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WO2025149508A1 - Élimination d'une odeur désagréable dans des compositions polymères remplies de carbonate de calcium - Google Patents

Élimination d'une odeur désagréable dans des compositions polymères remplies de carbonate de calcium

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Publication number
WO2025149508A1
WO2025149508A1 PCT/EP2025/050314 EP2025050314W WO2025149508A1 WO 2025149508 A1 WO2025149508 A1 WO 2025149508A1 EP 2025050314 W EP2025050314 W EP 2025050314W WO 2025149508 A1 WO2025149508 A1 WO 2025149508A1
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Prior art keywords
calcium carbonate
natural calcium
group
inorganic peroxide
ppm
Prior art date
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Pending
Application number
PCT/EP2025/050314
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English (en)
Inventor
Joris BARANGER
Matthias Welker
Louise MCCULLOCH
Fabio Ippolito
Samuel Rentsch
Craig Deporter
René Vinzenz Blum
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Omya International AG
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Omya International AG
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Application filed by Omya International AG filed Critical Omya International AG
Publication of WO2025149508A1 publication Critical patent/WO2025149508A1/fr
Pending legal-status Critical Current
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    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C09C1/022—Treatment with inorganic compounds
    • C09C1/024—Coating
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention relates to a manufacturing process comprising mixing at least one inorganic peroxide with a (ground) natural calcium carbonate comprising an oxidizable sulfur impurity and the use of at least one inorganic peroxide for reducing the odor of a calcium carbonate-containing polymer compound.
  • Calcium carbonate is widely used as a filler component in a variety of applications, such as in papers, coatings, paints and plastics. Calcium carbonate can be used as a “functional” filler to provide advantageous properties in such applications, for example, improved whiteness, improved mechanical properties, improved breathability and/or improved barrier properties.
  • One of the advantages of calcium carbonate, compared to other conventionally employed fillers, such as titanium dioxide, kaolin, carbon black, barium sulfate, or silica is its relatively low price, because calcium carbonate is a relatively abundant naturally occurring mineral. It is found, e.g., in mineral form as chalk, limestone, marble or dolomite, and in biological form as eggshells, oyster shells or seashells.
  • a manufacturing process comprises the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, wherein
  • step b) the at least one inorganic peroxide of step b) is mixed with the ground natural calcium carbonate of step c).
  • the present inventors found that the presence of oxidizable sulfur impurities, such as hydrogen sulfide, may lead to the evolution of an unpleasant smell during or after incorporation of the calcium carbonate into a polymer matrix, e.g. by extrusion, even though the smell may not be noticeable in the natural calcium carbonate. Moreover, it was surprisingly found that the smell could be reduced or even avoided, if the natural calcium carbonate is treated with at least one inorganic peroxide before the calcium carbonate is incorporated into the polymer matrix, for example already during the grinding process or during a surface-treatment process. Thus, the at least one inorganic peroxide can be used as an additive during the production of the final ground natural calcium carbonate or surface-treated natural calcium carbonate without the need for any additional process step. According to the inventive process, there is also no need to remove said additive or potential reaction products prior to further processing. Finally, the inventive process may even improve grinding efficiency and/or throughput.
  • oxidizable sulfur impurities such as hydrogen sulfide
  • the process further comprises the steps of d) providing at least one surface-treatment agent, and e) mixing the at least one surface-treatment agent of step d) with the ground natural calcium carbonate of step c) to obtain a surface-treated natural calcium carbonate.
  • the process further comprises the steps of f) providing at least one polymer, and g) compounding the ground natural calcium carbonate of step c) and/or the surface-treated calcium carbonate of step e) with the at least one polymer of step f) to obtain a calcium carbonate- containing polymer compound.
  • the natural calcium carbonate of step a) is a natural calcium carbonate-containing mineral, preferably selected from the group consisting of chalk, limestone, marble, dolomite and mixtures thereof.
  • the natural calcium carbonate of step a) may have an oxidizable sulfur impurity content of at least 0.7 mg/kg, preferably at least 2 mg/kg, more preferably at least 5 mg/kg, even more preferably at least 10 mg/kg and most preferably at least 25 mg/kg, based on the total weight of the natural calcium carbonate.
  • the oxidizable sulfur impurity may be selected from the group consisting of sulfides, polysulfides, elemental sulfur, sulfites, thiosulfates, mercaptans, dialkyl mercaptans and mixtures thereof, preferably selected from the group consisting of sulfides, polysulfides, elemental sulfur and mixtures thereof and most preferably the oxidizable sulfur impurity is a sulfide.
  • a grinding aid is present, preferably wherein the grinding aid is selected from at least one polyol, optionally wherein the polyol comprises amine groups, more preferably wherein the grinding aid is selected from at least one diol or triol, optionally comprising amine groups, even more preferably wherein the grinding aid is selected from the group consisting of ethanediol, propanediol, glycerol, diethanolamine, triethanolamine and mixtures thereof, and most preferably wherein the grinding aid is 1 ,2-propanediol.
  • the grinding aid is present in an amount of at least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm and most preferably at least 500 ppm, based on the total dry weight of the natural calcium carbonate.
  • the grinding aid may be present in an amount ranging from 50 ppm to 20,000 ppm, preferably 100 to 10,000 ppm, and most preferably 200 to 8,000 ppm, e.g., 500 to 7,000 ppm, based on the total dry weight of the natural calcium carbonate.
  • the surface-treatment agent is selected from i. a phosphoric acid ester blend of one or more phosphoric acid monoester and/or one or more phosphoric acid di-ester and/or a salt thereof, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid preferably having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, and/or
  • the surface-treatment agent is added in an amount from 0.1 to 2 wt.-%, preferably from 0.2 to 1 .5 wt.-% and most preferably from 0.4 to 1 .2 wt.-%, based on the total dry weight of the ground natural calcium carbonate and/or wherein the surface-treatment agent is added in an amount from 0.5 to 5 mg/m 2 , preferably from 1 to 4 mg/m 2 and most preferably from 1 .3 to 3 mg/m 2 , based on the total surface area of the ground natural calcium carbonate.
  • a second aspect of the present invention relates to the use of at least one inorganic peroxide for reducing the odor of a calcium carbonate-containing polymer compound, wherein the at least one inorganic peroxide is contacted with a particulate natural calcium carbonate comprising an oxidizable sulfur impurity prior to compounding it with the polymer.
  • the at least one inorganic peroxide is contacted with the particulate natural calcium carbonate in an amount of at least 100 ppm by weight, preferably in an amount from 100 to 5000 ppm by weight, more preferably in an amount from 200 to 3000 ppm by weight, based on the total dry weight of the particulate natural calcium carbonate.
  • the at least one inorganic peroxide is selected from the group consisting of hydrogen peroxide, alkali metal peroxides, alkaline earth metal peroxides, peroxyborates, peroxycarbo nates, peroxysulfates and mixtures thereof, preferably selected from the group consisting of hydrogen peroxide, alkali metal peroxides, alkaline earth metal peroxides and mixtures thereof, more preferably selected from the group consisting of hydrogen peroxide, alkaline earth metal peroxides and mixtures thereof, and most preferably wherein the at least one inorganic peroxide is hydrogen peroxide.
  • oxidizable sulfur impurity in the meaning of the present invention refers to a chemical compound comprising at least one sulfur atom, which is able to react with the at least one inorganic peroxide in an oxidation reaction, for example, by ‘replacing’ a free electron pair of the sulfur atom by an oxygen atom, optionally by additionally breaking sulfur-sulfur bonds.
  • a “natural calcium carbonate” refers to a calcium carbonate of natural origin.
  • the c/9s(wt) value is the particle size at which 98 wt.% of all particles are smaller than that particle size.
  • the “particle size” can be described as volume-based particle size distribution c/ x (vol).
  • the value c/ x (vol) represents the diameter relative to which x % by volume of the particles have diameters less than c/ x (vol).
  • the c/2o(vol) value is the particle size at which 20 vol.% of all particles are smaller than that particle size.
  • the cfeo(vol) value is thus the volume median particle size, i.e. 50 vol.% of all particles are smaller than that particle size and the cfo8(vol) value, referred to as volume-based top cut, is the particle size at which 98 vol.% of all particles are smaller than that particle size.
  • the term “specific surface area” (in m 2 /g), which is used to define calcium carbonate or other materials, refers to the specific surface area as determined by using the BET method (using nitrogen as adsorbing gas), as measured according to ISO 9277:2010.
  • polymer generally includes homopolymers and co-polymers such as, for example, block, graft, random and alternating copolymers, as well as blends and modifications thereof.
  • the polymer can be an amorphous polymer, a crystalline polymer, or a semi-crystalline polymer, i.e. a polymer comprising crystalline and amorphous fractions.
  • the degree of crystallinity is specified in percent and can be determined by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • An amorphous polymer may be characterized by its glass transition temperature and a crystalline polymer may be characterized by its melting point.
  • a semi-crystalline polymer may be characterized by its glass transition temperature and/or its melting point.
  • a natural calcium carbonate is provided.
  • the type of natural calcium carbonate is not particularly limited.
  • the natural calcium carbonate may be, e.g., a natural calcium carbonate-containing mineral, preferably selected from the group consisting of chalk, limestone, marble, dolomite and mixtures thereof.
  • Such natural calcium carbonate can be distinguished from, e.g., precipitated calcium carbonate.
  • a “precipitated calcium carbonate” (PCC) in the meaning of the present invention is a synthesized material, obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment.
  • precipitated calcium carbonate can also be obtained by reacting calcium- and carbonate salts, for example calcium chloride and sodium carbonate, in an aqueous environment.
  • PCC may have a vateritic, calcitic or aragonitic crystalline form.
  • PCCs are described, for example, in EP 2 447 213 A1 , EP 2 524 898 A1 , EP 2 371 766 A1 , EP 2 840 065 A1 , or WO 2013/142473 A1 .
  • the natural calcium carbonate is not a precipitated calcium carbonate.
  • the natural calcium carbonate may be from biological sources, such as eggshells, oyster shells or seashells.
  • the eggshell may be a bird eggshell, preferably a quail eggshell, a chicken eggshell, a duck eggshell, a goose eggshell, or an ostrich eggshell.
  • the chicken eggshell may be a white chicken eggshell, a brown chicken eggshell, or a combination of both.
  • the natural calcium carbonate comprises at most 20 wt.-%, preferably at most 5 wt.-%, more preferably from 0 to 3 wt.-% and most preferably from 0.05 to 1 .5 wt.-% of compounds (e.g., minerals) other than calcium carbonate CaCCh (or dolomite CaMg(CC>3)2), based on the total dry weight of the natural calcium carbonate.
  • compounds e.g., minerals
  • the form and particle size of the natural calcium carbonate is not particularly limited.
  • the natural calcium carbonate may have a particle size in the range from 0.1 to 10 mm, preferably from 0.2 to 5 mm, and most preferably from 0.5 to 4 mm.
  • the natural calcium carbonate may have undergone one or more pre-treatment steps, such as a crushing step or a beneficiation step. If the initial particle size of the crude natural calcium carbonate is above the specified range, i.e., above 10 mm, preferably above 5 mm, more preferably above 4 mm, a crushing step is performed as a pre-treatment step.
  • the oxidizable sulfur impurity content may be measured by any method known to the skilled person, for example, by ion-exchange chromatography or colorimetric methods.
  • the presence and amount of hydrogen sulphide may be determined with a colorimetric analysis using methylene blue as coloration reagent.
  • this method involves dissolving the samples with HCI and passing the resulting gases (CO2 and H2S) into a zinc acetate solution where the H2S is trapped.
  • the coloration reagent is added and the absorbance of this solution is then measured at 666nm (UV-VIS).
  • the total sulfur content may be determined, e.g., by ICP-OES, by XRF spectrometry (e.g.
  • ASTM E1621-21 or ISO 29581-2:2010 by elemental analysis (also termed CHNS analysis), by UV fluorescence or microcoulometry, and the amount of non-oxidizable sulfur impurities that may additionally be present, i.e., sulfate, may be subtracted.
  • the sulfate content may be determined, e.g. by ASTM C1580-20. A representative method is provided by Mahanta et al., Atomic Spectroscopy 2017, 38, pages 99-105. If the sample does not contain sulfur impurities other than the oxidizable sulfur impurity, the total sulfur content corresponds to the oxidizable sulfur impurity content.
  • Sulfides are understood to include hydrogen sulfide (H2S) and salts with an S 2- or HS- anion, e.g., alkali sulfide salts, such as sodium or potassium sulfide, or alkaline earth sulfide salts, e.g., calcium or magnesium sulfide.
  • H2S hydrogen sulfide
  • salts with an S 2- or HS- anion e.g., alkali sulfide salts, such as sodium or potassium sulfide, or alkaline earth sulfide salts, e.g., calcium or magnesium sulfide.
  • Polysulfides are understood to be anions comprising S-S bonds, e.g., S n 2- . Elemental sulfur is understood to encompass all allotropes of sulfur, preferably a-, p- and/or y-Sa.
  • Sulfites are understood to be salts with the anion SOa 2- or HSO3"
  • Thiosulfates are understood to include salts with the anion S2O3 2- or HS2O3-.
  • a mercaptan in the meaning of the present invention is an organic compound including a sulfur atom bound to at least one carbon atom, i.e., R 1 -S n -R 2 , with R 1 being an organyl group, R 2 being hydrogen, a cation (such as an alkali or alkaline earth metal cation), or an organyl group, and n being 1 , 2 or more, preferably 1 .
  • R 1 being an organyl group
  • R 2 being hydrogen, a cation (such as an alkali or alkaline earth metal cation), or an organyl group
  • n being 1 , 2 or more, preferably 1 .
  • mercaptans examples include dimethyl sulfide, dimethyl disulfide, methanethiol, ethanethiol, tert-butylthiol, propanethiol, thiophenol, and benzyl mercaptane.
  • a dialkyl mercaptan accordingly, is understood to be a compound R 1 -S-R 2 with R 1 and R 2 being independently from another alkyl groups.
  • step b) of the inventive process at least one inorganic peroxide is provided.
  • the peroxide is capable of reacting with the oxidizable sulfur impurity, which is transformed into an oxidized sulfur impurity.
  • organic sulfides such as dialkyl mercaptanes can be oxidized to the corresponding sulfoxide or sulfone, and elemental sulfur or sulfides can be oxidized to sulfites and/or sulfates.
  • calcium sulfide can be oxidized to calcium sulfate, which may remain in the product, as it is a non-odorous mineral.
  • the at least one inorganic peroxide is mixed with the natural calcium carbonate of step a) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, more preferably in a total amount from 200 to 2000 ppm by weight, even more preferably in a total amount from 200 to 1000 ppm by weight or from 200 to 500 ppm based on the total dry weight of the natural calcium carbonate.
  • the at least one inorganic peroxide is mixed with the ground natural calcium carbonate of step c) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, more preferably in a total amount from 200 to 2000 ppm by weight, even more preferably in a total amount from 200 to 1000 ppm by weight, based on the total dry weight of the ground natural calcium carbonate.
  • the at least one inorganic peroxide is selected from the group consisting of hydrogen peroxide (H2O2), alkali metal peroxides, alkaline earth metal peroxides, peroxyborates, peroxycarbonates, peroxysulfates and mixtures thereof, preferably selected from the group consisting of hydrogen peroxide, alkali metal peroxides, alkaline earth metal peroxides and mixtures thereof, more preferably selected from the group consisting of hydrogen peroxide, alkaline earth metal peroxides (such as calcium peroxide) and mixtures thereof, and most preferably wherein the at least one inorganic peroxide is hydrogen peroxide.
  • H2O2 hydrogen peroxide
  • alkali metal peroxides alkaline earth metal peroxides
  • peroxyborates peroxycarbonates
  • peroxysulfates and mixtures thereof
  • Suitable alkali metal peroxides include lithium peroxide, sodium peroxide and potassium peroxide.
  • Suitable alkaline earth metal peroxides include calcium peroxide, magnesium peroxide, strontium peroxide and barium peroxide.
  • Suitable peroxyborates include sodium perborate.
  • Suitable peroxycarbonates include sodium percarbonate.
  • Suitable peroxysulfates include sodium peroxo mo nosulfate, potassium peroxomonosulfate, sodium persulfate, ammonium persulfate and potassium persulfate.
  • the at least one inorganic peroxide is hydrogen peroxide, which is mixed with the natural calcium carbonate of step a) and/or the ground natural calcium carbonate of step c) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, more preferably in a total amount from 200 to 2000 ppm by weight, based on the total dry weight of the respective natural calcium carbonate.
  • the at least one inorganic peroxide is hydrogen peroxide, which is mixed with the natural calcium carbonate of step a) and/or the ground natural calcium carbonate of step c) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, more preferably in a total amount from 200 to 2000 ppm by weight, based on the total dry weight of the ground natural calcium carbonate, and the oxidizable sulfur impurity is selected from the group consisting of sulfides, polysulfides, elemental sulfur and mixtures thereof, preferably the oxidizable sulfur impurity is a sulfide.
  • step c) of the inventive process the natural calcium carbonate of step a) is ground to a desired particle size to obtain a ground natural calcium carbonate.
  • the ground natural calcium carbonate may be obtained by dry grinding or by wet grinding and optionally subsequent drying. Preferably, the ground natural calcium carbonate is obtained by dry grinding.
  • the grinding step can be carried out with any conventional grinding device, for example, under conditions such that comminution predominantly results from impacts with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man, preferably in a ball mill and/or a pin mill.
  • a ball mill a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man, preferably in a ball mill and/
  • the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled man.
  • the wet processed ground natural calcium carbonate thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, filtration or forced evaporation prior to drying.
  • the total solids content of the slurry preferably is in the range from 20 to 80 wt.-%, more preferably from 30 to 70 wt.-%.
  • the subsequent step of drying may be carried out in a single step such as spray drying, or in at least two steps.
  • the associated moisture content may be reduced to a level which is not greater than about 0.5 wt.-%, based on the total dry weight of the GNCC.
  • the residual total moisture content of the filler can be measured by the Karl Fischer coulometric titration method, desorbing the moisture in an oven at 195°C and passing it continuously into the KF coulometer (Mettler Toledo coulometric KF Titrator C30, combined with Mettler oven DO 0337) using dry N2 at 100 ml/min, e.g. for 10 min.
  • the residual total moisture content may be further reduced by applying a second heating step to the GNCC.
  • the first step may be carried out by heating in a hot current of air, while the second and further drying steps are preferably carried out by an indirect heating in which the atmosphere in the corresponding vessel comprises a surface treatment agent.
  • the (ground) natural calcium carbonate is subjected to a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities either before or after grinding step c).
  • a crushing step using, for example, a jaw crusher or a hammer mill, can be employed before grinding step c) (either before or after the optional beneficiation step) in order to provide the natural calcium carbonate with an optimal particle size for grinding the same.
  • the natural calcium carbonate is crushed to a particle size in the range from 0.1 to 10 mm, preferably from 0.2 to 5 mm, and most preferably from 0.5 to 4 mm.
  • step c) is a dry grinding step.
  • step c) is a wet grinding step comprising grinding in a horizontal ball mill, and subsequently drying using the well-known process of spray drying.
  • a grinding aid may be present.
  • the type of grinding aid is not particularly limited as long as it assists in the grinding process and facilitates grinding of the natural calcium carbonate.
  • the grinding aid should be selected such that it does not react with the at least one inorganic peroxide to a large extent, if the latter is present during the grinding process.
  • the grinding aid is at least one diol or triol, optionally comprising amine groups, preferably 1 ,2-propanediol, and is present during grinding step c) in an amount from 50 ppm to 20,000 ppm preferably 100 to 10,000 ppm, and most preferably 200 to 8,000 ppm, based on the total dry weight of the natural calcium carbonate.
  • the natural calcium carbonate is ground to obtain a ground natural calcium carbonate (GNCC) with a desired particle size.
  • the particle size is not particularly limited and depends on the intended application of the GNCC. For example, if the GNCC is to be incorporated into thin films or fibers or breathable films, the GNCC should be ground to a relatively small particle size. For other polymer applications, such as injection molded parts, the particle size may be greater.
  • the residual total moisture content of the calcium carbonate-comprising filler material is preferably from 0.01 to 0.1 wt.- %, more preferably from 0.02 to 0.08 wt.-%, and most preferably from 0.04 to 0.07 wt.-%, based on the total dry weight of the GNCC.
  • the at least one inorganic peroxide provided in step b) is
  • the at least one inorganic peroxide provided in step b) is mixed with the ground natural calcium carbonate of step c), i.e., after the grinding step.
  • the at least one inorganic peroxide is mixed with the ground natural calcium carbonate of step c) before and/or during a surface-treatment step e), as will be described further below.
  • the at least one inorganic peroxide is mixed with the ground natural calcium carbonate in a separate mixing step, preferably with heating to remove excess inorganic peroxide.
  • the separate mixing step may be carried out in suspension, e.g., at a solids content from 10 to 85 wt.-%, preferably from 30 to 75 wt.-%.
  • the separate mixing step may be performed by any conventional means known to the skilled person.
  • the separate mixing step may be performed with a Pendraulik-type stirrer, for example, with a toothed disk with a diameter of 3.5 cm as the stirrer.
  • the mixing step may be carried out by using a ploughshare mixer.
  • Ploughshare mixers function according to the principle of the mechanically produced fluidized bed. Ploughshare blades rotate close to the inside wall of a horizontal cylindrical drum and convey the components of the mixture out of the product bed into the open mixing space.
  • the mechanically produced fluidized bed ensures an intense mixing effect even with large batches in a very short period of time.
  • Choppers and/or dispersers are used to disperse lumps when operating dry.
  • the equipment used is available from the company Gebruder Lbdige Maschinenbau GmbH, Paderborn, Germany.
  • the mixing step is performed in a tubular mixing apparatus through an intake tube.
  • a tubular mixing apparatus is available, for example from Ystral GmbH, Ballrechten-Dottingen, Germany.
  • mixing may also be carried out in a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, a ribbon blender or other such equipment known to the skilled man.
  • the mixture may be heated to a temperature above roomtemperature, e.g. to a temperature from 30 to 90 °C, preferably from 50 to 85 °C, e.g. to about 80 °C. Heating may take place autogenously and/or by external heating.
  • the inventive process comprises the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, wherein the at least one inorganic peroxide of step b) is present during grinding step c).
  • the surface-treatment agent is selected from i. a phosphoric acid ester blend of one or more phosphoric acid monoester and/or one or more phosphoric acid di-ester and/or a salt thereof, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid preferably having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, and/or
  • At least one aliphatic aldehyde, and/or iv. at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or a salt thereof, and/or v. at least one polydialkylsiloxane, and/or vi. mixtures of the materials according to i. to v..
  • the at least one surface-treatment agent is at least one mono-substituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or a salt thereof.
  • the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic, and cyclic group having a total amount of carbon atoms from C3 to C20 in the substituent.
  • the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic, and cyclic group having a total amount of carbon atoms from C4 to C18 in the substituent.
  • the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a linear alkyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
  • the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a branched alkyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
  • the at least one mono-substituted succinic anhydride is at least one linear or branched alkyl mono-substituted succinic anhydride.
  • the at least one alkyl mono-substituted succinic anhydride is selected from the group comprising ethylsuccinic anhydride, propylsuccinic anhydride, butylsuccinic anhydride, triisobutyl succinic anhydride, pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof.
  • the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a linear or branched alkenyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C20 in the substituent.
  • the at least one mono-substituted succinic anhydride may be provided in the present invention in combination with at least one mono-substituted succinic acid and/or a salt thereof.
  • the surface treatment agent may comprise at least one mono-substituted succinic acid and/or a salt thereof.
  • the at least one mono-substituted succinic acid and/or a salt thereof represents a surface treatment agent and consists of succinic acid and/or its salt mono-substituted with a group selected from any linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C2 to C30 in the substituent.
  • the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid and/or a salt thereof may comprise the same or different substituent.
  • the succinic acid molecule and/or its salt of the at least one mono-substituted succinic acid and/or a salt thereof and the succinic anhydride molecule of the at least one mono-substituted succinic anhydride are mono-substituted with the same group selected from any linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
  • the at least one mono-substituted succinic anhydride is provided in combination with at least one mono-substituted succinic acid and/or a salt thereof, the at least one mono-substituted succinic acid is present in an amount of ⁇ 10 mol.-%, based on the molar sum of the at least one monosubstituted succinic anhydride and the at least one mono-substituted succinic acid and/or its salt.
  • the at least one mono-substituted succinic acid is present in an amount of ⁇ 5 mol.-%, preferably of ⁇ 2.5 mol.-% and most preferably of ⁇ 1 mol.-%, based on the molar sum of the at least one mono-substituted succinic anhydride and the at least one mono-substituted succinic acid and/or its salt.
  • the at least one mono-substituted succinic acid is provided in a blend together with the at least one mono-substituted succinic anhydride.
  • the surface-treatment agent forms a surface-treatment layer on the surface of the ground natural calcium carbonate.
  • the surface-treatment agent is a mixture of alkenyl succinic anhydrides and/or alkenyl succinic acids, wherein the alkenyl succinic anhydrides and/or alkenyl succinic acids are mono-substituted with a group selected from any linear or branched mono-alkenyl group having a total amount of carbon atoms from C12 to C20, preferably from C15 to C20.
  • the alkenyl succinic anhydride will typically comprise at least 80 wt.-% of the mixture, based on the total weight of the mixture, preferably at least 85 wt.-%, more preferably at least 90 wt.-% and most preferably at least 93 wt.-%.
  • the at least one carboxylic acid is selected from saturated unbranched carboxylic acids, that is to say the aliphatic carboxylic acid and/or salt thereof is preferably selected from the group of carboxylic acids consisting of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, their salts, their anhydrides and mixtures thereof.
  • the at least one carboxylic acid is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof.
  • the aliphatic carboxylic acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid, their salts, and mixtures thereof.
  • the aliphatic carboxylic acid and/or salt thereof is stearic acid and/or a stearic acid salt or stearic anhydride.
  • the at least one carboxylic acid and/or a salt thereof may be combined with alkenyl carboxylic acids and/or salts thereof, preferably selected from the group consisting of pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, myristoleic acid, pentadecenoic acid, palmitoleic acid, sapienic acid, heptadecenoic acid, oleic acid, elaidic acid, vaccenic acid, nonadecenoic acid, paullinic acid, gadoleic acid, gondoic acid, erucic acid, nervonic acid, linoleic acid, their salts, their anhydrides and isomers and/or mixtures thereof.
  • alkenyl carboxylic acids and/or salts thereof preferably selected from the group consisting of penteno
  • the surface treatment agent is a salt of a carboxylic acid.
  • salt of a carboxylic acid refers to a carboxylic acid, wherein the active acid group is partially or completely neutralized.
  • partially neutralized carboxylic acid refers to a degree of neutralization of the active acid groups in the range from 40 and 95 mol-%, preferably from 50 to 95 mol-%, more preferably from 60 to 95 mol-% and most preferably from 70 to 95 mol-%.
  • completely neutralized carboxylic acid refers to a degree of neutralization of the active acid groups of > 95 mol-%, preferably of > 99 mol-%, more preferably of > 99.8 mole-% and most preferably of 100 mol-%.
  • the active acid groups are partially or completely neutralized.
  • phosphoric acid di-ester in the meaning of the present invention refers to an 0- phosphoric acid molecule di-esterified with two alcohol molecules selected from the same or different, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from Cato C30, preferably from Ca to C22, more preferably from Ca to C20 and most preferably from Ca to Cia in the alcohol substituent.
  • phosphoric acid tri-ester in the meaning of the present invention refers to an 0- phosphoric acid molecule tri-esterified with three alcohol molecules selected from the same or different, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from Ca to C30, preferably from Ca to C22, more preferably from Ca to C20 and most preferably from Ca to Cia in the alcohol substituent.
  • the surface treatment agent is a salt of a phosphoric acid ester.
  • the salt of a phosphoric acid ester may further comprise minor amounts of a salt of phosphoric acid.
  • the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent.
  • the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • Alkyl esters of phosphoric acid are well known in the industry especially as surfactants, lubricants and antistatic agents (Die Tenside; Kosswig und Stache, Carl Hanser Verlag Munchen, 1993).
  • the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated and linear or branched and aliphatic alcohols having a total amount of carbon atoms from Ce to C30 in the alcohol substituent.
  • the one or more phosphoric acid mono-ester consists of an 0- phosphoric acid molecule esterified with one alcohol selected from saturated and linear or branched and aliphatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated and linear and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated and branched and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent.
  • the one or more phosphoric acid di-ester consists of an 0- phosphoric acid molecule esterified with two fatty alcohols selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • the two alcohols used for esterifying the phosphoric acid may be independently selected from the same or different saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent.
  • the one or more phosphoric acid di-ester may comprise two substituents being derived from the same alcohols or the phosphoric acid di-ester molecule may comprise two substituents being derived from different alcohols.
  • the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and linear and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
  • completely neutralized phosphoric acid esters refers to a degree of neutralization of the active acid group(s) of > 95 mole-%, preferably of > 99 mole-%, more preferably of > 99.8 mole-% and most preferably of 100 mole-%.
  • the active acid group(s) is/are partially or completely neutralized.
  • the salt of the phosphoric acid ester is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic.
  • the surface-treatment composition comprises at least one aliphatic aldehyde.
  • the at least one aliphatic aldehyde represents a saturated surface treatment agent and may be selected from any linear, branched or alicyclic, substituted or non-substituted, saturated or aliphatic aldehyde.
  • Said aldehyde is preferably chosen such that the number of carbon atoms is greater than or equal to 6 and more preferably greater than or equal to 8.
  • said aldehyde has generally a number of carbon atoms that is lower or equal to 14, preferably lower or equal to 12 and more preferably lower or equal to 10.
  • the number of carbon atoms of the aliphatic aldehyde is between 6 and 14, preferably between 6 and 12 and more preferably between 6 and 10.
  • Suitable aldehydes suitable for use in the present invention are known to the skilled person, e.g., from WO 2011/147802 A1 .
  • the at least one surface treatment agent is abietic acid (also named: abieta-7,13-dien-18-oic acid, CAS-No.: 514-10-3).
  • the salt of abietic acid is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic.
  • the at least one surface-treatment agent is an a trialkoxysilane, which is represented by the formula R 3 -Si(OR 4 )3.
  • the substituent R 3 represents any kind of substituent, i.e., any branched, linear or cyclic moiety having a total amount of carbon atoms from C2 to C30, such as a methyl, ethyl, propyl, butyl, decyl, dodecyl, hexadecyl, octadecyl, allyl, propargyl, butenyl, crotyl, prenyl, pentenyl, hexenyl, cyclohexenyl or vinylphenyl moiety.
  • OR 4 is a hydrolyzable group, wherein substituent R 4 represents any saturated or unsaturated, branched, linear, cyclic or aromatic moiety from having a total amount of carbon atoms from C1 to C30, such as a methyl, ethyl, propyl, allyl, butyl, butenyl, phenyl or benzyl group.
  • R 4 is a linear alkyl group having a total amount of carbon atoms from C1 to C15, preferably from C1 to C8 and most preferably from C1 to C2.
  • the hydrolysable alkoxy group is a methoxy or an ethoxy group.
  • specific or preferred examples of trialkoxysilanes suitable for use in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane or allyltriethoxysilane.
  • the surface-treatment agent is at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or a salt thereof.
  • the so-obtained surface-treated natural calcium carbonate comprises a surface-treatment layer formed from the reaction of the surface-treatment agent with the ground natural calcium carbonate.
  • the surface-treatment layer is formed on at least a part of the ground natural calcium carbonate by contacting the ground natural calcium carbonate with the surfacetreatment agent as described hereinabove.
  • a chemical reaction may take place between the ground natural calcium carbonate and the surface treatment agent.
  • the surface-treatment layer may comprise the surface treatment agent and/or salty reaction products thereof.
  • the surface-treatment layer may further comprise a salt formed from the reaction of the mono- or di-substituted succinic anhydride with the ground natural calcium carbonate.
  • the surface-treatment layer may further comprise a salt formed from the reaction of stearic acid with the ground natural calcium carbonate. Analogous reactions may take place when using alternative surface treatment agents according to the present invention.
  • the treatment layer formed on the surface of the ground natural calcium carbonate comprises the at least one mono-substituted succinic anhydride and/or salty reaction products thereof obtained from contacting the untreated ground natural calcium carbonate with the at least one mono-substituted succinic anhydride.
  • Methods for preparing a surface-treatment layer with at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and suitable compounds for coating are described e.g. in WO 2016/023937 A1 , which is thus incorporated herewith by reference.
  • the surface-treatment layer is formed by contacting the ground natural calcium carbonate with a surface-treatment composition comprising two or more surface-treatment agents
  • the two or more surface-treatment agents may be provided as a mixture prior to contacting the ground natural calcium carbonate with the surface-treatment composition.
  • the ground natural calcium carbonate may be contacted with a surface-treatment composition comprising the first surface-treatment agent, and the second surface-treatment agent is added subsequently, that is, the surface-treatment composition is formed upon contacting the mixture of the ground natural calcium carbonate and the first surface-treatment agent with the second surfacetreatment agent.
  • the surface treatment is carried out in the wet state, i.e. the surface treatment is carried out in the presence of an aqueous solvent, preferably water.
  • the ground natural calcium carbonate may be provided in form of an aqueous suspension having a solids content in the range from 5 to 80 wt.-%, based on the total weight of the aqueous suspension.
  • the solids content of the aqueous suspension is in the range from 10 to 70 wt.-%, more preferably in the range from 15 to 60 wt.-% and most preferably in the range from 15 to 40 wt.-%, based on the total weight of the aqueous suspension.
  • aqueous suspension refers to a system, wherein the liquid phase comprises, preferably consists of, water. However, said term does not exclude that the liquid phase of the aqueous suspension comprises minor amounts of at least one water-miscible organic solvent selected from the group comprising methanol, ethanol, acetone, acetonitrile, tetrahydrofuran and mixtures thereof.
  • the surface-modification is performed in the dry state, i.e. the surface treatment is carried out in the absence of solvents.
  • the untreated ground natural calcium carbonate which may contain a residual amount of moisture, e.g., less than 10 wt.-%, preferably less than 5 wt.-%, more preferably less than 2 wt.-%, is contacted with the surfacetreatment composition, and subsequently mixed.
  • Suitable dry surface-treatment processes are known to the skilled person and are taught, e.g., in WO 2014/060286 A1 and WO 2018/229061 A1 .
  • the at least one inorganic peroxide of step b) is mixed with the ground natural calcium carbonate of step c) before and/or during mixing step e). Accordingly, the at least one inorganic peroxide may be present during surface-treatment step e).
  • the at least one inorganic peroxide is not only capable of reacting with the oxidizable sulfur impurity comprised in the (ground) natural calcium carbonate, but can also react with (oxidizable sulfur) impurities contained in the surface-treatment agent, thus further reducing the odor of such surface-treated calcium carbonate, once incorporated into a polymer compound.
  • the at least one inorganic peroxide of step b) is mixed with the ground natural calcium carbonate of step c) during mixing step e), it may be provided separately from the surface-treatment agent, e.g., in that the at least one inorganic peroxide and the surface-treatment agent are added subsequently or simultaneously. Additionally or alternatively, the at least one inorganic peroxide may be mixed with the surface-treatment agent.
  • the at least one inorganic peroxide is mixed with the ground natural calcium carbonate of step c) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, more preferably in a total amount from 200 to 2000 ppm by weight, even more preferably in a total amount from 200 to 1000 ppm by weight, for example from 200 to 500 ppm by weight, based on the total dry weight of the respective ground natural calcium carbonate.
  • the at least one inorganic peroxide is mixed with the ground natural calcium carbonate of step c) in a total amount of at least 100 ppm by weight, preferably at least 200 ppm by weight, more preferably at least 300 ppm by weight and most preferably at least 500 ppm by weight.
  • the surface-treatment step may be performed by any conventional means known to the skilled person, e.g., those described above with respect to the separate mixing step.
  • the surface-treatment step is performed under heating.
  • the temperature during the surface-treatment step may be equal to or higher than the melting point of the at least one hydrophobizing agent.
  • the temperature may range from 30 to 150 °C, preferably 40 to 140 °C and most preferably from 50 to 130 °C, e.g., at about 80 °C.
  • the heating facilitates decomposition of excess inorganic peroxide.
  • the at least one inorganic peroxide may be added prior to grinding step c) and/or during grinding step c), and/or before and/or during mixing step e).
  • the at least one inorganic peroxide is added prior to grinding step c) and/or during grinding step c) (so that it is present during grinding step c)), or the at least one inorganic peroxide is added during prior to grinding step c) and/or during grinding step c), and before and/or during mixing step e) (so that it is present during grinding step c) and mixing step e)).
  • the inventive process leads to a reduction of the amount of oxidizable sulfur impurities in the natural calcium carbonate.
  • a preferred embodiment of the present invention relates to a manufacturing process, comprising the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, d) providing at least one surface-treatment agent, and e) mixing the at least one surface-treatment agent of step d) with the ground natural calcium carbonate of step c) to obtain a surface-treated natural calcium carbonate, wherein
  • step b) the at least one inorganic peroxide of step b) is mixed with the natural calcium carbonate of step a) prior to grinding step c) and/or during grinding step c), and/or
  • step b) the at least one inorganic peroxide of step b) is mixed with the ground natural calcium carbonate of step c) before and/or during mixing step e).
  • the inventive process comprises the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, d) providing at least one surface-treatment agent, and e) mixing the at least one surface-treatment agent of step d) with the ground natural calcium carbonate of step c) to obtain a surface-treated natural calcium carbonate, wherein the at least one inorganic peroxide of step b) is mixed with the natural calcium carbonate of step a) during grinding step c).
  • a process comprising the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, d) providing at least one surface-treatment agent, and e) mixing the at least one surface-treatment agent of step d) with the ground natural calcium carbonate of step c) to obtain a surface-treated natural calcium carbonate, wherein the at least one inorganic peroxide of step b) is present during grinding step c).
  • a process comprising the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, d) providing at least one surface-treatment agent, and e) mixing the at least one surface-treatment agent of step d) with the ground natural calcium carbonate of step c) to obtain a surface-treated natural calcium carbonate, wherein the at least one inorganic peroxide of step b) is present during mixing step e).
  • a further preferred embodiment of the present invention relates to a manufacturing process, comprising the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity selected from the group consisting of sulfides, polysulfides, elemental sulfur, most preferably a sulfide, in an amount of at least 2 mg/kg, preferably at least 5 mg/kg, based on the total weight of the natural calcium carbonate, b) providing at least one inorganic peroxide selected from the group consisting of hydrogen peroxide, alkaline earth metal peroxides and mixtures thereof, most preferably hydrogen peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate, preferably wherein the ground natural calcium carbonate has a weight median particle size dso value in the range from 0.1 pm to 25 pm, preferably from 0.25 pm to 5 pm and most preferably from 0.5 pm to 4 pm, d) providing at least one surface-treatment agent being at
  • the at least one inorganic peroxide of step b) is mixed with the ground natural calcium carbonate of step c) before and/or during mixing step e) in a total amount of at least 100 ppm by weight, preferably in a total amount from 100 to 5000 ppm by weight, based on the total dry weight of the ground natural calcium carbonate.
  • filler materials and especially calcium carbonate-containing filler materials are often used as particulate fillers in thermoplastic polymer products, fibers, filaments, films, threads, sheets, pipes, profiles, molds, injection molds and/or blow molds, usually made of polyethylene (PE), polypropylene (PP), polyurethane (PU), polyvinylchloride (PVC), polycarbonate (PC), polyester (PES) and/or polyamide (PA).
  • PE polyethylene
  • PP polypropylene
  • PU polyurethane
  • PVC polyvinylchloride
  • PC polycarbonate
  • PET polyester
  • PA polyester
  • PA polyamide
  • the polymer is selected from the group consisting of polyolefins, halogen-containing polymers, polyesters, polypeptides, polyethers, poly(meth)acrylates, polysaccharides and derivatives thereof, polyurethanes, polyimides, polyamides, polycarbonates, polyethylene imine), poly(acrylonitrile), poly(vinyl pyrrolidone), poly(vinyl alcohol), polyaniline, poly(vinylidene fluoride), aryl polysulfones, elastomers, and mixtures and co-polymers of the foregoing.
  • polyolefins halogen-containing polymers
  • polyesters polypeptides, polyethers, poly(meth)acrylates, polysaccharides and derivatives thereof, polyurethanes, polyimides, polyamides, polycarbonates, polyethylene imine), poly(acrylonitrile), poly(vinyl pyrrolidone), poly(vinyl alcohol), polyaniline, poly(viny
  • the polymer may be selected from hydrocarbon polymers, i.e., polymers being composed essentially of carbon and hydrogen atoms, e.g., comprising more than 95 mol-% of carbon and hydrogen atoms.
  • hydrocarbon polymers i.e., polymers being composed essentially of carbon and hydrogen atoms, e.g., comprising more than 95 mol-% of carbon and hydrogen atoms. Examples include polyolefins and polystyrene.
  • the polyolefin can be polyethylene and/or polypropylene and/or polybutylene homopolymers or copolymers. Accordingly, if the polyolefin is polyethylene, the polyolefin is selected from the group comprising homopolymers and/or copolymers of polyethylene like high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE) and ultra-high molecular weight polyethylene (UHMWPE).
  • HDPE high-density polyethylene
  • MDPE medium-density polyethylene
  • LDPE low-density polyethylene
  • VLDPE very low-density polyethylene
  • LLDPE linear low-density polyethylene
  • UHMWPE ultra-high molecular weight polyethylene
  • the polyethylene preferably contains units derivable from ethylene as major components.
  • the copolymer of polyethylene preferably comprises, more preferably consists of, units derived from ethylene and C2 and/or at least one C4 to C10 a-olefin.
  • the copolymer of polyethylene comprises, preferably consists of, units derived from ethylene and at least one a-olefin selected from the group consisting of propylene, 1 butene, 1 pentene, 1 -hexene and 1 -octene.
  • the polypropylene preferably contains units derivable from propylene as major components.
  • the copolymer of polypropylene preferably comprises, preferably consists of, units derived from propylene and C2 and/or at least one C4 to C10 a-olefin.
  • the copolymer of polypropylene comprises, preferably consists of, units derived from propylene and at least one a-olefin selected from the group consisting of ethylene, 1 -butene, 1 -pentene, 1 -hexene and 1 -octene.
  • the polymer may be a halogen-containing polymer, i.e. hydrocarbon polymers additionally comprising chlorine, bromine, fluorine and iodine moieties.
  • the halogen-containing polymer preferably is selected from polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
  • the polyethers may be selected from polyalkylene glycols, preferably polyethylene glycols.
  • polyethylene oxide is considered synonymous to polyethylene glycol.
  • the poly(meth)acrylates may be selected from the group consisting of poly(alkyl acrylates), poly(alkyl methacrylates), poly(methyl acrylate), poly(ethyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), copolymers thereof, and copolymers of the foregoing with acrylic acid and/or methacrylic acid and/or salts thereof.
  • the polyimides may be selected from the group consisting of poly(succinimide) (PSI), poly(bismaleic imide) (PBMI), poly(imidosulfone) (PISO), poly(methacrylimide) (PMI), and mixtures thereof.
  • PSI poly(succinimide)
  • PBMI poly(bismaleic imide)
  • PISO poly(imidosulfone)
  • PMI poly(methacrylimide)
  • a grinding aid is present during the grinding step, preferably wherein the grinding aid is selected from at least one polyol, optionally wherein the polyol comprises amine groups, more preferably wherein the grinding aid is selected from at least one diol or triol, optionally comprising amine groups, even more preferably wherein the grinding aid is selected from the group consisting of ethanediol, propanediol, glycerol, diethanolamine, triethanolamine and mixtures thereof, and most preferably wherein the grinding aid is 1 ,2-propanediol.
  • the grinding aid may be present during grinding step c) in an amount of at least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm and most preferably at least 500 ppm. Specifically, the grinding aid may be present in an amount ranging from 50 ppm to 20,000 ppm preferably 100 to 10,000 ppm, and most preferably 200 to 8,000 ppm, e.g., 500 to 7,000 ppm, based on the total dry weight of the natural calcium carbonate.
  • the particulate natural calcium carbonate has i) a weight median particle size dso value in the range from 0.1 pm to 25 pm, preferably from 0.25 pm to 5 pm and most preferably from 0.5 pm to 4 pm, and/or ii) a top cut (cfos) of ⁇ 100 pm, preferably ⁇ 40 pm, more preferably ⁇ 25 pm and most preferably ⁇ 15 pm, and/or iii) a specific surface area (BET) of from 0.5 to 150 m 2 /g, preferably from 0.5 to 50 m 2 /g, more preferably from 0.5 to 35 m 2 /g and most preferably from 0.5 to 10 m 2 /g as measured by the BET nitrogen method, and/or iv) a residual total moisture content of from 0.01 wt.-% to 1 wt.-%, preferably from 0.01 to 0.2 wt.-%, more preferably from 0.02 to 0.2 wt.-% and most
  • the surface-treatment agent is selected from i. a phosphoric acid ester blend of one or more phosphoric acid monoester and/or one or more phosphoric acid di-ester and/or a salt thereof, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid preferably having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, and/or iii. at least one aliphatic aldehyde, and/or iv.
  • At least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or a salt thereof, and/or v. at least one polydialkylsiloxane, and/or vi. mixtures of the materials according to i. to v..
  • the surface-treatment agent is added in an amount from 0.1 to 2 wt.-%, preferably from 0.2 to 1 .5 wt.-% and most preferably from 0.4 to 1 .2 wt.-%, based on the total dry weight of the ground natural calcium carbonate and/or wherein the surface-treatment agent is added in an amount from 0.5 to 5 mg/m 2 , preferably from 1 to 4 mg/m 2 and most preferably from 1 .3 to 3 mg/m 2 , based on the total surface area of the particulate natural calcium carbonate.
  • the at least one inorganic peroxide is contacted with the particulate natural calcium carbonate in an amount of at least 100 ppm by weight, preferably in an amount from 100 to 5000 ppm by weight, more preferably in an amount from 200 to 2000 ppm by weight, even more preferably in a total amount from 200 to 1000 ppm by weight, based on the total dry weight of the particulate natural calcium carbonate.
  • An exemplary embodiment of the present invention relates to the use of at least one inorganic peroxide for reducing the odor of a calcium carbonate-containing polymer compound, wherein the at least one inorganic peroxide is used in a process as described hereinabove.
  • the use of at least one inorganic peroxide for reducing the odor of a calcium carbonate-containing polymer compound manufacturing process comprises the steps of a) providing a natural calcium carbonate comprising an oxidizable sulfur impurity, b) providing at least one inorganic peroxide, c) grinding the natural calcium carbonate of step a) to a desired particle size to obtain a ground natural calcium carbonate.
  • the calcium carbonate-containing polymer compound has a melt flow index (MFI) that does not substantially differ from the MFI of a polymer compound containing a calcium carbonate that has not undergone treatment with at least one inorganic peroxide.
  • MFI melt flow index
  • the MFI differs by less than 5 g/10min, more preferably less than 2 g/10 min, even more preferably less than 1 .5 g/10 min.
  • the MFI differs by less than 50%, more preferably by less than 30%, even more preferably by less than 20%, and most preferably by less than 10%.
  • the MFI (5 kg, 190°C) of the calcium carbonate-containing polymer compound may be in the range from 0.3 to 150 g/10 min, preferably from 1 to 100 g/10min, more preferably from 2 to 50 g/10min, and most preferably from 3 to 30 g/10min.
  • melt flow rate MFR
  • MFI melt flow index
  • MFR mass of the polymer, given in g/10 min, which is discharged through a defined die under specified temperature and pressure conditions.
  • MFR mass of the polymer
  • MFI melt flow index
  • the MFI is a measure of the viscosity of the polymer, which is mainly influenced by the molecular weight of the polymer, but also by the degree of branching or the polydispersity.
  • the calcium carbonate-containing polymer compound has an impact strength that does not substantially differ from the impact strength of a polymer compound containing a calcium carbonate that has not undergone treatment with at least one inorganic peroxide.
  • the impact strength differs by less than 30%, more preferably by less than 20%, and most preferably by less than 10%.
  • the impact strength of the calcium carbonate-containing polymer compound may be at least 1 kJ/m 2 , preferably at least 2 kJ/m 2 , more preferably at least 5 kJ/m 2 .
  • the calcium carbonate- containing polymer compound may not break, there is no particular upper limit of the impact strength.
  • the impact strength may be in the range from 1 to 50 kJ/m 2 , preferably from 3 to 40 kJ/m 2 , and most preferably from 5 to 30 kJ/m 2 .
  • the impact strength can be determined according to ISO 179-1eA.
  • the E modulus of the calcium carbonate-containing polymer compound may be in the range from 200 to 5000 N/mm 2 , preferably from 400 to 4000 N/mm 2 , most preferably from 600 to 3000 N/mm 2 .
  • the yield strength of the calcium carbonate-containing polymer compound may be in the range from 5 to 50 N/mm 2 , preferably from 10 to 30 N/mm 2 , most preferably from 12 to 25 N/mm 2 .
  • the calcium carbonate-containing polymer compound has an elongation at break that does not substantially differ from the elongation at break of a polymer compound containing a calcium carbonate that has not undergone treatment with at least one inorganic peroxide.
  • the elongation at break differs by less than 30%, more preferably by less than 20%, and most preferably by less than 10%.
  • the elongation at break of the calcium carbonate-containing polymer compound may be in the range from 100% to 800%, preferably from 125 to 500%, most preferably from 150% to 250%.
  • the tensile properties (e.g., E modulus, yield strength, elongation at break) may be determined according to ISO527-1 Type BA(1 :2). Examples
  • the specific surface area (in m 2 /g) of the mineral filler is determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled man (ISO 9277:2010).
  • the total surface area (in m 2 ) of the mineral filler is then obtained by multiplication of the specific surface area and the mass (in g) of the mineral filler prior to treatment.
  • volume determined median particle size cfeo(vol) and the volume determined top cut particle size cfei(vol) as well as the volume particle sizes cfoo(vol) and c/io(vol) may be evaluated in a wet (Hydro LV) or dry (Aero S) unit using a Malvern Mastersizer 3000 Laser Diffraction System (Malvern Instruments Pic., Great Britain).
  • the cfeo(vol) or cfo8(vol) value indicates a diameter value such that 50 % or 98 % by volume, respectively, of the particles have a diameter of less than this value.
  • the raw data obtained by the measurement was analyzed using the Mie theory, with a particle refractive index of 1 .57 and an absorption index of 0.005.
  • the methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments. Determination of sulfide content via the UV-VIS method:
  • the calcium carbonate sample is dissolved using hydrochloric acid.
  • the hydrogen sulfide that is encapsulated in the stone is liberated, flowed and captured in a solution of N,N-dimethyl-p- phenyldiamine dihydrochloride and iron ammonium sulfate.
  • the amount of H2S is then quantified by colorimetric analysis with a spectrophotometer.
  • the method may be carried out in an instrument as shown in Fig. 1 and/or using a method as follows:
  • the nitrogen gas flow 1 is maintained until 5 minutes after the reaction is finished (no more evolving bubbles are visible).
  • the nitrogen flow is closed.
  • 10 mL of coloration reagent solution and 1 mL of iron ammonium sulfate (III) solution are added to the absorption glassware 6. After shaking and letting react for 10 minutes, the solution is transferred into a 100 mL volumetric flask and filled to 100 mL with ultrapure water.
  • the elemental sulfur specified as SO3 is measured by XRF following the standard norm ISO 29581- 2:2010 using a XRF spectrometer Perform’X from Thermo Fischer Scientific. Samples are prepared as fused bead(s) with a LOI-free ratio flux material : sample of 9:0.9 (g/g). The LOI (Loss On Ignition) is determined prior to each measurement (using TGA or oven). As flux material a 66:34 mixture of Li Tetraborate and Li Metaborate (purity of the mixture 99.98%), to which 0.20% LiBr is added, is used. The prepared fused bead(s) is/are measured by XRF (X-Ray Fluorescence) using external calibration.
  • XRF X-Ray Fluorescence
  • the result represents the average of two measurements.
  • the calibration procedure is a standard calibration commonly used for XRF instruments.
  • the calibration is made by 26 certified reference materials (CRM) prepared as fused beads.
  • CCM certified reference materials
  • the drift of the XRF signal occurring with time is corrected by drift monitors (also CRM, also a standard method in XRF).
  • the system is regularly controlled by standard samples with well-known concentrations.
  • the pellets were stored after the extrusion process inside a closed glass container for one day at room temperature, then a testing panel of 7 people assessed the smell intensity of each sample based on the following table:
  • the calcium carbonate CC1 is an untreated marble from Gebze (Turkey) pre-crushed with a particle size d5o of 4 mm containing 25 mg/kg of H2S measured via the UV-VIS method as explained in the description.
  • the grinding aid GA-01 is a 60% monopropylene glycol solution (CAS No. 57-55-6).
  • the grinding aid GA-02 is a 60% food grade monopropylene glycol solution (CAS No. 57-55-6).
  • the hydrophobizing agent HA-01 is a fatty acid mixture consisting of about 40% stearic acid and about 60% palmitic acid. 10. Hydrophobizing agent HA-02:
  • the polymer matrix used is a linear low density polyethylene that can be obtained from Dow under the tradename Dowlex 2631.10UE.
  • Table 4 Preparation and composition of Compounds CP-1 to CP-9
  • Table 5 Smell evaluation results As can be seen in Table 5, the use of hydrogen peroxide leads to a significant decrease of the unpleasant smell, matching the low-smell level of unfilled resin.
  • compositions used for the grinding process are presented in Table 6:
  • Example 4 Use of hydrogen peroxide during the grinding process of renewable calcium carbonate (eggshells):
  • a commercially available material C1 (a calcium carbonate with a dso of 1 .9 pm and dga of 7.5 pm with a surface-treatment of a mixture of stearic and palmitic acid; OFM 750-GZ with Omyacid 39) was used for comparison.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un procédé de fabrication consistant à faire réagir une impureté de soufre oxydable d'un carbonate de calcium naturel avec au moins un peroxyde inorganique et à utiliser au moins un peroxyde inorganique pour réduire l'odeur d'un composé polymère contenant du carbonate de calcium.
PCT/EP2025/050314 2024-01-10 2025-01-08 Élimination d'une odeur désagréable dans des compositions polymères remplies de carbonate de calcium Pending WO2025149508A1 (fr)

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