Finely divided, starch-containing polymer dispersions, processes for their preparation and use as sizes in papermaking

Abstract

A finely divided, starch-containing polymer dispersion which is obtainable by free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and starch, wherein (a) from 0 to less than 40% by weight of at least one optionally substituted styrene, (b) from greater than 60 to 100% by weight of at least one C 1 -C 12 -alkyl acrylate and/or C 1 -C 12 -alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum (a)−(b)+(c) being 100% and being based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch which has a molar mass M w of from 1000 to 65 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d), are used as the starch, and the polymerization being carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one terpene containing chain-transfer agent, and in which the polymer dispersion optionally comprises an aluminium compound. The use of the finely divided, starch-containing polymer dispersions as sizes for paper, board and cardboard is also claimed.

1 - 16 . (canceled) 
     
     
         17 : A finely divided, starch-containing polymer dispersion obtained by a process comprising: free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and at least one starch, wherein the ethylenically unsaturated monomers comprise:
 (a) 15 to 35% by weight of at least one optionally substituted styrene;   (b) 65 to 85% by weight of at least one C 1 -C 12 -alkyl acrylate and/or C 1 -C12-alkyl methacrylate; and   (c) 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer;   wherein the sum (a)+(b)+(c) is 100% based on active monomer content and the starch comprises:   (d) 15 to 40%) by weight of at least one degraded starch which has a molar mass M w  of from 1000 to 65 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d); and   the polymerization is carried out in the presence of at least one terpene-containing chain-transfer agent of at least 0.01% by weight, based on the monomers used and   the polymer dispersion may comprise an aluminium compound.   
     
     
         18 : The finely divided, starch-containing polymer dispersion of  claim 17 , wherein the ethylenically unsaturated monomers comprise:
 (a) 15 to 35% by weight of at least one optionally substituted styrene;   (b) 65 to 85% by weight of at least one C 1 -C 12 -alkyl acrylate and/or C 1 -C 12 -alkyl methacrylate; and   (c) 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer;   wherein the sum (a)+(b)+(c) is 100% based on active monomer content and the starch comprises:   (d) 25 to 35%) by weight of at least one degraded starch which has a molar mass M w  of from 1000 to 65 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d);   the polymerization is carried out in the presence of at least one terpene-containing chain-transfer agent of at least 0.01% by weight, based on the monomers used and   the polymer dispersion may comprise 0.1 to 50%) of an aluminium compound based on the total weight of solids content of the polymer dispersion.   
     
     
         19 : The finely divided, starch-containing polymer dispersion of  claim 18 , wherein the ethylenically unsaturated monomers comprise:
 (a) 15 to 35% by weight of at least one optionally substituted styrene;   (b) 65 to 80% by weight of a C 1 -C 12 -alkyl acrylate or C 1 -C 12 -alkyl methacrylate and   (c) 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer;   wherein the sum (a)+(b)+(c) is 100% based on active monomer content and the starch comprises:   (d) 25 to 35% by weight of at least one degraded starch which has a molar mass M w  of from 2500 to 35 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d); and   the polymerization is carried out in the presence of at least one terpene-containing chain-transfer agent of at least 0.01 % by weight, based on the monomers used and   the polymer dispersion may comprise 0.1 to 50% of an aluminium compound based on the total weight of the solids content of the polymer dispersion.   
     
     
         20 : The finely divided, starch-containing polymer dispersion of  claim 18 , wherein the ethylenically unsaturated monomers comprise:
 (a) 20 to 35% by weight of at least one optionally substituted styrene;   (b) 65 to 75%:. by weight of a C 1 -C 12 -alkyl acrylate; and   (c) 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer;   wherein the sum (a)+(b)+(c) is 100% based on active monomer content and the starch comprises:   (d) 25 to 35% by weight of a degraded anionic starch which has a molar mass M w  of from 2500 to 35 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d); and   the polymerization is carried out in the presence of at least one terpene-containing chain-transfer agent of at least 0.01% by weight, based on the monomers used and   the polymer dispersion may comprise 0.1 to 50% of an aluminium compound based on the total weight of the solids content of the polymer dispersion.   
     
     
         21 : The finely divided, starch-containing polymer dispersion of  claim 17 , wherein the terrene-containing chain-transfer agent is used in an amount of 0.01 to 10% by weight, based on the monomers. 
     
     
         22 : The finely divided, starch-containing polymer dispersion of  claim 17 , wherein the terpene-containing chain-transfer agent is used in an amount of 0.05 to 5% by weight, based on the monomers. 
     
     
         23 : The finely divided, starch-containing polymer dispersion of  claim 17 , wherein the chain-transfer agent is a monocyclic monoterpene; and wherein the monocyclic monoterpene is terpinolene. 
     
     
         24 : The finely divided, starch-containing polymer dispersion of  claim 17 , wherein the polymerization is carried out in the presence of 0.05 to 5% by weight of terpinolene as the chain-transfer agent. 
     
     
         25 : A process for the preparation of finely divided, starch-containing polymer dispersions of  claim 17 , comprising:
 polymerizing the ethylenically unsaturated monomers in the presence of a redox initiator in an aqueous medium;   wherein the ethylenically unsaturated monomers comprise:   (a) 15 to 35% by weight of at least one optionally substituted styrene;   (b) 65 to 85% by weight of at least one C 1 -C 12 -alkyl acrylate and/or C 1 -C 12 -alkyl methacrylate; and   (c) 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer;   wherein the sum (a)+(b)+(c) is 100% and being based on the active monomer content; and the starch comprises:   (d) 15 to 40% by weight of at least one degraded starch which has a molar mass M w  of from 1000 to 65 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d); and   wherein the polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one terpene-containing chain-transfer agent; and   the polymer dispersion may comprise an aluminium compound.   
     
     
         26 : The process of  claim 25 , wherein the chain-transfer agent is a monocyclic monoterpene; and
 wherein the monocyclic monoterpene is terpinolene.   
     
     
         27 : The process of  claim 25 , wherein the polymerization is carried out in the presence of from 0.05 to 5% by weight of at least one terpene-containing chain-transfer agent. 
     
     
         28 : The process of  claim 27 , wherein the polymerization is carried out in the presence of from 0.05 to 5% by weight of terpinolene as the chain-transfer agent. 
     
     
         29 : The process of  claim 25 , further comprising:
 adding an initiator to the polymer dispersion after polymerization selected from the group consisting of hydrogen peroxide, peroxides, hydroperoxides and azo initiators; and   postpolymerizing the polymer dispersion.   
     
     
         30 : The process of  claim 25 , further comprising:
 adding tert-butyl hydroperoxide to the polymer dispersion during postpolymerization.