US 8,912,307 B2 · Flame-retarding carbon dioxide/epoxide copolymer and method for preparing the same

Abstract

There is provided a method for preparing a low-molecular weight poly(alkylene carbonate) of which the molecular weight and chain shape are precisely controlled, by introducing a phosphorous compound having a hydroxyl group as a chain transfer agent in order to regulate the molecular weight, in alternating copolymerizing an epoxide compound and carbon dioxide by using trivalent metal complex prepared from a Salen type ligand containing a quaternary ammonium salt, and a polymer prepared by the method. Since poly(alkylene carbonate) prepared according to the present invention includes a phosphate or phosphonate group in the polymer chain, it has flame-retarding property.

A method for preparing poly(alkylene carbonate), comprising using a complex of Chemical Formula 1 below as a catalyst, under the presence of a compound of Chemical Formula 5 below, and alternating copolymerizing carbon dioxide and at least one epoxide compound selected from the group consisting of (C2-C20)alkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy, or (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy;

(C4-C20)cycloalkyleneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy or (C6-C20)ar(C1-C20)alky(aralkyl)oxy;
and (C8-C20)styreneoxide substituted or unsubstituted with halogen, (C1-C20)alkoxy, (C6-C20)aryloxy, (C6-C20)ar(C1-C20)alkyl(aralkyl)oxy, or (C1-C20)alkyl,
wherein, in Chemical Formula 1,
M represents trivalent cobalt or trivalent chromium;
A represents an oxygen or sulfur atom;
Q represents a diradical linking two nitrogen atoms;
R1 through R10 each independently represents hydrogen;
halogen;
(C1-C20)alkyl;
(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C2-C20)alkenyl;
(C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C1-C20)alkyl(C6-C20)aryl;
(C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C6-C20)aryl(C1-C20)alkyl;
(C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C1-C20)alkoxy;
(C6-C30)aryloxy;
formyl;
(C1-C20)alkylcarbonyl;
(C6-C20)arylcarbonyl;
or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
two of R1 through R10 may be linked to each other to form a ring;
at least one of hydrogens included in R1 through R10 and Q is substituted with a cationic group selected from the group consisting of Chemical Formula a, Chemical Formula b, and Chemical Formula c below;
X− each independently represents a halide ion;
HCO3−;
BF4−;
ClO4−;
NO3−;
PF6−;
(C6-C20)aryloxy anion;
(C6-C20)aryloxy anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkylcarboxyl anion;
(C1-C20)alkylcarboxyl anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C6-C20)arylcarboxyl anion;
(C6-C20)arylcarboxyl anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkoxy anion;
(C1-C20)alkoxy anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkylcarbonate anion;
(C1-C20)alkylcarbonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C6-C20)arylcarbonate anion;
(C6-C20)arylcarbonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkylsulfonate anion;
(C1-C20)alkylsulfonate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkylamido anion;
(C1-C20)alkylamido anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C6-C20)arylamido anion;
(C6-C20)arylamido anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
(C1-C20)alkylcarbamate anion;
(C1-C20)alkylcarbamate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
or (C6-C20)arylcarbamate anion;
(C6-C20)arylcarbamate anion containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom, and phosphorus atom;
Z represents a nitrogen or phosphorus atom;
R21, R22, R23, R31, R32, R33, R34 and R35 each independently represents (C1-C20)alkyl;
(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C2-C20)alkenyl;
(C2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C1-C20)alkyl(C6-C20)aryl;
(C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C6-C20)aryl(C1-C20)alkyl;
(C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
and two of R21, R22 and R23, or two of R31, R32, R33, R34 and R35 may be liked to each other to form a ring;
R41, R42 and R43 each independently represent hydrogen, (C1-C20)alkyl;
(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C2-C20)alkenyl;
(β2-C20)alkenyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C1-C20)alkyl(C6-C20)aryl;
(C1-C20)alkyl(C6-C20)aryl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
(C6-C20)aryl(C1-C20)alkyl;
(C6-C20)aryl(C1-C20)alkyl containing one or more atoms selected from halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom;
or a metalloid radical of group 14 metal substituted with (C1-C20)alkyl or (C6-C20)aryl;
and two of R41, R42 and R43 may be liked to each other to form a ring;
X′ represents an oxygen atom, a sulfur atom, or N—R (here, R represents (C1-C20)alkyl);
n represents an integer obtained by adding 1 to the total number of cationic groups contained in R1 to R10 and Q;
X− may be coordinated to M;
and
a nitrogen atom of imine may be coordinated to M or may be decoordinated from M,
wherein, in Chemical Formula 5, E represents O or S;
G represents (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C6-C60)aryloxy, (C1-C60)alkyl substituted with carboxyl, (C1-C60)alkoxy substituted with carboxyl, (C1-C60)alkyl substituted with hydroxyl, or (C1-C60)alkoxy substituted with hydroxyl;
y represents an integer of 0 to 3,
when y represents an integer of 2 or more, respective G's may be the same as or different from each other, and may be linked via neighboring G and —O-L-[L represents (C2-C60)alkylene, (C2-C60)alkenylene, or (C6-C60)arylene] to form a fused ring;
and
when y represents 3, at least one of three G represents (C1-C60)alkyl substituted with carboxyl, (C1-C60)alkoxy substituted with carboxyl, (C1-C60)alkyl substituted with hydroxyl, or (C1-C60)alkoxy substituted with hydroxyl.

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Flame-retarding carbon dioxide/epoxide copolymer and method for preparing the same

Life of this patent

Flame-retarding carbon dioxide/epoxide copolymer and method for preparing the same

Life of this patent

Abstract

Claims8