化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能

doi:10.7503/cjcu20130935

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (4): 873.doi: 10.7503/cjcu20130935

化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能

张祺, 陆甦晖, 郑安呐(), 管涌, 危大福, 黄添华, 李书召()

华东理工大学材料科学与工程学院, 上海市先进聚合物材料重点实验室, 超细材料制备与应用教育部重点实验室, 上海 200237

收稿日期:2013-09-22 出版日期:2014-04-10 发布日期:2014-03-06
作者简介:联系人简介: 郑安呐, 男, 教授, 博士生导师, 主要从事高分子反应加工研究. E-mail: zan@ecust.edu.cn;李书召, 男, 博士, 讲师, 主要从事高分子树脂材料改性研究. E-mail: lsz@ecust.edu.cn
基金资助:
上海市自然科学基金(批准号: 13ZR1411400, 12ZR1407800)资助

Preparation and Characterization of Long-acting Antimicrobial Polyethylene Terephthalate via Covalent Bonding Method^†

ZHANG Qi, LU Suhui, ZHENG Anna^*(), GUAN Yong, WEI Dafu, HUANG Tianhua, LI Shuzhao^*()

School of Materials Science and Engineering, Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Received:2013-09-22 Online:2014-04-10 Published:2014-03-06
Contact: ZHENG Anna,LI Shuzhao E-mail:zan@ecust.edu.cn;lsz@ecust.edu.cn
Supported by:
† Supported by the Natural Science Foundation of Shanghai, China(No.13ZR1411400, 12ZR1407800)

摘要/Abstract

摘要：

通过化学反应将抗菌剂聚六亚甲基盐酸胍(PHMG)键合到聚对苯二甲酸乙二醇酯(PET)基体上, 制得抗菌剂质量分数为15% 的PET抗菌母料(PET-g-PHMG), PHMG与PET的键合效率达93.7%. 透射电子显微镜(TEM)结果表明, 化学键的键合作用提高了PHMG与PET的相容性, 使得极性的PHMG以纳米尺寸均匀分布在PET-g-PHMG 中. 在PET基体中添加少量PET-g-PHMG, 可制成不同抗菌剂含量的PET样品, 抗菌母料PET-g-PHMG的添加可抑制PET基体的降解, 提高抗菌PET样品的特性黏度. 所得抗菌PET样品对大肠杆菌和金黄色葡萄球菌的抑菌率均在99%以上, 即使反复水洗, 抗菌性能也无明显降低. 该抗菌PET样品具有良好的可纺性, 通过熔融纺丝可以制成抗菌PET纤维, 其抗菌性能具有耐水洗性, 抗菌动力学测试结果表明, 该抗菌PET样品对革兰氏阴性和阳性细菌还具有较快速的杀灭作用.

关键词: 聚对苯二甲酸乙二醇酯, 化学键合, 长效抗菌, 接枝改性, 胍盐抗菌剂

Abstract:

Polyhexamethylene guanidine hydrochloride(PHMG) was uesd to produce a long-acting antimicrobial polyethylene terephthalate(PET) masterbatch(PET-g-PHMG), which was obtained by covalently bonding 15% PHMG based on total weight onto PET matrix. Attributed to the higher grafting efficiency(93.7%), the hydrophilic PHGH is uniformly dispersed in PET matrix without any aggregate, which potentially enhances its antimicrobial activity. Several antimicrobial PET samples can be prepared by adding specific amount of PET-g-PHMG into the PET matrix. It was found that the addition of PET-g-PHMG did not cause the degradation of PET matrix, instead, increased the intrinsic viscosity because of the presence of some un-reactive functional groups in the PET-g-PHMG. The antimicrobial PET samples showed quickly and efficiently antimicrobial activity against both Gram-positive and Gram-negative bacteria. Furthermore, the antimicrobial activity of the antimicrobial PET fibers prepared by a spun-bonded method remained even after constant water washing for 10 d, indicating its long-acting antimicrobial ability via a contact activity rather than a release mechanism.

Key words: Polyethylene terephthalate, Covalent bonding, Long-acting antibacterial, Graft modification, Guanidine-based antimicrobial polymers polyhexamethylene guanidine hydrochloride

中图分类号:

O631

TrendMD:

张祺, 陆甦晖, 郑安呐, 管涌, 危大福, 黄添华, 李书召. 化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能. 高等学校化学学报, 2014, 35(4): 873.

ZHANG Qi, LU Suhui, ZHENG Anna, GUAN Yong, WEI Dafu, HUANG Tianhua, LI Shuzhao. Preparation and Characterization of Long-acting Antimicrobial Polyethylene Terephthalate via Covalent Bonding Method^†. Chem. J. Chinese Universities, 2014, 35(4): 873.

图/表 11

Scheme 1 Chemical structure of PHMG

Fig.1 1H NMR spectra of PHMG(A) and PHMG-e(B)

Scheme 2 Reaction scheme of producing PET-g-PHMG

Fig.2 Torque variations with time in Haake

Fig.3 FTIR spectra of PET/antibacterial masterbatch before and after extraction a. PET; b. PET-g-PHMG before extraction; c. PET-g-PHMG after extraction.

Fig.4 SEM images of fracture surface of PET/PHMG(A) and antibacterial PET with 1%PHMG(B)

Fig.5 TEM images of ultrathin section of PET/PHMG(A) and PET-g-PHMG(B)

Table 1 intrinsic viscosity test of PET samples

Sample	Content of antibacterial master batch(%)	PHMG content(%)	Processing temperature/℃	Intrinsic viscosity^*/(dL·g^-1)	Antibacterial rate(%)
Sample	Content of antibacterial master batch(%)	PHMG content(%)	Processing temperature/℃	Intrinsic viscosity^*/(dL·g^-1)	E.coli	S. aureus
PET		0	270	0.812	0	0
processed PET		0	270	0.694
PET-g-PHMG		15
PET-0.5	3.3	0.5	270	0.805	99.32	99.13
	3.3	0.5	300	0.725	99.02	99.17
PET-0.8	5.3	0.8	270	0.782	99.41	99.59
PET-1	6.7	1	270	0.749	99.94	99.98
PET/PHMG	0	1	270	0.579	61.59	36.11

Fig.6 Antibacterial performance of PET(A), PET/PHMG washed by water(B) and PET-0.5 washed by water(C) against Gram-Negative E.coli

Fig.7 Antibacterial performance against Gram-Negative E.coli of PET fibre(A) and antibcterial PET fibre(B)

Fig.8 Antimicrobial kinetics test of antimicrobial PET fibers against E.coli(a) and S.aureus(b)

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化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能

Preparation and Characterization of Long-acting Antimicrobial Polyethylene Terephthalate via Covalent Bonding Method^†

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化学键合法制备长效抗菌聚对苯二甲酸乙二醇酯材料及其性能

Preparation and Characterization of Long-acting Antimicrobial Polyethylene Terephthalate via Covalent Bonding Method†

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Preparation and Characterization of Long-acting Antimicrobial Polyethylene Terephthalate via Covalent Bonding Method^†