Polymerisation of ethylenically unsaturated monomers

Abstract

Ethylenically unsaturated, particularly acrylic, monomers are polymerised using a catalyst system including a manganese carbonyl initiator, an organic halogen reactive substrate and an allylic halide chain termination agent. Desirably the manganese carbonyl initiator is a dimanganese compound, particularly dimanganese decacarbonyl (Mn 2 (CO) 10 ). The catalysis mechanism appears to involve initiator homolysis, abstraction of halogen from the reactive substrate forming an organic free radical which acts as a chain initiator for polymerisation and eventual reaction of the propagating chain radical with the chain terminating agent. The speed or extent of reaction may be modified by the inclusion of Lewis acids in the reaction mixture. The resulting polymers are telechelic and may have different end groups. The polymers can be reacted further to functionalise them and/or to form block copolymers.

1 . A polymer or copolymer of one or more ethylenically unsaturated monomers having at one end of the (co)polymeric chain a residue of a reactive substrate and a residue of an allylic halogen substituted chain termination agent at the other. 
     
     
         2 . A polymer or copolymer as claimed in  claim 1  wherein the (co)polymeric chain includes residues of one or more monomers selected from acrylic monomers, vinyl acetate, vinyl halide, styrene, α-methyl styrene, vinyl toluene, vinyl caprolactone, vinyl caprolactam and/or N-vinyl pyrollidone. 
     
     
         3 . A polymer or copolymer as claimed in  claim 2  wherein the monomer includes at least 40 mole % of acrylic monomer or monomers. 
     
     
         4 . A polymer or copolymer as claimed in  claim 2  wherein the acrylic monomer is or includes monomer of the formula (IV):
   R 10 —CR 11 ═CR 12 —COR 13   (IV)   where   R 10  is methyl or, and desirably, hydrogen;   R 11  is methyl or, and desirably, hydrogen;   R 12  is methyl or hydrogen;   provided that at least one of R 11  and R 12  is hydrogen, and   R 13  is —OR 14 , or —NR 15 R 16  where R 14 , R 15  and R 16  are each hydrogen, hydrocarbyl, or a polyalkyleneoxy chain.   
     
     
         5 . A method as claimed in  claim 4  wherein the monomer is or includes one or more acrylate or methacrylate ester; acrylic or methacrylic acid; acrylic or methacrylic amide; or a sulphonated acrylic monomer. 
     
     
         6 . A polymer or copolymer as claimed in  claim 1  wherein the residue of the chain terminating agent is or includes the residue of an allylic halogen substituted chain termination agent of the formula (II):
   Hal-CHR 3 —CR 4 ═CH2  (II)   where   Hal is halogen; and   R 3  and R 4  are each independently hydrogen, or a group: (Link) n -R 5 , where: n is 0 or 1, Link is a linking group; and   R 5  is halogen, glycidyl, an ethylenic double bond, carbonyl, carboxyl, cyano, hydroxyl, amino or quaternary amino or ammonium, a phosphorus containing species, a sulphur containing species, a hydrogen bond donor or acceptor, an aromatic ring, a heterocyclic ring, or a saccharide residue.   
     
     
         7 . A polymer or copolymer as claimed in  claim 6  wherein Hal is a chlorine or bromine atom. 
     
     
         8 . A polymer or copolymer as claimed in  claim 1  wherein the reactive substrate is also a chain terminating agent. 
     
     
         9 . A polymer or copolymer as claimed in  claim 1  wherein the residue of the reactive substrate is or includes the residue of a halogen substituted alkane, alcohol or carboxylic acid ester, an aromatic substituted alkyl halide, a ring substituted benzyl halide, and/or a sulphonyl halide. 
     
     
         10 . A metpolymer or copolymer as claimed in  claim 9  wherein the reactive substrate has multiple halogen substitution. 
     
     
         11 . A polymer or copolymer as claimed in  claim 9  wherein the reactive substrate is or includes at least one of carbon tetrachloride, carbon tetrabromide, chlorotribromomethane, trichloro-methane, tribromomethane, dichloromethane, dibromomethane, 1,1-dichloroethane, 1,1-dibromoethane, 1,1,1-trichloroethane, 1,1,1-tribromoethane, 2,2-dichloroethanol, 2,2-dibromoethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, trichloroacetic acid, C 1  to C 6  alkyl esters of trichloroacetic acid, C 2  to C 6  alkyl 2-bromo-2-methyl propionates, benzyl halides, 2-halo-2-phenylethanes, 4-alkyl benzyl halides, 4-fluorobenzyl bromide, 4-chloro-benzyl bromide, 4-fluorobenzyl chloride, 4-chlorobenzyl chloride, 1,2-di(bromomethyl)-benzene, benzene sulphonyl chloride and/or toluene sulphonyl chloride. 
     
     
         12 . A block copolymer comprising a block of a polymer or copolymer of one or more ethylenically unsaturated monomers having at one end of the (co)polymeric chain a residue of a reactive substrate and a residue of an allylic halogen substituted chain termination agent at the other, linked to at least one second polymer block covalently bound to one or both ends of the first polymer block. 
     
     
         13 . A block copolymer as claimed in  claim 12  wherein the second block comprises a polyester, a polyhydroxyacid, a polyalkoxylate, a polyurethane, a vinylic polymer or a polysaccharide. 
     
     
         14 . A block copolymer as claimed in  claim 13  wherein the polyester is a polyterephthalate; the polyhydroxyacid is polyhydroxystearic acid, polylactic acid or a polylactone; the poly-alkoxylate is polyethylene glycol (PEG) or polypropylene glycol (PPG); the polyurethane is based on the reactions between toluene di-isocyanate or methylene diphenyldiisocyanate and polyols; the vinylic polymer is an acrylate polymer; and the polysaccharide is a dextrin or a starch. 
     
     
         15 . A block copolymer as claimed in  claim 14  wherein the polyester is polyethylene terephthalate, the polylactone is polycaprolactone; the vinylic polymer is polymethyl methacrylate (PMMA) or a copolymer including residues of other (meth)acrylate esters or polystyrene. 
     
     
         16 . A method of making a block copolymer comprising a first block of a polymer or copolymer of one or more ethylenically unsaturated monomers having at one end of the (co)polymeric chain a residue of a reactive substrate and a residue of an allylic halogen substituted chain termination agent at the other and linked through the residue of chain terminating agent to a second block comprising a polyester, a polyhydroxyacid, a polyalkoxylate, a polyurethane, a vinylic polymer or a polysaccharide, which comprises polymerising the second block onto the first block. 
     
     
         17 . A method of making a block copolymer comprising a first block of a polymer or copolymer of one or more ethylenically unsaturated monomers having at one end of the (co)polymeric chain a residue of a reactive substrate and a residue of an allylic halogen substituted chain termination agent at the other and linked through the residue of chain terminating agent to a second block comprising a polyester, a polyhydroxyacid, a polyalkoxylate, a polyurethane, a vinylic polymer or a polysaccharide, which comprises reacting a preformed second block onto the first block.