Classifications

• • 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
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  • 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
  • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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  • 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
  • C09C1/36—Compounds of titanium
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  • 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
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3676—Treatment with macro-molecular 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
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
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  • 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
  • C09C1/40—Compounds of aluminium
  • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
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  • 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
  • C09C1/40—Compounds of aluminium
  • C09C1/407—Aluminium oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C09C1/40—Compounds of aluminium
  • C09C1/42—Clays
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  • 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
  • C09C3/10—Treatment with macromolecular organic compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
  • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
• • 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
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
• • 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
  • C01P2006/62—L* (lightness axis)
• • 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

Definitions

• the process relates to mineral material slurries used in concrete, sealants, paper, paint or plastic applications.
• ground calcium carbonate slurry is used in paint and paper industry as filler or coating pigment.
• Natural sources of such pigments include traces of coloured impurities, such as oxides, e.g. iron oxide, sulphides, such as iron sulphide, silicates, such as feldspars and mica but also carbon sources, such as crystalline and/or amorphous carbon, for example graphite.
• oxides e.g. iron oxide, sulphides, such as iron sulphide, silicates, such as feldspars and mica
• carbon sources such as crystalline and/or amorphous carbon, for example graphite.
• the problem the printing and plastics industry faces today is often a slight gray or dark veil-like appearance on the slurry surface coming from small traces of coloured impurities, for example graphite as mentioned above.
• the problem to be solved by the present invention is to increase the surface whitening of water based mineral matter slurries.
• US 2002/0004541 relates to low pour point ethylene oxide/propylene oxide block copolymer surfactants, and a process for preparing the same.
• the object of the invention which is again entirely outside of that of the present invention, is achieved by combining the indicated copolymer with low molecular weight glycol, water and a clialkyl sulfosuccinate. It is further described that such block copolymers may be used as grinding aids, however no indication is provided as to the nature of the material ground, whether this grinding is wet or dry, nor the efficiency of the grinding process.
• US 2005/01 7493 discloses a method for producing coated, fine-particle inorganic solids, the surface of which is coated with fine inorganic solid particles, which may be carbonates, containing at least two different organic additives, it is indicated thai the second additive may be a polyethylene glycol. It is possible to carry out the modification, which may take place via a grinding process. However, again, no information is provided regarding the grinding efficiency, nor is a dry grinding process exemplified or discussed in any detail. Furthermore, the goal of the invention is entirely different from that of the present invention, namely to obtain a uniform distribution of the additives over the solid surface.
• DE 102005043542 discloses an aqueous graphite dispersion including graphite particles dispersed in water along with stabilizers acting as dispersants, and additives.
• the graphite particles are at least partially spherical.
• Polyethylene glycol is described, for example, as a good dispersant. However this does not provide a solution to increase the surface whitening of mineral material slurries, as polyethylene glycol works as a collector in this environment, which finally will lead to a darkening of the slurry surface.
• the applicant has surprisingly found a process using a selective group of additives to prevent flotation of coloured mineral matter to the surface of white mineral matter slurries and thereby increasing the whitening of the mineral matter slurry surface.
• a further advantage of the process of the present invention is, that no or only very little waste material is produced by the inventive process.
• a further aspect of the present invention is that the product produced by the inventive process does not provoke dark stripes during wall painting or paper coating by formed agglomerates a/o aggregates on the mineral matter slurry surface.
• a further problem to solve is the whiteness measurement of liquid slurry surface. Whiteness measurement of liquid slurry surface is not possible with today' s common equipment such as Elrepho powder whiteness measurement instruments.
• step a) adding during and/or after step a) 0.005 wt.% to 0.5 wt.% in respect to dry mineral matter of at least one alkylene oxide block or random co-polymer, preferably a block-copolymer
• step (c) optionally adding 0.005 wt.% to 5 wt.% in respect to dry mineral matter of at least one dispersing a/o grinding aid during and/or after step (a) and / or step (b) .
• grinding or grinding process shall be understood as a synonym for milling or milling process, which may also be autogenous.
• the mineral matter used in the process of the present invention can be chosen from kaolin, natural or precipitated calcium carbonates, talc, mica, dolomite, bentonite, Ti0 2 , Al(OH) , or mixtures thereof.
• the calcium carbonate is natural calcium carbonate, such as marble, limestone, chalk, calcite or mixtures thereof.
• the mineral matter suitable to be used in the process of the present invention comprises dark hydrophobic impurities. Such impurities can be FeS2 (Pyrite) or graphite or mixtures thereof but are not limited to these.
• the water based slurry obtained by the process of the present invention is a mineral matter slurry, wherein the mineral matter is calcium carbonate, preferred is natural calcium carbonate, such as marble, limestone, chalk or calcite and/or mixtures thereof.
• the water based mineral matter slurry used in the process of the present invention is prepared either by dry grinding of mineral matter until the mineral matter has a d$o from about 0.2 ⁇ - 100 ⁇ , preferably from about 0.3 ⁇ - 50 ⁇ , more preferably from about 0.3 ⁇ - 30 ⁇ , and most preferably from about 0.3 ⁇ ⁇ - 2 ⁇ .
• Said dry ground mineral matter is provided in an aqueous suspension of water in amounts of up to 20 wt-%, preferably up to 30 wt-%, more preferably up to 40 wt-% in respect to dry mineral material.
• said dry ground mineral matter is further subjected to wet grinding until d 5 o is in the range of about 0.2 ⁇ - 10 ⁇ , preferably in the range from about 0.3 ⁇ - 5 ⁇ , most preferably in the range from about 0.3 ⁇ - 2 ⁇ .
• the wet grinding is done in a range from about 5 wt% to about 80 wt%, preferably in a range from about 30 wt% - 75 wt%, more preferably in a range from about 40 wt% - 75 wt%, most preferably from about 50 wt%-75 wt% solids with respect to dry mineral matter in water in a mill.
• Said milling process can be carried out batch wise or continuously.
• Beads suitable for milling said mineral material are known to the skilled person, such as exemplified but not limited to zircon silicate beads in the range of from 0.2 mm - 4 mm, in particular in the range from 1 mm - 1 .5 mm.
• the milling may also be autogenous.
• the water based mineral matter slurry used in the process of the present invention optionally comprises at least one anionic dispersant or grinding aid.
• Said anionic dispersing a/o grinding aids are organic or inorganic dispersing a/o grinding aids.
• the organic dispersing and/or grinding aid can be selected from citrate, maleate, fumarate, itaconate, polyacrylates and homo- or copolymers of acrylic- or methacryiic acid and combinations thereof.
• the inorganic dispersing a/o grinding aid is selected from pyrophosphate or polyphosphates such as hexamctaphosphate, tripolyphosphate, ammonium zirconium carbonate or potassium zirconium carbonate.
• the dispersant is partially or fully neutralized by at least one mono- and/or bivalent and/or trivalent and/or tetravalent neutralizing agent.
• partially neutralized means that the at least one anionic polymeric dispersant is up to 100 mol % neutralized, by at least one mono and/or bivalent neutralizing agent.
• the at least one anionic polymeric dispersant may be neutralized at a level of from 90 %, or 80 %, or 70 %, or 60 %, or 50 %, or 40 %, or 30 %, or 20 %, or 10 % to about 10 %, or 20 %, or 30 % or 40 %, or 50 %, or 60 %, or 70 % or 80 %, or 90 % by at least one mono- and/or bivalent and/or trivalent neutralizing agent.
• the at least one mono- or bivalent neutralizing agent can be chosen from alkali or earth alkali metal ions and or their salts, such as lithium, sodium, potassium, magnesium, calcium, ammonium and combinations thereof. Further suitable grades of neutralisation of dispersant are also known from FR2683537 and FR2683538. Therefore the previously mentioned anionic dispersing a/o grinding aids can also be selected amongst polymers of sodium citrate sodium maleate, sodium fumarate, sodium itaconate, and homo- or copolymers of sodium acrylate or sodium
• sodium pyrophosphate or sodium polyphosphates such as sodium hexametaphosphate, or sodium
• Potassium-Zirconium calcium carbonate ( ZC) or Ammonium Zirconium Calcium carbonate (AZC) might be present additionally.
• the at least one anionic polymeric dispersant as disclosed herein can be chosen, for example, from polymeric dispersants comprising at least one group chosen form a hydroxyl group, an amido group, a carboxyl group, a sulfo group and a phospono group, and alkali metal and ammonium salts thereof.
• polymeric dispersants comprising at least one group chosen form a hydroxyl group, an amido group, a carboxyl group, a sulfo group and a phospono group, and alkali metal and ammonium salts thereof.
• the polymeric acrylic dispersants can have a weight average molecular weight (Mw) of for example, from about 1000 g mol to 30000 g/mol, preferably from about 1300 g moi to 20000 g/mol, more preferably from about 1500 g/mol to 17000 g mol, still more preferably from about 2500 g/mol to 16000g/mol, still more preferably from about 3 100 g/mol to 15000 g/mol, still more preferably from about 3200 g/mol to 13000 g mol, still further preferred in the range from about 3300 g/mol to 7500 g/mol, still further preferred in the range from about 500 g/mol to about 6000 g/mol. Yet another range is from about 1800 g/mol to about 4800 g/mol.
• suitable polymeric dispersant of the above claimed ranges are polyacrylic
• corresponding polydispersity of the different acrylic polymers are measured as 100 mol% sodium salt at pH 8 according to an aqueous Gel Permeation Chromatography (GPC) method calibrated with a series of five sodium polyacrylate standards supplied by Polymer Standard Service with references PSS-PAA 1 8 , PSS-PAA 8 , PSS- PAA 5 , PSS-PAA 4K and PSS-PAA 3K.
• GPC Gel Permeation Chromatography
• polydispersity of the different alkyloxy polymers are measured at pH 8 according to an aqueous Gel Permeation Chromatography (GPC) method calibrated with a series of different polyethylene glycols.
• GPC Gel Permeation Chromatography
• the dispersant suitable for the preparation of the water based mineral slurry from the grinding processes described above is a sodium/calcium polyacrylate having a molecular weight (Mw) in the range from about 2000 g/mol to 30000 g mol, preferably in the range from about 3000 g/mol to 20000 g/mol, most preferably in the range from about 4000 g/mol to 10000 g/moi, still further preferred in the range from about 5000 g mol to 9000 g/mol, and a polydispersity index PD1 in the range from about 1 .2 to 5.0, preferably from about 1 .5 to 3.0, most preferably from about 1 .8 to 2.7, the solids content is 1 wt% to 100 wt.% preferably in the range from about 30 wt% - 45 wt%.
• Mw molecular weight
• the polyacrylate being present in the aqueous mineral matter slurry is in the range from about 0.01 wt% to 2 wt%, preferably in the range from about 0.1 wt% to 1 .5 wt%, more preferably in the range from about 0.15 wt% to 1.2 wt% solids with respect to dry mineral matter depending on solids of the aqueous mineral matter slurry and fineness and specific surface of the mineral matter particles.
• the alkylene oxide block or random co-polymer of the present invention are ethylene oxide and/or propylene oxide or butyl ene oxide block co-polymers; or propylene oxide and/or ethylene oxide or butyl ene oxide block co-polymers; or ethylene oxide and propylene oxide and ethylene oxide, or propylene oxide and ethylene oxide and propylene oxide block co-polymer, or random co-polymers of ethylene oxide with propylene oxide or butylene oxide. Further, also combinations of the above mentioned polymers are suitable to carry out the present invention.
• block copolymers being also denoted as tri-block or bi-block copolymers such as EO/PO/EO, wherein the propylene oxide units are located between two ethylene oxide units, or vice versa such as PO/EO/PO, wherein the ethylene oxide units arc located between two propylene oxide units, or EO/PO or PO/EO, their synthesis being amply described in the prior art.
• x, y, and z may each independently represent any single integer between, or equal to 1 and 120, preferably between, or equal to 1 and 80, more preferably between, or equal to 3 and 70, still more preferably between, or equal to 5 and 34, and wherein x and z are the same or different integer(s), or (II)
• RO-(CHCH 2 0 HCH2CH2O R ' wherein d, e, f or g may each independent represent any single integer between, or equal, to 1 and 120, preferably between, or equal to 1 and 80, more preferably between, or equal to 2 and 70, still more preferably between, or equal to 4 and 40, and wherein d and e are the same or different integer(s), as well as f or g being the same or different integer(s).
• lt and R' in the formulae mentioned above may represent alkyl residues and/or hydrogen.
• block copolymers being also denoted as EO/PO/EO or triblock copolymers, thus propylene oxide units located between two ethylene oxide units, or vice versa, PO/EO/PO, wherein an ethylene oxide unit is located between two propylene oxide units, or EO/PO or PO/EO, their synthesis being amply described in the prior art.
• the ethylene oxides, or propylene oxides also denoted as polyethylene glycols or polypropylene glycols, the abbreviations being PEG, or PPG.
• polyethylene glycol of a certain molecular weight will thus be indicated as PEG[250], which means a polyethylene glycol having a molar mass of 250 g/mol.
• PEG[250] polyethylene glycol having a molar mass of 250 g/mol.
• a further arrangement of block copolymer is: PPG[58-4'640]-PEG[44-3 '520]-PPG[58-4'640]
• block copolymers being structured the following way: PPG-PEG-PPG- PEG or PPG-PEG-PPG-PEG-PPG, or PEG-PPG-PEG-PPE, and further permutations the skilled person can readily derive thereof, or multiples thereof such as (PPG- PEG)i, or (PEG-PPG) j , or (PPG-PPG-PEG) k or (PPG-PEG-PPG), or (PEG-PPG- PPG) m or (PPG-PEG-PEG) n or (PEG-PPG-PEG) 0 or (PEG-PEG-PPG),, or (PPG- PPG-PEG-PEG) q or (PPG-PEG-PPG-PEG),.
• any single integer between, or equal to, 1 and 120 means, 1 , 2, 3, 4, 5, 6, 7, . . .20, 21 ,. . ..30, 3 1 ,. . ..40, 41 , ..50, 51 , . . .60, 61 ,..70, 71 ,.. .80, 81 , . . .90, 91 , . . . 100, 101 ,. . . 1 1 0, 1 1 1 , . . ..120.
• propylene oxide unit can be replaced with structurally related alkylene oxides, such as butylene oxide, or other alkylene oxides with carbon atom backbones containing C5, C6, C7, C8, C9, CI 0 or more carbon atoms, said carbon atom backbones being further branched or not.
• structurally related alkylene oxides such as butylene oxide, or other alkylene oxides with carbon atom backbones containing C5, C6, C7, C8, C9, CI 0 or more carbon atoms, said carbon atom backbones being further branched or not.
• the propylene oxide units can be replaced with the alkylene oxides mentioned before, but also the ethylene oxide units.
• alkylene oxide block copolymers are, but not limited to:
• Such blends are in the ratio range of from about 1 : 100 (w/w) to 100: 1 (w/w), preferably in the range from about 1 :50 (w/w) to 50: 1 (w/w), more preferably in the range from about 1 :30 (w/w) to 30: 1 (w/w), most preferably in the range from about 1 : 1 0 (w/w) to about 10: 1 (w/w).
• Still further ranges are from about 1 : 5 (w/w) to about 5 : 1 (w/w), preferably from about 1 :3 (w/w) to about 3 : 1 (w/w), more preferably from about 1 :2 (w/w) to about 2: 1 (w/w): a particular blend being 1 : 1 (w/w).
• blends can not only be made out of two of the above mentioned components but from more, such as blending at least three or more of the alkylene oxides mentioned above, and ranges of the at least three blended alkylene oxides, would lie in ranges of from 1 : (100 - 1 ) for each of the at least three alkylene oxides.
• triblock copolymers refer to
• alkylene oxides of different classes as previously mentioned.
• the polymerisation processes employed being well known to the skilled person.
• the alkylene oxides mentioned above can also be combined with still other alkylene oxides, such as Bevaloid 2565, a propylene oxide ethylene oxide block copolymer from Kemira Chimie SA.
• a particular preferred combination but not limited to is Lumiten-P-T/Bevaloid 2565 (2: 1 w/w).
• Th e alkylene oxides of the present invention can be employed in the mineral matter slurries as a single component, or as a preformulated blend or added in serial order during or after the milling process.
• the employed total amount of the alkylene oxides i.e.
• additives of the present invention is in the range of from about 200 ppm to 10000 ppm, preferably from about 300 ppm to about 7500 ppm, more preferably from about 400 ppm to about 5000 ppm, most preferably from about 500 ppm to about 2500 ppm.
• Other total amounts of the alkylene oxides employed in the present invention are, but not limited to, in the lower ppm ranges from about 1 50 ppm to about 1 000 ppm, preferably in the range from about 250 ppm to about 850 ppm, more preferably from about 350 ppm to about 750 ppm, most preferably from about 450 ppm to about 650 ppm in respect to dry mineral matter.
• alkylene oxides to be employed in total amounts are from about 10 ppm to about 100 ppm, preferably from about 30 ppm to about 80 ppm, more preferably from about 40 ppm to about 60 ppm, still more preferably from about 45 ppm to about 55 ppm, in respect to dry mineral matter.
• the skilled person will thus also recognize that the ppm values are convertible to wt% values.
• a workable range of the alkylene oxides of the present invention such as 50 ppm to 5000 ppm is equivalent for the range of 0.005 wt% to 0.5 wt%.
• the process for preparing the slurry of mineral matter of the present invention is performed at a temperature in the range of from about 5°C to about 100°C, preferably in the range from about 1 5°C to about 80°C, more preferably in the range from about 20°C to about 60°C, most preferably from about 25°C to about 50°C.
• a preferred ambient temperature being 23°C, with possible deviations of ⁇ 3°C, being applicable to the ambient temperature as well as to the ranges just mentioned above.
• the molecular weight of the alkylene oxides of the present invention can be readily determined by the skilled man using e.g. Gel Permeation Chromatography (GPC), as described in WO/201 0/072769, and according to DIN 55672- 1 .
• GPC Gel Permeation Chromatography
• polyethylene glycol standard, analytical standard set M p 400 - 40000 from Fluka (product number 81396) was used.
• the ratio of the EO/PO can be determined according to ! H-NMR
• step b) add during and/or after step a) 0.005 wt.% to 0.5 wt.% in respect to dry mineral matter of at least one ethylene oxide and/or propylene oxide and/or butylene oxide block copolymers,
• step (c) optionally adding 0.005 wt.% to 5 wt.% in respect to dry mineral matter of at least one dispersing a/o grinding aid during and/or after step (a) and / or step (b)
• the mineral matter slurry of the present in invention has a solids content of at least 5 wt%, preferably 50 - 80 wt%, more preferably 70 - 79 wt%, most preferably 72 - 78.5 wt% based on dry mineral matter.
• Higher solid contents such as 82 wt% based in dry mineral matter can be achieved by up concentrating the aqueous based mineral matter slurry. Such upconcentratmg methods being known to the skilled person, such as thermal or mechanical upconcentration.
• Lumiten P ⁇ T BASF produced by Viscosity (Contraves polymerisation of EO and Rheometcr; DIN 53 019 PO STV, MS 45/11): ⁇ 500 mPa-s
• Brookfield viscosity is measured after 1 minute of stirring by the use of a RV DV- III ultra
• BrookfieldTM viscometer and a rotation speed of 100 rpm (revolutions per minute) with the appropriate disc spindle 4)
• PPG polypropyleneglycol
• PEG polycthyleneglycol
• Blend of Chinese / Vietnamese / Malaysian Marble (approximately 50:25 :25 in respect to dry weight)
• Mineralogy of the HCl-insoluble part Graphite, Muscovite, Chlorite, Feldspar, Talc, Amphibole, Quartz
• Dry ground Marble blend having a of 45 ⁇ , is wet ground to a d o of 1 .4 ⁇ .
• the wet grinding is done at 78 wt% solids in tap water in a vertical attritor mill having a volume of 1 '500 litres in a continuous mode, using zircon silicate beads of 3 - 1 .5 mm diameter and using 0.63 wt% of a sodium/calcium polyacrylate dispersant having a molecular weight (Mw) of 5 '500 and polydispersity of 2.7.
• Mw molecular weight
• the final product further had a £ ⁇ 4 8 of 7 ⁇ and a BET specific surface area of 6.7 m /g determined according to ISO standard 9277.
• the test method used was the static volumetric method, with multipoint determination. Degas conditions were 250°C / 30min.
• the fraction ⁇ 2 pm was 62 wt%, and the fraction ⁇ 1 ⁇ was 37 wt%.
• the final solids was 77.4 wt%.
• the degree of colour was measured pouring the slurry into a glass receptacle of 60mm height and 1 1 mm diameter and taking a photograph of the slurry surface in between 5 to 1 5 min after pouring the slurry into the glass receptacle.
• Imaging was performed with a readily available digital camera device, e.g. Canon PowerShot A640 ( 1/1 .8 inch CCD sensor). The picture was taken at a resolution of 2272 x 1704 pixels with a bit depth of 24, in colour mode, Zoom 1 at a distance of the objective to slurry surface at 1 1 cm and a shutter speed of 1 /50 s. Light conditions were the following as set out in the table of the experimental set up. The photographing setup was protected from ambient light.
• an image section of 1 500 x 1200 x 24 resolution was selected and submitted to computational calculation for determining the whiteness value.
• the "zero whiteness" value was determined from a picture taken with closed objective, i.e. with the protective light tight lid clamped on.
• an image section of a BaS0 4 tablet ( l Og of BaS0 4 powder was used to press a tablet in an Omyapress 2000, said press being commercially available) was taken at a resolution of 2'272 x 704 pixels with a bit depth of 24, in colour mode, Zoom 1 (1 x magnification) at a distance of the objective to slurry surface at 1 1 cm and a shutter speed of 1 /50 s, an image section of ⁇ 500 x 1 '200 x 24 resolution was selected and submitted to the same computational calculation for defining an arbitrary 1 00% whiteness definition.
• the wet surface whiteness is 3 % above the whiteness of the same slurry with no alkylene oxide present in the step b), more preferably the wet surface whiteness is 4 % above the whiteness of the same slurry with no alkylene oxide present in the step b).
• the present invention provides for a water based mineral matter slurry with a wet slurry surface whiteness of more than 96%, preferably of > 97 %, more preferably of > 98 %, still more preferably of > 99 %, most preferably of 100 %, compared to the BaS0 4 standard, meaning thus that the wet slurry surface whiteness of the present invention comprises between more than 96 % and less or equal 100 % compared to the standard whiteness reference of BaS04, representing 1 00 % whiteness, when measured according to the measuring method of the present invention.
• wet slurry surface whiteness of the present in invention is comprised between more than 96% and equal or less than 100% compare to the standard whiteness reference of BaS0 4 , presenting 100% whiteness, when measured according to the measuring method of the present invention.
• values are absolute values in the scale of 0% to 100 %.
• the method for measuring the wet mineral matter slurry surface whiteness comprises the steps of:
• the present embodiment for measuring the wet mineral matter slurry surface whiteness is however not to be construed to be of limiting character. It remains within the discretion of the skilled person to choose alternative imaging systems which provide for whiteness values for computational comparison, such as analog imaging and subsequent digitalization of the images, video capturing and subsequent computational comparative analysis of whiteness values.
• step (b) providing a suitable receptacle to carry the wet mineral matter slurry of step (a)
• imaging and computational analysis can be performed in different sequences separated in time and place, other than as herein described.
• step (b) providing a suitable receptacle to carry the wet mineral matter slurry of step (a)

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