V ol. 26 N o. 3 2 0 0 5 3 CHEM ICAL JOU RNAL O F CH IN ESE UN IV ERS IT IES 575 579,, (, 10027),, 110 150 nm (FA ) (MMA ) (BMA ). GPC, FT IR 1 H NM R,,., A IBN FA 2MMA 2BMA.,. (113 115),,. ; ; ; O 631 A 025120790 (2005) 0320575205, [1 ], [2 ]. FA Q 2e ( ), [3 ]., FA [4 ], [5 ],, [6 10 ].,, FA, [9 ], [10 ]. 20 70 [11 ], 50 500 nm, [12, 13 ],,,.,, FA 2MM A 2BM A,. 1 1. 1 Zonyl TM fluoromonom er, CH 2 CH COOCH 2CH 2C nf 2n+ 1 (n= 6, 8, 10), D u Pont, - 5 ;,,, - 5 ; (N P240) (C 18TAB ),, ; (A IBN ),,, ;. 1. 2 C 18TAB N P240 2 1 60 ml, 10 m in, 012 g A IBN 16 g (FA 2MM A 2BM A 7 4 5) : 2004202209. : ( : 20376070) ( : 404295). : (1964 ),,,. E2m ail: xlzhan@ zju. edu. cn
576 V ol. 26, 0 m in, 2 m in, (, 21% ), 100 ml, 0 m in, 70, 6 h,, 011 g, ph 7. 1. 3 ; M alven Sizer 2000 ; JY282 ; FT IR TH F, KB r, N icolet N exus670 ; 1 H NM R B ruker DM X2500, ; W aters 150C, PST. 2 2. 1,,,,,,,, TH F, KB r FT IR. 1 a BM A FT IR, 950 970 cm - 1 OC 4H 9 C H. 1 b BM A 2MM A FT IR, 1 385, 1 450 960 cm - 1 MM A OCH 3 C H, 1 150 1 240 cm - 1 MM A BM A O C. 1 c FA 2MM A 2BM A FT IR,, 1 200 cm - 1, F C [14 ], 700 cm - 1 CF 2CF 3,. F ig. 1 FTIR spectra of P (BM A) (a), P (MM A-BM A) (b) and P (MM A-BM A-FA) (c) 2. 2 1 H NM R F ig. 2 1 H NM R spectrum of polymer P (FA-MM A-BM A), 500 M H z 1 H NM R, 2., MM A O CH 3 16, 23105; M BA O CH 2 19, 12196. FA OCH 2 413 [14 ], 4179. ( 23105g3) ( 12196g2) ( 4179g2) = 7168 6148 2140,, GC2M S 529, 6190 4117 5, (7 4 5). 2. 3,.,, 65 80,
N o. 3 : 577 015% 1%, 0 m in 60%, h 90%.,,, 015%,, 90%. F ig. 3 GPC chroma togram s of la texes w (Em ulsifier) = 2%, w (A IBN ) = 112% (w eight percent respect to the disperse phase), m ass ratio of FA to LMA to MMA: samp le 1, 2 4 4; samp le 2, 312 314 314; samp le 3, 5 215 215. t= 70.,, 113 115 ( 1),,.,,,,,,,. 2. 4 Table 1 Average molecular and polydispersity Samp le M n M w Polydispersity 1 586 421 857 171 11461 7 2 524 364 708 206 11350 6 3 558 936 791 621 11416 3,, [15 ], [16, 17 ]. O stw ald,,, [11 ]., 2 112%, ( D [4 3 ]) 134 nm, %, 111 nm,,,,,,. 2,,,. Samp le m (Em ulsifier) (% ) Table 2 Character istics of poly (FAgMM AgM BA) la tex particles using differen t amoun ts of emulsif ier and coemulsif ier 3 c(coem ulsifier) (% ) The latex particle size distribution and conventional em ulsion of polym erization p rocess(nm ) 0 m in 30 m in 60 m in 120 m in 180 m in 360 m in 1 112 0 138 136 136 135 134 134 2 211 0 123 123 121 122 119 118 3 310 0 116 115 115 113 113 111 4 115 3 139 137 137 135 132 132 5 214 6 135 133 132 130 130 127 In all cases, the ratio of three monom ers and the concentration of it to w ater w ere stable.,,,,.,,,,,,, MM A BM A,.
578 V ol. 26 2. 5 5 15 d,. 48 h,,,,,., 000 rgm in 120 m in,. Table 3 The cen tr ifuga l stabil ity of copolymer emulsion in differen t parameters 3 Samp le m (Em ulsifier) (% ) m (Coem ulsifier) (% ) Sedim entation ratio of centrifugal p rogress(% ) 30 m in 60 m in 90 m in 120 m in 1 115 0 0 0 01082 01109 0 2 211 0 0 0 01075 01892 0 3 310 0 0 0 01042 01068 0 4 211 2 0 0 01045 01062 5 In all cases the ratio of three monom ers and the concentration of it to w ater w ere stable.,, 000 rgm in 90 m in,,,,,,,. 2. 6,,. [17 ],,.., 60 24 h, ( 4), 20%,,,. 0%, 120, 90,.,.,,, [18 ].,,,,. Table 4 Effect of the amoun t of f luoromonomer on o il and wa ter con tact angle 3 Samp le m (Em ulsifier) (% ) m (F luoromonom er) (% ) Contact angles to w aterg( ) Contact angles to hexadecaneg( ) 1 115 20 11210 8015 2 115 25 11810 8810 3 211 32 12315 9210 4 211 43 12510 9410 5 211 51 12610 9515 The content of em ulsifier w as relative to monom ers and content of fluoromonom er w as relative to copolym eṙ 3,, 110 150 nm,,, 500 000 600 000, 113 115.,
N o. 3 : 579, A IBN.,, 0%. [ 1 ] L yengar D. H., Penct S. M., Dai C. A.. M acromolecules[j ], 1996, 29: 1229 1234 [ 2 ] Am eduri B., Boutevin B.. A ctual. Chim. [J ], 2000, 2: 23 32 [ 3 ] M arita M., O gisu H., Kubo M.. J. App l. Polym. Sci. [J ], 1999, 73: 1741 1749 [ 4 ] Huang Z. H., Shi C. M., Xu J. H. et al.. M acromolecules[j ], 2000, 33: 5437 5442 [ 5 ] Park İ J., L ee S. B., Choi C. K. et al.. J. Colloid. Interface. Sci. [J ], 1996, 181 (1) : 284 288 [ 6 ] Park İ J., L ee S. B., Choi C. K.. M acromolecules[j ], 1998, 31: 7555 7558 [ 7 ] Cheng S. Y., Chen Y. J., Chen Z. G.. J. App l. Polym. Sci. [J ], 2002, 85: 1147 1153 [ 8 ] ZHOU Yu2M ing ( ), XU Q un2hua ( ), HUAN G J ing2yan ( ). Chem. J. Chinese U niversities( ) [J ], 2001, 22 (12) : 2126 2127 [ 9 ] L inem ann R. F., M alner T. E., B randsch R. et al.. M acromolecules[j ], 1999, 32: 1715 1721 [ 10 ] Ha J. W., Park İ J., L ee S. B. et al.. M acromolecules[j ], 2002, 35: 6811 6818 [ 11 ] U gelstad J., E l2a asser M. S., V anderhoff J. W.. Polym. L etter[j ], 1973, 11: 503 507 [ 12 ] L andfaster K., Bechthold M., T iarks F. et al.. M acromolecules[j ], 1999, 32: 2679 2683 [ 13 ] ZHAN G Hong2Tao ( ), TAN B i2en ( ), HU Fang ( ) et al.. Chem. J. Chinese U niversities( ) [J ], 2000, 21 (1) : 156 159 [ 14 ] L i K., W u P., Han Z.. Polym er[j ], 2002, 43: 4079 4086 [ 15 ] L andfaster K.. M acrom al. Rap id. Comm un. [J ], 2001, 22: 896 936 [ 16 ] Chem C. S., Chen T. J.. Colloid. Polym. Sci. [J ], 1997, 275: 1060 1067 [ 17 ] Hom as R., A nton D., Graham W. et al.. M acromolecules[j ], 1997, 30: 2883 2890 [ 18 ] Kin D. K., L ee S. B., Doh K. S.. J. Colloid Interface Sci. [J ], 1998, 205: 417 422 Syn thesis of Fluor inated Acrylate Ternary Copolymer Latex by M in iemulsion Polymer ization and Character ization ZHAN G Q ing2h ua, ZHAN X iao2l i 3, CH EN Feng2Q iu (D ep artm ent of Chem ical E ng ineering, Z hej iang U niversity, H ang zhou 310027, Ch ina) Abstract Stable fluoroacrylate copolym er em ulsion in the size range of 110 150 nm w as m ade by m iniem ulsion polym erization under emp loym ent of low dose of em ulsifiers and no coem ulsifiers, w ith fluo2 roacrylate (FA ), butyl m ethylacrylate (BM A ), m ethyl m ethyl2acrylate (MM A ) as the monom erṡ T he molecular w eigh t and composition of copolym er w ere demonstrated by GPC, FT IR and 1 H NM R, the change of latex partical sizer in the po lym erization p rocess w as determ ined, and the surface p roperty of film s w as studied by W ilhelm y m ethod. It is show n that m ixed monom er species allow s efficient copoly2 m erization to occur, and p roducts w ith a h igh conversion of fluoromonom er (95% ) and narrow molecular w eigh t distribution (1. 3 1. 5) w ere obtained, and the polym er particles w ere found to be one2to2one copy of the monom er drop lets and drop nucleation w as the dom inant m echanism in the polym erization p rocess, som e p roperties of fluoroacrylate copolym er latex of m iniem ulsion w ere imp roved, the excellent w ater and oil repellency of the copolym er film w ithout coem ulsifiers influence w ere p reserved w h ile the amount of flu2 orinated compounds required in the polym er is reduced considerably. Keywords F luoroacrylate; M iniem ulsion polym erization; T ernary copolym er; L ow surface energy (Ed. : Y, Z)