CN1312344A - 氨基甲酸官能聚酯聚合物或低聚物和涂料组合物 - Google Patents
氨基甲酸官能聚酯聚合物或低聚物和涂料组合物 Download PDFInfo
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- CN1312344A CN1312344A CN01112026A CN01112026A CN1312344A CN 1312344 A CN1312344 A CN 1312344A CN 01112026 A CN01112026 A CN 01112026A CN 01112026 A CN01112026 A CN 01112026A CN 1312344 A CN1312344 A CN 1312344A
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Abstract
公开了一种有氨基甲酸侧基的聚酯聚合物。该聚合物通过下列步骤制备:(a)将环状碳酸羟烷基酯化合物与有至少一个环状酸酐基的化合物反应生成含环状碳酸基的半酯酸,(b)将步骤(a)半酯上的环状碳酸基与氨,氢氧化铵或伯胺反应以将环状碳酸酯开环从而生成包括酸基,羟基和氨基甲酸侧基的化合物,和(c)将包括步骤(b)的化合物且任选包括一种多元醇或一种多元酸或两者皆有的混合物反应以形成有氨基甲酸侧基的聚酯。
Description
本发明涉及聚合物，特别涉及含聚合物的可固化涂料组合物。
有氨基甲酸官能基因的聚合物和低聚物已用于各种可固化组合物中。例如在U.S.Patent 5,356,669和WO94/10211中描述了氨基甲酸官能丙烯酸类聚合物。这些聚合物可用氨基甲酸官能丙烯酸类单体加成聚合或通过羟基官能丙烯酸类与氨基甲酸烷基酯转氨基甲酰化来制备。JP51/4124描述了用羟基官能聚酯转氨基甲酰化制备的氨基官能聚酯。
聚酯现在广泛用于可固化组合物如涂料组合物中。这些树脂提供了许多有益的性能如良好的寿命，良好的挠性，通过并入适当的离子或非离子稳定基团在含水体系中良好的分散性，耐冲击强度，良好的粘性和其他物理性能如应力释放。与用于可固化组合物的聚酯树脂有关的一个方法是向其中并入足够量的官能基以获得所需的固化特性。羟基是在可固化组合物常规的官能基。但有侧羟基的聚酯树脂很难制备，因为在聚酯生成期间侧羟基将与酸基反应而消耗掉。羟官能基通常通过使用多元醇封端剂如三羟甲基丙烷并入到聚酯树脂中，获得端OH，但不能获得侧OH。这类树脂在固化时仅提供有限的交联密度。虽然交联密度通过使用支化聚酯可增加一些。该支化聚酯通过将三官能或多官能多元醇或多元酸并到聚酯反应混合物中制备。但由于凝胶作用支化度常常受限制。在可固化聚酯树脂体系中低交联密度通常必须使用高分子量树脂来补偿，而该高子量树脂更像热塑性树脂而不像热固性树脂。
氨基甲酸官能聚酯被描述在JP51/4124。该文献描述了通过典型的羟基官能聚酯与氨基甲酸酯的酯基转移制备有氨基甲酸端基的聚酯的方法。
因此，本发明涉及制备有氨基甲酸侧基的聚酯聚合物或低聚物的新方法。
按照本发明，提供一种包括下列步骤的制备聚酯聚合物的方法：
(a)将环状碳酸羟烷基酯化合物与有至少一个环状酸酐基的化合物反应生成含环状碳酸基的半酯酸，
(b)将步骤(a)半酯上的环状碳酸基与氨，氢氧化铵或伯胺反应以将环状碳酸酯开环从而生成包括酸基，羟基和氨基甲酸侧基的化合物，和
(c)将包括步骤(b)的化合物且任选包括一种多元醇或一种多元酸或两者皆有的混合物反应以形成有氨基甲酸侧基的聚酯。
在本发明另一个实施方案中，提供用上述方法制得的聚合物或低聚物。
在本发明第三个实施方案中，提供包括上述氨基甲酸官能聚酯和可与氨基甲酸反应的固化剂的涂料组合物。
可用来实施本发明环状碳酸羟烷基酯可用许多方法来制备。一些环状碳酸羟烷基酯如碳酸3-羟丙基酯(即碳酸甘油酯)可商购。环状碳酸酯化合物可用几种不同方法的任何一种来制备。一种方法为将含环氧基化合物与CO2，优选在有催化剂加压下反应。有用的催化剂包括任何活化环氧乙烷环的化合物如叔胺的季盐(如溴化四甲基铵)，锡或磷配合盐(如（CH3)3SNI:(CH3)4PI)。在这类催化剂存在下环氧化物也可与β-丁内酯反应。在另一种方法中，二元醇如甘油在至少为80℃(通常在回流下)和催化剂(如碳酸钾)存在下与碳酸二乙酯反应生成碳酸羟烷基酯，另外，含下式结构的1,2-二元醇酮缩醇的官能化合物在至少60℃下，优选有痕量酸存在下用水开环，以生成1,2-乙二醇，然后再与碳酸二乙基酯反应生成环状碳酸酯。
从本领域可知，环状碳酸酯通常为5或6元环。优选5元环，因为它们易于合成和可商购。
用于本发明中优选的环状碳酸羟烷基酯可用下式表示：
其中R是1-18碳原子，优选1-6个碳原子，更优选1-3个碳原子羟烷基，R可被1个或多个其他取代基如保护后的胺或不饱和基团取代。更优选R是-CmH2mOH其中羟基可为伯或仲羟基，和m是1到8，再优选R是-(CH2)p-OH其中羟基是伯羟基和p是1到2。
与环状碳酸羟烷基酯反应的环状酸酐可以是能与环状酸羟烷基酯反应的单酸酐或多酸酐，包括邻苯二甲酸酐，对苯二甲酸酐，1,2,4-苯三酸酐，1,2,4,5-苯四酸二酐，六氢化邻苯二甲酸酐，甲基六氢化邻苯二甲酸酐，马来酐，谷氨酸酐，1,2,4,5-双-酸酐环己烷。酸酐反应通常在温度为120℃，优选110℃，最好为90℃下反应。该反应比较好，因为它不会使氨基甲酸二元酵酯置于严酷的反应条件下。
然后环状碳酸羟烷基酯与环状酸酐化合物的反应产物本身与氨、氢氧化铵或伯胺反应。该反应在温和的条件(例如，0-60℃，在水，甲醇或其他已知的溶剂中)下反应。与氨或氢氧化铵反应生成伯氨基甲酸酯且是优选的。与伯胺反应生成仲(N-取代的)氨基甲酸酯。氨，氢氧化铵或伯胺与环状碳酸酯基的开环反应生成如上所述的氨基甲酸基和伯或仲羟基，该羟基在本发明下一步中参加在生成聚氨酯反应中，这样获得的反应产物包括氨基甲酸侧基和端羟基。
在本发明聚酯上的氨基甲酸侧基可以是伯或仲基。伯氨基甲酸基可用下式表示；
仲氨基甲酸基可用下式表示：
其中R是1-8，优选1-4，更优选1个碳原子的取代或未取代烷基，或环脂肪烃基。应该明白术语烷基和环烷基包括取代的烷基和环烷基如卤素取代的烷基或环烷基或不饱和基取代的烷基，但应避免选择对固化后材料有不利影响的取代基。伯氨基甲酸基是经使用氨或氢氧化铵作为开环反应物在上述环碳酸酯的开环反应中生成的。反应结果是一种包括来自环状酸酐开环反应的酸基和来自环状碳酸酯开环反应的羟基和氨基甲酸基的化合物。
按照本发明，含该化合物的混合物置于酯化缩合反应条件下以生成聚酯。在此以前，将在环状碳酸酯基开环反应期间被胺盐化了的酸基再酸化是有利的。另外，足够的热可使用以离解酸盐并推动酯化反应。
聚酯反应通常在140℃和260℃之间进行3到15小时，使用或不使用酸酯化反应催化剂，如0.01到2.0％(重量)的磷酸或甲苯磺酸。反应任选在一种溶剂如本领域公知的芳烃存在下进行。反应可以单级或多级如二级来进行。这样制备的聚酯通常有1000到60000的数均分子量。
聚酯反应混合物除了含有包括至少一个酸基、至少一个羟基和至少一个氨基甲酸侧基的化合物外还包括一个或多个多元酵和/或多元酸。这些附加的多元醇和/或多元酸参加在生成聚酯的酯化缩合反应中。这些化合物的量可调节以使聚合物有所需的官能氨基甲酸基。
用于实施本发明的多元酸可在脂肪或芳香部分含2到34个碳原子和至少2个，优选不多于4个羧基，羧基也可为酸酐基形式。多元酸可以是多元酸本身或在聚酯反应期间能被含氨基甲酸基的二元醇或其他多元醇开环以形成用于聚酯缩合反应的酸基的多元酸的环状酸酐。有用的多元酸的例子包括邻苯二甲酸酐、对苯二甲酸酐、间苯二酸，己二酸，丁二酸，戊二酸，富马酸，马来酸，环己二酸，1,2,4-苯三酸酐，壬二酸，癸二酸，二聚酸，1,2,4,5-苯四酸二酐，取代的马来酸和富马酸如柠康酸，氯代马来酸或中康酸和取代的丁二酸如阿康酸和衣康酸。多元酸的混合物也可使用。
可用于实施本发明的多元醇通常有大于2个，优选2到约10个，更优选约2到8碳原子及2到约6，优选2到约4个羟基。一些优选的多元醇的例子是下列的一个或多个：新戊二醇，乙二醇，丙二醇，丁二醇，六亚甲基二醇，1,2-环己烷二甲醇，1,3-环己烷二甲醇，1,4-环己烷二甲醇，三羟甲基丙烷，季戊四醇，新戊二醇羟基新戊酸酯，二乙二醇，三乙二醇，四乙二醇，二丙二醇，聚丙二醇，己二醇，2-甲基-2-乙基-1,3-丙二醇，2-乙基-1,3-己二醇，1,3-戊二醇，硫二甘醇，1,3-丙二醇，1,3-丁二醇，2,3-丁二醇，1,4-丁二醇，2,2,4-三甲基-1,3-戊二醇,1,2-环己二醇，1,3-环己二醇，1,4-环己二醇，丙三醇，三羟甲基丙烷，三羟甲基乙烷，1,2,4-丁三醇，1,2,6-己三醇，二季戊四醇，三季戊四醇，甘露糖醇，山梨醇，甲基苷，本领域技术人员显而易见的化合物和它们的混合物。根据最终树脂所需性质，一些其他多元醇可并到反应混合物中如脂肪多元醇，酚类多元醇(例如氢醌，酚酞，双酚A)，低聚或聚合多元醇(例如预成聚酯多元醇)。另外，其他化合物如反应调节剂，催化剂，溶剂，分散剂等本领域已知的化合物也可并入。
可选择多元酸及多元醇和任何其他活性化合物的比例以获得酸基终端聚酯或羟基终端聚酯。这可通过使用化学计量过量的多元酸或醇来实现。
如果水溶性是需要的，重要的是将水稳定基团嵌入到聚酯中。这可通过将水稳定的多醚多元醇并到反应混合物中以使它们并列聚酯中或通过在反应混合物中使用二甲醇丙酸作为多元醇来实现。
通过在聚酯反应混合物中使用过量的多元酸或多元醇组分，中间体聚酯树脂可制成具有羟基或酸基端基。树脂的端基然后可通过这些端基与本领域已知的过量的封端剂反应来控制。如果中间体树脂是酸端基，单或多官能醇可用来在所需阶段(通过测定粘度和异氰酸基浓度来确定)终止反应(将游离酸基封端)。多官能醇如乙二醇，三羟甲基丙烷和羟基终端的聚酯也可以这样方式使用。在仅有氨基甲酸基官能度而无羟基官能度的树脂中，中间体聚酯树脂优选用单官能醇(例如正丁醇)封端。同样，羟端基中间体树脂可通过与过量的单或多官能酸反应来封端。
按本发明制备的树脂可掺入到可固化组合物如涂料组合物中。在本发明的可固化组合物中。固化通过氨基官能化聚酯组分与组分(2)反应来进行。组分(2)是有多个与聚酯上氨基甲酸侧基反应的官能基化合物。这类活性基团包括在氨基塑料交联剂或其他化合物如酚/甲醛加合物上的羟甲基或甲基烷氧基，硅氧烷基和酸酐基。固化剂的例子包括密胺甲醛树脂(包括单体的或聚合的密胺树脂和部分或全部烷基化的密胺树脂)，脲树脂(例如，羟甲基脲类如脲甲醛树脂，烷氧基脲类如丁基化脲甲醛树脂)，聚酸酐(如聚丁二酸酐)，和聚硅氧烷类(如，三甲氧基硅氧烷)，氨基塑料树脂如密胺甲醛树脂或脲甲醛树脂是特别优选的。
在可固化组合物中，可任选使用溶剂。虽然本发明的组合物可以基本上为固体粉末或分散体使用，但通常希望该组合物基本上为液态，这可使用溶剂来实现。这种溶剂应对氨基甲酸官能基树脂和固化剂都起到溶剂的作用。通常，根据组分溶解度特性，溶剂可以是任何有机溶剂和/或水。在一优选的实施方案中，溶剂是极性有机溶剂。更优选，溶剂是极性脂肪溶剂或极性芳香溶剂。再优选，溶剂是酮，酯，乙酸酯，非极性酰胺，非极性亚砜或非极性胺。有用溶剂的例子包括甲乙酮，甲异丁酮，乙酸间-戊基酯，乙二醇丁基醚-乙酸酯，丙二醇单甲醚乙酸酯，二甲苯，N-甲基吡咯烷酮或芳烃的混合物。在另一个优选的实施方案中，溶剂是水或水与少量助溶剂的混合物。
用于实施本发明的可固化组合物可包括催化剂以提高固化反应。例如，当使用氨基塑料化合物特别是单体密胺时，强酸催化剂可用来提高固化反应。这类催化剂是本领域公知的且包括例如对-甲苯磺酸，二壬基萘二磺酸，十二烷基苯磺酸，苯甲酸磷酸酯，马来酸单丁基酯，磷酸丁酯和羟基磷酸酯。强酸催化剂常常例如用胺来保护，可用于本发明中的其他催化剂包括路易斯酸，锌盐和锡盐。
在本发明一优选实施方案中，可固化组合物中溶剂量为约0.01％～99％(重量)，优选约10％～60％(重量)，更优选约30％～50％(重量)。
涂料组合物可用本领域已知的大量方法涂到物品上。这些方法包括例如喷涂，浸涂，辊涂，幕涂等。对于汽车表盘，优选喷涂。
任何附加使用的试剂例如表面活性剂，填料稳定剂，润湿剂，分散剂，粘合促进剂，UV吸收剂，HALS等都可并入列涂料组合物中。虽然这些试剂是先有技术中公知的，使用量必须控制以避免对涂料性质有不利影响。
按照本发明的可固化涂料优选用于高光泽涂料中和/或作为颜色+透明度的复合涂料的透明涂层使用。用于本文中的高光泽涂料是有20°的光泽度(ASTMD523-89)或DOI为至少80(ASTME430-91)的涂料。用于本文中的高光涂涂料也可作为颜色＋透明度复合涂料的底涂层来使用。
当本发明的涂料组合物作为高光泽度的颜料漆涂料时，颜料可为任何有机或无机化合物或色料，填料，金属或其他无机薄片材料如云母或铝溥片和其他类型通常称为颜料的材料。颜料基于组分A和B的总固体量为1％到100％(重量)(即颜料：B为0.1到1)。
当本发明的涂料组合物用作颜色＋透明度的复合涂料的透明涂层时，颜料底层涂层组分可为本领域已知的大量类型的任一种，而且无须详细解释。用于底层涂层的本领域已知的聚合物包括丙烯酸类聚合物，乙烯类聚合物，聚氨酯，聚碳酸酯，聚酯，醇酸树脂和聚硅氧烷。优选的聚合物包括丙烯酸类聚合物和聚氨酯。在一优选的本发明实施方案中，底涂层组合物也使用氨基甲酸官能丙烯酸类聚合物。底涂层聚合物可为热塑性的，但优选是可交联的且包括一种或多种可交联官能基。这类基团包括例如，羟基，异氰酸基，胺基，环氧基，丙烯酸基，乙烯基，硅烷基和乙酰乙酸基。这些基团可用这样的方式保护，以使它们在所需的固化条件下通常为升温下可脱保护并为交联反应使用。有用的可交联官能基包括羟基，环氧基，酸基，酸酐基，硅烷基和乙酰乙酸基。优选的可交联官能基包括羟官能基和氨基官能基。
底涂层可为自交联的或需要与聚合物官能剂反应的另外的交联剂。
当聚合物包括羟基官能基时，例如交联剂可为氨基塑料树脂，异氰酸基和保护的异氰酸基(包括异氰脲酸基类)和酸或酸酐官能交联剂。
描述在本文中的涂料组合物优选置于固化涂料涂层的条件下。虽然可使用各种固化方法，但优选热固化。通常热固化通过将涂布后的物品暴露在高温(主要由热辐射源提供)下来进行。固化温度将随用于交联剂中的特定保护剂而变化，但通常在93℃到177℃之间。本发明的化合物在比较低的固化温度下仍是反应性的。这样，在优选的实施方案中，对于保护的酸催化体系，因化温度优选在115℃到150℃之间，更优选在115℃到138℃之间。对于未保护酸催化体系，固化温度优选在82℃到99℃。固化时间随所用的具体组分，和物理参数如层的厚度而变化，但典型的固化时间对保护的催化体系为15到60分钟，优选15-25分钟；对未保护酸催化体系为10-20分钟。
本发明进一步用下列实施例来描述。实施例1用羟基官能碳酸酯对酸酐开环来制备酸官能碳酸酯中间体
一个三颈圆底烧瓶装有一个带50毫升溶剂阱的Claisen应接器旁路器，冷凝器，搅拌器，氮气进气管，和热电偶，该反应器装有下列组分：组分 重量六氢化4-甲基邻苯二酸酐 1200.00环状碳酸羟烷基酯 842.86二甲苯溶剂 300.00
2342.86
搅拌器与氮气进气管，冷凝器冷却水一起打开，热浴缓慢加热到98℃。在热浴加热到98℃时，注意到有轻微的放热且温度升到105℃，在放热结束时，将热浴加热到110℃，并在该温度下保持1.5小时。此时用酸值来监测反应直至反应结束。在反应结束后，将反应产品加到5升烧瓶中以将环状碳酸酯氨化。
一个5升三颈烧瓶装有一指形回流真空冷凝器，搅拌器，装有多孔碎玻璃片的氨进气管和热电偶。将该装置放入作为冷浴的金属容器中，该容器装有干冰，水，丙酮和氯化钠以控制反应温度。然后向反应器中装入800克甲醇。反应温度下降至15℃，此时向反应器中鼓氨气直到反应温度增至32℃。此时，搅拌反应物并冷却到15℃。该操作连续进行直至在红外谱图上观察不到碳酸酯峰。根据浴尺寸和氨浓度这将需要约12小时。
在所有的环状碳酸酯被转化成氨基甲酸甘醇酯后，将反应设备改装以便能进行热直空汽提。直空汽提在室温下进行以防止崩沸或体系的膨胀。温度在真空度为28英寸汞高下缓慢升温(体系允许的)到80℃。当气相色谱清扫氨和甲醇时真空汽提结束。
然后检查反应固体并用二甲苯调整到含53.00％非挥发性物。
反应的下一步是含氨基甲酸侧官能基的聚酯多醇缩合阶段。
一个三颈圆底烧瓶装有多孔3板精馏柱，搅拌器，带有50毫升溶剂阱的Claisen应接器，冷凝器，氮气进气管和热电偶。该反应器装有下列组分：组分 重量实施例1的带有氨基甲酸侧官能 1200.00基的羟基酸二聚脂肪Acidempol1010 1400.001,6-己二醇 285.80二丁基锡二月酸酯 0.15
2885.95
打开搅拌器，将50克甲苯加到收集肼中且缓慢加热反应物到137.7℃。反应混合物达到137.7℃时，在该温度下保持3小时(一些甲苯和水的共沸物可看到)。在3小时后，升温至170℃，此时可观察到甲苯和水的强共沸物。反应温度在170℃保持8小时，此时测量第一酸值。然后每小时测酸值一次直到反应达(5-10)AN值或(0.089-0.178)毫当量/克。在反应达到预定酸值时，冷却反应物到100℃。此时可加入任何补加溶剂以使固体达到规定的指标。
本发明已参照其优选实施方案进行详细描述。但应该明白在本发明的精神和范围内可作各种变化和变型。
Claims (6)
1．一种可固化涂料组合物，其特征在于，它包括：
(A)一种聚酯，它是包括下列化合物的混合物的酯化产物
(1)一种包括至少一种酸基，至少一种羟基，和至少一种
氨基甲酸侧基的化合物，和
(2)任选的一种多元醇或一种多元酸或两者。
(B)一种有多个与氨基甲酸反应的基团的固化剂。
2．按照权利要求1的可固化涂料组合物，其特征在于，固化剂是一种氨基塑料。
3．按照权利要求2的可固化涂料组合物，其特征在于，氨基塑料是一种蜜胺树脂。
4．按照权利要求1的可固化涂料组合物，其特征在于，化合物(1)是下列化合物的酯化缩合反应产物：
(a)一种含环状碳酸基的半酯酸，它是下列化合物的反应产物：
(ⅰ)环状碳酸羟烷基酯化合物
(ⅱ)有至少一种环状酸酐的化合物，和
(b)氨，氢氧化铵或伯铵。
5．按照权利要求4的可固化涂料组合物，其特征在于，所述混合物进一步包括一种多元醇。
6．按照权利要求4或5的可固化涂料组合物，其特征在于，所述混合物进一步包括一种多元酸。
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| CN1980983B (zh) * | 2004-06-18 | 2010-05-05 | 科聚亚公司 | 聚合物和它们作为涂料的用途 |
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- 1995-12-09 ES ES95119415T patent/ES2183849T3/es not_active Expired - Lifetime
- 1995-12-09 EP EP95119415A patent/EP0718337B1/en not_active Expired - Lifetime
- 1995-12-09 DE DE69528345T patent/DE69528345T2/de not_active Expired - Lifetime
- 1995-12-12 CA CA002165038A patent/CA2165038A1/en not_active Abandoned
- 1995-12-20 KR KR1019950053033A patent/KR100351533B1/ko not_active IP Right Cessation
- 1995-12-20 AU AU40572/95A patent/AU692001B2/en not_active Ceased
- 1995-12-20 CN CN95120877A patent/CN1078598C/zh not_active Expired - Fee Related
- 1995-12-20 BR BR9505973A patent/BR9505973A/pt not_active IP Right Cessation
- 1995-12-21 JP JP33379795A patent/JP3425283B2/ja not_active Expired - Fee Related
-
2001
- 2001-03-27 CN CN01112026A patent/CN1312344A/zh active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980983B (zh) * | 2004-06-18 | 2010-05-05 | 科聚亚公司 | 聚合物和它们作为涂料的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0718337A1 (en) | 1996-06-26 |
| CN1133308A (zh) | 1996-10-16 |
| JPH08231694A (ja) | 1996-09-10 |
| CN1078598C (zh) | 2002-01-30 |
| US5508379A (en) | 1996-04-16 |
| EP0718337B1 (en) | 2002-09-25 |
| KR100351533B1 (ko) | 2002-11-07 |
| KR960022665A (ko) | 1996-07-18 |
| DE69528345T2 (de) | 2003-05-15 |
| BR9505973A (pt) | 1997-12-23 |
| AU4057295A (en) | 1996-06-27 |
| JP3425283B2 (ja) | 2003-07-14 |
| ES2183849T3 (es) | 2003-04-01 |
| AU692001B2 (en) | 1998-05-28 |
| MX185139B (es) | 1997-06-26 |
| CA2165038A1 (en) | 1996-06-22 |
| DE69528345D1 (de) | 2002-10-31 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |