CN113773475A - 一种含双噻吩结构的催化剂及其在光调控下环酯开环聚合中的应用 - Google Patents
一种含双噻吩结构的催化剂及其在光调控下环酯开环聚合中的应用 Download PDFInfo
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Abstract
本发明公开了一种含双噻吩结构的催化剂及其在光调控下环酯开环聚合中的应用,所述催化剂含有双噻吩‑尿素或双噻吩‑硫脲的结构。本发明以所述催化剂作为丙交酯和戊内酯开环聚合的催化剂,可以实现光调控下的开环聚合,对比已知的光调控开环聚合催化剂,具有合成简便,对空气和水不敏感,调控聚合效果明显,在光照下聚合速率明显加快等优点。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种含双噻吩结构的催化剂及其在光调控下环酯开环聚合中的应用。
背景技术
通过光、电化学、超分子和机械力等外部刺激调节聚合为聚合物合成的智能化和功能化创造了新的机会。特别是,与其他刺激因素相比,光具有一些特殊的优势,包括成本低、普遍性和非侵入性,并且对聚合的空间和时间都有独特的控制。这使得光调控成为一类理想的控制手段。
利用不同催化/引发体系,实现环酯的开环聚合制备的生物降解聚酯,具有可循环、可降解等特性,可解决塑料应用的白色污染问题,在生物医药、组织工程等领域均具有巨大应用潜力。
光作为一种理想的外部刺激,易操作、无创、用途广泛。近年来,光催化在聚合物合成领域得到了广泛的应用。然而,光调控的开环聚合催化剂却鲜有研究和报导。2019年,中国科学技术大学的陈昶乐教授团队报道了一类含偶氮苯基团的水杨醛胺锌(II)的光控开环聚合的催化剂,提出了一种可以控制聚合过程以及所产生聚合物的组成的新手段--两种催化活性状态之间的可逆光开关。但是由于其催化剂结构含有金属,自身比较敏感且合成较难,适用性并不广泛。2016年,新南威尔士大学的徐江涛教授团队报道了一种在可逆光催化下进行可见光调节开环聚合的新方法。结合光诱导自由基聚合技术,研究了一种双波长光控正交聚合系统,用于在两种不同单体之间切换聚合。但是聚合速率在光照之后变慢了,而且整体活性都很低。因此对于光调控下的聚合速率的保持和控制也是一个问题。
发明内容
有鉴于此,本发明提供了一种含双噻吩结构的催化剂及其在光调控下环酯开环聚合中的应用。本发明催化剂易合成,适用性广,可耐受S原子,能够实现催化光调控的开环聚合以及对光调控下开环聚合速率的调控。
本发明含双噻吩结构的催化剂,其结构通式如下式(Ⅰ)、(Ⅱ)所示:
本发明催化剂的骨架为双噻吩结构;苯胺由含苯环取代基的尿素或硫脲构成。苯环取代基包括环己烷、间二三氟甲苯以及苯环。
催化剂的结构举例示意如下:
本发明含双噻吩结构的催化剂的制备方法,包括:
方法一:将双噻吩光致变色基团和取代尿素在惰性气体保护下,于有机溶剂中反应;
方法二:将双噻吩光致变色基团和取代硫脲在惰性气体保护下,于有机溶剂中反应。
进一步地,方法一中双噻吩光致变色基团和取代尿素的投料摩尔比为1:3;方法二中双噻吩光致变色基团和取代硫脲的投料摩尔比为1:3。
反应温度为常温,所示反应的时间为24h。
所述有机溶剂选自自二氯甲烷、1,2-二氯乙烷、三氯甲烷、四氢呋喃、甲基叔丁基醚、二乙醚、甲苯、苯、氯苯、丙酮、二甲基亚砜和乙腈中的一种或多种。
本发明含双噻吩结构的催化剂应用,是在光调控下催化环酯的开环聚合反应。具体包括如下步骤:
在常压、常温下,向反应器中分别加入催化剂、引发剂、有机溶剂,然后在常温下加入环酯进行开环聚合反应,反应结束后,用甲醇淬灭。各部分投料摩尔比为环酯:催化剂:引发剂=100:1:3。
所述引发剂为CH3OK或者DBU中的一种。
所述有机溶剂为甲苯、苯、四氢呋喃中的一种或几种。
所述环酯包括丙交酯、戊内酯等。
本发明的有益效果体现在:
本发明催化剂为有机催化剂,相较于普通金属催化剂比如工业上使用的辛酸亚锡催化剂,金属残留很少且没有重金属,其催化合成的聚合物更加绿色安全,实用性广。其次双噻吩结构可实现光调控开环聚合,并且可控效果比较理想。
附图说明
图1为催化剂a的1H NMR谱图。
图2为催化剂a的12C NMR谱图。
图3为催化剂b的1H NMR谱图。
图4为催化剂b的19F NMR谱图。
图5为催化剂c的1H NMR谱图。
图6为催化剂c的12C NMR谱图。
图7为催化剂d的1H NMR谱图。
图8为催化剂d的19F NMR谱图。
图9为催化剂e的1H NMR谱图。
图10为催化剂e的12C NMR谱图。
图11为催化剂f的1H NMR谱图。
图12为催化剂f的12C NMR谱图。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明提供的催化剂体系及其应用进行详细说明。本发明的保护范围不受以下实施例的限制。
由于研究光调控的开环聚合催化剂的报道很少,目前报道的体系也有包括催化剂本身比较敏感、催化速率缓慢等问题。基于此,本发明希望利用一种易合成且不敏感的双噻吩结构催化剂,来实现催化速率不减的光调控下环酯的开环聚合。
本发明提供了六种具有双噻吩结构的化合物。
实施例1:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(2,6-二异丙基-4,1-苯撑)双(3-环己基硫脲)的合成。
1、在-10℃下0.33g化合物1的50ml四氢呋喃溶液中加入11ml正丁基锂(2.5M),常温反应半小时,再加入0.69g三叔丁基硼酸反应2h;在0.62g的4-碘-2,6-双(1-甲基乙基)苯胺的四氢呋喃溶液中加入1g四(三苯基膦)钯反应15分钟后,加入上述处理过的1,再加100ml碳酸钠70℃反应1天,得到产物2。
2、在氮气保护下,化合物2和0.42g的环己基异硫氰酸酯在二氯甲烷中室温反应过夜,得到产物。产物催化剂a为浅黄色。1H NMR(400MHz,CDCl3)δ7.64(d,2H),7.22(d,4H),6.99(dt,2H),5.05-5.03(t,2H),4.21-4.14(m,2H),3.08(m,4H),2.80(m,4H),2.07(m,2H),2.02(m,6H),1.88(m,5H),1.53(m,7H),1.49(m,4H),1.28(m,24H),0.88(m,4H).13C NMR(101MHz,CDCl3)δ179,148.46,138.95,136.88,135.73,135.26,134.87,128.62,124.79,121.43,53.83,38.31,32.92,28.57,25.35,24.85,24.40,23.29,14.58。
实施例2:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(2,6-二异丙基-4,1-苯撑)双(3-(3,5-双(三氟甲基)苯基)硫脲的合成。
制备过程与实施例1类似,不同的是将实施例1中的环己基异硫氰酸酯改为用0.81g3,5-双(三氟甲基)苯基异硫氰酯。
1H NMR(400MHz,CDCl3)δ9.25(d,2H),7.88(d,4H),7.66(dt,2H),7.41(t,4H),7.11(m,4H),3.08(m,4H),2.80(m,4H),2.07(m,2H),2.02(m,6H),1.31(m,24H)。19F NMR(400MHz,CDCl3)δ62.98(s)。
实施例3:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(4,1-苯撑)双(3-环己基硫脲)的合成。
制备过程与实施例1类似,不同的是将实施例1中的4-碘-2,6-双(1-甲基乙基)苯胺改为用0.44g对碘苯胺。
1H NMR(400MHz,CDCl3)δ9.25(d,2H),7.88(d,4H),7.66(dt,2H),7.41(t,4H),7.11(m,4H),3.08(m,4H),2.80(m,4H),2.07(m,2H),2.02(m,6H),1.31(m,24H)。13C NMR(101MHz,CDCl3)δ178.76,138.45,136.89,135.10,134.69,126.69,125.16,124.42,53.93,38.54,32.63,25.45,24.78,23.04,14.52。
实施例4:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(4,1-苯撑)双(3-(3,5-双(三氟甲基)苯基)硫脲)的合成。
制备过程与实施例1类似,不同的是将实施例1中的4-碘-2,6-双(1-甲基乙基)苯胺改为用0.44g对碘苯胺;环己基异硫氰酸酯改为用0.81g3,5-双(三氟甲基)苯基异硫氰酯。
1H NMR(400MHz,CDCl3)δ8.09(d,2H),7.99(d,4H),7.69(dt,2H),7.60(t,2H),7.58(m,4H),7.30(m,4H),7.07(m,2H),2.85(m,4H),2.11(m,2H),2.09(m,6H)。19F NMR(400MHz,CDCl3)δ62.95(s)。
实施例5:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(2,6-二异丙基-4,1-苯撑)双(3-苯基脲)的合成。
制备过程与实施例1类似,不同的是将实施例1中的环己基异硫氰酸酯改为用0.357g异氰酸苯酯。
1H NMR(400MHz,CDCl3)δ8.74(d,2H),7.67(d,2H),7.44(dt,4H),7.42(t,10H),7.24(m,2H),3.17(m,4H),2.88(m,4H),2.04(m,8H),1.15(m,24H)。13CNMR(101MHz,CDCl3)δ154.21,147.30,140.25,139.12,136.54,134.40,133.39,132.45,131.72,128.67,124.27,121.33,119.67,117.77,28.04,23.21,22.53,14.05。
实施例6:1,1'-((环戊烯-1,2-二酰基双(5-甲基噻吩-4,2-二酰基))双(4,1-苯撑)双(3-苯基脲)的合成。
制备过程与实施例1类似,不同的是将实施例1中的4-碘-2,6-双(1-甲基乙基)苯胺改为用0.44g对碘苯胺;环己基异硫氰酸酯改为用0.357g异氰酸苯酯。
1H NMR(400MHz,CDCl3)δ8.78(d,2H),8.69(d,2H),7.46(dt,12H),7.26(t,4H),7.18(m,2H),6.99(m,2H),2.83(m,4H),2.04(m,2H),1.92(m,6H)。13C NMR(101MHz,CDCl3)δ152.37,139.60,136.55,134.11,132.42,128.76,127.44,125.37,122.95,121.86,118.48,118.23,22.21,13.99。
实施例7:使用催化剂a催化和引发丙交酯开环聚合
在氮气保护下,将266毫克左旋丙交酯溶解于2毫升无水二氯甲烷中,迅速加入到实施例1中制备的混合物催化剂溶液中,在35摄氏度下反应10秒后,加入10毫克苯甲酸淬灭反应,取出少量溶液真空除去溶剂后采用核磁共振氢谱分析测得左旋丙交酯单体的转化率,并用凝胶渗透色谱测得所得聚乳酸的分子量和分子量多分散指数,剩余聚乳酸产物通过在甲醇中沉淀后真空干燥的方法获得。
实施例8:使用催化剂b催化和引发丙交酯开环聚合。
聚合方法和实施例7类似。
实施例9:使用催化剂c催化和引发丙交酯开环聚合
聚合方法和实施例7类似。
实施例10:使用催化剂d催化和引发丙交酯开环聚合
聚合方法和实施例7类似。
实施例11:使用催化剂e催化和引发丙交酯开环聚合
聚合方法和实施例7类似。
实施例12:使用催化剂f催化和引发丙交酯开环聚合
聚合方法和实施例7类似。
实施例13:催化剂b催化和引发戊内酯开环聚合
聚合方法和实施例7类似。
聚合数据表示,六组催化剂,催化剂a的聚合效果最好。催化剂a、b、c、f均可以在引发剂引发下实现光照后丙交酯聚合速率变快。因为光照之后,体系更偏向缺电子体系,催化剂对丙交酯的酸活化机制提升,催化剂一边是酸一边是碱,双功能催化剂使得聚合速率变快。对于戊内酯,由于其位阻小,酸活化提高不明显,键活化变弱,因此聚合速率略有提高。
Claims (8)
3.一种权利要求1所述的含双噻吩结构的催化剂的应用,其特征在于:在光调控下催化环酯的开环聚合反应。
4.根据权利要求3所述的应用,其特征在于:
在常压、常温下,向反应器中分别加入催化剂、引发剂、有机溶剂,然后在常温下加入环酯进行开环聚合反应,反应结束后,用甲醇淬灭。
5.根据权利要求4所述的应用,其特征在于:
所述引发剂为CH3OK或DBU。
6.根据权利要求4所述的应用,其特征在于:
所述有机溶剂为甲苯、苯、四氢呋喃中的一种或几种。
7.根据权利要求4所述的应用,其特征在于:
所述环酯包括丙交酯、戊内酯。
8.根据权利要求4、5或7所述的应用,其特征在于:
环酯、催化剂和引发剂的投料摩尔比为100:1:3。
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