Aqueous hybrid dispersions

Abstract

The invention relates to a process for the preparation of an aqueous hybrid polymer dispersion comprising an auto-oxidatively crosslinkable polymer and an addition polymer. The invention further relates to the aqueous hybrid polymer dispersion obtainable by said process, the use thereof for the manufacture of coating compositions, ink compositions or adhesives and to coating compositions includes the hybrid polymer dispersion as a binder. The process includes a first polymerization step wherein a first hybrid polymer dispersion is formed by addition polymerization of vinyl monomers in the presence of dispersed auto-oxidatively crosslinkable polymer and a second polymerization step wherein secondary polymerization loci are provided in the first hybrid polymer dispersion to polymerise residual vinyl monomer of the first polymerisation step. The aqueous hybrid polymer dispersions have very low residual vinyl monomer content by achieving a high if not full conversion of the vinyl monomers at the end of the polymerization.

What is claimed is: 
     
         1 . A process for the preparation of an aqueous hybrid polymer dispersion comprising a hybrid polymer of an auto-oxidatively crosslinkable polymer and an addition polymer, wherein in a first polymerization step a first hybrid polymer dispersion is formed by addition polymerization of vinyl monomers in the presence of dispersed auto-oxidatively crosslinkable polymer, wherein, in a second polymerization step secondary polymerization loci are provided in the first hybrid polymer dispersion to polymerise residual vinyl monomer of the first polymerisation step. 
     
     
         2 . The process according to  claim 1 , wherein the first polymerization step is a mini-emulsion polymerisation. 
     
     
         3 . The process according to  claim 1 , wherein the first polymerization step comprises the steps of:
 a. providing a mixture of
 i. an aqueous dispersion of 10 to 90 wt % of the auto-oxidatively crosslinkable polymer (wt % relative to total polymer weight) 
 ii. 90 to 10 wt % vinyl monomers 
 iii. 1 to 15 wt % surfactant (relative to total polymer and surfactant weight) 
   b. converting the mixture to a mini-emulsion,   c. adding a radical initiator to the mixture of step a or before, during or after step b,   d. polymerising the vinyl polymers to form the first hybrid polymer dispersion preferably until reaching the limiting conversion;   and the second addition polymerization step comprises the steps of   e. providing the secondary polymerization loci in the first hybrid polymer dispersion,   f. polymerise residual vinyl monomer of the first polymerisation step.   
     
     
         4 . The process according to  claims 1 , wherein the secondary polymerisation loci are provided after at least 85% conversion of the vinyl monomers in the first polymerisation step. 
     
     
         5 . The process according to  claim 4 , wherein the secondary polymerisation loci are micelles formed by adding surfactant in an amount above the critical micelle concentration and adding an initiator. 
     
     
         6 . The process according to  claim 1 , wherein the secondary polymerisation loci are formed by addition of monomer having limited water solubility and a water soluble initiator. 
     
     
         7 . The process according to  claim 6 , wherein the monomer comprises styrene. 
     
     
         8 . The process according to  claim 1 , wherein the total residual monomer content after the second polymerisation step is below 1.0 wt. %. 
     
     
         9 . The process according to  claim 1 , wherein the auto-oxidative polymer is an alkyd having unsaturated fatty acids. 
     
     
         10 . The process according  claim 1 , wherein in the second polymerisation step additional vinyl monomer is added. 
     
     
         11 . The process according to  claim 1 , wherein the total amount of vinyl polymer formed in the secondary nucleation loci is less than 20 wt % (relative to the total weight of vinyl monomers). 
     
     
         12 . The process of  claim 1 , wherein the dispersion comprises two different populations; a first population of particles comprise the hybrid polymer comprising the auto-oxidatively crosslinkable polymer and the addition polymer and a second population of particles comprises a second addition polymer. 
     
     
         13 . An aqueous hybrid polymer dispersion comprising a hybrid polymer of an auto-oxidatively crosslinkable polymer and an addition polymer, wherein in a first polymerization step a first hybrid polymer dispersion is formed by addition polymerization of vinyl monomers in the presence of dispersed auto-oxidatively crosslinkable polymer, wherein, in a second polymerization step secondary polymerization loci are provided in the first hybrid polymer dispersion to polymerise residual vinyl monomer of the first polymerisation step. 
     
     
         14 . The aqueous hybrid polymer dispersion of  claim 13 , wherein the dispersion comprises two populations of particles wherein a first population of particles comprises a hybrid polymer comprising the auto-oxidatively crosslinkable polymer and the first addition polymer and a second population of particles comprises a second addition polymer. 
     
     
         15 . The aqueous hybrid polymer dispersion of  claim 13 , wherein the total amount of vinyl monomer formed in the secondary nucleation loci is less than 20 wt % (relative to the total weight of the vinyl monomers). 
     
     
         16 . The aqueous hybrid polymer dispersion according to  claim 13 , which dispersion has a residual monomer concentration below 1.0 wt %. 
     
     
         17 . The aqueous hybrid polymer dispersion according to  claim 13 , wherein the dispersion is used in the manufacture of coating compositions, ink compositions or adhesives. 
     
     
         18 . A coating composition comprising a binder material and coating additives, wherein the binder material is the aqueous hybrid polymer dispersion according to  claim 13 . 
     
     
         19 . The composition according to  claim 13 , wherein the first polymerization step comprises the steps of:
 a. providing a mixture of
 i. an aqueous dispersion of 10 to 90 wt % of the auto-oxidatively crosslinkable polymer (wt % relative to total polymer weight) 
 ii. 90 to 10 wt % vinyl monomers 
 iii. 1 to 15 wt % surfactant (relative to total polymer and surfactant weight) 
   b. converting the mixture to a mini-emulsion,   c. adding a radical initiator to the mixture of step a or before, during or after step b,   d. polymerising the vinyl polymers to form the first hybrid polymer dispersion preferably until reaching the limiting conversion;   and the second addition polymerization step comprises the steps of   e. providing the secondary polymerization loci in the first hybrid polymer dispersion,   f. polymerise residual vinyl monomer of the first polymerisation step.   
     
     
         20 . The composition to  claim 13 , wherein the secondary polymerisation loci are provided after at least 75% conversion of the vinyl monomers in the first polymerisation step. 
     
     
         21 . The composition of  claim 20 , wherein the secondary polymerisation loci are micelles formed by adding surfactant in an amount above the critical micelle concentration and adding an initiator. 
     
     
         22 . The composition according to  claim 13 , wherein the secondary polymerisation loci are formed by self precipitation of oligomers, formed upon the addition of water soluble initiator and additional monomers, that have limited water solubility. 
     
     
         23 . An aqueous hybrid polymer dispersion comprising:
 a first hybrid polymer dispersion comprising a hybrid polymer formed by polymerization of vinyl monomers in the presence of auto-oxidatively crosslinkable polymer,   and the polymerization product of residual vinyl monomer in secondary polymerization loci.   
     
     
         24 . The aqueous hybrid dispersion according to  claim 23 , wherein the polymerization of the auto-oxidatively crosslinkable polymer and vinyl monomer is formed by a mini-emulsion polymerisation. 
     
     
         25 . The aqueous hybrid dispersion according to  claim 23 , wherein the secondary polymerisation loci are provided after at least 75% conversion of the vinyl monomers in the addition polymerization of vinyl monomers in the presence of dispersed auto-oxidatively crosslinkable polymer. 
     
     
         26 . The aqueous hybrid dispersion according to  claim 23 , wherein the secondary polymerisation loci are micelles formed by adding surfactant in an amount above the critical micelle concentration and adding an initiator. 
     
     
         27 . The aqueous hybrid dispersion according to  claim 23 , wherein the secondary polymerisation loci are formed by addition of monomer having limited water solubility and a water soluble initiator. 
     
     
         28 . The aqueous hybrid dispersion according to  claim 23 , wherein the vinyl monomer is styrene. 
     
     
         29 . The aqueous hybrid dispersion according to  claim 23 , wherein the total residual monomer content after the second polymerisation step is below 1.0 wt. %. 
     
     
         30 . The aqueous hybrid dispersion according to  claim 23 , wherein the auto-oxidative polymer is an alkyd having unsaturated fatty acids. 
     
     
         31 . The aqueous hybrid dispersion according to  claim 23 , wherein the total amount of vinyl polymer formed in the secondary nucleation loci is less than 20 wt % (relative to the total weight of vinyl monomers). 
     
     
         32 . The aqueous hybrid dispersion according to  claim 23 , wherein the secondary polymerisation loci are micelles formed by adding surfactant in an amount above the critical micelle concentration and adding an initiator. 
     
     
         33 . The aqueous hybrid dispersion according to  claim 23 , wherein the dispersion is used in the manufacture of coating compositions, ink compositions or adhesives. 
     
     
         34 . An aqueous hybrid dispersion comprising two different populations, wherein:
 a first population of particles comprises a hybrid polymer comprising an auto-oxidatively crosslinkable polymer and vinyl polymer, and   a second population of particles comprises a second vinyl polymer.   
     
     
         35 . The aqueous hybrid dispersion of  claim 34 , wherein the total residual monomer content in the dispersion is below 1.0 wt %. 
     
     
         36 . The aqueous hybrid dispersion of  claim 34 , wherein the auto-oxidatively crosslinkable polymer is selected from the group consisting of: alkyds, uralkyds, hydroxyl terminated polybutadienes, and polymers having pendant allyl groups. 
     
     
         37 . The aqueous hybrid dispersion of  claim 36 , wherein the alkyds have unsaturated fatty acids. 
     
     
         38 . The aqueous hybrid dispersion of  claim 34 , wherein the addition polymer is prepared by free-radical polymerization of one or more olefinically unsaturated monomers. 
     
     
         39 . The aqueous hybrid dispersion of  claim 38 , wherein the monomers are styrene. 
     
     
         40 . The aqueous hybrid dispersion of  claim 34 , wherein the total amount of vinyl polymer is less than 20 wt % (relative to the total weight of vinyl monomers which are constituents of the first and second vinyl polymers). 
     
     
         41 . The aqueous hybrid dispersion of  claim 34 , wherein the hybrid polymer is a alkyd-acrylic polymer, and wherein the second addition polymer is a acrylic polymer. 
     
     
         42 . The aqueous hybrid dispersion of  claim 34 , wherein the dispersion is used in the manufacture of coating compositions, ink compositions or adhesives.