CN112266760B - 一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法 - Google Patents

一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法 Download PDF

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CN112266760B
CN112266760B CN202011152959.9A CN202011152959A CN112266760B CN 112266760 B CN112266760 B CN 112266760B CN 202011152959 A CN202011152959 A CN 202011152959A CN 112266760 B CN112266760 B CN 112266760B
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梁万根
张超
许倩倩
崔卫华
费潇瑶
孙志利
卞文
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Yifeng New Material Co.,Ltd.
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Abstract

本发明涉及聚氨酯胶粘剂技术领域，尤其涉及一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法。首先使用四溴双酚A对硫醇化合物进行改性，然后将改性硫醇化合物、聚醚多元醇、异氰酸酯、催化剂、填料进行反应制备而成。该生产工艺简单可行，易于控制。其不仅具有优异的阻燃性能，而且具有更长的适用期、更好的热稳定性。满足了客户和市场的需求，具有较大的社会和经济价值。

Description

一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法
技术领域
本发明涉及聚氨酯胶粘剂技术领域，尤其涉及一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法。
背景技术
胶粘剂是一种能将同种和异种材料表面紧密连接起来起着传递作用，又能满足一定物理化学性能要求的非金属物质。聚氨酯胶粘剂是近几年来国内外发展比较快的一种胶粘剂。
由于其结构中含有亚氨基和异氰酸酯基团，除了具备良好的粘结性能，其耐化学药品性、耐冲击性、柔韧性、屈挠性、耐低温性能和耐磨性能也特别优异，使得聚氨酯胶粘剂的使用范围越来越广泛，日渐成为人类生活中重要的合成材料。
硫醇广泛应用于环氧树脂胶粘剂领域，具有低温快速固化和固化后粘结强度高的优点，但是其较好的流动性，极大的限制了其应用范围。专利CN201911000136.1提出将硫醇与聚氨酯胶粘剂相结合，进一步提高了聚氨酯胶粘剂的性能。
然而，目前市场上开发的聚氨酯胶粘剂主要是集中在提高固化速度和粘结强度等方面，大多数没有进行阻燃处理，很容易遇火燃烧产生危险，大大限制了其应用范围。
发明内容
针对上述存在的技术问题，本发明提供了一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，首先使用四溴双酚A对硫醇化合物进行改性，然后将改性硫醇化合物、聚醚多元醇、异氰酸酯、催化剂、填料进行反应制备而成，该生产工艺简单可行，易于控制。其不仅具有优异的阻燃性能，而且具有更长的适用期、更好的热稳定性。满足了客户和市场的需求，具有较大的社会和经济价值。
为了实现上述目的，本申请采取的技术方案如下：
一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其具体工艺包括如下步骤：
(1)使用四溴双酚A对硫醇化合物进行改性，然后与填料进行混合，制备A组分；
(2)按照配比将催化剂、聚醚多元醇和异氰酸酯混合均匀，制备B组分；
(3)将A组分和B组分混合后，真空搅拌脱气反应得到含硫聚氨酯复合阻燃型胶粘剂。
所述硫醇化合物含有两个或两个以上巯基基团；四溴双酚A用量为硫醇化合物质量的5％-10％。
优选的，所述异氰酸酯含有两个或两个以上—NCO基团。
优选的，硫醇化合物与异氰酸酯的质量比为1：0.7-1.5，更优选为1:1-1.5。
优选的，催化剂的用量为硫醇化合物和异氰酸酯质量的0.05％-1％，更优选为0.5％-1％；聚醚多元醇的用量为硫醇化合物和异氰酸酯质量的5％-10％，更优选为7％-9％；填料的用量为硫醇化合物和异氰酸酯质量的3％-8％，更优选为5％-7％。
更为优选的，四溴双酚A的用量为硫醇化合物质量的6％-8％；
优选的，步骤(1)中所述硫醇化合物选自季戊四醇四(2-巯基乙酸)酯、2，3-双(2-巯基乙硫基)-1-丙硫醇、3-(2-巯基乙硫基)-1，2-丙二硫醇、1，2-乙二硫醇中的一种或多种。
优选的，步骤(1)中所述异氰酸酯选自甲苯二异氰酸酯、多苯基多亚甲基二异氰酸酯、甲基环己烷二异氰酸酯、间苯二亚甲基二异氰酸酯中的一种或多种。
优选的，步骤(1)中所述聚醚多元醇选自聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚四氢呋喃二元醇中的一种或几种。
优选的，步骤(1)中所述催化剂选自二氯化二丁基锡、二氯化二甲基锡、二月桂酸二丁基锡、二硫醇烷基锡中的一种或几种。
步骤(1)中所述填料选自氢氧化铝、氢氧化镁、三氧化二铋、碳酸钙。
优选的，步骤(1)中混合温度为15-30℃，混合时间为1-1.5h。
优选的，步骤(3)中反应温度为70-90℃，反应时间为2-4h。
四溴双酚A具有较好的阻燃性能，硫醇化合物中含有多个巯基，在本发明特定的条件下(尤其是各组分间的比例关系)，其中的一个或两个巯基与四溴双酚A的溴反应，连接在一起，对其进行改性，增加阻燃性能的同时，硫醇化合物上的其他巯基继续参与后续与异氰酸酯的反应。另外，为了能够使阻燃效果更佳，本发明在制备胶黏剂过程中还加入了特定的填料，利用四溴双酚A和填料协同作用，共同达到优异的阻燃效果。
综上所述，本发明所述生产工艺简单可行，易于控制。最终所制得含硫聚氨酯的复合阻燃型胶粘剂，在保证原有性能的基础上，使其具有优异的阻燃性能，而且具有更长的适用期、更好的热稳定性。满足了客户和市场的需求，具有较大的社会和经济价值。
具体实施方式
下面结合具体实施例对发明作进一步说明，可以使本领域的技术人员进一步理解本发明，但不作为对发明内容的限制，凡基于本发明所述原理的技术均属于本发明的范围。
实施例1
(1)向反应瓶中加入40g3-双(2-巯基乙硫基)-1-丙硫醇和2.4g四溴双酚A混合均匀后，再加入5g氢氧化镁，20℃搅拌1h混匀制备组分A。
(2)按照配比将1g二硫醇烷基锡、9g聚氧化乙烯二元醇和60g多苯基多亚甲基二异氰酸酯于20℃搅拌1h混合均匀，制备B组分。
(3)将A组分和B组分混合后，升温至80℃真空搅拌脱气3h反应得到复合阻燃型含硫聚氨酯胶粘剂。
采用LFY-606B数显氧指数测定仪对实施例1制备的复合阻燃型含硫聚氨酯胶粘剂进行检测，氧指数为30。
经检测，本发明实施例1得到的复合阻燃型含硫聚氨酯胶粘剂的巯基含量为25％，异氰酸酯含量为0.33％，粘度为10450mpa*s。
实施例2
(1)向反应瓶中加入45g 1，2-乙二硫醇和3.6g四溴双酚A混合均匀后，再加入5g氢氧化铝，25℃搅拌1h混匀制备组分A。
(2)按照配比将0.8g二氯化二丁基锡、9g聚四氢呋喃二元醇和55g间苯二亚甲基二异氰酸酯于25℃搅拌1h混合均匀，制备B组分。
(3)将A组分和B组分混合后，升温至90℃真空搅拌脱气2h反应得到复合阻燃型含硫聚氨酯胶粘剂。
采用LFY-606B数显氧指数测定仪对实施例2制备的复合阻燃型含硫聚氨酯胶粘剂进行检测，氧指数为32。
经检测，本发明实施例2得到的复合阻燃型含硫聚氨酯胶粘剂的巯基含量为23％，异氰酸酯含量为0.31％，粘度为10650mpa*s。
实施例3
(1)向反应瓶中加入50g季戊四醇四(2-巯基乙酸)酯和3g四溴双酚A混合均匀后，再加入5g碳酸钙镁，30℃搅拌1h混匀制备组分A。
(2)按照配比将0.5g二月桂酸二丁基锡、8g聚氧化丙烯二元醇和50g甲苯二异氰酸酯于30℃搅拌1h混合均匀，制备B组分。
(3)将A组分和B组分混合后，升温至85℃真空搅拌脱气2.5h反应得到复合阻燃型含硫聚氨酯胶粘剂。
采用LFY-606B数显氧指数测定仪对实施例3制备的复合阻燃型含硫聚氨酯胶粘剂进行检测，氧指数为31。
经检测，本发明实施例3得到的复合阻燃型含硫聚氨酯胶粘剂的巯基含量为22％，异氰酸酯含量为0.3％，粘度为10780mpa*s。
实施例4
(1)向反应瓶中加入40g2，3-双(2-巯基乙硫基)-1-丙硫醇和2.4g四溴双酚A混合均匀后，再加入5g三氧化二铋，20℃搅拌1h混匀制备组分A。
(2)按照配比将1g二氯化二甲基锡、9g聚氧化乙烯二元醇和60g甲基环己烷二异氰酸酯于20℃搅拌1h混合均匀，制备B组分。
(3)将A组分和B组分混合后，升温至80℃真空搅拌脱气3h反应得到复合阻燃型含硫聚氨酯胶粘剂。
采用LFY-606B数显氧指数测定仪对实施例4制备的复合阻燃型含硫聚氨酯胶粘剂进行检测，氧指数为33。
经检测，本发明实施例4得到的复合阻燃型含硫聚氨酯胶粘剂的巯基含量为24％，异氰酸酯含量为0.43％，粘度为20450mpa*s。
空白对照例
向反应瓶中加入40g3-双(2-巯基乙硫基)-1-丙硫醇，再按照配比加入1g二硫醇烷基锡、9g聚氧化乙烯二元醇和60g苯基多亚甲基二异氰酸酯于20℃搅拌1h混合均匀，然后升温至80℃真空搅拌脱气3h反应得到聚氨酯胶粘剂。
采用LFY-606B数显氧指数测定仪对空白例制备的含硫聚氨酯胶粘剂进行检测，氧指数为20。
经检测，本发明空白例得到的聚氨酯胶粘剂的巯基含量为24％，异氰酸酯含量为0.31％，粘度为10220mpa*s。

Claims (7)

1.一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，具体工艺包括如下步骤：
（1）使用四溴双酚A对硫醇化合物进行改性，然后与填料进行混合，制备A组分；
（2）按照配比将催化剂、聚醚多元醇和异氰酸酯混合均匀，制备B组分；
（3）将A组分和B组分混合后，真空搅拌脱气反应得到含硫聚氨酯复合阻燃型胶粘剂；
所述硫醇化合物含有两个或两个以上巯基基团；四溴双酚A用量为硫醇化合物质量的5%-10%；
步骤（1）中所述硫醇化合物选自2，3-双（2-巯基乙硫基）-1-丙硫醇、3-（2-巯基乙硫基）-1，2-丙二硫醇、1，2-乙二硫醇中的一种或多种；
步骤（1）中所述填料选自氢氧化铝、氢氧化镁、三氧化二铋、碳酸钙；
硫醇化合物与异氰酸酯的质量比为1：0.7-1.5；催化剂的用量为硫醇化合物和异氰酸酯质量的0.05%-1%；聚醚多元醇的用量为硫醇化合物和异氰酸酯质量的5%-10%；填料的用量为硫醇化合物和异氰酸酯质量的3%-8%。
2.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，所述异氰酸酯含有两个或两个以上—NCO基团。
3.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，所述的四溴双酚A的用量为硫醇化合物质量的6%-8%。
4.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，步骤（2）中所述异氰酸酯选自甲苯二异氰酸酯、多苯基多亚甲基二异氰酸酯、甲基环己烷二异氰酸酯、间苯二亚甲基二异氰酸酯中的一种或多种。
5.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，步骤（2）中所述聚醚多元醇选自聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚四氢呋喃二元醇中的一种或几种。
6.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，步骤（2）中所述催化剂选自二氯化二丁基锡、二氯化二甲基锡、二月桂酸二丁基锡、二硫醇烷基锡中的一种或几种。
7.根据权利要求1所述的一种含硫聚氨酯的复合阻燃型胶粘剂的制备方法，其特征在于，步骤（1）中混合温度为15-30℃，混合时间为1-1.5h；步骤（3）中反应温度为70-90℃，反应时间为2-4h。
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