US 7,714,075 B1Granted

Polymerization with living characteristics

AssigneeCommonwealth Scientific and Industrial Research Organisation

InventorsTam Phuong Le, Graeme Moad, Ezio Rizzardo, San Hoa Thang

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Abstract

This invention concerns a free radical polymerization process, selected chain transfer agents employed in the process and polymers made thereby, in which the process comprises preparing polymer of general Formula (A) and Formula (B) comprising contacting: (i) a monomer selected from the group consisting of vinyl monomers (of structure CH2═CUV), maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers; (ii) a thiocarbonylthio compound selected from Formula (C) and Formula (D) having a chain transfer constant greater than about 0.1; and (iii) free radicals produced from a free radical source; the polymer of Formula (A) being made by contacting (i), (ii) C and (iii) and that of Formula (B) by contacting (i), (ii) D, and (iii); and (iv) controlling the polydispersity of the polymer being formed by varying the ratio of the number of molecules of (ii) to the number of molecules of (iii); wherein Q, R, U, V, Z, Z′, m, p and q are as defined in the text.

A process for the synthesis of a block polymer of the general formula:

comprising contacting:
(i) one or more vinyl monomers of structure CH2═CUV, and;
(ii) a chain transfer agent:
having a chain transfer constant greater than about 0.1;
and
(iii) free radicals produced from a free radical source;
wherein:
Q is a polymer comprising the repeating units of:
wherein;
U is selected from the group consisting of hydrogen, halogen, and optionally substituted C1-C4 alkyl wherein the substituents are independently selected from the group that consists of hydroxy, OR″, carboxy, O2CR″, and CO2R″;
V is selected from the group consisting of hydrogen, R″ and halogen, provided when Q comprises styrene or methyl methacrylate, Z is not alkoxy;
wherein:
Z is optionally substituted alkylthio;
optionally substituted alkoxy;
dialkyl- or diaryl-phosphonato;
or dialkyl- or diaryl-phosphinato;
R is selected from the group consisting of optionally substituted alkyl;
optionally substituted alkenyl;
optionally substituted alkynyl;
an optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring;
and a polymer chain prepared by any polymerization mechanism;
in agent C, R. is a free-radical leaving group that initiates free radical polymerization;
R″ is selected from the group consisting of optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, alkaryl wherein the substituents are independently selected from the group that consists of epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy and carboxylates, sulfonic acid and sulfonates, alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo, and dialkylamino;
q is 1 or an integer greater than 1 wherein when q=1, then Q is a homopolymer chain resulting from a single monomer species and R is said polymer chain prepared by any polymerization mechanism;
wherein when q≧2, then Q is a copolymer chain resulting from two or more monomer species in irregular sequence and R is said polymer chain prepared by any polymerization mechanism;
or
wherein when q≧2, then Q is a block copolymer chain resulting from two or more monomer species in discreet sequence and p is 1.

24 more elements

Abstract

Claims23