PHMG PET 93. 7%. TEM PHMG. PET-g-PHMG. PET PET PET PHMG. PET-g-PHMG PET PET 99%
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1 Vol 35 No CHEMICAL JOURNAL OF CHINESE UNIVERSITIES 873 ~ 880 doi /cjcu PHMG PET 15% PET PET-g-PHMG PHMG PET 93 7% TEM PHMG PET PHMG PET-g-PHMG PET PET-g-PHMG PET-g-PHMG PET PET PET 99% PET PET PET O631 A 1 2 ~ ~ ATRP PET PET 16 PHMG PHMG PHMG 24 PHMG PET ZR ZR zan@ ecust edu cn lsz@ ecust edu cn
2 874 Vol 35 PET PET PET PET PET PET PET 0 81 dl /g PHMG M n = 1000 DMF 8099 ATCC6538 Magna-IR550 FTIR Nicolet KBr 500 ~ 4000 cm - 1 JSM-6360LV SEM JEM-2100F200 kv TEM AVANCE Ⅲ 500 MHz 1 H NMR Spectrospin D 2 O 1 2 PHMG- PHMG-e PHMG Scheme ml 34 g PHMG 28 g 150 ml DMF PHMG 0 45 g 60 4 h 20 5 g 25 8 h Scheme 1 Chemical structure of PHMG DMF PHMG-e 1 3 PET-g-PHMG PET h 51 g PET 9 g PHMG-e PHMG-e 15% Haake Haake min PET PET-g-PHMG Haake 1 4 PET PET PET-g-PHMG h PET PET-g- PHMG Haake 0 5% 0 8% 1% PET PET-0 5 PET-0 8 PET-1 Haake min 1 5 PET PET-g-PHMG PET h MATE-Ⅴ Tokyo m /min 0 13 tex 1 6 GB /T g PET 75 ml cfu /ml h cfu /ml 0 1 ml h 5 Y Y = A - B /A 100% A B
3 No PHMG PHMG-e PHMG PHMG-e 1 H NMR 1 1 A δ 1 28 ~ 1 51 t CH 2 δ 2 61 ~ 2 66 PHMG m NH 2 δ 3 1 m CH 2 NH δ 4 7 t NH 1 B δ 2 61 ~ 2 66 m NH 2 δ 2 8 ~ 2 9 t CH CH 2 δ 3 2 s CH CH 2 δ 3 5 m CH 2 CH CH 2 PHMG-e Fig 1 1 H NMR spectra of PHMG A and PHMG-e B 2 2 PET PHMG-e Haake PET PHMG-e PHMG-e PET Scheme 2 Scheme 2 Reaction scheme of producing PET-g-PHMG 2 PET PHMG-e 2 PET 1 PET PHMG-e 1 1 min 1 PET PHMG-e Haake 2 PET PHMG-e PET-g-PHMG PET PET Fig 2 Torque variations with time in Haake PET PET-g-PHMG FTIR PET FTIR 3 a 1720 cm - 1 PET PET 3 b PET-g-PHMG 1640 cm PHMG C N PHMG PET-
4 876 Vol 35 g-phmg h PHMG PET PHMG 3 c PET-g-PHMG 1640 cm - 1 C N PHMG PET PHMG PET P P = 1 - m - m / m 15% 100% m Fig 3 FTIR spectra of PET / antibacterial masterbatch before and after extraction m a PET b PET-g-PHMG before extraction P = 93 7% c PET-g-PHMG after extraction 2 4 PET PHMG PET PET SEM 4 4 A PET /PHMG PET PHMG PET /PHMG PHMG PET PHMG PET 4 A 4 B PET-g-PHMG PHMG PET PHMG PET Fig 4 SEM images of fracture surface of PET /PHMG A and antibacterial PET with 1%PHMG B PHMG PET PET-g-PHMG TEM 5 PET /PHMG PET-g-PHMG OsO 4 TEM 5 A PET /PHMG PHMG PET 5 B PHMG PET PHMG PET PHMG PET PHMG Fig 5 TEM images of ultrathin section of PET /PHMG A and PET-g-PHMG B
5 No PET PET PET-g-PHMG PET PET-g-PHMG PET Haake 5 min PHMG 0 5% 0 8% 1 0% PET 1 PET /PHMG 1% PHMG PET 5 min Processed PET PET min Sample Content of antibacterial master batch % Table 1 PHMG content % intrinsic viscosity test of PET samples Processing temperature / viscosity * Intrinsic / dl g - 1 Antibacterial rate % E coli S aureus PET processed PET PET-g-PHMG 15 PET PET PET PET /PHMG * Test solution filtered 1 PHMG PET PHMG PET PET /PHMG 0 57 dl /g PET-1 PHMG 1% 0 75 dl /g PET PET PET-g-PHMG PHMG PET PET PET-1 PET Processed PET PET-g-PHMG PET PET-1 Processed PET PET PET-g-PHMG PET PET dl /g PET PET-g-PHMG PET PET PET 300 PET min PET dl /g 2 6 PET PET /PHMG PET-0 5 PET-0 8 PET-1 E coli S aureus 1 1 PET PET % PET-g-PHMG PET % PHMG PET PET /PHMG 61 59% 25 PHMG PP PE 99% PET PHMG PET PET
6 878 Vol 35 PHMG PHMG PHMG PET PET PET-0 5 PET /PHMG h 6 A B C PET PET /PHMG PET PET /PHMG 20% PET PET /PHMG PET % PHMG PET PET 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 2 7 PET PET-0 5 PET 10 d PET 7 PET PET 7 A 7 B PET % PET PET 8 PET cfu /ml 2 GB /T % 8 70% 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
7 No min 22 PET PET PET-1 PET PET-1 10 min 90% 8 36 min PET 90% 94% PHMG PET 15% PET-g-PHMG PHMG 93 7% PET PET-g-PHMG PHMG PET PHMG PET PET-g- PHMG PET 3 PET PET-g- PHMG PET PET 99% PET PET 100% 1 Tang Z R Textile Auxiliaries Braydich-Stolle L Hussain S Schlage J J Hofmann M C Toxicol Sci Wen H C Lin Y N Jian S R Tseng S C Weng M X Liu Y P Lee P T Chen P Y Hsu R Q Wu W F Chou C P J Phys Conf Ser Gopinath P Gogoi S K Chattopadhyay A Gosh S S Nanobiotechnol Hussain S M Javorina M K Schrand A M Duhart H M Ali S F Schlager J J Toxicol Sci Hussain S M Hess K L Gearhart J M Geiss K T Schlager J J Toxicol in Vitro Buche ska J J Appl J Polym Sci Park J S Kim J H Nho Y C Kwon O H J Appl Polym Sci Chu C L Bi S M Bao J Y New Chemical Material Xiang Z H Application of Silver Loading Multi-walled Carbon Nanotubes Antibacterial Agents in Fiber Taiyuan University of Technology Taiyuan 2011 PET Kerkeni A Behary N Dhulster P Chihib N E Perwuelz A J Appl Polym Sci Holl nder A Thome J Keusgen M Degener I Klein W Appl Surf Sci / Ping X Irradiation Grafting and Induced Compatibilized Modification of PET University of Science and Technology of China Hefei 2011 PET Kurt P Wood L Ohman D E Wynne K J Langmuir Cerkez I Worley S D Broughton R M Huang T S Prog Org Coat / SalIe A J Fundamental Principles of Bacteriology McGraw-Hili Book Company New York Sideridou I Tserki V Papanastasiou G Biomaterials Pereira S G Nunes T G Kalachandra S Biomaterials Wei D F Ma Q X Guan Y Hu F Z Zheng A N Zhang X Teng Z Jiang H Mater Sci Eng C Qian L Y Guan Y He B H Xiao H N Polymer Zhou Z X Wei D F Guan Y Zheng A N Zhong J J J Appl Microbiol Guan Y Qian L Xiao H Zheng A Cellulose Guan Y Xiao H Sullivan H Zheng A Carbohydr Polym Zheng A N Guan Y Zhou Q Cheng Y Plastics Packaging Ma Q X Wei D F Hu F Z Zheng A N Journal of Functional Polymers / /
8 880 Vol 35 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 China 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 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 Keywords Polyethylene terephthalate Covalent bonding Long-acting antibacterial Graft modification Guanidine-based antimicrobial polymers polyhexamethylene guanidine hydrochloride Ed W Z Supported by the Natural Science Foundation of Shanghai China No 13ZR ZR
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