Method for emulsion polymerisation of olefins

Abstract

Process for the emulsion polymerization of one or more olefins by reacting a quinoid compound with a metal compound and a phosphine compound which is substituted by at least one polar radical and subsequently using the reaction product for the polymerization or copolymerization of olefins in water or in a solvent mixture which contains at least 50% by weight of water and at least one emulsifier.

1 - 10 . (canceled) 
   
   
       11 . An aqueous polymer dispersion prepared by the process, comprising:
 preparing a catalyst by reacting a quinoid compound of the formula Ia or Ib or a mixture of at least two of the compounds Ia or Ib   
     
       
         
         
             
             
         
       
       where R in each case is one or more of the following radicals: hydrogen, halogen, a nitrile, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 7 -C 15 -aralkyl group, a C 6 -C 14 -aryl group, unsubstituted or substituted by: C 1 -C 12 -alkyl groups, halogens, C 1 -C 12 -alkoxy groups, C 3 -C 12 -cycloalkyl groups, C 1 -C 12 -thioether groups, optionally carboxyl groups or sulfo groups present in the form of their salts, and amino groups with hydrogen and/or C 1 -C 12 -alkyl radicals; 
       amino groups NR 1 R 2 , where R 1  and R 2  together or separately are hydrogen, C 1 -C 12 -alkyl groups, C 7 -C 15 -aralkyl radicals and C 6 -C 14 -aryl groups and optionally additionally form a saturated or unsaturated 5- to 10-membered ring, unsubstituted or substituted by: C 1 -C 12 -alkyl groups, halogens, C 1 -C 12 -alkoxy groups, C 3 -C 12 -cycloalkyl groups, C 1 -C 12 -thioether groups, optionally carboxyl groups or sulfo groups present in the form of their salts, and amino groups with hydrogen and/or C 1 -C 12 -alkyl radicals, 
       wherein identical or different compounds of the formulae Ia and Ib, are optionally bridged by one or more C 1 -C 12 -alkylene bridges, C 2 -C 12 -alkylated azo bridges or bridges of the formula II 
     
     
       
         
         
             
             
         
       
       wherein Y is silicon or germanium and R 3  and R 4  are hydrogen and/or a C 1 -C 12 -alkyl group; 
       with a phosphine compound which is a compound III of the formula (R′) a PH 3-a , wherein a is 1, 2 or 3; R′ is a C 1 -C 12 -alkyl group, C 3 -C 12 -cycloalkyl group, C 7 -C 15 -aralkyl group or C 6 -C 14 -aryl group, which is substituted by at least one polar radical P which is selected from the group consisting of
 hydroxyl, carboxyl, sulfo, hydroxysulfonyloxy or phosphono groups and the alkali metal, alkaline earth metal and/or ammonium salts thereof, 
 alkanolammonium, pryidinium, imidazolinium, oxazolinium, morpholinium, thiazolinium, quinolinium, isoquinolinium, tropylium, sulfonium, guanidinium and phosphonium groups and ammonium groups of the formula IV 
 —N ⊕ R 7 R 8 R 9  (IV), where R 7 , R 8  and R 9 , independently of one another, are hydrogen or a C 1 -C 12 -alkyl group; or 
 a group of the formula V, VI or VII 
 -(EO) k —(PO) I —R 10  V, 
 —(PO) I -(EO) k —R 10  VI, 
 -(EO k /(PO I )—R 10  VII; where EO is a —CH 2 —CH 2 —O— group, 
 PO is a —CH 2 —CH(CH 3 )—O— or a —CH(CH 3 )—CH 2 —O— group, k and I are numerical values from 0 to 50, but k and I are not simultaneously 0, 
 R 10  is hydrogen, a C 1 -C 12 -alkyl group or a sulfo group or an alkali metal, alkaline earth metal and/or ammonium salt thereof, 
 
       and/or a diphosphine compound VIII of the formula (R′) b PH 2-b -G-PR″ 2 , where R″ is hydrogen or has the same meaning as R′, G is a C 1 -C 12 -alkylene group, C 3 -C 12 -cycloalkylene group, C 7 -C 15 -aralkylene group or C 6 -C 14 -arylene group, and b is 1 or 2; 
       and with a metal compound of the formula M(L 2 ) 2 , M(L 2 ) 2 (L 1 ) z1  or M(L 1 ) z2  wherein 
       M is a transition metal of groups 7 to 10 of the Periodic Table of the Elements; 
       L 1  is a phosphane (R 5 ) x PH 3-x  or amine (R 5 ) x NH 3-x  having identical or different radicals R 5 , an ether (R 5 ) 2 O, water, an alcohol (R 5 )OH, pyridine, a pyridine derivative of the formula C 5 H 5-x (R 5 ) x N, carbon monoxide, C 1 -C 12 -alkylnitrile, C 6 -C 14 -arylnitrile or an ethylenically unsaturated double bond system, where x is an integer ranging from 0 to 3; 
       R 5  is hydrogen, a C 1 -C 12 -alkyl group, which in turn may be substituted by O(C 1 -C 6 -alkyl) or N—(C 1 -C 6 -alkyl) 2  groups;
 a C 3 -C 12 -cycloalkyl group, a C 7 -C 15 -aralkyl radical or a C 6 -C 14 -aryl group, 
 
       L 2  is a halide ion, an amide anion (R 6 ) y NH 2-y —, where y is an integer ranging from 0 to 2 and R 6  is a C 1 -C 12 -alkyl group, and furthermore a C 1 -C 6 -alkyl anion, allyl anion, benzyl anion or aryl anion, where L 1  and L 2  may be linked to one another by one or more covalent bonds; 
       z1 is an integer ranging from 1 to 4; and 
       z2 is an integer ranging from 1 to 6; and
 subsequently (co)polymerizing at least one olefin in the presence of the prepared catalyst in water or in a solvent mixture which contains at least 50% by weight of water, in the presence of an emulsifier. 
 
     
   
   
       12 : A method of producing paper, textile or leather products, comprising:
 in the steps of preparing said paper, textile or leather product, employing the aqueous polymer dispersion according to  claim 11  in the process of production.   
   
   
       13 : A method of producing molding foams, carpet backing coatings and pharmaceutical formulations, comprising:
 in the steps of preparing said molding foams, carpet backing coatings and pharmaceutical formulations, employing the aqueous polymer dispersion according to  claim 11  in the process of production.   
   
   
       14 : A method of producing adhesives, sealing compounds, plastics renders, coating materials and paints, comprising:
 in the steps of preparing said molding foams, carpet backing coatings and pharmaceutical formulations, incorporating the aqueous polymer dispersion according to  claim 11  as a component of each material.   
   
   
       15 : A polymer powder prepared from an aqueous polymer dispersion according to  claim 11 .