8 1 2002 2 EL ECTROCHEMISTR Y Vol 8 No 1 Feb 2002 :1006-3471 (2002) 01-0093- 07 2,,, (,,350007) 3 : ( EPU) 2 ( EPU- Ni 2 + ) X (DM TA) TG-DTA (AES) ( EPU- Ni 2 + AES : 7 5 % Ni 2 + EPU,, : ; ; ; : TQ 151 5 : A [1 3, ] [4 6 ], ( EPU), ( EPU) - OH, [7 ], EPU-Ni 2 +, X (DM TA) TG-D TA (AES) 1 1 1 :, ; :AR ; :CP ; 1 2 1 2 1 (2 cm 5 cm),, 20 min, :2001-08-30, : 2001-10-16 3 : ( E9910016) 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
94 2002 6,, 1 2 2 : [8 ] 1 2 3 EPU, Pt,, 0 1 mol L - 1 Na 2 SO 4, 9 ml, 81 ml, /,, 1 mol L - 1 p H 2 0 0 05 g ml - 1 50 min,, EPU 1 2 4 ( EPU-Ni 2 + ) Ni 2 +, EPU- 1 3 XPS ES3000 ; FT- IR Nicolet-750 ;DM TA DM TA- IV, :1 0HZ, :2 0 min - 1, :0 03 %, : 5 0 g ; HPD-1A ; TG-D TA D T-40, = 10 min - 1, : Pt, :N 2, :45 ml min - 1 2 2 1 (1) 1 ( ),, 0 4 V, Pt, 0 4 V,, Pt, 1 0 68 V 1 20 V ( SCE, ) Fig 1 The steady- state polarized curves of urushiol, electrochemical polymerization on different, electrodes Pt electrode stainless electrode 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
1 : 2 95 Pt, 0 80 1 00 V 1 40 1 60 V, 1 60 V ( ) 1 00 V ( Pt ) (2) p H, NaOH,, H 2 SO 4 HCl HNO 3 HClO 4, p H, p H 2 3,,, p H 2, (3), NaSO 4 0 05 mol/ L, CuCl 2 CuSO 4 NiCl 2,,, (4) /, Na 2 SO 4, /, Na 2 SO 4,,,,,,,,, 9 1 (5) 1, 0 102 1 276 g/ 20 ml, 0 600 g/ 20 ml, 0 1 mol/ L 1 Tab 1 Effect of urushiol concentration on thickness and color of polymer film Urushiol concentration 0 102 g/ 20 ml 0 324 g/ 20 ml 0 628 g/ 20 ml 1 276 g/ 20 ml Thickness thinner thin thick thicker Color buff yellow brown black (6),, ( ),, 45 min 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
96 2002 (7),,,,, - 0 20 V 1 40 V, 40 mv/ s 200 mv/ s,, 0 50 ma 2 50 ma (8) Pt Pb Al Ni Cu 7, Pt, 2 Materials of electrode 2 Tab 2 The effect of materials of electrodes on polymerization Stainless steel Pt Graphite Pb Al Ni Cu Cyclic voltammetry Potentiostant Galvanostant Cyclic voltammetry at 60 mv/ s between 0 and 2 00 V ; Galvanostant at 0 10 ma ; Potentiostant at 0 80 V or 1 80 V :reactable ; :unreactable 2 2 - (1) XPS XPS, [9, ] 3 : EPU-Ni 2 + 531 74 ev 532 50 ev 1 s,, 1 s (531 74 ev) (531 74 ev), 1 s (532 50 ev), 0 76 ev ; Ni 2p 3/ 2 856 7 ev ; NiCl 2 Ni 2p 3/ 2 858 1 ev 3 EPU NiCl 2 EPU- Ni 2 + XPS (ev) 1 4 ev, Tab 3 XPS data of EPU NiCi 2 and EPU- Ni 2 +,EPU NiCl 2, Sample O1s Ni2 p3/ 2 EPU EPU 531 74 Ni 2 +, NiCl 2 858 1, O Ni, EPU-Ni 2 + EPU- Ni 2 + 51 74,532 50 856 7 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
1 : 2 97 (2) FT- IR Ni 2 +, ; ) CH = CH ( 1 606 4 1 594 8 cm - 1, EPU-Ni 2 + 1, 1 608 3 cm - 1,, Ni 2 + C = C ; 1095 4 cm - 1 C-OH, 1103 1 cm - 1, EPU Ni 2 +, C-O, C-O, EPU-Ni 2 + C-O 2 EPU EPU- Ni 2 + Fig 2 FT- IR spectra of EPU and EPU- Ni 2 + 2 3 EPU EPU- Ni + DM TA Fig 3 DM TA curves of EPU and EPU- Ni 2 + (3) DM TA [10 DM TA, ] 3, Tg (179 5 ) (91 9 ), Ni 2 + EPU,,, [11 ],, Ni 2 + EPU,,,, 114 3, 178 5, EPU,,,,, EPU Ni 2 +, 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
98 2002 (4) TG-D TA 4, EPU D TA 435, TG 255, 255 430,430 480,480 TG 590, 62 5 % EPU-Ni 2 + D TA 450, TG 280, 280 430,430 480,480 TG 580, 61 8 %, EPU-Ni 2 + EPU,, EPU Ni 2 +, 4 EPU EPU- Ni 2 + TG-DTA Fig 4 TG-DTA curves of EPU and (5) EPU-Ni 2 + EPU- Ni 2 + EPU NiCl 2, Ni 2 +, EPU-Ni 2 + EPU-Ni 2 +, XPS, EPU 2OH Ni 2 +, EPU-Ni 2 + AES, 7 5 % 5,Ni 2 + 8 6 %,, Ni 2 + 3 EPU, 1 60 V ( 5 EPU- Ni 2 + ) 1 00 V ( Pt ) EPU Fig 5 The Structure of EPU- Ni 2 + ( EPU-Ni 2 + ), EPU FT- IR XPS TG-D TA DM TA, Ni 2 + ( EPU), EPU, EPU-Ni 2 + AES : 7 5 % 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet
1 : 2 99 Electrochemical Synt hesis and Characterization of t he Nickel Electropolyurushiol Coordination Polymer GAO Feng,SHEN Guo-cai, TAN G Jie-yuan,ZHAN G Wen-gong ( Instit ute of Polymer Science, Fujian Teachers U niversity, Fuz hou 350007, China) Abstract : The nickel electropolyurushiol coordination polymer ( EPU2Ni 2 + ) was obtained by t he reaction between nickel chloride isopropyl alcohol solution wit h elect ropolyurushiol ( EPU) The elect rochemical polymerization of urushiol and t he preparation of nickel elect ropolyurushiol coordination polymer were investigated The coordination polymer was characterized by XPS, F T- IR,DM TA and AES methods,and its composition and structure were determined The content of Ni 2 + reached up to 7 5 % It was shown that there was certain coordination between Ni 2 + and elect ropolyurushiol in t he coordination polymer,t hus cross-links were formed Therefore t he glass t ransition temperat ure of t he coordination polymer increased and heat resistance was enhanced considerably Key words : Urushiol, Elect rochemical polymerization,nickel,coordination polymer Reference s : [1 ] Yamazaki N Electrolytically initiated polymerization In :Advances in polymer science,vol t [ M ] Edited by Cantow H J et al New York :Springer- Verlag,1969 377 [ 2 ] Silvestri G, Gambino S,Filardo G Electrochemical production of initiation for polymerrization process In : Ad2 vances in polymer science,vol 38[ M ] Edited by Cantow H J et al New York :Springer- Verlag,1981 27 [3 ] Guerra G D Electroinitiated Polymerizations In :Comprehensive polymer science,vol 4[ M ] Edited by Allen G,Bevington J C Oxford : Pergamon Press,1989 543 [4 ] Kobayashi T, Yonevama N, Tamura H Electrochemical reactions concerned with electrochromism of polyani2 line film-coated electrodes [J ]Journal of Electroanal chemistry,1984,177 :218 291 [5 ] Qian Ren-yuan,Li Yong-fang Conducting polypyrrole[j ] Science(Shanghai),1998,50 (3) :18 20 [6 ] Wu Fei-peng,Zhou Wen- hui,zhang Yun-long Electrochemical polymerization of two- dimensional porphyrinthophene copolymers and their electric properties[j ]Journal of Functional Polymers,1999,12(1) :79 82 [7 ] Tang Jie-yuan, Gao Feng, Zhang Weng- gong, Wang Wen Synthersis and property of polymeric complex of electropolyurushiol( EPU) with Europium[J ]Journal of Applied Chemistry(in Chinese),2000,17 (3) :325 327 [8 ] Zhang Weng- gong, Gan Jing- hao The omposition analysis of Chinese raw lacquer- Part One : new method of purification of raw lacquer [J ] Journal of Fujian Teachers University ( Natural Science) (in Chinese), 1978 (1) :1 5 [9 ] Cheng Chun Xuan Physical Chemistry of Surface[ M ] Beijing :Scientific Technical Document Press,1995 676 682 [10 ] Guo Mei-li Advanced Dynamic Mechanical Thermal Analysizer (DM TA) and application[j ] Mordent Sci2 entific Instruments,1996(4) :57 59 [11 ] He Man-jun,Chen Wei- xiao,dong Xi- xia Polymeric Physics[ M ] Rev Ed Shanghai : Fudan Univ Press), 1990 349 350 1994-2008 China Academic Journal Electronic Publishing House All rights reserved http://wwwcnkinet