小分子外交联法制备超高交联聚苯乙烯血液灌流吸附剂

doi:10.11949/0438-1157.20241118

化工学报 ›› 2025, Vol. 76 ›› Issue (6): 3093-3103.DOI: 10.11949/0438-1157.20241118

• 材料化学工程与纳米技术 • 上一篇下一篇

小分子外交联法制备超高交联聚苯乙烯血液灌流吸附剂

彭新艳¹(), 刘云鸿¹(), 陈凌宇¹^,², 韦跃兰¹, 陈淑琴¹, 胡柱东³

^1.泉州师范学院化工与材料学院，福建泉州 362000
^2.福建师范大学化学与材料学院，福建福州 350007
^3.佛山大学材料与能源学院，广东佛山 528000

收稿日期:2024-10-09 修回日期:2024-12-03 出版日期:2025-06-25 发布日期:2025-07-09
通讯作者: 刘云鸿
作者简介:彭新艳（1985—），女，博士，副教授，pengxinyan@qztc.edu.cn
基金资助:
国家自然科学基金项目(82100793);福建省自然科学基金项目(2020J05152);福建省自然科学基金项目(2020J05153);福建省自然科学基金项目(2021J05181);泉州市科技计划项目(2021C023R)

Preparation of hypercrosslinked polystyrene hemosorbents based on small-molecule external cross-linkers

Xinyan PENG¹(), Yunhong LIU¹(), Lingyu CHEN¹^,², Yuelan WEI¹, Shuqin CHEN¹, Zhudong HU³

^1.College of Chemical Engineering and Materials Science, Quanzhou Normal University, Quanzhou 362000, Fujian, China
^2.College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, Fujian, China
^3.Schoolof Materials Science and Energy Engineering, Foshan University, Foshan 528000, Guangdong, China

Received:2024-10-09 Revised:2024-12-03 Online:2025-06-25 Published:2025-07-09
Contact: Yunhong LIU

摘要/Abstract

摘要：

超高交联聚苯乙烯树脂可作为血液灌流吸附剂，在临床血液灌流疾病治疗领域发挥重要作用。然而，目前临床使用的超高交联聚苯乙烯树脂，存在制备过程烦琐、毒性大等问题，有待进一步地改进和优化。采用二甲氧基甲烷（FDA）和二乙氧基甲烷（DTM）两种不同外交联剂对预交联聚苯乙烯微球P(St-DVB)进行一步法外交联反应，制备出超高交联聚苯乙烯吸附树脂HCP-FDA和HCP-DTM。利用红外光谱、光电子能谱、扫描电子显微镜及气体吸附法等表征了吸附树脂的化学结构和微观孔结构。结果表明，小分子外交联剂可有效实现树脂内部的化学交联，所制备的HCP-FDA和HCP-DTM具有多级层次分布的三维纳米网络结构。吸附实验结果表明，所制备的HCP-FDA和HCP-DTM对尿毒症中大分子毒素具有优异的吸附性能，同时，展示出较好的血液相容性，有望作为一种全血灌流吸附剂，为临床尿毒症血液灌流净化治疗提供新型技术方案。

关键词: 小分子外交联剂, 超高交联树脂, 血液灌流, 吸附性能, 血液相容性

Abstract:

As a promising blood perfusion adsorbent, hypercrosslinked polystyrene resin plays an important role in the field of blood purification. However, the hypercrosslinked polystyrene resin currently used in clinical practice has problems such as cumbersome preparation process and high toxicity, which need to be further improved and optimized. In this study, the hypercrosslinked polystyrene resins named HCP-FDA and HCP-DTM were prepared through one-step Friedel-Crafts post-crosslinking reaction of pre-crosslinked polystyrene microspheres named P(St-DVB), using two types of small-molecule external crosslinkers with different molecular weight. The chemical structure and micropore structure of the adsorption resins were characterized by FTIR, XPS, SEM, and BET measurements. The results show that the small-molecule external cross-linking agent can effectively construct chemical cross-linking in the resin, and the prepared HCP-FDA and HCP-DTM have a three-dimensional multilevel (hierarchical) nanonetwork structure. Adsorption experiments show that the prepared HCP-FDA and HCP-DTM have excellent adsorption performance towards medium-to large-molecular-weight uremic toxins, coupled with good blood compatibility. They are expected to serve as novel whole blood perfusion adsorbents, providing a new technical solution for clinical blood perfusion purification therapy in uremia.

Key words: small-molecule external crosslinkers, hypercrosslinked resin, hemoperfusion, adsorption performance, blood compatibility

中图分类号:

O 631

彭新艳, 刘云鸿, 陈凌宇, 韦跃兰, 陈淑琴, 胡柱东. 小分子外交联法制备超高交联聚苯乙烯血液灌流吸附剂[J]. 化工学报, 2025, 76(6): 3093-3103.

Xinyan PENG, Yunhong LIU, Lingyu CHEN, Yuelan WEI, Shuqin CHEN, Zhudong HU. Preparation of hypercrosslinked polystyrene hemosorbents based on small-molecule external cross-linkers[J]. CIESC Journal, 2025, 76(6): 3093-3103.

图/表 10

图1 (a)HCP-FAD和HCP-DTM的合成路线示意图；(b)基于FDA傅克烷基化的反应机理

Fig.1 (a) Schematic diagram of the route to fabricate the HCP-FAD and HCP-DTM; (b) The possible mechanism of Friedel-Crafts reactions based on FDA crosslinker

图2 样品的光学显微照片

Fig.2 Optical microscopy micrographs of the beads

图3 不同样品的SEM图片：(a) P(St-DVB)；(b) HCP-FDA；(c) HCP-DTM（中间为样品表面，右侧为样品横截面）

Fig.3 SEM images of (a) P(St-DVB), (b) HCP-FDA and (c) HCP-DTM (middle are the surface zone, right are the cross-section zone)

图4 P(St-DVB)、HCP-FDA和HCP-DTM样品的氮气吸附脱附曲线(a)和孔径分布情况(b)

Fig.4 N2 adsorption-desorption isotherms (a), micropore size distributions (b) of P(St-DVB), HCP-FDA and HCP-DTM calculated by the NLDFT method

表1 P（St-DVB）、HCP-FDA和HCP-DTM树脂的孔结构参数

Table 1 Textural properties of P（St-DVB）， HCP-FDA and HCP-DTM

Sample			P(St-DVB)	HCP-FDA	HCP-DTM
specific surface area/(m²/g)	S_BET		102	738	625
	S_micro（0.35~2.00）		0	501	417
	S_meso	2~10	58	281	244
	S_meso	10~50	58	86	62
	S_macro（50~100）		9	4	16
pore volume/(cm³/g)	V_P		0.5212	1.0522	0.9101
	V_micro（0.35~2.00）		0	0.2182	0.1789
	V_meso	2~10	0.0540	0.2254	0.1880
	V_meso	10~50	0.3342	0.5629	0.3433
	V_macro（50~100）		0.1304	0.0854	0.2355
Average pore size/nm			20.45	5.70	5.82

图5 P(St-DVB)、HCP-DTM和HCP-FDA样品的红外光谱图(a)和在水中的润湿情况(b)

Fig.5 FTIR spectra (a) and water wettability (b) of P(St-DVB), HCP-DTM and HCP-FDA

图6 (a) P(St-DVB)、HCP-DTM和HCP-FDA样品的XPS谱图；(b) O 1s区域局部放大图；(c) HCP-FDA的O 1s XPS谱图；(d) HCP-DTM的O 1s XPS谱图

Fig.6 (a)Survey XPS spectra of P(St-DVB), HCP-DTM and HCP-FDA; (b) Highly magnified micrographs of the O 1s regions; (c) O 1s XPS spectra of HCP-FDA; (d) O 1s XPS spectra of HCP-DTM

图7 HCP-FDA、HCP-DTM和商用树脂HA在人血浆环境中对PTH和β2-MG(a)、IL-6和TNF-α(b)毒素的吸附率

Fig.7 Adsorption rate of HCP-FDA, HCP-DTM and commercial HA resin for PTH and β2-MG(a), IL-6 and TNF-α(b) in the human plasma with the treatment time of 2 h

图8 树脂样品和对照样品的溶血率[(+)表示去离子水, (-) PBS表示溶液]

Fig.8 Hemolysis ratio test of the controls and adsorbents [(+) is deionized water, (-) is PBS solution]

图9 树脂样品和对照样品的复钙时间[(+)表示亲水玻璃珠，(-)表示空试管]

Fig.9 Recalcification time of the adsorbents and controls [ (+) is hydrophilic glass beads, (-) is blank tube]

参考文献 30

[1]	Rahnama Haratbar P, Nasiri M, Ghaemi A. Hypercrosslinked polystyrene-based adsorbents for the removal of lead ions from aqueous effluents: experimental and RSM modeling[J]. Iranian Polymer Journal, 2023, 32(7): 929-946.
[2]	Huang J, Turner S R. Hypercrosslinked polymers: a review[J]. Polymer Reviews, 2018, 58(1): 1-41.
[3]	Masoumi H, Ghaemi A, Ghanadzadeh Gilani H. Experimental and RSM study of hypercrosslinked polystyrene in elimination of lead, cadmium and nickel ions in single and multi-component systems[J]. Chemical Engineering Research and Design, 2022, 182: 410-427.
[4]	Liao Q, Kim E J, Tang Y X, et al. Rational design of hyper-crosslinked polymers for biomedical applications[J]. Journal of Polymer Science, 2024, 62(8): 1517-1535.
[5]	Liu Q Q, Xia B J, Huang J, et al. Hypercrosslinked polystyrene microspheres with ultrahigh surface area and their application in gas storage[J]. Materials Chemistry and Physics, 2017, 199: 616-622.
[6]	Liu Y H, Peng X Y. Multi-functional hypercrosslinked polystyrene as high-performance adsorbents for artificial liver blood purification[J]. Frontiers in Chemistry, 2022, 9: 789814.
[7]	潘鹏飞, 宋云林, 李文哲, 等. 血液吸附技术在脓毒症中的应用进展[J]. 重庆医学, 2019, 48(14): 2451-2454.
	Pan P F, Song Y L, Li W Z, et al. Application of blood adsorption technologies in sepsis[J]. Chongqing Medicine, 2019, 48(14): 2451-2454.
[8]	Magomedov M A, Kim T G, Masolitin S V, et al. Use of sorbent based on hypercrosslinked styrene-divinylbenzene copolymer with immobilized LPS-selective ligand in hemoperfusion for treatment of patients with septic shock[J]. General Reanimatology, 2021, 16(6): 31-53.
[9]	Davankov V A, Tsyurupa M P. Structure and properties of hypercrosslinked polystyrene—the first representative of a new class of polymer networks[J]. Reactive Polymers, 1990, 13(1): 27-42.
[10]	Kirillov A S, Gorshkov N I, Shevchenko N N, et al. Tuning the porosity of hypercrosslinked styrene-divinylbenzene copolymers for efficient adsorption of rifampicin from aqueous media[J]. Journal of Polymer Research, 2023, 30(11): 405.
[11]	Peng X Q, Yang P P, Dai K, et al. Synthesis, adsorption and molecular simulation study of methylamine-modified hyper-cross-linked resins for efficient removal of citric acid from aqueous solution[J]. Scientific Reports, 2020, 10(1): 9623.
[12]	Ghanooni S, Karimi B, Nikfarjam N. Preparation of a dual-functionalized acid-base macroporous polymer via high internal phase emulsion templating as a reusable catalyst for one-pot deacetalization-henry reaction[J]. ACS Omega, 2022, 7(35): 30989-31002.
[13]	He Y H, Tao J J, Zhang X, et al. Facile synthesis of magnetic hyper-crosslinked porous polymer for efficient extraction and sensitive determination of nitroimidazole antibiotics[J]. Microchemical Journal, 2024, 200: 110285.
[14]	Zhou C C, Yan J, Cao Z N. Postcrosslinking of macroporous styrene-divinylbenzene copolymers via pendant vinyl groups: effect of the starting copolymers on the pore structure of the postcrosslinked products[J]. Journal of Applied Polymer Science, 2002, 83(8): 1668-1677.
[15]	Ghafari M, Atkinson J D. One-step hyper-cross-linking of porous styrenic polymers using dichloroalkane cross-linkers to maintain hydrophobicity[J]. Polymer, 2017, 116: 278-286.
[16]	Fu Z Y, Jia J Z, Li J, et al. Transforming waste expanded polystyrene foam into hyper-crosslinked polymers for carbon dioxide capture and separation[J]. Chemical Engineering Journal, 2017, 323: 557-564.
[17]	Castaldo R, Gentile G, Avella M, et al. Microporous hyper-crosslinked polystyrenes and nanocomposites with high adsorption properties: a review[J]. Polymers, 2017, 9(12): 651.
[18]	Dawson R, Stöckel E, Holst J R, et al. Microporous organic polymers for carbon dioxide capture[J]. Energy & Environmental Science, 2011, 4(10): 4239-4245.
[19]	Kewley A, Stephenson A, Chen L J, et al. Porous organic cages for gas chromatography separations[J]. Chemistry of Materials, 2015, 27(9): 3207-3210.
[20]	Slater A G, Cooper A I. Function-led design of new porous materials[J]. Science, 2015, 348(6238): eaaa8075.
[21]	Tan L X, Tan B E. Hypercrosslinked porous polymer materials: design, synthesis, and applications[J]. Chemical Society Reviews, 2017, 46(11): 3322-3356.
[22]	Liao G F, Zhong L, Cheung C S, et al. Direct synthesis of hypercrosslinked microporous poly(para-methoxystyrene) for removal of iron(Ⅲ) ion from aqueous solution[J]. Microporous and Mesoporous Materials, 2020, 307: 110469.
[23]	Li C, Che W, Liu S Y, et al. Hypercrosslinked microporous polystyrene: from synthesis to properties to applications[J]. Materials Today Chemistry, 2023, 29: 101392.
[24]	刘云鸿, 彭新艳. 新型蛋白结合类毒素血液灌流吸附剂的制备及吸附性能[J]. 高等学校化学学报, 2021, 42(6): 1952-1964.
	Liu Y H, Peng X Y. Preparation and property of a novel hemoperfusion adsorbent for protein-bound uremic toxins[J]. Chemical Journal of Chinese Universities, 2021, 42(6): 1952-1964.
[25]	Liu Y H, Peng X Y, Hu Z D, et al. Fabrication of a novel nitrogen-containing porous carbon adsorbent for protein-bound uremic toxins removal[J]. Materials Science & Engineering. C, Materials for Biological Applications, 2021, 121: 111879.
[26]	Li B Y, Gong R N, Wang W, et al. A new strategy to microporous polymers: knitting rigid aromatic building blocks by external cross-linker[J]. Macromolecules, 2011, 44(8): 2410-2414.
[27]	李发达, 徐媛媛, 于均超, 等. 超高交联树脂的氯代烷烃后交联法制备及对咖啡因的吸附研究[J]. 离子交换与吸附, 2022, 38(1): 48-59.
	Li F D, Xu Y Y, Yu J C, et al. Preparation of hypercrosslinked polystyrene via post-crosslinking by chloroalkanes and adsorption of caffeine[J]. Ion Exchange and Adsorption, 2022, 38(1): 48-59.
[28]	李发达. 超交联和极性修饰聚苯乙烯的制备及其对有机污染物的吸附研究[D]. 长沙: 湖南师范大学, 2021.
	Li F D. Study on preparation of hypercrosslinked and polar modified polystyrene and its adsorption of organic pollutants[D]. Changsha: Hunan Normal University, 2021.
[29]	Law R V, Sherrington D C, Snape C E, et al. Solid-state ¹³C MAS NMR studies of hyper-cross-linked polystyrene resins[J]. Macromolecules, 1996, 29(19): 6284-6293.
[30]	Malik D J, Webb C, Holdich R G, et al. Synthesis and characterization of size-selective nanoporous polymeric adsorbents for blood purification[J]. Separation and Purification Technology, 2009, 66(3): 578-585.

小分子外交联法制备超高交联聚苯乙烯血液灌流吸附剂

Preparation of hypercrosslinked polystyrene hemosorbents based on small-molecule external cross-linkers

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