CN107163178B - 一种常温下快速制备超支化聚丙烯酸树脂的方法 - Google Patents
一种常温下快速制备超支化聚丙烯酸树脂的方法 Download PDFInfo
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Abstract
一种常温下快速制备超支化聚丙烯酸树脂的方法,属于高分子合成、树脂材料的制备领域。本发明采用二乙烯基苯为支化单体在单电子转移活性可控自由基聚合法常温下快速制备支化聚丙烯酸树脂。以丙烯酸甲酯或丙烯酸丁酯作为乙烯基单体,二乙烯苯DVB作为支化单体,2‑溴丙酸甲酯MBP为引发剂,铜粉和溴化铜与五甲基二乙烯三胺PMDETA形成络合物作为催化剂,溶剂DMSO,除氧,常温搅拌下进行单电子转移活性可控自由基聚合,各组分配比可设计为[MA]:[DVB]:[MBP]:[PMDETA]:[Cu(0)]:[CuBr2]=(10~100):(0.7~1.1):1:0.1:0.1:0.005,制备出一系列的不同分子量及其支化度的支化聚丙烯酸树脂。
Description
技术领域
本发明涉及用二乙烯基苯为支化单体在单电子转移活性可控自由基聚合法常温下快速制备支化聚丙烯酸树脂,属于高分子合成、树脂材料制备领域。
背景技术
支化聚合物由于其独特的三维球状结构,因此,独特键接方式直接影响到大分子链间的相互缠绕和相互作用力。支化结构的形成改变了大分子的形态,因此表现出不同的溶液性能和熔体性能,并且具有与线性聚合物不同的结晶度、熔点、热稳定性等物理性能和机械性能。这种结构使其分子链间无缠绕作用,从而大大提高了其溶解性和兼容性,与相同分子量的线性分子相比,超支化分子呈椭球形,结构紧凑,熔体和溶液粘度较低。超支化聚合物可用作大分子引发剂、药物缓释剂、固化剂、交联剂。超支化聚合物大分子表面富集大量的端基,这些端基赋予了超支化大分子较高的反应活性,超支化聚合物的性能介于线形聚合物和体形聚合物之间,根据超支化聚合物的性质只要用作聚合物的共混改性剂、热固性树脂增韧剂、染色助剂、加工助剂和流变助剂等;此外,超支化聚合物中的核组分、支臂组分以及端基对聚合物的性能都有很大影响,通过适当的物理或化学手段,还可以赋予超支化聚合物其它一些特殊性能,如光物理、光化学性能、阻燃性、吸附及解吸附性能等,所以超支化聚合物在涂料、薄膜、高分子液晶等方面也获得较广泛应用。
支化聚合物多用ABx型单体逐步聚合的方法合成,但是能发生此反应的单体结构类型相对有限,为此越来越多的科学家把目光投向活性自由基聚合。1995年,Fréchet提出了由自引发单体(Inimer)合成超支化聚合物的自缩合乙烯基聚合物聚合反应(SCVP)(Fréchet J M J,Gitsov I,Aoshima S,et al.Science,1995,269:1080-1083),但是该聚合方法所必须使用的Inimer不但制作过程繁琐,而且造价昂贵。2004年,Sherrington DC等人提出可以使用双烯化合物为支化单体制备支化聚合物,并成功制备了支化聚甲基丙烯酸甲酯(Isaurea F,Coemack P AG,Graham S,et al.Chemical Communication,2004,9:1138-1139.)。2006年,Bannisteri等人在ATRP条件下,对双烯化合物和普通单烯的聚合行为进行了具体研究(Bannnister I,Billingham N C,Armes S P,et al.Macromolecules,2006,39(22):7483-7492)。但是原子转移自由基聚合也存在着明显的不足,如聚合速度较慢,后处理麻烦等缺点。
Percec提出了一种新的准活性自由基聚合方法克服了以上缺点,该聚合方法被命名为单电子转移自由基聚合(SET-LRP,),该聚合方法的机理简单的说就是在Cu(0)/配位剂催化下,在强极性溶剂中,以有机卤化物(R-X)为引发剂,引发单体在室温或更低温度下进行的准活性自由基聚合。SET-LRP使用普通的铜丝或铜粉作为催化剂,聚合结束后将铜丝取出或将铜粉过滤即可。此外,如果使用铜丝作为催化剂,可在任意时间将铜丝取出,聚合即可中止,将铜丝再放入后,聚合仍可继续。因此,由于催化体系易于脱除、反应进程易于控制、常温反应能耗低等特点,使得SET-LRP具有很好的工业应用前景。研究表明,SET-LRP所制备聚合物往往具备更高分子量,最高可达106,而ATRP所获得聚合物的分子量一般只能在104~105范围内。因此,SET-LRP受到广泛关注。基于其反应速率快、聚合温度低、聚合条件温和等优点,该方法可应用于制备支化聚丙烯酸树脂。
发明内容
本专利公开了一种超支化聚丙烯酸树脂的制备方法,采用单电子转移自由基聚合方法,以价格低廉的二乙烯苯为支化单体合成支化聚合物,操作简单方便,可以在室温或者更低的温度下进行,且反应时间大大缩减,制备出高分子量支化聚丙烯酸树脂,可有助于降低基体树脂的粘度,大大提高树脂固含量,有效降低VOC排放和节能减排的目标,广泛用于高固体含量树脂涂料、不饱和树脂和酚醛树脂等材料中。
附图说明
图1:聚合反应动力学,常温下140分钟后聚合反应结束,单体反应完成,形成高分子量及高支化度支化聚合物;
图2:不同单体转化率下聚合物溶液的凝胶渗透色谱(GPC)测试结果,表明随着单体转化率提升,聚合物分布变宽,向高分子量转变,形成高支化度结构的支化聚合物;
图3:不同转化率下聚合物分子量与支化度的关系,随着反应的进行,支化因子逐渐下降,说明聚合物支化程度逐渐提高;在最终转化率下,聚合物的支化度已经降至约0.1,最终成功制备了具有高度支化结构的聚合物。
图4:支化聚合物的核磁谱图(1H-NMR),5.18ppm、5.61ppm处的峰分别对应于二乙烯基苯上双键的两个氢。随着单体转化率的提高,悬垂双键上的氢原子所对应的峰在不断减小,说明悬垂双键在不断消耗,形成支化聚合物。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于同行进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对同行来说,在不脱离本发明构思的前提下,还可以做出若干改进。这些都属于本发明的保护范围。
实施例1
称取丙烯酸甲酯(17.20g,200mmol),二乙烯苯DVB(1.04g,8.0mmol),2-溴丙酸甲酯MBP(1.66g,10.0mmol),五甲基二乙烯三胺PMDETA(1.73g,10.0mmol)加入到带有搅拌子的100mL标口球瓶反应瓶(具高真空阀)中,再加入与丙烯酸甲酯质量相等的溶剂DMSO,在搅拌的同时,抽真空、通氩气3次后置于氩气保护下;按实验配比称取铜粉(0.64g,10.0mmol)和溴化铜(0.07g,0.5mmol),加入反应器中,迅速加橡胶塞后抽真空、通氩气3次,瓶口包裹四氟乙烯带密封;各组分的配比为[MA]:[DVB]:[MBP]:[PMDETA]:[Cu(0)]:[CuBr2]=20:0.8:1:0.1:0.1:0.005,将反应器置于恒温(25℃)水浴中反应,反应结束后,加入THF充分溶解聚合物,用滤纸过滤于石油醚中,得到聚合物沉淀;沉淀于室温静置48h后倒去上层石油醚,在真空烘箱中于常温干燥,得粘稠状固体,为支化聚丙烯酸甲酯。
实施例2,相同条件下,改变[MA]:[DVB]:[MBP]=20:0.9:1,20:1:1,30:0.8:1,50:0.8:1,制备一系列不同分子量和支化度的超支化聚合物。
实施例3
称取丙烯酸丁酯BA(25.60g,300mmol),二乙烯苯DVB(1.04g,8.0mmol),2-溴丙酸甲酯MBP(1.66g,10.0mmol),五甲基二乙烯三胺PMDETA(1.73g,10.0mmol)加入到带有搅拌子的100mL标口球瓶反应瓶(具高真空阀)中,再加入与丙烯酸甲酯质量相等的溶剂DMSO,在搅拌的同时,抽真空、通氩气3次后置于氩气保护下;按实验配比称取铜粉(0.64g,10.0mmol)和溴化铜(0.07g,0.5mmol),加入反应器中,迅速加橡胶塞后抽真空、通氩气3次,瓶口包裹四氟乙烯带密封;各组分的配比为[BA]:[DVB]:[MBP]:[PMDETA]:[Cu(0)]:[CuBr2]=30:0.8:1:0.1:0.1:0.005,将反应器置于恒温(25℃)水浴中反应,反应结束后,加入THF充分溶解聚合物,用滤纸过滤于石油醚中,得到聚合物沉淀;沉淀于室温静置48h后倒去上层石油醚,在真空烘箱中于常温干燥,得粘稠状固体,为支化聚丙烯酸丁酯。
实施例4,相同条件下,改变[BA]:[DVB]:[MBP]=20:0.9:1,20:1:1,30:0.8:1,50:0.8:1,制备一系列不同分子量和支化度的超支化聚合物。
Claims (1)
1.一种常温下快速制备超支化聚丙烯酸树脂的方法,采用价格低廉的二乙烯基苯为支化单体,常温下,单电子转移活性可控自由基聚合法快速制备支化聚丙烯酸树脂;以丙烯酸甲酯或丙烯酸丁酯作为乙烯基单体,二乙烯苯DVB作为支化单体,2-溴丙酸甲酯MBP为引发剂,铜粉和溴化铜与五甲基二乙烯三胺PMDETA形成络合物作为催化剂,溶剂DMSO,进行单电子转移活性可控自由基聚合,制备出一系列的不同分子量及其支化度的支化聚丙烯酸树脂,其制备方法为:
(1)超支化聚丙烯酸甲酯的制备方法,称取丙烯酸甲酯MA,二乙烯苯DVB,2-溴丙酸甲酯MBP,五甲基二乙烯三胺PMDETA加入到带有搅拌子和高真空阀的反应瓶中,再加入与丙烯酸甲酯质量相等的溶剂DMSO,在搅拌的同时,抽真空、通氩气3次后置于氩气保护下;按实验配比称取铜粉Cu(0)和溴化铜CuBr2加入反应器中,迅速加橡胶塞后抽真空、通氩气3次,瓶口包裹四氟乙烯带密封;各组分的摩尔比设计为[MA]:[DVB]:[MBP]:[PMDETA]:[Cu(0)]:[CuBr2]=20:0.8:1:0.1:0.1:0.005、20:0.9:1:0.1:0.1:0.005、20:1:1:0.1:0.1:0.005、30:0.8:1:0.1:0.1:0.005和50:0.8:1:0.1:0.1:0.005,将反应器置于25℃恒温水浴中反应,反应结束后,加入四氢呋喃THF充分溶解聚合物,用滤纸过滤于石油醚中,得到聚合物沉淀;沉淀于室温静置48h后倒去上层石油醚,在真空烘箱中于常温干燥,得粘稠状固体,为支化聚丙烯酸甲酯;
(2)超支化聚丙烯酸丁酯的制备方法,称取丙烯酸丁酯BA,二乙烯苯DVB,2-溴丙酸甲酯MBP,五甲基二乙烯三胺PMDETA加入到带有搅拌子和高真空阀的反应瓶中,再加入与丙烯酸丁酯质量相等的溶剂DMSO,在搅拌的同时,抽真空、通氩气3次后置于氩气保护下;按实验配比称取铜粉Cu(0)和溴化铜CuBr2加入反应器中,迅速加橡胶塞后抽真空、通氩气3次,瓶口包裹四氟乙烯带密封;各组分的摩尔比设计为[BA]:[DVB]:[MBP]:[PMDETA]:[Cu(0)]:[CuBr2]=30:0.8:1:0.1:0.1:0.005、20:0.9:1:0.1:0.1:0.005、20:1:1:0.1:0.1:0.005、30:0.8:1:0.1:0.1:0.005和50:0.8:1:0.1:0.1:0.005,将反应器置于25℃恒温水浴中反应,反应结束后,加入THF充分溶解聚合物,用滤纸过滤于石油醚中,得到聚合物沉淀;沉淀于室温静置48h后倒去上层石油醚,在真空烘箱中于常温干燥,得粘稠状固体,为支化聚丙烯酸丁酯。
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CN104870485A (zh) * | 2012-12-18 | 2015-08-26 | 汉高知识产权控股有限责任公司 | 支化聚丙烯酸酯的受控自由基聚合的方法 |
CN103497293B (zh) * | 2013-10-10 | 2015-11-04 | 河北工业大学 | 单电子转移活性自由基聚合制备dmaema基两亲嵌段共聚物的方法 |
CN106366229B (zh) * | 2016-09-06 | 2019-03-22 | 常州大学 | 一种含多环支化聚合物的合成方法 |
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