CN112279984A - 聚合诱导自组装制备催化纳米微球的方法 - Google Patents
聚合诱导自组装制备催化纳米微球的方法 Download PDFInfo
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Abstract
本发明公开了一种聚合诱导自组装制备催化纳米微球的方法,包括如下步骤:1)、亲水性的RAFT聚合大分子链转移试剂的制备:利用RAFT聚合链转移试剂、亲水性大分子聚合物、二环己基碳二亚胺和4‑二甲氨基吡制备而得;2)、小分子单体的制备:利用2‑(甲基‑4‑吡啶基)‑乙醇、三乙胺、丙烯酰氯制备而得;3)、催化纳米微球的制备:利用亲水性大分子的链转移试剂、2,2‑偶氮二(2‑甲基丙基咪)二盐酸盐、小分子单体、疏水性单体等制备而得。本发明利用该催化纳米微球作为催化纳米反应器,能实现水相高效有机催化反应。
Description
技术领域
本发明属于有机高分子材料领域,具体涉及一种聚合诱导自组装制备催化纳米微球的方法。
背景技术
提高催化剂的催化活性和催化选择性一直是化学界关注的一个重要方面。在自然界中,化学反应的进行通常是在几个纳米的酶空间中完成的。受到大自然的启发,化学家们设计构建各种类型的纳米反应器,利用纳米反应器的小尺寸效应、表面效应、约束效应和协同效应等,实现在化学催化反应中高效、高选择性的目的。同时纳米反应器的制备对改善单体催化剂的环境毒性以及在其回收利用方面具有重要意义。
嵌段共聚物的自组装行为是高分子领域的研究热点,通过嵌段共聚物自组装制备纳米微球一般在10~1000nm之间;可极大地增大材料的物理、化学、生物等性能,在催化等领域应用价值巨大。但传统的自组装方法制备的纳米微球具有步骤繁琐、形貌单一、重复性差、产量低和固含量低等缺点,这在一定的程度上阻碍了工业上的大规模生产。
聚合诱导自组装的方法简便,可合成球形、囊泡、柱状等多种结构的聚合物纳米材料,且可实现高固含量生产。通过聚合诱导自组装法制备催化纳米微球具有众多优点:制备方法简单,通过亲水性大分子链转移试剂、疏水单体、催化功能性单体一步构建催化纳米微球,从而制得催化纳米反应器;可直接用水作溶剂,制备得到水相纳米微球,并应用于水相催化反应,符合绿色化学要求;通过控制单体的浓度及亲疏水链段的长度比例,而构建不同形貌的纳米微球;利用该方法含固量高的特点,可以在工业生产中规模应用。
目前现有的聚合诱导自组装法制备催化纳米微球的技术多用于研究纳米粒子的形貌特征或是制备蛋白质纳米粒子。
发明内容
本发明要解决的技术问题是提供一种通过聚合诱导自组装法制备催化纳米微球的方法。为了解决上述技术问题,本发明提供一种聚合诱导自组装制备催化纳米微球的方法,包括如下步骤:
1)、亲水性的RAFT聚合大分子链转移试剂的制备:
将RAFT聚合链转移试剂、亲水性大分子聚合物(分子量为1000~5000)溶解到无水四氢呋喃(THF)中,在冰浴条件下,滴加二环己基碳二亚胺(DCC)和4-二甲氨基吡(DMAP)的无水四氢呋喃溶液,于室温酯化反应4~48h;
RAFT聚合链转移试剂、亲水性大分子聚合物、二环己基碳二亚胺(DCC)、4-二甲氨基吡(DMAP)的摩尔比为1:0.5~3.5:1~1.5:0.1~0.2;
反应产物用乙醚(冷乙醚)沉淀,得粗产品;
粗产品纯化(利用柱色谱纯化),真空干燥,得到亲水性RAFT聚合大分子链转移试剂;
2)、小分子单体(含DMAP类似物的小分子单体)的制备:
在氮气保护和冰浴条件下,向2-(甲基-4-吡啶基)-乙醇滴加丙烯酰氯和三乙胺的二氯甲烷溶液,然后继续在氮气保护和室温下反应2~12h;
2-(甲基-4-吡啶基)-乙醇、三乙胺、丙烯酰氯的摩尔比为1:1.5~3:1.1~4;
将所得的反应液倒入氢氧化钠溶液(氢氧化钠的质量浓度约为25%)中,分别得有机相和水相,水相用氯仿萃取,将萃取层与有机相合并后浓缩、再纯化(利用柱色谱纯化),得到小分子单体(含DMAP类似物的小分子单体);
3)、催化纳米微球的制备
步骤1)所得亲水性大分子的链转移试剂,2,2-偶氮二(2-甲基丙基咪)二盐酸盐(AIBA),步骤2)所述小分子单体、疏水性单体的混合物称为单体,在单体中加入极性溶剂后除氧(通氮气除氧15min),在密封条件下于50~100℃反应2~24h;得催化纳米微球(含DMAP类似物的纳米微球,乳液状);
亲水性大分子的链转移试剂:小分子单体:疏水性单体=1:20~100:50~200的摩尔比(优选1:25~26:70~80);2,2-偶氮二(2-甲基丙基咪)二盐酸盐(AIBA):亲水性大分子的链转移试剂=1:3~5的摩尔比。
作为本发明的聚合诱导自组装法制备催化纳米微球的方法的改进,步骤1)中:
RAFT聚合链转移试剂为4-氰基-4-((((乙硫基)羰基硫酰)硫基)戊酸(CEPA);
亲水性大分子聚合物为聚乙二醇甲基丙烯酸甲酯、聚丙烯酸、聚乙二醇单甲醚、聚丙烯酰胺、聚乙二醇月桂酸酯(n≈55)。
作为本发明的聚合诱导自组装法制备催化纳米微球的方法的进一步改进,步骤3)中:疏水性单体为4-羟基丁基丙烯酸酯、2-羟基丁基丙烯酸酯、丙烯酸四氢呋喃酯中的至少一种。
作为本发明的聚合诱导自组装法制备催化纳米微球的方法的进一步改进,步骤3)中:极性溶剂为水、乙醇、甲酰胺、三氟乙酸中的至少一种(即,为其中的一种,或几种溶剂按一定比例的混合溶剂)。
作为本发明的聚合诱导自组装法制备催化纳米微球的方法的进一步改进,步骤3)中:所述单体:极性溶剂=25%~50%的质量比。
作为本发明的聚合诱导自组装法制备催化纳米微球的方法的进一步改进,步骤3)中:反应时间到达后冷却到室温,并敞口暴露到空气中淬灭反应。
在本发明中:
步骤1),亲水性的大分子聚合物与CEPA通过缩合反应,制得亲水性大分子的链转移试剂。
步骤3),可在安瓿瓶中发生聚合反应,
步骤(1)中的亲水性的大分子聚合物可以是聚乙二醇甲基丙烯酸甲酯、聚丙烯酸、聚乙二醇单甲醚、聚丙烯酰胺中的一种或几种。
本次发明将功能性结构作为疏水部分接到聚合物上,作为内核,稳定性强。本发明是聚合诱导自组装法在小分子催化剂的负载和其催化应用领域的拓展。
本发明具有如下有益效果:本发明利用亲水性大分子链转移试剂和疏水性单体通过聚合诱导自组装,成功将有机小分子催化剂DMAP类似物固定在纳米微球的内部,用作催化纳米反应器,既获得了高效的催化体系,又简化了制备纳米反应器的方法。该发明的亲疏水性单体的类型和其使用比例的选择范围较广,制备方法简单。
综上所述,本发明利用该催化纳米微球作为催化纳米反应器,能实现水相高效有机催化反应。该方法简化了催化纳米反应器的制备方法,极大地提高了催化反应的效率,并且可以实现催化剂的回收利用。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1为实施例1步骤(3)最终得到的乳液的扫描电子显微镜(SEM)图;
图2为实施例2步骤(3)最终得到的乳液的动态光散射(DLS)图;
图3为实施例3步骤(3)最终得到的乳液的动态光散射(DLS)图;
图2、图3中,volume代表体积分布,number代表数量分布,intensity代表强度分布。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
THF,四氢呋喃
CEPA,4-氰基-4-((((乙硫基)羰基硫酰)硫基)戊酸
Et3N,三乙胺
DCC,二环己基碳二亚胺
DMAP,4-二甲氨基吡啶。
实施例1、一种聚合诱导自组装法制备催化纳米微球的方法,依次进行如下步骤:
(1)亲水性的RAFT聚合大分子链转移试剂的制备
将0.58g(2.2mmol)链转移试剂CEPA,5.5g(1.1mmol)聚乙二醇单甲醚(mPEG113,分子量为5000)溶于20mL无水THF中,得混合液;
将0.45g(2.2mmol)二环己基碳二亚胺(DCC)和0.027g(0.22mmol)DMAP溶于2ml的无水THF中,然后在冰浴条件下滴加至上述混合液中(滴加时间约为15~30分钟),然后于室温下酯化反应48h。
反应所得的混合物用冷乙醚(0~4℃的乙醚约400ml)沉淀,得到粗产品。
粗产品采用柱色谱(内装200~300目的柱层析硅胶)进行纯化,采用二氯甲烷:甲醇=95:5(v/v)作为洗脱剂,洗脱剂的用量约为700ml,收集所有的洗脱液,于真空条件下40℃干燥至恒重,得到mPEG113-CEPA(约4.8g)。
(2)含DMAP类似物的小分子单体的制备
称取1.5g(1mmol)2-(甲基-4-吡啶基)-乙醇到密闭的圆底烧瓶中;通氮气,冰浴中冷却待用;向上述体系中滴加由8ml二氯甲烷和1.58g(1.5mmol)Et3N、1.50g(1.1mmol)丙烯酰氯组成的二氯甲烷溶液(滴加时间约为15~30分钟),氮气保护下室温反应12h。
反应结束后,将反应液倒入25ml氢氧化钠溶液(氢氧化钠的质量浓度为25%)中,分别得到位于下层的有机相和位于上层的水相;收集有机相;水相用氯仿萃取3次(每次氯仿的用量为50ml)。将3次的氯仿萃取相与上述收集的有机相合并后,用无水硫酸钠去除水分,再于40℃浓缩至为原体积的2%,利用柱色谱(内装200~300目的柱层析硅胶)纯化,采用二氯甲烷:甲醇=10:1(v/v)作为洗脱剂,洗脱剂的用量约为1.2L,收集所有的洗脱液,于真空条件下40℃干燥至恒重,得到含DMAP类似物的小分子单体(功能性催化剂小分子),命名为2-(N-甲基-N-(4-吡啶)氨基)丙烯酸乙酯。
(3)含DMAP类似物的纳米微球的制备
0.1g(0.019mmol)步骤1)所得的mPEG113-CEPA、1.7mg(0.006mmol)2,2-偶氮二(2-甲基丙基咪)二盐酸盐、0.11g(0.48mmol)步骤2)所得的功能性催化剂小分子、0.2g(1.425mmol)丙烯酸四氢呋喃酯组成单体;
将上述单体加入至聚合瓶中,再加入1.4g超纯水(即,单体:极性溶剂≈29%的质量比),密封通氮气除氧15min,然后在密封条件下100℃反应4h。反应结束后冷却到室温,并敞口暴露到空气中淬灭反应,得催化纳米微球。
该催化纳米微球的扫描电子显微镜照片(SEM),如图1所示。
实施例2、
将实施例1步骤(3)中的丙烯酸四氢呋喃酯改成4-羟基丁基丙烯酸酯,摩尔用量保持不变,仍然为1.425mmol;其余等同于实施例1。
最终所得的含有催化纳米微球的乳液动态光散射(DLS)图,如图2所示。
实施例3、
将实施例1步骤(3)中的丙烯酸四氢呋喃酯改成2-羟基丁基丙烯酸酯,摩尔用量保持不变,仍然为1.425mmol;其余等同于实施例1。
最终所得的含有催化纳米微球的乳液动态光散射(DLS)图,如图3所示。
实施例4、
将实施例1步骤(1)中的聚乙二醇单甲醚(mPEG113,分子量为5000)改成了聚乙二醇月桂酸酯(n≈55),摩尔量相同,仍然为1.1mmol;其余等同于实施例1。
所得产物为:
实施例5、
将实施例1步骤(1)中的聚乙二醇单甲醚(mPEG113,分子量为5000)改成了聚乙二醇单甲醚(mPEG42,分子量为1900),摩尔量相同,仍然为1.1mmol;
且,将实施例1步骤(3)中的1.425mmol的丙烯酸四氢呋喃酯改成0.676mmol的2-羟基丁基丙烯酸酯;
其余等同于实施例1。
实验1~实验5、将实施例1~实施例5制备而得的催化纳米微球,用于催化底物发生酰基化反应,反应内容具体如下:催化纳米微球0.005mmol、醇类化合物0.1mmol,N,N-二异丙基乙胺0.15mmol,乙酸酐0.3mmol,纯净水1ml,在室温下反应1h。用乙醚萃取,得到产物。
反应通过GC-MS监测,结果如下表1所示。
表1、含4-二甲氨基吡啶(DMAP)的乳液催对醇的酰基化
对比例1、将实施例1步骤(3)改为:
0.019mmol步骤(1)所得的mPEG113-CEPA、40微升浓度为1mg/mL的氯化三(2,2,-联吡啶)钌水溶液、0.48mmol步骤2)所得的功能性催化剂小分子、1.425mmol丙烯酸四氢呋喃酯组成单体;
将上述单体加入至聚合瓶中,再加入30ml超纯水,密封通氮气除氧15min;再LED灯照射下反应12h。反应结束后冷却到室温,并敞口暴露到空气中淬灭反应,最后得催化纳米微球均一度较差,甚至不能形成很好纳米微球。
将所得产物按照实验1进行1h,Yield为23%。
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (6)
1.聚合诱导自组装制备催化纳米微球的方法,其特征在于包括如下步骤:
1)、亲水性的RAFT聚合大分子链转移试剂的制备:
将RAFT聚合链转移试剂、亲水性大分子聚合物溶解到无水四氢呋喃中,在冰浴条件下,滴加二环己基碳二亚胺和4-二甲氨基吡的无水四氢呋喃溶液,于室温酯化反应4~48h;
RAFT聚合链转移试剂、亲水性大分子聚合物、二环己基碳二亚胺、4-二甲氨基吡的摩尔比为1:0.5~3.5:1~1.5:0.1~0.2;
反应产物用乙醚沉淀,得粗产品;
粗产品纯化,真空干燥,得到亲水性RAFT聚合大分子链转移试剂;
2)、小分子单体的制备:
在氮气保护和冰浴条件下,向2-(甲基-4-吡啶基)-乙醇滴加丙烯酰氯和三乙胺的二氯甲烷溶液,然后继续在氮气保护和室温下反应2~12h;
2-(甲基-4-吡啶基)-乙醇、三乙胺、丙烯酰氯的摩尔比为1:1.5~3:1.1~4;
将所得的反应液倒入氢氧化钠溶液中,分别得有机相和水相,水相用氯仿萃取,将萃取层与有机相合并后浓缩、再纯化,得到小分子单体;
3)、催化纳米微球的制备:
步骤1)所得亲水性大分子的链转移试剂,2,2-偶氮二(2-甲基丙基咪)二盐酸盐,步骤2)所述小分子单体、疏水性单体的混合物称为单体,在单体中加入极性溶剂后除氧,在密封条件下于50~100℃反应2~24h;得催化纳米微球;
亲水性大分子的链转移试剂:小分子单体:疏水性单体=1:20~100:50~200的摩尔比;2,2-偶氮二(2-甲基丙基咪)二盐酸盐:亲水性大分子的链转移试剂=1:3~5的摩尔比。
2.根据权利要求1所述的聚合诱导自组装法制备催化纳米微球的方法,其特征在于步骤1)中:
RAFT聚合链转移试剂为4-氰基-4-((((乙硫基)羰基硫酰)硫基)戊酸;
亲水性大分子聚合物为聚乙二醇甲基丙烯酸甲酯、聚丙烯酸、聚乙二醇单甲醚、聚丙烯酰胺、聚乙二醇月桂酸酯。
3.根据权利要求2所述的聚合诱导自组装法制备催化纳米微球的方法,其特征在于步骤3)中:疏水性单体为4-羟基丁基丙烯酸酯、2-羟基丁基丙烯酸酯、丙烯酸四氢呋喃酯中的至少一种。
4.根据权利要求3所述的聚合诱导自组装法制备催化纳米微球的方法,其特征在于步骤3)中:极性溶剂为水、乙醇、甲酰胺、三氟乙酸中的至少一种。
5.根据权利要求1~4任一所述的聚合诱导自组装法制备催化纳米微球的方法,其特征在于步骤3)中:
所述单体:极性溶剂=25%~50%的质量比。
6.根据权利要求1~4任一所述的聚合诱导自组装法制备催化纳米微球的方法,其特征在于步骤3)中:反应时间到达后冷却到室温,并敞口暴露到空气中淬灭反应。
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CN114805711A (zh) * | 2022-05-27 | 2022-07-29 | 浙江理工大学 | 一种空间位点隔离的聚合物基酸碱催化剂的制备方法 |
CN114805711B (zh) * | 2022-05-27 | 2024-01-30 | 浙江理工大学 | 一种空间位点隔离的聚合物基酸碱催化剂的制备方法 |
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