CN104788653B - 一种储存稳定的高酸值饱和聚酯树脂及其制备方法 - Google Patents
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Abstract
本发明公开了一种储存稳定的高酸值饱和聚酯树脂，按重量份计包括：对苯二甲酸二甲酯100重量份；新戊二醇0～30重量份；乙二醇20～50重量份；醋酸锌5～15重量份；偏苯三酸酐40～70重量份；对苯二甲酸20～45重量份；苯酐8～15重量份；亚磷酸三苯基酯35～55重量份；葵二酸10～20重量份；己二酸4～12重量份。还公开了该种储存稳定的高酸值饱和聚酯树脂的制备方法。本发明得到的聚酯树脂具有良好储存稳定性，玻璃化温度高，耐化学性能好，流平性能优异，具有高酸值的特性，特别适用于户外粉末涂料。
Description
技术领域
本发明属于户外粉体涂料技术领域，涉及一种储存稳定的高酸值饱和聚酯树脂，还涉及该种储存稳定的高酸值饱和聚酯树脂的制备方法。
背景技术
热固性聚酯环氧型粉末涂料是以聚酯树脂为主要成膜物质，加入环氧树脂、流平剂、助剂、颜料、填料等组分。经混合、熔融等工序加工制成粉末涂料，经静电喷涂于磷化后的制件上，在一定的温度、时间内，树脂熔融、交联后固化成平整、坚硬而又有柔性的涂膜。固化后的涂膜不会因温度的升高二重新软化。该涂料无溶剂、无污染，100％成膜，既省资源，又省能源。涂层具有光泽度高，流平性好，漆膜丰满，颜色浅，耐泛黄性即耐紫外线好等特性。广泛用于电冰箱、洗衣机、吸尘器及各种仪表外壳、自行车、铁窗栅栏、家具等表面涂装，与丙烯酸粉末涂料相比，具有更好的附着力、机械强度和涂装、施工性能。
热固性聚酯环氧型粉末涂料用聚酯树脂分饱和与不饱和两大类，以饱和型聚酯树脂最为理想，有较好的耐候性和保光性。饱和型聚酯树脂有羟基型和羧基型两种，羟基型一般用异氰酸醋等为固化剂，羧基型一般用含有环氧基团的树脂为固化剂。
发明内容
本发明的目的是提供一种储存稳定的高酸值饱和聚酯树脂，具有良好储存稳定性，玻璃化温度高，耐化学性能好，流平性能优异，具有高酸值的特性。
本发明的另一目的是提供该种储存稳定的高酸值饱和聚酯树脂的制备方法。
为解决技术问题，本发明采用如下技术方案：
一种储存稳定的高酸值饱和聚酯树脂，包括以下组分，各组分按照重量份分别为：
该种储存稳定的高酸值饱和聚酯树脂的制备方法，其制备过程包括：在反应釜中加入对苯二甲酸二甲酯、新戊二醇、乙二醇和醋酸锌，边搅拌边缓慢升温，同时通入氮气保护，升温至150℃后保持恒温，进行酯交换反应3～5小时，然后加入偏苯三酸酐、对苯二甲酸和苯酐，继续通入氮气保护，在醋酸锌的作用下升温至170～240℃，进行酯化反应3～5小时，直到反应釜内溶液澄清且无气泡时，加入亚磷酸三苯基酯，搅拌3～4分钟，然后抽真空，进行缩聚反应1～1.5小时，反应温度保持在240～250℃，真空度为0.08～0.095Mpa，反应结束后以氮气消真空，降温至165～175℃，加入葵二酸和己二酸后，升温至180～200℃，进行醋化反应，封闭1.5小时候反应结束，得到储存稳定的高酸值饱和聚酯树脂产物。
本发明将季铵盐类的固化促进剂改成了改性的叔胺类固化促进剂，在储存稳定性能上更加稳定。树脂的相对分子质量大小及其分布与醇酸的物质的量比及合成工艺有关，玻璃化温度主要与高分子链的柔顺性、相对分子量及其分布、结晶等有关，影响粉末涂料的贮存稳定性，一般玻璃化温度越高，粉末的贮存稳定性越好。混合型聚酯树脂的玻璃化温度一般要求在50℃以上，软化点主要决定树脂的耐热性能和易冷却性，树脂的熔融黏度主要与分子间的作用力大小和酸值有关，影响粉末涂层的流平性，一般树脂熔融黏度越小，涂层流平性就越好。
优选的，储存稳定的高酸值饱和聚酯树脂包括以下组分，各组分按照重量份分别为：
优选的，储存稳定的高酸值饱和聚酯树脂包括以下组分，各组分按照重量份分别为：
当乙二醇的含量一定时，树脂的粘度随着新戊二醇含量的增加而呈下降趋势，因此，新戊二醇含量较多时能获得较低的粘度，从而获得更加优异的流平性能。
优选的，储存稳定的高酸值饱和聚酯树脂包括以下组分，各组分按照重量份分别为：
优选的，储存稳定的高酸值饱和聚酯树脂包括以下组分，各组分按照重量份分别为：
当不含新戊二醇时，树脂的粘度随着乙二醇含量的增加而下降，此时能获得较好的流平性能。另外，随着己二酸含量的增加，树脂的粘度、软化点和玻璃化温度也在一定范围内有所下降。
与现有技术相比，本发明具有以下有益效果：
本发明采用了真空缩聚解聚法，将多元醇、多元酸单体及酯化催化剂进行酯交换反应，再与酸酐进行酯化反应，然后加入亚磷酸三苯基酯进行真空缩聚反应，再加入解酸剂和助剂进行醋化反应，最终得到浅黄色透明的具有特定酸值的聚酯树脂，得到的聚酯树脂具有良好储存稳定性，玻璃化温度高达57～63℃，耐化学性能好，粘度低至2500～3500mPa·s，流平性能优异，酸值高达57～63mgKOH/g，特别适用于户外粉末涂料。
下面结合具体实施方式对本发明作进一步描述：
具体实施方式
本发明一种储存稳定的高酸值饱和聚酯树脂实施例1，包括以下组分，各组分按照重量份分别为：
该种储存稳定的高酸值饱和聚酯树脂的制备方法如下：在反应釜中加入对苯二甲酸二甲酯、新戊二醇、乙二醇和醋酸锌，边搅拌边缓慢升温，同时通入氮气保护，升温至150℃后保持恒温，进行酯交换反应3～5小时，然后加入偏苯三酸酐、对苯二甲酸和苯酐，继续通入氮气保护，在醋酸锌的作用下升温至170～240℃，进行酯化反应3～5小时，直到反应釜内溶液澄清且无气泡时，加入亚磷酸三苯基酯，搅拌3～4分钟，然后抽真空，进行缩聚反应1～1.5小时，反应温度保持在240～250℃，真空度为0.08～0.095Mpa，反应结束后以氮气消真空，降温至165～175℃，加入葵二酸和己二酸后，升温至180～200℃，进行醋化反应，封闭1.5小时候反应结束，得到储存稳定的高酸值饱和聚酯树脂产物。
本发明一种储存稳定的高酸值饱和聚酯树脂实施例2，包括以下组分，各组分按照重量份分别为：
该种储存稳定的高酸值饱和聚酯树脂的制备方法与实施例1相同。
本发明一种储存稳定的高酸值饱和聚酯树脂实施例3，包括以下组分，各组分按照重量份分别为：
该种储存稳定的高酸值饱和聚酯树脂的制备方法与实施例1相同。
本发明一种储存稳定的高酸值饱和聚酯树脂实施例4，包括以下组分，各组分按照重量份分别为：
该种储存稳定的高酸值饱和聚酯树脂的制备方法与实施例1相同。
现有技术中的饱和聚酯树脂对比例，包括以下组分，各组分按照重量份分别为：
该种饱和聚酯树脂的制备方法如下：将反应釜加热升温至95～100℃，加入新戊二醇、间苯二甲酸和钛白粉，边搅拌边缓慢升温，同时通入氮气保护，升温至245℃后保持恒温，反应12～15小时，直到反应物澄清且酸值在42～48mgKOH/g，然后抽真空，真空度为0.06～0.08Mpa，直到反应物粘度在4500～5500mPa·s，酸值在32～34mgKOH/g，停止抽真空，降温到200～210℃，加入抗氧剂，搅拌0.5小时，得到饱和聚酯树脂产物。
对实施例1～4得到的储存稳定的高酸值饱和聚酯树脂产物的酸值、粘度、玻璃化温度、软化点和180℃下的固化时间等进行检测，同时与现有技术对比例进行比较，检测结果如表1所示。
表1
测试结果表明，本发明实施例1～4得到的储存稳定的高酸值饱和聚酯树脂产物的酸值在60±3mgKOH/g，粘度在3000±500mPa·s，玻璃化温度在60±3℃，软化点在115±10℃，180℃下的固化时间在12±2min。实施例1～4的玻璃化温度与对比例相当，但是软化点比对比例有明显提高，说明耐热性能有所增加，粘度比对比例有明显下降，说明其流平性能比对比例更加优异，酸值远远高于对比例，具有特定酸值的特性，在180℃下的固化时间比对比例大大下降，现有技术中较好的能做到20±2min，本发明却能下降到12±2min，说明固化所需要的时间更短，明显优于对比例，可见产物的综合性能均比现有技术有明显提高。
当乙二醇的含量一定时，树脂的粘度随着新戊二醇含量的增加而呈下降趋势；当不含新戊二醇时，树脂的粘度随着乙二醇含量的增加而下降；随着己二酸含量的增加，树脂的粘度、软化点和玻璃化温度也在一定范围内有所下降。因此，实施例2的粘度比实施例1有进一步下降，其流平性能也相对有一定提高，虽然玻璃化温度、软化点也略有下降，但是下降不多。而实施例4的粘度比实施例3也有进一步下降，玻璃化温度、软化点也基本相当，但是固化时间有所下降，可见，实施例2和实施例4为较理想的实施例。
另外，储存稳定性能评定：
按标准对样品进行热固性粉末贮存稳定性的评定，取实施例1～4得到的储存稳定的高酸值饱和聚酯树脂产物和对比例各100g样品，将其分别放在试管底部，塞住试管在40℃恒温环境下放置7天，到时间后取出试管冷却2小时，将样品倒在清洁表面上，观察样品现象得出评定，对比例粉末涂料出现轻微压实现象评定为1级，实施例1～4粉末涂料均无变化，评定为0级，说明本发明实施例1～4的产物在储存稳定性能上比现有技术对比例更加稳定。
耐化学性能评定：
分别用丙酮和MEK对实施例1～4得到的储存稳定的高酸值饱和聚酯树脂产物和对比例进行擦拭试验，对擦拭前后进行失光率以及铅笔硬度的比较，用丙酮擦拭的失光率由对比例的15％下降为实施例1～4的8％左右，铅笔硬度由对比例的B增加到实施例1～4的HB；用MEK擦拭的失光率由对比例的20％下降为实施例1～4的12％左右，铅笔硬度由对比例的B增加到实施例1～4的HB；说明实施例1～4在耐化学性能上比对比例得到了明显提升。
以上所述仅为本发明的具体实施例，但本发明的技术特征并不局限于此，任何本领域的技术人员在本发明的领域内，所作的变化或修饰皆涵盖在本发明的专利范围之中。
Claims (1)
1.一种储存稳定的高酸值饱和聚酯树脂，其特征在于：包括以下组分，各组分按照重量份分别为：
对苯二甲酸二甲酯
100重量份；
新戊二醇
0～30重量份；
乙二醇
20～50重量份；
醋酸锌
5～15重量份；
偏苯三酸酐
40～70重量份；
对苯二甲酸
20～45重量份；
苯酐
8～15重量份；
亚磷酸三苯基酯
35～55重量份；
癸二酸
10～20重量份；
己二酸
4～12重量份；
其制备过程包括：在反应釜中加入对苯二甲酸二甲酯、新戊二醇、乙二醇和醋酸锌，边搅拌边缓慢升温，同时通入氮气保护，升温至150℃后保持恒温，进行酯交换反应3～5小时，然后加入偏苯三酸酐、对苯二甲酸和苯酐，继续通入氮气保护，在醋酸锌的作用下升温至170～240℃，进行酯化反应3～5小时，直到反应釜内溶液澄清且无气泡时，加入亚磷酸三苯基酯，搅拌3～4分钟，然后抽真空，进行缩聚反应1～1.5小时，反应温度保持在240～250℃，真空度为0.08～0.095MPa，反应结束后以氮气消真空，降温至165～175℃，加入癸二酸和己二酸后，升温至180～200℃，进行醋化反应，封闭1.5小时候反应结束，得到储存稳定的高酸值饱和聚酯树脂产物。
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