CN105061714B - 一种硅烷封端聚氨酯预聚物的合成方法及其应用 - Google Patents
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Abstract
本发明涉及一种硅烷封端聚氨酯预聚物的合成方法及应用。合成方法包括二苯基甲烷二异氰酸酯先与聚醚二元醇反应生成端NCO基反应物,而后再与双‑(3‑甲氧基硅丙基)胺或双‑(3‑乙氧基硅丙基)胺进行聚合反应,反应完成后,滴加适量N‑正丁基‑3‑氨丙基三甲氧基硅烷将未完全封闭的NCO官能团全部封端并调整粘稠度,得到一款硅烷封端的聚氨酯预聚物,此预聚物可广泛应用于胶粘剂配方,可以明显增加胶粘剂的抗老化性能和提高界面粘接力。
Description
技术领域
本发明涉及一种硅烷封端聚氨酯预聚物的合成方法及应用。
背景技术
近年来,硅烷封端聚氨酯应用技术越来越广泛。通常的技术路线是先用聚醚或聚酯二元醇和二异氰酸酯反应,得到端异氰酸酯基聚氨酯预聚物,再与带有活性氢的硅氧基硅烷反应,得到硅烷封端的聚氨酯预聚物。基于此种合成方法得到的预聚物为线性低聚物,相对端NCO基封闭率不全,硅烷的官能度化相对较低,应用于胶粘剂的原料配合物,一是无法有效得到预先设计的粘接力,二是贮存稳定性和耐候性也无法得到有效提高。
发明内容
为了解决现有技术中相对端NCO基封闭率不全,烷氧基官能度较低的情况,粘接力差的问题,本发明提供了一种硅烷封端的聚氨酯低聚物,烷氧基官能度可达8-10,此预聚物可广泛应用于胶粘剂配方,可以明显增加胶粘剂的贮存稳定性和提高界面粘接力。
本发明解决上述技术问题的技术方案如下:
先使分子量为2000的聚醚二元醇与二苯基甲烷二异氰酸酯(MDI-100)进行聚合反应,反应生成端NCO基聚氨酯预聚物,NCO含量控制为10-15%;
而后将反应物再与双-(3-甲氧基硅丙基)胺或双-(3-乙氧基硅丙基)胺进行聚合反应,通过计算设计,使得NCO封闭率控制在90%左右,得到交联型端NCO低聚物和部分端NCO预聚物的混合物,NCO含量控制在3-4%;
反应完成后,滴加N-正丁基-3-氨丙基三甲氧基硅烷,将未完全封闭的3-4%余量的NCO官能团全部封端,并同时调整粘稠度,得到一款硅烷封端的聚氨酯预聚物。
进一步具体的合成技术条件如下:
第一步,将称量好的分子量为2000的聚醚二元醇(市售牌号为D2120,羟值56)放入三口烧瓶中,在120±5℃下真空脱水2~3h,然后降温至60℃以下,分次加入计量好的二苯基甲烷二异氰酸酯(MDI-100),控制反应温度80±5℃,反应2h;
第二步,第一步完成后降温至60℃以下,用滴液漏斗开始滴加双[3-(三甲氧基硅)丙基]胺(市售牌号为Dynasylan 1124)或双[3-(三乙氧基硅)丙基]胺(市售牌号为Dynasylan 1122),滴加速度为1-2滴每秒,控制反应温度为80±5℃,直至滴加完成后,继续反应2h,反应完成后,降温,充氮气保护;
第三步,第二步反应完成后,用滴液漏斗开始滴加N-正丁基-3-氨丙基三甲氧基硅烷(市售牌号为Dynasylan 1189),滴加速度为1-2滴每秒,控制反应温度为80±5℃,直至滴加完成后,继续反应2h,反应完成后,得到胶粘剂用预聚物。
本发明还涉及这种硅烷封端聚氨酯预聚物在胶粘剂以及在聚氨酯热熔胶中的应用。
与现有技术相比,本发明制备的预聚物中,作为软段的聚硅氧烷链段和聚醚链段在使用温度区处于粘弹态,而硬段如氨基甲酸酯基、脲基处于玻璃态或结晶态,软段的存在使材料具有良好的弹性,硬段部分作为物理交联点使材料强度增加,使用本发明的预聚物制成反应性聚氨酯热熔胶,除了不产生气泡外,还可降低极性聚氨酯胶黏剂的表面能,实现对低极性材料的浸润粘接。
具体实施方式
实施方式1:
称量聚醚二元醇(市售牌号为D2120,羟值56)132克放入到三口烧瓶中,在120±5℃下真空脱水2.5h,然后降温至60℃以下,分次加入计量好的二苯基甲烷二异氰酸酯(MDI-100)100克,控制反应温度80±5℃,反应2h;
到时间后降温到50℃,用滴液漏斗开始滴加双[3-(三乙氧基硅)丙基]胺(市售牌号为Dynasylan 1122)188克,滴加速度为1-2滴每秒,滴加完成后,控制反应温度为80±5℃,继续反应2h,反应完成后,降温,充氮气保护;反应完成后,降温,充氮气保护;
用滴液漏斗开始滴加N-正丁基-3-氨丙基三甲氧基硅烷(市售牌号为Dynasylan1189)100克,滴加速度为2滴每秒,控制反应温度为80±5℃,直至滴加完成后,继续反应2h,反应完成后,得到胶粘剂用预聚物。
实施方式2:
称量聚醚二元醇(市售牌号为D2120,羟值56)132克放入到三口烧瓶中,在120±5℃下真空脱水2.5h,然后降温至60℃以下,分次加入计量好的二苯基甲烷二异氰酸酯(MDI-100)100克,控制反应温度80±5℃,反应2h;
到时间后降温到50℃,用滴液漏斗开始滴加双[3-(三甲氧基硅)丙基]胺(市售牌号为Dynasylan 1124)150克,滴加速度为1-2滴每秒,滴加完成后,控制反应温度为80±5℃,继续反应2h,反应完成后,降温,充氮气保护;反应完成后,降温,充氮气保护;
用滴液漏斗开始滴加N-正丁基-3-氨丙基三甲氧基硅烷(市售牌号为Dynasylan1189)90克,滴加速度为2滴每秒,控制反应温度为80±5℃,直至滴加完成后,继续反应2h,反应完成后,得到胶粘剂用预聚物。
实施例3:预聚体应用于胶粘剂。
将本发明实施例1的预聚物350份,疏水性气相硅39份,二月桂酸二丁基锡0.4份,在无水的条件下,捏混均匀,制得一款粘接型胶粘剂。该胶粘剂室温固化24小时后,铝铝粘接强度可达5-6MPa,室温固化7天后,铝铝粘接强度可达10MPa以上,表现出优异的粘接力。该胶粘剂初始粘度为450Pa.s,在密封容器中室温存放21天后,粘度为460Pa.s,表现出良好的贮存稳定性。
实施例4:预聚体应用于热熔胶。
将PUR用异氰酸酯预聚物100份,本发明实施例2的预聚物10份,增粘树脂10份,双(2,2-吗啉乙基)醚0.05份,抗氧剂2份,在氮气氛围下,加热到80度混合均匀,制得一款PUR热熔胶。该热熔胶对PC的粘接强度24小时即可以达到8MPa以上,表现出非常优异的浸润粘接能力。
Claims (4)
1.一种硅烷封端聚氨酯预聚物的合成方法,包含如下步骤 :
1)先使分子量为 2000 的聚醚二元醇与二苯基甲烷二异氰酸酯进行聚合反应,反应生成端 NCO 基聚氨酯预聚物,NCO 含量控制为 10-15% ;
2)而后将反应物再与双 -(3- 甲氧基硅丙基)胺或双 -(3- 乙氧基硅丙基)胺进行聚合反应,通过计算设计,使得 NCO 封闭率控制在 80%,得到交联型端 NCO 低聚物和部分端NCO 预聚物的混合物,NCO 含量控制在 3-4% ;
3)反应完成后,滴加 N- 正丁基 -3- 氨丙基三甲氧基硅烷,将未完全封闭的 3-4% 余量的NCO 官能团全部封端,并同时调整粘稠度,得到一款硅烷封端的聚氨酯预聚物。
2.根据权利要求 1 所述的一种硅烷封端聚氨酯预聚物的合成方法,其特征在于 :
步骤 1)的技术条件是 :将称量好的分子量为 2000 的聚醚二元醇放入三口烧瓶中,在120±5℃下真空脱水 2-3h,然后降温至 60℃以下,分次加入计量好的二苯基甲烷二异氰酸酯,控制反应温度 80±5℃,反应 2h ;
步骤 2)的技术条件是 :步骤 1)完成后降温至 60℃以下,用滴液漏斗开始滴加双 -(3- 甲氧基硅丙基)胺或双 -(3- 乙氧基硅丙基)胺,滴加速度为 1-2 滴每秒,控制反应温度为 80±5℃,直至滴加完成后,继续反应 2h,反应完成后,降温,充氮气保护 ;
步骤 3)的技术条件是 :步骤 2)反应完成后,用滴液漏斗开始滴加 N- 正丁基 -3-氨丙基三甲氧基硅烷,滴加速度为 1-2 滴每秒,控制反应温度为 80±5℃,直至滴加完成后,继续反应 2h,反应完成后,得到胶粘剂用预聚物。
3.权利要求 1 或 2 所述的一种硅烷封端聚氨酯预聚物的合成方法制备胶粘剂中的应用。
4.权利要求 1 或 2 所述的一种硅烷封端聚氨酯预聚物的合成方法制备聚氨酯热熔胶中的应用。
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