CN108165069B - 一种高含量的水性石墨烯分散液及其制备方法 - Google Patents
一种高含量的水性石墨烯分散液及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种高含量的水性石墨烯分散液，由MMP、乙醇、润湿剂、石墨烯、三元嵌段共聚物分散剂、其它助剂和水组成；所述的三元嵌段共聚物分散剂由衣康酸、乙烯基苯磺酸钠、甲基丙烯酰氧烷基醇磷酸单酯，RAFT链转移剂、偶氮类引发剂，通过RAFT技术合成；其Mn为3000～8000，PDI≤1.2；本发明制得一种高含量的水性石墨烯分散液，具有良好的纳米粒径及窄分布、透明性、相容性、贮存稳定性，优异的耐腐蚀性、导电性、润滑性、耐油性、耐醇性、耐水性和耐盐雾性。广泛用于水性防腐涂料、水性UV/LED涂料、复合材料、导电薄膜材料、摩擦材料及传感器等领域。
Description
技术领域
本发明涉及一种水性石墨烯分散液，尤其涉及一种高含量的水性石墨烯分散液及其制备方法，属于石墨烯技术领域。
背景技术
石墨烯是一种二维蜂窝状碳质材料，由于其独特的结构而具有非凡的电学性能、光学性能、热力学性能以及力学性能。石墨烯的电子迁移率(2×105cm2·v-1·s-1)，比硅半导体高100倍。广泛用于纳米电子器件，传感器，纳米复合材料、电池、超级电容器、储氢装置等。高浓度稳定分散的石墨烯分散液有着巨大的应用前景，可以应用于石墨烯复合材料、防腐涂料、透明导电薄膜等工业化生产。
但是石墨烯具有高的比表面积，不亲水也不亲油，并且由于范德华力还容易发生团聚，难以长时间稳定分散在溶液中。
对于如何改善石墨烯的分散性问题，有大量的科研人员在这方面作了一系列研究，其方法主要集中在对石墨炼的表面改性、引入外来分子如负载纳米粒子、加入表面活性剂分子、引入高分子以及掺杂芳香族大分子等，也有利用还原的氧化石墨炼面内或边缘含氧官能团的静电排斥作用以减弱片层间的范德华力来达到稳定分散的目的。近来有报道在不加任何表面活性剂或稳定剂的情况下，通过调节分散介质的pH值达到稳定分散石墨烯的效果。
用于分散石墨烯的体系主要有三种:(1)表面活性剂水溶液，(2)有机溶剂，(3)超酸。目前，在水溶液中使用表面活性剂所得到的石墨烯的分散液浓度都偏低，一般为5％，近来较高浓度10％石墨烯分散液提供，但是其稳定性、石墨烯粒径及分布不是很理想，如果石墨烯达不到理想的粒径，其性能大打折扣。若能在水溶液体系中得到高浓度稳定的石墨烯分散液，无疑能促进石墨烯在多领域中的广泛应用，这正是石墨烯研究领域中的一个重要课题。
据公开的专利报导，目前用于分散石墨烯液常的表面活性剂，如十二烷基磺酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、聚乙烯醇(PVA)、木质素磺酸钠(SLS)、十六烷基三甲基溴化铵(CTAB)、DNA、胆酸钠(SC)、聚苯乙烯磺酸钠(PSS)、聚乙烯吡咯烷酮(PVP)、硅烷偶联剂、钛酸酯偶联剂、聚氧乙烯蓖麻油等。但这些分散剂制备的石墨烯分散液浓度低、稳定性差。
发明内容
本发明旨在提供一种高含量的水性石墨烯分散液及其制备方法。
本发明采用一种RAFT合成的、三元嵌段共聚物作为分散剂，该分散剂具有A-B-C嵌段结构，其锚固基团羧酸盐离子、磺酸盐离子、磷酸酯盐离子吸附石墨烯粒子表面上H+形成双电层产生静电排斥，聚乙烯基苯环的嵌段梳状分布能与石墨烯形成π-π共扼键，聚甲基丙烯酰氧烷基的嵌段梳状分布产生空间位阻不会相互缠绕，并伸展在分散体系中形成架桥网状分布，从而形成稳定的悬浮体系；该分散剂含多个锚固基团，完全与粒子表面上的H+离子结合，且吸附量大，锚固效果好，有效防止水分子中-OH渗入到石墨烯粒子表面与H+形成氢键。本发明所述的石墨烯分散液在防腐涂料、复合材料、导电薄膜、传感器等的应用上使石墨烯处于纳米级分布状态而不团聚，充分体现石墨烯具有的独特性能。
本发明所述的三元嵌段共聚物分散剂，其分子末端含有磷酸酯盐基团，其制备的石墨烯分散液用于水性防锈防腐涂料时，能与金属底材上生成一层磷化膜，提高与基材的附着力和致密性，从而提高涂料的耐水性和耐盐雾性。
本发明为了提高石墨烯分散液的稳定性和相容性，选用3-甲氧基丙酸甲酯(MMP)为助溶剂，MMP中的醚酯基、线性结构以及分子中心的丙酰基使得这种材料兼有了其他溶剂所不具备的一些性质：强溶解力，能很好的分散石墨烯等难容物质；低表面张力、高电阻率，有防止石墨烯团聚的特殊功能；具有轻度气味、挥发彻底，在薄膜表面无残留气味，能增加薄膜的流平性，光泽，透明度；还起到防沉降的效果。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种高含量的水性石墨烯分散液，按重量百分比计，其组成为：MMP 5.0％～15.0％、乙醇15.0％～40.0％、润湿剂2.0～5.0％、石墨烯10.0％～20.0％、三元嵌段共聚物分散剂10.0％～25.0％、pH调节剂0.1％～0.5％、消泡剂0.1％～0.5％、其余为去离水。
其中，所述的石墨烯为Hummers法、Staudemaier法、电化学法或Brodie法制备石墨烯中的一种。
所述的三元嵌段共聚物分散剂，采用RAFT技术合成，其分子结构式如下所示：
其中，分子式中的n＝5～20，p＝4～10，m＝4～10；所述锚固基团为羧酸盐阴离子、磺酸盐阴离子、磷酸酯盐阴离子。
所述的三元嵌段共聚物分散剂，其数均分子量为3000～8000，多分散系数PDI≤1.2。
所述的三元嵌段共聚物分散剂，由以下步骤制备：
按重量份计，依次将10.0～30.0份衣康酸、5.0～15.0份对苯乙烯磺酸钠、10.0～20.0份甲基丙烯酰氧烷基醇磷酸酯、1.0～3.0份的RAFT链转移剂、40.0～80.0份溶剂加入到反应釜中，通N2保护，开启搅拌溶解均匀后，升温至50～100℃，然后均匀滴加8.0～15.0份含10％引发剂的溶剂溶液，在0.5h内滴完，保持在50～100℃继续反应6～8h；然后缓慢加入碱溶液和去离子水，调至pH为7～8，得所述的三元嵌段共聚物分散剂。
其中，所述的甲基丙烯酰氧烷基醇磷酸酯为甲基丙烯酰氧乙基醇单磷酸酯、甲基丙烯酰氧丙基醇单磷酸酯、甲基丙烯酰氧丁基醇单磷酸酯、甲基丙烯酰氧戊基醇单磷酸酯、甲基丙烯酰氧己基醇单磷酸酯、甲基丙烯酰氧庚基醇单磷酸酯中的至少一种。
所述的引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒盐酸盐中的至少一种。
所述的RAFT链转移剂为4,4’-二硫代苯乙酸、α-二硫代苯甲酯基对苯亚甲基氯化吡啶盐、S,S’-双(α,α’-二甲基-α”-乙酸)三硫代碳酸酯、二硫代二异丙基黄原酸酯、二乙基二硫代氨基甲酸酯型季铵盐中的至少一种。
所述的溶剂为水、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、丙二醇甲醚、丙二醇丁醚、二乙二醇丁醚中的至少一种。
所述的碱溶液为氢氧化钠、氢氧化钾、氨水中的至少一种。
本发明提出一种高含量的水性石墨烯分散液的制备方法，步骤如下：按配方重量份比计，在分散桶中加入去离子水、乙醇、3-甲氧基丙酸甲酯、润湿剂、三元嵌段共聚物分散剂，搅拌均匀后加入石墨烯粉，在1000～1200r/min高速下分散30～45min，再移到纳米砂磨机循环研磨6～12h直到粒径D50＜350nm，转入调缸中在300～500r/min转速下加入pH调节剂、消泡剂，搅拌20～30min，用200目滤网过滤，包装，得所述高含量的水性石墨烯分散液。
所述的纳米砂磨机为陶瓷涡轮纳米砂磨机，锆珠粒径为0.3～0.4mm。
本发明制得一种高含量的水性石墨烯分散液，具有良好的纳米粒径及窄分布、透明性、相容性、贮存稳定性，优异的耐腐蚀性、导电性、润滑性、耐油性、耐醇性、耐水性和耐盐雾性。广泛用于水性防腐涂料、水性UV/LED涂料、复合材料、导电薄膜材料、摩擦材料及传感器等领域。
具体实施方式
下面结合实施例对本发明的一种高含量的水性石墨烯分散液做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种三元嵌段共聚物分散剂A，其步骤如下：
按重量份计，依次将25.0份衣康酸、12.0份对苯乙烯磺酸钠、19.0份甲基丙烯酰氧丁基醇单磷酸酯、1.6份的S,S’-双(α,α’-二甲基-α”-乙酸)三硫代碳酸酯、80.0份乙醇加入到反应釜中，通N2保护，开启搅拌溶解均匀后，升温至75℃，均匀滴加10.0份含10％偶氮二异丁腈的乙醇溶液，在0.5h内滴完，保持在75℃继续反应6h；然后缓慢加入10％NaOH溶液和去离子水，调至pH为7～8，得所述的三元嵌段共聚物分散剂A。
实施例2
一种三元嵌段共聚物分散剂B，其步骤如下：
按重量份计，依次将22.0份衣康酸、13.0份对苯乙烯磺酸钠、15.0份甲基丙烯酰氧乙基醇单磷酸酯、3.0份的4,4’-二硫代苯乙酸、70.0份异丙醇加入到反应釜中，通N2保护，开启搅拌溶解均匀后，升温至70℃，均匀滴加8.0份含10％偶氮二异丁基脒盐酸盐的异丙醇溶液，在0.5h内滴完，保持在70℃继续反应6h；然后缓慢加入10％NaOH溶液和去离子水，调至pH为7～8，得所述的三元嵌段共聚物分散剂B。
实施例3
一种三元嵌段共聚物分散剂C，其步骤如下：
按重量份计，依次将16.0份衣康酸、10.0份对苯乙烯磺酸钠、12.0份甲基丙烯酰氧烷基丙醇单磷酸酯、2.0份的二乙基二硫代氨基甲酸酯型季铵盐、60.0份水加入到反应釜中，通N2保护，开启搅拌溶解均匀后，升温至85℃，均匀滴加12.0份含10％偶氮二异丁腈的水溶液，在0.5h内滴完，保持在85℃继续反应6h；然后缓慢加入10％NaOH溶液和去离子水，调至pH为7～8，得所述的三元嵌段共聚物分散剂C。
本发明实施例中制得的三元嵌段共聚物分散剂技术指标如表1所示：
表1三元嵌段共聚物水性分散剂技术指标
| 项目 | 实施例1 | 实施例2 | 实施例3 |
| 外观 | 淡黄色液体 | 淡黄色液体 | 淡黄色液体 |
| 固含量，％ | 41.6 | 42.3 | 40.5 |
| pH | 7～8 | 7～8 | 7～8 |
| 数均分子量，Mn | 4278 | 3865 | 7256 |
| 多分散系数，PDI | 1.17 | 1.16 | 1.2 |
实施例4
一种10％固含的水性石墨烯分散液，按重量百分比计，其组成为：去离水38.5份、3-甲氧基丙酸甲酯8.0份、乙醇25.0份、润湿剂4.0份、常州第六元素石墨烯10.0份、三元嵌段共聚物分散剂A 14.0份、pH调节剂0.3份、消泡剂0.2份。
实施例5
一种12％固含的水性石墨烯分散液，按重量百分比计，其组成为：去离水34.0份、3-甲氧基丙酸甲酯10.0份、乙醇25.0份、润湿剂3.5份、深圳贝特瑞石墨烯12.0份、三元嵌段共聚物分散剂B 15.0份、pH调节剂0.3份、消泡剂0.2份。
实施例6
一种15％固含的水性石墨烯分散液，按重量百分比计，其组成为：去离水27.5份、3-甲氧基丙酸甲酯10.0份、乙醇25.0份、润湿剂4.5份、石墨烯15.0份、三元嵌段共聚物分散剂C 17.5份、pH调节剂0.3份、消泡剂0.2份、。
将本发明实施例4、5、6制备的水性石墨烯分散液，其技术数据如表2所示：
表2水性石墨烯分散液技术指标
尽管本发明已作了详细说明并引用了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。
Claims (5)
1.一种高含量的水性石墨烯分散液，其特征在于：按重量百分比计，其组成为：3-甲氧基丙酸甲酯5.0%～15.0%、乙醇15.0%～40.0%、润湿剂2.0～5.0%、石墨烯10.0%～20.0%、三元嵌段共聚物分散剂10.0%～25.0%、pH调节剂0.1%～0.5%、消泡剂0.1%～0.5%、其余为去离子水；
其中，所述的三元嵌段共聚物分散剂，采用RAFT受控技术合成，其制备步骤如下：
按重量份计，依次将10.0～30.0份衣康酸、5.0～15.0份对苯乙烯磺酸钠、10.0～20.0份甲基丙烯酰氧烷基醇磷酸酯、1.0～3.0份的RAFT链转移剂、40.0～80.0份溶剂加入到反应釜中，通N2保护，开启搅拌溶解均匀后，升温至50～100℃，然后均匀滴加8.0～15.0份含10%引发剂的溶剂溶液，在0.5h内滴完，保持在50～100℃继续反应6～8h；然后缓慢加入碱溶液和去离子水，调至pH为7～8，得所述的三元嵌段共聚物分散剂；
所述的三元嵌段共聚物分散剂，具有A-B-C嵌段结构，其分子结构中含有多个锚固基团：羧酸盐阴离子、磺酸盐阴离子和磷酸酯盐阴离子，聚乙烯基苯环的嵌段梳状分布能与石墨烯形成π-π共扼键；
所述的三元嵌段共聚物分散剂，其数均分子量为3000～8000，多分散系数PDI≤1.2；
所述的甲基丙烯酰氧烷基醇磷酸酯为甲基丙烯酰氧乙基醇单磷酸酯、甲基丙烯酰氧丙基醇单磷酸酯、甲基丙烯酰氧丁基醇单磷酸酯、甲基丙烯酰氧戊基醇单磷酸酯、甲基丙烯酰氧己基醇单磷酸酯、甲基丙烯酰氧庚基醇单磷酸酯中的至少一种；
所述的RAFT链转移剂为4,4’-二硫代苯乙酸、α-二硫代苯甲酯基对苯亚甲基氯化吡啶盐、S,S’-双(α,α’-二甲基-α”-乙酸)三硫代碳酸酯、二硫代二异丙基黄原酸酯、二乙基二硫代氨基甲酸酯型季铵盐中的至少一种；
所述的引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒盐酸盐中的至少一种。
2.如权利要求1所述的一种高含量的水性石墨烯分散液，其特征在于：所述的石墨烯为Hummers法、Staudemaier法、电化学法或Brodie 法制备石墨烯中的一种。
3.如权利要求1所述的一种高含量的水性石墨烯分散液，其特征在于：所述的碱溶液为氢氧化钠、氢氧化钾、氨水中的至少一种。
4.一种如权利要求1所述高含量的水性石墨烯分散液的制备方法，其特征在于：所述的制备方法，其步骤如下：
按配方重量份比计，在分散桶中加入去离子水、乙醇、3-甲氧基丙酸甲酯、润湿剂、三元嵌段共聚物分散剂，搅拌均匀后加入石墨烯，在1000～1200r/min高速下分散30～45min，再移到纳米砂磨机循环研磨6～12h直到粒径D50＜350nm，转入调缸中在300～500r/min转速下加入pH调节剂、消泡剂，搅拌20～30min，用200目滤网过滤，包装，得所述高含量的水性石墨烯分散液。
5.如权利要求4所述的制备方法，其特征在于：所述的纳米砂磨机为陶瓷涡轮纳米砂磨机，锆珠粒径为0.3～0.4mm。
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