CN108017775B - 一种聚氨酯raft试剂的制备方法 - Google Patents

一种聚氨酯raft试剂的制备方法 Download PDF

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CN108017775B
CN108017775B CN201711398790.3A CN201711398790A CN108017775B CN 108017775 B CN108017775 B CN 108017775B CN 201711398790 A CN201711398790 A CN 201711398790A CN 108017775 B CN108017775 B CN 108017775B
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郑劼
廖承莉
王珊
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Leping Libang Chemical Co ltd
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Abstract

本发明涉及一种聚氨酯RAFT试剂的制备方法。其制备方法如下：二异氰酸酯与含卤二元醇和亲水扩链剂溶于溶剂，并在催化剂作用下反应得到聚氨酯预聚体，并以正辛醇封端得到功能化聚氨酯；以十二烷基硫醇、二硫化碳和氢氧化钠为原料反应得到十二烷基三硫酯钠盐后，加入功能化聚氨酯，加热下搅拌反应数小时后，于甲醇/水中沉淀得到聚氨酯RAFT试剂。该方法合成简单，提纯方便，可用于制备接枝共聚物。

Description

一种聚氨酯RAFT试剂的制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种用于可逆加成断裂链转移聚合的含三硫酯官能团的聚合物——聚氨酯RAFT试剂的制备方法。
背景技术
1956年Szwarc提出了活性聚合概念，该聚合特征表现为无终止、无转移、引发速率远大于增长速率，即使聚合反应终止，聚合物链仍然保持活性，继续加入新的单体，聚合反应即可继续进行。1998年，Rizzardo等人首次提出了可逆加成断裂链转移(RAFT)活性自由基聚合，其特征是通过增长自由基与特殊链转移剂发生的可逆链转移反应，从而实现对增长自由基浓度的控制，达到“活性”可控聚合，得到聚合度可控、窄分散的聚合物。提出以来，受到广泛关注并已被应用于制备嵌段、梳形、星形、环形和超支化等结构的共聚物。
聚氨酯是一种性能优异的高分子材料，具有耐磨、耐低温、抗拉伸等特点，被广泛应用于泡沫塑料、弹性体材料、涂料、胶黏剂、合成皮革涂饰剂和助剂等领域。由于聚氨酯分子结构易于调节，可以通过分子设计制备得到一系列具有精细结构的多功能材料，两亲性聚氨酯更是可以通过自组装特性，应用到药物输送领域，自组装得到的聚氨酯胶束内核具有疏水性，非常适合作为疏水药物的载体，调节内核的尺寸可以控制载药量，实现聚氨酯疏水侧链的聚合度调节是关键因素，在聚氨酯侧链引入RAFT基团，通过RAFT聚合可制备聚氨酯接枝共聚物，可调节支链聚合度，在药物载体方面有着潜在的应用价值。
美国专利(US8137754B2和US2012/0171914A1)公开了羟基封端的三硫酯化合物以及聚氨酯的制备方法，通过将三硫酯试剂羟基化，可用于与多异氰酸酯反应制得主链含有三硫酯的聚氨酯RAFT试剂。中国专利(CN103113512B，授权日2014年12月10日)公开了一种大分子链转移剂及其制备方法，该大分子链转移剂是由小分子链转移剂CPAD的活性基团(-COOH)与甲基丙烯酸甲酯和甲基丙烯酸羟乙酯无规共聚物酯化得到的，用于RAFT法聚合制备梳形共聚物。中国专利(CN104877903A，公开日2015年09月02日)公开了一种双端羟基封端的丙烯酸酯类聚合物的制备方法，其公开的双端羟基封端的RAFT试剂可用于聚氨酯材料的改性，可得到主链含有三硫酯的聚氨酯材料。中国专利(CN105199050A，公开日2015年12月30日)公开了一种聚氨酯接枝共聚物及其制备方法，通过含有三硫酯基的二元醇和任选的多元醇与多异氰酸酯化合物发生加成聚合反应，生成侧基含有RAFT链转移基团的聚氨酯聚合物，并通过RAFT聚合制备聚氨酯接枝共聚物。具有RAFT聚合功能的聚氨酯，利用RAFT聚合合成的聚合物方法简单，分子量及分子量分布可控。
上述聚氨酯RAFT试剂其三硫酯基团位置多以主链为主，CN105199050A所述聚氨酯RAFT试剂其三硫酯基团位置在侧链上，但是是以含有三硫酯的二元醇为原料制备，该原料需要另行制备和纯化，且产率不高，工艺复杂，无法大规模生产。针对上述的问题，我们提出了一种侧基含有三硫酯的聚氨酯RAFT试剂的制备方法，该方法合成简单，提纯方便，在RAFT聚合中具有高效的链转移效果，有利于推进大分子RAFT试剂及接枝共聚物的工业化生产。
发明内容
本发明的目的在于提供一种侧基含有三硫酯的聚氨酯RAFT试剂的制备方法。该方法合成简单，纯化方便，可用RAFT聚合方法制备接枝共聚物。
为解决现有技术问题，本发明提供的技术方案是：
提供一种聚氨酯RAFT试剂的制备方法，其特征在于，具体步骤如下：二异氰酸酯与含卤二元醇和亲水扩链剂溶于溶剂，并在催化剂作用下反应得到聚氨酯预聚体，并以正辛醇封端得到功能化聚氨酯；以十二烷基硫醇、二硫化碳和氢氧化钠为原料反应得到十二烷基三硫酯钠盐后，加入功能化聚氨酯，加热下搅拌反应数小时后，于甲醇/水中沉淀得到聚氨酯RAFT试剂。
在上述的聚氨酯RAFT试剂的制备方法，其特征在于，聚氨酯RAFT试剂结构式如下：
Figure GSB0000198150500000021
式中R1为：
Figure GSB0000198150500000022
式中R2为：CH3(CH2)6CH2。
式中x为10，y为0或1，z为1～12。
本发明中，所用溶剂为丙酮或丁酮，使用前需要进行无水处理。
本发明中，所用二异氰酸酯为异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯。
本发明中，所用含卤二元醇为3-氯-1，2-丙二醇或2，2-二溴甲基-1，3-丙二醇，使用前需要进行无水处理。
本发明中，所用亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸，使用前需要进行无水处理。
本发明中，所用催化剂为二月桂酸二丁基锡。
本发明中，所用甲醇/水的比例是甲醇∶水体积比为2∶1～6。
与现有技术相比，本发明的技术优点是：
1、本发明工艺简单，纯化方便，可用于RAFT活性聚合。
2、本发明所制备聚氨酯RAFT试剂，可用于聚氨酯接枝共聚物材料的制备。
附图说明
图1：聚氨酯RAFT试剂的核磁谱图。
图2：聚氨酯RAFT试剂的红外谱图。
具体实施方式
下面通过实施例进一步说明本发明。
实施例1
步骤1、在反应釜中加入8.91g(0.04mol)异佛尔酮二异氰酸酯、3.08g(0.028mol)3-氯-1，2-丙二醇、1.48g(0.01mol)二羟甲基丁酸、0.04g(6.33×10-5mol)二月桂酸二丁基锡、5.00mL无水丙酮，于80℃下搅拌反应，反应6h，加入0.52g(0.004mol)正辛醇反应2h，反应结束，备用。
步骤2、反应釜置于冰浴上，向其中加入5.67g(0.028mol)十二烷基硫醇，磁力搅拌下，向烧瓶中缓慢滴加入30wt％的NaOH水溶液3.73g，15min后在搅拌下加入丙酮5.00mL，待充分溶解后，加入2.13g(0.028mol)CS2，继续搅拌反应1h。随后加入步骤1制备得到的聚氨酯，在30℃下搅拌反应12小时，产物于250mL体积比1∶1甲醇/水中沉淀，沉淀于室温下晾干后，置于真空干燥箱90℃干燥过夜，得到聚氨酯RAFT试剂。
实施例2
步骤1、在反应釜中加入8.91g(0.04mol)异佛尔酮二异氰酸酯、7.33g(0.028mol)2，2-二溴甲基-1，3-丙二醇、1.48g(0.01mol)二羟甲基丁酸、0.04g(6.33×10-5mol)二月桂酸二丁基锡、5.00mL无水丙酮，于80℃下搅拌反应，反应6h，加入0.52g(0.004mol)正辛醇反应2h，反应结束，备用。
步骤2、反应釜置于冰浴上，向其中加入5.67g(0.028mol)十二烷基硫醇，磁力搅拌下，向烧瓶中缓慢滴加入30wt％的NaOH水溶液3.73g，15min后在搅拌下加入丙酮5.00mL，待充分溶解后，加入2.13g(0.028mol)CS2，继续搅拌反应1h。随后加入步骤1制备得到的聚氨酯，在30℃下搅拌反应12小时，产物于250mL体积比1∶1甲醇/水中沉淀，沉淀于室温下晾干后，置于真空干燥箱90℃干燥过夜，得到聚氨酯RAFT试剂。
实施例3
步骤1、在反应釜中加入6.73g(0.04mol)六亚甲基二异氰酸酯、3.08g(0.028mol)3-氯-1，2-丙二醇、1.07g(0.008mol)二羟甲基丙酸、0.05g(7.92×10-5mol)二月桂酸二丁基锡、5.00mL无水丙酮，于85℃下搅拌反应，反应8h，加入1.04g(0.008mol)正辛醇反应2h，反应结束，备用。
步骤2、反应釜置于冰浴上，向其中加入5.67g(0.028mol)十二烷基硫醇，磁力搅拌下，向烧瓶中缓慢滴加入30wt％的NaOH水溶液3.73g，15min后在搅拌下加入丙酮5.00mL，待充分溶解后，加入2.13g(0.028mol)CS2，继续搅拌反应1h。随后加入步骤1制备得到的聚氨酯，在50℃下搅拌反应6小时，产物于250mL体积比2∶1甲醇/水中沉淀，沉淀于室温下晾干后，置于真空干燥箱90℃干燥过夜，得到聚氨酯RAFT试剂。
实施例4
步骤1、在反应釜中加入8.91g(0.04mol)异佛尔酮二异氰酸酯、7.33g(0.028mol)2，2-二溴甲基-1，3-丙二醇、1.07g(0.008mol)二羟甲基丙酸、0.05g(7.92×10-5mol)二月桂酸二丁基锡、5.00mL无水丙酮，于80℃下搅拌反应，反应9h，加入1.04g(0.008mol)正辛醇反应2h，反应结束，备用。
步骤2、反应釜置于冰浴上，向其中加入5.67g(0.028mol)十二烷基硫醇，磁力搅拌下，向烧瓶中缓慢滴加入30wt％的NaOH水溶液3.73g，15min后在搅拌下加入丙酮5.00mL，待充分溶解后，加入2.13g(0.028mol)CS2，继续搅拌反应1h。随后加入步骤l制备得到的聚氨酯，在30℃下搅拌反应12小时，产物于250mL体积比l∶1甲醇/水中沉淀，沉淀于室温下晾干后，置于真空干燥箱90℃干燥过夜，得到聚氨酯RAFT试剂。

Claims (8)

1.一种聚氨酯RAFT试剂的制备方法，其特征在于，具体步骤如下：
二异氰酸酯与含卤二元醇和亲水扩链剂溶于溶剂，并在催化剂作用下反应得到聚氨酯预聚体，并以正辛醇封端得到功能化聚氨酯；以十二烷基硫醇、二硫化碳和氢氧化钠为原料反应得到十二烷基三硫酯钠盐后，加入功能化聚氨酯，加热下搅拌反应数小时后，于甲醇/水中沉淀得到聚氨酯RAFT试剂。
2.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，
聚氨酯RAFT试剂结构式如下：
Figure FSB0000198801480000011
式中R1为：
Figure FSB0000198801480000012
或-CH2(CH2)4CH2-
式中R2为：CH3(CH2)6CH2-
式中x为10，y为0或1，z为1～12。
3.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述溶剂为丙酮或丁酮，使用前需要进行无水处理。
4.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯。
5.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述含卤二元醇为3-氯-1，2-丙二醇或2，2-二溴甲基-1，3-丙二醇，使用前需要进行无水处理。
6.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸，使用前需要进行无水处理。
7.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述催化剂为二月桂酸二丁基锡。
8.如权利要求1所述的聚氨酯RAFT试剂的制备方法，其特征在于，所述甲醇/水的比例是甲醇∶水体积比为2∶1～6。
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