) | 2007-09-25 |
TW200613475A (en) | 2006-05-01 |
BRPI0510100B1 (pt) | 2016-09-27 |
EP1740621A2 (en) | 2007-01-10 |
US20050261388A1 (en) | 2005-11-24 |
JP2007534800A (ja) | 2007-11-29 |
KR20070042503A (ko) | 2007-04-23 |
ATE470680T1 (de) | 2010-06-15 |
ES2345157T3 (es) | 2010-09-16 |
WO2005108452A3 (en) | 2006-10-19 |
CA2563358A1 (en) | 2005-11-17 |
US7524565B2 (en) | 2009-04-28 |
EP1740621B1 (en) | 2010-06-09 |
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