WO2008068319A1 - Coated alkaline-earth metal carbonate particles, process for manufacturing such particles and plastic compositions containing such particles - Google Patents

Coated alkaline-earth metal carbonate particles, process for manufacturing such particles and plastic compositions containing such particles Download PDF

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Publication number
WO2008068319A1
WO2008068319A1 PCT/EP2007/063476 EP2007063476W WO2008068319A1 WO 2008068319 A1 WO2008068319 A1 WO 2008068319A1 EP 2007063476 W EP2007063476 W EP 2007063476W WO 2008068319 A1 WO2008068319 A1 WO 2008068319A1
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equal
earth metal
alkaline
metal carbonate
carbonate particles
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PCT/EP2007/063476
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French (fr)
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Gaëlle RODARY
Karine Cavalier
Graham Carr
Stewart Derbyshire
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Solvay (Societe Anonyme)
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Publication of WO2008068319A1 publication Critical patent/WO2008068319A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • Coated alkaline-earth metal carbonate particles process for manufacturing such particles and plastic compositions containing such particles
  • the invention is related to coated alkaline-earth metal carbonate particles. More specifically, the invention is related to alkaline-earth metal carbonate particles coated with a coating agent comprising a polymer.
  • Alkaline-earth metal carbonates are used as additive in various materials, in particular in plastics (Rainer Wolf, Bansi LaI Kaul, Ullmann's Encyclopedia of Industrial Chemistry, VCH-Publisher, Inc., 1992, Vol. A20, p. 496).
  • Calcium carbonate particles for instance, are often surface treated (i.e. coated) in order to improve their dispersion in plastics. Surface treatments vary depending on the plastic type and on the properties searched for the filled plastic (improvement of mechanical, optical, thermal, electrical properties, etc.) and generally different calcium carbonates with different coatings must be manufactured for different plastics applications. So the calcium carbonate and the coating have to be adapted to the plastic and the plastic applications, which is a laborious time consuming and costly procedure. It is therefore desirable to dispose of a unique product which could be used in several plastics and which characteristics would fulfill the requirements of the applications the plastics are used for.
  • the goal of the present invention is to provide coated alkaline-earth metal carbonate particles which could be used as additives in plastic compositions for applications requiring different properties.
  • the invention is then related to alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula
  • the invention is also related to a process for manufacturing such particles.
  • the coated alkaline-earth metal carbonate particles of the invention can be used as filler, preferably as filler in paper, plastics, rubber, ink, paint, plastisols, sealants, food, pharmaceutical, cosmetics and constructions materials.
  • the invention is therefore also related to the use of such particles as filler.
  • the invention is finally also related to plastic compositions comprising at least one plastic component and particles of alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula
  • alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula (A) or (B) according to the invention will be further indifferently designated by the expressions "at least partly coated alkaline-earth metal carbonate particles” or “coated alkaline-earth metal carbonate particles” or "alkaline-earth metal carbonate particles”.
  • a coating agent comprising at least one polymer complying with formula (A) or (B) according to the invention
  • the at least partly coated alkaline-earth metal carbonate particles of the invention can be added as filler in plastic compositions as different as polycarbonate, polymethylmethacrylate, polyamide, polyurethane and polyvinyl chloride, improving the properties required by the applications of such plastic compositions as for example, scratch resistance, impact strength, resistance to traction, thermal stability and resistance to visible and ultra violet light, while keeping an excellent transparency for compositions containing polycarbonate and polymethylmethacrylate, and a good rigidity and surface aspect for compositions based on polyvinyl chloride, polyamide and polyurethane for rigid applications.
  • the expressions « polymer » and « plastic » are used in their general acceptation and invariably designate a homopolymer, a copolymer, or a mixture thereof.
  • the « polymer » and « plastic » definitions emcompass also the oligomers.
  • the polymer can be a natural or a synthetic polymer. Synthetic polymers are preferred.
  • the polymer and the plastic can be identical or different. They are frequently different.
  • the divalent hydrocarbon groups E and E' are preferably a (CHi) n group where n is an integer higher than or equal to 1 and lower than or equal to 10, preferably equal to 3, 4 or 5, more preferably equal to 4 and 5, and most preferably equal to 5.
  • x is preferably higher than or equal to 5, more preferably higher than or equal to 10 and most preferably higher than or equal to 20.
  • R 1 , R 2 and R 3 are each an alkylene group, linear or branched, substituted or not, alicyclic or not, containing at least 1 and at most 50 carbon atoms.
  • R 1 is preferably an alkylene group, linear or branched, substituted or not, alicyclic or not, containing at least 2 and at most 50 carbon atoms, preferably a polymethylene group (CH 2 X where r is an integer higher than or equal to 2 and - A -
  • R 2 is preferably an alkylene group, linear or branched, substituted or not, alicyclic or not containing at least 1 and at most 50 carbon atoms, preferably, a polymethylene group (CH 2 ) S where s is an integer higher than or equal to 1 and lower than or equal to 6, isopropylene [CH 2 CH(CHs)], isobutylene
  • the Z group is preferably a R 1 radical and most preferably a tetramethylene (CH 2 ) 4 group.
  • the Z' group is preferably a
  • the Z group when m is equal to 3, can be selected among the radicals CH 2 C(OH)CH 2 and C 6 H 3 and the Z' group can be selected among the radicals CH 2 CHCH 2 and CH 3 CH 2 C(CH 2 ) 3 .
  • the Z' group when m is equal to 4, can be a C(CHi) 4 group.
  • the polymer exhibits a molecular weight higher generally than or equal to 500 g/mol and preferably higher than or equal to 750 g/mol. That molecular weight is generally lower than or equal 5 000 g/mol, preferably lower than or equal to 4 000 g/mol and most preferably lower than or equal to 2 500 g/mol.
  • the acid number is generally lower than or equal to 300 mg of KOH/g of polymer and often lower than or equal to 116 mg of KOH/g of polymer.
  • the hydroxyl number is generally lower than or equal to 300 mg of KOH/g of polymer, often lower than 200 mg of KOH/g of polymer and frequently lower than or equal to 116 mg of KOH/g of polymer.
  • the polymer when the polymer complies formula (A), the polymer can be obtained by reaction between a di- or a tri-carboxylic acid and a lactone, or an hydroxy acid or a mixture of a lactone and a hydroxy acid.
  • the polymer when the polymer complies formula (B), the polymer can be obtained by reaction between a di-, a tri- or a tetra-ol and a lactone, or an hydroxy acid or a mixture of a lactone and a hydroxy acid.
  • the lactone is preferably selected from ⁇ -valerolactone, ⁇ -butyrolactone and ⁇ -caprolactone.
  • the lactone is more preferably ⁇ -caprolactone.
  • the dicarboxylic acid is preferably selected among succinic and adipic acid. Adipic acid is the most preferred.
  • the triacid is preferably citric acid.
  • the diol is preferably a polycarbonate polymer end terminated by hydroxyl groups.
  • a commercial product of that type is CAP A ® 7203 of SOLVAY CAPROLACTONES.
  • the coating agent may contain other compounds than the polymer like for instance, fatty acids, rosins acids, polyacrylic acids, sulfonic acids, derivatives of those acids like salts and esters, alkylsulfates, alkylsulfosuccinates and mixtures thereof.
  • the content of the coating agent is generally higher than or equal to 4 g/kg of coated alkaline-earth metal carbonate particles, often higher than or equal to 8 g/kg and frequently higher than or equal to 13 g/kg. That content is generally lower than or equal to 130 g/kg of coated alkaline-earth metal carbonate particles, often lower than or equal to 100 g/kg and frequently lower than or equal to 80 g/kg.
  • the content of the polymer is generally higher than or equal to 1 g/kg of coated alkaline-earth metal carbonate particles, often higher than or equal to 5 g/kg and frequently higher than or equal to 10 g/kg. That content is generally lower than or equal to 100 g/kg of coated alkaline-earth metal carbonate particles, often lower than or equal to 70 g/kg and frequently lower than or equal to 50 g/kg.
  • the alkaline-earth metal is preferably selected from magnesium, calcium, strontium, barium and mixtures thereof. Calcium is more preferred.
  • the alkaline-earth metal carbonate particles of the invention can be particles of natural or synthetic alkaline-earth metal carbonate.
  • Natural magnesium carbonate can be natural magnesite or hydromagnesite.
  • Natural calcium carbonate can be natural calcite or aragonite, chalk or marble.
  • Natural magnesium and calcium carbonate can occur as calcium-magnesium carbonate containing minerals like huntite and dolomite.
  • Natural strontium carbonate can be natural strontianite.
  • Natural barium carbonate can be natural whiterite.
  • Synthetic alkaline-earth metal carbonates are preferred. Synthetic precipitated alkaline-earth metal carbonates are more preferred. Synthetic precipitated calcium carbonate is the most preferred.
  • Primary particles are defined as the smallest discrete particles that can be seen by Electron Microscopy analysis.
  • the alkaline-earth metal carbonate of the invention may be substantially amorphous or substantially crystalline.
  • the term "substantially amorphous or crystalline” is intended to mean that more 50 %, in particular more than 75 % and preferably more than 90 % by weight of the alkaline-earth metal carbonate is in the form of amorphous or crystalline material when analyzed by the X-ray diffraction technique.
  • Substantially crystalline alkaline-earth metal carbonates are preferred.
  • Substantially crystalline calcium carbonate is preferred.
  • the magnesium carbonate may consist of barringtonite, nesquehonite, lansfordite or of a mixture of at least two of these crystallographic varieties.
  • the strontium carbonate may consist of aragonite type, of calcite type or of a mixture of at least two of these crystallographic varieties.
  • the barium carbonate may consist of aragonite type.
  • the calcium carbonate may consist of calcite, of vaterite or of aragonite or of a mixture of at least two of these crystallographic varieties.
  • Calcium carbonate particles presenting at least partly a calcite crystallographic structure are preferred.
  • the calcium carbonate particles presenting the calcite crystallographic structure amount generally for at least 20 % by weight of the total calcium carbonate particles, often for at least 50 %, frequently for at least 80 % and most specifically for at least 95 %.
  • the alkaline-earth metal carbonate particles of the invention can exhibit various morphologies.
  • the particles can have the form of needles, scalenohedra, rhombohedra, hexagons, cubes, spheres, platelets or prisms.
  • the calcium carbonate particles of the invention can exhibit various morphologies.
  • the particles can have the form of needles, scalenohedra, rhombohedra, cubes, spheres, platelets or prisms.
  • the corners and edges of several of such forms, for instance rhombohedra and cubes can be rounded.
  • the scalenohedra and rhombohedra forms are preferred.
  • Calcium carbonate particles presenting a rhomboedric morphology are more preferred.
  • the calcium carbonate particles presenting the rhomboedric morphology amount generally for at least 20 % by number of the total calcium carbonate particles, often for at least 50 %, frequently for at least 80 % and most specifically for at least 95 %. The % by number can be obtained from Scanning Electron Microscopy measurements.
  • the alkaline-earth metal carbonate particles according to the invention have a BET specific surface area generally greater than or equal to 1 mVg, often greater than or equal to 5 m 2 /g, frequently greater than or equal to 20 m 2 /g and in particular greater than or equal to 40 m 2 /g.
  • a specific surface area of greater than or equal to 70 m 2 /g gives good results.
  • the BET specific surface area of the particles is generally less than or equal to 300 m 2 /g, often less than or equal to 150 m 2 /g and frequently less than or equal to 100 m 2 /g.
  • the specific surface area is measured by the standardized BET method (standard ISO 9277-1995).
  • the alkaline-earth carbonate particles of the invention have generally a mean primary particle size (dp) higher than or equal to 0.010 ⁇ m, often higher than or equal to 0.030 ⁇ m, frequently higher than or equal to 0.050 ⁇ m, specifically higher than or equal to 0.070 ⁇ m and more specifically higher than or equal to 0.100 ⁇ m.
  • the mean primary particle size is generally lower than or equal to 20 ⁇ m, frequently lower than or equal to 10 ⁇ m, often lower than or equal to 1 ⁇ m and most often lower than or equal to 0.75 ⁇ m.
  • the size distribution of the precipitated calcium carbonate particles according to the invention is obtained by Gravitational Liquid Sedimentation Methods (standard ISO 13317-3-2001).
  • the average size of the particles (equal to the value of D 50 defined below) is commonly higher than or equal to 0.030 ⁇ m, often higher than or equal to 0.050 ⁇ m, frequently higher than or equal to 0.070 ⁇ m, specifically higher than or equal to 0.100 ⁇ m and most specifically higher than or equal to 0.150 ⁇ m.
  • the average size of the particles is generally lower than or equal to 20 ⁇ m, frequently lower than or equal to 10 ⁇ m, often lower than or equal to 5 ⁇ m, specifically lower than or equal to 3 ⁇ m and most specifically lower than or equal to 2 ⁇ m.
  • D 50 is the particle size value which expresses that 50 % by vol of the particles have a size value lower than or equal to D 50 .
  • the alkaline-earth metal carbonate particles of the invention can occur as clusters of primary particles, which highest dimension is generally higher than or equal to 10 nm, often higher than or equal to 20 nm , frequently higher than or equal to 50 nm, specifically higher than or equal to 80 nm and in particular higher than or equal to 140 nm. That highest dimension is generally lower than or equal to 40 ⁇ m, often lower than or equal to 4 ⁇ m and frequently lower than or equal to 0.3 ⁇ m.
  • Those clusters exhibit a smallest dimension which is generally higher than or equal to 5 nm, often higher than or equal to 10 nm , frequently higher than or equal to 25 nm, specifically higher than or equal to 40 nm and in particular higher than or equal to 70 nm.
  • That smallest dimension is generally lower than or equal to 10 ⁇ m, often lower than or equal to 0.7 ⁇ m and frequently lower than or equal to 0.2 ⁇ m.
  • Those dimensions can be obtained by measuring the highest and lowest dimensions of the clusters on photographs obtained by Scanning Electron Microscopy.
  • Any coating procedure can be used to obtain the coated alkaline-earth carbonate particles according to the invention.
  • the process for manufacturing the coated alkaline-earth metal carbonate particles comprises the following steps :
  • step (c) Eliminating a fraction of the solvent from the coating medium of step (b) in order to obtain a concentrated coating medium, or wet at least partly coated alkaline-earth metal carbonate particles.
  • the process may comprise an additional step (d) :
  • step (d) Drying the concentrated medium or the wet at least partly coated alkaline- earth metal carbonate particles of step (d).
  • a dry solid i.e. a solid with a water content usually lower than or equal to 10 % by weight. This content is preferably lower than or equal to 3 % by weight and more particularly lower than or equal to 1 % by weight.
  • moist cake By moist cake, one intends to denote a solid with a water content normally greater than 10 % by weight, more specifically greater than or equal to 30 % by weight. This content is generally lower than or equal to 70 % by weight and preferably lower than or equal to 50 % by weight.
  • the solid content of the aqueous suspension of alkaline-earth metal carbonate particles in step (a) is usually higher than or equal to 25 g/L, frequently higher than or equal to 50 g/L, and often higher than or equal to 100 g/L. That content is usually lower than or equal to 250 g/L, frequently lower than or equal to 200 g/L, and often lower than or equal to 180 g/L.
  • the powder, the moist cake and the suspension of alkaline-earth metal carbonate particles can be obtained by any known method.
  • Natural alkaline-earth metal carbonates can be processed by mechanically crushing and grading alkaline-earth metal carbonates containing ores to obtain particles adjusted to the desired size.
  • Synthetic alkaline-earth metal carbonate particles are usually prepared by precipitation.
  • Precipitated magnesium carbonates may be prepared by reacting magnesium hydroxide with carbon dioxide at high pressure.
  • Precipitated calcium carbonate may be manufactured by first preparing a calcium oxide (quick lime) by subjecting limestone to calcination by burning a fuel, such as coke, a petroleum fuel (such as heavy or light oil), natural gas, petroleum gas (LPG) or the like, and then reacting the calcium oxide with water to produce a calcium hydroxide slurry (milk or lime), and reacting the calcium hydroxide slurry with the carbon dioxide discharged from a calcination furnace for obtaining the calcium oxide from limestone to obtain the desired particle size and shape precipitated calcium carbonate (carbonation process).
  • a fuel such as coke, a petroleum fuel (such as heavy or light oil), natural gas, petroleum gas (LPG) or the like
  • LPG petroleum gas
  • Precipitation of calcium carbonate can also be carried out by adding an alkali metal carbonate starting with lime water (causticisation method) or precipitation by the addition of an alkali metal carbonate starting with solutions containing calcium chloride. Precipitated calcium carbonate obtained from the carbonation process is preferred.
  • Strontium and barium carbonates may be prepared by precipitating the carbonates from strontium or barium sulfide solutions with carbon dioxide.
  • Barium carbonate may also be prepared by precipitating the carbonate from barium sulfide solutions with sodium carbonate.
  • the solution (dissolved coating agent) or suspension (solid coating agent) or emulsion (liquid coating agent) of the coating agent in a solvent can be obtained by any known method.
  • the solvent can be an organic solvent or an inorganic solvent or a mixture thereof. It is preferred to use an emulsion of the coating agent in an inorganic solvent.
  • the inorganic solvent is preferably water.
  • the stirring conditions i.e. stirring speed, temperature and duration of step (b) are adjusted to obtain the desired coating level of the calcium carbonate particles.
  • the temperature of step (b) is usually higher than or equal to 2O 0 C, frequently higher than or equal to 5O 0 C, and often higher than or equal to 75 0 C. That temperature is usually lower than or equal to 100 0 C and frequently lower than or equal to 8O 0 C.
  • the duration of step (b) is usually higher than or equal to 1 min, frequently higher than or equal to 5 min and often higher than or equal to 20 min. That duration is usually lower than or equal to 60 min and frequently lower than or equal to 45 min.
  • the coating agent is present in the precipitation medium before the precipitation of alkaline-earth metal carbonate particles occurs.
  • the process comprises the following steps :
  • step B Adding respectively a carbonate or an alkaline-earth metal containing compound to the precipitation medium of step A so as to precipitate alkaline- earth metal carbonate particles and coat the precipitated particles at least partly with the coating agent.
  • the process may comprise an additional step (C)
  • step B Separating the at least partly coated alkaline-earth metal carbonate particles from the precipitation medium of step B, in order to obtain wet at least partly coated calcium carbonate particles.
  • the process may comprise an additional step (D)
  • the solvent can be an organic solvent or an inorganic solvent or a mixture thereof. It is preferred to use an inorganic solvent, preferably water.
  • Any alkaline-earth metal containing compound can be used.
  • the coating agent may contain a crystallization controller i.e. a substance able to control the crystallographic phase, the morphology and/or the size of the precipitated alkaline-earth metal carbonate particles.
  • Plastic compositions comprising at least one plastic component and the at least partly coated alkaline-earth metal carbonate particles are also an object of the invention.
  • the plastic component can be selected from homopolymers and copolymers of ethylene, propylene, styrene, vinyl chloride, vinylidene chloride, acrylic acid, alkyl acrylates, methacrylic acid, alkyl methacrylates, acrylonitrile, vinyl acetate, vinyl alcohol, isoprene, chloroprene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, copolymers of ethylene and alpha-olefins, copolymers of propylene and alpha-olefins other than propylene, copolymers of vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and alkyl acrylates, copolymers of vinylidene chloride and alkyl methacrylates as mtehyl metahcrylate, copolymers of styrene, butadiene and rubber, copolymers of acrylonitrile and buta
  • Plastic component selected from polycarbonate, polymethylmethacrylate, polyamides, polyvinyl chloride, polyurethane, polysulfones and epoxy resins are preferred.
  • the plastic component of the composition can be a crystalline or an amorphous polymer.
  • crystalline polymer By crystalline polymer, one intends to denote a polymer which has a cristallinity as measured according to Standard ASTD D 3418-03 higher than or equal to 15 %, preferably higher than or equal to 50 %, more preferably higher than or equal to 90 % and most preferably higher than or equal to 95 %.
  • amorphous polymer one intends to denote a polymer which has a cristallinity lower than 15 %, preferably lower than or equal to 5 %, more preferably lower than or equal to 1 % and most preferably lower than or equal to 0.5 %.
  • Amorphous polymers are preferred.
  • the plastic component of the plastic composition can be a transparent polymer.
  • transparent polymer By transparent polymer, one intends to denote a polymer which has a transparency, expressed as the percentage of visible light transmitted through a sheet of 4 mm of thickness, higher than or equal to 75 %, preferably higher than or equal to 85 % and most preferably higher than or equal to 90 %. If the polymer can not be obtained as a sheet of 4 mm of thickness, by transparent polymer, one intends to denote as a polymer which has a transparency, expressed as the percentage of visible light transmitted through a film of 100 ⁇ m of thickness, higher than or equal to 85 %, preferably higher than or equal to 90 % and most preferably higher than or equal to 95 %.
  • the transparency measurement is made according to standard ASTM D 1746-03 (2003).
  • Transparent polymers are generally amorphous polymers. Those polymers can be selected among polyolefins, vinylic polymers, epoxy resins, silicones, polyurethanes, polyamides, saturated and unsaturated polyesters, polysulfones, cellulosic polymers, aminoplasts, polycarbonates, copolymers of an alpha olefin and a vinylic monomer, and mixtures thereof.
  • Polyolefins can be selected from polymethylpentene, polystyrene, natural and synthetic rubbers and copolymers based on cyclic olefins. Polymethylpentene, polystyrene and copolymers based on cyclic olefins are preferred.
  • Vinylic polymers can be selected among polyvinyl chloride, polyvinyl acetate and polymethylmethacrylate. Polyvinyl acetate and polymethylmethacrylate are preferred.
  • Other preferred transparent amorphous polymers can be selected from epoxy resins, polyamides, polysulfones, cellulose-based polymers, aminoplasts and polycarbonates.
  • the coated alkaline-earth metal carbonate particles of the invention can be added as a filler in the plastic compositions, while keeping an excellent transparency.
  • the plastic component of the plastic composition can be a rigid polymer.
  • glass-transition temperature is generally higher than or equal to O 0 C, often higher than or equal to 5O 0 C, frequently higher than or equal to 75 0 C, specifically higher than or equal to 100 0 C and most specifically higher than or equal to 15O 0 C.
  • the glass transition temperature is measured according to Standard ASTM D 3418-03.
  • Rigid polymers can be amorphous or crystalline. Amorphous rigid polymers are preferred. Polycarbonates, epoxy resins, polymethylmethacrylate, polyvinyl chloride, polysulfones, polystyrene and polyurethanes are more preferred amorphous rigid polymers. Polyvinyl chloride is the most preferred.
  • the impact resistance has been improved by adding coated alkaline-earth metal carbonate particles of the invention as a filler in the plastic composition, while keeping an excellent surface aspect.
  • coated calcium carbonate particles of the invention can replace the Ca-Zn stabilizers.
  • the content of the coated alkaline-earth metal carbonate particles in the plastic composition is generally higher than or equal to 0.5 % by weight of the composition, often higher than or equal to 1 % by weight and in particular higher than or equal to 3 % by weight. This content is usually lower than or equal to
  • composition often lower than or equal to 75 % by weight and in particular lower than or equal to 60 % by weight.
  • plastic compositions may also contain other components known in the art generally such as for examples heat stabilizers, plasticizers, impact modifiers, lubricants, flame retardants, pigments, microbiocides, anti- oxidants, light stabilizers and processing aids.
  • compositions comprising at least one plastic component and the particles of coated alkaline-earth metal carbonate particles of the invention can be obtained by any known methods like for instance, melt blending, solvent blending and in situ polymerization.
  • the process for preparing the plastic composition of the invention consists of melt blending and/or melt extruding of a mixture of the plastic component and of the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles.
  • the dried coated particles contains usually at most 100 g of water/kg of coated particles, preferably at most 80 g/kg and most preferably at most 50/kg.
  • the dried coated particles contain usually at least 0.5 g of water/kg.
  • the process for preparing the plastic composition of the invention comprises the following steps : (1) the plastic component is dissolved in a solvent so as to form a solution of the plastic component in the solvent (2) the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles are introduced in the solution of step (1) after or during the dissolution, so as to produce a first suspension,
  • a non-solvent of the plastic component is injected in the first suspension of step (2) so as to precipitate the plastic component and to produce a second suspension of a intimate mixture of the plastic component and coated alkaline-earth metal carbonate particles
  • step (3) the intimate mixture of step (3) is filtrated so as to obtain a solid
  • the process for preparing the plastic composition comprises the following steps : i. the plastic component is dissolved in a solvent so as to form a solution of the plastic component in the solvent ii. the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles are introduced in a non-solvent of the plastic component so as to produce a first suspension, iii. the suspension of step (ii) is injected in the solution of step (i) so as to precipitate the plastic component and to produce a second suspension of a intimate mixture of the plastic component and coated alkaline-earth metal carbonate particles iv. the intimate mixture of step (iii) is filtrated so as to obtain a solid v. the solid filtrated in step (iv) is dried.
  • the non- solvent is introduced in liquid form.
  • the solvent is preferably an organic solvent or a mixture of organic solvents, and the non solvent is preferably water.
  • the non- solvent is introduced in a liquid form in a quantity such that no inversion of phase occurs and further introduced at least partially in the form of vapor.
  • the solvent is preferably an organic solvent or a mixture of organic solvents, and the non solvent is preferably water and the vapor is preferably steam.
  • polycarbonate a mixture of toluene and cyclohexanone is especially useful as solvent.
  • Example 1 (according to the invention) - Preparation of coated precipitated calcium carbonate A precipitated calcium carbonate slurry (200 g/L) has been prepared according to the process described in example 7 of SOLVAY patent application WO 2006/045768. After completion of the precipitation, the temperature of the slurry has been raised to 75 0 C.
  • An emulsion of a polymer with formula (A) according to the invention, where Z is (CH 2 ) 4 and E is (CH 2 )s with a hydroxyl number of 71 mg of KOH per g of polymer and a molecular weight of 1580 g/mol has been prepared according to the following process.
  • the polymer (6 g) has been melted in 300 mL water at 8O 0 C under stirring.
  • An ammonia aqueous solution (20 % by weight) has then been added to the polymer water mixture at a weight ratio ammonia/polymer of 0.6 and the resulting mixture has been further stirred for 10 minutes.
  • An aqueous emulsion of the polymer has been obtained.
  • the entirety of the aqueous emulsion of the polymer has then been added to 1 L of the precipitated calcium carbonate slurry and the resulting mixture has been stirred at 75 0 C for 20 minutes.
  • the mixture has then been filtered, and the filtered resulting solid has been dried at 105 0 C for 24 h at 1 bar and grinded.
  • a milk of lime slurry (200 g of Ca(OH) 2 expressed as calcium carbonate/L) has been prepared by slaking the corresponding amount of lime into 1 L of water and kept at 2O 0 C.
  • An emulsion of a polymer has been prepared according to example 1.
  • Example 3 (not according to the invention) An uncoated precipitated calcium carbonate has been used with the characteristics summarized in Table 1.
  • a polycarbonate polymer (Makrolon AL 2647 from BAYER, 100 g) has been introduced in a mixer (BRABENDER GmbH and Co.) at 28O 0 C and kept for 1 minute after complete melting of the polymer before introducing the coated calcium carbonate (1 g) of example 1 (plastic of example 4) or of example 2 (plastic of example 5) or of example 3 (plastic of example 6). The resulting mixture has been mixed for 8 minutes at the 28O 0 C. The hot mixture has then been transferred to a press and pressed to obtain plates with a 4 mm thickness.
  • the dry blend has then been introduced in a twin screw extruder at 175 0 C at 20 rpm.
  • Test samples with dimensions 80 x 10 x 2 mm (length x width x thickness) have been prepared.

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Abstract

Alkaline-earth metal carbonate particles coated with a coating agent comprising at least one polymer complying with formula (A) or with formula (B) Process for manufacturing such particles and polymeric compositions containing such particles.

Description

Coated alkaline-earth metal carbonate particles, process for manufacturing such particles and plastic compositions containing such particles
The invention is related to coated alkaline-earth metal carbonate particles. More specifically, the invention is related to alkaline-earth metal carbonate particles coated with a coating agent comprising a polymer.
Alkaline-earth metal carbonates are used as additive in various materials, in particular in plastics (Rainer Wolf, Bansi LaI Kaul, Ullmann's Encyclopedia of Industrial Chemistry, VCH-Publisher, Inc., 1992, Vol. A20, p. 496). Calcium carbonate particles, for instance, are often surface treated (i.e. coated) in order to improve their dispersion in plastics. Surface treatments vary depending on the plastic type and on the properties searched for the filled plastic (improvement of mechanical, optical, thermal, electrical properties, etc.) and generally different calcium carbonates with different coatings must be manufactured for different plastics applications. So the calcium carbonate and the coating have to be adapted to the plastic and the plastic applications, which is a laborious time consuming and costly procedure. It is therefore desirable to dispose of a unique product which could be used in several plastics and which characteristics would fulfill the requirements of the applications the plastics are used for.
The goal of the present invention is to provide coated alkaline-earth metal carbonate particles which could be used as additives in plastic compositions for applications requiring different properties. The invention is then related to alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula
Figure imgf000002_0001
or with formula
Figure imgf000002_0002
(B) wherein m is an integer equal to 2, 3 or 4, x is an integer higher than or equal to 1 and lower than or equal to 500 Z and Z' represent a hydrocarbon group having from 1 to 30 000 C atoms, optionally comprising oxygen, sulfur and fluorine atoms and/or aromatic rings E and E' represent a linear or branched divalent hydrocarbon group.
The invention is also related to a process for manufacturing such particles. The coated alkaline-earth metal carbonate particles of the invention can be used as filler, preferably as filler in paper, plastics, rubber, ink, paint, plastisols, sealants, food, pharmaceutical, cosmetics and constructions materials. The invention is therefore also related to the use of such particles as filler.
The invention is finally also related to plastic compositions comprising at least one plastic component and particles of alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula
Figure imgf000003_0001
or with formula
Figure imgf000003_0002
wherein m is an integer equal to 2, 3 or 4, x is an integer higher than or equal to 1 and lower than or equal to 500 Z and Z' represent a hydrocarbon group having from 1 to 30 000 C atoms, optionally comprising oxygen, sulfur and fluorine atoms and aromatic rings E and E' represent a linear or branched divalent hydrocarbon group. The alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula (A) or (B) according to the invention will be further indifferently designated by the expressions "at least partly coated alkaline-earth metal carbonate particles" or "coated alkaline-earth metal carbonate particles" or "alkaline-earth metal carbonate particles". By the expression "coated" alkaline-earth metal carbonate particles, one intends to denote "surface treated" alkaline-earth metal carbonate particles.
It has surprisingly be found that the at least partly coated alkaline-earth metal carbonate particles of the invention can be added as filler in plastic compositions as different as polycarbonate, polymethylmethacrylate, polyamide, polyurethane and polyvinyl chloride, improving the properties required by the applications of such plastic compositions as for example, scratch resistance, impact strength, resistance to traction, thermal stability and resistance to visible and ultra violet light, while keeping an excellent transparency for compositions containing polycarbonate and polymethylmethacrylate, and a good rigidity and surface aspect for compositions based on polyvinyl chloride, polyamide and polyurethane for rigid applications.
In the coated alkaline-earth metal carbonate particles and in the plastic compositions of the invention, the expressions « polymer » and « plastic » are used in their general acceptation and invariably designate a homopolymer, a copolymer, or a mixture thereof. The « polymer » and « plastic » definitions emcompass also the oligomers. The polymer can be a natural or a synthetic polymer. Synthetic polymers are preferred. The polymer and the plastic can be identical or different. They are frequently different. In the at least partly coated alkaline-earth metal carbonate particles of the invention, the divalent hydrocarbon groups E and E' are preferably a (CHi)n group where n is an integer higher than or equal to 1 and lower than or equal to 10, preferably equal to 3, 4 or 5, more preferably equal to 4 and 5, and most preferably equal to 5. In the at least partly coated alkaline-earth metal carbonate particles of the invention, x is preferably higher than or equal to 5, more preferably higher than or equal to 10 and most preferably higher than or equal to 20.
In the at least partly coated alkaline-earth metal carbonate particles of the invention, when m is equal to 2, the Z and Z' group can be selected among the radicals R1, (R2O)PR2 and (R3O[R3O(C=O)O]qR3) where
R1, R2 and R3 are each an alkylene group, linear or branched, substituted or not, alicyclic or not, containing at least 1 and at most 50 carbon atoms.
R1 is preferably an alkylene group, linear or branched, substituted or not, alicyclic or not, containing at least 2 and at most 50 carbon atoms, preferably a polymethylene group (CH2X where r is an integer higher than or equal to 2 and - A -
lower than or equal to 6, isobutylene [CH2CH2CH(CHs)], cyclohexyldimethylene [CH2CyCH2], dimethylpropylene [(CH2)C(CHs)2CH2], di(hydroxymethyl) propylene [(CH2)C(CH2OH)2CH2], an Ar group or a Ar-J-Ar' group where Ar and Ar' represent an aromatic ring substituted or non substituted, preferably a phenylene group and J represents a O=S=O group, a S=O group, a C=O group, a C(CHs)2 group or a C(CFs)2 group.
R2 is preferably an alkylene group, linear or branched, substituted or not, alicyclic or not containing at least 1 and at most 50 carbon atoms, preferably, a polymethylene group (CH2)S where s is an integer higher than or equal to 1 and lower than or equal to 6, isopropylene [CH2CH(CHs)], isobutylene
[CH2CH2CH(CH3)], cyclohexyldimethylene [CH2CyCH2], dimethylpropylene [CH2C(CHs)2CH2], methylcarboxypropylene [CH2C(CH3)(COOH)CH2], or di(hydroxymethyl) propylene [CH2C(CH2OH)2CH2], an Ar group or a group Ar- J-Ar' where Ar and Ar' represent an aromatic ring substituted or non substituted, preferably a phenylene group and J represents a O=S=O group, a S=O group, a C=O group, a C(CH3)2 group or a C(CF3)2 group, and p is an integer higher than or equal to 1 and lower than or equal to 500.
R3 is preferably an alkylene group, linear or branched, substituted or not, alicyclic or not containing at least 2 and at most 50 carbon atoms, preferably, a polymethylene group (CH2)t where t is an integer higher than or equal to 2 and lower than or equal to 6, isopropylene [CH2CH(CH3)], isobutylene [CH2CH2CH(CH3)], cyclohexyldimethylene [CH2CyCH2], dimethylpropylene [(CH2)C(CHs)2CH2], di(hydroxymethyl) propylene [(CH2)C(CH2OH)2CH2], an Ar group or a group Ar-J-Ar' where Ar and Ar' represent an aromatic ring substituted or non substituted, preferably a phenylene group and J represents a O=S=O group, a S=O group, a C=O group, a C(CH3)2 group or a C(CF3)2 group and q is an integer higher than or equal to 1 and lower than or equal to 500.
When the polymer complies with formula (A), the Z group is preferably a R1 radical and most preferably a tetramethylene (CH2)4 group. When the polymer complies with formula (B) the Z' group is preferably a
(R3O[R3O(C=O)O]qR3) radical, more preferably with R3 being a hexamethylene group (CH2)6.
In the at least partly coated alkaline-earth metal carbonate particles of the invention, when m is equal to 3, the Z group can be selected among the radicals CH2C(OH)CH2 and C6H3 and the Z' group can be selected among the radicals CH2CHCH2 and CH3CH2C(CH2)3. In the coated alkaline-earth metal carbonate particles of the invention, when m is equal to 4, the Z' group can be a C(CHi)4 group.
In the at least partly coated alkaline-earth metal carbonate particles of the invention, the polymer exhibits a molecular weight higher generally than or equal to 500 g/mol and preferably higher than or equal to 750 g/mol. That molecular weight is generally lower than or equal 5 000 g/mol, preferably lower than or equal to 4 000 g/mol and most preferably lower than or equal to 2 500 g/mol.
In the at least partly alkaline-earth metal carbonate particles of the invention when the polymer complies formula (A), the acid number is generally lower than or equal to 300 mg of KOH/g of polymer and often lower than or equal to 116 mg of KOH/g of polymer.
In the at least partly coated alkaline-earth metal carbonate particles of the invention when the polymer complies with formula (B), the hydroxyl number is generally lower than or equal to 300 mg of KOH/g of polymer, often lower than 200 mg of KOH/g of polymer and frequently lower than or equal to 116 mg of KOH/g of polymer.
In the at least partly coated alkaline-earth metal carbonate particles of the invention, when the polymer complies formula (A), the polymer can be obtained by reaction between a di- or a tri-carboxylic acid and a lactone, or an hydroxy acid or a mixture of a lactone and a hydroxy acid.
In the at least partly coated alkaline-earth metal carbonate particles of the invention, when the polymer complies formula (B), the polymer can be obtained by reaction between a di-, a tri- or a tetra-ol and a lactone, or an hydroxy acid or a mixture of a lactone and a hydroxy acid.
The lactone is preferably selected from δ-valerolactone, γ-butyrolactone and ε-caprolactone. The lactone is more preferably ε-caprolactone.
The dicarboxylic acid is preferably selected among succinic and adipic acid. Adipic acid is the most preferred. The triacid is preferably citric acid. Methods of preparation of polymer complying with formula (A) are described in PCT patent application WO 2006/040355 in the name of SOLVAY SA, from page 5, line 28, to page 6, line 24.
The diol is preferably a polycarbonate polymer end terminated by hydroxyl groups. A commercial product of that type is CAP A® 7203 of SOLVAY CAPROLACTONES. The coating agent may contain other compounds than the polymer like for instance, fatty acids, rosins acids, polyacrylic acids, sulfonic acids, derivatives of those acids like salts and esters, alkylsulfates, alkylsulfosuccinates and mixtures thereof. The content of the coating agent is generally higher than or equal to 4 g/kg of coated alkaline-earth metal carbonate particles, often higher than or equal to 8 g/kg and frequently higher than or equal to 13 g/kg. That content is generally lower than or equal to 130 g/kg of coated alkaline-earth metal carbonate particles, often lower than or equal to 100 g/kg and frequently lower than or equal to 80 g/kg.
The content of the polymer is generally higher than or equal to 1 g/kg of coated alkaline-earth metal carbonate particles, often higher than or equal to 5 g/kg and frequently higher than or equal to 10 g/kg. That content is generally lower than or equal to 100 g/kg of coated alkaline-earth metal carbonate particles, often lower than or equal to 70 g/kg and frequently lower than or equal to 50 g/kg.
The alkaline-earth metal is preferably selected from magnesium, calcium, strontium, barium and mixtures thereof. Calcium is more preferred.
The alkaline-earth metal carbonate particles of the invention can be particles of natural or synthetic alkaline-earth metal carbonate. Natural magnesium carbonate can be natural magnesite or hydromagnesite. Natural calcium carbonate can be natural calcite or aragonite, chalk or marble. Natural magnesium and calcium carbonate can occur as calcium-magnesium carbonate containing minerals like huntite and dolomite. Natural strontium carbonate can be natural strontianite. Natural barium carbonate can be natural whiterite.
Synthetic alkaline-earth metal carbonates are preferred. Synthetic precipitated alkaline-earth metal carbonates are more preferred. Synthetic precipitated calcium carbonate is the most preferred.
By particles, one intends to denote primary particles and clusters of primary particles. Primary particles are defined as the smallest discrete particles that can be seen by Electron Microscopy analysis.
The alkaline-earth metal carbonate of the invention may be substantially amorphous or substantially crystalline. The term "substantially amorphous or crystalline" is intended to mean that more 50 %, in particular more than 75 % and preferably more than 90 % by weight of the alkaline-earth metal carbonate is in the form of amorphous or crystalline material when analyzed by the X-ray diffraction technique. Substantially crystalline alkaline-earth metal carbonates are preferred. Substantially crystalline calcium carbonate is preferred.
When the alkaline-earth metal carbonate is magnesium carbonate, the magnesium carbonate may consist of barringtonite, nesquehonite, lansfordite or of a mixture of at least two of these crystallographic varieties.
When the alkaline-earth metal carbonate is strontium carbonate, the strontium carbonate may consist of aragonite type, of calcite type or of a mixture of at least two of these crystallographic varieties.
When the alkaline-earth metal carbonate is barium carbonate, the barium carbonate may consist of aragonite type.
When the alkaline-earth metal carbonate is calcium carbonate, the calcium carbonate may consist of calcite, of vaterite or of aragonite or of a mixture of at least two of these crystallographic varieties. Calcium carbonate particles presenting at least partly a calcite crystallographic structure are preferred. The calcium carbonate particles presenting the calcite crystallographic structure amount generally for at least 20 % by weight of the total calcium carbonate particles, often for at least 50 %, frequently for at least 80 % and most specifically for at least 95 %.
The alkaline-earth metal carbonate particles of the invention can exhibit various morphologies. The particles can have the form of needles, scalenohedra, rhombohedra, hexagons, cubes, spheres, platelets or prisms.
The calcium carbonate particles of the invention can exhibit various morphologies. The particles can have the form of needles, scalenohedra, rhombohedra, cubes, spheres, platelets or prisms. The corners and edges of several of such forms, for instance rhombohedra and cubes can be rounded.
These forms are determined by means of Scanning Electron Microscopy. The scalenohedra and rhombohedra forms are preferred. Calcium carbonate particles presenting a rhomboedric morphology are more preferred. The calcium carbonate particles presenting the rhomboedric morphology amount generally for at least 20 % by number of the total calcium carbonate particles, often for at least 50 %, frequently for at least 80 % and most specifically for at least 95 %. The % by number can be obtained from Scanning Electron Microscopy measurements.
The alkaline-earth metal carbonate particles according to the invention have a BET specific surface area generally greater than or equal to 1 mVg, often greater than or equal to 5 m2/g, frequently greater than or equal to 20 m2/g and in particular greater than or equal to 40 m2/g. A specific surface area of greater than or equal to 70 m2/g gives good results. The BET specific surface area of the particles is generally less than or equal to 300 m2/g, often less than or equal to 150 m2/g and frequently less than or equal to 100 m2/g. The specific surface area is measured by the standardized BET method (standard ISO 9277-1995). The alkaline-earth carbonate particles of the invention have generally a mean primary particle size (dp) higher than or equal to 0.010 μm, often higher than or equal to 0.030 μm, frequently higher than or equal to 0.050 μm, specifically higher than or equal to 0.070 μm and more specifically higher than or equal to 0.100 μm. The mean primary particle size is generally lower than or equal to 20 μm, frequently lower than or equal to 10 μm, often lower than or equal to 1 μm and most often lower than or equal to 0.75 μm. The mean primary particle size is measured according to a method derived from standard NF XIl- 601 - 1974 (Lea & Nurse method) with a permeable porosity (ε) value around 0.45 and using the equation of Carman and Malherbe and a final conversion of the surfacic diameter (ds) to the particle diameter by the relation : dp = ds exp[-3.2 ((measured ε) - 0.45)]
The size distribution of the precipitated calcium carbonate particles according to the invention is obtained by Gravitational Liquid Sedimentation Methods (standard ISO 13317-3-2001). The average size of the particles (equal to the value of D50 defined below) is commonly higher than or equal to 0.030 μm, often higher than or equal to 0.050 μm, frequently higher than or equal to 0.070 μm, specifically higher than or equal to 0.100 μm and most specifically higher than or equal to 0.150 μm. The average size of the particles is generally lower than or equal to 20 μm, frequently lower than or equal to 10 μm, often lower than or equal to 5 μm, specifically lower than or equal to 3 μm and most specifically lower than or equal to 2 μm. D50 is the particle size value which expresses that 50 % by vol of the particles have a size value lower than or equal to D50.
The alkaline-earth metal carbonate particles of the invention can occur as clusters of primary particles, which highest dimension is generally higher than or equal to 10 nm, often higher than or equal to 20 nm , frequently higher than or equal to 50 nm, specifically higher than or equal to 80 nm and in particular higher than or equal to 140 nm. That highest dimension is generally lower than or equal to 40 μm, often lower than or equal to 4 μm and frequently lower than or equal to 0.3 μm. Those clusters exhibit a smallest dimension which is generally higher than or equal to 5 nm, often higher than or equal to 10 nm , frequently higher than or equal to 25 nm, specifically higher than or equal to 40 nm and in particular higher than or equal to 70 nm. That smallest dimension is generally lower than or equal to 10 μm, often lower than or equal to 0.7 μm and frequently lower than or equal to 0.2 μm. Those dimensions can be obtained by measuring the highest and lowest dimensions of the clusters on photographs obtained by Scanning Electron Microscopy.
Any coating procedure can be used to obtain the coated alkaline-earth carbonate particles according to the invention.
According to a first embodiment, the process for manufacturing the coated alkaline-earth metal carbonate particles comprises the following steps :
(a) Contacting a powder, a moist cake or an aqueous suspension of alkaline- earth metal carbonate particles with the coating agent or a solution or a suspension or an emulsion of the coating agent in a solvent, such as to obtain a coating medium, and (b) Heating and stirring the coating medium, such as to coat the alkaline-earth metal carbonate particles at least partly with the coating agent. The process may comprise an additional step (c) :
(c) Eliminating a fraction of the solvent from the coating medium of step (b) in order to obtain a concentrated coating medium, or wet at least partly coated alkaline-earth metal carbonate particles.
The process may comprise an additional step (d) :
(d) Drying the concentrated medium or the wet at least partly coated alkaline- earth metal carbonate particles of step (d).
By powder one intends to denote a dry solid, i.e. a solid with a water content usually lower than or equal to 10 % by weight. This content is preferably lower than or equal to 3 % by weight and more particularly lower than or equal to 1 % by weight.
By moist cake, one intends to denote a solid with a water content normally greater than 10 % by weight, more specifically greater than or equal to 30 % by weight. This content is generally lower than or equal to 70 % by weight and preferably lower than or equal to 50 % by weight.
The solid content of the aqueous suspension of alkaline-earth metal carbonate particles in step (a) is usually higher than or equal to 25 g/L, frequently higher than or equal to 50 g/L, and often higher than or equal to 100 g/L. That content is usually lower than or equal to 250 g/L, frequently lower than or equal to 200 g/L, and often lower than or equal to 180 g/L. The powder, the moist cake and the suspension of alkaline-earth metal carbonate particles can be obtained by any known method.
Natural alkaline-earth metal carbonates can be processed by mechanically crushing and grading alkaline-earth metal carbonates containing ores to obtain particles adjusted to the desired size.
Synthetic alkaline-earth metal carbonate particles are usually prepared by precipitation.
Precipitated magnesium carbonates may be prepared by reacting magnesium hydroxide with carbon dioxide at high pressure. Precipitated calcium carbonate may be manufactured by first preparing a calcium oxide (quick lime) by subjecting limestone to calcination by burning a fuel, such as coke, a petroleum fuel (such as heavy or light oil), natural gas, petroleum gas (LPG) or the like, and then reacting the calcium oxide with water to produce a calcium hydroxide slurry (milk or lime), and reacting the calcium hydroxide slurry with the carbon dioxide discharged from a calcination furnace for obtaining the calcium oxide from limestone to obtain the desired particle size and shape precipitated calcium carbonate (carbonation process). Precipitation of calcium carbonate can also be carried out by adding an alkali metal carbonate starting with lime water (causticisation method) or precipitation by the addition of an alkali metal carbonate starting with solutions containing calcium chloride. Precipitated calcium carbonate obtained from the carbonation process is preferred.
Strontium and barium carbonates may be prepared by precipitating the carbonates from strontium or barium sulfide solutions with carbon dioxide. Barium carbonate may also be prepared by precipitating the carbonate from barium sulfide solutions with sodium carbonate.
The solution (dissolved coating agent) or suspension (solid coating agent) or emulsion (liquid coating agent) of the coating agent in a solvent can be obtained by any known method. In particular, one can use the polymerization medium of the polymer. The solvent can be an organic solvent or an inorganic solvent or a mixture thereof. It is preferred to use an emulsion of the coating agent in an inorganic solvent.
The inorganic solvent is preferably water.
The stirring conditions, i.e. stirring speed, temperature and duration of step (b) are adjusted to obtain the desired coating level of the calcium carbonate particles. The temperature of step (b) is usually higher than or equal to 2O0C, frequently higher than or equal to 5O0C, and often higher than or equal to 750C. That temperature is usually lower than or equal to 1000C and frequently lower than or equal to 8O0C. The duration of step (b) is usually higher than or equal to 1 min, frequently higher than or equal to 5 min and often higher than or equal to 20 min. That duration is usually lower than or equal to 60 min and frequently lower than or equal to 45 min.
According to a second embodiment, especially, useful when alkaline-earth metal carbonate particles are precipitated alkaline-earth metal carbonate particles, the coating agent is present in the precipitation medium before the precipitation of alkaline-earth metal carbonate particles occurs. The process comprises the following steps :
(A) Obtaining a precipitation medium by mixing an alkaline-earth metal containing compound or a carbonate containing compound, and the coating agent in a solvent, and
(B) Adding respectively a carbonate or an alkaline-earth metal containing compound to the precipitation medium of step A so as to precipitate alkaline- earth metal carbonate particles and coat the precipitated particles at least partly with the coating agent.
The process may comprise an additional step (C)
(C) Separating the at least partly coated alkaline-earth metal carbonate particles from the precipitation medium of step B, in order to obtain wet at least partly coated calcium carbonate particles. The process may comprise an additional step (D)
(D)Drying the wet at least partly coated alkaline-earth metal carbonate particles of step C.
This process is particularly well suited when the precipitated alkaline-earth metal carbonate is calcium carbonate. The solvent can be an organic solvent or an inorganic solvent or a mixture thereof. It is preferred to use an inorganic solvent, preferably water.
Any alkaline-earth metal containing compound can be used. For calcium, it is preferred to use quick lime.
Any carbonate containing compound can be used. It is preferred to use carbon dioxide. The coating agent may contain a crystallization controller i.e. a substance able to control the crystallographic phase, the morphology and/or the size of the precipitated alkaline-earth metal carbonate particles.
Plastic compositions comprising at least one plastic component and the at least partly coated alkaline-earth metal carbonate particles are also an object of the invention.
The plastic component can be selected from homopolymers and copolymers of ethylene, propylene, styrene, vinyl chloride, vinylidene chloride, acrylic acid, alkyl acrylates, methacrylic acid, alkyl methacrylates, acrylonitrile, vinyl acetate, vinyl alcohol, isoprene, chloroprene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, copolymers of ethylene and alpha-olefins, copolymers of propylene and alpha-olefins other than propylene, copolymers of vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and alkyl acrylates, copolymers of vinylidene chloride and alkyl methacrylates as mtehyl metahcrylate, copolymers of styrene, butadiene and rubber, copolymers of acrylonitrile and butadiene, copolymers of styrene and acrylonitrile, copolymers of acrylonitrile, butadiene and styrene, copolymers of vinylidene fluoride and hexafluoropropylene, polyesters, polyamides, polyurethanes, polycarbonates, epoxy resins, polyphenylene ethers, polyimides, polyamide imides, polybenzimidazoles, polyalkylene oxides, polyetherether ketones, polyether sulfones, polyisocyanates, polyphenylene sulfides and mixtures thereof.
Plastic component selected from polycarbonate, polymethylmethacrylate, polyamides, polyvinyl chloride, polyurethane, polysulfones and epoxy resins are preferred.
The plastic component of the composition can be a crystalline or an amorphous polymer.
By crystalline polymer, one intends to denote a polymer which has a cristallinity as measured according to Standard ASTD D 3418-03 higher than or equal to 15 %, preferably higher than or equal to 50 %, more preferably higher than or equal to 90 % and most preferably higher than or equal to 95 %. By amorphous polymer, one intends to denote a polymer which has a cristallinity lower than 15 %, preferably lower than or equal to 5 %, more preferably lower than or equal to 1 % and most preferably lower than or equal to 0.5 %. Amorphous polymers are preferred. The plastic component of the plastic composition can be a transparent polymer. By transparent polymer, one intends to denote a polymer which has a transparency, expressed as the percentage of visible light transmitted through a sheet of 4 mm of thickness, higher than or equal to 75 %, preferably higher than or equal to 85 % and most preferably higher than or equal to 90 %. If the polymer can not be obtained as a sheet of 4 mm of thickness, by transparent polymer, one intends to denote as a polymer which has a transparency, expressed as the percentage of visible light transmitted through a film of 100 μm of thickness, higher than or equal to 85 %, preferably higher than or equal to 90 % and most preferably higher than or equal to 95 %. The transparency measurement is made according to standard ASTM D 1746-03 (2003).
Transparent polymers are generally amorphous polymers. Those polymers can be selected among polyolefins, vinylic polymers, epoxy resins, silicones, polyurethanes, polyamides, saturated and unsaturated polyesters, polysulfones, cellulosic polymers, aminoplasts, polycarbonates, copolymers of an alpha olefin and a vinylic monomer, and mixtures thereof.
Polyolefins can be selected from polymethylpentene, polystyrene, natural and synthetic rubbers and copolymers based on cyclic olefins. Polymethylpentene, polystyrene and copolymers based on cyclic olefins are preferred.
Vinylic polymers can be selected among polyvinyl chloride, polyvinyl acetate and polymethylmethacrylate. Polyvinyl acetate and polymethylmethacrylate are preferred.
Other preferred transparent amorphous polymers can be selected from epoxy resins, polyamides, polysulfones, cellulose-based polymers, aminoplasts and polycarbonates.
It has surprisingly been found that the coated alkaline-earth metal carbonate particles of the invention can be added as a filler in the plastic compositions, while keeping an excellent transparency. The plastic component of the plastic composition can be a rigid polymer.
By rigid polymer, one intends to denote as a polymer which exhibits a glass- transition temperature which is at least 1O0C higher than the temperature of use of the polymer. The glass-transition temperature is generally higher than or equal to O0C, often higher than or equal to 5O0C, frequently higher than or equal to 750C, specifically higher than or equal to 1000C and most specifically higher than or equal to 15O0C. The glass transition temperature is measured according to Standard ASTM D 3418-03.
Rigid polymers can be amorphous or crystalline. Amorphous rigid polymers are preferred. Polycarbonates, epoxy resins, polymethylmethacrylate, polyvinyl chloride, polysulfones, polystyrene and polyurethanes are more preferred amorphous rigid polymers. Polyvinyl chloride is the most preferred.
It has surprisingly be found that the impact resistance has been improved by adding coated alkaline-earth metal carbonate particles of the invention as a filler in the plastic composition, while keeping an excellent surface aspect. Moreover the coated calcium carbonate particles of the invention can replace the Ca-Zn stabilizers.
The content of the coated alkaline-earth metal carbonate particles in the plastic composition is generally higher than or equal to 0.5 % by weight of the composition, often higher than or equal to 1 % by weight and in particular higher than or equal to 3 % by weight. This content is usually lower than or equal to
90 % by weight of the composition, often lower than or equal to 75 % by weight and in particular lower than or equal to 60 % by weight.
The plastic compositions may also contain other components known in the art generally such as for examples heat stabilizers, plasticizers, impact modifiers, lubricants, flame retardants, pigments, microbiocides, anti- oxidants, light stabilizers and processing aids.
The compositions comprising at least one plastic component and the particles of coated alkaline-earth metal carbonate particles of the invention can be obtained by any known methods like for instance, melt blending, solvent blending and in situ polymerization.
According to a first aspect, the process for preparing the plastic composition of the invention consists of melt blending and/or melt extruding of a mixture of the plastic component and of the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles. The dried coated particles contains usually at most 100 g of water/kg of coated particles, preferably at most 80 g/kg and most preferably at most 50/kg. The dried coated particles contain usually at least 0.5 g of water/kg.
Melt blending and extrusion techniques are described in Plastic, Processing (Gert Burkhardt, Ulrich Hϋsgen, Matthias Kalwa, Gerhard Pδtsch, Claus Schwenzer, Germany, Ullmann's Encyclopedia of Industrial Chemistry, VCH Publishers, Inc., 1992, Vol. A 20, pp 664-756). According to a second aspect, the process for preparing the plastic composition of the invention comprises the following steps : (1) the plastic component is dissolved in a solvent so as to form a solution of the plastic component in the solvent (2) the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles are introduced in the solution of step (1) after or during the dissolution, so as to produce a first suspension,
(3) a non-solvent of the plastic component is injected in the first suspension of step (2) so as to precipitate the plastic component and to produce a second suspension of a intimate mixture of the plastic component and coated alkaline-earth metal carbonate particles
(4) the intimate mixture of step (3) is filtrated so as to obtain a solid
(5) the solid filtrated in step (4) is dried. According to a third aspect, the process for preparing the plastic composition comprises the following steps : i. the plastic component is dissolved in a solvent so as to form a solution of the plastic component in the solvent ii. the dried coated alkaline-earth metal carbonate particles obtained in the steps (d) or D of the processes for preparing such particles are introduced in a non-solvent of the plastic component so as to produce a first suspension, iii. the suspension of step (ii) is injected in the solution of step (i) so as to precipitate the plastic component and to produce a second suspension of a intimate mixture of the plastic component and coated alkaline-earth metal carbonate particles iv. the intimate mixture of step (iii) is filtrated so as to obtain a solid v. the solid filtrated in step (iv) is dried.
According to a first variant of those second and third aspects, the non- solvent is introduced in liquid form. Such a process is described in patent application WO 03/064504 of SOLVAY SA the content of which is incorporated herein by reference. The solvent is preferably an organic solvent or a mixture of organic solvents, and the non solvent is preferably water.
According to a second variant of those second and third aspects, the non- solvent is introduced in a liquid form in a quantity such that no inversion of phase occurs and further introduced at least partially in the form of vapor. Such a process is described in patent application WO 05/014705 of SOLVAY SA the content of which is incorporated herein by reference. The solvent is preferably an organic solvent or a mixture of organic solvents, and the non solvent is preferably water and the vapor is preferably steam.
For polycarbonate, a mixture of toluene and cyclohexanone is especially useful as solvent.
The following examples further illustrate the invention but are not to be construed as limiting its scope.
Example 1 (according to the invention) - Preparation of coated precipitated calcium carbonate A precipitated calcium carbonate slurry (200 g/L) has been prepared according to the process described in example 7 of SOLVAY patent application WO 2006/045768. After completion of the precipitation, the temperature of the slurry has been raised to 750C.
An emulsion of a polymer with formula (A) according to the invention, where Z is (CH2)4 and E is (CH2)s with a hydroxyl number of 71 mg of KOH per g of polymer and a molecular weight of 1580 g/mol has been prepared according to the following process. The polymer (6 g) has been melted in 300 mL water at 8O0C under stirring. An ammonia aqueous solution (20 % by weight) has then been added to the polymer water mixture at a weight ratio ammonia/polymer of 0.6 and the resulting mixture has been further stirred for 10 minutes. An aqueous emulsion of the polymer has been obtained.
The entirety of the aqueous emulsion of the polymer has then been added to 1 L of the precipitated calcium carbonate slurry and the resulting mixture has been stirred at 750C for 20 minutes. The mixture has then been filtered, and the filtered resulting solid has been dried at 1050C for 24 h at 1 bar and grinded.
The characteristics of the grinded product are summarized in Table 1 Example 2 (according to the invention) - Preparation of coated precipitated calcium carbonate
A milk of lime slurry (200 g of Ca(OH)2 expressed as calcium carbonate/L) has been prepared by slaking the corresponding amount of lime into 1 L of water and kept at 2O0C.
An emulsion of a polymer has been prepared according to example 1.
All of the aqueous polymer emulsion has been added to 1 L of the milk of lime and the resulting mixture has been stirred for 10 minutes. The carbonation of the milk of lime has then been carried out as described in example 7 of
SOLVAY patent application WO 2006/045768. The resulting slurry has been then filtered, and the filtered resulting solid has been dried at 1050C for 24 h at 1 bar and grinded.
The characteristics of the grinded product are summarized in Table 1 Example 3 (not according to the invention) An uncoated precipitated calcium carbonate has been used with the characteristics summarized in Table 1.
Examples 4 to 6 (according to the invention) - Preparation of plastic compositions
A polycarbonate polymer (Makrolon AL 2647 from BAYER, 100 g) has been introduced in a mixer (BRABENDER GmbH and Co.) at 28O0C and kept for 1 minute after complete melting of the polymer before introducing the coated calcium carbonate (1 g) of example 1 (plastic of example 4) or of example 2 (plastic of example 5) or of example 3 (plastic of example 6). The resulting mixture has been mixed for 8 minutes at the 28O0C. The hot mixture has then been transferred to a press and pressed to obtain plates with a 4 mm thickness.
The plates have been tested for transparency according to standard DIN 6174. The L parameter derived from the Cielab formula is taken as a measure of the transparency of the plates. The results are summarized in Table 2. Examples 7 to 8 (according to the invention) - Preparation of plastic compositions
All the following materials have been loaded into a preheated (8O0C) mixing chamber and stirred at 2000 rpm : 100 phr (per hundred of resin) of a PVC resin, 7 phr of a shock modifier, 4.5 phr of a heat stabilizer, 1 phr of a processing aid, 4 phr of titanium dioxide and 10 phr of a precipitated calcium carbonate of example 1 (plastic of example 7) or of example 3 (plastic of example 8). When the temperature reached 2000C, the blend was discharged into a cooling chamber and stirred slightly for ten minutes.
The dry blend has then been introduced in a twin screw extruder at 1750C at 20 rpm.
Test samples with dimensions 80 x 10 x 2 mm (length x width x thickness) have been prepared.
The notched Schock Charpy impact resistance has then been measured at O0C according to Standard ISO 179-1, Type A notch. The results are summarized in Table 3. Table 1
Figure imgf000019_0001
Table 2
Figure imgf000019_0002
Table 3
Figure imgf000019_0003

Claims

C L A I M S
1. - Alkaline-earth metal carbonate particles at least partly coated with a coating agent comprising at least one polymer complying with formula
Figure imgf000020_0001
or with formula
Figure imgf000020_0002
wherein
m is an integer equal to 2, 3 or 4,
x is an integer higher than or equal to 2 and lower than or equal to 500
Z and Z' represent a hydrocarbon group having from 1 to 30 000 C atoms, optionally comprising oxygen, sulfur and fluorine atoms and aromatic rings
E and E' represent a linear or branched divalent hydrocarbon group.
2 - Alkaline-earth metal carbonate particles according to claim 1 wherein the alkaline-earth metal is selected from magnesium, calcium, strontium, barium and mixtures thereof, and wherein the alkaline-earth metal is preferably calcium.
3. - Alkaline-earth metal carbonate particles according to claim 1 or 2 wherein the divalent hydrocarbon groups E and E' represent a (CHi)n group where n is an integer higher than or equal to 1 and lower than or equal to 10, n being preferably equal to 4 or to 5.
4. - Alkaline-earth metal carbonate particles according to any of claims 1 to 3 wherein : when m is equal to 2, the Z and Z' groups are selected among the radicals R1, (R2O)PR2, and R3O[R3O(C=O)O]qR3 wherein
R1, R2 and R3 are each an alkylene group, linear or branched, substituted or not, alicyclic or not, containing at least 1 and at most 50 carbon atoms,
when m is equal to 3, the Z group is selected among the radicals CH2C(OH)CH2 and COH3 and the Z' group is selected among the radicals CH2CCH2 and
Figure imgf000021_0001
when m is equal to 4, the Z' group is the radical C(CH2)4.
5. - Alkaline-earth metal carbonate particles according to any of claims 1 to 4 wherein the polymer exhibits a molecular weight higher than or equal to 500 g/mol and lower than or equal to 5000 g/mol and when the polymer complies with formula (A), it exhibits an acidity number lower than or equal to 300 mg of KOH/g of polymer or when the polymer complies with formula (B), it exhibits a hydroxyl number lower than or equal to 300 mg of KOH/g of polymer.
6. - Alkaline-earth metal carbonate particles according to any of claims 1 to 5 which exhibit at least one of the following characteristics :
(a) The alkaline-earth metal carbonate is precipitated alkaline-earth metal carbonate
(b) When the alkaline-earth metal is calcium, the particles present at least partly a calcite cristallographic structure
(c) When the alkaline-earth metal is calcium, at least 20 % by number of the particles present a rhomboedric morphology
(d) The BET specific area of the particles is higher than or equal to 1 m2/g and lower than or equal to 300 m /g
(e) The mean primary particle size measured by air permeation (dp) is higher than or equal to 0.010 μm and lower than or equal to 20 μm.
(f) The average particle size measured by sedigraphy (D50) is higher than or equal to 0.030 μm and lower than or equal to 20 μm. (g) The content of the coating agent is higher than or equal to 4 g/kg of coated particles and lower than or equal to 130 g/kg of coated particles.
7. - Process for manufacturing alkaline-earth metal carbonate particles according to any of claims 1 to 6, comprising the following steps :
(a) Contacting a powder, a moist cake or an aqueous suspension of alkaline-earth metal carbonate particles, with the coating agent or with a solution or a suspension or an emulsion of the coating agent in a solvent, such as to obtain a coating medium,
(b) Heating and stirring the coating medium, such as to coat the alkaline-earth metal carbonate particles at least partly with the coating agent,
(c) Eliminating at least a fraction of the solvent from the coating medium of step (b) in order to obtain a concentrated coating medium, or wet at least partly coated alkaline-earth metal carbonate particles, and
(d) Drying the concentrated coating medium or the wet coated alkaline-earth metal carbonate particles of step (c).
8. - Process for manufacturing alkaline-earth metal carbonate particles according to any of claims 1 to 6, comprising the following steps :
(A) Obtaining a precipitation medium by mixing a alkaline-earth metal containing compound or a carbonate containing compound, and the coating agent in a solvent,
(B) Adding respectively a carbonate or a alkaline-earth metal containing compound to the precipitation medium of step A so as to precipitate alkaline- earth metal carbonate particles and coat at least partly the precipitated particles with the coating agent,
(C) Separating the at least partly coated alkaline-earth metal carbonate particles from the precipitation medium of step B, in order to obtain wet at least partly coated alkaline-earth metal carbonate particles, and
(D)Drying the wet coated alkaline-earth metal carbonate particles of step C.
9. - Plastic compositions comprising at least one plastic component and the at least partly coated alkaline-earth metal carbonate particles according to any of claims 1 to 6, and wherein the plastic component is preferably selected from polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyurethane and epoxy resins.
10. - Use of alkaline-earth metal carbonate particles according to any of claims 1 to 6, as a filler, preferably in paper, plastic, rubber, ink, paint, plastisols, sealants, food, pharmaceuticals and construction materials.
PCT/EP2007/063476 2006-12-07 2007-12-06 Coated alkaline-earth metal carbonate particles, process for manufacturing such particles and plastic compositions containing such particles WO2008068319A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018537565A (en) * 2015-12-01 2018-12-20 オムヤ インターナショナル アーゲー Method for producing fine granules containing surface-reacted calcium carbonate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030129401A1 (en) * 2000-01-20 2003-07-10 Dino Manfredi Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions
WO2006045768A1 (en) * 2004-10-25 2006-05-04 Solvay (Société Anonyme) Suspensions comprising calcium carbonate particles exhibiting a controlled state of aggregation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030129401A1 (en) * 2000-01-20 2003-07-10 Dino Manfredi Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions
WO2006045768A1 (en) * 2004-10-25 2006-05-04 Solvay (Société Anonyme) Suspensions comprising calcium carbonate particles exhibiting a controlled state of aggregation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018537565A (en) * 2015-12-01 2018-12-20 オムヤ インターナショナル アーゲー Method for producing fine granules containing surface-reacted calcium carbonate

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