Aqueous oligomer / polymer emulsion with cationic functionality

Abstract

An aqueous emulsion comprising at least a covalently bound vinyl oligomer and vinyl polymer, wherein said vinyl oligomer comprises 5 to 85 mol % of vinyl monomers bearing quaternary ammonium ion functional groups or quaternisable amine functional groups and is obtained by a controlled radical polymerisation of at least one vinyl monomer via a reversible addition-fragmentation chain transfer mechanism in solution in the presence of a control agent and a source of free radicals; wherein said vinyl polymer is obtained by emulsion polymerisation of vinyl monomers in the presence of the vinyl oligomer; wherein the weight % ratio of vinyl oligomer to vinyl polymer is in the range of from 0.5:99.5 to 65:35.

1 . An aqueous emulsion comprising at least a covalently bound vinyl oligomer and vinyl polymer, wherein said vinyl oligomer comprises 5 to 85 mol % of vinyl monomers bearing quaternary ammonium ion functional groups and/or quaternisable amine functional groups and is obtained by a controlled radical polymerisation of at least one vinyl monomer via a reversible
 addition-fragmentation chain transfer mechanism in solution in the presence of a control agent and a source of free radicals; wherein said vinyl polymer is obtained by radical emulsion polymerisation of vinyl monomers in the presence of the vinyl oligomer;   wherein the weight % ratio of vinyl oligomer to vinyl polymer is in the range of from 0.5:99.5 to 65:35.   
   
   
       2 . An aqueous emulsion according to  claim 1 , wherein said vinyl oligomer comprises 5 to 85 mol % of vinyl monomer bearing quaternary ammonium ion functional groups. 
   
   
       3 . An aqueous emulsion comprising at least a covalently bound vinyl oligomer and vinyl polymer, wherein said vinyl oligomer comprises 5 to 85 mol % of vinyl monomers bearing quaternary ammonium ion functional groups and is obtained by a controlled radical polymerisation of at least one vinyl monomer via a reversible addition-fragmentation chain transfer mechanism in the presence of a control agent and a source of free radicals; wherein said vinyl polymer is obtained by radical emulsion polymerisation of vinyl monomers in the presence of the vinyl oligomer. 
   
   
       4 . An aqueous emulsion according to  claim 1  wherein the vinyl oligomer is a block copolymer comprising at least a block [A] comprising an ethylenically unsaturated monomer bearing quaternary ammonium ion and/or quaternisable amine functional groups and optionally other ethylenically unsaturated monomers; and a block [B] comprising ethylenically unsaturated monomers selected from the group consisting of acrylates, methacrylates or vinyl monomers; and optionally a third block or more. 
   
   
       5 . An aqueous emulsion according to  claim 1  comprising:
 a) 10 to 100 wt % of covalently bound vinyl oligomer polymer;   b) 0 to 40 wt of free vinyl oligomer;   c) 0 to 90 wt % of free vinyl polymer;   wherein a)+b)+c) add up to 100%.   
   
   
       6 . An aqueous emulsion according to  claim 1  wherein the weight % ratio of vinyl oligomer to vinyl polymer, whether covalently bound or free, is in the range of from 0.5:99.5 to 65:35. 
   
   
       7 . An aqueous emulsion according to  claim 1  wherein the Tg of the vinyl oligomer is in the range of from −100° C. to 0° C. 
   
   
       8 . An aqueous emulsion according to  claim 1  where the vinyl oligomer has a number average molecular weight Mn<50,000 g/mol. 
   
   
       9 . An aqueous emulsion according to  claim 1  wherein the vinyl oligomer is a block copolymer. 
   
   
       10 . An aqueous emulsion according to  claim 1  where the covalently bound vinyl oligomer polymer has a weight average molecular weight>20,000 g/mol. 
   
   
       11 . An aqueous emulsion according to  claim 1  where the vinyl polymer has a calculated Tg>0° C. 
   
   
       12 . An aqueous emulsion according to  claim 1 , said emulsion comprising a vinyl oligomer in the form of a block copolymer and a vinyl polymer [P];
 wherein the block copolymer comprises at least blocks [A] x [B] y , where at least block [A] is obtained by a controlled radical polymerisation of at least one ethylenically unsaturated monomer via a reversible addition-fragmentation chain transfer (RAFT) mechanism in solution in the presence of a control agent and a source of free radicals;   and wherein the block copolymer comprises:   5 to 90 wt % of block [A] comprising:
 10 to 100 mol % of ethylenically unsaturated monomers bearing quaternary ammonium ion and/or quaternisable amine functional groups; 
 0 to 90 mol % of ethylenically unsaturated monomers bearing water-dispersing or potentially water-dispersing functional groups; 
 0 to 50 mol % of C 1  to C 18  alkyl(meth)acrylates and/or styrenic monomers; 
 0 to 10 mol % of ethylenically unsaturated monomers different from those from i), ii) and iii); 
 where i), ii), iii) and iv) add up to 100 mol %, 
   and 10 to 85 wt % of block [B] comprising:
 0 to 10 mol % of ethylenically unsaturated monomers bearing quaternary ammonium ion and/or quaternisable amine functional groups; 
 0 to 5 mol % of ethylenically unsaturated monomers bearing water-dispersing or potentially water-dispersing functional groups; 
 50 to 100 mol % of C 1  to C 18  alkyl(meth)acrylates and/or styrenic monomers; 
 0 to 50 mol % of ethylenically unsaturated monomers different from those from i), ii) and iii); 
 where i), ii), iii) and iv) add up to 100 mol %; and 
 wherein vinyl polymer [P] is prepared by radical emulsion polymerisation of vinyl monomers in the presence of blocks [A] x [B] y  wherein vinyl polymer [P] comprises: 
 i) 0 to 5 wt % of ethylenically unsaturated monomers bearing quaternary ammonium ion and/or quaternisable amine functional groups; 
 ii) 0 to 5 wt % of ethylenically unsaturated monomers bearing water-dispersing or potentially water-dispersing functional groups; 
 iii) 40 to 100 wt % of C 1  to C 18  alkyl(meth)acrylates and/or styrenic monomers; 
 iv) 0 to 60 wt % of ethylenically unsaturated monomers different from those from i), ii) and iii); 
 where i), ii), iii), and iv) add up to 100 wt %; 
 where [A] has an average degree of polymerisation x, where x is an integer in the range of from 3 to 80; 
 where [B] has an average degree of polymerisation y, where y is an integer > 3 . 
   
   
   
       13 . An aqueous emulsion according to  claim 1  wherein the control agent is selected from the group consisting of dithioesters,
 thioethers-thiones, trithiocarbonates, dithiocarbamates, xanthates and mixtures thereof.   
   
   
       14 . An aqueous emulsion comprising a substantially insoluble vinyl oligomer in the form of a block copolymer comprising at least blocks [A]x[B]y, where at least block [A] is obtained by a controlled radical polymerisation of at least one ethylenically unsaturated monomer via a reversible addition-fragmentation chain transfer (RAFT) mechanism in solution in the presence of a control agent and a source of free radicals; and wherein the block copolymer comprises:
 5 to 90 wt % of block [A] comprising:
 i) 10 to 100 mol % of ethylenically unsaturated monomers bearing quaternary ammonium ion and/or quaternisable amine functional groups; 
 ii) 0 to 90 mol % of ethylenically unsaturated monomers bearing water-dispersing or potentially water-dispersing functional groups; 
 iii) 0 to 50 mol % of C 1  to C 18  alkyl(meth)acrylates and/or styrenic monomers; 
 iv) 0 to 10 mol % of ethylenically unsaturated monomers different from those from i), ii) and iii); 
 where i), ii), iii) and iv) add up to 100 mol %, and 
   10 to 85 wt % of block [B] comprising:
 i) 0 to 10 mol % of ethylenically unsaturated monomers bearing quaternary ammonium ion and/or quaternisable amine functional groups; 
 ii) 0 to 5 mol % of ethylenically unsaturated monomers bearing water-dispersing or potentially water-dispersing functional groups; 
 iii) 50 to 100 mol % of C 1  to C 18  alkyl(meth)acrylates and/or styrenic monomers; 
 iv) 0 to 50 mol % of ethylenically unsaturated monomers different from those from i), ii) and iii); 
 where i), ii), iii) and iv) add up to 100 mol %; 
 where [A] has an average degree of polymerisation x, where x is an integer in the range of from 3 to 80; 
 where [B] has an average degree of polymerisation y, where y is an integer >3. 
   
   
   
       15 . An aqueous emulsion according to  claim 1  additionally comprising a polymer [Q], wherein the solids content of the vinyl oligomer polymer is >1 wt % and <35 wt % based on total solids content of vinyl oligomer polymer and polymer [Q] together. 
   
   
       16 . A process for preparing an aqueous emulsion according to  claim 1  comprising the following steps:
 1. synthesis in a solvent by means of a RAFT radical polymerisation process of an vinyl oligomer;   2. optional removal of the control agent before, during or after dispersing said vinyl oligomer in water;   3. optional removal of the solvent from said vinyl oligomer;   4. dispersion of said vinyl oligomer in water optionally containing monomers, by adding either water to the vinyl oligomer or adding the vinyl oligomer to water, optionally using surfactants;   5. optional removal of solvent from the vinyl oligomer dispersion (if solvent is still present from step 4.);   6. performing an emulsion polymerisation process of monomers in the presence of the vinyl oligomer dispersion prepared in step 4 and or step 5 to obtain vinyl polymer.   
   
   
       17 . A coating having a permanent cationic surface comprising an aqueous emulsion according to  claim 1 . 
   
   
       18 . An antimicrobial agent comprising an aqueous emulsion according to  claim 1 . 
   
   
       19 . An antimicrobial surface obtained by coating a surface of a substrate with an aqueous emulsion according to  claim 1 . 
   
   
       20 . An antistatic surface obtained by coating a surface of a substrate with an aqueous emulsion according to  claim 1 . 
   
   
       21 . An antibleeding coating comprising an aqueous emulsion according to  claim 1 . 
   
   
       22 . A substrate coated with a primer coating comprising an aqueous emulsion according to  claim 1  and at least one top coating.