CN115386247B - In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof - Google Patents
In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof Download PDFInfo
- Publication number
- CN115386247B CN115386247B CN202211034207.1A CN202211034207A CN115386247B CN 115386247 B CN115386247 B CN 115386247B CN 202211034207 A CN202211034207 A CN 202211034207A CN 115386247 B CN115386247 B CN 115386247B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- film forming
- situ
- modified calcium
- auxiliary agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 358
- 239000000945 filler Substances 0.000 title claims abstract description 73
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 145
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical group [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- -1 organic carbonate compound Chemical class 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- XTIIITNXEHRMQL-UHFFFAOYSA-N tripotassium methoxy(trioxido)silane Chemical compound [K+].[K+].[K+].CO[Si]([O-])([O-])[O-] XTIIITNXEHRMQL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000011282 treatment Methods 0.000 abstract description 23
- 230000004048 modification Effects 0.000 abstract description 22
- 238000012986 modification Methods 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000004381 surface treatment Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000002245 particle Substances 0.000 description 21
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 10
- 238000011066 ex-situ storage Methods 0.000 description 10
- AIPVRBGBHQDAPX-UHFFFAOYSA-N hydroxy(methyl)silane Chemical compound C[SiH2]O AIPVRBGBHQDAPX-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 150000005677 organic carbonates Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
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
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
-
- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The embodiment of the invention relates to the technical field of material processing, and particularly discloses an in-situ surface coating modified calcium carbonate filler, and a preparation method and application thereof, wherein the in-situ surface coating modified calcium carbonate filler comprises the following raw materials: a calcium carbonate base material, a surface treatment agent, a film forming auxiliary agent and a solvent; wherein the surface treating agent is sodium methyl silicate or potassium methyl silicate aqueous solution, and the film forming auxiliary agent is an organic carbonate compound. According to the embodiment of the invention, the in-situ surface coating technology is adopted, the surface treatment agent is matched, and meanwhile, the organic carbonate compound is used as the film forming auxiliary agent, so that the surface organic modification of the calcium carbonate is realized, the oil absorption of the modified calcium carbonate filler can be effectively reduced, the cost is low, no waste water and waste residues are generated in the treatment process, the economic and environment-friendly advantages are realized, the problem that the surface treatment effect cannot be ensured while the environment protection and the production cost reduction are realized in the conventional calcium carbonate filler surface treatment process is solved, and the wide market prospect is realized.
Description
Technical Field
The invention relates to the technical field of material processing, in particular to an in-situ surface coating modified calcium carbonate filler, and a preparation method and application thereof.
Background
With the continuous development of material processing technology, the demands for inorganic fillers in the market are increasing, and more inorganic fillers are used in the demands of improving strength, rigidity, weather resistance, surface gloss, acoustic performance and the like. Among them, calcium carbonate is used as an inexpensive and easily available inorganic filler, and has wide application in industries such as building materials, rubber, plastics, papermaking, paint, daily chemicals, food additives and the like. Calcium carbonate can be classified into light calcium carbonate and heavy calcium carbonate according to its properties and sources. Because the surface of the calcium carbonate has a large number of strong polar hydroxyl groups, the calcium carbonate has hydrophilic and oleophobic properties, has large polarity difference with organic polymers, has poor compatibility, and is difficult to form a strong bonding interface and high-strength bonding. Therefore, the calcium carbonate used as the filler of the polymer material needs to be subjected to surface modification to improve the compatibility with the organic polymer, and the surface modified calcium carbonate is also called active calcium carbonate or modified calcium carbonate.
In the prior art, the surface modification of calcium carbonate generally comprises coating the surface of calcium carbonate with a surface treating agent by chemical or physical methods to activate the surface of the calcium carbonate. The most commonly used treatment method is to treat the material by adopting a wet process by taking a surfactant or a coupling agent as a modifier: the calcium carbonate filler is added into the water solution or emulsion of the surface treating agent for stirring reaction, and the surface treating agent coated calcium carbonate can be obtained through the procedures of filtering, drying and crushing. Among them, the commonly used surfactants are fatty acids (salts) and phosphates, while the coupling agents used in many cases are aluminate coupling agents and titanate coupling agents. These conventional treatment methods have the following problems: (1) The commonly used surface treating agent has higher price, so that the production cost is increased; (2) A large amount of wastewater can be generated in the treatment process or after the treatment is finished, and the environmental protection performance is poor; (3) The treating agent itself can hydrolyze and polymerize in the aqueous solution, resulting in reduced treating effect and shortened use period of the treating agent solution.
To solve the above problems in wet treatment processes, those skilled in the art are continually making improvements in surface treatments, treatment conditions and methods. Among them, chinese patent publication No. CN114369290a discloses a technique for surface treatment of talc powder surface using aqueous solution of methyl sodium silicate as surface treatment agent, in which methyl sodium silicate is adsorbed on the surface of talc powder filler particles by physical or chemical adsorption, and then reacts with carbon dioxide in air or carbon dioxide introduced by physical means in the post-drying process to form an organosilicon film coated on the surface of talc powder particles, thereby realizing organic modification of the talc powder particle surface. The oil absorption of the talcum powder with organically modified surface prepared by the method is effectively reduced, and the technology has the characteristics of environmental protection and low production cost.
However, the above technical solution has the following drawbacks in practical application: when the technique of surface-treating the talc surface using an aqueous solution of sodium methyl silicate as a surface treating agent is applied to the treatment of a calcium carbonate filler, the treatment effect is not satisfactory, and the oil absorption of calcium carbonate cannot be effectively reduced.
Disclosure of Invention
The embodiment of the invention aims to provide an in-situ surface coating modified calcium carbonate filler, so as to solve the problem that the surface treatment effect cannot be ensured while protecting the environment and reducing the production cost in the conventional calcium carbonate filler surface treatment process.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
an in-situ surface-coated modified calcium carbonate filler, comprising the following raw materials: a calcium carbonate base material, a surface treatment agent, a film forming auxiliary agent and a proper amount of solvent; wherein the surface treating agent is aqueous solution of sodium methyl silicate or aqueous solution of potassium methyl silicate, and the film forming auxiliary agent is an organic carbonate compound.
As a further scheme of the embodiment of the invention: the organic carbonate compound may be a cyclic organic carbonate or a linear organic carbonate.
As a further scheme of the embodiment of the invention: the cyclic organic carbonate is represented by the formula:
wherein R is H, or alkyl C n H 2n+1
When R is H, the cyclic organic carbonate is ethylene carbonate; r is CH 3 The cyclic organic carbonate is propylene carbonate.
As a further scheme of the embodiment of the invention: the linear organic carbonates are shown in the following formula:
wherein R is 1 、R 2 Is alkyl C n H 2n+1 May be the same or different.
As a still further scheme of the embodiment of the invention: the solvent is deionized water. At the moment, the preparation formula of the in-situ surface coating modified calcium carbonate filler comprises the following components in parts by weight:
wherein the surface treating agent is sodium methyl silicate aqueous solution with the mass percentage concentration of 20-40% and the pH value of more than 13; the film forming additive consists of one or two of ethylene carbonate and propylene carbonate.
As a still further scheme of the embodiment of the invention: the surface treating agent is sodium methyl silicate aqueous solution with the mass percentage concentration of 30% and the pH value of more than 13.
Another object of the embodiment of the present invention is to provide a method for preparing an in-situ surface-coated modified calcium carbonate filler, which specifically includes the following steps:
1) Weighing the film forming auxiliary agent according to the proportion, adding the film forming auxiliary agent into a proper amount of solvent, and uniformly mixing to obtain a film forming auxiliary agent solution;
2) Weighing a calcium carbonate base material according to a proportion, adding the calcium carbonate base material into the film forming auxiliary agent solution prepared in the step 1), and uniformly mixing to obtain a calcium carbonate suspension containing the film forming auxiliary agent;
3) Weighing a surface treating agent according to a proportion, and uniformly mixing the surface treating agent with a proper amount of solvent to obtain a surface treating agent solution;
4) Slowly adding the surface treating agent solution prepared in the step 3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step 2) at the temperature of 25-50 ℃ while stirring; after the charging is completed, stirring is continued for 1-4 hours to obtain a reaction mixed solution;
5) And (3) carrying out suction filtration on the reaction mixed solution obtained in the step (4), and then drying the obtained filter cake according to the conditions of heat preservation at 40-60 ℃ for 1-2 hours, heat preservation at 80-100 ℃ for 1-2 hours and heat preservation at 100-120 ℃ for 2-3 hours in sequence to obtain a dried product, and grinding the dried product into powder to obtain the in-situ surface-coated modified calcium carbonate filler.
Another object of the embodiment of the invention is to provide an application of the in-situ surface-coated modified calcium carbonate filler in coating processing or polymer material preparation.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the in-situ surface coating modified calcium carbonate filler provided by the embodiment of the invention realizes the surface organic modification of calcium carbonate by adopting an in-situ surface coating technology and taking sodium methyl silicate or potassium methyl silicate aqueous solution as a surface treating agent and simultaneously taking a carbonate compound as a film forming auxiliary agent, wherein the sodium methyl silicate or the potassium methyl silicate aqueous solution is in strong alkalinity, and when the sodium methyl silicate or the potassium methyl silicate is added into a calcium carbonate suspension containing the film forming auxiliary agent (namely organic carbonate), the organic carbonate is hydrolyzed to generate carbon dioxide and micromolecular alcohol (for example, ethylene carbonate can be hydrolyzed to generate carbon dioxide and ethylene glycol, and propylene carbonate can be hydrolyzed to generate carbon dioxide and propylene glycol); methyl silicate can generate methyl silanol under the action of water and carbon dioxide; hydroxyl groups in methyl silanol and hydroxyl groups on the surfaces of calcium carbonate powder particles shrink small molecular water under alkaline conditions to bond, and the residual hydroxyl groups in the methyl silanol are continuously polycondensed with other methyl silanol to form a polymer containing lateral methyl groups; meanwhile, the small molecular alcohol generated by the hydrolysis of the organic carbonate can promote the polymerization of methyl silanol; in this way, in situ surface coating of the calcium carbonate particles is achieved by means of chemical reactions in "in situ" or "in situ" polymerization. In the later stage, methyl sodium silicate molecules physically adsorbed on the surfaces of the calcium carbonate particles are secondarily solidified under the action of water and carbon dioxide in air, so that the physical coating of a polymer film containing lateral methyl on the surfaces of the calcium carbonate particles is formed, and the coating effect is further improved; finally, organic groups methyl are introduced to the surfaces of the calcium carbonate particles in a chemical bonding and physical coating mode, so that the surfaces of the calcium carbonate particles are organically modified, the surfaces of the inorganic calcium carbonate particles and organic polymers are favorably combined strongly, the oil absorption of the modified calcium carbonate filler is effectively reduced, the cost is low, no waste water and waste residues are generated in the treatment process, the economic and environment-friendly advantages are realized, the generation of a large amount of waste water and waste residues is avoided, and the problem that the surface treatment effect cannot be ensured while the environment protection and the production cost reduction are realized in the existing calcium carbonate filler surface treatment process is solved. Compared with the traditional process, the embodiment of the invention has the following effective effects: (1) The invention discloses a novel filler in-situ surface coating technology, which is beneficial to improving the organic surface coating modification effect of the filler; (2) The sodium methyl silicate is adopted to replace a surfactant and a coupling agent with higher price to perform activation treatment on the calcium carbonate, so that the cost is low, no waste water and waste residue are generated in the treatment process, and the method has the advantages of economy and environmental protection; (3) The calcium carbonate surface treatment method adopted by the embodiment of the invention has the advantages of simple and convenient process, simple operation and mild reaction conditions, can be used for in-situ organized surface coating modification of other types of inorganic fillers, and has wide market prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the embodiments of the invention. These are all within the scope of embodiments of the present invention.
Aiming at the problems of high cost, poor environmental protection and unsatisfactory treatment effect in the existing calcium carbonate filler surface treatment technology, the embodiment of the invention can realize effective modification of calcium carbonate by providing the in-situ surface coated modified calcium carbonate filler and the preparation method thereof, and the method has the advantages of excellent treatment effect, low cost and environmental protection.
The in-situ surface coating modified calcium carbonate filler provided by the embodiment of the invention comprises the following raw materials: a calcium carbonate base material, a surface treatment agent, a film forming auxiliary agent and a proper amount of solvent; wherein the surface treating agent is aqueous solution of sodium methyl silicate or aqueous solution of potassium methyl silicate, and the film forming auxiliary agent is an organic carbonate compound. The in-situ surface coating modified calcium carbonate filler provided by the embodiment of the invention has the characteristics of good environmental protection, low production cost, excellent treatment effect and simple and convenient process operation. The method adopts an in-situ surface coating technology, takes a sodium methyl silicate aqueous solution as a surface treatment agent and simultaneously takes an organic carbonate compound as a film forming auxiliary agent, so that the oil absorption of the modified calcium carbonate filler is reduced, and adopts sodium methyl silicate to replace a surfactant and a coupling agent with higher price to perform activation treatment on calcium carbonate.
As a further scheme of the embodiment of the invention: the organic carbonate compounds are carbonic acid molecule derivatives, including linear and cyclic carbonates. The linear carbonates include dimethyl carbonate, diethyl carbonate, methylethyl carbonate, etc.; the cyclic organic carbonates include ethylene carbonate, propylene carbonate, and the like.
As another preferred embodiment of the present invention, the calcium carbonate base material is one or two of heavy calcium carbonate or light calcium carbonate. That is, in the specific modification treatment, the filler may be either a heavy calcium carbonate filler or a light calcium carbonate filler. Calcium carbonate can be classified into light calcium carbonate and heavy calcium carbonate according to its properties and sources. The light calcium carbonate is prepared by calcining and emulsifying limestone and then carrying out precipitation reaction with carbon dioxide, so that the light calcium carbonate is called as precipitated calcium carbonate; heavy calcium carbonate is obtained by physically pulverizing natural ore with high content of calcium carbonate.
As another preferred embodiment of the present invention, the organic carbonate compound is selected from one or two of ethylene carbonate and propylene carbonate. That is, the film forming auxiliary agent is composed of one or two of ethylene carbonate and propylene carbonate.
As another preferred embodiment of the present invention, the organic carbonate compound is selected from ethylene carbonate or propylene carbonate.
As another preferred embodiment of the invention, an in-situ surface coating modified calcium carbonate filler is prepared from the following components in parts by weight: 5-75 parts of calcium carbonate base stock, 1-20 parts of surface treatment agent, 0-10 parts of film forming auxiliary agent and 50-400 parts of solvent.
As another preferred embodiment of the present invention, the in-situ surface-coated modified calcium carbonate filler comprises the following raw materials in parts by weight: 15-50 parts of calcium carbonate base stock, 1-15 parts of surface treatment agent, 1-5 parts of film forming auxiliary agent and 160-260 parts of solvent.
As another preferable embodiment of the invention, the surface treating agent is sodium methyl silicate aqueous solution with the mass percent concentration of 10-50% and the pH value of more than 12.
As another preferable embodiment of the invention, the surface treating agent is sodium methyl silicate aqueous solution with the mass percent concentration of 20-40% and the pH value of more than 13.
As another preferred embodiment of the present invention, the solvent is selected from any one of deionized water, mineral water, distilled water, and soft water, which is not limited thereto, and may be selected as needed.
Preferably, the solvent is selected from deionized water. At this time, the in-situ surface coating modified calcium carbonate filler is composed of the following components in parts by weight:
15-50 parts of calcium carbonate base stock, 1-15 parts of surface treatment agent, 1-5 parts of film forming auxiliary agent and 160-260 parts of solvent
Wherein the surface treating agent is sodium methyl silicate aqueous solution with the mass percentage concentration of 20-40% and the pH value of more than 13; the film forming additive consists of one or two of ethylene carbonate and propylene carbonate.
Further preferably, the surface treatment agent is a sodium methyl silicate aqueous solution with a mass percent concentration of 30% and a pH of more than 13.
The embodiment of the invention also provides a preparation method of the in-situ surface-coated modified calcium carbonate filler, which comprises the following steps:
1) Weighing the film forming auxiliary agent according to the proportion, adding the film forming auxiliary agent into a proper amount of solvent, and uniformly mixing to obtain a film forming auxiliary agent solution;
2) Weighing a calcium carbonate base material according to a proportion, adding the calcium carbonate base material into the film forming auxiliary agent solution prepared in the step 1), and uniformly mixing to obtain a calcium carbonate suspension containing the film forming auxiliary agent;
3) Weighing a surface treating agent according to a proportion, and uniformly mixing the surface treating agent with a proper amount of solvent to obtain a surface treating agent solution;
4) Slowly adding the surface treating agent solution prepared in the step 3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step 2) at the temperature of 20-50 ℃ while stirring; after the charging is completed, stirring is continued for 1-4 hours to obtain a reaction mixed solution;
5) And (3) carrying out suction filtration on the reaction mixed solution obtained in the step (4), and then drying the obtained filter cake according to the conditions of heat preservation at 40-60 ℃ for 1-2 hours, heat preservation at 80-100 ℃ for 1-2 hours and heat preservation at 100-120 ℃ for 2-3 hours in sequence to obtain a dried product, and grinding the dried product into powder to obtain the in-situ surface-coated modified calcium carbonate filler.
As another preferred embodiment of the present invention, the solvent is deionized water. In this case, preferably, the preparation method of the in-situ surface-coated modified calcium carbonate filler comprises the following steps:
1) Weighing the film forming auxiliary agent according to the proportion, adding the film forming auxiliary agent into deionized water accounting for 40-70 wt% of the total weight required by the formula, mixing and dissolving, and uniformly mixing to obtain a film forming auxiliary agent solution;
2) Weighing a calcium carbonate base material according to a proportion, adding the calcium carbonate base material into the film forming auxiliary agent solution prepared in the step 1), fully stirring, and uniformly mixing to obtain a calcium carbonate suspension containing the film forming auxiliary agent;
3) Weighing the surface treating agent according to a proportion, and uniformly mixing the surface treating agent with the rest deionized water in the formula requirement to obtain a surface treating agent solution;
4) Slowly adding the surface treating agent solution prepared in the step 3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step 2) at the temperature of 25-50 ℃ while stirring; after the charging is completed, stirring is continued for 1-4 hours to obtain a reaction mixed solution;
5) Carrying out suction filtration on the reaction mixed solution in the step 4), and placing a filter cake into a baking oven to be dried according to the conditions of heat preservation at 40-60 ℃ for 1-2 hours, heat preservation at 80-100 ℃ for 1-2 hours and heat preservation at 100-120 ℃ for 2-3 hours in sequence to obtain a dried product;
6) Grinding and crushing the dried product in the step 5) into fine powder to obtain the in-situ surface coating modified calcium carbonate filler.
It should be noted that, when sodium methyl silicate or potassium methyl silicate is added to a calcium carbonate suspension containing a film forming aid (i.e., an organic carbonate), the organic carbonate is hydrolyzed to form carbon dioxide and a small molecular alcohol (e.g., ethylene carbonate may be hydrolyzed to form carbon dioxide and ethylene glycol, and propylene carbonate may be hydrolyzed to form carbon dioxide and propylene glycol); methyl silicate can generate methyl silanol under the action of water and carbon dioxide; hydroxyl groups in methyl silanol and hydroxyl groups on the surfaces of calcium carbonate powder particles shrink small molecular water under alkaline conditions to bond, and the residual hydroxyl groups in the methyl silanol are continuously polycondensed with other methyl silanol to form a polymer containing lateral methyl groups; meanwhile, the small molecular alcohol generated by the hydrolysis of the organic carbonate can promote the polymerization of methyl silanol; in this way, in situ surface coating of the calcium carbonate particles is achieved by means of chemical reactions in "in situ" or "in situ" polymerization. In the later stage, methyl sodium silicate molecules physically adsorbed on the surfaces of the calcium carbonate particles are secondarily solidified under the action of water and carbon dioxide in air, so that the physical coating of a polymer film containing lateral methyl on the surfaces of the calcium carbonate particles is formed, and the coating effect is further improved; finally, organic groups methyl are introduced to the surfaces of the calcium carbonate particles in a chemical bonding and physical coating mode, so that the surfaces of the calcium carbonate particles are subjected to organic modification, and the surfaces of the inorganic calcium carbonate particles and organic polymers are favorable to form strong bonding, so that the cost is reduced while the environment is protected, the surfaces of the calcium carbonate particles are subjected to organic modification, the oil absorption of the calcium carbonate can be reduced, and a stronger interface layer is favorable to be formed with a polymer matrix.
The embodiment of the invention also provides the in-situ surface coating modified calcium carbonate filler prepared by the preparation method of the in-situ surface coating modified calcium carbonate filler.
The embodiment of the invention also provides application of the in-situ surface coating modified calcium carbonate filler in coating processing or polymer material preparation. In particular to products such as paint, rubber, fiber, plastic, adhesive, polymer matrix composite and the like. According to the embodiment of the invention, the surface organic modification of the calcium carbonate filler is realized through in-situ surface coating, so that the oil absorption of the calcium carbonate filler can be reduced, and the filler dosage can be increased in a coating system; in the preparation of the high polymer material, the surface organic modification is also beneficial to the formation of a stronger interface layer between the filler and the high polymer matrix, thereby improving the strength of the material.
As another preferred embodiment of the present invention, the polymer material is any one of polypropylene composite material, polyethylene composite material, polycarbonate composite material, ABS plastic, rubber, or paint.
The technical effects of the in-situ surface-coated modified calcium carbonate filler of the examples of the present invention are further illustrated by the following examples.
Firstly, preparing in-situ surface coating modified calcium carbonate and ex-situ surface coating modified calcium carbonate reference.
Example 1
An in-situ surface-coated modified calcium carbonate filler, comprising the following raw materials: 30 g of heavy calcium carbonate, 200 g of deionized water, 3 g of ethylene carbonate and 10 g of 30% sodium methyl silicate aqueous solution.
In this embodiment, the preparation method of the in-situ surface-coated modified calcium carbonate filler specifically includes the following steps:
(1) 3 g of ethylene carbonate is taken as a film forming auxiliary agent to be added into 100g of weighed deionized water, and the solution is mixed and dissolved to obtain a film forming auxiliary agent solution.
(2) Adding 30 g of heavy calcium carbonate as a calcium carbonate base material into the film forming auxiliary agent solution prepared in the step (1), and fully stirring to obtain a calcium carbonate suspension containing the film forming auxiliary agent.
(3) Uniformly mixing 10 g of sodium methyl silicate water solution with the mass percentage concentration of 30% serving as a surface treating agent with the rest 100g of deionized water to obtain a surface treating agent solution;
(4) Slowly adding the surface treating agent solution prepared in the step (3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step (2) at room temperature, and stirring while adding; after the addition is completed, stirring is continued for 3 hours to obtain a reaction mixed solution;
(5) Filtering the reaction mixed solution obtained in the step (4), placing the filter cake into a baking oven, and drying the filter cake according to the heat preservation of 40 ℃ for 2 hours and 100 ℃ for 5 hours;
(6) Grinding and crushing the dried product obtained in the step (5) into fine powder to obtain the in-situ surface coating modified calcium carbonate filler.
Example 2
As a reference to example 1, example 2 prepared an ex-situ surface-coated modified calcium carbonate, the formulation of which was prepared as follows:
heavy calcium carbonate 30 g
200 g of deionized water
30% sodium Methylsilicate aqueous solution 10 g
The preparation method comprises the following steps:
(1) 30 g of heavy calcium carbonate as a calcium carbonate base was added to 100g of deionized water and stirred well to obtain a calcium carbonate suspension.
(2) Uniformly mixing 10 g of 30% sodium methyl silicate aqueous solution (namely 10 g of 30% sodium methyl silicate aqueous solution with mass percent concentration) with 100g of deionized water to obtain a surface treating agent solution;
(3) Slowly adding the surface treating agent solution prepared in the step (2) into the calcium carbonate suspension prepared in the step (1) at room temperature, and stirring while adding; after the addition is completed, stirring is continued for 3 hours to obtain a reaction mixed solution;
(4) Filtering the reaction mixed solution obtained in the step (3), placing the filter cake into a baking oven, and drying the filter cake according to the heat preservation of 40 ℃ for 2 hours and 100 ℃ for 5 hours;
(5) Grinding and crushing the dried product obtained in the step (4) into fine powder to obtain the reference-ex-situ surface coating modified calcium carbonate of the embodiment 1.
Example 3
Compared with the example 1, the in-situ surface coating modified calcium carbonate filler comprises the following raw materials: 20 g of heavy calcium carbonate, 210 g of deionized water, 2 g of propylene carbonate and 20 g of 30% sodium methyl silicate aqueous solution.
In this embodiment, the preparation method of the in-situ surface-coated modified calcium carbonate filler specifically includes the following steps:
(1) 2 g of propylene carbonate is taken as a film forming auxiliary agent to be added into 150 g of weighed deionized water, and the solution is mixed and dissolved to obtain a film forming auxiliary agent solution.
(2) And (2) adding 20 g of heavy calcium carbonate as a calcium carbonate base material into the film forming auxiliary agent solution prepared in the step (1), and fully stirring to obtain a calcium carbonate suspension containing the film forming auxiliary agent.
(3) Uniformly mixing 20 g of sodium methyl silicate water solution with the mass percentage concentration of 30% serving as a surface treating agent with the rest 60 g of deionized water to obtain a surface treating agent solution;
(4) Slowly adding the surface treating agent solution prepared in the step (3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step (2) at 50 ℃ while stirring; after the addition is completed, stirring is continued for 4 hours to obtain a reaction mixed solution;
(5) Filtering the reaction mixed solution obtained in the step (4), and placing the filter cake into a baking oven to be dried sequentially according to the heat preservation at 60 ℃ for 2 hours, 80 ℃ for 2 hours and 120 ℃ for 3 hours;
(6) Grinding and crushing the dried product obtained in the step (5) into fine powder to obtain the in-situ surface coating modified calcium carbonate filler.
Example 4
As a reference to example 3, example 4 prepared an ex-situ surface-coated modified calcium carbonate prepared according to the following formulation:
heavy calcium carbonate 20 g
Deionized water 210 g
30% sodium Methylsilicate aqueous solution 20 g
The preparation method comprises the following steps:
(1) 20 g of heavy calcium carbonate was added as a calcium carbonate base to 150 g of deionized water and stirred well to obtain a calcium carbonate suspension.
(2) Uniformly mixing 20 g of 30% sodium methyl silicate aqueous solution (namely 30% sodium methyl silicate aqueous solution with mass percent concentration) with 60 g of deionized water to obtain a surface treating agent solution;
(3) Slowly adding the surface treating agent solution prepared in the step (2) into the calcium carbonate suspension prepared in the step (1) at 50 ℃ while stirring; after the addition is completed, stirring is continued for 3 hours to obtain a reaction mixed solution;
(4) Filtering the reaction mixed solution obtained in the step (3), and placing the filter cake into a baking oven to be dried sequentially according to the heat preservation at 60 ℃ for 2 hours, 80 ℃ for 2 hours and 120 ℃ for 3 hours;
(5) Grinding and crushing the dried product obtained in the step (4) into fine powder to obtain the reference-ex-situ surface coating modified calcium carbonate of the embodiment 3.
Example 5
Compared with the example 1, the in-situ surface coating modified calcium carbonate filler comprises the following raw materials: 25 g of light calcium carbonate, 250 g of deionized water, 5 g of ethylene carbonate and 5 g of sodium methyl silicate aqueous solution with the mass percent concentration of 30 percent.
In this embodiment, the preparation method of the in-situ surface-coated modified calcium carbonate filler specifically includes the following steps:
(1) 5 g of ethylene carbonate is taken as a film forming auxiliary agent to be added into 200 g of weighed deionized water, and the solution is mixed and dissolved to obtain a film forming auxiliary agent solution.
(2) And (2) adding 25 g of light calcium carbonate as a calcium carbonate base material into the film forming auxiliary agent solution prepared in the step (1), and fully stirring to obtain a calcium carbonate suspension containing the film forming auxiliary agent.
(3) Uniformly mixing 5 g of sodium methyl silicate water solution with the mass percentage concentration of 30% serving as a surface treating agent with the rest 50 g of deionized water to obtain a surface treating agent solution;
(4) Slowly adding the surface treating agent solution prepared in the step (3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step (2) at the temperature of 30 ℃ and stirring the mixture while adding the solution; after the addition is completed, stirring is continued for 1 hour to obtain a reaction mixed solution;
(5) Filtering the reaction mixed solution obtained in the step (4), and placing the filter cake into a baking oven to be dried sequentially according to the heat preservation at 60 ℃ for 1 hour, 80 ℃ for 1 hour and 120 ℃ for 2 hours;
(6) Grinding and crushing the dried product obtained in the step (5) into fine powder to obtain the in-situ surface coating modified calcium carbonate filler.
Example 6
As a reference to example 5, example 6 prepared an ex-situ surface-coated modified calcium carbonate, the formulation of which was prepared as follows:
light calcium carbonate 25 g
Deionized water 250 g
30% sodium Methylsilicate aqueous solution 5 g
The preparation method comprises the following steps:
(1) 25 g of light calcium carbonate was added as a calcium carbonate base to 200 g of deionized water and stirred well to obtain a calcium carbonate suspension.
(2) Uniformly mixing 5 g of 30% sodium methyl silicate aqueous solution (namely 30% sodium methyl silicate aqueous solution with mass percent concentration) with 50 g of deionized water to obtain a surface treating agent solution;
(3) Slowly adding the surface treating agent solution prepared in the step (2) into the calcium carbonate suspension prepared in the step (1) at the temperature of 30 ℃ while stirring; after the addition is completed, stirring is continued for 1 hour to obtain a reaction mixed solution;
(4) Filtering the reaction mixed solution obtained in the step (3), and placing the filter cake into a baking oven to be dried sequentially according to the heat preservation at 60 ℃ for 1 hour, 80 ℃ for 1 hour and 120 ℃ for 2 hours;
(5) Grinding and crushing the dried product obtained in the step (4) into fine powder to obtain the reference-ex-situ surface coating modified calcium carbonate in the example 5.
Example 7
Compared with the example 3, the in-situ surface coating modified calcium carbonate filler comprises the following raw materials: 40 g of light calcium carbonate, 250 g of deionized water, 3 g of propylene carbonate and 8 g of 30% sodium methyl silicate aqueous solution. The preparation method is that the surface treating agent solution is slowly added into the calcium carbonate suspension containing the film forming additive at 40 ℃, stirring is carried out while adding, stirring is continued for 3 hours after the addition is finished, and the filter cake is put into an oven to be dried according to the heat preservation of 60 ℃ for 1 hour, 80 ℃ for 2 hours and 120 ℃ for 3 hours in sequence.
Example 8
As a reference to example 7, example 8 prepared an ex-situ surface-coated modified calcium carbonate, the formulation of which was prepared as follows:
40 g of light calcium carbonate
Deionized water 250 g
30% sodium methyl silicate aqueous solution 8 g
The preparation method comprises the following steps:
(1) 40 g of light calcium carbonate is added into 200 g of deionized water as a calcium carbonate base material and stirred fully to obtain calcium carbonate suspension.
(2) Uniformly mixing 8 g of 30% sodium methyl silicate aqueous solution (namely 30% sodium methyl silicate aqueous solution with mass percent concentration) with 50 g of deionized water to obtain a surface treating agent solution;
(3) Slowly adding the surface treating agent solution prepared in the step (2) into the calcium carbonate suspension prepared in the step (1) at the temperature of 40 ℃ while stirring; after the addition is completed, stirring is continued for 3 hours to obtain a reaction mixed solution;
(4) Filtering the reaction mixed solution obtained in the step (3), and placing the filter cake into a baking oven to be dried sequentially according to the heat preservation at 60 ℃ for 1 hour, 80 ℃ for 2 hours and 120 ℃ for 3 hours;
(5) Grinding and crushing the dried product obtained in the step (4) into fine powder to obtain the reference-ex-situ surface coating modified calcium carbonate in the example 5.
The pH of the sodium methylsilicate solution used in the above examples was > 13.
Comparative example 1
The unmodified heavy calcium carbonate raw material in example 1 was used as a reference sample, and compared with other examples.
Comparative example 2
The unmodified light calcium carbonate raw material in example 5 was used as a reference sample, and compared with other examples.
Performance detection
The prepared materials of examples 1 to 8 and the unmodified calcium carbonate of comparative examples 1 to 2 were subjected to oil absorption detection. Specifically, according to the general test method of GB/T5211.15-2014 pigment and extender pigment, part 15: oil absorption measurement the oil absorption measurement was carried out, and the test results are shown in tables 1 and 2, wherein tables 1 and 2 are the test results of the heavy calcium carbonate and the light calcium carbonate, respectively. Therefore, the calcium carbonate surface treatment technology provided by the invention can reduce the oil absorption of calcium carbonate, and proves that the surface organic modification is realized.
TABLE 1 coating modified heavy calcium carbonate and results of measurement of oil absorption of unmodified heavy calcium carbonate
| Group of | Oil absorption (g/100 g) | Reference standard of detection |
| Example 1 | 22.52 | GB/T5211.15-2014 |
| Example 2 | 28.10 | GB/T5211.15-2014 |
| Example 3 | 21.75 | GB/T5211.15-2014 |
| Example 4 | 27.56 | GB/T5211.15-2014 |
| Comparative example 1 | 32.15 | GB/T5211.15-2014 |
Table 2 table of oil absorption measurement results of coated modified light calcium carbonate and unmodified light calcium carbonate
As can be seen from the data in tables 1 and 2, the oil absorption of the in-situ surface-coated modified calcium carbonate filler prepared by the embodiment of the invention is obviously reduced compared with that of the unmodified calcium carbonate, which indicates that the surface of the calcium carbonate is already covered with organic groups; therefore, the oil absorption of heavy calcium carbonate and light calcium carbonate can be reduced by utilizing the surface coating modification, and the effect of in-situ surface coating modification is better than that of ex-situ surface coating modification. The oil absorption has important guiding significance on selecting the filler, and the processing performance of the high polymer material is directly influenced, because the high oil absorption of the filler can reduce the flowability of the high polymer material and the molding process performance is poor. According to the embodiment of the invention, the in-situ surface coating technology is adopted, the sodium methyl silicate aqueous solution is used as a surface treating agent, and the organic carbonate compound is used as a film forming auxiliary agent, so that the organic modification of the surface of the calcium carbonate is realized, the oil absorption of the calcium carbonate can be reduced, and the effective adhesion and combination between the calcium carbonate and a high polymer compound matrix material interface are facilitated. In addition, the surface treating agent adopted by the invention has high storage stability, can be used for a long time, does not generate organic volatile matters in the treatment process, and has excellent environmental protection performance.
In the technique disclosed in the prior art, sodium methyl silicate is adsorbed on the surface of talcum powder filler particles by a physical or chemical adsorption mode, and then reacts with carbon dioxide in air or carbon dioxide introduced by a physical mode in a later drying process to form an organosilicon film to cover the surface of talcum powder particles, so that the surface of talcum powder particles is organically modified. The oil absorption of the talcum powder with organically modified surface prepared by the method is effectively reduced, and the technology has the characteristics of environmental protection and low production cost. However, when this technique is applied to the treatment of calcium carbonate, the treatment effect is not ideal, which may be due to the fact that sodium methyl silicate and calcium carbonate have a large difference in structure or polarity, and an effective coating cannot be formed, resulting in the unsatisfactory treatment effect.
Wherein, the calcium carbonate is white fine crystal powder, is odorless and odorless, and has two forms of amorphous and crystalline. Sodium methyl silicate is an organic compound, is colorless liquid, and has good osmotic crystallinity. The molecular structure of the modified polyurethane has silanol groups. Talcum powder is water-containing magnesium silicate, which has silicate bond and hydroxyl, calcium carbonate is inorganic material, has amorphous and crystalline forms, and does not contain silicate bond and hydroxyl, so that calcium carbonate and sodium methyl silicate have large difference in structure or polarity, cannot form effective coating, and the treatment effect is not ideal. According to the embodiment of the invention, the in-situ surface coating technology is adopted, the sodium methyl silicate aqueous solution is used as a surface treating agent, and the organic carbonate compound is used as a film forming auxiliary agent, so that the organic modification of the surface of the calcium carbonate is realized, the oil absorption of the modified calcium carbonate filler can be effectively reduced, the cost is low, and no waste water and waste residues are generated in the treatment process.
According to the results, the in-situ surface coating modified calcium carbonate filler provided by the embodiment of the invention has the beneficial effects that the in-situ surface coating technology is adopted, the sodium methyl silicate aqueous solution is used as a surface treatment agent, and the organic carbonate compound is used as a film forming auxiliary agent, so that the organic modification of the calcium carbonate surface is realized.
While the preferred embodiments of the present invention have been described in detail, the present embodiments are not limited to the above embodiments, and various changes may be made without departing from the spirit of the present embodiments within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the embodiments of the present invention.
Claims (9)
1. The in-situ surface-coated modified calcium carbonate filler is characterized by comprising the following raw materials: a calcium carbonate base material, a surface treatment agent, a film forming auxiliary agent and a proper amount of solvent; wherein the surface treatment agent is sodium methyl silicate aqueous solution or potassium methyl silicate aqueous solution, the film forming auxiliary agent is an organic carbonate compound, and the organic carbonate compound is selected from one or two of ethylene carbonate and propylene carbonate.
2. The in-situ surface-coated modified calcium carbonate filler of claim 1, wherein the calcium carbonate base is one or both of heavy calcium carbonate and light calcium carbonate.
3. The in-situ surface-coated modified calcium carbonate filler according to claim 1, wherein the organic carbonate compound is selected from the group consisting of ethylene carbonate and propylene carbonate.
4. The in-situ surface-coated modified calcium carbonate filler according to claim 1, characterized in that it comprises the following raw materials in parts by weight: 5-75 parts of calcium carbonate base stock, 1-20 parts of surface treatment agent, 1-10 parts of film forming auxiliary agent and 50-400 parts of solvent.
5. The in-situ surface-coated modified calcium carbonate filler according to claim 4, wherein the in-situ surface-coated modified calcium carbonate filler comprises the following raw materials in parts by weight: 15-50 parts of calcium carbonate base stock, 1-15 parts of surface treatment agent, 1-5 parts of film forming auxiliary agent and 160-260 parts of solvent.
6. The in-situ surface-coated modified calcium carbonate filler according to claim 1, wherein the surface treatment agent is an aqueous solution of sodium methyl silicate with a mass percentage concentration of 10-50% and a pH > 12.
7. The in-situ surface-coated modified calcium carbonate filler of claim 6, wherein the surface treatment agent is an aqueous solution of sodium methyl silicate having a mass percent concentration of 20-40% and a pH > 13.
8. A method of preparing the in-situ surface-coated modified calcium carbonate filler according to any one of claims 1 to 7, comprising the steps of: 1) Weighing the film forming additive, adding the film forming additive into a proper amount of solvent, and uniformly mixing to obtain a film forming additive solution; 2) Weighing a calcium carbonate base material, adding the calcium carbonate base material into the film forming additive solution prepared in the step 1), and uniformly mixing to obtain a calcium carbonate suspension containing the film forming additive; 3) Weighing a surface treating agent and mixing the surface treating agent with a proper amount of solvent uniformly to obtain a surface treating agent solution; 4) Slowly adding the surface treating agent solution prepared in the step 3) into the calcium carbonate suspension containing the film forming auxiliary agent prepared in the step 2) at the temperature of 25-50 ℃ while stirring; after the charging is completed, stirring is continued for 1-4 hours to obtain a reaction mixed solution; 5) And (3) carrying out suction filtration on the reaction mixed solution obtained in the step (4), and then drying the obtained filter cake according to the conditions of heat preservation at 40-60 ℃ for 1-2 hours, heat preservation at 80-100 ℃ for 1-2 hours and heat preservation at 100-120 ℃ for 2-3 hours in sequence to obtain a dried product, and grinding the dried product into powder to obtain the in-situ surface-coated modified calcium carbonate filler.
9. Use of the in-situ surface-coated modified calcium carbonate filler according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 in coating processing or polymer material preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034207.1A CN115386247B (en) | 2022-08-26 | 2022-08-26 | In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034207.1A CN115386247B (en) | 2022-08-26 | 2022-08-26 | In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115386247A CN115386247A (en) | 2022-11-25 |
| CN115386247B true CN115386247B (en) | 2023-06-27 |
Family
ID=84122220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211034207.1A Active CN115386247B (en) | 2022-08-26 | 2022-08-26 | In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115386247B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374178A (en) * | 1980-12-29 | 1983-02-15 | Union Carbide Corporation | Silanated calcium carbonate fillers |
| CN101910324A (en) * | 2007-11-02 | 2010-12-08 | 欧米亚发展股份公司 | Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products |
| WO2012073258A2 (en) * | 2010-11-30 | 2012-06-07 | Pradeep Vasant Joshi | A composition suitable for use in building construction |
| CN102884140A (en) * | 2010-04-09 | 2013-01-16 | Omya发展股份公司 | Use of surface modified calcium carbonate in adhesives, sealants and/or caulks |
| CN104129809A (en) * | 2014-07-27 | 2014-11-05 | 许盛英 | Acidified calcium carbonate |
| CN107075273A (en) * | 2014-11-07 | 2017-08-18 | 欧米亚国际集团 | Method for preparing flocculation filler particles |
| CN114369290A (en) * | 2021-12-13 | 2022-04-19 | 马鞍山顾地塑胶有限公司 | Surface organic modified talcum powder filler and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005023524A2 (en) * | 2003-08-29 | 2005-03-17 | Z Corporation | Absorbent fillers for three-dimensional printing |
-
2022
- 2022-08-26 CN CN202211034207.1A patent/CN115386247B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374178A (en) * | 1980-12-29 | 1983-02-15 | Union Carbide Corporation | Silanated calcium carbonate fillers |
| CN101910324A (en) * | 2007-11-02 | 2010-12-08 | 欧米亚发展股份公司 | Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products |
| CN102884140A (en) * | 2010-04-09 | 2013-01-16 | Omya发展股份公司 | Use of surface modified calcium carbonate in adhesives, sealants and/or caulks |
| WO2012073258A2 (en) * | 2010-11-30 | 2012-06-07 | Pradeep Vasant Joshi | A composition suitable for use in building construction |
| CN104129809A (en) * | 2014-07-27 | 2014-11-05 | 许盛英 | Acidified calcium carbonate |
| CN107075273A (en) * | 2014-11-07 | 2017-08-18 | 欧米亚国际集团 | Method for preparing flocculation filler particles |
| CN114369290A (en) * | 2021-12-13 | 2022-04-19 | 马鞍山顾地塑胶有限公司 | Surface organic modified talcum powder filler and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115386247A (en) | 2022-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5411761A (en) | Process of producing hydrophobic titanium oxide fine particle | |
| CN1146626C (en) | Acid-resistant, thermoplastic resin composition containing magnesium hydroxide and its use | |
| DE68918716T2 (en) | Surface treated polysilsesquioxane powder. | |
| US4089883A (en) | Process for the production of organic hydroxy silicate compounds and their condensation products | |
| DE3905785C2 (en) | Process for the production of fine polyorganosilsesquioxane particles | |
| CN102884140B (en) | Use of surface modified calcium carbonate in adhesives, sealants and/or caulks | |
| CN101305064A (en) | Binding agent, sealant and paint containing glass particle as filling material | |
| US2884402A (en) | Treated pigments and methods of preparing same | |
| JPH0470335B2 (en) | ||
| CN114891183B (en) | Aqueous polyurethane modified starch dispersion liquid and preparation method thereof | |
| JPH07103238B2 (en) | Method for producing polyorganosilsesquioxane fine particles | |
| CN115386247B (en) | In-situ surface-coated modified calcium carbonate filler and preparation method and application thereof | |
| CN109306047B (en) | Modified polyurethane fireproof water-based paint and preparation method thereof | |
| TWI276669B (en) | Process for production of titanium dioxide pigment and resin compositions containing the pigment | |
| JPH06200034A (en) | Layered organosilicon polymer, its molding and their preparation | |
| US5777001A (en) | Graft polymerized metal oxide compositions and methods | |
| CN114369290A (en) | Surface organic modified talcum powder filler and preparation method and application thereof | |
| CN1259380C (en) | Modified paint formula containing hectorite combination | |
| WO2001044111A1 (en) | Titanium dioxide pigment and method for production thereof | |
| JPS60166221A (en) | Vaterite type calcium carbonate composition of fine powder | |
| JPS6225708B2 (en) | ||
| JPH03188196A (en) | Zeolite suspension containing siliconate | |
| JP2000302878A (en) | Impalpable powder of water-repellent silicone resin | |
| US3962067A (en) | Process for the production of an aqueous solution of silicoformic acid | |
| JPS59191764A (en) | Production of surface-treated calcium carbonate highly affinitive with organic vehicle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A modified calcium carbonate filler with in-situ surface coating and its preparation method and application Granted publication date: 20230627 Pledgee: China Postal Savings Bank Co.,Ltd. Ma'anshan Branch Pledgor: MAANSHAN GOODY PLASTIC CO.,LTD. Registration number: Y2024980007063 |