Continuous-Flow Polymerization-Induced Self-Assembly

doi:10.6023/A26030073

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (7): 1153-1164.DOI: 10.6023/A26030073 Previous Articles Next Articles

Review

连续流聚合诱导自组装

李牧舟^a, 徐婷婷^a, 胡欣^b^,^*(), 孙冰^c^,^*(), 朱宁^a^,^*()

^a 南京工业大学生物与制药工程学院材料化学工程全国重点实验室材料化学工程全国重点实验室南京 211800
^b 南京工业大学材料科学与工程学院南京 211800
^c 中石化安全工程研究院有限公司化学品安全全国重点实验室化学品安全全国重点实验室青岛 266000

投稿日期:2026-03-12 发布日期:2026-06-12

作者简介:

胡欣, 西安交通大学材料科学与工程专业博士, 南京工业大学材料科学与工程学院教授. 主要从事功能高分子材料开发及微化工制备研究, 加入南工至今以第一或通讯作者(含共同作者)在Adv. Sci.、ACS Appl. Mater. Interfaces、ACS Macro Lett.、Chem. Eng. J.、Carbohydr. Polym.等期刊发表论文40余篇, 主持国家自然科学基金面上项目和青年项目各1项、企业委托开发项目3项, 获中国化工学会基础研究成果奖一等奖, 入选江苏省科技副总.

孙冰, 美国加州理工学院博士, 中石化安全工程研究院化工过程安全研究所所长、研究员, 主要从事化工过程安全技术开发、新型本质安全化工艺与装备开发工作. 在Angew. Chem. Int. Ed.等期刊发表SCI论文70余篇, 获国内外授权发明专利80余件, 研究成果曾获化工学会基础研究一等奖、石化联合会科技进步一等奖等科技奖励, 担任国家重点研发计划首席科学家, 获得侯德榜化工科学技术创新奖等荣誉.

朱宁, 浙江大学高分子化学与物理专业博士, 南京工业大学生物与制药工程学院教授. 主要研究化工新材料绿色制造, 加入南工以来作为第一或通讯作者(含共同)在Nat. Mater.、Angew. Chem. Int. Ed.、Adv. Funct. Mater.、Adv. Sci.、AIChE J.等期刊发表论文60余篇, 获授权中国发明专利70余件、美国专利5件, 主持科技部项目课题1项/子课题1项、国家自然科学基金面上项目3项/青年项目1项、企业委托开发项目6项, 获省部级科研奖励6项.

基金资助:
国家自然科学基金(22478188); 国家自然科学基金(22278223); 国家自然科学基金(22278205); 化学品安全全国重点实验室开放课题(SKLCS-2025008)

Continuous-Flow Polymerization-Induced Self-Assembly

Muzhou Li^a, Tingting Xu^a, Xin Hu^b^,^*(), Bing Sun^c^,^*(), Ning Zhu^a^,^*()

^a College of Biotechnology and Pharmaceutical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China
^b College of Materials Science and Engineering, Nanjing Tech University, Nanjing, Jiangsu 211800, China
^c SINOPEC Research Institute of Safety Engineering Co., Ltd., State Key Laboratory of Chemical Safety, Qingdao, Shandong 266000, China

Received:2026-03-12 Published:2026-06-12
Contact: * E-mail: xinhu@njtech.edu.cn; sunb.qday@sinopec.com; ningzhu@njtech.edu.cn
Supported by:
National Natural Science Foundation of China(22478188); National Natural Science Foundation of China(22278223); National Natural Science Foundation of China(22278205); R&D Program of State Key Laboratory of Chemical Safety(SKLCS-2025008)

As an efficient strategy for preparing polymer nano-objects with high solid contents and diverse morphologies, polymerization-induced self-assembly (PISA) has attracted growing research interest in the fields such as polymer chemistry. Compared with the traditional batch reactions, the combination of microreactor-based flow chemistry with PISA offers unique advantages, including but not limited to accelerated reaction rates, access to higher-order morphologies, and easy to integrations of new technologies. This review focuses on continuous-flow PISA, covering continuous-flow thermal-initiated PISA, continuous-flow photo-induced PISA, and continuous-flow PISA integrated with emerging technologies. Opportunities and challenges in the related topics are proposed and discussed with the aim to promote the development of flow chemistry and polymerization-induced self-assembly.

Key words: continuous-flow, polymerization-induced self-assembly, block copolymer, nano-object, controlled polymerization

Cite this article

Muzhou Li, Tingting Xu, Xin Hu, Bing Sun, Ning Zhu. Continuous-Flow Polymerization-Induced Self-Assembly[J]. Acta Chimica Sinica, 2026, 84(7): 1153-1164.

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Fig. & Tab. 10

Figure 1. (a) Polymerization-induced self-assembly (V and lc denote the volume and the length of the core-forming block and α0 is the effective interfacial area of the block junction). (b) Microreactor-based flow chemistry

Figure 2. Mechanism of RAFT polymerization

Figure 3. Thermal-initiated RAFT-PISA in a continuous-flow microreactor

Figure 4. Continuous-flow synthesis of PDMAm macro-CTA and PDMAm-b-PDAAm diblock copolymer

Figure 5. (a) Conversion vs. time curves for the continuous-flow RAFT aqueous dispersion polymerization of diacetoneacrylamide (DAAm) using a PDMAm113 macro-CTA targeting DPs of 50, 100, and 200. (b) DLS traces for PDMAm113-b-PDAAmy polymer nano-objects. (c) GPC traces for a series of PDMAm46-b-PDAAmy diblock copolymer nanoparticles (y=50~200) synthesized in a microreactor. (d) TEM images of PDMAm46-b-PDAAmy nanoparticles (y=50, 75, 100, 200, 300, 400) synthesized in a microreactor[85]. Copyright 2020, Royal Society of Chemistry, under the terms of the CC BY 3.0

Figure 6. Mechanisms of photo-induced RAFT polymerizations

Figure 7. (a) General scheme for synthesis of PEG-b-PHPMA nanoparticles via visible-light-mediated iniferter polymerization in a continuous process. (b) TEM images for aqueous RAFT dispersion PISA in flow for targeted degrees of polymerization. (c) Reactor setup for the synthesis of PEG-b-PHPMA nanoparticles enabling monitoring of particle morphology[100]. Copyright 2018, American Chemical Society

Figure 8. (a) RAFT polymerization with photoinitiator for synthesis of mPEG-b-PHPMA under purple and blue light irradiation in water with mPEG-CEPA as macro-CTA, Eosin Y/AscA as catalytic system, and SPTP as type I photoinitiator. (b) Digital image of the flow reactor used for dual-wavelength photo-PISA and schematic illustration of the flow reactor including all dimensions. (c) Polymerization kinetics of aqueous photo-PISA of HPMA performed in a continuous-flow reactor through dual-/single-wavelength light irradiation. (d) Plots of dual-wavelength aqueous photo-PISA of HPMA (15% (w)) performed in a continuous-flow reactor. (e) Evolution of Mn and Đ with monomer conversion for aqueous dual-wavelength photo-PISA of HPMA (15% (w)) performed in a continuous-flow reactor. (f) GPC traces of diblock copolymers formed by dual-wavelength aqueous photo-PISA of HPMA (15% (w)) in a continuous-flow reactor. (g, h) Representative TEM images of mPEG-b-PHPMA diblock copolymer nano-objects prepared by dual-wavelength aqueous photo-PISA of HPMA in the flow reactor and batch reactor[109]. Copyright 2020, American Chemical Society

Figure 9. (a) A schematic of the reactor platform comprising a heated tubular coil reactor, a quench coil at 20 ℃, a SAXS compatible flow cell in an evacuated sample chamber and sample collection. (b) Schematic representation of the change in particle dimensions when the DP of the PDMAm macro-CTA is increased from 47 to 143 while maintaining a constant PDAAm core DP of approximately 400. (c) In situ SAXS patterns obtained for the same reactions where experimental SAXS data are shown as hollow circles whilst the fitted model is indicated by the solid line. (d) Diameter of the particle (DParticle) as a function of residence time for a series of PDMAmx-b-PDAAm400 copolymers synthesized by RAFT dispersion polymerization was x=47, 62, 80, 98, and 143. (e) Hydrodynamic diameter (Dh; determined by DLS) and core diameter (Dcore; determined by SAXS) as a function of PDMAm degree of polymerization for samples obtained after 1500 s. Error bars shown are determined by PDI of the hydrodynamic diameter[115]. Copyright 2023, American Chemical Society

Figure 10. (a) Schematic of the reactor platform for synthesis and inline characterization of PDMAm-b-PDAAm block copolymer nanoparticles. (b) Particle size summary with particle size distributions (inset) for seven PDMAm150-b-PDAAmn block copolymers measured during steady-state sample collection by inline SRDLS. (c) Relationship between targeted hydrophobic block length and resulting particle size (black solid line) obtained from screening data (black squares)[116]. Copyright 2025, American Chemical Society, under the terms of the CC BY 4.0

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连续流聚合诱导自组装

Continuous-Flow Polymerization-Induced Self-Assembly

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