高分子化学课件-离子聚合

1、1高高 分分 子子 化化 学学2 A BAB - +ABA + B极化共价化合物极化分子离子化紧密离子对溶剂化溶剂分离离子对离解自由离子A / B反应活性增加反应活性增加离解程度增加离解程度增加34+ H2CCHYR CH2CHYX单体聚合R X抗衡阳离子（counterion)5H2C CCNCNH2OCH2CCNCN()nnCH2CHX+ ROHCH2CH2X+ RO6 7H2CCHXX: -NO2, -CN, -COOR, -Ph, -CH=CH2H2CCHXR CH2CHX8H2CCHClH2CCHO C CH3O氯乙烯乙酸乙烯酯9ONHOOO环氧化合物内酰胺内酯10Na + CH2=

2、CH-CH=CH2Na+ - CH2CH=CHCH2Na+ - CH2CH=CHCH22Na+ -CH2CH=CHCH2CH2CH=CHCH2-+Na引发聚合双阴离子活性种11Na +Na+苯乙烯+CHH2C -Na+CHH2C -Na+2Na+HC CH2CH2CH-Na+引发聚合12R M+ H2CCHXR CH2CHXM聚合R M13以KNH2为例2K + NH32KNH2 + H2KNH2K+ + NH2-NH2- + H2CCHXH2N CH2CHX-14 2 Na + 2 CH3OH 2 CH3ONa + H2 CH3O-Na+ + H2CCHXH3CO CH2CHX-Na+15B

3、uLi +H2CCHXBuCH2CHX-Li+16 K Na Li Mg Al 17185. 部分部分19KdH+ M MH 20l CH2 CHA + MMA CH2 CH CH2 CA COOCH3CH3 CH2 CA COOCH3CH3+ CH2 CH不能不能212223CHHCMe+XH+ CH2=CHXCHCXHH3C CXH+活化能高24CH2CHCHCHNa H . . CH2CHCH CH+ H . . . Na CH2H2CCCOOCH3CH3CH2COCCH3CH2Li+LiOCH3+链转移25CHX A + CO2CHCOOA X CHCOOHX H+ + CHX A C

4、H2 CH2O CHCH2CH2OX A 26端胺基化反应端胺基化反应CH C N R NCOX OA A CH3O + X CHCH2CH2OHCH3OH O C N R NCO+ A X CHCH C NH R NH2X O H2O 27 l 2829 ：CMnnMMnX303132M2 + A M1 M1M2 M2 A 33M A + SiCl4 nSi M M M M nnnn3435A BCH2 CHR+CH2 CRA BH3637CH2 CH2CH2 CHCH3CH2 CHC2H538H+CH2 CHC2H5CH3 CHC2H5(CH3)3CCH2 CCH3CH3CH2 C CH2

5、 CCH3CH3CH3CH339CH2 COHCH2 COHRRORCH2 CH404142ONHOOOOONHO环氧乙烷四氢呋喃环乙亚胺二氧戊环己内酰胺己内酯4344H AHAH ACH2 CHXCH3 CHXA+45CH3 CHXACH3 CHXA(CH3)3C Cl(CH3)3C Cl4647BF3 + H2O H (BF3OH)CH3CH2 C + CH3H (BF3OH)CH3CH3 C CH3(BF3OH)48SnCl4 + RX R (SnCl5)CH3CH2 C + CH3R (SnCl5)CH3R CH2 C CH3(SnCl5)49(BF3OH)CH3 CH2 C CH3+

6、 H2O+ H (BF3OH)CH3 CH2 C OH CH3+ H2OBF3H (BF3OH)H2O(H3O) (BF3OH)50NCHCHH2TCE-+NCHCH2+ TCE51I2 +I2I (I3)CH3C (ClO4) + M OCH3CM (ClO4)O52KC + RHH (CR)H (CR) + M HM (CR)ki53K = H (CR) C RHC RHH (CR) = K Ri = ki C RH M = ki K C RH MH (CR) Ri = ki 54Rp = kp HM (CR) M55CH2 CH CH3 CH CH3 CH2 CH2 C CH3 CH3

7、5657H CH2 C CH3 CH3 CH2 C CH3 CH3 CH3 (BF3OH)CH3CH2 CCH3+H+ n(BF3OH)H CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 CH3CH3 CCH3+n58Rtr,m = ktr,m HM (CR) Mnn+1ktr,mHM (CR)+MM+HM M (CR)59HMnM (CR)Mn+1+H (CR)ktnH CH2 C CH3 CH3 CH2 C CH3 CH3 CH3 (BF3OH)+H CH2 C CH3 CH3 CH2 C CH2 CH3 CH3 H (BF3OH)n60HMnM (CR)HMnM(CR)C

8、H3 CH2 CCH3(BF3OH)CH3 CH2 CCH3OH + BF3Rt = kt HM (CR) 61HMnM (CR)+ XAHMnMA + X (CR)ktr,s+(CR)2OHHO2 HMnM2 建立稳态建立稳态Ri = ki H (CR) MRi = K ki C RH MMHM (CR) Rp = kp Ri = RtK ki C RH MHM (CR) = ktRt = kt HM (CR) ：Rp = C RH M2K ki kpktXn =RPRt=kp HM (CR) Mkt HM (CR) =kPktMXn1=kPktM+ CM+ CSMS1=MCMktr,MkP=ktr,m HM (CR) MHM (CR) kp =Rtr,MRPXn =67l A B A B A B A B +l 68l l 69l ki kR = kp kt e-(Ei + Ep - Et) / RT At Ap = kR Ai 21 41.8 kJ / mol = Ei + Ep