CN111253536A - 一种对温度和pH响应的聚丙烯三嵌段共聚物及其制备方法 - Google Patents
一种对温度和pH响应的聚丙烯三嵌段共聚物及其制备方法 Download PDFInfo
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Abstract
本发明公开一种对温度和pH响应的聚丙烯三嵌段共聚物及其制备方法；聚丙烯是非极性材料，对聚丙烯进行功能化，可以显著地改善聚合物材料的柔韧性、粘附力、防护性能、表面性能、耐溶剂性，此外，功能化改性的聚烯烃材料，还可以附加新的功能，如光电、医用、双亲性等，拓展聚丙烯在其它领域的应用；本发明以单末端羟基聚丙烯和3‑苄基三硫代丙酸、N‑异丙基丙烯酰胺、2‑乙烯基吡啶为原料，制备得到对温度和pH响应的聚丙烯三嵌段共聚物；聚合得到的聚丙烯三嵌段共聚物的力学性能优异，不存在聚合物间难以相容的情况，在温敏和pH敏材料上具有潜在的应用。
Description
技术领域
本发明属高分子材料化学领域，具体涉及一种对温度和pH响应的聚丙烯三嵌段共聚物及其制备方法。
背景技术
聚烯烃(以聚乙烯、聚丙烯为代表)是工业上产量最大的高分子材料，基于聚烯烃的聚合物材料对人类的生活有着重大的意义。由于聚烯烃是非极性材料，因此对聚烯烃进行功能化，可以显著地改善聚合物材料的柔韧性、粘附力、防护性能、表面性能、耐溶剂性、与其它聚合物的混溶性以及流变性等性能，此外，功能化改性的聚烯烃材料，还可以附加新的功能，如光电、医用、双亲性等等，拓展聚烯烃在其它领域的应用。聚烯烃功能化改性一直是学术界和工业领域一个重要课题和挑战。
目前，对聚烯烃功能化改性常用的方法有三种：
(1)极性单体和乙烯共聚；(2)对聚烯烃产物进行后功能化改性；(3)引入活性官能团，使烯烃配位聚合与其它聚合方式结合。第一种方法主要是使用配位聚合方式，通过烯烃和极性单体共聚，一步到位地制备功能化聚烯烃，精确控制聚合物结构和组成，一直是烯烃聚合领域关注的具挑战性的研究课题。第三种方法是基于聚烯烃中引入特殊活性官能团，直接或通过化学转化，作为极性单体聚合反应的引发位点，进行极性单体的聚合(如阴离子聚合和可控自由基聚合)，制备带有可控极性链段的功能化聚烯烃。目前，大部分的聚烯烃是通过配位聚合生产，在聚烯烃中引入活性基团，第二步采用活性/可控聚合方式在聚烯烃上引入具有可控特征的极性接枝或嵌段(包括链长、分子量分布和结构等)，可以制备聚烯烃基共聚物。目前常用的活性/可控聚合方法可分为四种：(1)阴离子聚合；(2)氮氧化合物媒介的自由基聚合(NMRP)；(3)原子转移自由基聚合(ATRP)；(4)可逆加成-断裂链转移聚合(RAFT)。林尚安等(高分子学报.1997,4,462-468.)报道茂钛催化剂催化合成间规聚苯乙烯-b-聚丙烯嵌段共聚物(PS-b-PP),王洪振等(聚丙烯-聚磷酸酯嵌段共聚物的设计与合成(高分子学报.2013,4,518-524.)等报道了通过原子转移自由基聚合(ATRP)的方法，合成了一种新型的聚丙烯-聚磷酸酯嵌段共聚物(PP-b-PDEVBP)。Zhu等(Macromol.Chem.Phys.2010,211,1452.)报道用配位聚合和ATRP相结合，制备了线型聚乙烯嵌段聚甲基丙烯酸寡聚乙二醇酯(PE-b-POEGMA)共聚物，Kashiwa等(Polym.Bull.2006,57,805.)报道用配位聚合和RAFT相结合，制备了线型聚乙烯嵌段聚甲基丙烯酸甲酯共聚物(PE-b-PMMA)。
聚丙烯是非极性材料，对聚丙烯进行功能化，可以显著地改善聚合物材料的柔韧性、粘附力、防护性能、表面性能、耐溶剂性，此外，功能化改性的聚烯烃材料，还可以附加新的功能，如光电、医用、双亲性等，拓展聚丙烯在其它领域的应用。目前国内使用聚丙烯制备温敏或pH敏材料的方法一般以聚丙烯为基底，在聚丙烯材料的表面涂上一层或两层温度敏感性或pH敏感材料的涂层，此种方法制备得到的材料不仅需要添加很多其他添加剂，而且还存在聚合物不相容的问题，相比之下，聚丙烯三嵌段共聚物力学性能更优异。
发明内容
本发明的目的在于提供一种对温度响应的聚丙烯三嵌段共聚物。
本发明的另一目在于是提供上述对温度和pH响应的聚丙烯三嵌段共聚物的制备方法。
本发明上述目的通过以下技术方案实现：
一种对温度和pH响应的聚丙烯三嵌段共聚物，其结构式如下式(Ⅰ)所示：
一种聚丙烯三嵌段共聚物的合成过程如下：
三嵌段共聚物的制备方法包括以下步骤：
(1)以KOH的碱性水溶液为溶剂，巯基丙酸、二硫化碳、苄基溴为原料，按巯基丙酸、二硫化碳、苄基溴的摩尔比为1:1:1进行反应，得到3-苄基三硫代丙酸。
(2)以甲苯为溶剂，单末端羟基聚丙烯与3-苄基三硫代丙酸为原料，单末端羟基聚丙烯与3-苄基三硫代丙酸的摩尔比为1:5进行酯化反应，得到聚丙烯大分子转移剂。
(3)以四氢呋喃THF为反应溶剂、偶氮二异丁腈为引发剂、N-异丙基丙烯酰胺为单体，聚丙烯大分子转移剂为链转移剂，温敏性单体N-异丙基丙烯酰胺在聚合体系中的浓度为1mol/L，偶氮二异丁腈、聚丙烯大分子转移剂、温敏性单体N-异丙基丙烯酰胺的摩尔比为1:9:1200进行聚合反应，得到聚丙烯与聚(N-异丙基丙烯酰胺)两嵌段共聚物(PP-b-PNIPAM)。
(4)以聚丙烯与聚(N-异丙基丙烯酰胺)嵌段共聚物作为第二转移剂、偶氮二异丁腈为引发剂、2-乙烯基吡啶为pH敏感性单体、四氢呋喃THF为反应溶剂，pH敏性单体2-乙烯基吡啶在聚合体系中的浓度为1mol/L，偶氮二异丁腈、第二转移剂、pH敏性单体2-乙烯基吡啶的摩尔比为1:4:1200进行聚合反应，得到聚丙烯三嵌段共聚物(PP-b-PNIPAM-b-P2VP)。
与现有技术相比，本发明具有如下优点和有益效果：
(1)本发明制备得到具有温敏和pH敏效应的聚丙烯三嵌段共聚物(PP-b-PNIPAM-b-P2VP)。
(2)本发明制备得到的聚丙烯三嵌段共聚物不存在几种共聚物共混时难以相容的情况，具有温敏和pH敏效应的链段的引入，可以实现聚丙烯基嵌段共聚物水溶液的聚集体在不同环境下的溶解与不溶解的转化，在温敏和pH敏材料上具有潜在的应用。
附图说明
图1为PP-b-PNIPAM-b-P2VP三嵌段共聚物水溶液聚集体的流体力学直径(Dh)与温度的关系。
图2为PP-b-PNIPAM-b-P2VP三嵌段共聚物水溶液聚集体的流体力学直径(Dh)与pH的关系。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
3-苄基三硫代丙酸的合成。
将巯基丙酸(0.53g,5mmoL)滴入溶有KOH的碱性水溶液中，然后逐滴加入二硫化碳(0.38g,5mmoL)，在室温下搅拌5h后，加入苄基溴(0.86g,5mmoL)，80℃下反应8h。二氯甲烷萃取，旋蒸，过柱，得橙黄色产物1.44g，产率为81.4％。1H-NMR(400MHz,CDCl3),δ(ppm):12.37(s,1H,OH),7.24-7.30(m,5H,Ph),4.75(s,2H,CH2),3.22(t,2H,CH2),2.82(t,2H,CH2).13C-NMR(100MHz,CDCl3),δ(ppm):226.34,177.82,136.56,127.36,127.13,45.12,35.34,32.53.
实施例2
聚丙烯大分子转移剂的合成。
在50mL支口烧瓶中，将在装有搅拌子的支口瓶中加入单末端羟基聚丙烯PP-OH(1g,0.25mmol)，抽充N2三次后，在N2气氛下，用一次性注射器打入30ml无水甲苯，升温至75℃，不断搅拌下，单末端羟基聚丙烯完全溶解后，加入1ml吡啶，搅拌20min后，缓慢滴加溶于适量甲苯溶液的RAFT试剂3-苄基三硫代丙酸(0.46g,1.25mmol)，80℃下搅拌2h，结束反应后，经甲苯/甲醇不断溶解/沉淀循环两次后，真空40℃下烘干至恒重，得到浅黄色固体粉末0.63g，产率为89％，即聚丙烯大分子转移剂。
实施例3
聚丙烯与聚(N-异丙基丙烯酰胺)两嵌段共聚物的合成。
在50mL的支口烧瓶中，将引发剂AIBN(1.64mg,0.01mmol)，聚丙烯大分子转移剂(0.29g,0.09mmol)，单体NIPAM(1.36g,12.0mmol)分别加入烧瓶中，用有机溶剂12mL二氧六环溶解，经过三次液氮冷冻-抽气-解冻循环，在75℃油浴中进行聚合反应，待聚合物溶解后，反应0.5h立即将Schlenk瓶取出放入液氮中冷却，经THF/乙醚不断溶解/沉淀循环两次，真空40℃下烘干至恒重，得黄色固体粉末1.34g，产率为81％，即聚丙烯与聚(N-异丙基丙烯酰胺)两嵌段共聚物。
实施例4
聚丙烯三嵌段共聚物PP-b-PNIPAM-b-P2VP的合成。
在50mL的支口烧瓶中，将引发剂AIBN(1.64mg,0.01mmol)，实施例3制备得到的聚丙烯与聚(N-异丙基丙烯酰胺)两嵌段共聚物(0.14g,0.04mmol)，单体2-乙烯基吡啶(1.26g,12.0mmol)分别加入烧瓶中，用有机溶剂12mL二氧六环溶解，经过三次液氮冷冻-抽气-解冻循环，在75℃油浴中进行聚合反应，待聚合物溶解后，反应0.5h立即将Schlenk瓶取出放入液氮中冷却，经THF/乙醚不断溶解/沉淀循环两次，真空40℃下烘干至恒重，真空45℃下烘干至恒重，得黄色固体粉末1.0g，产率为71％，即聚乙烯基三嵌段共聚物。
实施例5
聚丙烯三嵌段共聚物PP-b-PNIPAM-b-P2VP的温敏和pH敏响应性测试。
将聚丙烯三嵌段共聚物PP-b-PNIPAM-b-P2VP(实施例4合成的产物)2mg在20℃下溶于2mL纯水中，搅拌两周，聚合物逐渐溶解，溶液呈现淡蓝色光，显示聚合物胶束的形成，将聚丙烯三嵌段共聚物PP-b-PNIPAM-b-P2VP的水溶液置于不同的温度和pH条件下，观察进行聚合物溶液的变化(如图2所示)，显示了聚丙烯基三嵌段共聚物PP-b-PNIPAM-b-P2VP的水溶液具有明显的温度响应性和pH响应性。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (6)
1.一种对温度和pH响应的聚丙烯三嵌段共聚物，其特征在于，所述的聚丙烯三嵌段共聚物具有式(I)所示结构：
2.根据权利要求1所述的对温度和pH响应的聚丙烯三嵌段共聚物(I)的制备方法，其特征在于，包括如下步骤：
(1)以KOH的碱性水溶液为溶剂，巯基丙酸、二硫化碳、苄基溴为原料进行反应，得到3-苄基三硫代丙酸，其特征在于，具有式(Ⅱ)所示结构；
(2)单末端羟基聚丙烯与3-苄基三硫代丙酸进行酯化反应，得到聚丙烯大分子转移剂，其特征在于，具有式(III)所示结构；
(3)以偶氮二异丁腈为引发剂、四氢呋喃THF为反应溶剂、N-异丙基丙烯酰胺为单体，聚丙烯大分子转移剂为链转移剂进行聚合反应，得到聚丙烯与聚(N-异丙基丙烯酰胺)两嵌段共聚物(PP-b-PNIPAM)，其特征在于，具有式(Ⅵ)所示结构：
(4)以聚丙烯与聚(N-异丙基丙烯酰胺)嵌段共聚物作为第二转移剂、偶氮二异丁腈为引发剂、2-乙烯基吡啶为pH敏感性单体、四氢呋喃THF为反应溶剂进行聚合反应，得到聚丙烯三嵌段共聚物(PP-b-PNIPAM-b-P2VP)，其特征在于，具有式(Ⅵ)所示结构：
3.根据权利要求2所述的对温度和pH响应的聚丙烯三嵌段共聚物的制备方法，其特征在于，所述步骤(3)中的温敏性单体N-异丙基丙烯酰胺在聚合体系中的浓度为1mol/L，偶氮二异丁腈、聚丙烯大分子转移剂、温敏性单体N-异丙基丙烯酰胺的摩尔比为1:9:1200。
4.根据权利要求2所述的对温度和pH响应的聚丙烯三嵌段共聚物的制备方法，其特征在于，所述步骤(4)中的pH敏性单体2-乙烯基吡啶在聚合体系中的浓度为1mol/L，偶氮二异丁腈、第二转移剂、pH敏性单体2-乙烯基吡啶的摩尔比为1:4:1200。
5.根据权利要求2所述的三嵌段共聚物的制备方法，其特征在于所述的单末端羟基聚丙烯为线型，其分子量为2000～2000000g/mol，分子量分布为3～5，羟基封端率为72％～76％；聚合反应温度为70～85℃。
6.根据权利要求2所述3-苄基三硫代丙酸先溶于四氢呋喃中，加入氯化亚砜后，再将反应后的产物与所述单末端羟基聚丙烯在甲苯中进行酯化反应。
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| CN112160074A (zh) * | 2020-09-16 | 2021-01-01 | 曾小华 | 一种刚性超疏水聚氯乙烯膜及其制备方法 |
| CN113968948A (zh) * | 2021-10-27 | 2022-01-25 | 江苏理工学院 | 一种温度响应型正渗透汲取剂及其制备方法和应用 |
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| CN112160074A (zh) * | 2020-09-16 | 2021-01-01 | 曾小华 | 一种刚性超疏水聚氯乙烯膜及其制备方法 |
| CN113968948A (zh) * | 2021-10-27 | 2022-01-25 | 江苏理工学院 | 一种温度响应型正渗透汲取剂及其制备方法和应用 |
| CN113968948B (zh) * | 2021-10-27 | 2023-06-23 | 江苏理工学院 | 一种温度响应型正渗透汲取剂及其制备方法和应用 |
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