《高分子化學(xué)》第5章-離子聚合課件

1、 第五章第五章 離離 子子 聚聚 合合 5.1 5 5.2 1.A BCH2 CHR+CH2 CRA BHHn l 烯烴烯烴CH2 CH2CH2 CHCH3CH2 CHC2H5H( kJ/mol) 640757 791H+CH2 CHC2H5CH3 CHC2H5(CH3)3CCH2 CCH3CH3CH2 C CH2 CCH3CH3CH3CH3l CH2 COHCH2 COHRR:ORCH2 CH 2. H2SO4，H3PO4，HClO4， CF3COOH，CCl3COOHl H AHAH ACH2 CHXCH3 CHXA+ CH3 CHXACH3 CHXAl (CH3)3C Cl(CH3)3C

2、 Cln 如：如：BF3 + H2O H (BF3OH)CH3CH2 C + CH3H (BF3OH)CH3CH3 C CH3(BF3OH) BF3 AlCl3 TiCl4 SnCl4 ： 水 ：乙酸 ：甲醇 50 ：1. 5 ：1 SnCl4 + RX R (SnCl5)CH3CH2 C + CH3R (SnCl5)CH3R CH2 C CH3(SnCl5)(BF3OH)CH3 CH2 C CH3+ H2O+ H (BF3OH)CH3 CH2 C OH CH3+ H2OBF3H (BF3OH)H2O(H3O) (BF3OH)發(fā) I2 +I2I (I3)CH3C (ClO4) + M OCH3

3、CM (ClO4)O3 3 KC + RHH (CR)H (CR) + M HM (CR)ki CH2 CHN+ TCE CH CH2NTCE 引發(fā)活化能低， 8. 4 21 kJ/mol，故引發(fā)速率很快（與自由基慢引發(fā)Ed = 105 150 kJ/mol 截然不同)K = H (CR) C RHC RHH (CR) = K Ri = ki C RH M = ki K C RH MH (CR) Ri = ki : :HM (CR) + n MHMnM (CR) kpRp = kp HM (CR) M：: CH2 CH CH3 CH CH3 CH2 CH2 C CH3 CH3 l H CH2

4、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+n Rtr,m = ktr,m HM (CR) M：nn+1ktr,mHM (CR)+MM+HM M (CR) HMnM (CR)Mn+1+H (CR)kt:nH CH2 C CH3 CH3 CH2 C CH3 CH3 CH3 (BF3OH)+H CH2 C CH3 CH3 CH2 C CH2 CH3 CH3 H (BF3OH)n：u HMnM (CR)HMnM(CR)u CH3 CH2

5、CCH3(BF3OH)CH3 CH2 CCH3OH + BF3Rt = kt HM (CR) u HMnM (CR)+ XAHMnMA + X (CR)ktr,sOO+2 HMnM (CR)+(CR)2OHHO2 HMnM2 ： 建立穩(wěn)態(tài)Ri = ki H (CR) M增長增長Ri = K ki C RH MMHM (CR) Rp = kp 終止終止引發(fā)劑引引發(fā)劑引發(fā)生成碳發(fā)生成碳陽離子的陽離子的反是控制反是控制速率反應(yīng)速率反應(yīng)Ri = RtK ki C RH MHM (CR) = ktn 動(dòng)力學(xué)方程動(dòng)力學(xué)方程引發(fā)引發(fā):Rt = kt HM (CR) ：Rp = C RH M2K ki kpk

6、tl Xn =RPRt=kp HM (CR) Mkt HM (CR) =kPktMl Xn1=kPktM+ CM+ CSMS1=MCMktr,MkP=ktr,m HM (CR) MHM (CR) kp =Rtr,MRPXn =l kp ( l / mols) 7. 6 100 kt 4.9102 (s1) 10 7 ( l / mols) kp / kt 102 kp / kt1/2 102 活性種濃度活性種濃度 C* 103 M 108 Rp陽 Rp自5 5l A B A B A B A B +l l l l ki kR = kp kt e-(Ei + Ep - Et) / RT At Ap

7、 = kR Ai 21 41.8 kJ / mol = Ei + Ep - Et l e-(Ep - Et) / RT At Ap = k XnXnk = Ap Atr,M e-(Ep - Etr,m) / RT XnE = Ep - Etr,M XnE = Ep - Et MXn =kPktXn =kPktr,M5.3 l具有吸電子取代基的烯類單體原則上可以進(jìn)行陰離子聚合l 能否聚合取決于兩種因素是否具有共軛體系 吸電子基團(tuán)并具有共軛體系，能夠進(jìn)行陰離子聚合，如AN、MMA、硝基乙烯 吸電子基團(tuán)并不具有共軛體系，則不能進(jìn)行陰離子聚合，如VC、VAc與吸電子能力有關(guān) +e 值越大，吸電子能力越

8、強(qiáng)，易進(jìn)行陰離子聚合1.1.陰離子聚合單體陰離子聚合單體A BA B單體自由基陰離子單體自由基陰離子Na CH2 CHXNa + CH2 CHXCH CH2XNa XCH CH2Na 2XCH CH2 CH2 CH Na XNa 雙陰離子活性中心雙陰離子活性中心Na + Na THFNa CH2 CH+ CH CH2Na CH CH2Na CH2 CHNa + Na CH CH22 K 2 + 2 2 NH3KNH2+ H2KNH2K + NH2NH2CH2 CH+ CH2 CHH2Nl金屬烷基化合物 引發(fā)活性與金屬的電負(fù)性有關(guān) 金屬的電負(fù)性如下 K Na Li Mg Al R3N+ CH2

9、CHX R3NCH2 CHX X CH2 CH CH2 CHR3NX n 3. ：CH2CHCHCHNa H . . CH2CHCH CH+ H . . . Na CH2C CH CHH CH2CH. . Na + H CH2CH2. . + CH2C CH CHNa CHX A + CO2CHCOOA X CHCOOHX H+ + CHX A CH2 CH2O CHCH2CH2OX A 端胺基化反應(yīng)CH C NH R NH2X O H+ CH C N R NCOX OA A CH3O + X CHCH2CH2OHCH3OH O C N R NCO+ A X CH l ：CMnnMMnXnn2 C4H9-M Li (C4H9M Li )2 + C4H9M Li nM n+1C4