CN108329465B - 含氟环氧寡聚物基苯乙烯单体及其制备方法和应用 - Google Patents
含氟环氧寡聚物基苯乙烯单体及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种含氟环氧寡聚物基苯乙烯单体及其制备方法和应用,该含氟环氧寡聚物基苯乙烯单体的结构式为
Description
技术领域
本发明属于高分子化学化工技术领域,具体涉及一种含氟环氧寡聚物基苯乙烯单体及其制备方法和应用。
背景技术
含氟聚合物具有低摩擦系数,低表面自由能,良好的生物相容性,以及优良的耐水性、耐油性、耐候性和耐化学品等卓越性能,可用来制备高性能密封材料、润滑材料、医用材料、涂敷材料、表面活性剂及弹性体等,从而广泛应用于军事、医学、电子、机械、航天等领域。
含氟聚合物由含氟单体通过适当的方法聚合而成。文献(J.Polym.Sci.,Part A:Polym.Chem.,1980,18,1889)报道了在苯乙烯的苯环上引入较小的含氟基团,使其成为部分氟化的苯乙烯单体(如:对乙烯基三氟乙酰苯(VTFA)或对乙烯基三氟甲基酮(VTFK))。不仅此类含氟单体保持了苯乙烯良好的聚合反应性能,而且其聚合产物还具有类似于聚苯乙烯的良好加工性能。
含氟单体聚合方法主要包括水相聚合和溶液聚合两种方法。水相聚合获得的产物中往往残留有表面活性剂等杂质并且带有不稳定的羧基端基,无法获得超高纯度的含氟聚合物。溶液聚合所需的溶剂一般为氯氟烃(CFCs,这是破坏大气臭氧层的主要化学物质)或氟代烃(HFC,这是温室效应极为显著的化学物质),因而迫切需要寻找一种绿色高效的介质用于含氟单体的聚合。
近年来,超临界二氧化碳(scCO2)因其所具有的独特优势被越来越多的认为是一种环境友好的聚合反应介质。scCO2无毒无污染、不燃不***、化学惰性无链转移、廉价易回收、临界状态容易实现等。此外,scCO2具有低粘度和高扩散系数,对聚合物有塑化作用,可提高聚合体系的传质或扩散性能从而提高聚合速率,并且在聚合反应结束后,通过减压即可除去CO2,无溶剂残留。文献(Macromolecules,2012,45,4907)表明,包括苯乙烯在内的绝大多数乙烯基单体在scCO2中具有良好的溶解性能,但是其寡聚物或聚合物在scCO2中的溶解性能却很有限,导致众多单体在scCO2中难以实现均相或溶液聚合,并且随着聚合产物分子量增大,聚合体系均相性就越差。总体上,聚合物在scCO2中有限的溶解性在很大程度上影响着聚合过程的可控性以及聚合物的结构。文献(Green Chemistry,2015,17,4489)表明,六氟环氧丙烷寡聚物(PHFPO)在scCO2中具有优良的溶解性能。PHFPO可通过六氟环氧丙烷(HFPO)阴离子开环聚合来可控制备,该方法效率高,选择性好,成本低。因此,引入PHFPO设计制备新型含氟单体,对于构建scCO2均相或溶液聚合体系并在此基础上可控制备新型含氟聚合物功能材料具有重要意义。
发明内容
本发明所要解决的一个技术问题在于克服苯乙烯-聚苯乙烯体系在scCO2中溶解性能不佳、聚合过程可控性差等缺点,提供一种在scCO2中的溶解性能优良、聚合性能优良的含氟环氧寡聚物基苯乙烯单体。
本发明要解决的另一技术问题在于为上述含氟环氧寡聚物基苯乙烯单体提供一种操作简单的制备方法。
本发明还要解决的一个技术问题在于为上述含氟环氧寡聚物基苯乙烯单体提供一种新用途。
解决上述技术问题所采用的含氟环氧寡聚物基苯乙烯单体的结构式如下所示:
式中n为1~14的整数。
本发明含氟环氧寡聚物基苯乙烯单体的制备方法由下述步骤组成:
1、合成对苯乙烯基溴化镁
在惰性气体保护下,在镁粉中加入四氢呋喃和催化量的碘单质,再滴加对溴苯乙烯,室温反应1~3小时,得到对苯乙烯基溴化镁溶液。
2、合成对苯乙烯基铜(I)
在惰性气体保护及冰浴条件下,将步骤1得到的对苯乙烯基溴化镁溶液缓慢滴加到氯化亚铜的四氢呋喃悬浊液中,在室温反应1~2小时,得到对苯乙烯基铜(I)溶液。
3、合成含氟环氧寡聚物基苯乙烯单体
在惰性气体保护及冰浴条件下,将环氧寡聚物基酰卤逐滴加入到步骤2得到的对苯乙烯基铜(I)溶液中,室温反应4~6小时,反应产物经水解以及分离纯化,得到含氟环氧寡聚物基苯乙烯单体。
上述含氟环氧寡聚物基酰卤的结构式为Rf-COX,式中X为F或Cl,Rf为:
其中n为1~14的整数。
上述制备方法中,所述对溴苯乙烯与镁粉、氯化亚铜、含氟环氧寡聚物基酰卤的摩尔比为1:1.1~1.4:1~1.4:0.7~1.1。
本发明的含氟环氧寡聚物基苯乙烯单体在scCO2体系中制备含氟环氧寡聚物基苯乙烯聚合物的用途,具体使用方法为:将含氟环氧寡聚物基苯乙烯单体和自由基引发剂加入反应釜中,在压力为10~30MPa、温度为50~80℃条件下进行聚合,聚合结束后,关闭加热停止搅拌,反应釜温度降至室温后,通过缓慢放气将反应釜内压力降至常压,开釜,收集聚合产物。
本发明的含氟环氧寡聚物基苯乙烯单体制备方法简单高效,在scCO2介质中溶解性能优良,在较低压力下能够充分分散并溶解于scCO2中,甚至能够在温和的温度压力条件下与scCO2混溶。与目前常用的含氟单体相比,本发明的含氟环氧寡聚物基苯乙烯单体在scCO2中转变压力小,聚合压力低,条件温和,聚合过程均相性良好,产物性能优良且无溶剂残留,可应用于scCO2体系高性能含氟聚合物功能材料的可控制备。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
以制备下式的含氟环氧寡聚物基苯乙烯单体为例,其具体制备方法如下:
1、合成对苯乙烯基溴化镁
在氮气保护下,将10.05g(55mmol)对溴苯乙烯逐滴加入到装有1.61g(66mmol)镁粉、1~2粒碘单质和50mL四氢呋喃的三口烧瓶中,在搅拌状态下室温反应2小时,得到对苯乙烯基溴化镁溶液。
2、合成对苯乙烯基铜(I)
在氮气保护及冰浴条件下,将步骤1得到的对苯乙烯基溴化镁溶液逐滴加入到装有20mL四氢呋喃和5.45g(55mmol)氯化亚铜的三口烧瓶中,在搅拌下室温反应1小时,得到对苯乙烯基铜(I)溶液。
3、合成含氟环氧寡聚物基苯乙烯单体
在氮气保护及冰浴条件下,将18.26g(55mmol)含有酰氟端基的六氟环氧丙烷二聚体(CF3CF2CF2OCF(CF3)COF,由浙江环新氟材料股份有限公司提供)逐滴加入到步骤2得到的对苯乙烯基铜(I)溶液中,在搅拌状态下室温反应5小时,然后加入60mL水淬灭反应,用无水***(50mL×3次)萃取,合并有机相并用无水硫酸钠干燥,过滤,减压蒸馏除去滤液中的溶剂,剩余混合物用硅胶柱色谱法(以石油醚为洗脱剂)提纯,得到无色液体,即含氟环氧寡聚物基苯乙烯单体14.87g,产率为65.0%,波谱数据如下:
FT-IR(液膜法):3045,1692,1604,1190~1350,902,990cm-1。
1H NMR(600MHz,CDCl3):8.02(d,2ArH),7.54(d,2ArH),6.77(dd,CH=),5.94(dd,-CHH),5.51(dd,-CHH)。
13C NMR(600MHz,CDCl3):183.95,144.31,135.42,130.80,130.76,126.55,118.56ppm,100.00~130.00ppm。
HRMS(ESI):[M+Na]=439.0159。
采用文献(Macromolecules,2012,45,4907-4919)报道的高压原位红外光谱监测***及其在线监测方法分别在40、50、60及70℃下测定该含氟环氧寡聚物基苯乙烯单体在超临界二氧化碳介质中溶剂化分散过程,所得转变压力结果表明,在上述各温度条件下该含氟环氧寡聚物基苯乙烯单体能够与超临界二氧化碳介质相混溶,混溶压力温和,最大不超过13MPa,表明该含氟单体在超临界二氧化碳介质中的溶解性能优良。
实施例2
以制备下式的含氟环氧寡聚物基苯乙烯单体为例,其具体制备方法如下:
本实施例中,用等摩尔含有酰氟端基的六氟环氧丙烷三聚体(CF3CF2CF2OCF(CF3)CF2OCF(CF3)COF,由浙江环新氟材料股份有限公司提供)替换实施例1中含有酰氟端基的六氟环氧丙烷二聚体,其他步骤与实施例1相同,得到无色液体环氧寡聚物基含氟单体22.91g,产率为71.6%,波谱数据如下:
FT-IR(液膜法):3045,1692,1604,1190~1350,902,990cm-1。
1H NMR(600MHz,CDCl3):8.02(d,2ArH),7.54(d,2ArH),6.77(dd,CH=),5.94(dd,-CHH),5.51(dd,-CHH)。
13C NMR(600MHz,CDCl3):183.95,144.31,135.42,130.80,130.76,126.55,118.56ppm,100.00~130.00ppm。
HRMS(ESI):[M+Na]=605.0016。
采用文献(Macromolecules,2012,45,4907-4919)报道的高压原位红外光谱监测***及其在线监测方法分别在40、50、60及70℃下测定含氟环氧寡聚物基苯乙烯单体在超临界二氧化碳介质中溶剂化分散过程,所得转变压力结果表明,在上述各温度条件下含氟环氧寡聚物基苯乙烯单体能够与临界二氧化碳介质相混溶,混溶压力温和,最大不超过13MPa,表明该含氟单体在超临界二氧化碳介质中的溶解性能优良。
实施例3
以制备下式的含氟环氧寡聚物基苯乙烯单体为例,其具体制备方法如下:
本实施例中,用等摩尔含有酰氯端基的六氟环氧丙烷十五聚体(CF3CF2CF2O(CF(CF3)CF2O)13CF(CF3)COCl替换实施例1中含有酰氟端基的六氟环氧丙烷二聚体,反应时间延长至6小时,其他步骤与实施例1相同,得到无色液体环氧寡聚物基含氟单体65.28g,产率为50.4%,波谱数据如下:
FT-IR(液膜法):3045,1692,1604,1190~1350,902,990cm-1。
1H NMR(600MHz,CDCl3):8.02(d,2ArH),7.54(d,2ArH),6.77(dd,CH=),5.94(dd,-CHH),5.51(dd,-CHH)。
13C NMR(600MHz,CDCl3):183.95,144.31,135.42,130.80,130.76,126.55,118.56ppm,100.00~130.00ppm。
采用文献(Macromolecules,2012,45,4907-4919)报道的高压原位红外光谱监测***及其在线监测方法分别在40、50、60及70℃下测定该含氟环氧寡聚物基苯乙烯单体在超临界二氧化碳介质中溶剂化分散过程,所得转变压力结果如下:
结果表明在上述各温度条件下含氟环氧寡聚物基苯乙烯单体能够与临界二氧化碳介质相混溶,混溶压力温和,最大不超过13MPa,表明该含氟单体在超临界二氧化碳介质中的溶解性能优良。
本实施例含有酰氯端基的六氟环氧丙烷十五聚体的合成方法为:在氮气保护下,将250.00g(100mmol)含有羧酸端基的六氟环氧丙烷十五聚体(CF3CF2CF2O(CF(CF3)CF2O)13CF(CF3)COCl,由杜邦公司提供)滴加到35.70g(300mmol)二氯亚砜中,在搅拌状态下,80℃反应8小时,减压蒸馏除去剩余二氯亚砜,得到含有酰氯端基的六氟环氧丙烷十五聚体。
实施例4
实施例1的含氟环氧寡聚物基苯乙烯单体在超临界二氧化碳体系中制备含氟聚合物的用途,其具体使用方法为:
将配有蓝宝石可视窗口的不锈钢高压反应釜加热至60.0℃,接着向反应釜内充入氮气,而后抽真空,重复交替该操作三次以除去反应釜内残余氧气、水分及挥发性物质。通过进样样品管向高压反应釜内加入5.00mL(9.985g)实施例2中的含氟环氧寡聚物基苯乙烯单体,随后快速向高压反应釜内充入CO2,使高压反应釜内压力达到13MPa,开启搅拌促进单体溶解变为均相。将事先装入高压进样装置中的引发剂二苯甲酰基过氧(BPO)(9.98mg)用高压CO2冲入高压反应釜中,开始计时。持续搅拌并补充CO2保持高压反应釜内压力维持在25.0MPa下进行聚合,聚合反应时间为24小时。聚合结束后,关闭加热和搅拌,待高压反应釜降至室温后,缓慢放气减压至常压,开启高压反应釜,收集含氟环氧寡聚物基苯乙烯聚合物。
Claims (4)
2.一种权利要求1所述的含氟环氧寡聚物基苯乙烯单体的制备方法,其特征在于它由下述步骤组成:
(1)合成对苯乙烯基溴化镁
在惰性气体保护下,在镁粉中加入四氢呋喃和催化量的碘单质,再滴加对溴苯乙烯,室温反应1~3小时,得到对苯乙烯基溴化镁溶液;
(2)合成对苯乙烯基铜(I)
在惰性气体保护及冰浴条件下,将步骤(1)得到的对苯乙烯基溴化镁溶液滴加到氯化亚铜的四氢呋喃悬浮液中,室温反应1~2小时,得到对苯乙烯基铜(I)溶液;
(3)合成含氟环氧寡聚物基苯乙烯单体
在惰性气体保护及冰浴条件下,将含氟环氧寡聚物基酰卤逐滴加入到步骤(2)得到的对苯乙烯基铜(I)溶液中,室温反应4~6小时,反应产物经水解以及分离纯化,得到含氟环氧寡聚物基苯乙烯单体;
上述含氟环氧寡聚物基酰卤的结构式为Rf-COX,式中X为F或Cl,Rf为:
其中n为1~14的整数。
3.根据权利要求2所述的含氟环氧寡聚物基苯乙烯单体的制备方法,其特征在于:所述对溴苯乙烯与镁粉、氯化亚铜、含氟环氧寡聚物基酰卤的摩尔比为1:1.1~1.4:1~1.4:0.7~1.1。
4.权利要求1所述的含氟环氧寡聚物基苯乙烯单体在超临界二氧化碳体系中制备含氟环氧寡聚物基苯乙烯聚合物的用途。
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