氨基樹脂的固化反應(yīng)
由于氨基樹脂是用來將主要成膜材料分子交聯(lián)成一個網(wǎng)狀結(jié)構(gòu),因此令人感興趣的是氨基樹脂與漆料樹脂的共縮聚反應(yīng),典型例子是漆料樹脂上的羥基和氨基樹脂上烷氧基甲基的醚(交換)化反應(yīng)。
在微觀世界里三聚氰胺分子是如何與來自不同成膜高分子上的羥基拉起來的,從而聯(lián)成一個三維立體網(wǎng)絡(luò)結(jié)構(gòu),這個網(wǎng)絡(luò)結(jié)構(gòu)決定了漆膜的性能。
在熱和酸催化劑(通常固化條件)存在的條件下,交聯(lián)反應(yīng)很快地發(fā)生,連接了漆料上所有可用的羥基。實際上當聚合物網(wǎng)絡(luò)結(jié)構(gòu)形成時,反應(yīng)物的流動性在下降,有些羥基剩下未反應(yīng)掉。一般在涂料中存在比理想配比過量的氨基樹脂時,剩下的烷氧基可以參加其他反應(yīng)或留在涂膜中不反應(yīng)。在前面提到氨基樹脂很容易自交聯(lián)相互反應(yīng),結(jié)果是在生產(chǎn)中分子量增加了。這些反應(yīng)也發(fā)生于涂膜固化時。這樣與其說氨基樹脂一定程度的自交聯(lián)是一個消極因素,不如說是獲得良好耐久性的、緊密聚合物母體所必不可少的因素。氨基樹脂所有的三種官能團都參與自交聯(lián)反應(yīng),在以強酸催化的、充分烷基化的三聚氰胺樹脂涂料中,有證據(jù)顯示這些反應(yīng)發(fā)生于與涂料樹脂醚交換之后。在沒有外加催化劑或弱酸催化劑時,采用高亞氨基/或羥甲基官能度的三聚氰胺樹脂體系中,這些自交聯(lián)反應(yīng)發(fā)生到更高的程度。這兩種情況下,稍微的自聚反應(yīng)對良好的網(wǎng)絡(luò)結(jié)構(gòu)的形成是關(guān)鍵的。
在氨基樹脂交聯(lián)的涂膜固化時,發(fā)生的其它反應(yīng)是脫甲醛反應(yīng)和水解反應(yīng)。脫甲醛反應(yīng)在通常固化溫度下就很容易發(fā)生,這幾乎是造成氨基樹脂固化時釋放出甲醛的唯一原因,另外的甲醛是游離的甲醛。
氨基樹脂交聯(lián)成膜固化時都將會發(fā)生一些水解反應(yīng),其中有些烷氧基甲基轉(zhuǎn)化為羥甲基,高亞氨基或羥甲基含量的三聚氰胺樹脂的水解反應(yīng)能被堿所催化,甚至在室溫下也能緩慢發(fā)生水解,這樣氨基樹脂更容易自交聯(lián),并出現(xiàn)涂料在儲存時粘度上升的現(xiàn)象。為了避免這個現(xiàn)象的發(fā)生,可以在水性涂料中采用耐堿水解反應(yīng)的、充分甲醚化的三聚氰胺樹脂或助溶劑。充分烷基化的三聚氰胺樹脂在水性系統(tǒng)中耐堿催化的水解反應(yīng)。充分烷基化和部分烷基化的三聚氰胺樹脂在水性系統(tǒng)中不耐酸催化的水解反應(yīng),因此必須使用封閉性的酸催化劑在水性系統(tǒng)中。
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翁開爾有限公司
源自1925年的信賴
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