CN102352131A - Method for modifying heat-resisting surface of calcium carbonate - Google Patents
Method for modifying heat-resisting surface of calcium carbonate Download PDFInfo
- Publication number
- CN102352131A CN102352131A CN2011102369661A CN201110236966A CN102352131A CN 102352131 A CN102352131 A CN 102352131A CN 2011102369661 A CN2011102369661 A CN 2011102369661A CN 201110236966 A CN201110236966 A CN 201110236966A CN 102352131 A CN102352131 A CN 102352131A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- calcium carbonate
- surface modification
- lime carbonate
- heat
- 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.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 149
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 87
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000010298 pulverizing process Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 235000006708 antioxidants Nutrition 0.000 claims description 77
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 49
- 230000004048 modification Effects 0.000 claims description 44
- 238000012986 modification Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000002632 lipids Chemical class 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 16
- 239000004519 grease Substances 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 239000013543 active substance Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 5
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 229930003427 Vitamin E Natural products 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 4
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 4
- 235000019165 vitamin E Nutrition 0.000 claims description 4
- 229940046009 vitamin E Drugs 0.000 claims description 4
- 239000011709 vitamin E Substances 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000006035 Tryptophane Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- -1 tea-polyphenol Chemical compound 0.000 claims description 3
- 229960004799 tryptophan Drugs 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000013019 agitation Methods 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010094 polymer processing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000012430 stability testing Methods 0.000 description 4
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006701 autoxidation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 244000100068 Triphasia aurantiola Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 238000003490 calendering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention discloses a method for modifying the heat-resisting surface of calcium carbonate, which comprises the following steps of: firstly, adding an antioxidant into an organic solvent, and uniformly mixing antioxidant and the organic solvent through normal temperature or raised temperature agitation to prepare a 0.1-10% antioxidant solution; secondly, mixing the antioxidant solution with a liquid surfactant or surfactant emulsion; thirdly, adding the mixture into hot calcium carbonate slurry with the temperature of 75-95 DEG C, agitating the mixture and the hot calcium carbonate slurry for 30-60 min to obtain surface modified calcium carbonate slurry, reducing the temperature, filtering the surface modified calcium carbonate slurry, and drying and pulverizing the filter residue in 85-150 DEG C flowing air to obtain the heat-resisting surface modified calcium carbonate product; alternatively, respectively preheating the antioxidant solution and solid surface modified antioxidant, agitating the antioxidant solution and the solid surface modified antioxidant in 95-125 DEG C calcium carbonate dry powder for 5-30 min, and pulverizing the mixture to obtain the heat-resisting surface modified calcium carbonate product. The method provided by the invention has small antioxidant use amount, low production cost and good product quality and economic effects and is simple to operate.
Description
Technical field
The present invention relates to the organise method of surface modification of a kind of lime carbonate thermotolerance, said lime carbonate comprises water-ground limestone, micron order and nano level precipitated chalk.
Background technology
Lime carbonate is that macromolecular material technical grade superpolymer based composites field consumption is maximum, and indispensable filler is widely used in industries such as plastics, rubber, coating, viscose.Present global lime carbonate (containing heavy, light calcium carbonate) annual production is about 8,000 ten thousand tons, and Chinese lime carbonate annual production reached 1,600 ten thousand tons to 2009, accounted for 20% of Gross World Product, in recent years also in the speed increment with every year 10 ~ 15%.In the polymer processing industry, because the filling of lime carbonate, 1 year can reduce nearly 4,000 ten thousand tons of resin consumption at least, practices thrift crude oil above 200,000,000 barrels.The production of lime carbonate and utilisation technology progress are for development of world economy, and preserving our planet and relaxing oil crisis has very important significance.The lime carbonate industry development also helps to alleviate china natural resources and environmental stress, promotes sustainable economic development.
Lime carbonate not only can play the increment filling effect, reduces the material produce cost, can also improve material hardness, rigidity and dimensional stability, promotes other mechanical properties of material and gives material some special physicochemical character.But because lime carbonate belongs to inorganic materials; Its surface differs greatly with the surface or the interfacial property of most of superpolymer matrix; Consistency is bad, and the lime carbonate of long time without surface modification treatment is difficult to homodisperse in matrix, and direct or too much filling often causes some mechanical property of material seriously to descend.Therefore; Except requiring lime carbonate must satisfy the requirements such as certain pattern, granularity and size-grade distribution, also must carry out organic modification, to regulate its Surface Physical Chemistry characteristic to the lime carbonate surface; Improve consistency, reinforcing filler and the matrix interphase interaction power of itself and polymeric matrix.The nanometer precipitated chalk is less because of its particle diameter, and intercrystalline adsorptive power and self gravitation are suitable, and agglomeration traits is particularly serious.Disperse relatively poor nano-calcium carbonate to be filled in superpolymer, not only have a strong impact on products appearance, larger-size coacervate also very easily forms material internal defect.The nanometer precipitated chalk of long time without surface modification does not almost have using value; Multiple lipid acid (or salt), grease, coupling agent, tensio-active agent, dispersion agent and oligopolymer all can be used for calcium carbonate surface modifying to be handled; Lipid acid and salt super quality and competitive price thereof; Be to use the widest calcium carbonate surface modifying agent; Vegetable oil lipoprotein also is widely used in calcium carbonate surface modifying, particularly at home nanometer precipitated chalk surface modification in greasy consumption even present the trend that surmounts lipid acid.Just disclose in 1978 with lipid acid and grease technology like U.S. patent of invention US4151136 Surface Modification of Ground Calcium Carbonate.Chemical reaction does not generally take place with the lime carbonate surface between 15-55 ℃ grease in fusing point, only plays wetting action, and the low surface modification treatment cost of lime carbonate also can fall in the consistency between reinforcing filler and polymeric matrix.The lipid acid (salt) and the independent or compound technology that calcium carbonate surface modifying develops into widespread use gradually, the Canadian patent of invention CA120658 of being used for of grease that will contain for many years, non-saturated fatty acid; U.S. patent of invention US2663695, US2050193, US2199710; World inventions patent WO0132787, Chinese invention patent CN94115874, CN94115875; CN200910195686, CN200310114392, CN200380100804; CN200310122700; CN200510112375, CN200510112372, CN200410084715; CN200510025878; CN200910049441, CN201010022949, CN200810202557; CN201010242265; CN200910111962, CN200810071290, CN201010205633; CN201110061918; CN2009100444, CN200910014050, CN201010226648; CN200910014049; CN201010226657, CN201010226633, CN01126405 etc. disclose correlation technique successively.
In various calcium carbonate surface modifying, use wide by visible lipid acid (salt) of above-mentioned public technology and grease.But all must contain unsaturated fatty acids such as oleic acid in nearly all stearic acid and the Vegetable oil lipoprotein, it is the fact that everybody knows altogether that unsaturated acid is prone to oxidized rotten variable color, especially oxidized more easily under temperature higher as forming polymer processing.The forming polymer processing temperature is generally all more than 140 ℃; Can reach 200 ℃ like polyvinyl chloride (PVC) processing temperature; Acrylonitrile-styrene-butadienecopolymer (ABS) processing temperature can reach 230 ℃, Vilaterm (PE) and polypropylene (PP) processing temperature even up to 250 ℃.Some polymer processing time is longer; Possibly under comparatively high temps, mediate 2 hours like room temperature sealing silicone sulfide glue (RTV); The PVC calendered film is because of the high temperature action of moulding through refining and repeatedly roll-in also will be experienced the long period; The surface-modifying agent of the lime carbonate that filling is used under such situation is deterioration by oxidation very easily, more possibly cause bad products appearance for white goods.Although added all kinds of stablizers or antioxidant in the most polymers course of processing, all be to be directed against matrix resin, also do not appear in the newspapers to the heat-resisting antioxygen technology of pearl filler (mainly being surface-modifying agent) itself.Disclose a kind of zinc salt that coats on nanometer precipitated chalk surface improving the method for filled PVC thermostability like Chinese invention patent CN200910196953, but the thermally-stabilised function that zinc salt provided not is to the calcium carbonate surface modifying agent.Chinese invention patent CN201010226631 discloses a kind of preparation method who is used for the nano-calcium carbonate of high-temperature polymer; This technology neither be directed against the calcium carbonate surface modifying agent---lipid acid (salt); Thereby improve the polymkeric substance heat-resistant stability but reduce filled polymer processing viscosity through secondary surface preparation, this is not real high temperature resistant technology in fact.
Antioxidant is one type of organic compound that stops oxidative degradations such as plastics, rubber, grease and makeup.Add the antioxidant limit that can extend shelf life in the grease, the introducing antioxidant has been alleviated the polymeric matrix degradation with aging in some plastics and the Rubber processing process.Lipid acid, grease or polymkeric substance oxidation generally are considered to meet the free radical reaction theory, have initiation, growth and the termination three phases of chain.Under the effect of heat, free radical preferentially forms in active allylic, and the σ key of allylic is participated in the cycloaddition reaction of [2 π+4 π, σ].Under the initiation of light, heat, ray or profit, fracture also can take place and produce free radical in the c h bond that weak link goes out in lipid acid, grease or the polymer molecular structure.But the existence augmenting response activation energy of antioxidant makes that oxidizing reaction is difficult to carry out, thereby stops or delay the carrying out of oxidizing reaction.Antioxidant (or being referred to as main anti-oxidant) all is certain free radical inhibitors usually, or chain cessationer, mainly comprises some phenols, amine and P contained compound.Under light action or heavy metal ion when existing, oxidizing reaction is mainly carried out on two keys, and metal ion can utilize unpaired 3d unoccupied orbital to accept to bring out free-radical generating from the active electronics in lipid acid or the grease.When therefore having metal ion to exist, the antioxidant effect of phenols and antioxidants of Quinones significantly weakens, even loses efficacy.Therefore, but in lipid acid, grease or the polymeric matrix if the carrying out of trace heavy metals ion catalytic oxidation arranged.If some compounds can form complex compound with metal ion, make it lose katalysis, then can reduce the influence of metal ion to the antioxidant antioxidant effect.These compounds that can form complex compound with metal ion are exactly auxilliary antioxidant.Auxilliary antioxidant commonly used has vitamin-E, polyphosphate, phytic acid and Hydrocerol A etc.
The oxidation of polymeric matrix self is carried out automatically, and the initial stage of autoxidation reaction is very slow, as time passes; Self-catalysis is played in the radical pair autoxidation that local autoxidation produces; The oxidizing reaction acceleration, material property descends gradually, and this is so-called aging.Although to delaying the aging and technology of adding antioxidant of polymkeric substance comparative maturity, the oxidation stain of stuffing surface modification agent is out in the cold always.
Summary of the invention
The objective of the invention is provides the method for the heat-resisting surface modification of a kind of lime carbonate in order to overcome in the filled polymer course of processing, the be heated problem of oxidation stain of calcium carbonate surface modifying agent.
Technical scheme of the present invention:
The method of the heat-resisting surface modification of a kind of lime carbonate; Comprise the dissolving of antioxidant; Antioxidant mixes with tensio-active agent; The preheating of lime carbonate; Surface modification; Filter; Drying and pulverizing process; It is characterized in that: earlier antioxidant is added dissolving formation solution in the organic solvent; Mix with liquid surfactant or surface active agent emulsions then; Add again in the hot slurries of lime carbonate and stir; Or with in the solid surface modification antioxidant of antioxidant solution and preheating respectively and the lime carbonate dry powder fully stirring obtain the calcium carbonate product of heat-resisting surface modification, processing step comprises:
(1) dissolving of antioxidant: organic solvent is added in the dissolution kettle, add liquid main anti-oxidant and/or auxilliary antioxidant then, normal temperature or heating and stirring mix, and obtain antioxidant solution, and be subsequent use;
(2) antioxidant mixes with tensio-active agent: antioxidant solution solution is added thorough mixing in the certain quantity of fluid surface-modifying agent, if the calcium carbonate surface modifying antioxidant is a solid, then with oxidation inhibitor solution when the surface modification directly in the adding lime carbonate;
(3) preheating: calcium carbonate serosity is heated to 75 ~ 95 ℃, stirs; Or lime carbonate dry powder is heated with stirring to 95 ~ 125 ℃ in homogenizer;
(4) surface modification: the mixed solution of antioxidant solution and liquid surfactant or emulsion is added the also middle 30 ~ 60min of stirring of mixing of the hot slurries of lime carbonate; Or antioxidant solution and solid surface modification antioxidant add respectively in the homogenizer and also stir 5 ~ 30min in the lime carbonate dry powder of heating, accomplishes surface modification;
(5) filtration, drying and pulverizing: the calcium carbonate product that calcium carbonate serosity cooling, filtration, drying and the pulverizing that obtains is obtained heat-resisting surface modification.
It is the mass ratio 90.0 ~ 99.9: 0.1 ~ 10.0 with antioxidant that above-described organic solvent adopts in dehydrated alcohol, acetone or the sherwood oil one or more, its consumption.
Above-described main anti-oxidant adopts in butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), tea-polyphenol (TPP), halfcystine (CYS), tyrosine (TYR), tryptophane (TRP) and the proline(Pro) (PRO) one or more, and its consumption is 0.005 ~ 0.100% of a calcium carbonate dry matrix amount.
Above-described auxilliary antioxidant adopts in vitamin-E (VE), polyphosphate (PPT), phytic acid (PA) and the Hydrocerol A (CA) one or more, and its consumption is 0.002 ~ 0.050% of a calcium carbonate dry matrix amount.
In above-described tensio-active agent employing stearic acid, palmitinic acid, tetradecanoic acid and the lauric acid one or more are or/and the greasy mixture of Oleum Cocois; Its consumption is 1.0 ~ 3.5% of a calcium carbonate dry matrix amount; Lipid acid directly adds in the lime carbonate heat slurry solution; Or after saponifying agent NaOH or KOH saponification, add, the saponifying agent consumption is and 50 ~ 100% of lipid acid complete reaction aequum; When adopting soap and greasy composition, it is the soap emulsifying soln that grease needs the saponification liquor with lipid acid, and soap and greasy mass ratio are 10 ~ 90: 90 ~ 10.
Above-described lime carbonate drying is in temperature is 85 ~ 150 ℃ fluidizing air, to carry out, and control product moisture content is lower than 0.3%, and lime carbonate is pulverized and can be adopted eddy current mill or pin mill.
Above-described calcium carbonate serosity is that the quality solid content is 5 ~ 30% the water-ground limestone or the suspension-s of micron order precipitated chalk or nano level precipitated chalk; Wherein the meso-position radius of water-ground limestone is 1.0 ~ 45.0 μ m, and the BET specific surface area of micron order precipitated chalk is 4.0 ~ 20.0m
2/ g, the BET specific surface area of micron order precipitated chalk is 20.0 ~ 50.0m
2/ g.
Outstanding feature of the present invention and beneficial effect:
As stated above not only can so that tensio-active agent can be on lime carbonate surface uniform distribution, and can be so that antioxidant can be in tensio-active agent and lime carbonate surface uniform distribution.Utilize the lime carbonate surface of this method gained to have better heat-resisting property, be difficult for oxidation stain in preparation and filling application.Zhi Bei surface modified calcium carbonate not only self has better heat-resisting stability like this, can also improve the heat-resistant stability and the ageing resistance of filling polymer matrix.The method of the heat-resisting surface modification of lime carbonate that the present invention is open, the consumption of used antioxidant is little, and is simple to operate, and it is low to be applied to the industrial production cost, has technical economic benefit preferably.
Specific embodiment
Below in conjunction with embodiment the present invention is explained further details; So that technique means of the present invention, creation characteristic, reach purpose and effect easy to understand; But embodiment of the present invention is not subjected to the restriction of following embodiment; Other are any not to deviate from change, the modification done under spirit of the present invention and the principle, substitute, combination, simplify the substitute mode that all should be equivalence, is included within protection scope of the present invention.
Embodiment 1
The 1st step: 20 mass parts dehydrated alcohol organic solvents are added in the dissolution kettle, add 0.2 mass parts antioxidant BHT then, stirring at normal temperature mixes, and obtains antioxidant solution, and is subsequent use;
The 2nd step: 2000 mass parts water-ground limestones are added homogenizer stir; Heat; After the powder temperature rises to 100 ℃, add technical grade 1801 stearic acid 20 mass parts, continue to add above-mentioned said antioxidant solution of the 1st step behind the stirring 5min, continue to stir 10min afterwards again;
The 3rd step: to the calcium carbonate serosity cooling that obtains by the 2nd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 110 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 2
The 1st step: 15 mass parts acetone organic solvents are added in the dissolution kettle, add 0.3 mass parts antioxidant BHA then, stirring at normal temperature mixes, and obtains antioxidant solution, and is subsequent use;
The 2nd step: will add thorough mixing in the 30 mass parts Oleum Cocois by the solution of the 1st step gained;
The 3rd step: will add solid content by the 2nd step properties-correcting agent mixture that obtain is 10.0%, and temperature is in 85 ℃ the micron order precipitated chalk 20000 mass parts slurries, to continue to stir 40min afterwards;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 120 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 3
The 1st step: 20 mass parts sherwood oil organic solvents are added in the dissolution kettle, add 0.3 mass parts antioxidant TPP and 0.2 mass parts antioxidant PRO then, stirring at normal temperature mixes, and obtains antioxidant solution, and is subsequent use;
The 2nd step: 50 mass parts palmitinic acids are partly-hydrolysed with 6 mass parts KOH, will add thorough mixing in the saponification liquor by the solution of the 1st step gained again;
The 3rd step: will add 20000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 10.0% temperature is in 85 ℃ the nano level precipitated chalk slurries, and continues to stir 40min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 130 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 4
The 1st step: 20 mass parts dehydrated alcohol organic solvents are added in the dissolution kettle, add 0.25 mass parts antioxidant BHA and 0.25 mass parts antioxidant TYR then, heating 40 ℃ mixes, and obtains antioxidant solution, subsequent use;
The 2nd step: 30 mass parts stearic acid and 20 mass parts lauric acid are partly-hydrolysed with 6 mass parts NaOH, will add thorough mixing in the saponification liquor by the antioxidant solution of the 1st step gained again;
The 3rd step: will add 20000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 10.0% temperature is in 75 ℃ the nano level precipitated chalk slurries, and continues to stir 50min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 140 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 5
The 1st step: 0.5 mass parts antioxidant BHA and the auxilliary antioxidant CA of 0.3 mass parts are dissolved in the 20 mass parts dehydrated alcohols, and stirring at normal temperature mixes, and obtains antioxidant solution, and is subsequent use;
The 2nd step: 50 mass parts technical grades, 1801 stearic acid are partly-hydrolysed with 5 mass parts KOH, will add thorough mixing in the saponification liquor by the solution of the 1st step gained again;
The 3rd step: will add 20000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 10.0% temperature is in 95 ℃ the nano level precipitated chalk slurries, and continues to stir 30min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 120 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 6
The 1st step: 0.45 mass parts antioxidant TPP and the auxilliary antioxidant PA of 0.3 mass parts are dissolved in the 20 mass parts dehydrated alcohols, and heating 45 ℃ mixes, and obtains antioxidant solution, subsequent use;
The 2nd step: 50 mass parts technical grades, 1801 stearic acid are partly-hydrolysed with 6 mass parts NaOH, will add thorough mixing in the saponification liquor by the solution of the 1st step gained again;
The 3rd step: will add 20000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 10.0% temperature is in 85 ℃ the nano level precipitated chalk slurries, and continues to stir 40min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 120 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 7
The 1st step: 0.5 mass parts antioxidant TPP and the auxilliary antioxidant CA of 0.3 mass parts are dissolved in the 20 mass parts dehydrated alcohols, mix, obtain antioxidant solution, subsequent use;
The 2nd step: 20 mass parts technical grades, 1801 stearic acid are partly-hydrolysed with 3 mass parts NaOH, and 30 mass parts Oleum Cocois fully stir 10min after adding saponification liquor, form the emulsion of stearic acid and Oleum Cocois mass ratio 2 ︰ 3.To add thorough mixing in the emulsion by the solution of the 1st step gained;
The 3rd step: will add 20000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 10.0% temperature is in 85 ℃ the nano level precipitated chalk slurries, and continues to stir 40min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 120 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 8
The 1st step: 0.5 mass parts antioxidant TPP and the auxilliary antioxidant CA of 0.3 mass parts are dissolved in the 20 mass parts dehydrated alcohols, mix, obtain antioxidant solution, subsequent use;
The 2nd step: 50 mass parts technical grades, 1801 stearic acid are partly-hydrolysed with 4.5 mass parts KNaOH, will add thorough mixing in the saponification liquor by the solution of the 1st step gained again;
The 3rd step: will add 10000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 20.0% temperature is in 95 ℃ the nano level precipitated chalk slurries, and continues to stir 40min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 135 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
Embodiment 9
The 1st step: 0.5 mass parts antioxidant TPP and the auxilliary antioxidant PA of 0.3 mass parts are dissolved in the 20 mass parts acetone, and stirring at normal temperature mixes, and obtains antioxidant solution, and is subsequent use;
The 2nd step: 50 mass parts technical grades, 1801 stearic acid are partly-hydrolysed with 6. 5 mass parts NaOH, will add thorough mixing in the saponification liquor by the solution of the 1st step gained again;
The 3rd step: will add 10000 mass parts solid contents by the 2nd properties-correcting agent mixture that obtains of step is that 20.0% temperature is in 95 ℃ the nano level precipitated chalk slurries, and continues to stir 35min;
The 4th step: to the calcium carbonate serosity cooling that obtains by the 3rd step, filter, dry and pulverize the calcium carbonate product that obtains heat-resisting surface modification, dry used hot air temperature is 125 ℃, and is broken with the pin abrasive dust, obtains the surface modified calcium carbonate product.
The comparative example 1
Except that not adding antioxidant, all the other and embodiment 1 are together.
The comparative example 2
Except that not adding antioxidant, all the other and embodiment 2 are together.
The comparative example 3
Except that not adding antioxidant, all the other and embodiment 3 are together.
Calcium carbonate surface modifying product in the foregoing description is done heat stability testing, and method is: test all new preparation surface modified calcium carbonate whiteness; It is that 180 ℃ of electric heating air blast constant temperature ovens are placed 3h that each sample is put into temperature; Test is each sample whiteness after 180 ℃ of temperature bakings; Whiteness before and after relatively each sample toasts.
Calcium carbonate surface modifying product in the foregoing description is filled in PVC, is pressed into the even thin slice that thickness is 1.5mm with two roller mills.PVC filled compositions prescription is: PVC 100 mass parts; Dimixo-octyl phthalate (DOP) 48 mass parts; Surface modified calcium carbonate 50 mass parts; Tribasic lead sulfate 5 mass parts; Two alkali formula lead phosphates, 2 mass parts; Lead stearate 2 mass parts, barium stearate 2 mass parts, solid paraffin 0.2 mass parts.Each calcium carbonate-filled PVC sheet is done heat stability testing, and method is: test all new preparation PVC compressing tablet whiteness; It is that 170 ℃ of electric heating air blast constant temperature ovens are placed 1.5h that each compressing tablet is put into temperature; Test is each compressing tablet whiteness after 170 ℃ of temperature bakings; Whiteness before and after relatively each sample toasts.
Surface modified calcium carbonate and filled PVC compressing tablet heat stability testing data are seen table 1 among each embodiment.Whiteness test adopts color difference meter.
Table 1: surface modified calcium carbonate and filled PVC compressing tablet heat stability testing data
Claims (7)
1. the method for the heat-resisting surface modification of lime carbonate; Comprise the dissolving of antioxidant; Antioxidant mixes with tensio-active agent; The preheating of lime carbonate; Surface modification; Filter; Drying and pulverizing process; It is characterized in that: earlier antioxidant is added dissolving formation solution in the organic solvent; Mix with liquid surfactant or surface active agent emulsions then; Add again in the hot slurries of lime carbonate and stir; Or with in the solid surface modification antioxidant of oxidation inhibitor solution and preheating respectively and the lime carbonate dry powder fully stirring obtain the calcium carbonate product of heat-resisting surface modification, processing step comprises:
(1) dissolving of antioxidant: organic solvent is added in the dissolution kettle, add liquid main anti-oxidant and/or auxilliary antioxidant then, normal temperature or heating and stirring mix, and obtain antioxidant solution, and be subsequent use;
(2) antioxidant mixes with tensio-active agent: antioxidant solution is added thorough mixing in the certain quantity of fluid tensio-active agent, if the calcium carbonate surface modifying antioxidant is solid, then with antioxidant solution when the surface modification directly in the adding lime carbonate;
(3) preheating: calcium carbonate serosity is heated to 75 ~ 95 ℃, stirs; Or lime carbonate dry powder is heated with stirring to 95 ~ 125 ℃ in homogenizer;
(4) surface modification: the mixed solution of antioxidant solution and liquid surfactant or emulsion is added the also middle 30 ~ 60min of stirring of mixing of the hot slurries of lime carbonate; Or antioxidant solution and solid surface modification antioxidant add respectively in the homogenizer and also stir 5 ~ 30min in the lime carbonate dry powder of heating, accomplishes surface modification;
(5) filtration, drying and pulverizing: the calcium carbonate product that calcium carbonate serosity cooling, filtration, drying and the pulverizing that obtains is obtained heat-resisting surface modification.
2. according to the method for the said heat-resisting surface modification of lime carbonate of claim 1, it is characterized in that: it is the mass ratio 90.0 ~ 99.9: 0.1 ~ 10.0 with antioxidant that described organic solvent adopts in dehydrated alcohol, acetone or the sherwood oil one or more, its consumption.
3. according to the method for the said heat-resisting surface modification of lime carbonate of claim 1; It is characterized in that: described main anti-oxidant adopts in butylated hydroxy anisole, butylated hydroxytoluene, tea-polyphenol, halfcystine, tyrosine, tryptophane and the proline(Pro) one or more, and its consumption is 0.005 ~ 0.100% of a calcium carbonate dry matrix amount.
4. according to the method for the said heat-resisting surface modification of lime carbonate of claim 1; It is characterized in that: described auxilliary antioxidant adopts in vitamin-E, polyphosphate, phytic acid and the Hydrocerol A one or more, and its consumption is 0.002 ~ 0.050% of a calcium carbonate dry matrix amount.
5. according to the method for the said heat-resisting surface modification of lime carbonate of claim 1; It is characterized in that: one or more in described tensio-active agent employing stearic acid, palmitinic acid, tetradecanoic acid and the lauric acid are or/and the greasy mixture of Oleum Cocois; Its consumption is 1.0 ~ 3.5% of a calcium carbonate dry matrix amount; Lipid acid directly adds in the lime carbonate heat slurry solution; Or after saponifying agent NaOH or KOH saponification, add, the saponifying agent consumption is and 50 ~ 100% of lipid acid complete reaction aequum; When adopting soap and greasy composition, it is the soap emulsifying soln that grease needs the saponification liquor with lipid acid, and soap and greasy mass ratio are 10 ~ 90: 90 ~ 10.
6. lime carbonate drying according to claim 1 is in temperature is 85 ~ 150 ℃ fluidizing air, to carry out, and control product moisture content is lower than 0.3%, and lime carbonate is pulverized and can be adopted eddy current mill or pin mill.
7. according to the method for the said heat-resisting surface modification of lime carbonate of claim 1; It is characterized in that: described calcium carbonate serosity is that the quality solid content is 5 ~ 30% the water-ground limestone or the suspension-s of micron order precipitated chalk or nano level precipitated chalk; Wherein the meso-position radius of water-ground limestone is 1.0 ~ 45.0 μ m, and the BET specific surface area of micron order precipitated chalk is 4.0 ~ 20.0m
2/ g, the BET specific surface area of micron order precipitated chalk is 20.0 ~ 50.0m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110236966 CN102352131B (en) | 2011-08-18 | 2011-08-18 | Method for modifying heat-resisting surface of calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110236966 CN102352131B (en) | 2011-08-18 | 2011-08-18 | Method for modifying heat-resisting surface of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102352131A true CN102352131A (en) | 2012-02-15 |
| CN102352131B CN102352131B (en) | 2013-09-18 |
Family
ID=45575780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110236966 Active CN102352131B (en) | 2011-08-18 | 2011-08-18 | Method for modifying heat-resisting surface of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102352131B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263014A (en) * | 2014-06-17 | 2015-01-07 | 池州市大恒生化有限公司 | Preparing method of high-purity active calcium carbonate used for coating |
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN106675110A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | High-activity nano-calcium carbonate |
| CN109135746A (en) * | 2018-10-08 | 2019-01-04 | 广州市伟圣实业有限公司 | A kind of environment-friendly type fluorescent powder |
| CN111777872A (en) * | 2020-06-16 | 2020-10-16 | 嘉兴市轩禾园艺技术有限公司 | Preparation method of functional film for shielding infrared rays |
| CN114031860A (en) * | 2021-12-24 | 2022-02-11 | 广东翔龙科技股份有限公司 | Preparation method of sub-micron active heavy calcium carbonate applied to BOPP film |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000072940A (en) * | 1998-08-28 | 2000-03-07 | Tokyo Rubber Seisakusho:Kk | Composition for electrochemical-deterioration-resistant rubber hose and multilayer rubber hose |
| US20040225050A1 (en) * | 2003-05-09 | 2004-11-11 | Meade D. Mark | Synthetic carbide lime filler composition and method of making |
| US20080075963A1 (en) * | 2006-05-10 | 2008-03-27 | Stephen Dershem | Modified calcium carbonate-filled adhesive compositions and methods for use thereof |
| CN101585976A (en) * | 2008-05-20 | 2009-11-25 | 福建省三农碳酸钙有限责任公司 | Low-viscosity active calcium carbonate, preparation method and application thereof |
| CN101671494A (en) * | 2009-09-19 | 2010-03-17 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
| CN101671497A (en) * | 2009-10-10 | 2010-03-17 | 上海卓越纳米新材料股份有限公司 | Industrial preparing method for PVC dedicated filler nanometer calcium carbonate with thermostability function |
| CN101914311A (en) * | 2010-07-30 | 2010-12-15 | 浙江常山金雄有限公司 | Calcium carbonate surface modifying method |
| CN101967309A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing active calcium carbonate |
| CN101967308A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing nano calcium carbonate for high-temperature resistant polymers |
-
2011
- 2011-08-18 CN CN 201110236966 patent/CN102352131B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000072940A (en) * | 1998-08-28 | 2000-03-07 | Tokyo Rubber Seisakusho:Kk | Composition for electrochemical-deterioration-resistant rubber hose and multilayer rubber hose |
| US20040225050A1 (en) * | 2003-05-09 | 2004-11-11 | Meade D. Mark | Synthetic carbide lime filler composition and method of making |
| US20080075963A1 (en) * | 2006-05-10 | 2008-03-27 | Stephen Dershem | Modified calcium carbonate-filled adhesive compositions and methods for use thereof |
| CN101585976A (en) * | 2008-05-20 | 2009-11-25 | 福建省三农碳酸钙有限责任公司 | Low-viscosity active calcium carbonate, preparation method and application thereof |
| CN101671494A (en) * | 2009-09-19 | 2010-03-17 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
| CN101671497A (en) * | 2009-10-10 | 2010-03-17 | 上海卓越纳米新材料股份有限公司 | Industrial preparing method for PVC dedicated filler nanometer calcium carbonate with thermostability function |
| CN101967309A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing active calcium carbonate |
| CN101967308A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing nano calcium carbonate for high-temperature resistant polymers |
| CN101914311A (en) * | 2010-07-30 | 2010-12-15 | 浙江常山金雄有限公司 | Calcium carbonate surface modifying method |
Non-Patent Citations (2)
| Title |
|---|
| 唐艳军等: "纳米/微米碳酸钙的结构表征和热分解行为", 《物理化学学报》, vol. 23, no. 5, 31 May 2007 (2007-05-31) * |
| 马传国等: "纳米碳酸钙及其表面处理对等规聚丙烯结晶行为的影响", 《高分子学报》, no. 3, 30 June 2003 (2003-06-30) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263014A (en) * | 2014-06-17 | 2015-01-07 | 池州市大恒生化有限公司 | Preparing method of high-purity active calcium carbonate used for coating |
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN105482500B (en) * | 2015-11-25 | 2018-09-14 | 广西华纳新材料科技有限公司 | The surface modifying method of silicone sealant antioxidant nano-calcium carbonate |
| CN106675110A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | High-activity nano-calcium carbonate |
| CN109135746A (en) * | 2018-10-08 | 2019-01-04 | 广州市伟圣实业有限公司 | A kind of environment-friendly type fluorescent powder |
| CN111777872A (en) * | 2020-06-16 | 2020-10-16 | 嘉兴市轩禾园艺技术有限公司 | Preparation method of functional film for shielding infrared rays |
| CN114031860A (en) * | 2021-12-24 | 2022-02-11 | 广东翔龙科技股份有限公司 | Preparation method of sub-micron active heavy calcium carbonate applied to BOPP film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102352131B (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102352131B (en) | Method for modifying heat-resisting surface of calcium carbonate | |
| Österberg et al. | Spherical lignin particles: a review on their sustainability and applications | |
| CN102174275B (en) | Surface modification method for nano calcium carbonate | |
| US8329802B2 (en) | Surface-treated calcium carbonate and paste resin composition containing same | |
| CN101475759A (en) | Practical method for preparing high thixotropy surface treating nano calcium carbonate | |
| Sun et al. | Economical improvement on the performances of a soybean flour-based adhesive for wood composites via montmorillonite hybridization | |
| CN102492310B (en) | Surface treatment method of nano-calcium carbonate used for polyvinyl chloride plastisol | |
| CN102516821A (en) | Surface modification method of nano-grade calcium carbonate used in room-temperature vulcanized silicone adhesive | |
| Phulkerd et al. | Coal water slurry using dispersant synthesized from cashew nut shell liquid (CNSL) | |
| CN105733318B (en) | A kind of modified aluminium pigment and preparation method thereof | |
| CN100457620C (en) | Process for preparing natural magnesium aluminium silicate gel | |
| CN101967310A (en) | Method for preparing nano calcium carbonate with low viscosity and medium thixotropic property | |
| CN106634049A (en) | Method for preparing nano calcium carbonate for weather-resistant ink | |
| CN105482500A (en) | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant | |
| CN105504970B (en) | A kind of rub resistance oil polish and preparation method thereof | |
| CN104059390A (en) | Modified calcium carbonate with high specific surface area and preparation method thereof | |
| Isaac et al. | Extraction, characterization of African pear (Dacryodes edulis) oil and its application in synthesis and evaluation of surface coating driers | |
| CN101348689B (en) | Aqueous Malay paint | |
| CN105970721A (en) | Papermaking additive composition and preparation method thereof | |
| CN105199562A (en) | Anti-caking powder coating | |
| US2960413A (en) | Carbon pellets for news ink manufacture | |
| CN102268117A (en) | Low molecular weight alcohol-soluble thermoplastic solid acrylic resin | |
| CN107892318A (en) | A kind of preparation method of active nano-calcium carbonate | |
| CN102295707B (en) | Low viscosity carboxymethyl starch, and its preparation method and application | |
| WO2021197624A1 (en) | Solid state binder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120215 Assignee: ANHUI PROVINCE XUNCHENG CITY HUANA NEW MATERIAL TECHNOLOGY Co.,Ltd. Assignor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Contract record no.: 2014450000046 Denomination of invention: Method for modifying heat-resisting surface of calcium carbonate Granted publication date: 20130918 License type: Exclusive License Record date: 20140711 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for modifying heat-resisting surface of calcium carbonate Effective date of registration: 20150826 Granted publication date: 20130918 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: 2015990000720 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190322 Granted publication date: 20130918 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: 2015990000720 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: ANHUI PROVINCE XUNCHENG CITY HUANA NEW MATERIAL TECHNOLOGY Co.,Ltd. Assignor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Contract record no.: 2014450000046 Date of cancellation: 20190826 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| 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: Method for modifying heat-resistant surface of calcium carbonate Effective date of registration: 20220811 Granted publication date: 20130918 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 |