Block and Graft Copolymers of Poly(Alkylene Carbonate) and Various Polymers

Abstract

Provided is preparation of poly(alkylene carbonate) by alternating copolymerization of carbon dioxide and epoxide. To be specific, provided are a method for preparing block or graft copolymers of the polymer compound and poly(alkylene carbonate) by alternating-copolymerization of an epoxide compound and carbon dioxide by using a metal (III) compound prepared from salen-type ligand with a quaternary ammonium salt as a catalyst in the presence of a polymer compound having a functional group of hydroxyl or carboxylic acid, and block or graft copolymers prepared by the method.

What is claimed is: 
     
         1 . A block copolymer compound represents Chemical Formula 13 below:
   W—{CR e1 R e2 —CR e3 R e4 —OC(O)O} d —CR e1 R e2 —CR e3 R e4 —OH  [Chemical Formula 13]
   wherein the W is selected from R 70 —[O-L] m -O— (Chemical Formula d), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —[O-L] m -O— (Chemical Formula e), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O 2 C-[E-CO 2 —F—O 2 C] m -E-CO 2 — (Chemical Formula f), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O—[F—O 2 C-E-CO 2 ] m —F—O— (Chemical Formula g) or HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O 2 C-[E-CO 2 —F—O 2 C] m -E-CO 2 —F—O— (Chemical Formula h), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O-[G-CO 2 ] m — (Chemical Formula i), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O-[Q-OC(O)O] m -Q-O— (Chemical Formula j), —O—[(R 111 )(R 112 )Si—O] m —R 113  (Chemical Formula k), HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O—[(R 111 )(R 112 )Si—O] m — (Chemical Formula l), R 100 -[T] m -J- (Chemical Formula m) and HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d -J-[T] m -J- (Chemical Formula n);   R e1  to R e4  independently represent hydrogen or methyl;   R 70  represents (C1-C15)alkyl;   L represents —CH 2 CH 2 —, —CH 2 CH(CH 3 )— or —CH 2 CH 2 CH 2 CH 2 —;   E represents —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, para-phenylene, or 2,6-naphthalenediyl;   F represents —CH 2 CH 2 OCH 2 CH 2 —, —CH 2 CH 2 —, —CH 2 CH(CH 3 )—, —CH 2 CH 2 CH 2 —, —CH 2 C(CH 3 ) 2 CH 2 —, —CH 2 CH(CH 3 )CH 2 — or —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —;   G represents —CH 2 —, —CH(CH 3 )—, —CH(CH 3 )CH 2 —, —CH(CH 2 CH 3 )CH 2 — or —CH 2 CH 2 CH 2 CH 2 CH 2 —;   Q represents —CH 2 CH 2 CH 2 CH 2 — or —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —;   R 111  and R 112  independently represent methyl or phenyl;   R 113  represents hydrogen or (C1-C8)alkyl;   J represents —O— or —CO 2 —;   T represents —CH 2 CH 2 —, —CH 2 CH(CH 2 CH 3 )— or —CH 2 CH(C 6 H 5 )—;   R 100  represents hydrogen or butyl; and   a number average molecular weight (Mn) of R 70 —[O-L] m -, —O 2 C-[E-CO 2 —F—O 2 C] m -E-CO 2 —, —O—[F—O 2 C-E-CO 2 ] m —F—O—, —O 2 C-[E-CO 2 —F—O 2 C] m -E-CO 2 —F—O—, —O-[G-CO 2 ] m -, —O-[Q-OC(O)O] m -Q-O—, —O—[(R 111 )(R 112 )Si—O] m —R 113 , —O—[(R 111 )(R 112 )Si—O] m —, R 100 -[T] m -J- and -J-[T] m -J- block of Chemical Formulas d to n is 500 to 500,000.   
     
     
         2 . A block copolymer compound represents Chemical Formula 14 below:
   {HO—CR e3 R e4 —CR e1 R e2 —{OC(O)O—CR e3 R e4 —CR e1 R e2 } d —O-[G-CO 2 ] m } f —R 90   [Chemical Formula 14]
   wherein   G represents —CH 2 —, —CH(CH 3 )—, —CH(CH 3 )CH 2 —, —CH(CH 2 CH 3 )CH 2 — or —CH 2 CH 2 CH 2 CH 2 CH 2 —, f represents 1, R 90  represents hydrogen, (C1-C8)alkyl or (C2-C8)alkylcarbonyl, R e1  to R e4  independently represent hydrogen or methyl, a number average molecular weight (Mn) of —{O-[G-CO 2 ] m } f —R 90  block is 500 to 500,000, and d represents an integer of 10 to 5,000.   
     
     
         3 . A block copolymer compound represents Chemical Formula 15 below:
   -{[T] x -[CH 2 CR 121 (J-{CR e1 R e2 —CR e3 R e4 —OC(O)O} d —CR e1 R e2 —CR e3 R e4 —OH)] y } m —  [Chemical Formula 15]
   wherein   T represents —CH 2 CH 2 —, —CH 2 CH(C 6 H 5 )—, —CH 2 CH(CO 2 Me)-, —CH 2 CH(Cl)— or —CH 2 C(Me)(CO 2 Me)-; R 121  represents hydrogen or methyl; J represents —CO 2 —, and R e1  to R e4  independently represent hydrogen or methyl, a number average molecular weight (Mn) of a main chain is 500 to 500,000, and d represents an integer of 10 to 50,000.