ACTA POL YMERICA SINICA O C O C PPC, PPC PPC, CO 2 , PPC 36 38, ( EGDE) (BGE)

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1 ACTA POL YMERICA SINICA No. 10 Oct., ,2 1, ,3 ( ) ( ) ( ) 2 (PPC) PPC 3, PPC PPC. PPC, PPC, PPC, PPC.,,,,, [1 11 ], (PPC),PPC 1 [3, 6 7 ]. Fig. 1 Chemical structure of poly(propylene carbonate) PPC,,,., PPC.,PPC 36 38,,PPC, PPC, (40 ) (15 ), PPC. PPC PPC, PPC, PPC., PPC, PPC., PPC C C C O C O C,, C O C, PPC, PPC., PPC, 3 PPC, PPC PPC,. 1 PPC. CO 2, PPC [7,11 ]. PPC., 2, CO 2 ( EGDE) (BGE) (XGE),, , ; ( ) ; 33,E2mail jl. cn 913

2 ,, CO 2 PO, [12 ]. ZnEt 2,, , 50 % [12 ]. Fig. 2 Double propagation mechanism for the copolymerization of propylene oxide with CO 2 PPC. 3, T g,, PPC 4300 MPa, PPC 6900 MPa, 60 %. T g, PPC 175 MPa, PPC 10, , PPC , PPC 37 ( 4), PPC. Fig. 4 TGA curves of PPC with various molecular weights a) M n = ; b) M n = ; c) M n = Fig. 3 Plots of storage modulus ( E ) against temperature of ; d) M n = PPC with different M n M n = ; M n = ; M n = ; M n = , PPC, PPC

3 10 : 2 915,,, 2 (PCHC). 2 PPC, PPC,, 50 %., PPC.,,, PPC, PPC. PPC 5, CO 2 PO (AGE), PPC [13,14 ],, PPC [14 ]. 1,, PPC. PPC 0108 mol Πkg 0136 mol Πkg, PPC 6513 % 85 % mol Πkg PPC1, 65 %, PPC., 2. 2, PPC,65, PPC25 PPC20, PPC25 0, PPC. Table 1 Characterization of crosslinked PPC Sample Unsaturation for un2crosslinked PPC a Gel contents b M C (mol double bondsπkg polymer) ( %) (gπmol) PPC0 0 0 PPC PPC PPC a Determined by iodometry ; b The molar mass between crosslinking site ( M c ) was calculated from the hot set test Table 2 Effect of crosslinking on the hot set elongation and permanent deformation of PPC 3 Hot set elongation ( %) Permanent deformation ( %) Sample Un2crosslinked Crosslinked Un2crosslinked Crosslinked PPC a a PPC PPC PPC The hot set test was done at 65 using a nominal load of 0114 MPa ; a The result of PPC0 after UV irradiation in the same conditions 3 PPC Fig. 5 Preparation of crosslinked poly(propylene carbonate), C O (CH 2 O) C O (MeCH O) [15].,PPC 2 (H2H) 2 (H2T) 2 (T2T) 3 [16]. ( )., PPC PPC [17]. Coates, Lu CoIII(salen), 95 % PPC, ( ) [4,5],.

4 PO, PO, ( PPO). PO, PPO. ZnEt 2 2H 2 O, ZnEt 2 2 PO, PPO 90 % [18 ]. PO, PO., CO 2 PO, PPC ( ), PPC 60 % 70 % [3,6,7,17 ]. PO,,, PO [19 ], % PPC ( 6), PPC. Coates, Lu PPC, PPC. 7, 6917 % 8312 %,PPC 8, PPC. Fig. 7 DSC curves of different PPC sample a) H2T linkages :6917 % ; b) H2T linkages :7616 % ; c) H2T linkages :7912 % ; d) H2T linkages :8312 % Fig. 6 The carbonate region of 13 C2NMR spectra of PPC a) In the absence of Lewis base ; b) Molar ration of 1,102 phenanthroline (Lewis base) to ZnEt 2 was 012.,,,,, PPC. REFERENCES 1 Inoue S,Koinuma H,Tsuruta T.J Polym Sci Part B :Polym Lett,1969,7 : Chen X H,Shen Z Q,Zhang Y F. Macromolecules,1991,24 : Liu B Y,Zhao X J,Wang X H,Wang F S.J Polym Sci Part A :Polym Chem,2001,39 : Cohen C T,Chu T,Coates G W.J Am Chem Soc,2005,127 : Lu X B,Shi L,Wang Y.J Am Chem Soc,2006,128 : Liu B Y,Zhao X J,Wang X H,Wang F S. Polymer,2003,44 : Quan Z L,Wang X H,Zhao X J,Wang F S. Polymer,2003,44 : Xie D,Wang X H,Zhao X J,Wang F S. Chinese J Polym Sci,2005,23 : You Jinxi ( ),Cui Qi ( ),Zhang Min ( ),Liu Baohua ( ),Chen Liban ( ),Zhang Songwei ( ). Acta Polymerica Sinica ( ),2006, (6) : Cui Qi ( ),Zhang Min( ),Xu Shouping( ),Liu Baohua ( ),Chen Liban ( ). Acta Polymerica Sinica ( ),

5 10 : , (3) : Quan Z L,Min J D,Zhou Q H,Xie D,Liu J J,Wang X H,Zhao X J,Wang F S. Macromol Symp,2003,195 : Tao Y H,Wang X H,Zhao X J,Li J,Wang F S. Polymer,2006,47 : Zhang Nairong ( ),Zhao Xiaojiang ( ),Wang Xianhong ( ),Wang Fosong ( ). Acta Polymerica Sinica ( ), 2005, (4) : Tao Y H,Wang X H,Zhao X J,Li J,Wang F S.J Polym Sci Part A Polym Chem,2006,44 : Price C C. Acc Chem Res,1974,7 (9) : Lednor P W,Rol N C.J Chem Soc,Chem Commun,1985, Chisholm M H,Zhou Z J. Am Chem Soc,2004,126 : Borgne A L,Spassky N,Jun C L,Morntaz A. Makromol Chem,1988,189 : Darensbourg D J,Yarbrough J C.J Am Chem Soc,2002,124 : CHAIN STRUCTURE REGULATION OF CARBON DIOXIDE2PROPYL ENE OXIDE COPOLYMERS ZHOU Jian 1,2, TAO Youhua 1,2, WANG Xianhong 1, ZHAO Xiaojiang 1, WANG Fosong 1,3 ( 1 State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun ) ( 2 Graduate School of Chinese Academy of Sciences, Beijing ) ( 3 Chinese Academy of Sciences, Beijing ) Abstract This review summarizes our achievements in controlling the chain structures of carbon dioxide2propylene oxide copolymers( PPC). PPC with number average molecular weight ( M n ) over was obtained by double propagation mechanism,the resulted higher M n copolymers showed improved thermal and mechanical performance than common copolymers with M n lower than Another way to regulate chain structures was employing crosslinking strategy. PPC bearing small moiety of pendant C C groups was synthesized by terpolymerization of allyl glycidyl ether,propylene oxide and carbon dioxide. Once subjected to UV radiation crosslinking,the dimension stability of the crosslinked copolymer was improved. The third way to regulate chian structures of PPC was controlling its region structure. Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center,ppc with H2T linkages over 83 % and M n up to ,was synthesized at room temperature using Y ( CCl 3 OO) 3 2ZnEt 2 2glycerine catalyst and 1,102Phenanthroline cocatalyst. When H2T linkages increased from 6917 % to 8312 %,a 8 increase of T g was found,indicating that increase of H2T structure in PPC did raise its T g. Key words Carbon dioxide, Copolymerization, Chain structures, Molecular weight, Crosslinking, Region2regular structure