WO2017166914A1 - 一种具有平面共轭结构的三臂atrp引发剂及其制备方法 - Google Patents

一种具有平面共轭结构的三臂atrp引发剂及其制备方法 Download PDF

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WO2017166914A1
WO2017166914A1 PCT/CN2017/072222 CN2017072222W WO2017166914A1 WO 2017166914 A1 WO2017166914 A1 WO 2017166914A1 CN 2017072222 W CN2017072222 W CN 2017072222W WO 2017166914 A1 WO2017166914 A1 WO 2017166914A1
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white solid
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戴李宗
吴俣哲
袁丛辉
毛杰
李云同
许一婷
曾碧榕
罗伟昂
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Xiamen University
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  • the invention relates to a kind of polymerization reaction in polymer polymerization chemistry, in particular to a preparation method of a three-arm ATRP initiator having a planar conjugate structure.
  • Atom transfer radical polymerization is one of the most widely used methods for polymer synthesis.
  • the polymerization method has the dual characteristics of free radical polymerization and living polymerization, and has good universality, strong controllability and low cost.
  • the polymer synthesized by the method can not only achieve the expected polymerization molecular weight, but also achieve a narrow distribution range and high yield of the polymer, and thus is an effective tool for designing a novel macromolecular structure.
  • it has become common to synthesize multi-arm and star-shaped polymers by ATRP polymerization, and has gradually become a research hotspot in the field of polymer chemistry.
  • ATRP Atom transfer radical polymerization
  • the ATRP initiator can also be classified into a small molecule ATRP initiator and a macromolecular ATRP initiator depending on the molecular weight.
  • the small molecule initiators the three-arm small molecule ATRP initiator is characterized by a rich chemical structure and a complex spatial structure but also regular [Biomacromolecules-2015, 16, 723-732]. More importantly, small molecule initiators with highly planar conjugate properties and rich electrical properties are more conducive to the spatial arrangement and orientation of polymer chains, and are important tools for polymer structure design in polymer science.
  • a novel three-arm small molecule ATRP initiator was synthesized by nucleophilic substitution reaction of 1,3,5-tris(4-aminophenyl)benzene and bromoisobutyryl bromide under the catalysis of triethylamine.
  • the initiator has the characteristics of highly planar conjugate properties and rich electrical properties as well as efficient chain transfer. Its Learning structure:
  • the optimal reaction system and post-treatment method suitable for the initiator were screened out.
  • the three-arm amphiphilic polymer was synthesized by ATRP polymerization using the initiator to carry out corresponding self-assembly research.
  • the invention aims to provide a preparation method of a three-arm ATRP initiator having a planar conjugate structure and application thereof
  • the macromolecular chain transfer agent 0.3 to 1 part by volume of tris(2-dimethylaminoethyl)amine, 0.1 to 1 part of cuprous bromide, and 1 to 3 parts by volume of t-butyl acrylate are dissolved in the DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 3 to 5 parts by volume of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the mixture was precipitated with a mixed solution of methanol and water to a three-armed amphiphilic block polymer in the form of a white solid.
  • the structure of the three-arm initiator in the present invention is ingeniously designed, the synthesis step is simple, and the yield is high.
  • the initiator has a high degree of planar conjugation and power enrichment as well as efficient initiation activity and chain transfer.
  • the optimum reaction system and post-treatment method of the three-arm ATRP initiator are screened in the present invention.
  • the reaction system has good universality, strong operability, simple post-treatment process and little environmental pollution, and can be applied to ATRP controlled polymerization of various monomers.
  • the polymer synthesized by the initiator in the present invention can be self-assembled in a solvent, and the self-assembly behavior of the polymer can be artificially controlled and further researched and applied by controlling the degree of polymerization.
  • Figure 1 is a nuclear magnetic resonance spectrum of a three-arm ATRP initiator with a nuclear magnetic spectroscopy: 9.90 (3H, s), 7.90 to 7.81 (15H, m), 2.04 (18H, s);
  • Figure 2 is a GPC spectrum of a three-armed amphiphilic ATRP polymer
  • a macromolecular chain transfer agent 0.3 ml of tris(2-dimethylaminoethyl)amine, 0.1 cuprous bromide, and 1 t-butyl acrylate were dissolved in a DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 3 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.
  • a macromolecular chain transfer agent 0.5 ml of tris(2-dimethylaminoethyl)amine, 0.2 cuprous bromide, and t-butyl 2 acrylate were dissolved in a DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 5 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.
  • the macromolecular chain transfer agent 0.5 ml of tris(2-dimethylaminoethyl)amine, 0.6 cuprous bromide, and tert-butyl triacrylate were dissolved in the DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 5 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.

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Abstract

本发明涉及一种具有平面共轭结构的三臂原子转移自由基聚合引发剂的制备方法。首先通过1,3,5-三(4-氨苯基)苯和溴代异丁酰溴在三乙胺的催化下进行亲核取代反应合成了一种具有高度平面共轭性质和富电性质的高效三臂ATRP引发剂。其次，筛选出了该引发剂适用的的最佳反应体系和后处理方法。并利用该引发剂通过ATRP聚合反应合成了三臂的双亲性高分子聚合物进行了相应的自组装研究。所述的三臂ATRP引发剂不仅填补了平面共轭性富电子芳环ATRP引发剂的空白，同时还可适用于多种单体的聚合，具有良好的应用前景。

Description

一种具有平面共轭结构的三臂ATRP引发剂及其制备方法 技术领域
本发明涉及高分子聚合化学中的一类聚合反应，特别涉及一种具有平面共轭结构的三臂ATRP引发剂的制备方法。
背景技术
原子转移自由基聚合(atom transfer radical polymerization，ATRP)是一种应用范围最为广泛的聚合物合成方法。该聚合方法同时具备了自由基聚合和活性聚合的双重特点,普适性好,可控性强，成本低廉。通过该方法所合成的聚合物不仅可以达到预期的聚合分子量，同时能够实现聚合物的分布范围较窄，产率较高，因此是一种新型的大分子结构设计的有效工具。近年来，通过ATRP聚合反应合成多臂和星形的聚合物屡见不鲜，并且已经逐渐成为了高分子化学领域的一大研究热点。目前，通过对ATRP反应条件的调控，已经可以顺利实现无规共聚物，有规嵌段共聚物，三臂聚合物，多臂聚合物和星形聚合物及无机杂化材料的合成。
常见的ATRP引发剂主要包括有卤代烷RX(X＝Br,Cl)类，α-溴代酯类，α-溴代酮类等[Chemical Reviews,2009,109,5595–5619]。也可以根据分子量的大小把ATRP引发剂分为小分子ATRP引发剂和大分子ATRP引发剂。在小分子引发剂当中，三臂小分子ATRP引发剂的特点是化学结构多样性丰富，空间构型复杂但又富有规律[Biomacromolecules-2015,16,723-732]。更重要的是，具有高度平面共轭性质和富电性质的小分子引发剂更是有利于聚合物链在空间上的排布和取向，是高分子学科当中聚合物结构设计的重要工具。
目前，具有高度平面共轭性和富电性质的三臂小分子ATRP引发剂鲜有报道。其原因在于该类引发剂的化学结构设计复杂，合成工艺困难，原料难于获得，成本昂贵，适用的聚合反应体系也极其复杂，后处理困难因此本专利的主要目的在于克服现有技术的缺陷，提供一种新型的具有高度平面共轭性质和富电性质的三臂小分子ATRP引发剂。首先通过1,3,5-三(4-氨苯基)苯和溴代异丁酰溴在三乙胺的催化下进行亲核取代反应合成了一种新型的三臂小分子ATRP引发剂。该引发剂具有高度平面共轭性质和富电性质以及高效的链转移性等特点。其化 学结构式:
Figure PCTCN2017072222-appb-000001
其次，筛选出了适用于该引发剂的最佳反应体系和后处理方法。并利用该引发剂通过ATRP聚合反应合成了三臂的双亲性高分子聚合物进行了相应的自组装研究。
发明内容
发明目的在于提供一种具有平面共轭结构的三臂ATRP引发剂的制备方法及其应用
所述的三臂ATRP引发剂的合成方法及其应用按如下步骤实现：
一,三臂ATRP引发剂的合成：
(1)将0.5～1份的1,3,5-三(4-氨苯基)苯和1～3体积份溴代异丁酰溴溶解于10体积份二氯甲烷溶液当中，放置于冰浴条件于搅拌10分钟。缓慢加入2～5体积份三乙胺溶液，并且在室温条件下搅拌过夜。反应结束后，通过柱层析进行纯化，洗脱剂为石油醚和乙酸乙酯。所得到的固体用无水乙醇进行重结晶，即得到三臂的ATRP引发剂。
二,三臂ATRP引发剂的应用：
(1)将0.5～1份引发剂，0.3～1体积份三(2-二甲氨基乙基)胺，0.1～0.3份溴化亚铜，1～3体积份丙烯酸叔丁酯溶解于DMF溶液当中。连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液沉淀后得到白色固体聚合物。将白色固体聚合物和3～5体积份三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀就得到双亲性的三臂白色固体聚合物。
(2)将0.5～1份引发剂，0.3～1体积份三(2-二甲氨基乙基)胺，0.1～0.3份溴化亚铜，1～3体积份苯乙烯溶解于甲苯溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中 性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体。将大分子链转移剂，0.3～1体积份三(2-二甲氨基乙基)胺，0.1～1份溴化亚铜，1～3体积份丙烯酸叔丁酯溶解于DMF溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体。将嵌段聚合物白色固体和3～5体积份三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀后到白色固体状的三臂双亲性嵌段聚合物。
(3)将0.1～0.3份三臂双亲性聚合物固体溶解于1～3体积份四氢呋喃溶液，逐滴加入到10体积份蒸馏水当中，室温条件下避光搅拌过夜。所得到的液体就是该三臂双亲聚合物的自组装溶液。通过该自组装溶液进行更进一步的形貌研究和应用。
本发明所合成的三臂ATRP引发剂具有如下特点：
(1)本发明中三臂引发剂的结构设计巧妙，合成步骤简单，产率高，。该引发剂具有高度平面共轭性和富电性以及高效的引发活性和链转移性。
(2)本发明中筛选出了该三臂ATRP引发剂的最佳反应体系和后处理方法。反应体系普适性好，可操作性强，后处理过程简单，对环境污染小，可适用于各种单体的ATRP可控聚合。
(3)通过本发明中的引发剂所合成的聚合物能够在溶剂中发生自组装，通过聚合度的控制可以实现对聚合物的自组装行为进行人为的控制并做更进一步的研究和应用。
(4)目前市场上并没有可直接购买并使用的高度平面共轭性和富电性的三臂ATRP引发剂，本发明很好的弥补了这一空白，具有很好的市场前景。
附图说明
图1为三臂ATRP引发剂的核磁氢谱，其核磁解谱为:9.90(3H,s),7.90～7.81(15H,m),2.04(18H,s),；
图2为三臂双亲性ATRP聚合物的GPC图谱；
具体实施方式
下面结合实施例对本发明作进一步详细的描述。
实施例1
(1)将0.5g的1,3,5-三(4-氨苯基)苯和1ml溴代异丁酰溴溶解于10ml二氯甲烷溶液当中，放置于冰浴条件于搅拌10分钟。缓慢加入2ml三乙胺溶液，并且在室温条件下搅拌过夜。反应结束后，通过柱层析进行纯化，洗脱剂为石油醚和乙酸乙酯。所得到的固体用10ml无水乙醇进行重结晶，即得到三臂的ATRP引发剂的白色固体。
(2)将0.5g引发剂，0.3ml三(2-二甲氨基乙基)胺，0.1g溴化亚铜，1ml丙烯酸叔丁酯溶解于DMF溶液当中。连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后得到白色固体聚合物。将白色固体聚合物和3ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀就得到双亲性三臂聚合物的白色固体。
(3)将0.5g引发剂，0.3ml三(2-二甲氨基乙基)胺，0.1g溴化亚铜，1ml苯乙烯溶解于甲苯溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体。将大分子链转移剂，0.3ml三(2-二甲氨基乙基)胺，0.1溴化亚铜，1丙烯酸叔丁酯溶解于DMF溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体。将嵌段聚合物白色固体和3ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀后得到白色固体状的三臂双亲性嵌段聚合物。
(4)将0.1g三臂双亲性聚合物固体溶解于3ml四氢呋喃溶液，逐滴加入到10ml蒸馏水当中，室温条件下避光搅拌过夜。所得到的液体就是该三臂双亲聚合物的自组装溶液。通过该自组装溶液进行更进一步的形貌研究和 应用。
实施例2
(1)将1g的1,3,5-三(4-氨苯基)苯和2ml溴代异丁酰溴溶解于10ml二氯甲烷溶液当中，放置于冰浴条件于搅拌10分钟。缓慢加入3ml三乙胺溶液，并且在室温条件下搅拌过夜。反应结束后，通过柱层析进行纯化，洗脱剂为石油醚和乙酸乙酯。所得到的固体用15ml无水乙醇进行重结晶，即得到三臂的ATRP引发剂的白色固体。
(2)将1g引发剂，0.5ml三(2-二甲氨基乙基)胺，0.2g溴化亚铜，2ml丙烯酸叔丁酯溶解于DMF溶液当中。连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后得到白色固体聚合物。将白色固体聚合物和3ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀就得到双亲性三臂聚合物的白色固体。
(3)将1g引发剂，0.5ml三(2-二甲氨基乙基)胺，0.2g溴化亚铜，2ml苯乙烯溶解于甲苯溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体。将大分子链转移剂，0.5ml三(2-二甲氨基乙基)胺，0.2溴化亚铜，2丙烯酸叔丁酯溶解于DMF溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体。将嵌段聚合物白色固体和5ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀后得到白色固体状的三臂双亲性嵌段聚合物。
(4)将0.15g三臂双亲性聚合物固体溶解于5ml四氢呋喃溶液，逐滴加入到10ml蒸馏水当中，室温条件下避光搅拌过夜。所得到的液体就是该三臂双亲聚合物的自组装溶液。通过该自组装溶液进行更进一步的形貌研究和应用。
实施例3
(1)将1.5g的1,3,5-三(4-氨苯基)苯和4ml溴代异丁酰溴溶解于10ml二氯甲烷溶液当中，放置于冰浴条件于搅拌10分钟。缓慢加入5ml三乙胺溶液，并且在室温条件下搅拌过夜。反应结束后，通过柱层析进行纯化，洗脱剂为石油醚和乙酸乙酯。所得到的固体用20ml无水乙醇进行重结晶，即得到三臂的ATRP引发剂的白色固体。
(2)将1.5g引发剂，1ml三(2-二甲氨基乙基)胺，0.5g溴化亚铜，4ml丙烯酸叔丁酯溶解于DMF溶液当中。连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后得到白色固体聚合物。将白色固体聚合物和3ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀就得到双亲性三臂聚合物的白色固体。
(3)将1.5g引发剂，0.6ml三(2-二甲氨基乙基)胺，0.3g溴化亚铜，3ml苯乙烯溶解于甲苯溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体。将大分子链转移剂，0.5ml三(2-二甲氨基乙基)胺，0.6溴化亚铜，3丙烯酸叔丁酯溶解于DMF溶液当中。经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24小时。反应结束之后，通过中性氧化铝柱除去铜盐。再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体。将嵌段聚合物白色固体和5ml三氟乙酸溶解于二氯甲烷当中。室温条件下，搅拌反应24小时。反应结束后，再利用甲醇和水的混合溶液进行沉淀后得到白色固体状的三臂双亲性嵌段聚合物。
(4)将0.2g三臂双亲性聚合物固体溶解于5ml四氢呋喃溶液，逐滴加入到10ml蒸馏水当中，室温条件下避光搅拌过夜。所得到的液体就是该三臂双亲聚合物的自组装溶液。通过该自组装溶液进行更进一步的形貌研究和应用。

Claims (9)

  1. 一种具有平面共轭结构的三臂ATRP引发剂，其特征在于其化学结构式:
    Figure PCTCN2017072222-appb-100001
  2. 如权利要求1所述具有平面共轭结构的三臂ATRP引发剂的制备方法，其特征在于其具体步骤如下：
    将1,3,5-三(4-氨苯基)苯和溴代异丁酰溴溶解于二氯甲烷溶液中，冰浴条件下搅拌，再加入三乙胺溶液反应，然后通过柱层析进行纯化，所得固体用无水乙醇进行重结晶，即得具有平面共轭结构的三臂ATRP引发剂。
  3. 如权利要求2所述具有平面共轭结构的三臂ATRP引发剂的制备方法，其特征在于所述1,3,5-三(4-氨苯基)苯、溴代异丁酰溴、二氯甲烷溶液、三乙胺溶液的配比为(0.5～1)g∶(1～3)ml∶10ml∶(2～5)ml，其中，1,3,5-三(4-氨苯基)苯以质量计算，溴代异丁酰溴、二氯甲烷溶液、三乙胺溶液以体积计算。
  4. 如权利要求2所述具有平面共轭结构的三臂ATRP引发剂的制备方法，其特征在于所述冰浴条件下搅拌的时间为10min。
  5. 如权利要求2所述具有平面共轭结构的三臂ATRP引发剂的制备方法，其特征在于所述通过柱层析进行纯化采用的洗脱剂为石油醚和乙酸乙酯。
  6. 如权利要求1所述具有平面共轭结构的三臂ATRP引发剂在制备双亲性的三臂固体聚合物、三臂双亲性嵌段聚合物、三臂双亲聚合物的自组装溶液中应用。
  7. 如权利要求6所述应用，其特征在于具有平面共轭结构的三臂ATRP引发剂在制备双亲性的三臂白色固体聚合物的应用的具体方法如下：
    将0.5～1份具有平面共轭结构的三臂ATRP引发剂、0.3～1体积份三(2-二甲氨基乙基)胺、0.1～0.3份溴化亚铜和1～3体积份丙烯酸叔丁酯溶解于DMF溶液中，连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24h，反应结束后，通过中性氧化铝柱除去铜盐，再通过甲醇和水的混合溶液沉淀后得到白色固体聚合物；将白色固体聚合物和3～5份三氟乙酸溶解于二氯甲烷中，室温条件下搅拌反应24h，反应结束后，再利用甲醇和水的混合溶液进行沉淀，即得双亲性的三臂白色固体聚合物。
  8. 如权利要求6所述应用，其特征在于所述具有平面共轭结构的三臂ATRP引发剂在制备三臂双亲性嵌段聚合物的应用的具体方法如下：
    将0.5～1份具有平面共轭结构的三臂ATRP引发剂、0.3～1体积份三(2-二甲氨基乙基)胺、0.1～0.3份溴化亚铜和1～3体积份苯乙烯溶解于甲苯溶液中，经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24h，反应结束后，通过中性氧化铝柱除去铜盐，通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体；将大分子链转移剂、0.3～1体积份三(2-二甲氨基乙基)胺、0.1～1份溴化亚铜和1～3体积份丙烯酸叔丁酯溶解于DMF溶液中，经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24h，反应结束后，通过中性氧化铝柱除去铜盐，再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体，将嵌段聚合物白色固体和3～5体积份三氟乙酸溶解于二氯甲烷中，搅拌反应24h后，再利用甲醇和水的混合溶液进行沉淀，即得白色固体状的三臂双亲性嵌段聚合物。
  9. 如权利要求6所述应用，其特征在于所述具有平面共轭结构的三臂ATRP引发剂在制备三臂双亲聚合物的自组装溶液中的应用方法如下：
    1)将0.5～1份具有平面共轭结构的三臂ATRP引发剂、0.3～1体积份三(2-二甲氨基乙基)胺、0.1～0.3份溴化亚铜和1～3体积份苯乙烯溶解于甲苯溶液中，经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反应24h，反应结束后，通过中性氧化铝柱除去铜盐，通过甲醇和水的混合溶液进行沉淀后所得到大分子链转移剂白色固体；将大分子链转移剂、0.3～1体积份三(2-二甲氨基乙基)胺、0.1～1份溴化亚铜和1～3体积份丙烯酸叔丁酯溶解于DMF溶液中，经连续冻融脱气3次，充氩气保护后置于90℃的油浴锅中反 应24h，反应结束后，通过中性氧化铝柱除去铜盐，再利用甲醇和水的混合溶液进行沉淀后得到嵌段聚合物白色固体，将嵌段聚合物白色固体和3～5体积份三氟乙酸溶解于二氯甲烷中，搅拌反应24h后，再利用甲醇和水的混合溶液进行沉淀，即得白色固体状的三臂双亲性嵌段聚合物；
    2)将0.1～0.3份步骤1)所得三臂双亲性嵌段聚合物固体溶解于1～3体积份四氢呋喃溶液，再加入到10体积份蒸馏水中，避光搅拌过夜，所得液体即为三臂双亲聚合物的自组装溶液。
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