CN109627365B - 金属钴络合物催化丙烯酰胺分散聚合制备纳米微球的方法 - Google Patents
金属钴络合物催化丙烯酰胺分散聚合制备纳米微球的方法 Download PDFInfo
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Abstract
本发明公开了一种多齿脂肪族胺基双酚类金属钴络合物催化丙烯酰胺(AM)进行分散聚合制备聚丙烯酰胺(PAM)纳米微球的方法,制备方法包括如下步骤:采用分散聚合方法,将AM、引发剂偶氮二异丁腈(AIBN)和金属钴络合物溶解在乙醇‑水中,在分散剂PVP的作用下,形成均一稳定的PAM分散体系。经测定,粒径最小为200nm。较现有的PAM的分散体系制备方法,本发明的有益效果在于:没有使用乳化剂;在聚合配方中只用到单体、引发剂、催化剂和分散剂,聚合工艺简单易于操作,反应条件温和;使用金属钴络合物作为单一催化剂,不仅可以使AM在短时间内聚合,而且此类催化剂用量少,效率高,作用广泛,具有巨大的经济效益。
Description
技术领域
本发明涉及一种丙烯酰胺均聚物的制备方法,特别是该聚合在四种金属钴络合物(见附图)的作用下催化丙烯酰胺在在乙醇-水体系中进行分散聚合制备聚丙烯酰胺纳米微球的方法。
背景技术
该金属钴络合物是由胺双酚类配体配体的N原子和氧原子上的孤对电子与Co2+配位形成的金属钴配合物。金属钴络合物在材料化学、药物化学、电化学、光物理与光化学、分析化学、有机化学、仿生化学等领域都具有十分广阔的应用前景。该配合物能够很好的催化丙交酯和丙烯酸酯及丙烯酰胺类单体进行可控聚合。其活性中心单一,反应条件温和,转化率和选择性均较高,可有效的控制分子量以及分子量分布。
聚丙烯酰胺是丙烯酰胺均聚物以及和其他单体的各种共聚物的统称,由于其分子主链的侧基上含有大量酰胺基团,具有很高的极性和良好的反应活性,被广泛应用于油田、水处理、造纸、矿冶、纺织、建材、农业和医学上,被称为“百业助剂”,“万能产品”。聚丙烯酰胺是水溶性高分子化合物中应用最为广泛的品种之一。其微球由于亲水性强、非特异吸附、易于表面功能化且生物相容性好,广泛应用于许多领域。制备功能性聚丙烯酰胺微球,最初常用乳液聚合法与悬浮聚合法进行配置,但其聚合方法理论虽然比较成熟,但会用到多种表面活性剂以及大量乳化剂,一定程度上降低了体系的稳定性能,而且所获得到的微球单分散性比较差。而目前所使用的分散聚合和无皂乳液聚合渐渐替代了传统方法,能够大幅度提升体系的稳定性且操作十分简便,产物一般为固体微粒,聚合方法不同,产物的粒径也不同。现阶段,聚丙烯酰胺微球能够依据相关需求,引入功能性基团,同时还具有pH值响应性、磁性、温敏性等多种性能,能广泛应用于多个领域。近几年以来,相关研究人员把无机纳米微粒和聚丙烯酰胺有效复合而成有机、无机复合微球,从而扩大了功能性聚丙烯酰胺类微球在磁学、热学、光学和电学等各个领域的应用。Jianing Zhang等人将脂肪族胺基双酚类金属钴络合物应用于环内酯的开环不死聚合,丙烯酸酯活性自由基聚合(PDI=1.03-1.73)及其共聚的反应中(Applied Organometallic Chemistry,2018,32(2).)。LiyingWang等人研究了卟啉钴在丙烯酰胺分散聚合中的应用,在不加引发剂的条件下,得到了分子量分布较窄的聚合(PDI=1.09-1.35)但该络合物在该反应中的活性很低,不能达到较高的转化率(19.35%-45.6%)(Rsc Advances,2016,6(68).)。付雪峰等将(Salen)Co(II)运用到活性自由基聚合当中,得到了分子量分布较窄的聚合物(Macromolecules 2015,48,5132-5139.)。
综上所述,如今将钴金属络合物制备功能性聚丙烯酰胺类微球的方法越来越丰富,其不同的性能渐渐广泛用于医药、工业等多个领域,但其作用机理与评价手段仍需进一步完善。
发明内容
本发明的目的在于:在以乙醇-水作为分散介质,以金属钴络合物为催化剂,在加热的条件下,使丙烯酰胺单体进行分散聚合制得聚丙烯酰胺纳米微球。目前,关于聚丙烯酰胺微球的制备在国内外多采用微乳液聚合方法和悬浮乳液聚合的方法。本分散聚合过程不需要添加任何乳化剂,用金属钴络合物作为催化剂,以偶氮二异丁腈(AIBN)为引发剂,催化丙烯酰胺单体进行分散聚合,聚合工艺简单易于操作,成本低。反应条件温和,聚合时间较短。且合成的纳米级聚丙烯酰胺微球在分散介质中能稳定存在。得到聚合物微球的粒径分布窄,即得到粒径均匀的聚合物微球。该方法在生产中既安全又经济合理,逐渐成为聚丙烯酰胺的主要生产技术。
本发明包括以下步骤:在装有磁力搅拌器、连接氮气保护装置的Schlenk瓶中将一定摩尔比的丙烯酰胺单体、金属钴络合物、AIBN,用适当比例的乙醇-水使其完全溶解,并保证分散体系中的单体浓度。连接好装置,将其放入恒温油浴中,开始通入氮气,30分钟后,待油浴锅温度升至65℃,并在氮气的氛围中持续反应60-595min,聚合反应完成后即可得到均一稳定流动性好的聚丙烯酰胺分散体系。
上述金属钴络合物催化丙烯酰胺进行分散聚合制备纳米聚丙烯酰胺微球的方法,单体的质量分数为10%,单体的投料摩尔比单体/金属钴络合物为(1000~5000)/1。
上述金属钴络合物催化丙烯酰胺进行分散聚合制备纳米聚丙烯酰胺微球的方法,分散稳定剂占单体的质量百分数为20%。
上述金属钴络合物催化丙烯酰胺进行分散聚合制备聚丙烯酰胺纳米微球的方法,所述反应体系温度应控制在65℃,聚合时间60-595min。
上述金属钴络合物催化丙烯酰胺进行分散聚合制备聚丙烯酰胺纳米微球的方法,相较于现有的聚丙烯酰胺微球两性聚丙烯酰胺的制备方法,本发明的有益效果在于:得到的聚丙烯酰胺相对分子质量较高,最高可达到6.6×105,得到的最小的聚丙烯酰胺微球的粒径为200nm,在整个分散聚合过程中,没有使用乳化剂,操作过程简单,且不污染环境,系环境友好生产方法;使用单一催化剂,在整个聚合过程中,不仅操作简单,而且反应温和,催化剂用量少,效率高,所得分散聚合产物应用简单,储存和运输方便,具有巨大的经济效益。
附图说明
附图为四种钴络合物结构式。
具体实施方式
实施例1
本实施例中采用分散聚合法,在装有磁力搅拌器、连接氮气保护装置的Schlenk瓶中加入丙烯酰胺单体3.1949g,I催化剂0.0200g,AIBN 0.0222g,PVP 0.6390g,单体/催化剂/AIBN的摩尔比为1000/1/3;PVP占单体的质量分数为20%。用乙醇/水=7/3使其完全溶解,使单体质量分数为10wt%,连接好装置,将其放入恒温油浴中,开启搅拌,开始通入氮气,30分钟后,打开恒温油浴锅温度,待温度升高至65℃,并在氮气的氛围中持续搅拌,280min反应完毕即得到聚丙烯酰胺胺的均匀分散体系,转化率达93.93%。经过测试可得到聚合物相对分子质量为6.6×105,微球的平均粒径为500nm,PDI=1.303。
实施例2
除调节反应时间为60min外,其它条件均与实施例1相同,转化率达24.81%。经过测试可得到聚合物相对分子质量为4.1×104,PDI=1.478。
实施例3
除调节反应时间为90min外,其它条件均与实施例1相同,转化率达34.21%。经过测试可得到聚合物相对分子质量为4.2×104,PDI=1.468。
实施例4
除调节反应时间为120min外,其它条件均与实施例1相同,转化率达61.39%。经过测试可得到聚合物相对分子质量为4.0×104,PDI=1.539。
实施例5
除调节反应时间为140min外,其它条件均与实施例1相同,转化率达77.78%。经过测试可得到聚合物相对分子质量为4.4×104,PDI=1.399。
实施例6
除调节反应时间为160min外,其它条件均与实施例1相同,转化率达80.54%。经过测试可得到聚合物相对分子质量为4.5×104,PDI=1.388。
实施例7
除调节反应时间为200min外,其它条件均与实施例1相同,转化率达88.93%。经过测试可得到聚合物相对分子质量为5.3×104,PDI=1.263。
实施例8
除调节反应时间为240min外,其它条件均与实施例1相同,转化率达90.98%。经过测试可得到聚合物相对分子质量为5.8×104,PDI=1.259。
实施例9
在装有磁力搅拌器、连接氮气保护装置的Schlenk瓶中加入丙烯酰胺单体2.6990g,II催化剂0.0200g,AIBN 0.0187g,PVP 0.5398g,单体/催化剂/AIBN的摩尔比为1000/1/3,PVP占单体的质量分数为20%。用乙醇/水=7/3使其完全溶解,使单体质量分数为10wt%,连接好装置,将其放入恒温油浴中,开启搅拌,开始通入氮气,30分钟后,打开恒温油浴锅温度,待温度升高至65℃,并在氮气的氛围中持续拌,280min反应完毕即得到聚丙烯酰胺胺的均匀分散体系,转化率达91.83%。
实施例10
在装有磁力搅拌器、连接氮气保护装置的Schlenk瓶中加入丙烯酰胺单体2.5623g,III催化剂0.0200g,AIBN 0.0178g,PVP 0.5125g,单体与催化剂的摩尔比为1000/1/3;PVP占单体的质量分数为20%。用乙醇/水=7/3使其完全溶解,使单体质量分数为10wt%,连接好装置,将其放入恒温油浴中,开启搅拌,开始通入氮气,30分钟后,打开恒温油浴锅温度,待温度升高至65℃,并在氮气的氛围中持续搅拌,250min反应完毕即得到聚丙烯酰胺胺的均匀分散体系,转化率达86.54%。
实施例11
在装有磁力搅拌器、连接氮气保护装置的Schlenk瓶中加入丙烯酰胺单体2.5327g,IV催化剂0.0200g,AIBN 0.0176g,PVP 0.5125g,单体与催化剂的摩尔比为1000/1/3;PVP占单体的质量分数为20%。用乙醇/水=7/3使其完全溶解,使单体质量分数为10wt%,连接好装置,将其放入恒温油浴中,开启搅拌,开始通入氮气,30分钟后,打开恒温油浴锅温度,待温度升高至65℃,并在氮气的氛围中持续搅拌,250min反应完毕即得到聚丙烯酰胺胺的均匀分散体系,转化率达88.62%。
实施例12
除调节反应体系单体与催化剂和引发剂的摩尔比为2000/1/3,反应时间为310min外,即催化剂0.0100g,单体为3.1949g,AIBN 0.0111g。其它条件均与实施例1相同,微球粒径为590nm,转化率达89.86%。
实施例13
除调节反应体系单体与催化剂和引发剂的摩尔比为3000/1/3,反应时间为370min外,即催化剂0.0100g,单体为4.7923g,PVP为0.9585g。其它条件均与实施例1相同,微球的平均粒径为500nm,转化率达88.76%。
实施例14
除调节反应体系单体与催化剂和引发剂的摩尔比为5000/1/3,反应时间为595min外,即催化剂0.0050g,单体为3.9936g,PVP为0.7981g。其它条件均与实施例1相同,结果得到微球的平均粒径为510nm,转化率达84%。
实施例15
除调节反应体系乙醇/水=9/1,反应140min外,其它条件均与实施例1相同,结果得到微球粒径为200nm,转化率达84.59%。
实施例16
除调节反应体系乙醇/水=8/2,反应210min外,其它条件均与实施例1相同,结果得到微球粒径为300nm,转化率达85.38%。
实施例17
除调节反应体系乙醇/水=6/4,反应330min外,其它条件均与实施例1相同,结果得到微球粒径为550nm,转化率达88.45%。
实施例18
除调节反应体系单体与催化剂和引发剂的摩尔比为1000/1/1.5,反应时间为330min外,即催化剂0.0200g,AIBN0.0111g,其它条件均与实施例1相同,转化率达93.8%。
实施例19
除调节分散剂PVP占单体质量分数的30%,单体/催化剂/AIBN的摩尔比为2000/1/3,反应时间为433min外,其它条件均与实施例1相同,结果得到微球粒径为600nm,转化率达89.35%。
实施例20
除调节催化剂质量为0g,反应时间为82min外,其它条件均与实施例1相同,结果得到聚合物的相对分子质量为6.2×105,转化率达88.47%。
Claims (5)
2.根据权利要求1所述的一种多齿脂肪族胺基双酚类金属钴络合物以催化丙烯酰胺进行活性自由基分散聚合制备聚丙烯酰胺纳米微球的方法,其特征在于:单体质量分数为10%,PVP占单体的质量分数为20%,催化剂和引发剂摩尔比为1∶3。
3.根据权利要求1所述的一种多齿脂肪族胺基双酚类金属钴络合物以催化丙烯酰胺进行活性自由基分散聚合制备聚丙烯酰胺纳米微球的方法,其特征在于:单体与催化剂的摩尔比为(1000-5000)/1。
4.根据权利要求1所述的一种多齿脂肪族胺基双酚类金属钴络合物以催化丙烯酰胺进行活性自由基分散聚合制备聚丙烯酰胺纳米微球的方法,其特征在于:分散介质乙醇-水的比例为6/4,7/3,8/2或9/1。
5.根据权利要求4所述的一种多齿脂肪族胺基双酚类金属钴络合物以催化丙烯酰胺进行活性自由基分散聚合制备聚丙烯酰胺纳米微球的方法,其特征在于:分散介质乙醇-水的比例为7/3。
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