CN105400238B - A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste - Google Patents
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste Download PDFInfo
- Publication number
- CN105400238B CN105400238B CN201510946405.9A CN201510946405A CN105400238B CN 105400238 B CN105400238 B CN 105400238B CN 201510946405 A CN201510946405 A CN 201510946405A CN 105400238 B CN105400238 B CN 105400238B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- nano
- sodium sulphate
- conditioning agent
- saturated fatty
- 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 Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 130
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004381 surface treatment Methods 0.000 title claims abstract description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 230000003750 conditioning effect Effects 0.000 claims abstract description 41
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 31
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000012545 processing Methods 0.000 claims abstract description 25
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 23
- 229940066675 ricinoleate Drugs 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000004359 castor oil Substances 0.000 claims description 11
- 235000019438 castor oil Nutrition 0.000 claims description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 8
- 235000021357 Behenic acid Nutrition 0.000 claims description 7
- 229940116226 behenic acid Drugs 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 4
- 235000004443 Ricinus communis Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 229960001777 castor oil Drugs 0.000 claims 2
- 240000000528 Ricinus communis Species 0.000 claims 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims 1
- 229940073769 methyl oleate Drugs 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 14
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 phenyl ester Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002383 tung oil Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- WWUVLNPEWUTCEI-KRWDZBQOSA-N Flowerone Chemical compound C1=C(O)C(CC=C(C)C)=CC([C@H]2OC3=C(O)C(O)=CC(O)=C3C(=O)C2)=C1 WWUVLNPEWUTCEI-KRWDZBQOSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- ZSGQTIIPGPLLCX-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Na+].C(CCCCCCCCCCC)(=O)OCCOCCOC(CCCCCCCCCCC)=O.[Na+] Chemical compound S(=O)(=O)([O-])[O-].[Na+].C(CCCCCCCCCCC)(=O)OCCOCCOC(CCCCCCCCCCC)=O.[Na+] ZSGQTIIPGPLLCX-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019197 fats Nutrition 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
- 238000011049 filling Methods 0.000 description 1
- YVBUWVMMORNHHZ-UHFFFAOYSA-N flowerone Natural products CC(=C)CCc1cc(ccc1O)C1CC(=O)c2c(O)cc(O)c(O)c2O1 YVBUWVMMORNHHZ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Chemical group 0.000 description 1
- 239000003981 vehicle Substances 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprise the following steps：Nano-calcium carbonate slurries after carbonating are delivered in surface processing trough, control temperature stirs at 50~80 DEG C；Added under stirring by the saturated fatty acid that mass ratio is 1: 0.5~3 and the surface conditioning agent that ricinoleate ester sodium sulphate forms, persistently stir 60~90min, the surface for completing nano-calcium carbonate is modified；It is filtered again, it dry, pulverize, finally sieve, you can obtain product.This method is surface-treated using the compounding mixture of saturated fatty acid and ricinoleate ester sodium sulphate to nano-calcium carbonate, and the nano-calcium carbonate after processing can effectively improve the thixotropy of filled PVC plasticized paste, yield value and rheological stability etc..This method technique is simple, and cost is low, and operation is easy, is suitable for industrial production, has preferable economic benefit and social benefit.
Description
Technical field
The present invention relates to inorganic material-modified method, a kind of specifically nano-calcium carbonate of filled PVC plasticized paste
Surface treatment method.
Background technology
PVC plasticized pastes are uniformly mixed by PVC paste resin, plasticizer, solid filling material and other auxiliary agents etc.
Paste-form dispersion system, because its production and processing have the advantages that technique is simple, cost is low, high financial profit and widely closed
Note, and applied to fields such as automobile, leather, ink, coating, fluid sealant, adhesive, building materials.For automobile industry, PVC plasticising
Paste is mainly used in processing and forms priming paint, requires that it has good thixotropy in the application of reality, is using（Spraying）Process
It is middle that low-viscosity is shown because of high speed shear, it is easy to spraying, levelling, does not produce sagging after spray coating.
Main function inserts of the nano-calcium carbonate as PVC plasticized pastes, its particle shape, particle diameter and surface treatment pair
The influence of plasticized paste rheological property is very big, wherein being handled with calcium carbonate surface influences maximum.It is usually used in calcium carbonate surface processing
Fatty acid molecule one end is hydrophilic carboxyl, chemical bond can be formed with calcium carbonate surface, so as to prevent calcium carbonate particle group
It is poly-；The other end is oil loving Long carbon chain, can reduce the surface energy of calcium carbonate particle, is improved compatible between calcium carbonate and plasticizer
Property.But the calcium carbonate of stearic acid surface processing is also easy to produce solvation effect in plasticized paste, causes system viscosity to increase, stability
It is bad.And Long carbon chain and PVC paste interlaminar resin, without chemical reaction, active force is weak, causes plasticized paste yield value relatively low.
In recent years, constantly have tried to carry out surface modification, the correlation found to nano-calcium carbonate with various inorganic agents
Document is as follows：The heat-resisting carbon that a kind of coupling agent surface is modified is disclosed in the A of Chinese patent Chinese invention patent CN 103555006
The preparation method of sour calcium.This method is organic molten being dissolved in after tung oil, tung oil acid anhydride and part silane coupler KH55O uniformly mixing
Agent, use it for calcium carbonate and be surface-treated for the first time, then add di-n-octyl sebacate and tricresyl phosphate continues with.Institute
Obtain calcium carbonate surface and form one layer of tung oil diaphragm, heat resistance is good, and coupling agent can be such that calcium carbonate is contacted more with diaphragm
Closely.But this method technique is complex, and the calcium carbonate-filled PVC plasticized pastes viscosity of gained is higher, di-n-octyl sebacate and phosphorus
Sour front three phenyl ester etc. will aggravate plasticized paste system solvation, cause plasticized paste storage stability to decline.
A kind of preparation of anti-corrosive paints nanometer grade calcium carbonate is disclosed in the A of Chinese invention patent CN 103555032
Method.The processing of its one-time surface uses molybdenum using silane coupler KH580 and the compound of antioxidant, secondary surface treatment
The compound of sour ammonium, Isobutyl methacrylate and rosin resin.Gained nano-calcium carbonate has preferable lipophilic-hydrophobic property, together
When have the function that to form coating because of rosin resin so that its coating filled has etch-proof effect, but is used for filled PVC
Thixotropy is poor during plasticized paste.
At present the surface modifying method of nano-calcium carbonate be difficult to assign the good thixotropy of PVC plasticized pastes that it is filled,
Higher yield value and rheological stability.
The content of the invention
The problem of present invention exists for existing nono calcium carbonate modified method, there is provided one kind is used to fill vehicle paint base use
The surface treatment method of the nano-calcium carbonate of PVC plasticized pastes.This method uses saturated fatty acid and ricinoleate ester sodium sulphate
Compounding mixture is surface-treated to nano-calcium carbonate, and the nano-calcium carbonate after processing can effectively improve filled PVC plasticising
The thixotropy of paste, yield value and rheological stability etc..
Present invention is primarily based on the realization of following principle：
Wet process surface treatment technique is carried out for nano-calcium carbonate of the particle diameter between 40~80 nm, uses saturated fat
The compounding mixture of fat acid and ricinoleate ester sodium sulphate is surface-treated to nano-calcium carbonate.
Saturated fatty acid can assign nano-calcium carbonate preferable oleophilic drainage performance, have very to most polymers system
Good compatibility, the mutual entanglement between Long carbon chain in its molecule can improve the thixotropy of PVC plasticized pastes to a certain extent.
Ricinoleate ester sodium sulphate is introduced in surface modifier, the carboxylic acid ion that the ester group in its molecule generates in the basic conditions
Can be with the calcium binding of calcium carbonate molecular surface, and the electrostatic interaction between the polarity sulfonic group and calcium ion in its molecule enters one
Step strengthens the covered effect of surface conditioning agent, increases the distance between calcium carbonate granule, effectively increase the dispersiveness of powder from
And improve the yield value and rheological stability of filled plasticized paste system.Simultaneously because the presence of the highly polar group of sulfonic group,
Physics crosslinking points, increase physical crosslinking density, enhancing are easily produced because of the interaction between polarity in filled polymer
The network structure formed between calcium carbonate and high polymer, while plasticized paste yield value is improved because its strong network structure can
To improve its rheological stability during storage.Therefore, through saturated fatty acid and ricinoleate ester sodium sulphate complex treatment
The PVC plasticized pastes of nanon calcium carbonatefilled can obtain good thixotropy, yield value, and rheological stability.
Specific technical scheme of the invention is as follows：
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）Nano-calcium carbonate slurries after carbonating are delivered in surface processing trough, control temperature at 50~80 DEG C,
Stir, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
2~4%, persistently stir 60~90min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent is by mass ratio
Saturated fatty acid and ricinoleate ester sodium sulphate composition for 1: 0.5~3；
（3）Modified calcium carbonate slurries obtained above are filtered again, it dry, pulverize and sieve, you can obtain product.
Above-described ricinoleate ester sodium sulphate is to be esterified the ricinoleate ester sodium sulfate salt that carbon atom number is 1 ~ 5,
One or more preferably in methyl ricinolcic acid sodium sulphate, castor oil acid ethyl ester sodium sulphate, castor oil acid butyl ester sodium sulphate.
Above-described saturated fatty acid is the saturated fatty acid that carbon atom number is 18~22, preferably stearic acid, flower
One or more in raw acid, behenic acid.
Preferably, the specific surface area of above-described nano-calcium carbonate is 20-25m2/g。
The preparation method of above-described surface conditioning agent, comprises the following steps：Hydrogen is added in 95~100 DEG C of hot water
Sodium oxide molybdena or potassium hydroxide, addition are the 10~17% of saturated fatty acid dosage, and fully adding saturated fatty acid after dissolving enters
Row saponification, ricinoleate ester sodium sulphate is eventually adding, after being sufficiently stirred, obtains surface conditioning agent.
Compared with prior art, beneficial effects of the present invention：
1st, this method carries out wet method surface using saturated fatty acid and ricinoleate ester sodium sulphate compounding to nano-calcium carbonate
Processing, the nano-calcium carbonate of gained can effectively improve thixotropy, yield value and rheological stability of filled PVC plasticized paste etc..
2nd, the nano-calcium carbonate by this method surface treatment is filled applied to PVC plasticized pastes, and the plasticized paste of gained is touched
Become anchor ring product as 2.01 × 104~3.30 × 104 Pa/S, yield value are 189~316Pa, and viscosity is 4894~6548mPaS,
Its performance is superior to single saturated fatty acid and is modified.
3rd, this method technique is simple, and cost is low, and operation is easy, is suitable for industrial production, have preferable economic benefit and
Social benefit.
Brief description of the drawings
Fig. 1 is product viscosity change curve；
Identified in figure：1st, 2,3 be respectively embodiment 1, embodiment 2 and comparative example 1 be applied to prepare PVC plasticized pastes when
Product viscosity changes with time with standing time change curve.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but is not limited to protection scope of the present invention.
The preparation of nano-calcium carbonate slurries described in following examples after carbonating：
（1）Milk of lime after refined, ageing 36-72h is diluted, proportion is adjusted to 1.055-1.070, controls the temperature to be
20-26 DEG C, it is then delivered to the bubbling carbonizing tower with stirring；
（2）It is passed through the kiln gas after purification, cooling and carries out carbonation reaction, kiln gas flow is 6-10m3/h, carbon dioxide body
Product content is 25-35%, when reaction solution pH is dropped to below 7.0, continues to be passed through kiln gas and crosses carbonization 10min, carbonation reaction is complete
Into ripe slurry specific surface area control is 20-25m2/g。
Embodiment 1
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）To specific surface area be 21.3m after carbonating2/ g nano-calcium carbonate slurries are delivered in surface processing trough,
Temperature is controlled to stir at 50 DEG C, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
2.5%, persistently stir 90min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent be by mass ratio be 1:1
Stearic acid and methyl ricinolcic acid sodium sulphate composition；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 110 DEG C, is crushed, and finally crosses 100 mesh sieves, that is, obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 95 DEG C of hot water, is added
Enter 12% that amount is stearic acid dosage, fully adding stearic acid after dissolving carries out saponification, is eventually adding methyl ricinolcic acid
Sodium sulphate, after being sufficiently stirred, obtain surface conditioning agent.
Embodiment 2
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）To specific surface area be 22.8m after carbonating2/ g nano-calcium carbonate slurries are delivered in surface processing trough,
Temperature is controlled to stir at 60 DEG C, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
2%, persistently stir 80min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent be by mass ratio be 1:2
Arachidic acid and castor oil acid ethyl ester sodium sulphate composition；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 100 DEG C, is crushed, and finally crosses 100 mesh sieves, that is, obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 95 DEG C of hot water, is added
Enter 10% that amount is arachidic acid dosage, fully adding arachidic acid after dissolving carries out saponification, is eventually adding castor oil acid ethyl ester
Sodium sulphate, after being sufficiently stirred, obtain surface conditioning agent.
Embodiment 3
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）To specific surface area be 21.5m after carbonating2/ g nano-calcium carbonate slurries are delivered in surface processing trough,
Temperature is controlled to stir at 70 DEG C, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
3.5%, persistently stir 70min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent be by mass ratio be 1:3
Behenic acid and castor oil acid ethyl ester sodium sulphate composition；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 90 DEG C, is crushed, and finally crosses 100 mesh sieves, that is, obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 100 DEG C of hot water,
Addition is the 15% of behenic acid dosage, and fully adding behenic acid after dissolving carries out saponification, is eventually adding castor oil acid second
Ester sodium sulphate, after being sufficiently stirred, obtain surface conditioning agent.
Embodiment 4
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）To specific surface area be 24.8m after carbonating2/ g nano-calcium carbonate slurries are delivered in surface processing trough,
Temperature is controlled to stir at 80 DEG C, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
4%, persistently stir 60min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent be by mass ratio be 1:0.5
Stearic acid, behenic acid and castor oil acid butyl ester sodium sulphate composition, wherein the mass ratio of stearic acid and behenic acid be 1:3；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 100 DEG C, is crushed, and finally crosses 100 mesh sieves, that is, obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 100 DEG C of hot water,
Addition is the 17% of saturated fatty acid dosage, and fully adding saturated fatty acid after dissolving carries out saponification, is eventually adding castor
Sesame oil acid butyl ester sodium sulphate, after being sufficiently stirred, obtains surface conditioning agent.
Embodiment 5
A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, comprises the following steps：
（1）To specific surface area be 22.3m after carbonating2/ g nano-calcium carbonate slurries are delivered in surface processing trough,
Temperature is controlled to stir at 75 DEG C, obtain nano-calcium carbonate suspension slurry；
（2）Surface conditioning agent is added under stirring, the wherein addition of surface conditioning agent is calcium carbonate butt quality
3%, persistently stir 70min, complete nano-calcium carbonate surface be modified；Described surface conditioning agent be by mass ratio be 1:1
Stearic acid and castor oil acid diethylene glycol dilaurate sodium sulphate composition；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 90 DEG C, is crushed, and finally crosses 100 mesh sieves, that is, obtains nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 100 DEG C of hot water,
Addition is the 12% of stearic acid dosage, and fully adding stearic acid after dissolving carries out saponification, is eventually adding castor oil acid second
Glycol ethoxylate Bis-sodium Sulfate, after being sufficiently stirred, obtain surface conditioning agent.
Comparative example 1
（1）To specific surface area be 21.3m after carbonating2/ g nano-calcium carbonate slurries are delivered to surface processing trough
In, control temperature stirs at 50 DEG C, obtains nano-calcium carbonate suspension slurry；
（2）Stearic acid surface inorganic agent is added under stirring, wherein stearic addition is calcium carbonate dry matrix
The 2.5% of amount, persistently stirs 90min, and the surface for completing nano-calcium carbonate is modified；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 110 DEG C, crushes, finally crossed 100 mesh sieves, that is, obtain nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 95 DEG C of hot water, is added
Enter 12% that amount is stearic acid dosage, fully adding stearic acid after dissolving carries out saponification, after being sufficiently stirred, obtains surface
Inorganic agent.
Comparative example 2
（1）To specific surface area be 21.3m after carbonating2/ g nano-calcium carbonate slurries are delivered to surface processing trough
In, control temperature stirs at 50 DEG C, obtains nano-calcium carbonate suspension slurry；
（2）Methyl ricinolcic acid sodium sulphate surface conditioning agent, wherein methyl ricinolcic acid sulfuric acid are added under stirring
The addition of sodium is the 2.5% of calcium carbonate butt quality, persistently stirs 90min, and the surface for completing nano-calcium carbonate is modified；
（3）The modified nano-calcium carbonate slurries in surface are subjected to filter-press dehydration processing, dried using chain belt drying machine
Dry, drying temperature is 110 DEG C, crushes, finally crossed 100 mesh sieves, that is, obtain nano-calcium carbonate calcium product of the present invention.
The preparation method of above-described surface conditioning agent, step are as follows：Sodium hydroxide is added in 95 DEG C of hot water, is added
Enter 12% that amount is methyl ricinolcic acid sodium sulphate dosage, fully adding methyl ricinolcic acid sodium sulphate after dissolving carries out saponification
Reaction, after being sufficiently stirred, obtains surface conditioning agent.
Embodiment and the application test of comparative example product
The nano-calcium carbonate calcium product that each embodiment and comparative example are obtained is applied to PVC plasticized pastes and filled according to a conventional method,
The specific formula for preparing PVC plasticized pastes is as shown in table 1.Each embodiment and PVC plasticized paste performances obtained by comparative example are as shown in table 2.
Table 1：PVC formulation of plastisol
| Component | Mass percent（%） |
| PVC paste resin | 27 |
| Blending resin | 15 |
| Nano-calcium carbonate | 20 |
| Dioctyl phthalate | 38 |
Table 2：PVC plasticized paste performance products performances
| Sample | Thixotropic loop area/(Pa/S) | Yield value/Pa | Viscosity/(mPaS) |
| Embodiment 1 | 27340.3 | 295 | 4546 |
| Embodiment 2 | 20135.0 | 289 | 4646 |
| Embodiment 3 | 28432.9 | 198 | 4894 |
| Embodiment 4 | 33059.1 | 316 | 5352 |
| Embodiment 5 | 28974.1 | 301 | 6317 |
| Comparative example 1 | 9673.1 | 87 | 5844 |
| Comparative example 2 | 10692.0 | 128 | 4450 |
For thixotropic loop area to be measured using rotational rheometer, yield value is that thixotroping ring test first paragraph curve is entered in upper table
Row Ben-Hur linear fit and obtain, viscosity is measured using Brookfield viscosimeters.All samples are tested after placing 1d.From
As can be seen that carrying out surface-treatment applications to nano-calcium carbonate using saturated fatty acid and ricinoleate ester sodium sulphate compounding in table
When PVC plasticized pastes are prepared, the performance of product is superior to single saturated fatty acid or the surface treatment of ricinoleate ester sodium sulphate.
By the PVC plasticized pastes of embodiment 1,2 and the gained of comparative example 1 place respectively 0d, 2d, 5d, 10d, 15d, 20d,
30d, 45d, the change curve of measured viscosity are as shown in Figure 1.Obtained from testing result, by using saturated fatty acid and castor
Butylricinoleate sodium sulphate compounding carries out surface to nano-calcium carbonate, and the stability of the PVC plasticized paste products of preparation is preferable, and adopts
Poor with single saturated fatty acid Treatment Stability, the viscosity of product increases and increased over time.
Claims (3)
- A kind of 1. surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste, it is characterised in that：Comprise the following steps：（1）Nano-calcium carbonate slurries after carbonating are delivered in surface processing trough, control temperature is at 50~80 DEG C, stirring Uniformly, nano-calcium carbonate suspension slurry is obtained；（2）Add surface conditioning agent under stirring, wherein the addition of surface conditioning agent for calcium carbonate butt quality 2~ 4%, 60~90min is persistently stirred, the surface for completing nano-calcium carbonate is modified；（3）Modified calcium carbonate slurries obtained above are filtered again, it dry, pulverize and sieve, you can obtain product；Described surface conditioning agent is made up of the saturated fatty acid and ricinoleate ester sodium sulphate that mass ratio is 1: 0.5~3；Described ricinoleate ester sodium sulphate is to be esterified the ricinoleate ester sodium sulfate salt that carbon atom number is 1 ~ 5, including castor-oil plant One or more in methyl oleate sodium sulphate, castor oil acid ethyl ester sodium sulphate, castor oil acid butyl ester sodium sulphate；Described saturated fatty acid is the saturated fatty acid that carbon atom number is 18~22, including stearic acid, arachidic acid, behenic acid In one or more.
- 2. a kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste according to claim 1, its feature exist In：The specific surface area of described nano-calcium carbonate is 20-25m2/g。
- 3. a kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste according to claim 1, its feature exist In：The preparation method of described surface conditioning agent, comprises the following steps：Add sodium hydroxide or potassium hydroxide in 95~100 DEG C of hot water, addition for saturated fatty acid dosage 10~ 17%, fully add saturated fatty acid after dissolving and carry out saponification, be eventually adding ricinoleate ester sodium sulphate, be sufficiently stirred Afterwards, surface conditioning agent is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510946405.9A CN105400238B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510946405.9A CN105400238B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105400238A CN105400238A (en) | 2016-03-16 |
| CN105400238B true CN105400238B (en) | 2018-02-16 |
Family
ID=55466015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510946405.9A Active CN105400238B (en) | 2015-12-17 | 2015-12-17 | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105400238B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675110A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | High-activity nano-calcium carbonate |
| CN107936620A (en) * | 2017-10-18 | 2018-04-20 | 英德市日昇矿业有限公司 | A kind of shutter leaf modified heavy calcium carbonate and preparation method thereof |
| CN110229542A (en) * | 2019-07-22 | 2019-09-13 | 恩平燕怡新材料有限公司 | A kind of PVC pipe nm-class active calcium carbonate and preparation method thereof, PVC pipe |
| CN112592084A (en) * | 2021-01-16 | 2021-04-02 | 张家界恒亮新材料科技有限公司 | Preparation method of stone-like paint aggregate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451023A (en) * | 2007-12-04 | 2009-06-10 | 比亚迪股份有限公司 | Surface modified nano calcium carbonate and polychloroethylene plastisol thereof |
| CN102516821A (en) * | 2011-12-20 | 2012-06-27 | 广西华纳新材料科技有限公司 | Surface modification method of nano-grade calcium carbonate used in room-temperature vulcanized silicone adhesive |
| CN103013181A (en) * | 2012-11-27 | 2013-04-03 | 宜兴天力化工纳米科技有限公司 | Surface treatment method of nano calcium carbonate |
| CN104479411A (en) * | 2014-11-25 | 2015-04-01 | 广西华纳新材料科技有限公司 | Surface modification method of special nano calcium carbonate for silicone sealants |
| CN104497633A (en) * | 2014-11-25 | 2015-04-08 | 广西华纳新材料科技有限公司 | Nano calcium carbonate surface treatment method |
-
2015
- 2015-12-17 CN CN201510946405.9A patent/CN105400238B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451023A (en) * | 2007-12-04 | 2009-06-10 | 比亚迪股份有限公司 | Surface modified nano calcium carbonate and polychloroethylene plastisol thereof |
| CN102516821A (en) * | 2011-12-20 | 2012-06-27 | 广西华纳新材料科技有限公司 | Surface modification method of nano-grade calcium carbonate used in room-temperature vulcanized silicone adhesive |
| CN103013181A (en) * | 2012-11-27 | 2013-04-03 | 宜兴天力化工纳米科技有限公司 | Surface treatment method of nano calcium carbonate |
| CN104479411A (en) * | 2014-11-25 | 2015-04-01 | 广西华纳新材料科技有限公司 | Surface modification method of special nano calcium carbonate for silicone sealants |
| CN104497633A (en) * | 2014-11-25 | 2015-04-08 | 广西华纳新材料科技有限公司 | Nano calcium carbonate surface treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105400238A (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105400238B (en) | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste | |
| CN103897434B (en) | The preparation method that plastic master batch is Nano calcium carbonate dedicated | |
| CN104497633B (en) | Nano calcium carbonate surface treatment method | |
| CN102174275B (en) | Surface modification method for nano calcium carbonate | |
| CN102516821B (en) | Surface modification method of nano-grade calcium carbonate used in room-temperature vulcanized silicone adhesive | |
| CN103613955B (en) | Method for preparing special nano calcium carbonate (nano-CaCO3) for vehicle adhesive | |
| CN106700657B (en) | A kind of surface treatment method of thermostable silicone glue nano-calcium carbonate | |
| CN112724708B (en) | Surface treatment method of nano calcium carbonate for impact-resistant automobile chassis coating | |
| CN104087028B (en) | The preparation method that a kind of PVC advertisement film is Nano calcium carbonate dedicated | |
| CN101475759A (en) | Practical method for preparing high thixotropy surface treating nano calcium carbonate | |
| CN103665937B (en) | Method for preparing nano calcium carbonate specially used for middle and top grade silicone sealants | |
| CN109456740A (en) | Modified magnetic nano thickening agent of a kind of hydrophobic associated polymer and preparation method thereof | |
| CN104403433B (en) | The preparation method of the special winnofil of PVC stone-impact-proof paint | |
| CN109651975B (en) | Preparation method of nano calcium carbonate for double-component silane modified polyether sealant | |
| CN106928753A (en) | A kind of preparation method for PVC automobile chassis stone-impact-proof paint modified calcium carbonates | |
| CN102701255A (en) | Method for high-concentration carbonization production of spherical nano calcium carbonate | |
| CN106752102A (en) | A kind of preparation method of the high-dispersion nano calcium carbonate for being applied to nylon engineering plastic | |
| CN103289525B (en) | A kind of high rigidity powdery paints | |
| CN106277014A (en) | The method that dispersion surface modification prepares active superfine calcium carbonate in advance | |
| CN104479411A (en) | Surface modification method of special nano calcium carbonate for silicone sealants | |
| CN108929571A (en) | A kind of preparation of PVC weld seam glue nanometer calcium carbonate | |
| CN108676496A (en) | A kind of novel environment friendly water-repellent paint and preparation method thereof | |
| CN109486297B (en) | White fluorocarbon finish paint and preparation process thereof | |
| CN107739530A (en) | A kind of special high thixotropic nano calcium carbonate preparation method of coating | |
| CN105217673B (en) | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 530103 No.29, Ganwei street, Ganwei Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Warner New Material Co.,Ltd. Address before: 530103 No.29, Ganwei street, Ganwei Town, Wuming County, Nanning City, Guangxi Zhuang Autonomous Region Patentee before: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A kind of surface treatment method of nano calcium carbonate filled with PVC plastisol Effective date of registration: 20220811 Granted publication date: 20180216 Pledgee: Nanning Branch of China Everbright Bank Co.,Ltd. Pledgor: Guangxi Warner New Material Co.,Ltd. Registration number: Y2022450000133 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20180216 Pledgee: Nanning Branch of China Everbright Bank Co.,Ltd. Pledgor: Guangxi Warner New Material Co.,Ltd. Registration number: Y2022450000133 |