CN114805798B - 一种用于可见光诱导可控自由基聚合反应的多相催化剂 - Google Patents
一种用于可见光诱导可控自由基聚合反应的多相催化剂 Download PDFInfo
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Abstract
本发明公开了一种多相催化剂及其在水相中可见光诱导异相可控自由基聚合反应方面的应用,所述多相催化剂是以1,3,5‑三(溴甲基)苯和三乙烯二胺为原料,在乙腈和乙醚环境下合成中间体TD‑Br,再将中间体TD‑Br与碘离子交换制得。本发明中的催化剂易于合成,可大量制备,并能在水相中可见光照射下催化聚乙二醇甲基丙烯酸酯(PEGMA)等水溶性单体的聚合,且其可循环利用,具有良好的应用前景,能够满足可持续化学的要求。
Description
技术领域
本发明属于高分子材料制备领域,具体涉及一种用于水相中可见光诱导异相可控自由基聚合反应的多相催化剂及其应用。
背景技术
可控自由基聚合(CRP)可用于合成分子量精确、分子量分布窄的聚合物。通过可控自由基聚合合成的聚合物已广泛应用于生物医学、化妆品、纳米技术、临床医学等领域。近几十年来,可控自由基聚合发展了许多方法,如原子转移自由基聚合(ATRP)、氮氧化物介导的自由基聚合(NMP)、反式碘转移聚合(RITP)、可逆加成断裂链转移自由基聚合(RAFT)和可逆络合介导的自由基聚合(RCMP)。其中,RCMP可利用多种休眠物种和催化剂,使其能够合成具有复杂结构、链端功能化的均聚物和嵌段共聚物。同时,RCMP可以使用廉价的非金属催化剂并合成多种结构的聚合物,此外,它对官能团耐受性好、条件温和、节能环保、副反应少而备受关注,如以烷基碘化物为初始休眠物种,以胺、碘负离子和羰基溶剂为催化剂的RCMP引起了人们的关注。
光诱导的RCMP适用于各种疏水性和亲水性的官能团甲基丙烯酸酯,以及丙烯酸酯、苯乙烯和丙烯腈。因此,光诱导可逆络合介导的聚合反应受到了研究者们的广泛关注。2013年,发现了一种新型的光诱导的RCMP,它具有操作简单、节能、空间和时间可控、多分散性指数低、对官能团耐受力好、条件温和、副反应少等优点,其具体是利用可见光(350-600nm)和合适的催化剂(TBA、TDEAP、PMDETA)成功地聚合了甲基丙烯酸甲酯,并发现在无光条件下不发生聚合,这意味着该体系是一个理想的光控开关系统,聚合反应易于控制,通过调节辐照波长,使得聚合反应速率可调。2015年,Atsushi Goto通过扩展有机催化剂的类型,进一步将可见光的宽波长范围从600 nm扩大到750 nm。
然而,光催化剂的残留和毒性是光引发聚合体系进一步应用的障碍。可控自由基聚合正朝着环保、绿色、无毒、无金属的方向发展。因此,非均相的RCMP催化剂亟待开发。多相催化剂容易从与之相关的反应物中分离出来,比均相催化剂应用的范围更广,且易于回收利用,绿色环保。
发明内容
本发明的目的在于提供一种用于水相中可见光诱导异相可控自由基聚合反应的多相催化剂及其应用。
为实现上述目的,本发明采用如下技术方案:
所述多相催化剂的制备流程如下:
其具体步骤为:
1)称取1.313 g(3.68 mmol)的1,3,5-三(溴甲基)苯(TBMB)和0.43 g(3.86 mmol)的三乙烯二胺(DABCO),放入一个洁净干燥的250 mL的圆底烧瓶中,加入100 mL乙腈,在氮气保护环境下常温搅拌反应47 h,再加入25 mL乙醚,在氮气保护下遮光、常温搅拌反应1.5h,反应完毕后抽滤、真空干燥,得到白色粉末状中间产物TD-Br;
2)将1.5g步骤1)制备的TD-Br放入圆底烧瓶中,加入15 mL碘化钾饱和甲醇水溶液(其中甲醇与水的体积比为1:1)搅拌混合,并常温搅拌反应24 h,反应完毕后抽滤、真空干燥,得到淡黄色粉末;
3)将得到的淡黄色粉末按步骤2)重复三次,得到所述多相催化剂TD-I。
所述多相催化剂可用于水相中可见光诱导异相可控自由基聚合反应,其具体是在室温下,将所述多相催化剂与聚合单体、引发剂、水按一定比例加入到Schlenk管中,然后在惰性气体条件下用白色LED灯照射,以实现可逆络合介导聚合(RCMP)反应。
优选地,将10 mg多相催化剂与3.4 mmol聚合单体、0.11 mmol引发剂、1.5 mL水混合进行反应。
优选地,所述聚合单体为聚乙二醇甲基丙烯酸酯、甲基丙烯酸二乙氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸羟丙酯中的一种或多种。
优选地,所述引发剂为2-碘-2-甲基丙腈、α-碘代苯乙酸乙酯、3-碘苯乙腈、2-碘-2-甲基丙二酸二乙酯中的任意一种。
优选地,所述惰性气体为氮气或者氩气。
优选地,所用白色LED灯的功率为13 W·cm-1、辐照度为15 mW·cm-2。
相对于现有技术,本发明具有如下的优点及有益效果:
(1)本发明所提供的催化剂制备简易,可大量生产,经实验测得,该催化剂的循环利用率较高且易于回收,具有良好的应用前景,符合可持续发展理念。
(2)本发明所提供的一种水相中可见光诱导的异相催化可控自由基聚合反应,扩链实验表明,由该催化剂催化合成的聚合物具有较高的链端保真度。
(3)本发明所提供的一种水相中可见光诱导的异相催化可控自由基聚合反应,可以合成各种分子量可控、分子量分布窄的聚合物,经实验测得,该光催化体系是理想的光控“开关”体系,十分利于控制聚合反应的进行。
(4)本发明所提供的一种水相中可见光诱导的异相催化可控自由基聚合反应,运用了近年受到广泛关注的光诱导可逆络合介导的自由基聚合(RCMP)机理,应用前景广阔。
(5)本发明所提供的一种水相中可见光诱导的异相催化可控自由基聚合反应,利用光催化,无需加热,与传统热催化的合成方法相比更加节能环保。
附图说明
图1为实施例1所制备TD-I的核磁共振碳谱图。
图2为实施例1所制备TD-I的XRD谱图。
图3为实施例1所制备TD-Br和TD-I的XPS谱图。
图4为实施例2-4在白色LED灯照射下不同聚合度(DP)的聚合体系中M n和M w/M n与转化率的变化关系图(a)及ln([M]0/[M])与聚合时间的变化关系图(b)。
图5为实施例2及5-6在白色LED灯下不同催化剂用量(5 mg,10 mg,15 mg)的聚合体系中M n和M w/M n与转化率的变化关系图(a)及ln([M]0/[M])与聚合时间的变化关系图(b)。
图6为实施例7中催化剂循环使用次数与转化率、M w/M n的关系图。
图7为实施例8开/关实验的聚合动力学图。
图8为实施例10中聚甲基丙烯酸羟丙酯的GPC流出曲线图。
图9为实施例11中大分子引发剂的扩链GPC流出曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清晰明了,以下结合说明附图及实施例,对本发明进行详细说明。此处所描述的具体实施例仅用于解释本发明,并不用以限定本发明。
实施例1:
(1)称取1.313 g(3.68 mmol)的1,3,5-三(溴甲基)苯(TBMB)和0.43 g(3.86mmol)的三乙烯二胺(DABCO),放入一个洁净干燥的250 mL的圆底烧瓶中,加入100 mL乙腈,在氮气保护环境下常温搅拌反应47 h。再加入25 mL乙醚,在氮气保护下遮光、常温搅拌反应1.5 h,反应完毕后抽滤、真空干燥,得到白色粉末状中间产物TD-Br;
(2)取水和甲醇各10 mL,加入碘化钾固体配制成碘化钾饱和甲醇水溶液;将1.5g步骤(1)制备的TD-Br放入圆底烧瓶中,倒入15 mL上述配好的碘化钾饱和甲醇水溶液搅拌混合,并常温搅拌反应24 h,反应完毕后抽滤、真空干燥,得到淡黄色粉末;
(3)将上述得到的淡黄色粉末重复步骤(2)三次(共4次),得到可用于水相光诱导异相可控自由基聚合反应的多相催化剂TD-I。
图1为所制备TD-I的核磁共振碳谱图。由图中可以看出TD-I的成功合成。
图2为所制备TD-I的XRD谱图。由图中可以看出该催化剂为无定形结构。
图3为所制备的TD-Br和TD-I的XPS谱图。由图中可以看出TD-Br全部转化为了TD-I。
实施例2:
取实施例1所得TD-I(10 mg)、PEGMA(1.5 mL,3.4 mmol)、CP-I(13 μL,0.11mmol)、1.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
实施例3:
取实施例1所得TD-I(10 mg)、PEGMA(2.5 mL,5.5 mmol)、CP-I(13 μL,0.11mmol)、2.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
实施例4:
取实施例1所得TD-I(10 mg)、PEGMA(5 mL,11 mmol)、CP-I(13 μL,0.11 mmol)、5mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
图4为实施例2-4在白色LED灯照射下不同聚合度(DP)的聚合体系中M n和M w/M n与转化率的变化关系图(a)及ln([M]0/[M])与聚合时间的变化关系图(b)。由图中(a)可见,分子量随转化率的增加而线性增大,证明聚合物链端的高保真性,由图中(b)可见,其聚合动力学曲线呈一阶线性线,证明其为可控聚合。
实施例5:
取实施例1所得TD-I(5 mg)、PEGMA(1.5 mL,3.4 mmol)、CP-I(13 μL,0.11 mmol)、1.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
实施例6:
取实施例1所得TD-I(15 mg)、PEGMA(1.5 mL,3.4 mmol)、CP-I(13 μL,0.11mmol),1.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
图5为实施例2及5-6在白色LED灯下不同催化剂用量(5 mg,10 mg,15 mg)的聚合体系中M n和M w/M n与转化率的变化关系图(a)及ln([M]0/[M])与聚合时间的变化关系图(b)。由图中(a)可见,分子量随转化率的增加而线性增大,证明聚合物链端的高保真性,由图中(b)可见,其聚合动力学曲线呈一阶线性线,证明其为可控聚合。
实施例7:
取实施例1所得TD-I(10 mg)、PEGMA(1.5 mL,3.4 mmol)、CP-I(13 μL,0.11mmol),1.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射8 h后,用大量水和THF清洗Schlenk管,离心得到的催化剂,用THF溶剂进行过夜索氏提取洗涤,所得的催化剂真空干燥后用于循环实验。
图6为催化剂循环使用次数与转化率、M w/M n的关系图。由图6可见,经过三次循环,所用催化剂仍具有较高的转化率,证明其具有较强的可回收利用性。
实施例8:
取实施例1所得TD-I(10 mg)、PEGMA(1.5 mL,3.4 mmol),CP-I(13 μL,0.11mmol),1.5 mL的H2O,加入25 mL的Schlenk管中,在氮气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射2 h,关灯2 h,照射2 h,关灯2 h,照射2 h,关灯2 h,照射2 h,每两个小时取一次微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。
图7为开/关实验的聚合动力学曲线图。由图中可见,在黑暗中聚合几乎不进行,说明聚合受光的严格控制,具有良好的时空可控性。
实施例9:
取实施例1所得TD-I(10 mg)、CP-I(13 uL,0.11 mmol),DMAEMA(385 μL,2.2mmol)和385 μL的H2O,加入25 mL的Schlenk管中,在氩气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定分子量和分散度等参数;并测核磁计算其单体转化率。
实施例10:
取实施例1所得TD-I(10 mg)、CP-I(13 uL,0.11 mmol),HPMA(310 μL,2.2 mmol)和310 μL的H2O,加入25 mL的Schlenk管中,在氩气保护下用白色LED灯带(13 W·m-1,15mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤头除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定分子量和分散度等参数;并测核磁计算其单体转化率。
图8为聚甲基丙烯酸羟丙酯的GPC流出曲线图。由图中可见,流出曲线分布较为均匀,同时分布较窄,证明该催化体系还适用于除PEGMA以外的单体的可控自由基聚合。
实施例11:
取实施例1所得TD-I(10 mg),PEGMA(1.5 mL,3.4 mmol),CP-I(13 μL,0.11mmol),1.5 mL的H2O,加入25 mL的Schlenk管中,在氩气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射8 h后取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂后,再用凝胶渗透色谱仪(GPC)测定转化率、分子量和分散度等参数。因该聚合条件下,聚合转化率高于90%,大分子引发剂不需进行纯化后再使用。
取上述反应混合液1 mL,加入3.36 mmol的HPMA(0.455 mL)、水(0.455 mL)或PEGMA(1.58 mL)、水(1.58 mL),在氩气保护下用白色LED灯带(13 W·m-1,15 mW·cm-2)照射,在预定的时间取微量混合物,用四氢呋喃稀释并用无水氯化钙除水后,经过滤除去催化剂和除水剂,再用凝胶渗透色谱仪(GPC)测定分子量和分散度等参数;并测核磁计算其单体转化率。
图9为实施例11中大分子引发剂的扩链GPC流出曲线图。由图中可见,流出曲线明显左移,说明聚合物链的增长,链端无拖尾现象说明聚合物链端活性高。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
2.根据权利要求1所述的多相催化剂,其特征在于,所述饱和碘化钾甲醇水溶液中甲醇与水的体积比为1:1。
3.一种如权利要求1所述多相催化剂在水相中可见光诱导异相可控自由基聚合反应方面的应用,其特征在于,在室温下,将所述多相催化剂与聚合单体、引发剂、水按一定比例混合,然后在惰性气体条件下用白色LED灯照射,以实现可逆络合介导聚合反应。
4.根据权利要求3所述的应用,其特征在于,所述聚合单体为聚乙二醇甲基丙烯酸酯、甲基丙烯酸二乙氨基乙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸羟丙酯中的一种或多种。
5.根据权利要求3所述的应用,其特征在于,所述引发剂为2-碘-2-甲基丙腈、α-碘代苯乙酸乙酯、3-碘苯乙腈、2-碘-2-甲基丙二酸二乙酯中的任意一种。
6.根据权利要求3所述的应用,其特征在于,所述惰性气体为氮气或者氩气。
7. 根据权利要求3所述的应用,其特征在于,所用白色LED灯的功率13 W·cm-1、辐照度为15 mW·cm-2。
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