CN105646840B - 一种聚酯增韧型环氧潜固化剂的合成 - Google Patents

一种聚酯增韧型环氧潜固化剂的合成 Download PDF

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CN105646840B
CN105646840B CN201610199823.0A CN201610199823A CN105646840B CN 105646840 B CN105646840 B CN 105646840B CN 201610199823 A CN201610199823 A CN 201610199823A CN 105646840 B CN105646840 B CN 105646840B
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latent curing
polyester
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CN105646840A (zh
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许愿
王建斌
陈田安
解海华
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Yantai Darbond Technology Co Ltd
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Abstract

本发明涉及一种聚酯增韧型环氧潜固化剂的合成，由二苯基甲烷二异氰酸酯与ε‑己内酰胺CPL进行反应，将部分‑NCO基封闭，MDI和CPL的反应当量比设定为1：0.5‑0.6，而后用过量5%设计当量的聚酯二元醇将余量的‑NCO反应掉，反应完成后，得到聚酯增韧型环氧潜固化剂。制得的增韧型潜固化剂，添加使用于双组份环氧胶粘剂的环氧树脂组分中，能非常显著的延长胶粘剂的工艺开放时间（适用期），同时较大幅度的提高胶粘剂的剥离强度。

Description

一种聚酯增韧型环氧潜固化剂的合成
技术领域
本发明涉及一种聚酯增韧型环氧潜固化剂的合成，属于合成化学领域。
背景技术
固化剂是双组份环氧胶粘剂的重要组成部分，其化学类型常规有脂肪族胺、脂环族胺、聚醚胺、低份子聚酰胺等等。在胶粘剂配方设计之初，通常是依据环氧当量和活泼氢当量配比原则，设计各组分的添加量，形成树脂组份和固化剂组份的有效配比，最终形成双组份包装应用。长期以来，双组分胶粘剂面临的一个难题是，如何有效解决双组份胶粘剂施工前有较长的适用期（即足够长的工艺开放时间）和施工后有较快的固化快速这一矛盾。另外，如何实现环氧类胶粘剂的高效增韧，也是胶粘剂行业工艺应用中面临的一个长期课题。新的行业要求对增韧技术提出了更高要求，不单是引入新组分的添加类复配技术，各种合成应用技术陆陆续续都已经引入到了常规双组份胶粘剂的配方设计之中了。
发明内容
为了解决现有技术双组份环氧胶粘剂普遍存在的施工工艺时间太短问题，本发明提供了一种聚酯增韧型环氧潜固化剂，加入它到胶粘剂配方的甲组份中（环氧树脂组分，下同），由于潜固化剂的活性基团事先得到封闭，配套使用的乙组份（固化剂组份，下同）添加量相比于甲组份少加了相同当量的固化剂量。这样，在先期胶粘剂施工时，不等量的当量化学反应，使得工艺开改时实现了最大的延长。在施工后续的加热固化时，潜固化剂封闭的活性基团得以释放，与乙组份中的氨基进行交联固化反应，形成聚脲，使得粘接强度迅速上升。实验表明，使用聚酯改性的此潜固化剂，加入树脂量的10%即可以有效提高胶粘剂的剥离强度，在延长工艺开改时间的同时，也实现了胶粘剂的有效增韧。
本发明解决上述技术问题的技术方案如下：
由当量比为1：0.5-0.6的MDI（MDI-100和MDI-50的等当量混合物）和ε-己内酰胺(CPL)进行-NCO基封闭反应，反应结束后再与聚己二酸一缩乙二醇酯(POL-1180，羟值180）进行聚氨酯反应，聚酯的加入量为过量5%的剩余-NCO当量，反应完成后，生成聚酯增韧型环氧潜固化剂。
具体的合成技术条件如下：
1）将称量好的ε-己内酰胺（CPL）中放入真空干燥箱中抽真空除水，设定温度35℃，控制水分含量不得高于200ppm，除好水后充氮气放置备用；
2）将称量好的聚酯二元醇放入三口烧瓶中，在120±5℃下真空脱水2~3h，然后降温充氮气放置备用；
3）将称量好的二苯基甲烷二异氰酸酯MDI放入三口烧瓶中，充氮气，在氮气氛围下，加热温度到35-45℃后，开始用漏斗少量多次加入ε-己内酰胺（CPL），滴加频率控制在3-5克/分钟，加料过程中，设定反应温度为80±5℃，注意温度不得高于90℃，如果高于90℃，应立即停止滴加，直至加完ε-己内酰胺（CPL）后，继续反应2小时；
4）第3步完成后降温至60℃以下，开始用滴液漏斗滴加事先除过水的聚酯二元醇进行聚氨酯反应，可适量使用DBTDL作催化剂。滴加聚酯的速度控制在1-2滴/秒，滴加过程中，控制反应温度在80±5℃，直至加完后，反应1h后，然后降温出料，得到聚酯增韧型环氧潜固化剂。
本发明的有益效果是：本发明的聚酯增韧型环氧潜固化剂，添加使用于双组份环氧胶粘剂的环氧树脂组分（甲组分）中。加入环氧树脂组分的10%用量，即能非常显著的延长胶粘剂的工艺开放时间（适用期），同时较大幅度的提高胶粘剂的剥离强度。
实施例
将称量好的125.13克MDI-50和MDI-100等当量混合物，加入到烧瓶中，升温到40℃后，开始按3-5克/分钟的速度加入准备好的除过水的ε-己内酰胺（CPL）62.24克，反应温度控制在85℃，直至加完CPL后，反应2小时，降温到50℃，开始滴加准备好的除过水的POL-1180聚酯二元醇147.26克，滴加速度为2滴每秒，控制反应温度为80℃，直至滴加完成后，继续反应1小时，到时间后，降温出料，得到增韧型潜固化剂。
增韧型固化剂在胶粘剂中的应用对比举例。
取市售常规双组分环氧胶粘剂E-120HP，将胶粘剂均匀分为A、B两组。
在A组胶样的环氧树脂组分中（即甲组分）加入10%固化剂量的本发明潜固化剂。B组胶样作为空白对比。
对A、B两组胶样进行适用期和剥离强度测试，适用期的测试依据为GB/T7123-2002，剥离强度的测试依据国标GB/T2791-1995，试片选择铝片，测试数据见表一。
表一
从表一数据看，A组份胶中增韧型潜固化剂的加入有效提高了胶粘剂的工艺使用时间，效果明显，适用期从100分钟延长到了210分钟，相比较有延长了70%；同时，还明显提高了胶粘剂的剥离强度，从9.3增加到17.4，增加幅度达50%以上。

Claims (1)

1.一种聚酯增韧型环氧潜固化剂的合成方法，其特征在于，合成步骤如下：
将称量好的125.13克MDI-50和MDI-100等当量混合物，加入到烧瓶中，升温到40℃后，开始按3-5克/分钟的速度加入准备好的除过水的ε-己内酰胺CPL62.24克，反应温度控制在85℃，直至加完CPL后，反应2小时，降温到50℃，开始滴加准备好的除过水的POL-1180聚酯二元醇147.26克，滴加速度为2滴每秒，控制反应温度为80℃，直至滴加完成后，继续反应1小时，到时间后，降温出料，得到聚酯增韧型环氧潜固化剂。
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