CN101284927B - 聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法 - Google Patents
聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法 Download PDFInfo
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Abstract
聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法，将3，4-乙撑二氧噻吩与聚苯乙烯粒子乳液混合，搅拌数小时后，在50～80℃下加入氧化剂，搅拌下，滴加掺杂酸，反应18～24小时后，用甲醇、水多次离心洗涤，至上层的溶液变为无色为止，再分离、干燥，获得聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子，聚3，4-乙撑二氧噻吩壳层的厚度范围为50～100nm。
Description
(一)技术领域：
本发明属于高分子材料技术领域，具体涉及一种具有核壳结构的聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法。
(二)技术背景：
导电聚合物乳胶纳米复合粒子材料集高分子自身的导电性与纳米颗粒的功能性于一体，具有分子结构可设计，电导率可调节以及形态特征可控制等优点，并且其胶体分散的特性有望改善导电高分子普遍存在的加工困难的缺点，因而在电致变色元件、电致发光元件、生物医用传感器、金属表面抗腐蚀及抗静电涂层、新型吸波隐身涂层、二次可充电电池、石油裂解催化剂、超分子自组装等方面具有潜在的应用前景。
聚3，4-乙撑二氧噻吩是20世纪80年代后半期，德国拜耳公司成功开发的新一代导电聚合物，它具有导电性优良，透明性好，不易被氧化，环境稳定性好，且价格低廉等优点。特别是，高电导率与超稳定性完美结合的独特性能使之在工业上具有非常广泛的应用前景。因此，合成以聚3，4-乙撑二氧噻吩为导电功能组分并具有纳米结构的复合材料有着极为重要的实际意义。聚苯乙烯/聚3，4-乙撑二氧噻吩核壳型复合粒子是常见的复合方式与材料形态之一。就目前的状况而言，通常的制备方法是在聚苯乙烯模板物的存在下，进行3，4-乙撑二氧噻吩的化学氧化聚合，并使其沉淀在模板粒子表面上，从而形成复合物。S.P.Armes等先利用分散聚合方法制得聚乙烯基吡咯烷酮稳定的微米级别的聚苯乙烯粒子；将聚苯乙烯粒子乳液加入到装有一定量水圆底烧瓶中，电磁搅拌，通氮气除氧；然后加入氧化剂对甲苯磺酸铁；加热升温至反应温度；再用注射器将一定量的3，4-乙撑二氧噻吩的甲醇溶液加入到烧瓶中，使3，4-乙撑二氧噻吩在总体系中的浓度为1％的体积比；恒温反应24小时；最后氧化聚合产生的聚3，4-乙撑二氧噻吩沉淀在聚苯乙烯粒子表面形成聚3，4-乙撑二氧噻吩层(参考文献1：Langmuir，1999，15，3469-3475)。为了改善复合效果，也有对聚苯乙烯粒子先进行表面处理，以增强粒子与3，4-乙撑二氧噻吩之间的相互作用，促使3，4-乙撑二氧噻吩的聚合尽可能地发生在聚苯乙烯粒子的表面的做法。如Han等在经乳液聚合制得的交联聚苯乙烯粒子乳液中加入十二烷基苯磺酸，使其吸附在粒子的表面，利用其所带的磺酸基团增强聚苯乙烯粒子表面与3，4-乙撑二氧噻吩单体的相互作用，从而改善复合结构与效率(参考文献2：Adv. Mater.，2004，16，231-234)。上述制备方法的共同之处在于，其一，3，4-乙撑二氧噻吩是在聚苯乙烯粒子之外的介质中聚合；其二，提高聚苯乙烯粒子表面的诱导能力对增强沉积作用、改进复合结构和提高复合效率很重要。
(三)发明内容：
本发明的目的在于提出一种制备具有核壳结构的聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的新方法。
本发明同样采用了由聚苯乙烯粒子乳液和导电聚合物单体3，4-乙撑二氧噻吩所组成的水介质体系，通过3，4-乙撑二氧噻吩的化学氧化聚合制备聚3，4-乙撑二氧噻吩包覆的聚苯乙烯核壳复合粒子。本发明所提出方法的特征在于，采用了如下的制备过程：首先将3，4-乙撑二氧噻吩单体预先溶胀在固含量为4-6％的聚苯乙烯粒子乳液中，在反应温度50-80℃下，加入氧化剂氯化铁，然后将0.1-1.0M的掺杂酸以0.25-2.5毫摩尔/分钟的速度滴加到体系中，反应后获得包覆均匀的聚苯乙烯/聚3，4-乙撑二氧噻吩复合粒子，聚3，4-乙撑二氧噻吩壳层厚度为50-100nm。
本发明的特点是过程简单、产物结构与性能优良且可控，具体为：①所采用的种子粒子无需经过表面修饰、功能化或其它特别设计；②聚合过程中使用的酸不仅是聚3，4-乙撑二氧噻吩的掺杂剂，还被赋予了控制单体扩散的功能；③可以通过多种手段方便地控制聚合过程，进而有效地控制复合粒子的结构，最终获得壳层均匀完整、厚度可控(可控范围为50-100nm)的核壳型聚苯乙烯/聚3，4-乙撑二氧噻吩复合粒子。
本发明所提出聚苯乙烯/聚3，4-乙撑二氧噻吩核壳粒子的合成方法及其具体步骤如下：
1.将3，4-乙撑二氧噻吩加入到固含量4-6％的聚苯乙烯粒子乳液的水介质体系中，超声搅拌数小时。体系中3，4-乙撑二氧噻吩与聚苯乙烯粒子乳液中的粒子的质量比为1∶3-1∶12。
2.复合粒子的合成：将步骤1中制得的混合液搅拌数小时后加入氧化剂。向混合液中以0.25-2.5毫摩尔/分钟的速度滴加0.1-1.0M的掺杂酸溶液。滴加完毕后，在50-80℃下恒温反应18-24小时。停止反应后，分别用甲醇、水多次离心洗涤，直至上层的溶液变为无色为止，再经分离、干燥获得粉末状聚苯乙烯/聚3，4-乙撑二氧噻吩复合粒子。
体系中，氧化剂与3，4-乙撑二氧噻吩的摩尔比约为2.33∶1，掺杂酸与3，4-乙撑二氧噻吩的摩尔比为2∶1-6∶1。
本发明中，所用的氧化剂是氯化铁、硫酸高铈、硝酸铈铵、过硫酸铵、过硫酸钾、过氧化氢、碘酸钾、三氯化铁、氯酸钾、重铬酸钾中的一种。
本发明中，所用的掺杂酸是对甲苯磺酸、-萘磺酸、D-樟脑磺酸、聚磺化苯乙烯、盐酸、硫酸、磷酸、醋酸、丙烯酸、甲基丙烯酸中的一种。
(四)具体实施方式：
实施例1：
将0.080g 3，4-乙撑二氧噻吩加入到8.903g固含量为5.74％的聚苯乙烯粒子乳液中，超声作用下机械搅拌数小时后，加入氯化铁0.357g，搅拌5分钟后，以0.22毫摩尔/分钟的速度滴加22.5ml的对甲苯磺酸水溶液，其浓度为0.1M。在65℃下反应24小时。停止反应后，分别用甲醇、蒸馏水多次离心洗涤，直至上层溶液变为无色为止，再经离心将沉淀物和上层清液分离，最后经真空干燥获得粉末状样品。所得的样品外观呈蓝黑色，透射电镜下观察，粒子呈光滑的表面，具有核壳型结构，聚3，4-乙撑二氧噻吩壳层厚度约为70nm。
实施例2：
将0.0902g 3，4-乙撑二氧噻吩加入到10.041g固含量为5.74％的聚苯乙烯粒子乳液中，超声作用下机械搅拌数小时后，加入氯化铁0.400g，搅拌5分钟后，以0.25毫摩尔/分钟的速度滴加25ml的对甲苯磺酸水溶液，其浓度为0.1M。在75℃下反应24小时。停止反应后，分别用甲醇、蒸馏水多次离心洗涤，直至上层溶液变为无色为止，再经离心将沉淀物和上层清液分离，最后经真空干燥获得粉末状样品。所得的样品外观呈蓝黑色，透射电镜下观察，粒子呈均匀的凹凸状表面，具有核壳型结构，聚3，4-乙撑二氧噻吩壳层厚度约为80nm。
实施例3：
将0.150g 3，4-乙撑二氧噻吩加入10.450g固含量为5.74％的聚苯乙烯粒子乳液中，超声作用下机械搅拌数小时后，加入含氯化铁0.667g，搅拌5分钟后，以0.42毫摩尔/分钟的速度滴加42ml的对甲苯磺酸水溶液，其浓度为0.1M。在75℃下反应24小时。停止反应后，分别用甲醇、蒸馏水多次离心洗涤，直至上层溶液变为无色为止，再经离心将沉淀物和上层清液分离，最后经真空干燥获得粉末状样品。所得的样品外观呈蓝黑色，透射电镜下观察，粒子表面有均匀的细毛刺状凸起，具有核壳型结构，聚3，4-乙撑二氧噻吩壳层厚度约为100nm。
实施例4：
将0.1018g 3，4-乙撑二氧噻吩加入到10.662g固含量为5.74％的聚苯乙烯粒子乳液，超声作用下机械搅拌数小时后，加入氯化铁0.453g，搅拌5分钟后，以0.3毫摩尔/分钟的速度滴加6ml的对甲苯磺酸水溶液，其浓度为0.5M。在75℃下反应24小时。停止反应后，分别用甲醇、蒸馏水多次离心洗涤，直至上层溶液变为无色为止，再经离心将沉淀物和上层清液分离，最后经真空干燥获得粉末状样品。所得的样品外观呈蓝黑色，透射电镜下观察，粒子表面略有不规则凸起，具有核壳型结构，聚3，4-乙撑二氧噻吩壳层厚度约为50nm。
Claims (3)
1.聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法，采用聚苯乙烯粒子乳液和导电聚合物单体3，4-乙撑二氧噻吩组成的水介质体系，其特征是3，4-乙撑二氧噻吩先与聚苯乙烯乳液混合，搅拌数小时，待3，4-乙撑二氧噻吩溶胀于聚苯乙烯粒子后，在50～80℃下加入氧化剂，在搅拌情况下以0.25～2.5毫摩尔/分钟的速度滴加0.1～1.0M的掺杂酸，搅拌反应18～24小时后，分别用甲醇、水多次离心洗涤，直至上层的溶液变为无色为止，再分离、干燥，获得粉末状聚苯乙烯/聚3，4-乙撑二氧噻吩复合粒子，聚3，4-乙撑二氧噻吩壳层厚度为50～100nm；聚苯乙烯粒子乳液的固含量为4～6％，体系中3，4-乙撑二氧噻吩与聚苯乙烯粒子的质量比为1∶3～1∶12，氧化剂与3，4-乙撑二氧噻吩的摩尔比为2.33∶1，掺杂酸与3，4-乙撑二氧噻吩的摩尔比为2∶1～6∶1。
2.据权利要求1所述的聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法，其特征在于氧化剂是氯化铁、硫酸高铈、硝酸铈铵、过硫酸铵、过硫酸钾、过氧化氢、碘酸钾、三氯化铁、氯酸钾、重铬酸钾中的一种。
3.据权利要求1所述的聚苯乙烯/聚3，4-乙撑二氧噻吩导电高分子复合粒子的制备方法，其特征在于掺杂酸是对甲苯磺酸、β-萘磺酸、D-樟脑磺酸、聚磺化苯乙烯、盐酸、硫酸、磷酸、醋酸、丙烯酸、甲基丙烯酸中的一种。
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| CN103084126B (zh) * | 2013-01-21 | 2015-05-20 | 昆明理工大学 | 一种具有高振实密度和导电性的微球及其制备方法 |
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| CN103709417B (zh) * | 2013-12-24 | 2016-06-29 | 深圳新宙邦科技股份有限公司 | 一种聚噻吩类衍生物水分散体及其制备方法 |
| CN103923102B (zh) * | 2014-04-30 | 2017-04-05 | 南京工业大学 | 一种化合物5,8－二(3，4－乙撑二氧噻吩基)－喹啉合成方法 |
| CN105336867B (zh) * | 2015-09-30 | 2017-12-01 | 华南理工大学 | 一种萘磺酸甲醛缩合物分散聚3,4‑乙撑二氧噻吩导电复合物及制备与应用 |
| CN105842108B (zh) * | 2016-03-22 | 2019-05-14 | 中国石油大学(华东) | 一种催化裂化油浆固含量的测定方法 |
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| CN108329500A (zh) * | 2018-01-31 | 2018-07-27 | 重庆百惠电子科技有限公司 | 一种防静电塑料载带及其生产工艺 |
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