CN104861151B - 一种聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物的制备方法 - Google Patents

一种聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物的制备方法 Download PDF

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CN104861151B
CN104861151B CN201510306733.2A CN201510306733A CN104861151B CN 104861151 B CN104861151 B CN 104861151B CN 201510306733 A CN201510306733 A CN 201510306733A CN 104861151 B CN104861151 B CN 104861151B
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贾正
白雪
张筱瑾
孙仪琳
李坚
任强
汪称意
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Abstract

本发明涉及一种聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物的制备方法，包括步骤：端羟基聚甲基丙烯酸甲酯的制备和嵌段共聚物的制备。本发明的有益效果是：(1)利用ARGET ATRP法制备端羟基聚甲基丙烯酸甲酯，可以对聚合物的结构和分子量及分子量分布进行控制，并且反应体系中所用的催化剂浓度用量很低，可以降到几十ppm甚至更低，同时降低了反应体系中空气敏感性，可以存在少量空气；(2)利用ARGET ATRP制备端羟基聚甲基丙烯酸甲酯，再将端羟基聚甲基丙烯酸甲酯与二异氰酸酯反应，从而得到了一种新型聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物。

Description

一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法
技术领域
本发明属于化工材料领域，涉及一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法。
背景技术
聚甲基丙烯酸甲酯(Polymethylmethacrylate，简称PMMA，俗称有机玻璃)是迄今为止合成透明材料中质地最优异，价格又比较适宜的树脂。PMMA树脂是无毒环保材料，破碎时不易产生尖锐的碎片。但是PMMA树脂由于表面硬度不高、抗冲击性能低、成型流动性能差等特点，PMMA的改性相继出现。例如甲基丙烯酸甲酯与苯乙烯、丁二烯的共聚，PMMA与PC的共聚等。
聚氨酯(Polyurethane，简称PU)是一种由多异氰酸酯、多元醇、有机小分子多元醇(扩链剂)反应制成的重要高分子材料。它是由化学性质明显不同的软段和硬段组成的，软段由低聚物多元醇(通常是聚醚多元醇或聚酯多元醇)组成，硬段由多异氰酸酯与小分子扩链剂组成。聚氨酯具有耐磨、耐温、密封、隔音、加工性能好、可降解等优异性能。研究表明将聚甲基丙烯酸甲酯和聚氨酯共聚，能够克服各自的缺点，使两者优势得到互补，做到扬长避短。
要得到性能优异的端羟基聚甲基丙烯酸甲酯，就需要对聚合物的结构和聚合物分子量进行控制。活性聚合可以得到分子量分布极窄的聚合物，是控制聚合物分子量最理想的方法。原子转移自由基聚合(ATRP)就是活性聚合中的一种聚合技术。
在1995年提出的原子转移自由基聚合(ATRP)以反应条件温和，适用单体范围宽，分子设计能力强而受到了普遍的重视，并被用于制备丙烯酸酯类嵌段共聚物。限制ATRP规模化应用的主要问题是ATRP聚合所需的催化剂为低氧化态的金属盐类(最有代表性的是卤化亚铜)，易被氧化，使用前需精制且用量很大。大量催化剂的使用不仅提高了成本，聚会后催化剂的脱除和再利用也是一个不易解决的问题，工业化难度大不易进行。
电子转移再生催化剂原子转移自由基聚合(ARGET ATRP)的出现解决了上述提到的问题。使原子转移自由基聚合向工业化又迈进了一步。它是在体系中加入一种还原剂如辛酸亚锡、抗坏血酸、葡萄糖类等，将体系中少量的高价态金属络合物不断还原为低价态金属络合物。它解决了ATRP易被氧化、用量大、脱除困难的问题，促进了ATRP的工业化生产。在CN101456937A中公开了《聚亚甲基/聚(甲基)丙烯酸酯类嵌段共聚物及其制备方法》。它是采用常规ATRP法制备两嵌段共聚物，催化剂用量大，不易脱除。因此本发明采用ARGET ATRP法制备端羟基聚甲基丙烯酸甲酯，进而以端羟基聚甲基丙烯酸甲酯为原料制备聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
发明内容
本发明要解决的技术问题是：基于上述问题，本发明提供一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法。
本发明解决其技术问题所采用的一个技术方案是：一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，包括以下步骤：
(1)端羟基聚甲基丙烯酸甲酯的制备：将引发剂、甲基丙烯酸甲酯、催化剂、配体、还原剂和溶剂Ⅰ加入到反应容器中，将反应体系抽真空，充氮气5min，110℃反应0.5～10小时，制得端羟基聚甲基丙烯酸甲酯，分子量分布﹤2.0；
(2)嵌段共聚物的制备：将步骤(1)制得的端羟基聚甲基丙烯酸甲酯溶于甲苯中，加入二异氰酸酯，升温至80℃，保温反应3h，降温至60℃；将二元醇在120～150℃下脱除小分子5～10min，降温至60℃加入上述反应体系中；升温至80℃反应，保温反应3h；滴加小分子扩链剂，80℃保温反应3h，得到聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
进一步地，步骤(1)中引发剂为一个端基为Br，另一个端基为羟基的有机溴代化合物，有机溴代化合物为α-溴代异丁酸羟乙酯或α-溴代异丁酸羟丁酯；催化剂为氧化态的过渡金属卤化物CuCl2、CuBr2、FeCl3或FeBr3；配体为五甲基二亚乙基三胺、六甲基三乙四胺、双(二甲基氨基乙基)醚、联二吡啶胺或三-(N,N-二甲基氨基乙基)胺中的一种；还原剂为辛酸亚锡、抗坏血酸或葡萄糖中的一种；溶剂Ⅰ为甲苯、苯甲醚、N，N-二甲基甲酰胺、四氢呋喃、乙酸乙酯或1-甲基-2-吡咯烷酮中的一种。
进一步地，步骤(1)中甲基丙烯酸甲酯：引发剂的摩尔比为20：1～500：1，甲基丙烯酸甲酯：催化剂的摩尔比为1：0.0005～1：0.00005，催化剂：配体的摩尔比为1：10～1：30，催化剂：还原剂的摩尔比为1：10～1：25，溶剂Ⅰ用量为甲基丙烯酸甲酯质量的50％。
进一步地，步骤(2)中二异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1,5-二异氰酸酯、2,6-二异氰酸酯己酸甲酯、1,6-己基二异氰酸酯中的一种。
进一步地，步骤(2)中二元醇为聚酯二元醇、聚醚二元醇、丙烯酸二元醇、蓖麻油类二元醇、聚碳酸酯二元醇或聚四氢呋喃二元醇中的一种。
进一步地，步骤(2)中小分子扩链剂为1,4-丁二醇、1,6-己二醇、甘油、三羟甲基丙烷、二甘醇、三甘醇、新戊二醇、山梨醇、二乙氨基乙醇、乙二胺或N,N-二羟基苯胺中的一种。
进一步地，步骤(2)中二异氰酸酯、端羟基聚甲基丙烯酸甲酯、二元醇和小分子扩链剂，加小分子扩链剂前按照摩尔比NCO/OH＝3：1～6：1进行投料，然后按照摩尔比NCO/OH＝0.5：1～3：1加入小分子扩链剂。
本发明的有益效果是：(1)利用ARGET ATRP法制备端羟基聚甲基丙烯酸甲酯，可以对聚合物的结构和分子量及分子量分布进行控制，并且反应体系中所用的催化剂浓度用量很低，可以降到几十ppm甚至更低，同时降低了反应体系中空气敏感性，可以存在少量空气；(2)利用ARGET ATRP制备端羟基聚甲基丙烯酸甲酯，再将端羟基聚甲基丙烯酸甲酯与二异氰酸酯反应，从而得到了一种新型聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
具体实施方式
现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(1)分子量为10000的端羟基聚甲基丙烯酸甲酯的制备
在装有温度计的500mL的四口烧瓶中加入甲基丙烯酸甲酯100g、α-溴代异丁酸羟丁酯3.0253g(纯度为79％)、CuBr20.1117g、五甲基二亚乙基三胺0.8318g、辛酸亚锡3.0883g、甲苯50g，机械搅拌均匀混合，鼓泡5min排除体系中的氧气，在70℃的油浴锅中继续鼓泡反应3.5h，转化率为81％。用凝胶渗透色谱GPC测得分子量Mn＝11440，分子量分布PDI＝1.23。此反应中催化剂用量为单体摩尔量的500ppm，得到分子量可控，分子量分布较窄的聚合物。
(2)聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备
以端羟基聚甲基丙烯酸甲酯/二元醇＝50wt％的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物为例
将10g端羟基聚甲基丙烯酸甲酯、20g甲苯加入到装有搅拌桨的四口烧瓶中，升温至60℃，使端羟基聚甲基丙烯酸甲酯溶解均匀，然后加入7.2642g甲苯二异氰酸酯，升温至80℃反应3h，之后降温至60℃，将20g聚醚二元醇在120～150℃下脱除小分子5～10min后，降温至60℃加入上述反应体系中，然后升温至80℃反应3h，最后滴加2.1918g 1,4-丁二醇，滴加时间为30min为宜，保持反应体系温度80℃继续反应3h，控制-NCO/-OH＝1.2。反应结束，得到聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
按照以上方法，分别制备端羟基聚甲基丙烯酸甲酯/二元醇为20wt％、30wt％、40wt％、60wt％的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
实施例2
(1)分子量为8000的端羟基聚甲基丙烯酸甲酯的制备
在装有温度计的500mL的四口烧瓶中加入甲基丙烯酸甲酯100g、α-溴代异丁酸羟丁酯3.3194g(纯度为90％)、CuBr20.1115g、五甲基二亚乙基三胺0.8654g、辛酸亚锡3.0346g、苯甲醚50g，机械搅拌均匀混合，鼓泡5min排除体系中的氧气，在70℃的油浴锅中继续鼓泡反应3.5h，转化率为86％。用凝胶渗透色谱GPC测得分子量Mn＝7800，分子量分布PDI＝1.31。此反应中催化剂用量为单体摩尔量的500ppm，得到分子量可控，分子量分布较窄的聚合物。
(2)聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备
以端羟基聚甲基丙烯酸甲酯/二元醇＝60wt％的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物为例
将12g端羟基聚甲基丙烯酸甲酯、20g甲苯加入到装有搅拌桨的四口烧瓶中，升温至60℃，使端羟基聚甲基丙烯酸甲酯溶解均匀，然后加入7.4954g甲苯二异氰酸酯，升温至80℃反应3h，之后降温至60℃，将20g聚醚二元醇在120～150℃下脱除小分子5～10min后，降温至60℃加入上述反应体系中，然后升温至80℃反应3h，最后滴加2.2615g 1,4-丁二醇，滴加时间为30min为宜，保持反应体系温度80℃继续反应3h，控制-NCO/-OH＝1.2。反应结束，得到聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
按照以上方法，分别制备端羟基聚甲基丙烯酸甲酯/二元醇为20wt％、30wt％、40wt％、50wt％的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物。
实施例1的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物机械性能测试结果见下表：
实施例2的聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物机械性能测试结果见下表：

Claims (6)

1.一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：包括以下步骤：
（1）端羟基聚甲基丙烯酸甲酯的制备：将引发剂、甲基丙烯酸甲酯、催化剂、配体、还原剂和溶剂Ⅰ加入到反应容器中，将反应体系抽真空，充氮气5min，70℃反应0.5～10小时，制得端羟基聚甲基丙烯酸甲酯，分子量分布﹤2.0；
（2）嵌段共聚物的制备：将步骤（1）制得的端羟基聚甲基丙烯酸甲酯溶于甲苯中，加入二异氰酸酯，升温至80℃，保温反应3h，降温至60℃；将二元醇在120～150℃下脱除小分子5～10min，降温至60℃加入上述反应体系中；升温至80℃反应，保温反应3h；滴加小分子扩链剂，80℃保温反应3h，得到聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物；
步骤（1）中引发剂为一个端基为Br，另一个端基为羟基的有机溴代化合物；催化剂为氧化态的过渡金属卤化物CuCl2、CuBr2、FeCl3或FeBr3；配体为五甲基二亚乙基三胺、六甲基三乙四胺、双（二甲基氨基乙基）醚、联二吡啶胺或三-（N,N-二甲基氨基乙基）胺中的一种；还原剂为辛酸亚锡、抗坏血酸或葡萄糖中的一种；步骤（2）中二元醇为聚酯二元醇、聚醚二元醇、蓖麻油类二元醇或聚碳酸酯二元醇中的一种。
2.根据权利要求1所述的一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：所述的有机溴代化合物为α-溴代异丁酸羟乙酯或α-溴代异丁酸羟丁酯；溶剂Ⅰ为甲苯、苯甲醚、N，N-二甲基甲酰胺、四氢呋喃、乙酸乙酯或1-甲基-2-吡咯烷酮中的一种。
3.根据权利要求1所述的一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：所述的步骤（1）中甲基丙烯酸甲酯：引发剂的摩尔比为20：1～500：1，甲基丙烯酸甲酯：催化剂的摩尔比为1：0.0005～1：0.00005，催化剂：配体的摩尔比为1：10～1：30，催化剂：还原剂的摩尔比为1：10～1：25，溶剂Ⅰ用量为甲基丙烯酸甲酯质量的50%。
4.根据权利要求1所述的一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：所述的步骤（2）中二异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1,5-二异氰酸酯、2,6-二异氰酸酯己酸甲酯、1,6-己基二异氰酸酯中的一种。
5.根据权利要求1所述的一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：所述的步骤（2）中小分子扩链剂为1,4-丁二醇、1,6-己二醇、甘油、三羟甲基丙烷、二甘醇、三甘醇、新戊二醇、山梨醇、二乙氨基乙醇或乙二胺中的一种。
6.根据权利要求1所述的一种聚氨酯-聚甲基丙烯酸甲酯嵌段共聚物的制备方法，其特征是：所述的步骤（2）中二异氰酸酯、端羟基聚甲基丙烯酸甲酯、二元醇和小分子扩链剂，加小分子扩链剂前按照摩尔比NCO/OH=3：1～6：1进行投料，然后按照摩尔比NCO/OH=0.5：1～3：1加入小分子扩链剂。
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