CN106752106B - Anti-aging functional filler nano-calcium carbonate of bright white uvioresistant and its preparation method and application - Google Patents
Anti-aging functional filler nano-calcium carbonate of bright white uvioresistant and its preparation method and application Download PDFInfo
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- CN106752106B CN106752106B CN201710009275.5A CN201710009275A CN106752106B CN 106752106 B CN106752106 B CN 106752106B CN 201710009275 A CN201710009275 A CN 201710009275A CN 106752106 B CN106752106 B CN 106752106B
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- calcium carbonate
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- uvioresistant
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 124
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000012767 functional filler Substances 0.000 title claims abstract description 20
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 13
- 241001085205 Prenanthella exigua Species 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000741 silica gel Substances 0.000 claims abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 4
- 230000003749 cleanliness Effects 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 16
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- CJQXELDQWZWYLG-UHFFFAOYSA-L calcium zinc oxygen(2-) carbonate Chemical compound C([O-])([O-])=O.[Ca+2].[O-2].[Zn+2] CJQXELDQWZWYLG-UHFFFAOYSA-L 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- LWMJYFDWQCZRKF-UHFFFAOYSA-K calcium zinc carbonate hydroxide Chemical compound C([O-])([O-])=O.[Ca+2].[OH-].[Zn+2] LWMJYFDWQCZRKF-UHFFFAOYSA-K 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 14
- 229940007718 zinc hydroxide Drugs 0.000 description 14
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 14
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 230000003026 anti-oxygenic effect Effects 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- C09C1/022—Treatment with inorganic compounds
- C09C1/024—Coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a kind of anti-aging functional filler nano-calcium carbonate of bright white uvioresistant, by to reaction system concentration in preparation process, terminate pH value, reaction temperature, the formula of dispersant and the selection indices of covering are precisely controlled, it is 80nm 200nm to obtain particle diameter, whiteness reaches more than 92, oxide coated by zinc amount reaches 4%, soilless sticking phenomenon, with the high-performance multipurpose nano-calcium carbonate that uvioresistant is anti-aging, products obtained therefrom can be in rubber, silica gel, plastics, anti-oxidant anti-ultraviolet property and bright cleanliness of the field of papermaking as filler increase product.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of novel nano calcium carbonate and preparation method thereof and use
On the way.
Background technology
Calcium carbonate is a kind of important inorganic material, is widely used in the fields such as rubber, plastics, papermaking.Present calcium carbonate
Product is based on precipitated calcium carbonate, activated Calcium carbonate.Existing calcium carbonate product added value is not high, additional therefore, it is necessary to develop
The new product that value is high, market potential is big is to widen the development space of calcium carbonate enterprise.Zinc oxide is also a kind of important inorganic material
Material, it can also be used to which the field such as rubber, plastics, papermaking, it has downstream product preferable modifying function, but cost compares calcium carbonate
It is high.At present, existing nanon calcium carbonatefilled material, with modified effect has limitation, of high cost, product whiteness is poor, anti-
The shortcomings that ultraviolet antioxygenic property is poor.Therefore product of the present invention is in calcium carbonate surface, formation oxidation by oxide coated by zinc
The composite material of zinc and calcium carbonate, obtains a kind of functional filler nano-calcium carbonate calcium product, which is used for downstream product
In, you can the uvioresistant antioxygenic property of downstream product is effectively improved, improves the whiteness of product, and production cost can be reduced.
A kind of calcium carbonate-filled anti-flaming polypropylene material and preparation method thereof is disclosed in Chinese patent CN105348641A,
Raw material composition is 25-28 parts of acrylic resin, 10-60 parts of calcium carbonate, 1-10 parts of compound flame retardant, 1-20 parts of compatilizer, antioxygen
0.2-0.6 parts of agent, 0.2-1.0 parts of lubricant, 0.1-0.3 parts of White Mineral Oil.The anti-flaming polypropylene material fire resistance of the invention is excellent
Different, good mechanical properties, processing performance are excellent, cost is low.
Chinese patent CN201510884929.X<<<<Disclose a kind of modified rubber calcium carbonate and preparation method thereof；This
Invention is included count by weight percentage：Calcium carbonate 90%~98% and super carrier 2%~10%；First calcium carbonate is carried out
Surface treatment, then pelletizing is extruded by extruder modified rubber calcium carbonate is made.
Chinese patent CN201410507926.X discloses a kind of modified calcium carbonate of antiageing effect enhancing, its feature exists
In being made of the raw material of following parts by weight：Calcium carbonate 90-95, antioxidant NBC 1-2, nitrile rubber 6-8, PVC waste powder
5-6, calcined loess powder 2-3, DBPC 2,6 ditertiary butyl p cresol 1-2, the own ester 2-3 of tri trimellitate, tetramethylthiuram disulfide
1-2, tung oil 1-1.5, vegetable wax 1-2, modifying titanium dioxide 3-4；It is anti-ageing that the invention with the addition of DBPC 2,6 ditertiary butyl p cresol etc.
Agent and a variety of high molecular polymers are coated, and modified calcium carbonate intensity is big, good with reference to power.
Chinese patent CN201410507860.4 discloses a kind of modified calcium carbonate with flame retardant effect, its feature exists
In being made of the raw material of following parts by weight：Calcium carbonate 90-95, calcium carbide ground-slag 3-5, vermiculite power 3-4, antimony oxide 2-
4th, asbestos fibre 1-2, zinc borate 2-3, crushing shuck 2-4, Isooctyl acrylate monomer 6-8, acetyl citrate 5-7, EVA wax 3-
5th, tetrabromobisphenol a1-2, modifying titanium dioxide 3-4；The filler is used to produce the auxiliary agents such as coating, pigment, rubber.
Above is several patents on method of producing nano-calcium carbonate, there is modified effect to have limitation, product
The shortcomings that whiteness is poor, anti-oxidant anti-ultraviolet property is poor.
The content of the invention
The technical problem to be solved in the present invention is a variety of deficiencies for overcoming the prior art, there is provided a kind of bright white uvioresistant resists
Aging functional filler nano-calcium carbonate and its preparation method and application.
In order to solve the above technical problems, the technical solution used in the present invention is as follows.
The anti-aging functional filler nano-calcium carbonate of bright white uvioresistant, by dense to reaction system in preparation process
The selection indices for spending, terminating pH value, reaction temperature, the formula of dispersant and covering are precisely controlled, and obtain particle diameter
For 80nm-200nm, whiteness reach more than 92, oxide coated by zinc amount reach 4%, soilless sticking phenomenon, have uvioresistant it is anti-aging
High-performance multipurpose nano-calcium carbonate.
The preparation method of the above-mentioned anti-aging functional filler nano-calcium carbonate of bright white uvioresistant, includes the following steps：
A, calcium hydroxide slurry being prepared first and adding dispersant thereto, controlling reaction temperature is 40 DEG C -60 DEG C, then
It is passed through carbon dioxide to be reacted, reaction is terminated when being down to 6.3-6.8 to pH value of reaction system, obtains nano-calcium carbonate slurry；
B, sodium zincate is added in nano-calcium carbonate slurry obtained by step A, controlling reaction temperature is 55 DEG C -65 DEG C, is continued
30min-50min is stirred, forms zinc hydroxide-calcium carbonate primary composite material sizing agent；
C, slurry obtained by step B through being dehydrated, it is dry, obtain the powder of preliminary composite, then through heating treatment, make primary
The abundant dehydration in powder surface of composite material, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate.
As a kind of optimal technical scheme of above-mentioned preparation method, in step A, the dispersant is using sodium gluconate, hard
One or more combination in resin acid sodium, sodium laurate, calgon；Total dosage of the dispersant is nano-calcium carbonate weight
1%-3%.
As a kind of optimal technical scheme of above-mentioned preparation method, in step B, first received before sodium zincate is added by described
The weight percent concentration of rice calcium carbonate slurry is adjusted to 8%-18%.
As a kind of optimal technical scheme of above-mentioned preparation method, in step B, the sodium zincate addition is nano-calcium carbonate
The 1%-10% of calcium weight.
As a kind of optimal technical scheme of above-mentioned preparation method, in step B, the mixing speed is controlled to be in stir process
400r/min-800r/min。
As a kind of optimal technical scheme of above-mentioned preparation method, in step C, the heating treatment controls the final temperature to be
115 DEG C -150 DEG C, maintain 1-2h.
As a kind of optimal technical scheme of above-mentioned preparation method, in step C, the cladding of zinc oxide in the finished product
Measure as the 2-4% of nano-calcium carbonate weight.
As a kind of optimal technical scheme of above-mentioned preparation method, this method comprises the following steps：
A, calcium hydroxide slurry being prepared first and adding dispersant thereto, controlling reaction temperature is 50 DEG C, is then passed to
Carbon dioxide is reacted, and is terminated reaction when being down to 6.5 to pH value of reaction system, is obtained nano-calcium carbonate slurry；Wherein, it is described
Dispersant uses calgon, and total dosage of dispersant is the 2% of nano-calcium carbonate weight；
B, sodium zincate is added in nano-calcium carbonate slurry obtained by step A, controlling reaction temperature is 60 DEG C, lasting stirring
40min, forms zinc hydroxide-calcium carbonate primary composite material sizing agent；Wherein, first by the nano-sized carbon before sodium zincate is added
The weight percent concentration of sour calcium slurry is adjusted to 15%, and sodium zincate addition is the 6% of nano-calcium carbonate weight；Also, stirring
It is 600r/min to mix and mixing speed is controlled in processing；
C, slurry obtained by step B through being dehydrated, it is dry, obtain the powder of preliminary composite, be warming up to 130 DEG C, maintain
1.5h, makes the abundant dehydration in powder surface of preliminary composite, obtains zinc oxide-calcium carbonate composite material, the cladding of zinc oxide
Measure as the 4% of nano-calcium carbonate weight, up to functional filler nano-calcium carbonate.
The purposes of the above-mentioned anti-aging functional filler nano-calcium carbonate of bright white uvioresistant, in rubber, silica gel, plastics, makes
Anti-oxidant anti-ultraviolet property and bright cleanliness of the paper field as filler increase product.
It is using beneficial effect caused by above-mentioned technical proposal：
The present invention in preparation process by reaction system concentration, terminate pH value, reaction temperature, dispersant formula and
The selection indices of covering are precisely controlled, and are obtained particle diameter and are reached more than 92, zinc oxide bag for 80nm-200nm, whiteness
The amount of covering reaches 4%, soilless sticking phenomenon, has the anti-aging high-performance multipurpose nano-calcium carbonate of uvioresistant.As it can be seen that the present invention
Outstanding advantages are that have good uvioresistant, antioxygenic property and higher whiteness, can overcome and have nano-sized carbon at present
The shortcomings that sour calcium filler product whiteness is relatively low, uvioresistant is poor, antioxygenic property is poor, accommodation is relatively narrow.It is prepared by the present invention
Product can be applied in the materials such as rubber, silica gel, polypropylene, be remarkably improved the anti-oxidant anti-ultraviolet property of the material
And the whiteness of product.
Embodiment
The present invention is described in detail in following embodiments.Various raw materials used in the present invention and items of equipment are conventional city
Product is sold, can be bought and directly obtained by market.
Embodiment 1
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.5, is stirred with the speed of 600r/min, be passed through
It is 15% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 180g sodium zincates, with
The speed stirring of 600r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 130 DEG C of heating treatments, and maintain 130 DEG C
1.5h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbon
The oxide coated by zinc amount on sour calcium surface is the 4% of nano-calcium carbonate weight.
Embodiment 2
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.5, is stirred with the speed of 400r/min, be passed through
It is 16% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 180g sodium zincates, with
The speed stirring of 400r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 130 DEG C of heating treatments, and maintain 130 DEG C
1.5h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbon
The oxide coated by zinc amount on sour calcium surface is the 3.6% of nano-calcium carbonate weight.
Embodiment 3
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.3, is stirred with the speed of 600r/min, be passed through
It is 12% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 180g sodium zincates, with
The speed stirring of 600r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 130 DEG C of heating treatments, and maintain 130 DEG C
1.5h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbon
The oxide coated by zinc amount on sour calcium surface is the 3.3% of nano-calcium carbonate weight.
Embodiment 4
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.3, is stirred with the speed of 600r/min, be passed through
It is 15% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 150g sodium zincates, with
The speed stirring of 600r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 130 DEG C of heating treatments, and maintain 130 DEG C
1.5h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbon
The oxide coated by zinc amount on sour calcium surface is the 3.1% of nano-calcium carbonate weight.
Embodiment 5
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.3, is stirred with the speed of 600r/min, be passed through
It is 15% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 180g sodium zincates, with
The speed stirring of 600r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 150 DEG C of heating treatments, and maintain 150 DEG C
1.5h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbon
The oxide coated by zinc amount on sour calcium surface is the 2.0% of nano-calcium carbonate weight.
Embodiment 6
（1）The preparation of nano-calcium carbonate slurry
Calgon is added into calcium hydroxide slurry, control ph 6.3, is stirred with the speed of 600r/min, be passed through
It is 15% nano-calcium carbonate slurry that carbon dioxide, which obtains weight percent concentration,；
（2）The preparation of preliminary composite
After the completion of carbonization, 30kg nano-calcium carbonate slurries are added in 50L reaction kettles, add 180g sodium zincates, with
The speed stirring of 600r/min, sodium zincate hydrolysis generation zinc hydroxide.Zinc hydroxide is coated on calcium carbonate surface, forms hydroxide
Zinc-calcium carbonate primary composite material sizing agent；
（3）The surface treatment of composite material
Slurry is through being dehydrated, drying, obtains the powder of preliminary composite.Again through 130 DEG C of heating treatments, and maintain 150 DEG C
2h, makes surface dehydration, obtains zinc oxide-calcium carbonate composite material, i.e. functional filler nano-calcium carbonate, the filler nanometer carbonic acid
The oxide coated by zinc amount on calcium surface is the 3.6% of nano-calcium carbonate weight.
It is presented above the several instantiations for implementing the present invention.The present invention is in nano-calcium carbonate production process, carbonization
After the completion of, sodium zincate is added in calcium carbonate slurry, nano-calcium carbonate slurry pH value is controlled, continues to be passed through carbon dioxide, zincic acid
Sodium hydrolysis generation zinc hydroxide, zinc hydroxide are coated on calcium carbonate surface, form preliminary composite（Zinc hydroxide -- carbonic acid
Calcium）Slurry；Slurry is through being dehydrated, drying, obtains the powder of preliminary composite；Preliminary composite powder again through heating at
Reason, makes surface dehydration, obtains zinc oxide -- calcium carbonate composite material, i.e. functional filler nano-calcium carbonate；What the present invention obtained
Zinc oxide-calcium carbonate composite material, nano-calcium carbonate coated with zinc oxide, participates in reacting so that it has by calcium ion
Good anti-ultraviolet property and antioxygenic property.
Foregoing description only proposes as the enforceable technical solution of the present invention, not as to its technical solution single in itself
Restrictive condition.
Claims (2)
1. the preparation method of the anti-aging functional filler nano-calcium carbonate of bright white uvioresistant, by reaction in preparation process
System concentration, terminate pH value, reaction temperature, the selection indices of the formula of dispersant and covering and be precisely controlled, and obtains
Reach more than 92, oxide coated by zinc amount to particle diameter for 80nm-200nm, whiteness to reach 4%, soilless sticking phenomenon, with uvioresistant resist
The high-performance multipurpose nano-calcium carbonate of aging, it is characterised in that：This method comprises the following steps：
A, calcium hydroxide slurry being prepared first and adding dispersant thereto, controlling reaction temperature is 50 DEG C, then passes to dioxy
Change carbon to be reacted, terminate reaction when being down to 6.5 to pH value of reaction system, obtain nano-calcium carbonate slurry；Wherein, it is described scattered
Agent uses calgon, and total dosage of dispersant is the 2% of nano-calcium carbonate weight；
B, sodium zincate is added in nano-calcium carbonate slurry obtained by step A, controlling reaction temperature is 60 DEG C, persistently stirs 40min,
Form zinc hydroxide-calcium carbonate primary composite material sizing agent；Wherein, first the nano-calcium carbonate is starched before sodium zincate is added
The weight percent concentration of material is adjusted to 15%, and sodium zincate addition is the 4% of nano-calcium carbonate weight；Also, in stir process
It is middle that to control mixing speed be 600r/min；
C, slurry obtained by step B through being dehydrated, it is dry, obtain the powder of preliminary composite, be warming up to 130 DEG C, maintain 1.5h, make
The abundant dehydration in powder surface of preliminary composite, obtains zinc oxide-calcium carbonate composite material, the covering amount of zinc oxide is nanometer
The 4% of weight of calcium carbonate, up to functional filler nano-calcium carbonate.
2. the purposes of the anti-aging functional filler nano-calcium carbonate of bright white uvioresistant described in claim 1, rubber, silica gel,
The anti-oxidant anti-ultraviolet property and bright cleanliness of plastics, field of papermaking as filler increase product.
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| CN107541095A (en) * | 2017-07-21 | 2018-01-05 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of ultrawhite calcium carbonate |
| CN108585474A (en) * | 2018-06-06 | 2018-09-28 | 石家庄学院 | A kind of preparation method of anti-bacteria ceramic glaze filling nano-calcium carbonate |
| CN108587242B (en) * | 2018-06-06 | 2020-05-05 | 石家庄市红日钙业有限公司 | Preparation method of nano calcium carbonate composite material for filling wear-resistant and antioxidant ceramic glaze |
| CN113000058A (en) * | 2021-03-08 | 2021-06-22 | 北京化工大学 | Preparation method and application of nano zinc oxide/calcium carbonate composite powder |
| CN115627029B (en) * | 2022-10-25 | 2024-05-28 | 漳州市广益塑料有限公司 | Ageing-resistant plastic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101277706A (en) * | 2005-09-29 | 2008-10-01 | 聂洱 | Zinc oxide coated particles, compositions containing the same, and methods for making the same |
| CN101671497A (en) * | 2009-10-10 | 2010-03-17 | 上海卓越纳米新材料股份有限公司 | Industrial preparing method for PVC dedicated filler nanometer calcium carbonate with thermostability function |
| EP2791253A1 (en) * | 2011-12-16 | 2014-10-22 | Umicore | Production of zinc oxide coated powders |
-
2017
- 2017-01-06 CN CN201710009275.5A patent/CN106752106B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101277706A (en) * | 2005-09-29 | 2008-10-01 | 聂洱 | Zinc oxide coated particles, compositions containing the same, and methods for making the same |
| CN101671497A (en) * | 2009-10-10 | 2010-03-17 | 上海卓越纳米新材料股份有限公司 | Industrial preparing method for PVC dedicated filler nanometer calcium carbonate with thermostability function |
| EP2791253A1 (en) * | 2011-12-16 | 2014-10-22 | Umicore | Production of zinc oxide coated powders |
| US9216436B2 (en) * | 2011-12-16 | 2015-12-22 | Umicore | Production of zinc oxide coated powders |
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