CN109679495A - 一种耐高温聚酰亚胺改性pdms硅树脂的制备方法 - Google Patents

一种耐高温聚酰亚胺改性pdms硅树脂的制备方法 Download PDF

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CN109679495A
CN109679495A CN201811532139.5A CN201811532139A CN109679495A CN 109679495 A CN109679495 A CN 109679495A CN 201811532139 A CN201811532139 A CN 201811532139A CN 109679495 A CN109679495 A CN 109679495A
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姚伯龙
刘嘉成
陈昆
胡绪灿
刘竞
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Abstract

一种耐高温聚酰亚胺改性PDMS硅树脂的制备方法，属于功能涂料领域。本发明利用端羟丙基聚二甲基硅氧烷、异弗尔酮二异氰酸酯（IPDI）、三羟甲基丙烷(TMP)、1，3‑丙二胺合成四臂氨基封端的甲组分交联剂；用均苯二酸酐、对苯二胺、二苯甲酮四酸二酐合成乙组分酸酐封端的线性聚酰胺酸；甲乙组分混合后在高温下发生交联反应和热亚胺化反应，形成致密网络结构成膜，该涂层具有极高的耐热性和强度。

Description

一种耐高温聚酰亚胺改性PDMS硅树脂的制备方法
技术领域
本发明一种耐高温聚酰亚胺改性PDMS硅树脂的制备方法，涉及一种用聚酰亚胺改性PDMS硅树脂合成涂料，属于功能涂料领域。
背景技术
聚二甲基硅氧烷（PDMS）是一种成本低廉的有机硅化合物，其既具有丰富的硅羟基(Si-OH)，可与金属表面羟基发生缩合形成共价键；又带有与Si相连的有机基团(甲基(-CH3）)，与防腐涂层的面漆具有很好的相容性；同时由于Si-O键的高键能以及长键长，涂层环保、无毒、机械强度高、耐热、耐候性远优于其他防腐材料，因而，作为一种性能优良的防腐涂层材料，有机聚硅氧烷涂层具有广阔的应用前景。但其本身的化学结构决定了制得的涂层硬度普遍较低，所以需要进行改性处理。
聚酰亚胺树脂具有耐热性好、绝缘性高、机械强度大等优点, 在薄膜、机械零部件、光刻胶等领域已有广泛的应用, 在涂料领域也被广泛用作电线绝缘漆，将其与有机聚硅氧烷复合，能够增强涂层硬度的同时，且不会影响涂层的耐热性以及耐候性，具有良好市场前景。
发明内容
本发明目的在于克服现有技术的不足，提供一种耐高温聚酰亚胺-PDMS双组分涂料，其利用端羟丙基聚二甲基硅氧烷、异弗尔酮二异氰酸酯（IPDI）、三羟甲基丙烷(TMP)、1，3-丙二胺合成四臂氨基封端的甲组分交联剂；用均苯二酸酐、对苯二胺、二苯甲酮四酸二酐合成乙组分酸酐封端的线性聚酰胺酸；甲乙组分混合后在高温下发生交联反应和热亚胺化反应，形成致密网络结构成膜，该涂层具有极高的耐热性和强度。
本发明的技术方案是：一种耐高温聚酰亚胺改性PDMS硅树脂的制备方法，步骤为：
（1）甲组分交联剂的制备：
A、在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入端羟基PDMS、IPDI、催化剂，加入溶剂N-甲基吡咯烷酮NMP，通入氮气，开动搅拌，反应升温至45℃，反应2-2.5h，得到NCO封端的中间产物Ⅰ；
B、在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入一定量TMP，用NMP充分溶解后通入氮气，开动搅拌，升温至70℃，将中间产物Ⅰ用滴液漏斗缓慢滴入烧瓶，反应3h，得到四臂羟基封端的中间产物Ⅱ；
C、在含有中间产物Ⅱ的反应器中加入一定量的IPDI，反应温度为45℃，反应2h，得到四臂NCO封端的中间产物Ⅲ；
D、将中间产物Ⅲ降温至常温，加入过量的1，3丙二胺，常温反应1h得到四臂氨基封端的甲组分交联剂；
（2）乙组分线性聚酰氨酸的制备：
在装有电动搅拌器、氮气导管、滴液装置的500mL三颈烧瓶中将均苯二酸酐、对苯二胺、二苯甲酮四酸二酐按一定比例溶于NMP中，开动搅拌，常温反应24h得到聚酰胺酸混合物；
（3）涂层的制备：
将制得的甲组分加入至乙组分中充分搅拌，同时加入一定量的脱水剂，混合均匀后，将溶液取少量倒入聚四氟乙烯槽中，放入烘箱中80℃烘烤6h，然后升温至140℃烘烤12h，即得到淡红色涂层膜，即产品耐高温聚酰亚胺改性PDMS硅树脂。
本发明的有益效果：本发明提供一种耐高温聚酰亚胺-PDMS双组分涂料，其利用端羟丙基聚二甲基硅氧烷、异弗尔酮二异氰酸酯（IPDI）、三羟甲基丙烷(TMP)、1，3-丙二胺合成四臂氨基封端的甲组分交联剂；用均苯二酸酐、对苯二胺、二苯甲酮四酸二酐合成乙组分酸酐封端的线性聚酰胺酸；甲乙组分混合后在高温下发生交联反应和热亚胺化反应，形成致密网络结构成膜，该涂层具有极高的耐热性和强度。
具体实施方式
实施例1
中间产物Ⅰ的制备：将2.667g IPDI溶于50mL N-甲基吡咯烷酮（NMP）中，加入至四颈烧瓶中，并滴入0.1g催化剂二月桂酸二丁基锡，开动搅拌，通入氮气，设定油浴锅温度为45℃，开始升温；将12g分子量为2000的双端羟基PDMS溶于100mL N-甲基吡咯烷酮（NMP）中，加至滴液漏斗，缓慢滴入四颈烧瓶中，反应2h得到中间产物Ⅰ。
中间产物Ⅱ的制备：在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入1.608g TMP，用20ml NMP充分溶解后通入氮气，开动搅拌，升温至70℃，将中间产物Ⅰ用滴液漏斗缓慢滴入烧瓶，反应3h，得到四臂羟基封端的中间产物Ⅱ。
中间产物Ⅲ的制备：在含有中间产物Ⅱ的反应器中加入2.667g IPDI，反应温度为45℃，反应2h，得到四臂NCO封端的中间产物Ⅲ。
甲组分交联剂的制备：将中间产物Ⅲ降温至常温，加入1.2g 1,3丙二胺，常温反应1h得到四臂氨基封端的甲组分交联剂。
乙组分线性聚酰胺酸的制备：
在装有电动搅拌器、氮气导管、滴液装置的500ml三颈烧瓶中将4.36g均苯二酸酐、4.32g对苯二胺、6.433g二苯甲酮四酸二酐溶于50mL NMP中，开动搅拌，常温反应24h得到聚酰胺酸混合物。
双组分涂层制备：将制得的甲组分加入至乙组分中充分搅拌，同时加入2g DCC，混合均匀后，将溶液取50g倒入聚四氟乙烯槽中，放入烘箱中80℃烘烤6h，然后升温至140℃烘烤12h，即可得到淡红色涂层膜，即产品耐高温聚酰亚胺改性PDMS硅树脂。

Claims (2)

1.一种耐高温聚酰亚胺改性PDMS硅树脂的制备方法，其特征在于步骤为：
（1）甲组分交联剂的制备：
A、中间产物Ⅰ的制备：在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入端羟基PDMS、IPDI、催化剂，加入溶剂N-甲基吡咯烷酮NMP，通入氮气，开动搅拌，反应升温至45℃，反应2~2.5h，得到NCO封端的中间产物Ⅰ；
B、中间产物Ⅱ的制备：在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入一定量TMP，用NMP充分溶解后通入氮气，开动搅拌，升温至70℃，将中间产物Ⅰ用滴液漏斗缓慢滴入烧瓶，反应3h，得到四臂羟基封端的中间产物Ⅱ；
C、中间产物Ⅲ的制备：在含有中间产物Ⅱ的反应器中加入一定量的IPDI，反应温度为45℃，反应2h，得到四臂NCO封端的中间产物Ⅲ；
D、甲组分交联剂的制备：将中间产物Ⅲ降温至常温，加入过量的1，3丙二胺，常温反应1h得到四臂氨基封端的甲组分交联剂；
（2）乙组分线性聚酰氨酸的制备：
在装有电动搅拌器、氮气导管、滴液装置的500mL三颈烧瓶中将均苯二酸酐、对苯二胺、二苯甲酮四酸二酐按一定比例溶于NMP中，开动搅拌，常温反应24h得到聚酰胺酸混合物；
（3）双组分涂层的制备：
将制得的甲组分加入至乙组分中充分搅拌，同时加入一定量的脱水剂，混合均匀后，将溶液取少量倒入聚四氟乙烯槽中，放入烘箱中80℃烘烤6h，然后升温至140℃烘烤12h，即得到淡红色涂层膜，即产品耐高温聚酰亚胺改性PDMS硅树脂。
2.根据权利要求1所述耐高温聚酰亚胺改性PDMS硅树脂的制备方法，其特征在于具体步骤为：
中间产物Ⅰ的制备：在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中，将2.667g IPDI溶于50mL N-甲基吡咯烷酮NMP中，加入至四颈烧瓶中，并滴入0.1g催化剂二月桂酸二丁基锡，开动搅拌，通入氮气，设定油浴锅温度为45℃，开始升温；将12g分子量为2000的双端羟基PDMS溶于100mL N-甲基吡咯烷酮NMP中，加至滴液漏斗，缓慢滴入四颈烧瓶中，反应2h得到中间产物Ⅰ；
中间产物Ⅱ的制备：在装有电动搅拌器、冷凝管、氮气导管、滴液装置的500mL四颈烧瓶中加入1.608g TMP，用20mL NMP充分溶解后通入氮气，开动搅拌，升温至70℃，将中间产物Ⅰ用滴液漏斗缓慢滴入烧瓶，反应3h，得到四臂羟基封端的中间产物Ⅱ；
中间产物Ⅲ的制备：在含有中间产物Ⅱ的反应器中加入2.667g IPDI，反应温度为45℃，反应2h，得到四臂NCO封端的中间产物Ⅲ；
甲组分交联剂的制备：将中间产物Ⅲ降温至常温，加入1.2g 1,3丙二胺，常温反应1h得到四臂氨基封端的甲组分交联剂；
乙组分线性聚酰胺酸的制备：在装有电动搅拌器、氮气导管、滴液装置的500mL三颈烧瓶中将4.36g均苯二酸酐、4.32g对苯二胺、6.433g二苯甲酮四酸二酐溶于50mL NMP中，开动搅拌，常温反应24h得到聚酰胺酸混合物；
双组分涂层的制备：将制得的甲组分加入至乙组分中充分搅拌，同时加入2g 脱水剂二环己基碳二亚胺DCC，混合均匀后，将溶液取50g倒入聚四氟乙烯槽中，放入烘箱中80℃烘烤6h，然后升温至140℃烘烤12h，即可得到淡红色涂层膜，即产品耐高温聚酰亚胺改性PDMS硅树脂。
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CN108384453A (zh) * 2018-03-21 2018-08-10 广州市维思涂料科技有限公司 一种用于金属彩钢板表面的水性涂料及其制备方法

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