可交联磷酰胆碱聚合物改性聚甲基戊烯中空纤维膜

叶非华; 易国斌

doi:10.13801/j.cnki.fhclxb.20200522.001

可交联磷酰胆碱聚合物改性聚甲基戊烯中空纤维膜

doi: 10.13801/j.cnki.fhclxb.20200522.001

叶非华^{1, 2,},
易国斌^1, ,

1.
广东工业大学　轻工化工学院，广州 510006
2.
广东顺德工业设计研究院(广东顺德创新设计研究院)，佛山 528300

基金项目: 广东省高校创新强校重大科研项目(2017KZDXM026)

详细信息

通讯作者:
易国斌，博士，教授，博士生导师，研究方向为功能高分子材料、纳米材料与复合材料　E-mail：yigb@gdut.edu.cn

中图分类号: TB332；TQ316.6
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出版历程
- 收稿日期: 2020-04-01
- 录用日期: 2020-05-19
- 网络出版日期: 2020-05-22
- 刊出日期: 2021-02-15

Cross-linkable phosphonylcholine polymer modified polymethylpentene hollow fiber membrane

YE Feihua^{1, 2
,},
YI Guobin^{1
, ,}

1.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China
2.
Guangdong Shunde Industrial Design Institute (Guangdong Shunde Innovative Design Institute), Foshan 528300, China

摘要

摘要: 通过自由基聚合反应制备了可交联磷酰胆碱聚合物(Poly(MPC-co-LMA-co-TSMA), PMLT)。将该聚合物溶液涂覆在聚甲基戊烯中空纤维膜(PMPHFM)表面，经交联处理后可形成稳定的PMLT聚合物涂层，得到改性复合材料PMLT/PMPHFM。溶胀度测试表明PMLT聚合物膜具有良好的亲水性能，且溶胀度随着2-甲基丙烯酰氧基乙基磷酰胆碱(MPC)含量和温度的升高而增大。ATR-FTIR和XPS分析表明PMLT/PMPHFM表面的PMLT聚合物涂层含有磷酰胆碱基团。SEM和荧光测试结果显示PMLT/PMPHFM表面包覆有均匀的聚合物涂层，且该涂层能够抵抗乙醇溶液和十二烷基硫酸钠溶液的溶解。血小板黏附和全血接触测试表明，相比空白PMPHFM，PMLT聚合物涂层能够显著减少PMPHFM表面的血小板黏附，降低血液凝结风险。研究结果表明：可交联磷酰胆碱聚合物PMLT具有良好的亲水性能，能够均匀涂覆在PMPHFM的表面，得到具有良好血液相容性的复合材料PMLT/PMPHFM。
- 磷酰胆碱聚合物 /
- 表面改性 /
- 聚甲基戊烯中空纤维膜(PMPHFM) /
- 涂层 /
- 血液相容性
Abstract: Cross-linkable phosphorylcholine polymer (Poly(MPC-co-LMA-co-TSMA), PMLT) was prepared by free radical polymerization. Coating the copolymer solution on the surface of polymethylpentene hollow fiber membrane (PMPHFM) can form a stable polymer coating after the cross-linking treatment and obtain a modified composite material PMLT/PMPHFM. The swelling test shows that the PMLT copolymer has good hydrophilic properties, and the swelling degree increases with the increase of MPC content and temperature. ATR-FTIR and XPS analysis show that the polymer coating containing phosphorylcholine groups exist on the surface of PMLT/PMPHFM. SEM and fluorescence test results show that the surface of PMLT/PMPHFM is coated with a uniform polymer coating, and the coating could resist the dissolution of ethanol and SDS aqueous solution. Platelet adhesion and whole blood contact tests show that the coating could reduce platelet adhesion on the surface of PMPHFM, reduce the risk of blood clotting compared to bare PMPHFM. The results show that the PMLT copolymer has good hydrophilic property, and can be uniformly coated on the surface of PMPHFM to obtain a composite material PMLT/PMPHFM with good blood compatibility.
- phosphorylcholine polymer /
- surface modification /
- polymethylpentene hollow fiber membrane (PMPHFM) /
- coating /
- blood compatibility

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图 1 Poly(MPC-co-LMA-co-TSMA)(PMLT)聚合物合成路线

Figure 1. Synthesis route of poly(MPC-co-LMA-co-TSMA) (PMLT) copolymers

MPC—2-methacryloyloxyethyl phosphorylcholine; LMA—Lauryl methacrylate; TSMA —3-(trimethoxysilyl)propyl methacrylate; AIBN—2,2-azo diisobutyronitrile; IPA—Isopropyl alcohol

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图 2 PMLT聚合物涂层交联反应机制

Figure 2. Cross-linking reaction scheme for PMLT polymer coating

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图 3 PMLT聚合物膜的含水量与溶胀时间和温度的关系

Figure 3. Relation between water content with time and temperature of PMLT copolymers

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图 4 聚甲基戊烯中空纤维膜(PMPHFM)和PMLT/PMPHFM复合材料的FTIR图谱

Figure 4. FTIR spectra of polymethylpentene hollow fiber membrane (PMPHFM) and PMLT/PMPHFM composite

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图 5 PMPHFM和PMLT/PMPHFM复合材料的XPS图谱

Figure 5. XPS spectra of PMPHFM and PMLT/PMPHFM composite

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图 6 PMPHFM和PMLT/PMPHFM复合材料表面的SEM图像

Figure 6. SEM images of PMPHFM and PMLT/PMPHFM composite surface

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图 7 PMPHFM和PMLT/PMPHFM复合材料的荧光显微镜图像

Figure 7. Fluorescence microscope images of PMPHFM and PMLT/PMPHFM composite(Visible light microscope images of bare PMPHFM (a) and PMLT/PMPHFM (b); (c) and (d) are the same images viewed in fluorescence mode; (e) and (f) are fluorescence images of PMLT/PMPHFM after treatment with 90vol% ethanol aqueous solution or mass fraction 1wt% sodium dodecyl sulfonate (SDS) aqueous solution)

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图 8 PMPHFM和PMLT/PMPHFM复合材料表面血小板黏附的SEM图像

Figure 8. SEM images of platelet adhesion on the surface of PMPHFM and PMLT/PMPHFM composite

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图 9 PMPHFM和PMLT/PMPHFM复合材料表面全血接触的SEM图像

Figure 9. SEM images of whole blood contact on the surface of PMPHFM and PMLT/PMPHFM composite

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表 1 PMLT聚合物单体投料比

Table 1. Monomer feed ratio of PMLT copolymers

Sample	Monomer feed mole mass fraction/wt%
Sample	MPC	LMA	TSMA
PMLT15	15	75	10
PMLT25	25	65	10
PMLT35	35	55	10
PMLT45	45	45	10

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表 2 室温下PMLT聚合物膜的平衡含水量(W_e)

Table 2. Equilibrium water content (W_e) of PMLT copolymers at room temperature

	PMLT15	PMLT25	PMLT35	PMLT45
W_e/%	17.37	44.79	51.11	68.45

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