CN1137042A - 带酸官能团及环氧官能团的聚酯树脂 - Google Patents
带酸官能团及环氧官能团的聚酯树脂 Download PDFInfo
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- CN1137042A CN1137042A CN96100608A CN96100608A CN1137042A CN 1137042 A CN1137042 A CN 1137042A CN 96100608 A CN96100608 A CN 96100608A CN 96100608 A CN96100608 A CN 96100608A CN 1137042 A CN1137042 A CN 1137042A
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Abstract
适用于生产具有优良户外耐久性能的涂层的带叔碳羧酸官能团的线型聚酯树脂，该聚酯树脂可由以下物质反应来制备：a)至少一种芳香族和/或脂环族羧酸化合物，b)至少一种羟基化合物，c)至少一种羟基取代的羧酸化合物，d)非必须的一种含一个羧酸基的羧酸化合物。
这些树脂可与适宜的固化剂一起用于生产粉状涂料，或转化成相应的聚缩水甘油酯后与适宜固化剂一起用于生产粉状涂料。
Description
本发明涉及带叔碳羧酸官能团的线型聚酯树脂，涉及该树脂的生产方法，涉及通过所述带叔碳羧酸官能团的线型聚酯树脂的缩水甘油化而获得的聚缩水甘油酯树脂，涉及含所述带叔碳羧酸官能团的线型聚酯树脂的涂层组合物、尤其是粉状涂层组合物，涉及所述涂层组合物形成的固化产物。
基于2，2-双(4-羟基苯基)丙烷与表氯醇的固体反应产物的粉状涂层组合物已有多年历史。在这些组合物基础上制备的固化产物能耐水解，但是它们抗紫外能力较低，因此不适用于对户外耐久性能要求高的场合，如用作建筑材料或汽车表层涂层。
欧洲专利申请No.447360(EP-A-447,360)公开了可用于制备高质量户外耐久涂层及成型组合物的三缩水甘油酯。由于存在于三羧酸加成物母体中的羧酸端基的二重性质，在这些三羧酸加成物的缩水甘油化过程中应避免强碱性条件以避免形成的缩水甘油酯和/或树脂骨架上一个或多个酯基的水解。因此生成的三缩水甘油酯会含有大量的可水解氯和/或低分子量水解产物，这可能引起中毒问题。
EP-A-447,360的实施例2反映了高含量的可水解氯。该实施例涉及六氢化邻苯二甲酸酐与二羟甲基丙酸的2∶1加成物的缩水甘油化。所得产物含1.5％的氯。在涂层组合物中往往不希望有这么高的残余氯含量。另外，由于EP-A-447,360中报道的三缩水甘油酯是液态，因此不适用于粉状涂层组合物。
最常用的户外耐久粉状涂层体系是聚酯/异氰脲酸三缩水甘油酯(TGIC)。然而出于健康和安全的考虑，TGIC的使用仍存疑问。TGIC毒性较高(大鼠口服半数致死量为0.4克/千克)，埃姆斯诱变性试验表明该化合物有诱变作用。
对上述现有技术的讨论结果表明，存在着对特别适用于粉状涂层组合物的树脂体系的需求。该组合物与现在的聚酯/TGIC体系相比应相对无毒性且在其固化状态表现出优异的户外耐久性。
本发明的目的之一是提供带酸官能团的线型聚酯树脂，其中的酸官能团仅含脂肪族的叔碳羧酸官能团，它易于缩水甘油化以形成缩水甘油聚酯树脂。所述带叔碳羧酸官能团的线型聚酯树脂和所述缩水甘油聚酯树脂尤其适用于与环境相对顺适的户外耐久型粉状涂层组合物。本发明的树脂骨架不含任何易于水解的酯官能团，聚酯树脂也不含任何对紫外光敏感的官能团。本发明线型树脂的端基为羟基或非必须的酯化羟基。
因此，本发明提供一种可由下述物质反应制备的带叔碳羧酸官能团的线型聚酯树脂：a)至少一种芳香族和/或脂环族羧酸化合物A，其含两个芳香族和/或脂肪族仲碳羧基或其酸酐，b)至少一种羟基化合物B，其含两个脂肪族羟基，该基团可以分别是伯或叔碳羟基，c)至少一种羟基取代的羧酸化合物C，其含有至少一个脂肪族叔碳羧基和两个脂肪族羟基，该基团可以分别是伯或仲碳羟基，d)非必须的一种含一个羧酸基的羧酸化合物D，
化合物A∶B∶C∶D的摩尔比为(X+Y-1)∶X∶Y∶Z，其中X从2至8，Y从2至8，Z从0至2。
制备本发明聚酯树脂的过程最好进行至反应混合物中原存在的全部或几乎全部的非叔碳羧酸基团已反应为止。可以知道，除了使用纯(或几乎纯)的化合物A、B、C和D外，还可使用化合物A、B、C、D中两或更多种的混合物。
如果制备的带叔碳羧酸官能团的线型聚酯树脂的酸价与基于初始存在于反应混合物中的反应物的叔碳羧基的理论计算酸价几乎相当，该聚酯树脂中就几乎不存在非叔碳羧基。这里使用的术语“几乎”表明实际值与理论值的偏离最多为+/-8％，优选5％，更优选3％。该值由标准的碱量滴定法测定。
本领域内的技术人员都了解的是，采用本发明方法制得的树脂的分子量分布和数均分子量取决于特定反应物及其投料比。虽然化合物C中存在的脂肪族叔碳羧基在采用的酯化条件下几乎不反应，但在标准碱性条件下，这些脂肪族叔碳羧基与表卤醇的缩水甘油化反应可以进行，在这种条件下生成的聚缩水甘油酯中的可水解氯含量很低，通常低于该组合物总重量的0.5重量％。另外，在缩水甘油化期间几乎不出现树脂主链的水解，从而无低分子量产物生成，从不存在分子量较低的产物来看，本发明的聚酯树脂特别适用于制备粉状涂层。
可以知道，在酯化反应中，伯碳羟基的反应性比仲碳羟基的反应性高，而伯碳羟基和仲碳羟基的反应性比叔碳羟基高。羧基也具有相同顺序的反应活性。酸酐的反应活性比对应的(二)酸的反应活性要高。另外，在羟基或羧基的β位的取代基通常影响其反应性，通常是导致其反应活性降低。从反应活性的顺序出发，在基于化合物A、B、C和非必须的D的树脂的分子量分布范围内可以预测树脂最可能的化学结构。可以看到，在本发明的一个更优选的实施方案中，其中化合物A是六氢化邻苯二甲酸酐，化合物B是氢化二羟苯基丙烷，化合物C是二羟甲基丙酸，由于化合物B的反应活性比化合物C高，在含叔碳羧基的酯化反应中形成的最小的分子为由1分子C、2分子A和2分子B构成的树脂分子，其分子量约为900。这表明缩水甘油化后即使最小可能的分子也具有相对高的分子量，因此产物的毒性较低。
由于本发明涉及线型聚酯树脂，化合物A、B和C应具有双官能团，这些官能团参加酯化反应形成树脂主链上的酯基。因此，化合物A、B和C中的单或多官能团杂质的含量通常低于15％，优选低于7％，更优选低于3％。在剧烈的酯化反应条件下，一些酯化反应会出现在叔碳羧基上，产生支链型树脂。这通常发生在低于3％的反应混合物中存在的叔碳羧基上，在更优选的酯化条件下应低于1％。
可以根据传统的酯化方法来进行本发明的聚酯树脂的制备过程，其中优选采用共沸缩聚法。更具体的是，如下进行缩聚反应：将化合物A到C及非必须的D加入至反应器内，随后升温至120～230℃、优选180～220℃进行反应，反应进行至原存在于反应混合物中的非叔碳羧基消失为止。另一方法是：将化合物A和C加入反应器中，随后升温至100～220℃开始缩聚反应，然后向反应混合物中加入化合物B和非必须的化合物D，随后升温至120～230℃开始反应。按此方法进行反应，应确保化合物C不成为最终聚酯树脂产物中的末端基或末端基的一部分。
通常共沸移走水份的过程持续至反应产物的形成，该产物的酸价与上述理论酸价相当。通常不要求使用一种或多种酯化催化剂，如氧化二丁锡、对甲苯磺酸、辛酸锡、辛酸锌和蓖麻醇酸锂，优选不使用催化剂。但是，如果需要可以使用酯化催化剂。
本发明的聚酯树脂中的化合物A的适当来源是含两个脂肪族仲碳羧基的芳香族、尤其是脂环族的二羧酸及其酸酐。例如化合物A为邻苯二甲酸(PA)、四氢化邻苯二甲酸、六氢化邻苯二甲酸(HHPA)、甲基六氢化邻苯二甲酸、对苯二甲酸、间苯二甲酸、十氢化萘二羧酸、桥亚甲基四氢化邻苯二甲酸、甲基桥亚甲基四氢化邻苯二甲酸、1，4-环己烷二羧酸和1，3-环己烷二羧酸或其酸酐或其组合物；尤其优选HHPA，特别是其酸酐。
本发明的聚酯树脂中的化合物B的适当来源是含两个脂肪族仲碳羟基的化合物。优选的化合物B含一个或多个环己烷基且被两个仲碳羟基取代。
用于本发明的合适的化合物B包括支化的脂肪族、脂环族或芳脂族化合物，其含两个脂肪族羟基，分别是伯或仲碳羟基，例如丙二醇、新戊二醇、氢化二羟苯基丙烷(HDPP)、氢化二羟苯基甲烷、氢化4，4′-二羟基联苯、1，4-环己烷二甲醇、1，2-、1，3-或1，4-二羟基环己烷、羟基新戊基羟基新戊酸酯和2-丁基-2-乙基-1，3-丙二醇或其混合物；特别优选HDPP。
本发明的聚酯树脂中的化合物C的适当来源是含一个脂肪族叔碳羧基和两个伯碳羟基的化合物。优选的化合物C是二羟甲基丙酸。
本发明的聚酯树脂中的化合物D的适当来源是仅含一个羧酸基团的化合物。特别是脂肪、脂环或芳香酸，更特别是仲碳酸。优选的化合物D是芳香族或脂环族酸，更优选仲碳脂肪酸。优选的化合物D是环烷基羧酸、特别是C5-C8环烷基羧酸，更优选环己烷基羧酸。
化合物A、B、C和D可以也可以不被取代。取代基，例如烷基，尤其是C1-4烷基和羟基不应损害固化产品的户外耐久性。优选未取代的或被一个或多个烷基取代的化合物。
已发现，根据本发明的叔碳羧酸官能团线型聚酯树脂中的X优选从5至7，更优选6，而Y优选从3至5，更优选4。已发现化合物A的数量(X+Y-1)的少量偏离是允许的。通常该偏离应低于5％，优选低于3％，更优选低于1％。通常化合物A宁可少量，不要过量。如果似乎存在着不期望的过量化合物A，可以添中额外量的化合物B和C。如果使用了化合物D则Z可从0至2，优选从1至2，更优选2。
本发明还涉及通过以下物质反应制备如上所述带叔碳羧酸官能团的线型聚酯树脂的方法：a)至少一种芳香族和/或脂环族羧酸化合物A，其含两个芳香族和/或脂肪族仲碳羧基或其酸酐，b)至少一种羟基化合物B，其含两个脂肪族羟基，该基团可以分别是伯或叔碳羟基，c)至少一种羟基取代的羧酸化合物C，其含有至少一个脂肪族叔碳羧基和两个脂肪族羟基，该基团可以分别是伯或仲碳羟基，d)非必须的一种含一个羧酸基的羧酸化合物D，
化合物A∶B∶C∶D的摩尔比为(X+Y-1)∶X∶Y∶Z，其中X从2至8，Y从2至8，Z从0至2。该过程优选在100～230℃、优选180～220℃的温度下进行，直至反应混合物中原存在的非叔碳羧基几乎全反应为止。反应时间一般小于8小时，通常小于4小时。
如上指出，本发明的带叔碳羧酸官能团的线型聚酯树脂可通过本领域已知的方式容易地转化成聚缩水甘油酯树脂，如在适宜的碱的存在下及非必须的催化剂存在下，通过与过量的表卤醇反应。最合适的是采用表氯醇。
本发明的带叔碳羧酸官能团的聚酯树脂和聚缩水甘油酯树脂都适用于制备粉状涂层组合物，该组合物在固化状态下体现优良的户外耐久性。另外，从本发明的聚缩水甘油酯树脂的聚合性质来看，可以预计其毒性比TGIC更低，因此它们可较好地在粉末涂层中用做TGIC的替代物。
本发明的可固化粉状涂层组合物可以如下制备：将起交联作用的树脂加入至本发明方法制得的带叔碳羧酸官能团的线型聚酯树脂中或加入至通过缩水甘油化上述带叔碳羧酸官能团的线型聚酯树脂而获得的聚缩水甘油酯中。本发明的粉状涂层组合物中交联化合物的使用量应保证提供与带叔碳羧酸官能团的线型聚酯树脂中的叔碳羧基或与聚缩水甘油酯树脂中的环氧基相当的反应基团数。
与本发明带叔碳羧酸官能团的聚酯树脂一起使用的起交联作用的树脂有户外耐久型环氧树脂，比如对苯二甲酸二缩水甘油酯、本发明的聚缩水甘油酯树脂、欧洲专利申请公开518,408中公开的a，a′-双支链二羧酸二缩水甘油酯以及欧洲专利申请公开366,205中公开的基于每个a碳原子上都带有两个烷基取代基的多羧酸的聚缩水甘油酯。
与本发明的聚缩水甘油酯一起使用的起交联作用的树脂有(相应的)本发明的酸官能团聚酯树脂；固态多酸如癸二酸、己二酸和1，12-十四烷双酸；酸酐如多壬二酸酐和1，2，4-苯三酸酐；酸官能团聚酯如1摩尔三羟甲基丙烷与3摩尔六氢化邻苯二甲酸酐的反应产物、1，6-己二醇与摩尔过量的1，12-十四烷双酸的反应产物、4摩尔1，10-癸二羧酸、1.49摩尔己二醇、0.47摩尔1，1，1-三-(羟甲基)-丙烷和0.27摩尔季戊四醇的反应产物、4摩尔1，10-癸二羧酸、1.2摩尔己二醇、0.45摩尔三羟甲基丙烷、0.29摩尔季戊四醇和0.21摩尔二羟甲基丙酸的的反应产物及1摩尔六甲氧基甲基三聚氰胺和3摩尔羟基新戊酸的反应产物；氰尿酸；及固体碱性固化剂如双氰胺和BF3-配和物。
本发明的粉状涂层组合物还可以包括现有技术中已知的适用于粉状涂层组合物的催化剂和非必须的其它添加剂。
合适的催化剂有如季胺和磷盐；金属盐/化合物如辛酸锡(II)；碱性化合物如咪唑；及叔胺如1，8-二氮二杂环十一碳烯。
催化剂的使用量通常是在粉状涂层组合物总重量的0.1～2重量％范围内。
本发明的粉状涂层组合物适宜的固化时间及固化温度是传统的粉状涂层组合物所采用的。
本发明通过以下实施例来说明。
实施例1
将六氢化邻苯二甲酸酐(9摩尔)、氢化二苯羟基丙烷(6摩尔)和二羟甲基丙酸(4摩尔)加入至圆底玻璃反应器中，该反应器装有温控、通氮、搅拌及蒸馏装置。在30分钟内将混合物加热至150℃。在1小时内将反应混合物加热至180℃并保温1小时。施加9.5×104帕(950毫巴)的真空，将混合物温度升至200℃并保温。直至达到理论酸价。将所得带酸官能团聚酯出料并冷却至室温。
实施例2
将六氢化邻苯二甲酸酐(9摩尔)和二羟甲基丙酸(4摩尔)加入圆底玻璃反应器中，加热至150℃并保温直至反应完全(约需1-2小时)。向反应混合物中加入氢化二苯羟基丙烷(6摩尔)，将温度升至180℃再保温1小时。然后以与实施例1相同的方式继续反应。产物特性： 酸价 1180毫摩尔/千克
OH价 590毫摩尔/千克
烷点(koffler) 105-125℃
实施例3
将实施例1中制备的1羧基当量的脂肪族带叔碳羧酸官能团的线型聚酯树脂溶于10摩尔表氯醇和560毫升异丙醇中。将该溶液加至装有控温器、搅拌器和回流冷凝器的3升玻璃反应器中。升温至80℃，随后在170分钟内逐渐加入1.1摩尔的NaOH水溶液。再反应15分钟，静置反应器中的物料，分离水相与有机相。对有机相抽真空。所得产物溶于甲基异丁基酮，有机相用水冲洗三次，然后有机相抽真空。所得缩水甘油酯出料并冷却。特性： 环氧基含量 985毫摩尔/千克
OH价 553毫摩尔/千克
可水解氯 ＜0.45重量％
熔点(koffler) 78-98℃
实施例4
粉状涂层组合物：
1.如下制备的含羧酸官能团的半结晶聚酯。2.ModaflowIII是Monsanto公司出品的基于丙烯酸类的助流剂。3.Actiron SNO 30是Protex出品的固体催化剂。通过以下途径制得粉剂。
| 组分 | 重量(克) |
| 实施例3制备的缩水甘油酯 | 579.6 |
| 含羧酸基的半结晶聚酯1 | 216.1 |
| 二氧化钛 | 159.1 |
| Modaflow III2 | 9.7 |
| 二苯乙醇酮 | 6.3 |
| Actiron SNO 303 | 29.2 |
在室温下将组分混合，然后在110℃下在布斯单螺杆挤出机中进行熔融混合。挤出物进行冷却、刨片、超细粉碎并过106微米的筛进行分选。
将粉末静电喷涂在铬酸盐预处理的2毫米厚的铝板上。将涂覆板在200℃下烘烤15分钟。形成的涂层(40-60微米厚)十分光滑、坚硬、光亮且体现优良的机械和化学性能以及优良的耐候性(使用SAE 1960测试法在氙型风化仪中暴露1200小时后光泽度降低小于10％)。与基于(EPIKOTE，直线)的树脂和许多工业聚酯/丙烯酸树脂(阴影面积)的对比列于图1(％gloss gardner 60°与暴露小时时间的关系)。
上面提及的含羧基的半结晶聚酯如下制备。将4.0摩尔1，10-癸二羧酸、3.0摩尔1，6-己二醇和二甲苯(进料的5％)加入装有锚式搅拌器、温度计、迪安—斯达克榻分水器和通氮装置的玻璃反应烧瓶中。在170℃开始酯化反应，反应生成的水通过共沸蒸馏除去。将反应混合物温度升至220℃并保温直至所有的羟基基本反应为止。混合物冷却至约180℃并抽真空(200毫巴，2.0×104帕)以移去共沸溶剂(二甲苯)。最后，消除真空，将聚酯冷却至约160℃，出料至铝盘并冷却至室温。
实施例5
将六氢化邻苯二甲酸酐(9摩尔)、氢化二苯羟基丙烷(6摩尔)、二羟甲基丙酸(4摩尔)和环己烷羧酸(2摩尔)加入装有控温、通氮、搅拌和蒸馏设备的圆底烧瓶中。然后在30分钟内将混合物加热至150℃。在1小时内将反应混合物温度升至180℃并保温1小时。抽真空至9.5×104帕(950毫巴)，并将混合物升温至200℃并保温直至达到上述理论酸价。将所得酸官能团聚酯出料并冷却至室温。
实施例6
将六氢化邻苯二甲酸酐(9摩尔)和二羟甲基丙酸(4摩尔)加入圆底玻璃反应器，加热至150℃并保温直至完成酸酐/羟基反应(1-2小时)。将氢化二羟苯基丙烷(6摩尔)和环己烷羧酸(2摩尔)加至反应混合物中，按照实施例5继续制备过程。
实施例7
将氢化二羟苯基丙烷(6摩尔)和环己烷羧酸(2摩尔)加至圆底玻璃反应器中，加热至180℃并保温直至酸/羟基反应完成(1-2小时)。将六氢化邻苯二甲酸酐(9摩尔)和二羟甲基丙酸(4摩尔)加至反应混合物中，按照实施例5继续制备过程。
实施例8
分别进行实施例6的第一阶段及实施例7的第一阶段。在180℃将两混合物倒在一起按照实施例5继续制备过程。特性： 酸价 1170毫摩尔/千克
熔点(koffler) -
实施例9
将实施例6制备的与1羧基当量相当的脂肪族带叔碳官能团的线型聚酯树脂溶于10摩尔表氯醇(ECH)和异丙醇(IPA)中。将该溶液加入装有控温器、搅拌器和回流冷凝器的3升玻璃反应器中。升温至80℃，随后在170分钟内逐渐加入1.1摩尔NaOH水溶液。再反应15分钟，静置反应器内物料并将水相从有机相中分离出来。
对有机相抽真空以移走水份、IPA和ECH。将所得产物溶于甲基异丁基酮(MIBK)中，用水冲洗有机相三次，然后对有机相抽真空移走MIBK。将所得缩水甘油酯出料并冷却。特性： 环氧基含量 850-950毫摩尔/千克
可水解氯 166毫摩尔/千克
熔点(koffler)实施例10
制备含以下组分的粉状涂层组合物：
1.羧酸官能团半结晶聚酯，基于1，10-癸二羧酸(4.0摩尔)、1，6-己二醇(1.49摩尔)、1，1，1-三-(羟甲基)-丙烷(0.47摩尔)和季戊四醇(0.27摩尔)。2.ModaflowIII是Monsanto公司出品的基于丙烯酸类的助流剂。3.Actiron SNO 30是Protex出品的固体催化剂。通过下列过程来制备粉剂。
| 组分 | 重量(克) |
| 根据实施例9的缩水甘油酯 | 579.6 |
| 含羧酸官能团的半结晶聚酯1 | 216.1 |
| 二氧化钛 | 159.1 |
| Modaflow III2 | 9.7 |
| 二苯乙醇酮 | 6.3 |
| Actiron SNO 303 | 29.2 |
在室温混合组分，然后在110℃下在布斯单螺杆挤出机中熔融共混。挤出物进行冷却、刨片、超细粉碎并通过106微米的筛进行分选。
将粉剂静电喷涂在铬酸盐预处理的2毫米厚的铝板上。将涂覆板在200℃下烘烤15分钟。形成的涂层(40-60微米厚)十分光滑、坚硬、光亮且体现优良的机械及化学性能及优良的耐候性(使用SAE 1960测试法在氙型风化仪中暴露1200小时后光泽度降低低于10％)。
Claims (10)
1.一种可通过下列物质反应制备的带叔碳羧酸官能团的线型聚酯树脂：a)至少一种芳香族和/或脂环族羧酸化合物A，其含两个芳香族和/或脂肪族仲碳羧基或其酸酐，b)至少一种羟基化合物B，其含两个脂肪族羟基，该基团可以分别是伯或叔碳羟基，c)至少一种羟基取代的羧酸化合物C，其含有至少一个脂肪族叔碳羧基和两个脂肪族羟基，该基团可以分别是伯或仲碳羟基，d)非必须的一种含一个羧酸基的羧酸化合物D，
化合物A∶B∶C∶D的摩尔比为(X+Y-1)∶X∶Y∶Z，其中X从2至8，Y从2至8，Z从0至2。
2.根据权利要求1的带叔碳羧酸官能团的线型聚酯树脂，其中化合物A为含有两个脂肪族仲碳羧基的脂环二羧酸或其酸酐，化合物B包含两个脂肪族仲碳羟基，优选含一个或多个被两个仲碳羟基取代的环己烷环，化合物C含一个脂肪族叔碳羧基和两个伯碳羟基。
3.根据权利要求2的带叔碳羧酸官能团的线型聚酯树脂，其中化合物A为六氢化邻苯二甲酸或其酸酐，化合物B为氢化二羟苯基丙烷，化合物C为二羟甲基丙酸，化合物D为环己烷羧酸。
4.根据权利要求1至3中任一项的带叔碳羧酸官能团的线型聚酯树脂，其中X从5至7，优选X为6，Y从3至5，优选Y为4，Z从1至2，优选Z为2。
5.根据权利要求1至4中任一项的带叔碳羧酸官能团的线型聚酯树脂的制备方法，即通过以下物质反应：a)至少一种芳香族和/或脂环族羧酸化合物A，其含两个芳香族和/或脂肪族仲碳羧基或其酸酐，b)至少一种羟基化合物B，其含两个脂肪族羟基，该基团可以分别是伯或叔碳羟基，c)至少一种羟基取代的羧酸化合物C，其含有至少一个脂肪族叔碳羧基和两个脂肪族羟基，该基团可以分别是伯或仲碳羟基，d)非必须的一种含一个羧酸基的羧酸化合物D，
化合物A∶B∶C∶D的摩尔比为(X+Y-1)∶X∶Y∶Z，其中X从2至8，Y从2至8，Z从0至2。
6.根据权利要求5的方法，其中将化合物A至C及非必须的D加至反应器中，随后在120～230℃下、优选180～220℃下反应，继续反应直至反应混合物中原存在的非叔碳羧基消失。
7.根据权利要求5的方法，其中首先将化合物A至C加至反应器中，随后在100～220℃反应，然后将化合物B及非必须的化合物D加至反应混合物，随后在120～230℃反应。
8.通过权利要求1至4中任一项的带叔碳羧酸官能团的线型聚酯树脂与表卤醇、优选表氯醇在合适的碱存在下的反应制得的聚缩水甘油酯。
9.含权利要求8的聚缩水甘油酯和交联剂或含权利要求1至4中任一项的带叔碳羧酸官能团的线型聚酯树脂和交联剂的粉状涂层组合物。
10.涂覆有根据权利要求9的粉状涂层组合物的产品。
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| EP95200022.2 | 1995-01-06 |
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| CNB011112360A Expired - Fee Related CN1179005C (zh) | 1995-01-06 | 2001-03-08 | 带酸官能团及环氧官能团的聚酯树脂 |
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| AT (1) | ATE207093T1 (zh) |
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| CA (1) | CA2166585A1 (zh) |
| DE (1) | DE69615873T2 (zh) |
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| CN100362066C (zh) * | 2001-03-27 | 2008-01-16 | 住友化学工业株式会社 | 涂料用树脂组合物 |
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| US6136882A (en) * | 1998-08-19 | 2000-10-24 | Morton International Inc. | Non-hazing UV curable powder coatings containing crystalline resins |
| US6011080A (en) * | 1998-08-19 | 2000-01-04 | Morton International, Inc. | Non-hazing UV curable powder coatings containing crystalline resins |
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| US6451929B1 (en) | 1999-10-29 | 2002-09-17 | Resolution Performance Products, Llc | Glycidyl ester by reacting COOH polyester with epihalohydrin |
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| US6417292B1 (en) | 2000-04-07 | 2002-07-09 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions including ungelled reaction products of epoxy functional polyesters and amines coated substrates and methods of electrocoating using the same |
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1995
- 1995-12-18 JP JP7328730A patent/JPH08253566A/ja active Pending
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1996
- 1996-01-04 CA CA002166585A patent/CA2166585A1/en not_active Abandoned
- 1996-01-04 US US08/582,855 patent/US5739213A/en not_active Expired - Fee Related
- 1996-01-04 CN CN96100608A patent/CN1073585C/zh not_active Expired - Fee Related
- 1996-01-04 BR BR9600024A patent/BR9600024A/pt not_active Application Discontinuation
- 1996-01-05 ES ES96200027T patent/ES2167508T3/es not_active Expired - Lifetime
- 1996-01-05 AT AT96200027T patent/ATE207093T1/de active
- 1996-01-05 KR KR1019960000089A patent/KR960029365A/ko not_active Application Discontinuation
- 1996-01-05 DE DE69615873T patent/DE69615873T2/de not_active Expired - Fee Related
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1997
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362066C (zh) * | 2001-03-27 | 2008-01-16 | 住友化学工业株式会社 | 涂料用树脂组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08253566A (ja) | 1996-10-01 |
| CN1358809A (zh) | 2002-07-17 |
| CA2166585A1 (en) | 1996-07-07 |
| DE69615873T2 (de) | 2002-04-25 |
| US5739213A (en) | 1998-04-14 |
| KR960029365A (ko) | 1996-08-17 |
| BR9600024A (pt) | 1998-01-21 |
| CN1179005C (zh) | 2004-12-08 |
| DE69615873D1 (de) | 2001-11-22 |
| US5811198A (en) | 1998-09-22 |
| CN1073585C (zh) | 2001-10-24 |
| ES2167508T3 (es) | 2002-05-16 |
| ATE207093T1 (de) | 2001-11-15 |
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