Use as a rheology agent in a filled plastic paste of a dryground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group

Abstract

The invention resides in the use, as an agent reducing the viscosity of a thermoplastic or thermosetting paste filled with a calcium carbonate, of a calcium carbonate characterised in that it is obtained by dry-grinding, firstly, and in that it is dry-ground in the presence of a grinding aid agent which is a copolymer of (meth)acrylic acid with a monomer containing an alcoxy or hydroxy polyalkyleneglycol group, secondly. The invention also concerns the filled thermoplastic and thermosetting pastes obtained in this manner.

1 . A method for reducing the viscosity of a paste consisting of a thermoplastic or thermosetting resin and calcium carbonate, wherein said carbonate is dry-ground in the presence of a copolymer grinding aid agent comprising:
 a) at least one anionic monomer chosen from acrylic acid, methacrylic acid and their blends,   b) and of at least one non-ionic monomer, of formula (I):   
     
       
         
         
             
             
         
       
       where:
 m, n, p and q are integers such that: m, n, p≦150, q≧1, and 5≦(m+n+p)q≦150, 
 R 1  represents hydrogen or the methyl or ethyl radical, 
 R 2  represents hydrogen or the methyl or ethyl radical, 
 R represents a radical containing an unsaturated polymerisable function chosen from the group of vinylics, the group of acrylic, methacrylic, and maleic esters, the group of unsaturated urethanes selected from the group consisting of acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, and allylurethane, the group of allylic or vinylic ethers, whether or not substituted, the group of ethylenically unsaturated amides or imides, and the group consisting of acrylamide and methacrylamide, and 
 R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms, 
 
       or a blend of several monomers of formula (I), 
       c) and optionally at least one other monomer chosen from (meth)acrylic anhydride and (meth)acrylamide, the esters chosen from the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, and the hydroxylated methacrylates selected from the hydroxyethyl and hydroxypropyl methacrylates, the aromatic vinylic monomers chosen from styrene, α-methylstyrene, and styrene sulfonate, and acrylamido-2-methyl-2-propane-sulfonic acid, the organophosphate monomers chosen from the acrylate and methacrylate phosphates of ethylene glycol, and the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends. 
     
   
   
       2 . The method according to  claim 1 , wherein said copolymer comprises, expressed as a percentage by weight of the monomers in which the sum of the percentages by weight of all the monomers equals 100%:
 a) 0.5% to 50% of at least one anionic monomer chosen from acrylic acid, methacrylic acid and their blends,   b) 50% to 99.5% of at least one non-ionic monomer, of formula (I):   
     
       
         
         
             
             
         
       
       where:
 m, n, p and q are integers such that: m, n, p≦150, q≧1 and 5≦(m+n+p)q≦150, 
 R 1  represents hydrogen or the methyl or ethyl radical, 
 R 2  represents hydrogen or the methyl or ethyl radical, 
 R represents a radical containing an unsaturated polymerisable function chosen from the group of vinylics, the group of acrylic, methacrylic, and maleic esters, the group of unsaturated urethanes selected from the group consisting of acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, and allylurethane, the group of allylic and vinylic ethers, whether or not substituted, the group of ethylenically unsaturated amides or imides, and the group consisting of acrylamide and methacrylamide, and 
 R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms, 
 
       or a blend of several monomers of formula (I), and 
       c) 0% to 50% of at least one other monomer chosen from (meth)acrylic anhydride and (meth)acrylamide, the esters chosen from the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, and the hydroxylated methacrylates chosen from the hydroxyethyl and hydroxypropyl methacrylates, the aromatic vinylic monomers chosen from styrene, α-methylstyrene, and styrene sulfonate, and acrylamido-2-methyl-2-propane-sulfonic acid, the organophosphate monomers, chosen from the acrylate and methacrylate phosphates of ethylene glycol, and the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends. 
     
   
   
       3 . The method according to  claim 1 , wherein said copolymer is obtained in the acidic form and optionally distilled, and is optionally partially or totally neutralised by one or more neutralisation agents having a monovalent or polyvalent cation, where said agents are chosen from ammonia, and calcium and magnesium hydroxides and/or oxides, sodium, potassium and lithium hydroxides, and the aliphatic and/or cyclic primary, secondary or tertiary amines chosen from stearylamine, the ethanolamines, mono- and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methyl propanol, and morpholine. 
   
   
       4 . The method according to  claim 1 , wherein said copolymer is obtained by a polymerization process chosen from radical polymerisation in solution, in a direct or reverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and chain transfer agents, or a process of controlled radical polymerisation, chosen from nitroxide mediated polymerisation (NMP) or cobaloximes, atom transfer radical polymerisation (ATRP), and controlled radical polymerisation by sulphurated derivatives, chosen from carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates. 
   
   
       5 . The method according to  claim 3 , wherein said copolymer is, before or after the total or partial neutralisation reaction, treated and separated into several phases, according to static or dynamic processes, by one or more polar solvents selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, the butanols, acetone, tetrahydrofuran and their blends. 
   
   
       6 . The method according to  claim 1 , wherein 0.05% to 5% by dry weight of the said copolymer relative to the dry weight of calcium carbonate is used during the dry grinding of the said carbonate. 
   
   
       7 . The method according to  claim 1 , wherein the resin constituting the paste is a thermoplastic resin chosen from PVC, chlorinated polyvinyl chloride (PVCC), vinylidene polyfluoride (PVDF) styrenic resins, and thermoplastic elastomers, resins of the styrene-acrylonitrile type, acrylate-butadiene-styrene resins, styrene methylmethacrylate copolymers, acrylic resins, the polyolefines, the polycarbonate resins, the polyamide resins, and the thermoplastic polyesters and a blend of these resins. 
   
   
       8 . The method according to  claim 1 , wherein the resin constituting the paste is a thermosetting resin chosen from the vulcanisable elastomers or latexes, the epoxide, polyurethane, or unsaturated polyester resins, and their blends. 
   
   
       9 . Thermoplastic or thermosetting pastes, obtained by the method according to  claim 1 . 
   
   
       10 . Thermoplastic or thermosetting parts obtained from the thermoplastic or thermosetting pastes according to  claim 9 .