CN108424482B - 一种含有螺吡喃的多重响应性的树枝状聚合物及其制备方法 - Google Patents
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Abstract
本发明涉及一种含有螺吡喃的多重响应性的树枝状聚合物的制备方法。用树枝状聚酯和己内酯通过开环聚合制备树枝状聚己内酯,把得到的树枝状聚己内酯和二溴异丁酰溴以及三乙胺反应得到树枝状大分子引发剂,用大分子引发剂和甲基丙烯酸叔丁酯通过原子转移自由基聚合得到HPs‑Star‑PCL‑b‑PtbMA,将得到的产物经过水解得到HPs‑Star‑PCL‑b‑PMAA,把羟基螺吡喃和HPs‑Star‑PCL‑b‑PMAA通过酯化反应的到HPs‑Star‑PCL‑b‑PMAA‑SP。通过自组装形成胶束,本发明制备的胶束具有PH响应性和光响应性。通过紫外可见光照射或者酸碱性进行可逆调节,在生物细胞成像,光电器件,分子逻辑开关,药物控制释放等领域具有广泛应用。
Description
技术领域
本发明属于高分子材料、纳米材料及生物医学领域,具体涉及一种含有螺吡喃的多重响应性的树枝状聚合物及其制备方法。
背景技术
光致变色化合物是指受到一定波长的光照射下化合物A通过异构化反应生成化合物B,而化合物 B 在另一种波长的光照射或者热的作用下, 又可以转变恢复为 A. 利用光照前后分子结构上和光化学与光物理性质的变化, 将其作为分子光开关材料被广泛应用于光电器件、化学传感、药物控制释放等领域。
螺吡喃类化合物是一类重要的光致变色化合物,由于其优良的变色性质,热稳定性,抗疲劳性以及可作为良好的有机光储存材料等特点使之成为目前光致变色领域内研究的热点。当紫外光照射或PH减小时,疏水性的螺吡喃可以转化成亲水性的部花箐,当可见光照射或PH增大时,部花箐又可以逐渐恢复成螺吡喃。所以螺吡喃类两亲性聚合物组装成囊泡或胶束后,在紫外光和可见光的刺激下或者酸碱条件的改变下,可以使囊泡或胶束发生融合或者解体等一系列变化。
树枝状聚酯由于其在结构上具有高度的集合对称性、精确的分子结构、大量的官能团、分子内存在大量的空腔以及分子链的增长具有可控性等特点,使得其在工农业、国防、材料学、医学、生命科学、环境保护等领域具有广阔的应用前景。例如它可作为高效催化剂、信息贮存材料、药物缓释载体、液晶材料、分离膜、感光材料、污水处理材料等。
聚己内酯(PCL)是一种具有良好的药物通过性和生物相容性的疏水性聚合物,以PCL为疏水性嵌段的两亲性树枝状聚合物可以在水溶液中形成以PCL为核和亲水性聚合物为壳的稳定胶束。
甲基丙烯酸叔丁酯(tBMA)是一种反应活性高、疏水强的单体,在制备功能化微球和共聚物方面有较广泛的应用 . 其侧基上的叔丁易水解转化成羧酸,使其转化成亲水性的单体,从而使之聚合物具有其侧基上的叔丁易水解转化成羧酸,从而使之聚合物具有功能性。
用树枝状聚合物开环聚合接枝聚己内酯,然后溴化生成树枝状大分子引发剂,通过原子转移自由基聚合生成HPs-Star-PCL-b-PtbMA。把得到的产物水解后通过酯化反应接枝羟基螺吡喃得到HPs-Star-PCL-b-PMAA-SP。
发明内容
本发明的目的在于提供一种含有螺吡喃的多重响应性的树枝状聚合物的制备方法。
本发明的目的是把具有多重响应性的螺吡喃和树枝状聚酯引入到聚合物当中。实现制备光响应性,PH响应性的多重响应性的树枝状聚合物。用商品化的2,3,3 - 三甲基吲哚,2-溴代乙醇,5-硝基水杨醛制备N-羟乙基- 3’,3’ -二甲基 (2H-5-硝基-苯并螺吡喃-2, 2’-吲哚。再用商品化的树枝状聚酯和己内酯合成大分子引发剂,再用大分子引发剂通过原子转移自由基聚合的方法连接甲基丙烯酸叔丁酯,通过水解得到HPs-Star-PCL-b-PMAA,最后把HPs-Star-PCL-b-PMA和羟基螺吡喃相连接得到含有螺吡喃的多重响应性的树枝状聚合物。
本发明提出了一种含有螺吡喃的多重响应性的树枝状聚合物的制备方法,具体步骤如下:
(1)2, 3, 3-三甲基吲哚和2-溴代乙醇(摩尔比1:1.5)在溶剂A中混合回流搅拌1~24h,得到混合物;然后在混合物在室温下静置1~12h,过滤得固体,粗产物经溶剂B洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和5-硝基水杨醛溶于溶剂C中,在40~120℃下反应2~8h趁热将反应液倒入到100~400mL蒸馏水中,过滤,烘干,得到羟基螺吡喃;
(2)把树枝状聚酯和己内酯(摩尔比1:25)在真空环境下在40~180°C下反应1~4h,冷却至室温;加入辛酸亚锡的甲苯溶液在真空条件下反应12~24h,冷却至室温;加入溶剂D溶解后用沉淀剂E沉淀得到树枝状聚己内酯;
(3)用溶剂F溶解星状聚己内酯,加入三乙胺和二溴异丁酰溴后(摩尔比1:1.1:1.1),常温反应30h得到树枝状大分子引发剂;
(4)将得到的树枝状大分子引发剂、CuBr和甲基丙烯酸酯(摩尔比1:1:40)在溶剂G通过ATRP,反应10~24h,得到HPs-Star-PCL-b-PtbMA;
(5)用溶剂H溶解步骤(4)得到的HPs-Star-PCL-b-PtbMA,加入三氟乙酸,反应2~8h(摩尔比1:1),得到HPs-Star-PCL-b-PMAA;
(6)把步骤(5)得到的HPs-Star-PCL-b-PMAA和步骤(1)得到的羟基螺吡喃加入DCC和DMAP(摩尔比1:1.1:0.1)在溶剂I中反应3~12h,得到最终产物。
本发明中,根据步骤(1)所述的溶剂A为甲醇、乙醇或乙酸乙酯中的一种或几种,溶剂B为四氢呋喃、DMF或丙酮中的一种或几种,溶剂C为二氯甲烷、三氯甲烷或丙酮中的一种或几种。
本发明中,根据步骤(2)所述的溶剂D为二氯甲烷、三氯甲烷或四氢呋喃中的一种或几种,沉淀剂E为甲醇、***或正己烷中的一种或几种。
本发明中,根据步骤(3)所述的溶剂F为二氯甲烷、四氢呋喃或DMF中的一种或几种。
本发明中,根据步骤(4)所述的溶剂G为甲苯、二甲苯或DMF中的一种或几种。
本发明中,根据步骤(5)所述的溶剂H为二氯甲烷、三氯甲烷或甲苯中的一种或几种。
本发明中,根据步骤(6)所述的溶剂I为四氢呋喃、DMF或甲苯中的一种或几种。
本发明的有益效果在于:原料来源广泛,所用的原料如甲基丙烯酸叔丁酯、溶剂、催化剂等均可工业化生产,合成方法简单易行。合成的一种含有螺吡喃的多重响应性的树枝状聚合物。共聚物可以在水中自组装为稳定纳米胶束。所得共聚物同时具有光响应性、PH响应性,因而在生物细胞成像,光电器件,分子逻辑开关,药物控制释放等领域具有广泛应用。
附图说明
图1为实施例1制备的一种含有螺吡喃的多重响应性的树枝状聚合物的结构示意图。
具体实施方式
实施例1
将6g 2, 3, 3-三甲基吲哚和7g 2-溴代乙醇在甲醇中混合回流搅拌4h。然后在混合物在室温下静置3h,过滤得固体,粗产物经丙酮洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和4g 5-硝基水杨醛溶于二氯甲烷中,在40℃下反应2h趁热将反应液倒入到100 mL蒸馏水中,过滤,烘干得到螺吡喃SP。
把0.5g树枝状聚酯和10g己内酯在真空环境下在40°C下反应1h,冷却至室温。加入1ml辛酸亚锡的甲苯溶液在真空条件下反应12h,冷却至室温。加入二氯甲烷溶解,再用甲醇沉淀得到树枝状聚己内酯。用二氯甲烷溶解树枝状7g聚己内酯,加入2ml三乙胺,2ml二溴异丁酰溴后常温反应30h得到树枝状大分子引发剂。将得到的树枝状大分子引发剂200mgCuBr和4ml甲基丙烯酸酯在甲苯通过ATRP反应10h得到HPs-Star-PCL-b-PtbMA。用三氯甲烷溶解HPs-Star-PCL-b-PtbMA,加入2ml三氟乙酸反应2h得到HPs-Star-PCL-b-PMAA。把2gHPs-Star-PCL-b-PMAA和0.5g 羟基螺吡喃加入0.5g DCC,05g DMAP在DMF中反应3h得到最终产物。
实施例2
将8g 2, 3, 3-三甲基吲哚和6g 2-溴代乙醇在甲醇中混合回流搅拌5h。然后在混合物在室温下静置4h,过滤得固体,粗产物经四氢呋喃洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和5g 5-硝基水杨醛溶于二氯甲烷中,在60℃下反应2h趁热将反应液倒入到150 mL蒸馏水中,过滤,烘干得到螺吡喃SP。
把0.2g树枝状聚酯和11g己内酯在真空环境下在180°C下反应4h,冷却至室温。加入1.1 ml辛酸亚锡的甲苯溶液在真空条件下反应12h,冷却至室温。加入三氯甲烷溶解,再用***沉淀得到树枝状聚己内酯。用二氯甲烷溶解树枝状6g聚己内酯,加入2ml三乙胺,1ml二溴异丁酰溴后常温反应20h得到树枝状大分子引发剂。将得到的树枝状大分子引发剂250mg CuBr和4ml甲基丙烯酸酯在甲苯通过ATRP反应14h得到HPs-Star-PCL-b-PtbMA。用三氯甲烷溶解HPs-Star-PCL-b-PtbMA,加入2.5 ml三氟乙酸反应2h得到HPs-Star-PCL-b-PMAA。把2g HPs-Star-PCL-b-PMAA和0.5g 羟基螺吡喃加入0.5g DCC,05g DMAP在甲苯中反应4h得到最终产物。
实施例3
将8g 2, 3, 3-三甲基吲哚和6g 2-溴代乙醇在乙醇中混合回流搅拌6h。然后在混合物在室温下静置2h,过滤得固体,粗产物经丙酮洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和5g 5-硝基水杨醛溶于四氢呋喃中,在60℃下反应2h趁热将反应液倒入到250 mL蒸馏水中,过滤,烘干得到螺吡喃SP。
把0.6g树枝状聚酯和11g己内酯在真空环境下在100°C下反应4h,冷却至室温。加入1.1 ml辛酸亚锡的甲苯溶液在真空条件下反应12h,冷却至室温。加入四氢呋喃溶解,再用正己烷沉淀得到树枝状聚己内酯。用二氯甲烷溶解树枝状5g聚己内酯,加入2ml三乙胺,1ml二溴异丁酰溴后常温反应22h得到树枝状大分子引发剂。将得到的树枝状大分子引发剂230mg CuBr和4ml甲基丙烯酸酯在二甲苯中通过ATRP反应13h得到HPs-Star-PCL-b-PtbMA。用甲苯溶解HPs-Star-PCL-b-PtbMA,加入1.5 ml三氟乙酸反应6h得到HPs-Star-PCL-b-PMAA。把2g HPs-Star-PCL-b-PMAA和0.3g 羟基螺吡喃加入0.4g DCC,05g DMAP在甲苯中反应7h得到最终产物。
实施例4
将5.6g 2, 3, 3-三甲基吲哚和6.7g 2-溴代乙醇在乙酸乙酯中混合回流搅拌5h。然后在混合物在室温下静置4h,过滤得固体,粗产物经DMF洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和5。5g 5-硝基水杨醛溶于二氯甲烷中,在110℃下反应2h趁热将反应液倒入到170 mL蒸馏水中,过滤,烘干得到螺吡喃SP。
把3g树枝状聚酯和11g己内酯在真空环境下在112°C下反应4.5h,冷却至室温。加入1.3 ml辛酸亚锡的甲苯溶液在真空条件下反应12h,冷却至室温。加入三氯甲烷溶解,再用甲醇沉淀得到树枝状聚己内酯。用二氯甲烷溶解树枝状6g聚己内酯,加入2ml三乙胺,1ml二溴异丁酰溴后常温反应18h得到树枝状大分子引发剂。将得到的树枝状大分子引发剂200mg CuBr和3.4ml甲基丙烯酸酯在甲苯通过ATRP反应11.5h得到HPs-Star-PCL-b-PtbMA。用二氯甲烷溶解HPs-Star-PCL-b-PtbMA,加入2.5 ml三氟乙酸反应2h得到HPs-Star-PCL-b-PMAA。把2g HPs-Star-PCL-b-PMAA和0.5g 羟基螺吡喃加入0.5g DCC,05g DMAP在DMF中反应2.5h得到最终产物。
实施例5
将8g 2, 3, 3-三甲基吲哚和6。5g 2-溴代乙醇在乙醇中混合回流搅拌5h。然后在混合物在室温下静置4h,过滤得固体,粗产物经DMF洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和4g 5-硝基水杨醛溶于二氯甲烷中,在65℃下反应3h趁热将反应液倒入到220 mL蒸馏水中,过滤,烘干得到螺吡喃SP。
把0.4g树枝状聚酯和10.5g己内酯在真空环境下在140°C下反应4.5h,冷却至室温。加入1.1 ml辛酸亚锡的甲苯溶液在真空条件下反应5h,冷却至室温。加入二氯甲烷溶解,再用***沉淀得到树枝状聚己内酯。用四氢呋喃溶解树枝状4.5g聚己内酯,加入1ml三乙胺,1.5ml二溴异丁酰溴后常温反应10h得到树枝状大分子引发剂。将得到的树枝状大分子引发剂250mg CuBr和3.5ml甲基丙烯酸酯在二甲苯中通过ATRP反应14h得到HPs-Star-PCL-b-PtbMA。用三氯甲烷溶解HPs-Star-PCL-b-PtbMA,加入1.5 ml三氟乙酸反应2h得到HPs-Star-PCL-b-PMAA。把2g HPs-Star-PCL-b-PMAA和0.5g 羟基螺吡喃加入0.5g DCC,05gDMAP在四氢呋喃中反应4h得到最终产物。
Claims (1)
1.一种含有螺吡喃的多重响应性的树枝状聚合物的制备方法,其特征是具体步骤如下:
(1)2, 3, 3-三甲基吲哚和2-溴代乙醇在溶剂A中混合回流搅拌1~24h,得到混合物;然后将混合物在室温下静置1~12h,过滤得固体,粗产物经溶剂B洗涤后取固体溶于NaOH水溶液中,用氯仿萃取三次,合并有机相,无水Na2SO4干燥,蒸发掉溶剂后,剩余产品和5-硝基水杨醛溶于溶剂C中,在40~120℃下反应2~8h趁热将反应液倒入到100~400 mL蒸馏水中,过滤,烘干,得到羟基螺吡喃;
(2)把树枝状聚酯和己内酯在真空环境下在40~180°C下反应1~4h,冷却至室温;加入辛酸亚锡的甲苯溶液在真空条件下反应12~24h,冷却至室温;加入溶剂D溶解后用沉淀剂E沉淀,得到树枝状聚己内酯;
(3)用溶剂F溶解树枝状聚己内酯,加入三乙胺和二溴异丁酰溴后,常温反应30h,得到树枝状大分子引发剂;
(4)将得到的树枝状大分子引发剂、CuBr和甲基丙烯酸叔丁酯在溶剂G通过ATRP反应,得到HPs-Star-PCL-b-PtBMA;
(5)用溶剂H溶解步骤(4)得到的HPs-Star-PCL-b-PtBMA,加入三氟乙酸得到HPs-Star-PCL-b-PMAA;
(6)把步骤(5)得到的HPs-Star-PCL-b-PMAA和步骤(1)得到的羟基螺吡喃加入DCC和DMAP在溶剂I中反应3~12h,得到最终产物;
其中:溶剂A为甲醇、乙醇或乙酸乙酯中的一种或几种,溶剂B为四氢呋喃、DMF或丙酮中的一种或几种,溶剂C为二氯甲烷、三氯甲烷或丙酮中的一种或几种,溶剂D为二氯甲烷、三氯甲烷或四氢呋喃中的一种或几种,沉淀剂E为甲醇、***或正己烷中的一种或几—种,溶剂F为二氯甲烷、四氢呋喃或DMF中的一种或几种,溶剂G为甲苯、二甲苯或DMF中的一种或几种,溶剂H为二氯甲烷、三氯甲烷或甲苯中的一种或几种,溶剂I为四氢呋喃、DMF或甲苯中的一种或几种。
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