WO2016064941A1 - Carbonates modifiés permettant d'améliorer le transport d'une poudre et la stabilité du mélange sec - Google Patents

Carbonates modifiés permettant d'améliorer le transport d'une poudre et la stabilité du mélange sec Download PDF

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Publication number
WO2016064941A1
WO2016064941A1 PCT/US2015/056553 US2015056553W WO2016064941A1 WO 2016064941 A1 WO2016064941 A1 WO 2016064941A1 US 2015056553 W US2015056553 W US 2015056553W WO 2016064941 A1 WO2016064941 A1 WO 2016064941A1
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WIPO (PCT)
Prior art keywords
acid
earth metal
alkali earth
metal carbonate
filler composition
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PCT/US2015/056553
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English (en)
Inventor
Douglas Wicks
David ANSTINE
Christopher Paynter
David Taylor
Eric ERNST
David Skelhorn
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Imerys Pigments, Inc.
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Application filed by Imerys Pigments, Inc. filed Critical Imerys Pigments, Inc.
Priority to US15/518,702 priority Critical patent/US20170233553A1/en
Priority to EP15852373.8A priority patent/EP3209716A4/fr
Publication of WO2016064941A1 publication Critical patent/WO2016064941A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • compositions for use in transporting and processsng functional fillers for use with polymeric resins such as vinyl chloride-based polymeric resins.
  • Polymeric resins may be used in melt processing, in which the polymeric resin is melted down and processed to form, for example, molded articles, monofilament fibers, or polymer films.
  • Commercial products can also be formed from polymeric films, such as for packaging or protective layers.
  • polymeric-based products may be used to make staple fibers, yarns, fishing line, woven fabrics, non-woven fabrics, artificial furs, diapers, feminine hygiene products, adult incontinence products, artificial turf, packaging materials, wipes, towels, industrial garments, medical drapes, medical gowns, foot covers, sterilization wraps, table cloths, paint brushes, napkins, trash bags, various personal care articles, pipes, gloves, automotive parts, toys, fasteners, and many other household, industrial, or commercial products,
  • thermoplastic polymeric resin which may incorporate various mineral fillers, such as calcium carbonate, during production of fibrous products, polymeric films, and molded parts.
  • mineral fillers such as calcium carbonate
  • increasing polymeric resin prices have created cost- benefits associated with increasing the quantity of mineral fillers and decreasing the quantity of resin in many products.
  • the required amount of virgin polymer resin material decreases while the end product may have comparable quality in areas such as strength, texture, and appearance.
  • Calcium carbonate is a commonly used filler/extender for the polymer industry.
  • a filler material may not include a surface treatment when processing certain polymers, such as vinyl chloride-based polymers.
  • filler compositions may clump or agglomerate due to moisture pick-up by the calcium carbonate or due to reduced static forces on the calcium carbonate.
  • the carbonate filler Prior to the processing, the carbonate filler may be transported in dry form.
  • the carbonate particles may be susceptible to moisture pick-up, which may cause the particles to stick together. Additional moisture may also cause clumps to form in the fillers.
  • the filler may also be susceptible to processing problems caused by friction as the carbonate passes through the delivery pipes during processing. The moisture pick-up susceptibility, clump formation, and reduction of static charges may create processing disruptions, which can reduce or negate the cost savings of using an untreated filler composition.
  • too little filler may be added to a polymeric resin if a blockage inhibits the flow of the filler in the processing equipment or too much filler may be added if the filler forms clumps that pass into the polymer or if a blockage breaks down and passes into the polymeric resin.
  • the blockage may be a large agglomerate that disrupts the processing, texture, or smoothness of the finished polymer. The output of a compounding line may also be reduced because machine operators must shut down the line to clear blockages and restore proper flow.
  • filler composition that reduces clumping and/or processing problems of the filler composition. It may also be desirable to provide a filler composition with improved handling and transportation characteristics with improved stability. It may also be desirable to provide a method for processing a polymeric resin, such that the flow properties of the dry filler are improved.
  • a functional filler composition for use with a vinyl chloride polymeric resin may include a treated alkali earth metal carbonate and a humectant.
  • a method of forming a filled vinyl chloride-based polymer article may include mixing a vinyl chloride-based polymeric resin with a filler composition, wherein the filler composition may include a treated alkali earth metal carbonate and a humectant, and forming a polymer article from the mixture.
  • FIG. 1 shows a chart of static charge of exemplary compositions.
  • a functional filler composition for use with a vinyl chloride polymeric resin may include a treated alkali earth metal carbonate and a humectant.
  • a method of forming a filled vinyl chloride-based polymer article may include mixing a vinyl chloride-based polymeric resin with a filler composition, wherein the filler composition may include a treated alkali earth metal carbonate and a humectant, and forming a polymer article from the mixture. Forming the polymer article from the mixture may include extruding the mixture to form the polymer article.
  • a surface treatment of the treated alkali earth metal carbonate may include at least a monolayer concentration of the surface treatment. According to some embodiments, a surface treatment of the treated alkali earth metal carbonate may include less than a monolayer concentration of the surface treatment.
  • a filler material may include an alkali earth metal carbonate.
  • the alkali earth metal carbonate may include a carbonate of calcium, magnesium, barium, or strontium, or a carbonate of two or more alkaline earth metals, e.g., obtained from dolomite,
  • certain embodiments may tend to be discussed in terms of calcium carbonate, and/or in relation to aspects where the calcium carbonate is processed and/or treated.
  • the invention should not be construed as being limited to such embodiments and may be applicable to any alkali earth metal carbonate.
  • a calcium carbonate-containing material may be produced in a known way from marble, chalk, limestone, dolomite, calcite, aragonite, precipitated calcium carbonate (PCC), or ground calcium carbonate (GCC).
  • a magnesium carbonate may be produced from, for example, magnesite.
  • the alkali earth metal carbonate may also include a synthetic alkali earth metal carbonate, such as, for example, synthetic calcium carbonate produced as a precipitate by a reaction of calcium hydroxide and carbon dioxide in a known way.
  • the alkali earth metal carbonate may be a ground carbonate.
  • the ground carbonate may be prepared by attrition grinding.
  • 'Attrition grinding refers to a process of wearing down particle surfaces resulting from grinding and shearing stress between the moving grinding particles.
  • Attrition can be accomplished by rubbing particles together under pressure, such as by a gas flow.
  • the attrition grinding may be performed
  • alkali earth metal carbonate particles are ground only by other alkali earth metal carbonate particles of the same type (e.g., calcium carbonate being ground only by calcium carbonate).
  • the alkali earth metal carbonate may be ground by the addition of a grinding media other than calcium carbonate.
  • a grinding media can include ceramic particles (e.g., silica, alumina, zirconia, and aluminum silicate), plastic particles, or rubber particles.
  • the calcium carbonate is ground in a mill.
  • Exemplary mills include those described in U.S. Patent Nos. 5,238,193 and 6,834,224. As described in these patents, the mill may include a grinding chamber, a conduit for introducing the calcium carbonate into the grinding chamber, and an impeller that rotates in the grinding chamber, thereby agitating the calcium carbonate.
  • the calcium carbonate is dry ground, such as, for example, where the atmosphere in the mill is ambient air. In some embodiments, the calcium carbonate may be wet ground.
  • the ground calcium carbonate may be further subjected to an air sifter or hydrocyclone.
  • the air sifter or hydrocyclone can function to classify the ground calcium carbonate and remove a portion of residual particles greater than, for example, 10 microns.
  • the classification can be used to remove residual particles greater than 50 microns, greater than 40 microns, greater than 30 microns, greater than 20 microns, greater than 15 microns, or greater than 5 microns.
  • the ground calcium carbonate may be classified using a centrifuge, hydraulic classifier, or elutriator.
  • the ground calcium carbonate disclosed herein may be free of dispersant, such as a polyacrylate.
  • a dispersant may be present in a sufficient amount to prevent or effectively restrict flocculation or agglomeration of the ground calcium carbonate to a desired extent, according to normal processing requirements.
  • the dispersant may be present, for example, in levels up to about 1 % by weight relative to the dry weight of the alkali earth metal carbonate.
  • dispersants include polyelectrolytes such as polyacrylates and copolymers containing polyacrylate species, including polyacrylate salts (e.g., sodium and
  • aluminium optionally with a Group II metal salt
  • sodium hexametaphosphates sodium hexametaphosphates, non-ionic polyol, polyphosphoric acid, condensed sodium phosphate, non-ionic surfactants, alkanolamine, and other reagents commonly used for this function.
  • a dispersant may be selected from conventional dispersant materials commonly used in the processing and grinding of alkali earth metal carbonate, such as calcium carbonate. Such dispersants will be recognized by those skilled in this art. Dispersants are generally wafer-soluble salts capable of supplying anionic species, which in their effective amounts may adsorb on the surface of the alkali earth metal carbonate particles and thereby inhibit aggregation of the particles.
  • the unsolvated salts suitably include alkali metal cations, such as sodium. Solvation may in some cases be assisted by making the aqueous suspension slightly alkaline.
  • Suitable dispersants also include water soluble condensed phosphates, for example, polymetaphosphate salts (general form of the sodium salts: (NaPO 3 ) x ), such as tetrasodium metaphosphate or so-called "sodium hexametaphosphate” (Graham's salt); water-soluble salts of polysilicic acids; polyelectrolytes; salts of homopolymers or copolymers of acrylic acid or methacrylic acid; or salts of polymers of other derivatives of acrylic acid, suitably having a weight average molecular mass of less than about 20,000, Sodium hexametaphosphate and sodium polyacrylate, the latter suitably having a weight average molecular mass in the range of about 1 ,500 to about 10,000, are preferred.
  • polymetaphosphate salts generally form of the sodium salts: (NaPO 3 ) x )
  • sodium hexametaphosphate so-called "sodium hexametaphosphat
  • the production of the ground calcium carbonate includes using a grinding aid, such as propylene glycol, or any grinding aid known to those skilled in the art.
  • a grinding aid such as propylene glycol, or any grinding aid known to those skilled in the art.
  • the alkali earth metal carbonate may be treated to include a treatment layer located on the surface of the alkali earth metal carbonate mineral.
  • a surface-treatment may include a fatty-acid coating.
  • a surface treatment may include, for example, a treatment with an organic carboxylic acid.
  • the organic carboxylic acid may have the following general structure:
  • R is a carbon-containing compound having from 6 to 40 carbon atoms, such as, for example, from 8 to 40 carbon atoms.
  • organic carboxylic acid may include an aliphatic carboxylic acid, such as, for example, caproic acid, 2 ⁇ ethylhexanoic acid, capryiic acid, neodecanoic acid, capric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, Iignoceric acid, tall oil fatty acid, napthenic acid, montanic acid, coronanc acid, linoleic acid, linolenic acid, 4,7,10,13,16,19- docosahexaenoic acid, 5,8,1 1 ,14, 17-eicosapentaenoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, or combinations thereof.
  • an aliphatic carboxylic acid such as, for example, caproic acid, 2 ⁇ ethylhe
  • the aliphatic carboxylic acid may be a saturated or unsaturated aliphatic carboxylic acid.
  • the aliphatic carboxylic acid may include a mixture of two or more aliphatic carboxylic acids, such as, for example, a mixture of two or more of caproic acid, 2-ethylhexanoic acid, caprylic acid, neodecanoic acid, capric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, tall oil fatty acid, napthenic acid, montanic acid, coronaric acid, linoleic acid, linoienic acid, 4,7,10,13,16,19-docosahexaenoic acid, 5,8,1 1 ,14, 17- eicosapentaenoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and isononanoic acid.
  • caproic acid 2-ethylhexanoic acid
  • the weight ratio of a mixed aliphatic carboxylic acid including two component acids may range from about 90:10 to about 10:90 by weight, from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40:60 by weight.
  • the weight ratio of the component aliphatic carboxylic acids in an acid mixture may be about 50:50 by weight.
  • the aliphatic carboxylic acid may include one or more of a linear, branched, substituted, or non-substituted carboxylic acid.
  • the aliphatic carboxylic acid may be chosen from aliphatic monocarboxylic acids. Alternatively or additionally, the aliphatic carboxylic acid may be chosen from branched aliphatic monocarboxy!ic acids.
  • the surface treatment may include an aromatic carboxylic acid, such as, for example, alky!benzoic acid, hydro xybenzoic acid, aminobenzoic acid, protocatechuic acid, or combinations thereof.
  • aromatic carboxylic acid such as, for example, alky!benzoic acid, hydro xybenzoic acid, aminobenzoic acid, protocatechuic acid, or combinations thereof.
  • the surface treatment may include a Rosin acid, such as, for example, palustrinic acid, neoabietic acid, abietic acid, or levopimaric acid.
  • Rosin acid such as, for example, palustrinic acid, neoabietic acid, abietic acid, or levopimaric acid.
  • R may include one or more of a straight chain or branched alkyl, phenyl, substituted phenyl, G6-40 alkyl substituted with up to four OH groups, C6-40 alkyl, amido, maleimido, amino or acetyl substituted hydrocarbon radicals.
  • the surface treatment may include a combination of one or more of an aliphatic carboxylic acid, an aromatic carboxylic acid, or a Rosin acid.
  • the organic carboxylic acid may be a liquid at room temperature, such as, for example, an organic carboxylic acid having a viscosity of less than 500 mPa-s at 23 °C when measured in a DV 111 Ultra model Brookfield viscometer equipped with the disc spindle 3 at a rotation speed of 100 rpm and room temperature (23 ⁇ 1 °C).
  • the alkali earth metal carbonate may be treated by forming a treatment layer including at least one organic carboxylic acid and/or one or more reaction products of at least one organic carboxylic acid on the surface of the alkali earth metal carbonate filler resulting in a treated alkali earth metal carbonate filler.
  • the treated alkali earth metal carbonate may include a stearate treatment, such as, for example, ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
  • a stearate treatment such as, for example, ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
  • the treated alkali earth metal carbonate may include a salt of at least one of a valerate, stearate, laurate, palmitate, caprylate, neodecanoate, caproate, myrisfate, behenate, lignocerafe, napthenate, montanate, coronarate, linoleate,
  • the surface treatment may include a blend of a carboxylic acid and a salt of a carboxylic acid.
  • the weight ratio of a mixed carboxylic acid and salt thereof may range from about 90:10 to about 10:90 by weight (acid:salt), from about 80:20 to about 20:80, from about 70:30 to about 30:70, or from about 60:40 to about 40:60 by weight
  • the weight ratio of carboxylic acid and salt in a mixture may be about 50:50 by weight (acid:salt).
  • the treated alkali earth metal carbonate filler may have a volatile onset temperature of greater than or equal to about 100 X. According to some embodiments, the treated alkali earth metal carbonate filler may have a vo!aii!e onset temperature of greater than or equal to about 130 °C, greater than or equal to about 150 °C, greater than or equal to about 160 °C, greater than or equal to about 170 °C, greater than or equal to about 200 °C, greater than or equal to about 220 °C, greater than or equal to about 250 °C, greater than or equal to about 260 °C, such as, for example, greater than or equal to 270 °C, greater than or equal to 280 °C, greater than or equal to 290 °C, greater than or equal to 300 °C, greater than or equal to 310 °C, or greater than or equal to 320 °C.
  • polymer As used in this disclosure, the terms “polymer,” “resin,” “polymeric resin,” and derivations of these terms may be used interchangeably.
  • the polymeric resin may be a vinyl chloride-based polymeric resin chosen from conventional vinyl chloride-based polymeric resins that provide the properties desired for any particular yarn, woven product, non- woven product, film, mold, or other applications.
  • the vinyl chloride-based polymeric resin may be a thermoplastic polymer, including but not limited to polyvinyl chloride (PVC).
  • the vinyl chloride-based polymeric resin may include unplasticized polyvinyl chloride (uPVC).
  • the vinyl chloride-based polymeric resin may include a chlorinated polyvinyl chloride polymeric resin.
  • the vinyl chloride-based polymeric resin may include a co-polymer, in which one of the polymers is a vinyl chloride-based polymer.
  • the vinyl chloride-based polymeric resin may include a co- polymer of polyvinyl chloride and at least one of ethylene-vinyl acetate (EVA), chlorinated polyethylene (CPE), acrylonitrile butadiene styrene (ABS), methacrylate butadiene styrene (MBS), Acrylonitrile butadiene rubber (NBR), thermoplastic polyurethane (TPU), Thermoplastic polyester elastomers (TREE), or acrylic resins.
  • EVA ethylene-vinyl acetate
  • CPE chlorinated polyethylene
  • ABS acrylonitrile butadiene styrene
  • MVS methacrylate butadiene styrene
  • NBR Acrylonitrile butadiene rubber
  • TPU thermoplastic polyurethane
  • alkali earth metal carbonate fillers such as, for example, calcium carbonate-containing mineral fillers
  • processing problems such as clumping and reduced static charge, that may result in buildups in processing equipment, creating blockages that affect the flow of filler to a polymer.
  • the adverse effects resulting from buildup of the carbonate filler composition may be mitigated or reduced by adding a humectanf to the filler.
  • a "humectant” is generally described as a molecule having hydrophilic groups that form hydrogen bonds with water molecules by absorbing water from the surrounding atmosphere. In general, humectants may increase the moisture content of products and compositions.
  • Filler including humectant may act as a process aid for melt-processing polymers for the formation of polymer articles, such as, for example, polymer pipe (e.g., polyvinyl chloride (PVC) pipe) and other polymer articles.
  • PVC polyvinyl chloride
  • such filler including humectant may act as a process aid as defined by the Plastics Pipe Institute (PPI).
  • PPI Plastics Pipe Institute
  • the filler including humectant may be a pre-qualified ingredient exempted from stress-rupture testing for PVC pipe as defined by PPI Technical Reports TR-2 and TR-3.
  • the filler including humectant may be a process aid resulting in a PVC pipe having a hydrostatic design basis of 4,000 psi for water at 73°F (23°C) when evaluated according to ASTM D 2837, as defined by PPI Technical Reports TR-2 and TR-3.
  • the filler including humectant may improve the flow, reduce clumping, and/or improve dry-blend stability (e.g., reduce separation of the functional filler and polymer) of powder, pellets, and/or granules including a polymer and the filler including humectant.
  • the filler including humectant may have improved dispersion in the polymer melt and/or polymer article as compared to a filler comprising only an untreated alkali earth metal.
  • Improved flow and/or dispersion in the polymer may provide improved control of the polymer formulation and/or process (e.g., dosing of the functional filler), which may increase permissible loading levels and/or loading consistency, and/or may improve throughput of the processing, thereby achieving higher running rates.
  • the loading level of the filler including humectant in the polymer may be increased by at least 1 %, or at least 10%, as compared to the loading level of a filler including only an untreated alkali earth metal.
  • the filler including humectant may provide better wall control of polymer articles such as pipe (e.g., allowing more consistent wall thicknesses and/or production to tighter tolerances).
  • a functional filler composition for use with a vinyl chloride polymeric resin may include a treated alkali earth metal carbonate and a hurnectant.
  • a surface treatment of the treated alkali earth metal carbonate may include at least a monolayer concentration of the surface treatment. According to some embodiments, a surface treatment of the treated alkali earth metal carbonate may include less than a monolayer concentration of the surface treatment.
  • the additional moisture retained by the humectant may mitigate processing problems cause by the filler composition. It is also believed that the humectant may reduce the formation of dumps by absorbing water from the surrounding environment and preventing the carbonate particles from sticking together.
  • the addition of the humectant to a filler composition may help in reducing the buildup of filler in processing equipment, thereby improving the processing characteristics of fillers used with vinyl chloride-based polymeric resins and improving process output by reducing downtime that results from cleaning blockages from the processing equipment.
  • the humectant may include one or more of ethylene glycol, propylene glycol, trimethylol propanol, glycerol, pentaerythritol, sucrose, sucrose isomers, pentose, pentose isomers, triethy!ene glycol, diethylene glycol, trspropyiene glycol, dipropylene glycol, 1 ,3 propane diol, polyacrylamides, polyviny!acetates, polyvinyla!cohols, toluene diisocyanate, diphenylmethane diisocyanate, polyethylene glycol, polyphenyl polymethy!ene polyisocyanates, or combinations thereof.
  • the amount of humectant in the filler composition may range from about 0.1 % by weight to about 1 % by weight relative to the weight of the treated alkali earth metal carbonate in the filler composition, such as, for example, from about 0.1 % by weight to about 0.7% by weight or from about 0.2% by weight to about 0.5% by weight relative to the weight of the treated alkali earth metal carbonate in the filler composition.
  • a treated alkali earth metal carbonate may be treated with a monolayer concentration of the surface treatment.
  • “Monolayer concentration,” as used herein, refers to an amount sufficient to form a monolayer on the surface of the alkali earth metal carbonate particles. Such values will be readily calculable to one skilled in the art based on, for example, the surface area of the alkali earth metal carbonate particles.
  • a treated alkali earth metal carbonate may be treated with less than a monolayer concentration of the surface treatment.
  • a treated alkali earth metal carbonate may be treated with in excess of a monolayer concentration of the surface treatment.
  • the alkali earth metal carbonate may be surface treated in a treatment vessel containing a wafer-dry atmosphere in which the surface treatment is in a liquid (e.g., droplet) and/or vapor form.
  • calcium carbonate may be treated by exposing the calcium carbonate to a carboxylic acid, such as stearic acid, vapor or liquid. The amount of vapor or liquid in the reaction vessel may be controlled so as not to exceed a monolayer concentration of the surface treatment.
  • the mixture may be blended at a temperature sufficient for at least a portion of the carboxy!ic acid to react (e.g., sufficient for a majority of the carboxyiic acid to react) with at least a portion of the calcium carbonate.
  • the mixture may be blended at a temperature sufficient such that at least a portion of the carboxyiic acid may coat at least a portion of the calcium carbonate (e.g., the surface of the calcium carbonate).
  • the alkali earth metai carbonate may be treated by exposing the surface of the alkali earth metal carbonate to the surface treatment agent in the reaction vessel at a temperature at which surface treatment is in a fluid or vaporized state.
  • the temperature may be in the range from about 20 °C to about 300 °C, such as, for example, from about 25 °C to about 100 °C, from about 50 °C to about 150 °C, from about 100 °C to about 200 °C, or from about 100 °C to about 150 °C.
  • the temperature selected in the atmosphere of the treatment vessel may provide sufficient heat to ensure melting and good mobility of the molecuies of the surface treatment agent, and therefore, good contacting of and reaction with the surface of the alkali earth metal carbonate particles.
  • a mixture of the alkali earth metal carbonate and carboxyiic acid may be blended at a temperature high enough to melt the carboxyiic acid.
  • the alkali earth metal carbonate may be biended at a temperature in the range from about 65 °C to about 200 °C.
  • the mixture may be blended at a temperature in the range from about 65 °C to about 150 °C, for example, at about 120 °C.
  • the mixture may be blended at a temperature in the range from about 65 °C to about 100 °C.
  • the mixture may be blended at a temperature in the range from about 85 °C to about 90 °C.
  • the mixture may be blended at a temperature in the range from about 70 °C to about 90 °C.
  • Surface treating the alkali earth metal carbonate may be carried out in a heated vessel in which a rapid agitation or stirring motion is applied to the atmosphere during the reaction of the surface treatment and with the alkali earth metal carbonate, such that the surface treatment agent is well dispersed in the treatment atmosphere.
  • the agitation should not be sufficient to alter the surface area of the alkali earth metal carbonate because such an alteration may change the required surface treatment agent concentration to create, for example, a monolayer concentration
  • the treatment vessel may include, for example, one or more rotating paddles, including a rotating shaft having laterally extending blades including one or more propellers to promote agitation and deagglomerafion of the carbonate and contacting of the carbonate with the surface treatment agent,
  • a treated calcium carbonate may be prepared by combining (e.g., blending) the carbonate with stearic acid and water at room temperature in an amount greater than about 0.1 % by weight relative to the total weight of the mixture (e.g., in the form of a cake-mix).
  • the mixture may be blended at a temperature sufficient for at least a portion of the stearic acid to react (e.g., sufficient for a majority of the stearic acid to react) with at least a portion of the surface of the calcium carbonate.
  • the mixture may be blended at a temperature sufficient such that at least a portion of the stearic acid may coat the surface of the calcium carbonate in a monolayer concentration.
  • an alkali earth metal carbonate such as calcium carbonate
  • stearic acid or other carboxylic acid
  • water in an amount greater than about 1 % by weight relative to the total weight of the mixture (e.g., in the form of a cake-mix) to inhibit the formation of free stearic acid.
  • the mixture may be blended at a temperature sufficient for at least a portion of the stearic acid to react (e.g., sufficient for a majority of the acid to react, for example, with at least a portion of the calcium carbonate).
  • the mixture may be blended at a temperature sufficient such that at least a portion of the stearic acid may coat at least a portion of the calcium carbonate (e.g., the surface of the calcium carbonate).
  • Particle sizes, and other particle size properties, of the treated and untreated alkali earth metal carbonate may be measured using a SEDIGRAPH 5100 instrument, as supplied by Micromeritics Corporation.
  • the size of a given particle is expressed in terms of the diameter of a sphere of equivalent diameter, which sediments through the suspension, i.e., an equivalent spherical diameter or esd.
  • the particle size of the treated alkali earth metal carbonate is expressed in terms of the particle size prior to the surface treatment.
  • the alkali earth metal carbonate such as the treated alkali earth metal carbonate
  • the treated alkali earth metal carbonate may have a d 50 in the range from about 0.1 micron to about 50 microns, such as, for example, in the range from about 0.1 micron to about 30 microns, from about 0,1 micron to about 20 microns, from about 0.1 micron to about 10 microns, from about 0.1 micron to about 5 microns, from about 0.1 micron to about 3 microns, from about 0.1 micron to about 2 microns, from about 0.1 micron to about 1 micron, from about 0.5 microns to about 2 microns, from about 1 micron to about 5 microns, from about 5 microns to about 20 microns, or from about 5 microns to about 10 microns.
  • the alkali earth metal carbonate such as the treated alkali earth metal carbonate
  • d 98 top cut size
  • the treated alkali earth metal carbonate may have a dge in the range from about 2 microns to about 100 microns, such as, for example, in the range from about 5 microns to about 50 microns, from about 2 microns to about 20 microns, or from about 5 microns to about 20 microns.
  • a treated alkaii earth metal carbonate may be treated with an organic carboxylic acid or salt thereof, or a mixture of an organic carboxylic acid and salt of an organic carboxylic acid.
  • some or all of the stearic acid may be replaced by ammonium stearate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, zinc stearate, aluminum stearate, zirconium stearate, or cobalt stearate.
  • salts may include, for example, calcium valerate, barium valerate, magnesium valerate, strontium valerate, zinc valerate, aluminum valerate, zirconium valerate, or cobalt valerate, which may replace some or all of valeric acid.
  • some or all of the organic carboxylic acid may be replaced with a salt of the organic carboxylic acid.
  • carbolxylic acid may be replaced by a salt of at least one of a valerate, stearate, laurate, palmitate, caprylate, neodecanoate, caproate, myristate, behenate, lignocerate, napthenate, montanate, coronarate, linoleate,
  • the ratio of acid to salt may range from about 5:95 to about 95:5 (acid:salt) by weight, from about 10:90 to about 90:10 by weight, from about 80:20 to about 20:80 by weight, from about 70:30 to about 30:70 by weight, from about 60:40 to about 40:80 by weight, or from about 45:55 to about 55:45 by weight.
  • all of the stearic acid (or other surface treatment) may be replaced by a salt, such as stearate, which may be used to create a monolayer concentration on the alkali earth metal carbonate.
  • the alkali earth metal carbonate may be further subjected to an air sifter or hydrocyclone.
  • the air sifter or hydrocyclone can function to classify the ground calcium carbonate and remove a portion of residual particles greater than 20 microns.
  • the classification can be used to remove residual particles greater than 40 microns, greater than 30 microns, greater than 15 microns, greater than 10 microns, or greater than 5 microns.
  • the ground calcium carbonate may be classified using a centrifuge, hydraulic classifier, or elutriator.
  • a treated alkali earth metal carbonate may have some or all of an organic carboxylic acid replaced with a salt of the carboxylic acid.
  • the treated alkali earth metal carbonate may be optionally blended with an untreated alkali earth metal carbonate.
  • the treated alkali earth metal carbonate may include a first treated alkali earth metal carbonate and a second treated alkali earth metal carbonate.
  • the first treated alkali earth metal carbonate may have a different surface treatment from the second alkali earth metal carbonate.
  • the first treated aikaii earth metal carbonate may have a surface treatment that may include at least a monolayer concentration of the surface treatment
  • the second treated alkali earth metal carbonate may have a surface treatment that may include less than a monolayer concentration of the surface treatment.
  • the filler composition may have a static charge greater than or equal to about 1 kV/in after passing through 100 feet of 2 inch diameter PVC pipe, such as, for example, greater than or equal to about 2 kV/in, greater than or equal to about 3 kV/in, greater than or equal to about 4 kV/in, greater than or equal to about 5 kV/in, greater than or equal to about 6 kV/in, greater than or equal to about 7 kV/in, greater than or equal to about 8 kV/in, greater than or equal to about 9 kV/in, greater than or equal to about 10 kV/in after passing through 100 feet of 2 inch diameter PVC pipe.
  • Static charge may be measured using a hand-held static meter, such as, a Model 212 hand-held static meter, manufactured by ETS.
  • a filler composition including treated alkali earth metal carbonate and a humecfant may be used as a filler for a polymer product, such as, for example, a filler for a polymer fiber, film, extruded, or molded article.
  • the alkali earth metal carbonate filler may be incorporated into the vinyl chloride-based polymeric resin using any method conventionally known in the art or hereafter discovered.
  • alkali earth metal carbonate may be added to the vinyl chloride-based polymeric resin during any step prior to extrusion, for example, during or prior to the heating step or as a "masterbatch" in which the polymeric resin and the filler are premixed and optionally formed into granulates or pellets, and melted or mixed with additional virgin polymeric resin before forming a polymer-based article.
  • the filler may be mixed with pellets or powders of the polymeric resin prior to, or during, transport or processing of the polymeric resin.
  • the virgin polymeric resin may be the same or different from the vinyl chloride-based polymeric resin containing the filler.
  • the molten vinyl chloride-based polymer may then be continuously extruded through, for example, at least one spinneret to produce long filaments. Extrusion of the filled polymer from the spinnerets may be used ⁇ create, for example, a non-woven fabric. According to some embodiments, the molten vinyl chloride-based polymer may then be continuously extruded through a nozzle or dye to form polymeric articles, such as, for example, pipes, rods, honey-comb structures, or other articles having variously-shaped cross-sections. The extrusion rate may vary according to the desired application, and appropriate extrusion rates will be known to the skilled artisan.
  • a vinyl chloride-based polymeric film may be created from the molten, filled vinyl chloride-based polymer according to methods known in the art or hereinafter discovered.
  • melt compounding may also be used to extrude films, tubes, shapes, strips, and coatings onto other materials, injection molding, blow molding, or casting, and thermoforming and formation of tubes or pipes.
  • the melt compounding may, for example, be carried out in, for example, a suitable compounder or screw extruder.
  • a vinyl chloride-based polymer materia! to be compounded may suitably be in a granular or pelletized form.
  • the temperature of the compounding and molding, shaping or extrusion processes will depend upon the thermoplastic material being processed and materials incorporated therein. The temperature will be above the softening point of the thermoplastic material.
  • filled vinyl chloride-based polymer compositions may be produced according to any appropriate process or processes now known to the skilled artisan or hereafter discovered.
  • the filled vinyl chloride-based polymer may include a monofilament fiber.
  • monofilament fiber may include the production of a continuous monofilament fiber of at least one polymeric resin and at least one filler.
  • Exemplary techniques include, but are not limited to, melt spinning, dry spinning, wet spinning, spinbonding, or meltblowing processes.
  • Melt spinning may include an extrusion process to provide molten polymer mixtures to spinneret dies.
  • monofilament fibers may be produced by heating the polymeric resin to at least about its melting point as it passes through the spinneret dies.
  • Samples were prepared to determine the effect of a humectant on treated alkali earth metal filler compositions.
  • Sample A was a calcium carbonate having a d 50 of 1.6 microns and treated with a monolayer concentration of stearic acid.
  • Sample B was a calcium carbonate having a d 50 of 3 microns and treated with a monolayer concentration of stearic acid.
  • Sample C was a calcium carbonate having a d 50 of 0.7 microns and treated with a monolayer concentration of stearic acid and also included a dispersant.
  • Sample D was a calcium carbonate having a d 50 of 1.5 microns and treated with a monolayer concentration of stearic acid and also included a polyethylene glycol (PEG) humectant.
  • PEG polyethylene glycol

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition fonctionnelle de charge destinée à être utilisée avec une résine polymère de chlorure de vinyle pouvant comprendre un carbonate de métal alcalino-terreux traité et un humectant, un procédé de formation d'un article polymère à base de chlorure de vinyle chargé pouvant inclure le mélange d'une résine polymère à base de chlorure de vinyle avec une composition de charge et la formation d'un article polymère à partir du mélange. La composition de charge comprenant un carbonate de métal alcalino-terreux traité et un humectant. Un traitement de surface du carbonate de métal alcalino-terreux traité comprend au moins une concentration monocouche du traitement de surface.
PCT/US2015/056553 2014-10-22 2015-10-21 Carbonates modifiés permettant d'améliorer le transport d'une poudre et la stabilité du mélange sec WO2016064941A1 (fr)

Priority Applications (2)

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US15/518,702 US20170233553A1 (en) 2014-10-22 2015-10-21 Modified carbonates for improved powder transportation and dry-blend stability
EP15852373.8A EP3209716A4 (fr) 2014-10-22 2015-10-21 Carbonates modifiés permettant d'améliorer le transport d'une poudre et la stabilité du mélange sec

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US201462067288P 2014-10-22 2014-10-22
US201462067278P 2014-10-22 2014-10-22
US62/067,288 2014-10-22
US62/067,278 2014-10-22
US201562187838P 2015-07-02 2015-07-02
US62/187,838 2015-07-02

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310451A (en) * 1979-10-25 1982-01-12 Diamond Shamrock Plastics Corporation Free flowing rigid PVC resin powder compositions
US4559214A (en) * 1983-02-25 1985-12-17 Ciba Geigy Corporation Particulate calcium carbonate
US20070258877A1 (en) * 2004-01-23 2007-11-08 Solvay (Societe Anonyme) Surface-Treated Calcium Carbonate Particles
CN103788409A (zh) * 2014-01-04 2014-05-14 安徽雪城超细碳酸钙有限公司 一种耐磨表面改性碳酸钙填料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2901491B1 (fr) * 2006-05-24 2009-03-20 Coatex Sas Procede de broyage a sec de materiaux contenant un minerai carbonate
FR2954715B1 (fr) * 2009-12-24 2014-12-26 Coatex Sas Utilisation de glycerol comme agent ameliorant le caractere autodispersant d'une matiere minerale destinee a une composition aqueuse

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310451A (en) * 1979-10-25 1982-01-12 Diamond Shamrock Plastics Corporation Free flowing rigid PVC resin powder compositions
US4559214A (en) * 1983-02-25 1985-12-17 Ciba Geigy Corporation Particulate calcium carbonate
US20070258877A1 (en) * 2004-01-23 2007-11-08 Solvay (Societe Anonyme) Surface-Treated Calcium Carbonate Particles
CN103788409A (zh) * 2014-01-04 2014-05-14 安徽雪城超细碳酸钙有限公司 一种耐磨表面改性碳酸钙填料

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Title
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EP3209716A1 (fr) 2017-08-30

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