Progress in preparation and application of amphiphilic block copolymer stabilized high internal phase emulsion templates

doi:10.11949/0438-1157.20210761

Abstract

Abstract:

Porous polymeric materials that possess high porosity, good processability, and light mass are widely used in chemical engineering, biomedical engineering, and environmental engineering. High internal phase emulsion (HIPE) templating provides a simple and efficient way to prepare porous polymer materials (i.e., polyHIPEs), and the shape and structure of the as-prepared polyHIPEs can be well controlled, therefore, it receives a great deal of attentions. This article focuses on the recent research progress of amphiphilic block copolymer stabilized HIPEs and the preparation of porous polymers by HIPE templating. In addition, frontiers in the applications of such porous polymeric materials in the fields of adsorption and separation, biomedicine, energy storage, and catalytic materials are also introduced. Finally, the future development in both of the preparation and application of polyHIPEs are prospected.

Key words: high internal phase emulsion, polymerization, amphiphilic block copolymer, porous polymeric materials, product engineering

摘要：

多孔聚合物材料具有孔隙率高、加工性能好、质量轻的特点，在化学工程、生物医学工程及环境工程等领域具有广阔的应用前景。高内相乳液模板法为多孔聚合物材料提供了一种简单高效的制备途径，且以此方法制备的多孔材料形状及结构可控，因而引起了人们的广泛关注。本文聚焦于两亲嵌段共聚物稳定的高内相乳液及其所制备多孔聚合物的最新研究进展。同时，介绍了该类型多孔聚合物材料在吸附分离、生物医学、能量存储及催化材料等领域的应用。最后，对该领域的未来发展进行了展望。

关键词: 高内相乳液, 聚合, 两亲嵌段共聚物, 多孔聚合物材料, 产品工程

CLC Number:

TQ 317

Jinjin LI, You WU, Yinning ZHOU, Zhenghong LUO. Progress in preparation and application of amphiphilic block copolymer stabilized high internal phase emulsion templates[J]. CIESC Journal, 2021, 72(11): 5443-5454.

李锦锦, 吴优, 周寅宁, 罗正鸿. 两亲嵌段共聚物基高内相乳液模板的制备与应用研究进展[J]. 化工学报, 2021, 72(11): 5443-5454.

Figures/Tables 9

Fig.1 Synthesis of polyHIPE from stable HIPE templating[12]: HIPE stabilizers (a); emulsification method of HIPE (b); schematic representation for the preparation of polyHIPE and its interconnected porous structure (c)

Fig.2 Pluronic triblock copolymer: molecular structure of the copolymer (left) and the pluronic grid (right; colour code: physical state of copolymers under ambient conditions, green — liquid, red — paste, orange — flake) [25-26]

Fig.3 Preparation of BCP-based polyHIPEs and their amphiphilic uptakes[35]: a scheme illustrating the synthesis of polyHIPE through the polymerization of a reactive BCP in an O/W emulsion (a); typical porous structure (SEM) (b); comparison of dry polyHIPE sample with samples that underwent equilibrium swelling in a liquid (c)

Fig.4 Mechanism of di-block copolymer based polyHIPE surface functionalization[41]: optical micrograph of HIPE (a); SEM image of polyHIPE (b); HIPEs stabilized by di-block copolymers as surfactants can be surface functionalized through physical or chemical entanglement compared to low molecular weight surfactants (c)

Fig.5 Structure of star polymer, its stabilizing mechanism at oil-water interface and the as-prepared polyHIPE[50]

Fig.6 The proposed adsorption mechanism for the anionic OII and RB-19 dyes using polyHIPE as adsorbent[31]

Fig.7 Significance of the interconnectivity on scaffold design[54]: scaffolds that are implanted to the defect site (a); difference of cell penetration in the scaffold with low and interconnectivity (b); SEM image of the PCL-polyHIPE that shows tissue infiltration through the interconnected pores of the scaffold (c)

Fig.8 Stretchable battery with polyHIPE separator[74]

Fig.9 Macroporous poly(ionic liquid) monolith catalysts for transesterification and decarboxylation[75]

References 80

1	Tan L, Tan B. Hypercrosslinked porous polymer materials: design, synthesis, and applications[J]. Chemical Society Reviews, 2017, 46(11): 3322-3356.
2	de France K J, Xu F, Hoare T. Structured macroporous hydrogels: progress, challenges, and opportunities[J]. Advanced Healthcare Materials, 2018, 7(1): 1700927.
3	Wu J L, Xu F, Li S M, et al. Porous polymers as multifunctional material platforms toward task-specific applications[J]. Advanced Materials, 2019, 31(4): 1802922.
4	Zhang A, Bai H, Li L. Breath figure: a nature-inspired preparation method for ordered porous films[J]. Chemical Reviews, 2015, 115(18): 9801-9868.
5	Li C, Li Q, Kaneti Y V, et al. Self-assembly of block copolymers towards mesoporous materials for energy storage and conversion systems[J]. Chemical Society Reviews, 2020, 49(14): 4681-4736.
6	Silverstein M S. PolyHIPEs: recent advances in emulsion-templated porous polymers[J]. Progress in Polymer Science, 2014, 39(1): 199-234.
7	Zhang H F, Cooper A I. Synthesis and applications of emulsion-templated porous materials[J]. Soft Matter, 2005, 1(2): 107.
8	Zhang T, Sanguramath R A, Israel S, et al. Emulsion templating: porous polymers and beyond[J]. Macromolecules, 2019, 52(15): 5445-5479.
9	Cameron N R, Sherrington D C. High internal phase emulsions (HIPEs) — structure, properties and use in polymer preparation[M]//Biopolymers Liquid Crystalline Polymers Phase Emulsion. Berlin, Heidelberg: Springer Berlin Heidelberg, 1996: 163-214.
10	Silverstein M S. Emulsion-templated porous polymers: a retrospective perspective[J]. Polymer, 2014, 55(1): 304-320.
11	Silverstein M S. Emulsion-templated polymers: contemporary contemplations[J]. Polymer, 2017, 126: 261-282.
12	Moon S, Kim J Q, Kim B Q, et al. Processable composites with extreme material capacities: toward designer high internal phase emulsions and foams[J]. Chemistry of Materials, 2020, 32(11): 4838-4854.
13	Kramer S, Cameron N R, Krajnc P. Porous polymers from high internal phase emulsions as scaffolds for biological applications[J]. Polymers, 2021, 13(11): 1786.
14	Pulko I, Krajnc P. High internal phase emulsion templating - a path to hierarchically porous functional polymers[J]. Macromolecular Rapid Communications, 2012, 33(20): 1731-1746.
15	Kimmins S D, Cameron N R. Functional porous polymers by emulsion templating: recent advances[J]. Advanced Functional Materials, 2011, 21(2): 211-225.
16	Cameron N R, Sherrington D C, Albiston L, et al. Study of the formation of the open-cellular morphology of poly(styrene/divinylbenzene) polyHIPE materials by cryo-SEM[J]. Colloid and Polymer Science, 1996, 274(6): 592-595.
17	Menner A, Bismarck A. New evidence for the mechanism of the pore formation in polymerising high internal phase emulsions or why polyHIPEs have an interconnected pore network structure[J]. Macromolecular Symposia, 2006, 242(1): 19-24.
18	Luo Y W, Wang A N, Gao X. Pushing the mechanical strength of polyHIPEs up to the theoretical limit through living radical polymerization[J]. Soft Matter, 2012, 8(6): 1824-1830.
19	Luo Y W, Wang A N, Gao X. Miniemulsion template polymerization to prepare a sub-micrometer porous polymeric monolith with an inter-connected structure and very high mechanical strength[J]. Soft Matter, 2012, 8(29): 7547.
20	Ikem V, Menner A, Bismarck A. High internal phase emulsions stabilized solely by functionalized silica particles[J]. Angewandte Chemie International Edition, 2009, 48(4): 632.
21	Yang L, Liu Y, Filipe C D M, et al. Development of a highly sensitive, broad-range hierarchically structured reduced graphene oxide/polyHIPE foam for pressure sensing[J]. ACS Applied Materials & Interfaces, 2019, 11(4): 4318-4327.
22	Jiao B, Shi A M, Wang Q, et al. High-internal-phase Pickering emulsions stabilized solely by peanut-protein-isolate microgel particles with multiple potential applications[J]. Angewandte Chemie, 2018, 130(30): 9418-9422.
23	Zhu H, Lei L, Li B G, et al. Development of novel materials from polymerization of Pickering emulsion templates[M]//Pauer W. Polymer Reaction Engineering of Dispersed Systems. Advances in Polymer Science. Cham: Springer, 2017, 280: 101-119.
24	Ikem V O, Menner A, Horozov T S, et al. Highly permeable macroporous polymers synthesized from Pickering medium and high internal phase emulsion templates[J]. Advanced Materials, 2010, 22(32): 3588-3592.
25	Alexandridis P, Alan Hatton T. Poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure, dynamics, and modeling[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1995, 96(1/2): 1-46.
26	Pitto-Barry A, Barry N P E. Pluronic^® block-copolymers in medicine: from chemical and biological versatility to rationalisation and clinical advances[J]. Polym. Chem., 2014, 5(10): 3291-3297.
27	Utroša P, Onder O C, Žagar E, et al. Shape memory behavior of emulsion-templated poly(ε-caprolactone) synthesized by organocatalyzed ring-opening polymerization[J]. Macromolecules, 2019, 52(23): 9291-9298.
28	Parın F N, Mert E H. Hydrophilic closed-cell macroporous foam preparation by emulsion templating[J]. Materials Letters, 2020, 277: 128287.
29	Jurjevec S, Debuigne A, Žagar E, et al. An environmentally benign post-polymerization functionalization strategy towards unprecedented poly(vinylamine) polyHIPEs[J]. Polymer Chemistry, 2021, 12(8): 1155-1164.
30	Zhang T, Gui H G, Xu Z G, et al. Hydrophobic polyurethane polyHIPEs templated from mannitol within nonaqueous high internal phase emulsions for oil spill recovery[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2019, 57(12): 1315-1321.
31	Makrygianni M, Christofili A, Deimede V. Emulsion-templated macroporous ammonium based polymers: synthesis and dye adsorption study[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 610: 125634.
32	Jurjevec S, Žagar E, Kovačič S. Functional macroporous amphoteric polyelectrolyte monoliths with tunable structures and properties through emulsion-templated synthesis[J]. Journal of Colloid and Interface Science, 2020, 575: 480-488.
33	Zhang T, Li X M, Wang W J, et al. Interface-initiated polymerization enables one-pot synthesis of hydrophilic and oleophobic foams through emulsion templating[J]. Macromolecular Rapid Communications, 2019, 40(21): 1900288.
34	Jiang B, Zhang T, Xu Z G, et al. Wet-spun porous fibers from high internal phase emulsions: continuous preparation and high stretchability[J]. Journal of Polymer Science, 2021, 59(11): 1055-1064.
35	Zhang T, Silverstein M S. Microphase-separated macroporous polymers from an emulsion-templated reactive triblock copolymer[J]. Macromolecules, 2018, 51(10): 3828-3835.
36	Zhang T, Silverstein M S. Robust, highly porous hydrogels templated within emulsions stabilized using a reactive, crosslinking triblock copolymer[J]. Polymer, 2019, 168: 146-154.
37	Wang Y K, Wan X Z, He J X, et al. A one-step fabrication and modification of HIPE-templated fluoro-porous polymer using PEG-b-PHFBMA macrosurfactant[J]. Journal of Materials Science, 2020, 55(12): 4970-4986.
38	Azhar U, Zong C Y, Wan X Z, et al. Methyl methacrylate HIPE solely stabilized by fluorinated di-block copolymer for fabrication of highly porous and interconnected polymer monoliths[J]. Chemistry - A European Journal, 2018, 24(45): 11619-11626.
39	Azhar U, Yaqub R, Li H T, et al. Di-block copolymer stabilized methyl methacrylate based polyHIPEs: influence of hydrophilic and hydrophobic co-monomers on morphology, wettability and thermal properties[J]. Arabian Journal of Chemistry, 2020, 13(2): 3801-3816.
40	Wu Y, Zhou Y N, Xu Q J, et al. Porous PS- and PMMA-based polymeric monoliths prepared by PEO-PS block copolymers stabilized high internal phase emulsion templates[J]. Materials Today Communications, 2021, 26: 101962.
41	Viswanathan P, Johnson D W, Hurley C, et al. 3D surface functionalization of emulsion-templated polymeric foams[J]. Macromolecules, 2014, 47(20): 7091-7098.
42	Mathieu K, Jérôme C, Debuigne A. Influence of the macromolecular surfactant features and reactivity on morphology and surface properties of emulsion-templated porous polymers[J]. Macromolecules, 2015, 48(18): 6489-6498.
43	Azhar U, Huyan C X, Wan X Z, et al. A cationic fluorosurfactant for fabrication of high-performance fluoropolymer foams with controllable morphology[J]. Materials & Design, 2017, 124: 194-202.
44	Cameron N R. High internal phase emulsion templating as a route to well-defined porous polymers[J]. Polymer, 2005, 46(5): 1439-1449.
45	Li Z C, Liu H R, Zeng L, et al. The facile synthesis of PMMA polyHIPEs with highly interconnected porous microstructures[J]. Journal of Materials Science, 2016, 51(19): 9005-9018.
46	Lei M, Peng Z H, Dong Q, et al. A novel capsular tension ring as local sustained-release carrier for preventing posterior capsule opacification[J]. Biomaterials, 2016, 89: 148-156.
47	Khodabandeh A, Arrua R D, Mansour F R, et al. PEO-based brush-type amphiphilic macro-RAFT agents and their assembled polyHIPE monolithic structures for applications in separation science[J]. Scientific Reports, 2017, 7: 7847.
48	Gui H G, Guan G W, Zhang T, et al. Microphase-separated, hierarchical macroporous polyurethane from a nonaqueous emulsion-templated reactive block copolymer[J]. Chemical Engineering Journal, 2019, 365: 369-377.
49	Li W W, Yu Y, Lamson M, et al. PEO-based star copolymers as stabilizers for water-in-oil or oil-in-water emulsions[J]. Macromolecules, 2012, 45(23): 9419-9426.
50	Horowitz R, Lamson M, Cohen O, et al. Highly efficient and tunable miktoarm stars for HIPE stabilization and polyHIPE synthesis[J]. Polymer, 2021, 217: 123444.
51	Li C H, Weng S Q, Jin M, et al. Dendritic macrosurfactant assembly for physical functionalization of HIPE-templated polymers[J]. Polymers, 2020, 12(4): 779.
52	Feng Y Y, Wan Y J, Jin M, et al. Large-scale preparation of a 3D patchy surface with dissimilar dendritic amphiphiles[J]. Soft Matter, 2018, 14(6): 1043-1049.
53	Li C H, Jin M, Wan D C. Evolution of a radical-triggered polymerizing high internal phase emulsion into an open-cellular monolith[J]. Macromolecular Chemistry and Physics, 2019, 220(16): 1900216.
54	Aldemir D B, Claeyssens F. Basic principles of emulsion templating and its use as an emerging manufacturing method of tissue engineering scaffolds[J]. Frontiers in Bioengineering and Biotechnology, 2020, 8: 875.
55	Zhu Y F, Wang W B, Yu H, et al. Preparation of porous adsorbent via Pickering emulsion template for water treatment: a review[J]. Journal of Environmental Sciences, 2020, 88: 217-236.
56	Taylor-Pashow K M L, Pribyl J G. PolyHIPEs for separations and chemical transformations: a review[J]. Solvent Extraction and Ion Exchange, 2019, 37(1): 1-26.
57	Zhang T, Silverstein M S. Highly porous, emulsion-templated, zwitterionic hydrogels: amplified and accelerated uptakes with enhanced environmental sensitivity[J]. Polymer Chemistry, 2018, 9(25): 3479-3487.
58	Gui H G, Zhang T, Guo Q P. Nanofibrous, emulsion-templated syndiotactic polystyrenes with superhydrophobicity for oil spill cleanup[J]. ACS Applied Materials & Interfaces, 2019, 11(39): 36063-36072.
59	Li X M, Zhang T, Xu Z G, et al. Amphiphobic polyHIPEs with pH-triggered transition to hydrophilicity–oleophobicity for the controlled removal of water from oil–water mixtures[J]. Polymer Chemistry, 2020, 11(43): 6935-6943.
60	Yang X C, Yin Z Q, Zhang X Y, et al. Fabrication of emulsion-templated macroporous poly(ε-caprolactone) towards highly effective and sustainable oil/water separation[J]. Polymer, 2020, 204: 122852.
61	Golub D, Krajnc P. Emulsion templated hydrophilic polymethacrylates. Morphological features, water and dye absorption[J]. Reactive and Functional Polymers, 2020, 149: 104515.
62	Zhu J J, Wu L B, Bu Z Y, et al. Synthesis and CO₂ capture behavior of porous cross-linked polymers containing pendant triazole groups[J]. Industrial & Engineering Chemistry Research, 2017, 56(36): 10155-10163.
63	Zhu J J, Wu L B, Bu Z Y, et al. Polyethylenimine-grafted HKUST-type MOF/PolyHIPE porous composites (PEI@PGD-H) as highly efficient CO₂ adsorbents[J]. Industrial & Engineering Chemistry Research, 2019, 58(10): 4257-4266.
64	Ingavle G, Vaidya A, Kale V. Constructing three-dimensional microenvironments using engineered biomaterials for hematopoietic stem cell expansion[J]. Tissue Engineering Part B, Reviews, 2019, 25(4): 312-329.
65	Busby W, Cameron N R, Jahoda C A B. Emulsion-derived foams (polyHIPEs) containing poly(ε-caprolactone) as matrixes for tissue engineering[J]. Biomacromolecules, 2001, 2(1): 154-164.
66	Yadav A, Pal J, Nandan B, et al. Macroporous scaffolds of cross-linked poly(ɛ-caprolactone) via high internal phase emulsion templating[J]. Polymer, 2019, 176: 66-73.
67	Busby W, Cameron N R, Jahoda C A. Tissue engineering matrixes by emulsion templating[J]. Polymer International, 2002, 51(10): 871-881.
68	Pérez-García M G, Gutiérrez M C, Mota-Morales J D, et al. Synthesis of biodegradable macroporous poly(l-lactide)/poly(ε-caprolactone) blend using oil-in-eutectic-mixture high-internal-phase emulsions as template[J]. ACS Applied Materials & Interfaces, 2016, 8(26): 16939-16949.
69	Wang L W, Liu Y J, Bao L, et al. Preparation of acrylamide-based poly-HIPEs with enhanced mechanical strength using PVDBM-b-PEG-emulsified CO₂ -in-water emulsions[J]. Journal of Applied Polymer Science, 2018, 135(23): 46346.
70	Corti M, Calleri E, Perteghella S, et al. Polyacrylate/polyacrylate-PEG biomaterials obtained by high internal phase emulsions (HIPEs) with tailorable drug release and effective mechanical and biological properties[J]. Materials Science and Engineering: C, 2019, 105: 110060.
71	Gui H G, Zhang T, Guo Q P. Closed-cell, emulsion-templated hydrogels for latent heat storage applications[J]. Polymer Chemistry, 2018, 9(29): 3970-3973.
72	Zhang T, Xu Z G, Chi H J, et al. Closed-cell, phase change material-encapsulated monoliths from a reactive surfactant-stabilized high internal phase emulsion for thermal energy storage[J]. ACS Applied Polymer Materials, 2020, 2(7): 2578-2585.
73	Zhang T, Xu Z G, Li X M, et al. Closed-cell, phase change material-encapsulated, emulsion-templated monoliths for latent heat storage: flexibility and rapid preparation[J]. Applied Materials Today, 2020, 21: 100831.
74	Danninger D, Hartmann F, Paschinger W, et al. Stretchable polymerized high internal phase emulsion separators for high performance soft batteries[J]. Advanced Energy Materials, 2020, 10(19): 2000467.
75	Stiernet P, Aqil A, Zhu X M, et al. Multicomponent radziszewski emulsion polymerization toward macroporous poly(ionic liquid) catalysts[J]. ACS Macro Letters, 2020, 9(1): 134-139.
76	Mravljak R, Bizjak O, Božič B, et al. Flow-through polyHIPE silver-based catalytic reactor[J]. Polymers, 2021, 13(6): 880.
77	Foudazi R. HIPEs to polyHIPEs[J]. Reactive and Functional Polymers, 2021, 164: 104917.
78	Aldemir D B, Dikici S, Reilly G C, et al. A novel bilayer polycaprolactone membrane for guided bone regeneration: combining electrospinning and emulsion templating[J]. Materials, 2019, 12(16): 2643.
79	Li J J, Zhou Y N, Luo Z H, et al. Engineering bicontinuous polymeric monoliths through high internal phase emulsion templating[J]. Materials Today Communications, 2020, 22: 100813.
80	Wenger L, Radtke C P, Göpper J, et al. 3D-printable and enzymatically active composite materials based on hydrogel-filled high internal phase emulsions[J]. Frontiers in Bioengineering and Biotechnology, 2020, 8: 713.

[1]	Dian LIN, Guomei JIANG, Xiubin XU, Bo ZHAO, Dongmei LIU, Xu WU. Preparation and drag reduction effect of silicon-based liquid-like anti-crude-oil-adhesion coatings [J]. CIESC Journal, 2023, 74(8): 3438-3445.
[2]	Ao ZHANG, Yingwu LUO. Low modulus, high elasticity and high peel adhesion acrylate pressure sensitive adhesives [J]. CIESC Journal, 2023, 74(7): 3079-3092.
[3]	Xinyuan WU, Qilei LIU, Boyuan CAO, Lei ZHANG, Jian DU. Group2vec: group vector representation and its property prediction applications based on unsupervised machine learning [J]. CIESC Journal, 2023, 74(3): 1187-1194.
[4]	Xueting ZHANG, Jijiang HU, Jing ZHAO, Bogeng LI. Preparation of high molecular weight polypropylene glycol in microchannel reactor [J]. CIESC Journal, 2023, 74(3): 1343-1351.
[5]	Zhiyuan JIN, Guorong SHAN, Pengju PAN. Preparation and heat and salt resistance of AM/AMPS/SSS terpolymer [J]. CIESC Journal, 2023, 74(2): 916-923.
[6]	Wangkai XIANG, Yuanyuan LIU, Ying ZHENG, Pengju PAN. Preparation of medium- and high-molecular-weight poly(glycolic acid) by melt/solid-state polycondensation [J]. CIESC Journal, 2023, 74(2): 933-940.
[7]	Yuxiao LI, Qingyue WANG, Khak Ho LIM, Xiaohui LI, Erlita MASTAN, Bo PENG, Wenjun WANG. Characterization technique for kinetic coefficients of free radical polymerization [J]. CIESC Journal, 2023, 74(2): 559-570.
[8]	Yajing ZHAO, Jijiang HU, Suyun JIE, Bo-Geng LI. Modification of unsaturated polyester resin by HTPB: effect of introducing method of the rubber [J]. CIESC Journal, 2023, 74(2): 883-892.
[9]	Jianing LIU, Jiahao MA, Junying ZHANG, Jue CHENG. Construction and properties of sequential dual thermal curing thiol-acrylate-epoxy 3D network [J]. CIESC Journal, 2022, 73(9): 4173-4186.
[10]	Xiaobing JU, Xuechun LI, Fang SUN. Effect on dithiosalicylic acid derivative on properties of photocuring materials [J]. CIESC Journal, 2022, 73(9): 4187-4193.
[11]	Xuesong WANG, Xiangyu ZENG, Cuimei BO, Shuqi TANG, Chao DONG, Jun LI, Quanling ZHANG, Xiaoming JIN, Shengli YE. Dynamic economic optimal control for PTFE batch polymerization process with free terminal [J]. CIESC Journal, 2022, 73(9): 3973-3982.
[12]	Hongxin YANG, Xingya LI, Liang GE, Tongwen XU. Preparation of mono-/divalent anion permselective membranes with piperidinium-type long side-chain [J]. CIESC Journal, 2022, 73(8): 3739-3748.
[13]	Zhemiao YU, Zhi WANG, Menglong SHENG, Guangyu XING, Jixiao WANG. Preparation of ZIF-90/polyamide mixed matrix membrane with N₂ preferential permeation for CH₄ purification based on interfacial polymerization [J]. CIESC Journal, 2022, 73(7): 3273-3286.
[14]	Wentao LI, Huijuan LIN, Hai ZHONG. LiF-rich SEI generated by in-situ gel polymer electrolyte process for lithium metal rechargeable batteries [J]. CIESC Journal, 2022, 73(7): 3240-3250.
[15]	Xiaoqiang FAN, Zhengliang HUANG, Jingyuan SUN, Jingdai WANG, Xiaofei WANG, Xiaobo HU, Guodong HAN, Yongrong YANG, Wenqing WU. Development of cloudy gas-liquid fluidized bed ethylene polymerization process and high performance products [J]. CIESC Journal, 2022, 73(6): 2742-2747.