CN113087005A - Preparation method of cubic superfine calcium carbonate and preparation method of PVC (polyvinyl chloride) calendered film - Google Patents
Preparation method of cubic superfine calcium carbonate and preparation method of PVC (polyvinyl chloride) calendered film Download PDFInfo
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- CN113087005A CN113087005A CN202110441573.8A CN202110441573A CN113087005A CN 113087005 A CN113087005 A CN 113087005A CN 202110441573 A CN202110441573 A CN 202110441573A CN 113087005 A CN113087005 A CN 113087005A
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- Prior art keywords
- calcium carbonate
- hydroxide slurry
- mass
- calcium hydroxide
- carbonization
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 287
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 141
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 37
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000003490 calendering Methods 0.000 title claims abstract description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 128
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 128
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 128
- 239000002002 slurry Substances 0.000 claims abstract description 127
- 238000003763 carbonization Methods 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 42
- 238000000227 grinding Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 150000004645 aluminates Chemical class 0.000 claims description 19
- 235000012424 soybean oil Nutrition 0.000 claims description 19
- 239000003549 soybean oil Substances 0.000 claims description 19
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims description 3
- -1 acrylic acid-maleic acid ammonium salt Chemical compound 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- ZRGKYCBSAYCCTD-UAIGNFCESA-M sodium;(z)-but-2-enedioic acid;prop-2-enoate Chemical compound [Na+].[O-]C(=O)C=C.OC(=O)\C=C/C(O)=O ZRGKYCBSAYCCTD-UAIGNFCESA-M 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 22
- 239000000843 powder Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000006081 fluorescent whitening agent Substances 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 121
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100244540 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pop7 gene Proteins 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 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 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
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- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
The preparation method of the cubic ultrafine calcium carbonate comprises the following steps: firstly carbonizing calcium hydroxide slurry to obtain basic calcium carbonate cores when the carbonization rate is 15% -45%, adding secondary calcium hydroxide slurry, carrying out secondary carbonization to obtain a calcium carbonate dry base, heating the calcium carbonate dry base to 60-80 ℃, adding a coupling agent and a surface treating agent for activation treatment, and carrying out filter pressing, drying and crushing to obtain calcium carbonate dry powder; the preparation method of the PVC calendered film comprises the following steps: adding polyvinyl chloride resin, a plasticizer, a liquid stabilizer, rutile titanium dioxide, calcium carbonate, permanent violet and a fluorescent whitening agent in corresponding parts by mass into a high-speed mixer, stopping mixing when the temperature reaches 110 ℃ to obtain a premix, adding the premix into a double-roller open mill to prepare a mixture, and stretching and drawing the mixture to prepare the PVC calendered film. The PVC calendering film prepared by adopting the superfine calcium carbonate prepared by the invention has good processing performance, dispersibility and ink absorption performance.
Description
Technical Field
The invention relates to the technical field of preparation and application of superfine calcium carbonate, in particular to a preparation method of cubic superfine calcium carbonate and a preparation method of a PVC (polyvinyl chloride) calendered film.
Background
PVC calendered products are developed at home, and are mainly applied to the fields of greenhouse films, lamp box advertising films, inflatable toy films, anti-seepage geomembranes, grain storage films, packaging films, salt films, industrial films, tablecloth films, floor leathers, artificial leather, welt cloth leathers, waterproof coiled materials and the like. Some films need to be painted and printed outside, such as: advertisement cloth, packaging films, wood grain films, wallpaper, rain cape cloth and the like, so the ink absorption of the film is good, and printing ink is required to be bright in color, attractive and elegant in appearance, free of precipitation and the like.
The common fillers of the calendered film comprise heavy calcium carbonate, light calcium carbonate, nano calcium carbonate and the like, the heavy calcium carbonate is produced by grinding crystallized calcite, the heavy calcium carbonate is widely applied to PVC products due to low cost, the heavy calcium carbonate usually comprises irregular particles of 1-20 microns, the material distribution is wide, the particles are coarse, and the prepared product has low strength, poor gloss and poor ink absorption. The light calcium is precipitated calcium carbonate prepared by introducing CO2 into lime milk, consists of spindle sheet particles of 0.5-6 microns, and is low in strength and poor in gloss; the nano calcium carbonate is precipitated calcium carbonate prepared by introducing CO2 into lime milk under a controlled reaction condition, is composed of cubic particles of 0.02-0.1 micron, has small particle size and large surface energy, is easy to generate hard agglomeration in the drying and application processes, is particularly used for calendering films and the like, because the films are very thin, white spots and pinholes which are visible to naked eyes are generated in the presence of agglomeration, the appearance of products is influenced, and if the surface treatment process is not suitable, the defects of poor ink absorbability and the like are caused.
In the prior art, patent No. CN201310642377.2 discloses a preparation method of nano calcium carbonate special for a calendered film, limestone is used as a raw material, after carbonization, a composite activating agent is added for activation, and nano active calcium carbonate is obtained after dehydration, drying, crushing and classification.
In the prior art, patent No. CN201610995731.3 discloses a surface-modified nano calcium carbonate, which is composed of the following components in parts by mass: 550 parts of 500-doped nano calcium carbonate base material, 4-5 parts of potassium pyrophosphate, 2-3 parts of itaconic acid, 5-6 parts of basic magnesium carbonate, 4-5 parts of anhydrous calcium chloride, 3-4 parts of phosphorus pentoxide, 2-4 parts of anhydrous sodium sulfite, 1-2 parts of amino acid, 2-3 parts of sulfamic acid and 2-4 parts of disodium ethylene diamine tetraacetate, 1-2 parts of alanine, 2-3 parts of phthalimide, 1-2 parts of sorbitol, 2-3 parts of sodium hexametaphosphate, 3-4 parts of sodium benzoate, 4-5 parts of dodecyl dimethyl betaine, 4-5 parts of dodecyl dihydroxyethyl betaine, 4-5 parts of lauroyl amido propyl betaine, 1-2 parts of proline and 3-5 parts of allyl polyoxyethylene ether. The surface-modified nano calcium carbonate is prepared by adopting a brand-new surface modifier, and by adding the surface modifiers with different component proportions, the problem that the nano calcium carbonate is difficult to color when being applied to a rolling film and an edge sealing strip is solved, and the effect of easy ink absorption is achieved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation method of cubic superfine calcium carbonate, so that the prepared calcium carbonate powder particles are more uniform, the dispersibility is good, secondary aggregates are fewer, and compared with heavy calcium and light calcium, the strength is better, the gloss is better, and the processing performance is good; the preparation method of the PVC calendered film is also provided, so that the prepared calendered film has good mechanical property, luster and good ink absorption performance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of cubic superfine calcium carbonate comprises the following steps:
s1, preparing calcium hydroxide slurry: adding a dispersing agent into the calcium hydroxide slurry with the mass concentration of 10% -25%, and then grinding to obtain calcium hydroxide slurry;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be kept at 15-30 ℃, keeping the mass concentration at 6-12%, then adding a crystal form control agent, and introducing purified kiln gas containing CO2 to carry out carbonization;
s3, secondary carbonization, namely adding the secondary calcium hydroxide slurry obtained in the step S1 into the dry basis of the primary calcium hydroxide slurry when the carbonization rate is 15-45%, further carbonizing, and stopping carbonization when the pH value reaches 7-7.5;
s4, modification preparation: and heating the carbonized cooked slurry to 60-80 ℃, adding a water-soluble grinding aid, strongly stirring for 10min-30min, then adding an aluminate coupling agent, continuously stirring for 10min-30min, then adding a surface treating agent, continuously stirring for 60min-120min, and carrying out filter pressing, drying, crushing and packaging to obtain the finished product of the superfine calcium carbonate.
Preferably, the calcium hydroxide slurry obtained in the step S1 has an average particle diameter D50 ≤ 3 μm and a D97 ≤ 8 μm.
Preferably, the mass of the dispersant accounts for 0.1-1.0% of the mass of the calcium hydroxide slurry.
Preferably, the dispersant is one or a mixture of two or more of acrylic acid homopolymer, acrylic acid copolymer, acrylic acid sodium salt, acrylic acid ammonium salt, acrylic acid-maleic acid homopolymer, acrylic acid-maleic acid copolymer, acrylic acid-maleic acid sodium salt, acrylic acid-maleic acid ammonium salt, polyepoxysuccinic acid homopolymer, polyepoxysuccinic acid copolymer, polyepoxysuccinic acid sodium salt and polyepoxysuccinic acid ammonium salt.
Preferably, the calcium hydroxide slurry is put into an in-line emulsifying machine, a wet vertical sand mill or a wet horizontal sand mill for grinding in step S1.
Preferably, the crystal form control agent is one or a mixture of more than two of sulfuric acid, zinc sulfate, sodium sulfate and aluminum sulfate, and the mass of the crystal form control agent accounts for 0.3-1.5% of the mass of the primary calcium hydroxide slurry.
Preferably, the temperature of the secondary calcium hydroxide slurry added in the step S3 is 10 ℃ to 25 ℃, the mass concentration is 2% to 8%, and the mass of the secondary calcium hydroxide slurry accounts for 20% to 100% of the dry basis mass of the primary calcium hydroxide slurry.
Preferably, the mass of the water-soluble grinding aid accounts for 0.2-1.0% of the dry mass of the calcium carbonate, and the mass of the aluminate coupling agent accounts for 0.3-1.5% of the dry mass of the calcium carbonate.
Preferably, the surface treating agent is one or a mixture of two of sodium dodecyl benzene sulfonate and epoxidized soybean oil, the mass of the sodium dodecyl benzene sulfonate accounts for 0.5-2.0% of the mass of the dry calcium carbonate base, and the mass of the epoxidized soybean oil accounts for 0.5-2.0% of the mass of the dry calcium carbonate base.
The preparation method of the PVC calendered film comprises the following steps:
s10: adding the following raw materials in parts by mass into a high-speed mixer, wherein 100 parts of polyvinyl chloride resin, 36 parts of plasticizer, 2 parts of liquid stabilizer, 6 parts of rutile titanium dioxide, 60 parts of calcium carbonate prepared by the preparation method of cubic ultrafine calcium carbonate, 0.7 part of permanent violet and 0.1 part of fluorescent brightener are mixed to obtain a premix when the working temperature of the high-speed mixer reaches 110 ℃;
s20: adding the premix into a double-roller open mill, controlling the working temperature of the double-roller open mill to be 170-180 ℃, and mixing 10min-15min to prepare a mixture;
s30: and (3) adjusting the distance between two rollers of the two-roller open mill to be 18mm, and stretching and drawing the mixture to prepare a polyvinyl chloride rolled film (PVC rolled film).
After the technical scheme is adopted, the invention has the beneficial effects that:
1. the preparation method of cubic superfine calcium carbonate comprises the steps of grinding calcium hydroxide slurry, controlling the particle size, performing primary carbonization to obtain a primary carbonized calcium hydroxide slurry dry basis when the carbonization rate reaches 15-45%, adding secondary calcium hydroxide slurry, performing secondary carbonization to obtain a calcium carbonate dry basis, heating the carbonized calcium carbonate dry basis to 60-80 ℃, adding a coupling agent and a surface treating agent for activation treatment, and performing filter pressing, drying and crushing to obtain the superfine calcium carbonate. The obtained calcium carbonate powder has the advantages of uniform particles, better dispersibility, less secondary aggregates, less dosage of the required surface treating agent, better strength and better luster compared with heavy calcium and light calcium, good processability, simple production process and low preparation cost.
2. According to the preparation method of the PVC calendered film, the calcium carbonate prepared by the preparation method of the cubic superfine calcium carbonate is adopted, and the prepared calendered film has good mechanical property, luster and good ink absorption performance.
Drawings
FIG. 1 is a scanning electron microscope analysis of the crystal nuclei of the basic calcium carbonate prepared in example one;
FIG. 2 is a scanning electron microscope analysis chart of the finished product of ultrafine calcium carbonate prepared in the first embodiment;
FIG. 3 is a scanning electron microscope analysis of the crystal nuclei of the basic calcium carbonate prepared in example two;
FIG. 4 is a scanning electron microscope analysis chart of the finished product of ultrafine calcium carbonate prepared in example two;
FIG. 5 is a scanning electron microscope analysis of the crystal nuclei of the basic calcium carbonate prepared in example III;
FIG. 6 is a scanning electron microscope analysis chart of the finished product of ultrafine calcium carbonate prepared in example III;
FIG. 7 is a scanning electron microscope analysis chart of the nano calcium carbonate finished product prepared in the first comparative example;
FIG. 8 is a scanning electron microscope analysis chart of the nano calcium carbonate finished product prepared in comparative example II;
FIG. 9 is a scanning electron microscope analysis chart of the spindle calcium carbonate finished product prepared in comparative example three.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The first embodiment is as follows:
a preparation method of cubic superfine calcium carbonate comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9000 type dispersing agent into 14% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle size analyzer to obtain the calcium hydroxide slurry with the average particle size D50 of 2.1 mu m and D97 of 6 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 22 ℃ and the mass concentration of the primary calcium hydroxide slurry to be 8%, then adding a crystal form control agent which is 5% sulfuric acid and accounts for 0.4% of the dry basis mass of the primary calcium hydroxide slurry, and then introducing purified kiln gas containing CO2 and 28% of the dry basis mass of the primary calcium hydroxide slurry to be carbonized;
s3, secondary carbonization, namely when the carbonization rate is 20%, obtaining basic calcium carbonate crystal nuclei with the short diameter of 0.01 micrometer and the long diameter of 0.3 micrometer as shown in figure 1, then adding the secondary calcium hydroxide slurry obtained in the step S1 into the dry basis of the primary calcium hydroxide slurry, adjusting the temperature of the secondary calcium hydroxide slurry to 20 ℃ in advance and the concentration of the secondary calcium hydroxide slurry to be 5%, wherein the mass of the secondary calcium hydroxide slurry accounts for 30% of the mass of the dry basis of the primary calcium hydroxide slurry, further carbonizing the secondary calcium hydroxide slurry, and when the carbonization reaches the pH value of 7.0, stopping carbonization to obtain the dry basis of calcium carbonate;
s4, modification preparation: heating calcium carbonate dry base to 70 ℃, adding a water-soluble grinding aid, wherein the grinding aid is an AD666 type grinding aid accounting for 0.3 percent of the mass of the calcium carbonate dry base, strongly stirring the mixture for 20min, and then adding aluminateThe coupling agent is DL-411-D type aluminate coupling agent accounting for 0.5 percent of the dry mass of calcium carbonate, the aluminate coupling agent is continuously stirred for 20min, then the surface treating agent is added, the surface treatment is carried out, the mixture of sodium dodecylbenzene sulfonate and epoxidized soybean oil is adopted, the mass of the sodium dodecylbenzene sulfonate accounts for 0.8 percent of the dry mass of calcium carbonate, the mass of the epoxidized soybean oil accounts for 1.0 percent of the dry mass of calcium carbonate, the surface treating agent is continuously stirred for 70 min, and the superfine calcium carbonate finished product shown in figure 2 is obtained after pressure filtration, drying, crushing and packaging, wherein the detected data values of the superfine calcium carbonate are as follows: water content is 0.35%; the whiteness is 96.3; BET adsorption specific surface area of 16.8m2(ii)/g; cubes with an average particle size of 0.2 microns and an oil absorption of 18gDop/100 g.
In step S1, the concentration of the calcium hydroxide slurry is usually 10% to 25%, and the concentration is too thick, which is not favorable for grinding and dispersing; the concentration is too dilute, the grinding efficiency is too low, and the economic efficiency is too low. The molecular weight of the dispersant is preferably in the range of 2000-; too high a molecular weight is detrimental to the grinding to the proper fineness and viscosity, causing flocculation. The mass of the dispersant accounts for 0.1 to 1.0 percent of the mass of the calcium hydroxide slurry, and the dosage is too small to reduce the viscosity; the use amount is too much, and flocculation is easy to generate. The grinding effect of step S1 was measured using a pop6 laser particle size analyzer of zhhai ohmak instruments ltd. The average grain diameter D50 of the obtained calcium hydroxide slurry is less than or equal to 3 mu m, D97 is less than or equal to 8 mu m, and if the grain diameter of the calcium hydroxide slurry is too coarse, the produced calcium carbonate has poor grain diameter distribution and dispersibility and is easy to agglomerate.
In step S2, the initial temperature of the calcium hydroxide slurry for the first time is 15-30 ℃, the temperature is too low, the reaction speed is too slow, and the cost is high; when the temperature is too high, the produced calcium carbonate particles are coarse, large particles are easily formed, and cubes cannot be formed. The mass concentration is kept between 6 and 12 percent, the concentration is too low, the yield is too low, and the cost is high; the concentration is too high, and the reaction is exothermic, so that the system temperature is easily too high, fine cubes cannot be obtained, and coarse particles with other crystal forms are generated. Adding crystal form control agent can easily form needle crystal nucleus with short diameter of 0.005-0.1 micron and long diameter of 0.5-5 micron, and make the following secondary slurry-supplementing reaction continuously react on the crystal nucleus to form large cube. The addition amount of the crystal form control agent accounts for 0.3-1.5% of the mass of the primary calcium hydroxide slurry, and a large amount of crystal nuclei are difficult to form due to the insufficient addition amount; too much addition amount and too fine particles are easy to cause agglomeration.
In step S3, the carbonization ratio is the degree of progress of the carbonization reaction, and is measured by detecting the contents of calcium hydroxide and calcium carbonate during the carbonization process, as represented by the ratio of the amount of the reacted calcium hydroxide in the suspension to the amount of the calcium hydroxide in the original suspension. The temperature of the secondary calcium hydroxide slurry is 10-25 ℃, the mass concentration is 2-8%, and the mass of the secondary calcium hydroxide slurry accounts for 20-100% of the dry basis mass of the primary calcium hydroxide slurry. The addition amount of the secondary calcium hydroxide slurry is too small, the original particle size and crystal form are difficult to change, and the formed calcium carbonate particles are too small to form large particle size; the addition amount is too large, and coarse particles are easily formed. The temperature of the secondary calcium hydroxide slurry is too low, the cost is wasted, and the reaction speed is slow; when the temperature is too high, coarse particles are easily formed. The concentration of the secondary calcium hydroxide slurry is too low, so that the cost is wasted; too high concentration results in uneven dispersion of the slurry and uneven particle distribution.
In the step S4, the water-soluble grinding aid has the novel environment-friendly composite modifier integrating multiple functions of grinding aid, dispersion, coupling, plasticization and crosslinking, and can well disperse and wet an interface through in-situ modification, so that the functionality of the powder is improved, the oil absorption value is reduced, particles are dispersed, and the plasticization effect of the powder in plastics is enhanced. The aluminum coupling agent can obviously improve the compatibility of calcium carbonate and polyolefin, and the polyolefin plastic filled with calcium carbonate and the product thereof have good melt flow rate, elongation at break, impact strength and surface gloss. The surface treating agent of the embodiment adopts a mixture of sodium dodecyl benzene sulfonate and epoxidized soybean oil, and the superfine calcium carbonate can be coated and dispersed by adding the sodium dodecyl benzene sulfonate, and the epoxidized soybean oil is emulsified, so that the calcium carbonate has good ink absorption when being used for a PVC calendering film; the epoxy soybean oil is coated and dispersed with the superfine calcium carbonate, so that the oil absorption value of the superfine calcium carbonate can be reduced, and the epoxy soybean oil has good intermiscibility with a PVC calendering film, so that when the calcium carbonate is used for the PVC calendering film, the discharging is uniform, and the film is flat. The dosage of the sodium dodecyl benzene sulfonate is 0.5 to 2.0 percent of the dry mass of the calcium carbonate; the dosage of the epoxidized soybean oil is 0.5 to 2.0 percent of the dry mass of the calcium carbonate. The surface treating agent is too little to coat calcium carbonate, so that the dispersibility is poor, the dosage is too large, the cost is wasted, and the heat resistance is poor.
The indexes of the calcium carbonate powder obtained in the step S4 are required to meet the following requirements: the water content is less than or equal to 0.5 percent; the whiteness is 95-97; the BET adsorption method has a specific surface area of 5m2/g-18m2(ii)/g; cubes having an average particle size of from 0.1 to 1 μm and an oil absorption of from 15gdop/100g to 23gdop/100 g. If the moisture content of the calcium carbonate powder is too high, cavities and bubbles are easy to appear in the calendered film; if the whiteness is too low, color matching is not good, and particularly, light-color and white films are produced, so that the vividness is influenced; the BET nitrogen adsorption method has over-small specific surface area and over-large particle size, which affects the strength and smoothness of the surface of the calendered film, and has low gloss, so that the printing effect is not vivid and the resolution is poor; the BET nitrogen adsorption method has overlarge specific surface area and undersize particle size, so that the processing performance of PVC is poor and the PVC is easy to agglomerate; if the oil absorption value is too small, the plasticizer in the PVC calendered film is easy to separate out, so that the ink absorption is poor, the oil absorption value is too large, the processability is poor, a smooth film is not easy to form, and the appearance is influenced.
Example two:
a preparation method of cubic superfine calcium carbonate comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9002 type dispersing agent into 15% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle size analyzer to obtain the calcium hydroxide slurry with the average particle size D50 of 1.7 mu m and D97 of 5.5 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 25 ℃ and the mass concentration to be 9%, then adding a crystal form control agent, wherein the crystal form control agent is 10% aluminum sulfate and accounts for 0.5% of the dry basis mass of the primary calcium hydroxide slurry, and then introducing purified kiln gas containing CO2 and 30% of the dry basis mass to carry out carbonization;
s3, secondary carbonization, namely when the carbonization rate is 30%, obtaining basic calcium carbonate crystal nuclei with the short diameter of 0.01 micrometer and the long diameter of 0.25 micrometer as shown in the figure 3, then adding the secondary calcium hydroxide slurry obtained in the step S1 into the dry basis of the primary calcium hydroxide slurry, adjusting the temperature of the secondary calcium hydroxide slurry to 18 ℃ in advance and the concentration of the secondary calcium hydroxide slurry to be 4%, wherein the mass of the secondary calcium hydroxide slurry accounts for 60% of the mass of the dry basis of the primary calcium hydroxide slurry, further carbonizing the secondary calcium hydroxide slurry, and stopping carbonization when the pH value reaches 7.0 to obtain the dry basis of calcium carbonate;
s4, modification preparation: heating a calcium carbonate dry base to 70 ℃, adding a water-soluble grinding aid, wherein the grinding aid adopts an AD755 type grinding aid, accounts for 0.2 percent of the mass of the calcium carbonate dry base, strongly stirring the mixture for 20min, then adding an aluminate coupling agent, the aluminate coupling agent adopts a DL-411-D type aluminate coupling agent, accounts for 0.6 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 20min, then adding a surface treatment agent, performing surface treatment, and adopting a mixture of sodium dodecyl benzene sulfonate and epoxy soybean oil, the mass of the sodium dodecyl benzene sulfonate accounts for 0.5 percent of the mass of the calcium carbonate dry base, the mass of the epoxy soybean oil accounts for 0.8 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 90 min, and performing filter pressing, drying, crushing and packaging to obtain a finished product of the superfine calcium carbonate shown in figure 4, wherein the detected data values of the superfine calcium carbonate are as follows: water content is 0.35%; the whiteness is 96.5; BET adsorption specific surface area of 9.8m2(ii)/g; cubes with an average particle size of 0.4 microns and an oil absorption of 17gDop/100 g.
Example three:
a preparation method of cubic superfine calcium carbonate comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9300 type dispersant into 15% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle sizer to obtain the calcium hydroxide slurry with the average particle size D50 of 1.8 mu m and D97 of 5.8 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 28 ℃ and the mass concentration to be 9%, then adding a crystal form control agent which is zinc sulfate with the concentration of 10% and accounts for 0.6% of the dry basis mass of the primary calcium hydroxide slurry, and then introducing purified kiln gas containing CO2 with the concentration of 32% to carry out carbonization;
s3, secondary carbonization, namely when the carbonization rate is 35%, obtaining basic calcium carbonate crystal nuclei with the short diameter of 0.008 micrometer and the long diameter of 0.25 micrometer as shown in figure 5, then adding the secondary calcium hydroxide slurry obtained in the step S1 into the dry basis of the primary calcium hydroxide slurry, adjusting the temperature of the secondary calcium hydroxide slurry to 20 ℃ in advance and the concentration of the secondary calcium hydroxide slurry to be 5%, wherein the mass of the secondary calcium hydroxide slurry accounts for 80% of the mass of the dry basis of the primary calcium hydroxide slurry, further carbonizing the secondary calcium hydroxide slurry, and stopping carbonization when the pH value reaches 7.0 to obtain the dry basis of calcium carbonate;
s4, modification preparation: heating the dry calcium carbonate base to 75 ℃, adding a water-soluble grinding aid, wherein the grinding aid adopts JA-5 type grinding aid, accounts for 0.3 percent of the dry calcium carbonate base by mass, strongly stirring the mixture for 20min, then adding an aluminate coupling agent, wherein the aluminate coupling agent adopts DL-411-D type aluminate coupling agent which accounts for 0.5 percent of the dry mass of the calcium carbonate, continuously stirring for 20min, adding a surface treating agent, performing surface treatment by adopting a mixture of sodium dodecyl benzene sulfonate and epoxidized soybean oil, wherein the mass of the sodium dodecyl benzene sulfonate accounts for 0.6 percent of the mass of a calcium carbonate dry basis, the mass of the epoxidized soybean oil accounts for 0.6 percent of the mass of the calcium carbonate dry basis, and continuously stirring for 90 min, and performing filter pressing, drying, crushing and packaging to obtain the finished product of the superfine calcium carbonate shown in figure 6, wherein the detected data values of the superfine calcium carbonate are as follows: water content is 0.35%; the whiteness is 96.5; BET adsorption specific surface area of 8.4m2(ii)/g; cubes with an average particle size of 0.5 microns and an oil absorption of 16gDop/100 g.
Comparative example one:
the process for preparing calcium carbonate of this comparative example comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9000 type dispersing agent into 14% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle size analyzer to obtain the calcium hydroxide slurry with the average particle size D50 of 2.1 mu m and D97 of 6 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 22 ℃ and the mass concentration of the primary calcium hydroxide slurry to be 8%, then adding a crystal form control agent which is 5% sulfuric acid and accounts for 0.4% of the mass of the primary calcium hydroxide slurry dry basis, and then introducing purified kiln gas containing CO2 and 28% of the concentration of the kiln gas to carry out carbonization to obtain hydrochloric acid dry basis;
s3, modification preparation: heating a calcium carbonate dry base to 70 ℃, adding a water-soluble grinding aid, wherein the grinding aid adopts an AD666 type grinding aid which accounts for 0.3 percent of the mass of the calcium carbonate dry base, strongly stirring the mixture for 20min, then adding an aluminate coupling agent which adopts a DL-411-D type aluminate coupling agent and accounts for 0.5 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 20min, then adding a surface treating agent, performing surface treatment and adopting a mixture of sodium dodecyl benzene sulfonate and epoxy soybean oil, wherein the mass of the sodium dodecyl benzene sulfonate accounts for 0.8 percent of the mass of the calcium carbonate dry base, the mass of the epoxy soybean oil accounts for 1.0 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 70 min, and performing filter pressing, drying, crushing and packaging to obtain a calcium carbonate finished product shown in figure 7, wherein the detected data values of the calcium carbonate are as follows: water content is 0.36%; the whiteness is 96.2; BET adsorption specific surface area of 27.5m2(ii)/g; cubes with an average particle size of 0.07 microns and an oil absorption of 28gDop/100 g.
The difference between this comparative example and the first example is that the secondary calcium hydroxide slurry was not added and the secondary carbonization was not performed, and the nano calcium carbonate shown in fig. 7 was obtained.
Comparative example two:
the process for preparing calcium carbonate of this comparative example comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9000 type dispersing agent into 14% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle size analyzer to obtain the calcium hydroxide slurry with the average particle size D50 of 2.1 mu m and D97 of 6 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 22 ℃ and the mass concentration of the primary calcium hydroxide slurry to be 8%, then adding a crystal form control agent which is 5% sulfuric acid and accounts for 0.4% of the mass of the primary calcium hydroxide slurry dry basis, and then introducing purified kiln gas containing CO2 and 28% of the mass of the primary calcium hydroxide slurry to be carbonized to obtain a calcium carbonate dry basis;
s3, modification preparation: heating the calcium carbonate dry base to 70 ℃, then adding a surface treatment agent, carrying out surface treatment by adopting sodium stearate, wherein the mass of the sodium stearate accounts for 3.5 percent of the mass of the calcium carbonate dry base, continuously stirring for 70 min, carrying out filter pressing, drying, crushing and packaging to obtain a calcium carbonate finished product shown in figure 8, and detecting each data value of the superfine calcium carbonate as follows: water content is 0.36%; the whiteness is 96.5; BET adsorption specific surface area of 27.4m2(ii)/g; cubes with an average particle size of 0.07 microns and an oil absorption of 27gDop/100 g.
The difference between the comparative example and the first example is that no secondary calcium hydroxide slurry is added, no secondary carbonization is performed, and meanwhile, sodium stearate is used as the surface treatment agent, and no grinding aid and aluminate coupling agent are added, so that the nano calcium carbonate shown in FIG. 8 is obtained.
Comparative example three:
the process for preparing calcium carbonate of this comparative example comprises the following steps:
s1, preparing calcium hydroxide slurry: adding an Si nos9000 type dispersing agent into 14% calcium hydroxide slurry, grinding by using a vertical wet sand mill to obtain calcium hydroxide slurry, and detecting by using a laser particle size analyzer to obtain the calcium hydroxide slurry with the average particle size D50 of 2.1 mu m and D97 of 6 mu m or less;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be 22 ℃ and the mass concentration of the primary calcium hydroxide slurry to be 8%, then adding a crystal form control agent which is 5% sulfuric acid and accounts for 0.4% of the dry basis mass of the primary calcium hydroxide slurry, and then introducing purified kiln gas containing CO2 and 28% of the dry basis mass of the primary calcium hydroxide slurry to be carbonized;
s3, secondary carbonization, namely adding the secondary calcium hydroxide slurry obtained in the step S1 into the primary calcium hydroxide slurry dry base when the carbonization rate is 20%, adjusting the temperature of the secondary calcium hydroxide slurry to 20 ℃ in advance, adjusting the concentration of the secondary calcium hydroxide slurry to 5%, wherein the mass of the secondary calcium hydroxide slurry accounts for 150% of the mass of the primary calcium hydroxide slurry dry base, further carbonizing, and stopping carbonization when the pH value reaches 7.0 to obtain a calcium carbonate dry base;
s4, modification preparation: heating a calcium carbonate dry base to 70 ℃, adding a water-soluble grinding aid, wherein the grinding aid adopts an AD666 type grinding aid which accounts for 0.3 percent of the mass of the calcium carbonate dry base, strongly stirring the mixture for 20min, then adding an aluminate coupling agent which adopts a DL-411-D type aluminate coupling agent and accounts for 0.5 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 20min, then adding a surface treating agent, performing surface treatment and adopting a mixture of sodium dodecyl benzene sulfonate and epoxy soybean oil, wherein the mass of the sodium dodecyl benzene sulfonate accounts for 0.8 percent of the mass of the calcium carbonate dry base, the mass of the epoxy soybean oil accounts for 1.0 percent of the mass of the calcium carbonate dry base, continuously stirring the mixture for 70 min, and performing filter pressing, drying, crushing and packaging to obtain a calcium carbonate finished product shown in figure 9, wherein the detected data values of the superfine calcium carbonate are as follows: water content is 0.3%; the whiteness is 96.5; BET adsorption specific surface area of 4.8m2(ii)/g; oil absorption value is 18gDop/100 g; spindle calcium carbonate having a short diameter of 0.5 μm and a long diameter of 2.5. mu.m, and an average particle diameter of 1.5. mu.m.
The difference between this comparative example and the first example is that the secondary calcium hydroxide slurry added was 150% of the primary calcium hydroxide slurry on a dry basis, and spindle calcium carbonate as shown in FIG. 9 was obtained.
In the above examples and comparative examples, the laser particle size analyzer was a pop6 type laser particle size analyzer manufactured by Zhuhai Oumei Kerr instruments Co., Ltd; the dispersant is S i nos9000 type dispersant, Si nos9002 type dispersant and Si nos9300 type dispersant which are produced by Shandong Sono Si fine chemical Co., Ltd; the water-soluble grinding aid adopts AD666 type and AD755 type water-based grinding aid dispersants produced by Aoda environmental protection new material Co.Ltd in Dongguan and JA-5 grinding aid dispersants produced by Chongqing Jiashi technology development Co.Ltd; the aluminate coupling agent is DL-411-D type water-soluble aluminate coupling agent produced by Fujian university.
In conclusion, the preparation method of the cubic ultrafine calcium carbonate has the advantages of uniform calcium carbonate powder particles, better dispersibility, less secondary aggregates, less required surface treating agent consumption, simple production process and low preparation cost.
The application example is as follows:
the preparation method of the PVC calendered film comprises the following steps:
s10: adding the following raw materials in parts by mass into a high-speed mixer, wherein 100 parts of polyvinyl chloride resin (PVC), 36 parts of diisononyl phthalate plasticizer (D INP plasticizer), 2 parts of liquid stabilizer and 6 parts of rutile titanium dioxide, 60 parts of calcium carbonate prepared by the preparation methods of the calcium carbonate of the above examples and comparative examples, 0.7 part of permanent violet R and 0.1 part of fluorescent whitening agent are added, and when the working temperature of the high-speed mixer reaches 110 ℃, the mixing is stopped to obtain a premix;
s20: adding the premix into a double-roller open mill, controlling the working temperature of the double-roller open mill to be 170-180 ℃, and mixing 10min-15min to prepare a mixture;
s30: and (3) adjusting the distance between two rollers of the two-roller open mill to be 18mm, and stretching and drawing the mixture to prepare the polyvinyl chloride calendered film.
Wherein the polyvinyl chloride resin (PVC) adopts SG-5 type PVC produced by Xinjiang Tianye group Co., Ltd, the liquid stabilizer is a composite heat stabilizer, the rutile type titanium dioxide is R767 rutile type titanium dioxide, and the fluorescent brightener is OB-1.
The prepared PVC rolled film was tested, and the test data are shown in table 1. The glossiness of the rolled film is detected by a CS-300 glossiness meter and is detected by an angle of 60 degrees; detecting the dispersibility of the calendered film by naked eyes to check whether pores, pocks and pinholes exist; the ink absorption of the calendered film is tested by adopting an ink-jet test, and the more vivid and uniform the color of the calendered film after ink-jet is, the better the ink absorption is shown.
TABLE 1 Performance data Table for various PVC calendered films prepared with different calcium carbonates
As can be seen from Table 1, the ultrafine calcium carbonate prepared by the invention has good processability, and the prepared PVC calendered film has high glossiness, good dispersibility and ink absorption, low processing cost and good economic benefit.
The present invention is not limited to the above-described embodiments, and those skilled in the art will be able to make various modifications without creative efforts from the above-described conception, and fall within the scope of the present invention.
Claims (10)
1. The preparation method of cubic superfine calcium carbonate is characterized by comprising the following steps:
s1, preparing calcium hydroxide slurry: adding a dispersing agent into the calcium hydroxide slurry with the mass concentration of 10% -25%, and then grinding to obtain calcium hydroxide slurry;
s2, primary carbonization, namely, putting the primary calcium hydroxide slurry obtained in the step S1 into a carbonization kettle with a stirring function to be stirred, adjusting the temperature of the primary calcium hydroxide slurry to be kept at 15-30 ℃, keeping the mass concentration at 6-12%, then adding a crystal form control agent, and introducing purified kiln gas containing CO2 to carry out carbonization;
s3, secondary carbonization, namely adding the secondary calcium hydroxide slurry obtained in the step S1 into the primary calcium hydroxide slurry dry base when the carbonization rate is 15-45%, further carbonizing, and stopping carbonization when the pH value reaches 7-7.5 to obtain a calcium carbonate dry base;
s4, modification preparation: heating the carbonized calcium carbonate dry base to 60-80 ℃, adding a water-soluble grinding aid and strongly stirring for 10-30 min, then adding an aluminate coupling agent and continuously stirring for 10-30 min, then adding a surface treating agent and continuously stirring for 60-120 min, and obtaining a finished product of the superfine calcium carbonate through filter pressing, drying, crushing and packaging.
2. The method of claim 1, wherein the calcium hydroxide slurry obtained in step S1 has an average particle size of D50. ltoreq.3 μm, and D97. ltoreq.8 μm.
3. The method of claim 1, wherein the dispersant is present in an amount of 0.1 to 1.0% by weight based on the weight of the calcium hydroxide slurry.
4. The method for preparing cubic ultrafine calcium carbonate according to claim 1, wherein the dispersant is one or a mixture of two or more of acrylic acid homopolymer, acrylic acid copolymer, acrylic acid sodium salt, acrylic acid ammonium salt, acrylic acid-maleic acid homopolymer, acrylic acid-maleic acid copolymer, acrylic acid-maleic acid sodium salt, acrylic acid-maleic acid ammonium salt, polyepoxysuccinic acid homopolymer, polyepoxysuccinic acid copolymer, polyepoxysuccinic acid sodium salt, and polyepoxysuccinic acid ammonium salt.
5. The method of claim 1, wherein the calcium hydroxide slurry is ground in an in-line emulsifying machine, a wet vertical sand mill or a wet horizontal sand mill in step S1.
6. The method for preparing cubic ultrafine calcium carbonate according to claim 1, wherein the crystal form control agent is one or a mixture of more than two of sulfuric acid, zinc sulfate, sodium sulfate and aluminum sulfate, and the mass of the crystal form control agent accounts for 0.3-1.5% of the mass of the primary calcium hydroxide slurry.
7. The method for preparing cubic ultrafine calcium carbonate according to claim 1, wherein the temperature of the secondary calcium hydroxide slurry added in step S3 is 10 ℃ to 25 ℃, the mass concentration is 2% to 8%, and the mass of the secondary calcium hydroxide slurry is 20% to 100% of the mass of the primary calcium hydroxide slurry on a dry basis.
8. The method for preparing cubic ultrafine calcium carbonate according to claim 1, wherein the mass of the water-soluble grinding aid accounts for 0.2-1.0% of the dry mass of the calcium carbonate, and the mass of the aluminate coupling agent accounts for 0.3-1.5% of the dry mass of the calcium carbonate.
9. The method for preparing cubic superfine calcium carbonate according to claim 1, wherein the surface treating agent is one or a mixture of two of sodium dodecyl benzene sulfonate and epoxidized soybean oil, the mass of the sodium dodecyl benzene sulfonate accounts for 0.5-2.0% of the dry mass of the calcium carbonate, and the mass of the epoxidized soybean oil accounts for 0.5-2.0% of the dry mass of the calcium carbonate.
The preparation method of the PVC calendered film is characterized by comprising the following steps:
s10: adding the following raw materials in parts by mass into a high-speed mixer, wherein 100 parts of polyvinyl chloride resin, 36 parts of plasticizer, 2 parts of liquid stabilizer, 6 parts of rutile titanium dioxide, 60 parts of calcium carbonate prepared by the preparation method according to any one of claims 1 to 9, 0.7 part of permanent violet and 0.1 part of fluorescent brightener are mixed until the working temperature of the high-speed mixer reaches 110 ℃ to obtain a premix;
s20: adding the premix into a double-roller open mill, controlling the working temperature of the double-roller open mill to be 170-180 ℃, and mixing for 10-15 min to prepare a mixture;
s30: and adjusting the distance between two rollers of the two-roller open mill to be 18mm, and stretching and drawing the mixture to prepare the PVC calendered film.
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| CN111333096A (en) * | 2020-03-24 | 2020-06-26 | 立达超微工业（苏州）有限公司 | Production process of ultrafine calcium carbonate powder |
| CN115321571A (en) * | 2021-12-14 | 2022-11-11 | 襄阳兴发化工有限公司 | Preparation method of nano calcium carbonate for MS sealant |
| CN115974124A (en) * | 2022-12-09 | 2023-04-18 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of hollow spindle light calcium carbonate for PVC (polyvinyl chloride) calendered membrane |
| CN116443910A (en) * | 2023-04-04 | 2023-07-18 | 瀜矿科技(上海)有限公司 | Square calcium carbonate with low oil absorption value and preparation method thereof |
| CN117682544A (en) * | 2024-02-04 | 2024-03-12 | 山东宇信纳米科技有限公司 | Preparation method and application of composite crystal form nano calcium carbonate |
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