Vol 35 No 4 2014 4 CHEMICAL JOURNAL OF CHINESE UNIVERSITIES 873 ~ 880 doi 10 7503 /cjcu20130935 200237 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 ~ 4 5 6 2 7 ~ 10 11 12 13 14 15 ATRP PET PET 16 PHMG 17 18 PHMG 19 20 21 22 23 PHMG 24 PHMG PET 2013-09-22 13ZR1411400 12ZR1407800 E-mail zan@ ecust edu cn E-mail lsz@ ecust edu cn
874 Vol 35 PET PET PET PET PET PET 1 1 1 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 1 500 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 130 24 h 51 g PET 9 g PHMG-e PHMG-e 15% Haake Haake 270 5 min PET PET-g-PHMG Haake 1 4 PET PET PET-g-PHMG 130 24 h PET PET-g- PHMG Haake 0 5% 0 8% 1% PET PET-0 5 PET-0 8 PET-1 Haake 270 5 min 1 5 PET PET-g-PHMG PET 130 24 h MATE-Ⅴ Tokyo 285 300 290 290 290 300 305 1000 m /min 0 13 tex 1 6 GB /T 20944 3-2008 0 75 g PET 75 ml 1 10 5 cfu /ml 37 24 h 1 10 4 cfu /ml 0 1 ml 37 24 h 5 Y Y = A - B /A 100% A B
No 4 875 2 2 1 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 2 3 3 PET PET-g-PHMG FTIR PET FTIR 3 a 1720 cm - 1 PET PET 3 b PET-g-PHMG 1640 cm - 1 1 PHMG C N PHMG PET-
876 Vol 35 g-phmg 100 48 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
No 4 877 2 5 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 270 5 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 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 * 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-0 5 0 8 dl /g PET PET-g-PHMG PET PET PET 300 PET 1 300 5 min PET-0 5 0 725 dl /g 2 6 PET PET /PHMG PET-0 5 PET-0 8 PET-1 E coli S aureus 1 1 PET PET-1 99 9% PET-g-PHMG PET-0 5 99% PHMG PET PET /PHMG 61 59% 25 PHMG PP PE 99% PET PHMG PET PET
878 Vol 35 PHMG PHMG PHMG PET PET PET-0 5 PET /PHMG 100 48 h 6 A B C PET PET /PHMG PET-0 5 6 PET /PHMG 20% PET PET /PHMG PET-0 5 99 77% 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-0 5 100% PET PET 8 PET 1 10 4 cfu /ml 2 GB /T 20944 3-2008 70% 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
No 4 879 25 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 2002 19 4 23 26 2002 19 4 23 26 2 Braydich-Stolle L Hussain S Schlage J J Hofmann M C Toxicol Sci 2005 88 2 412 419 3 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 2007 61 445 449 4 Gopinath P Gogoi S K Chattopadhyay A Gosh S S Nanobiotechnol 2008 19 75 104 5 Hussain S M Javorina M K Schrand A M Duhart H M Ali S F Schlager J J Toxicol Sci 2006 92 2 456 463 6 Hussain S M Hess K L Gearhart J M Geiss K T Schlager J J Toxicol in Vitro 2005 19 7 975 983 7 Buche ska J J Appl J Polym Sci 1996 61 3 567 576 8 Park J S Kim J H Nho Y C Kwon O H J Appl Polym Sci 1998 69 11 2213 2220 9 Chu C L Bi S M Bao J Y New Chemical Material 2012 40 5 31 33 2012 40 5 31 33 10 Xiang Z H Application of Silver Loading Multi-walled Carbon Nanotubes Antibacterial Agents in Fiber Taiyuan University of Technology Taiyuan 2011 PET 2011 11 Kerkeni A Behary N Dhulster P Chihib N E Perwuelz A J Appl Polym Sci 2013 129 2 866 873 12 Holl nder A Thome J Keusgen M Degener I Klein W Appl Surf Sci 2004 235 1 /2 145 150 13 Ping X Irradiation Grafting and Induced Compatibilized Modification of PET University of Science and Technology of China Hefei 2011 PET 2011 14 Kurt P Wood L Ohman D E Wynne K J Langmuir 2007 23 9 4719 4723 15 Cerkez I Worley S D Broughton R M Huang T S Prog Org Coat 2013 76 7 /8 1082 1087 16 SalIe A J Fundamental Principles of Bacteriology McGraw-Hili Book Company New York 1973 293 17 Sideridou I Tserki V Papanastasiou G Biomaterials 2002 23 8 1819 1829 18 Pereira S G Nunes T G Kalachandra S Biomaterials 2002 23 18 3799 3806 19 Wei D F Ma Q X Guan Y Hu F Z Zheng A N Zhang X Teng Z Jiang H Mater Sci Eng C 2009 29 6 1776 1780 20 Qian L Y Guan Y He B H Xiao H N Polymer 2008 49 10 2471 2475 21 Zhou Z X Wei D F Guan Y Zheng A N Zhong J J J Appl Microbiol 2010 108 3 898 907 22 Guan Y Qian L Xiao H Zheng A Cellulose 2008 15 4 609 618 23 Guan Y Xiao H Sullivan H Zheng A Carbohydr Polym 2007 69 4 688 696 24 Zheng A N Guan Y Zhou Q Cheng Y Plastics Packaging 2002 12 2 32 34 2002 12 2 32 34 25 Ma Q X Wei D F Hu F Z Zheng A N Journal of Functional Polymers 2007 19 /20 1 80 84 2007 19 /20 1 80 84
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 200237 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 13ZR1411400 12ZR1407800