CN101056928B - 具有高的比表面积的碳酸钙包覆颗粒 - Google Patents
具有高的比表面积的碳酸钙包覆颗粒 Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 34
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 53
- -1 alkaline earth metal carbonate Chemical class 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 150000002632 lipids Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229960000878 docusate sodium Drugs 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 9
- 239000000194 fatty acid Substances 0.000 abstract description 9
- 229930195729 fatty acid Natural products 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 150000008051 alkyl sulfates Chemical class 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract 1
- 229920001944 Plastisol Polymers 0.000 description 13
- 239000004999 plastisol Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 9
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000010008 shearing Methods 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 5
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004438 BET method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VLHZUYUOEGBBJB-UHFFFAOYSA-N hydroxy stearic acid Natural products OCCCCCCCCCCCCCCCCCC(O)=O VLHZUYUOEGBBJB-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 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 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000005908 glyceryl ester group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 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 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 239000001095 magnesium carbonate 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
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RCIJACVHOIKRAP-UHFFFAOYSA-M sodium;1,4-dioctoxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCCCC RCIJACVHOIKRAP-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract
本发明涉及碱土金属碳酸盐的颗粒,所述颗粒至少部分地用至少一种包覆剂包覆,并在包覆前具有超过50m2g-1的比表面积。优选地,该碱土金属是钙,包覆剂包含选自有机磺酸、烷基硫酸盐、脂肪酸及它们的盐的化合物。
Description
本发明涉及碱土金属碳酸盐优选CaCO3的包覆颗粒,其至少部分地用至少一种包覆剂包覆,并在包覆前具有超过50m2g-1的比表面积。本发明也涉及这种颗粒的制备及其用途。
碳酸钙在油漆、橡胶、纸、药品、塑料等等中用作填料。这些碳酸钙得自天然沉积物,然后进行粉碎研磨,或者得自化学沉淀并对沉淀物进行干燥。也已知聚合物基体中填料的分散性依赖于填料的粒径而大大变化,并随着粒径的减小而特征性地降低;因此,为了在聚合物基体中使用非常细小的颗粒,必需延长混合时间或充分发挥混合器的剪切效力。这在使用热敏性聚合物时是达不到预期目标的,因为由于填料含量而引起的机械性能的任何改善都会由于伴随聚合物的热降解而损失。
已经提出用不同的溶液来克服碳酸钙与基本上亲脂的物质例如典型的天然和合成聚合物之间亲和性的不足。已知通过用溶剂中的聚合物溶液处理填料颗粒,然后干燥处理后的颗粒,可以对其表面进行改性;其他已知的方法包括用单体初步处理颗粒填料,然后聚合,第三种方法特征在于在填料颗粒表面上固定亲脂性化合物例如脂肪酸。最后,另一种方法的特征在于通过碳氢化合物和塑料材料与烷基芳基磺酸或盐接触的方法处理含钙填料来改善其湿润性,其中烷基芳基磺酸的钙盐基本上不溶于水,其量至少等于形成包覆颗粒或晶粒的整个表面的单分子层或涂层所需的量,如FR-A2 138 300所述。该公开文本特别涉及具有低的-约为0.5到3m2/g(BET法)-比表面积的碳酸钙粉末。FR-A2 480 771公开了用有机磺酸或其盐与脂肪酸化合物一起处理碳酸钙粉末。通过BET法测定初始碳酸钙具有的比表面积为50m2/g到0.2m2/g。
碳酸钙也可以在塑料溶胶中用作填料。塑料溶胶是聚合物的分散体,通常包含在具有高沸点的有机溶剂中的聚氯乙烯(PVC),并通常包含软化剂和稳定剂。塑料溶胶在例如用于包覆金属和其他基材如汽车底部密封剂、用于制备人造革等中是有用的。聚氯乙烯塑料溶胶作为密封组合物使用具有几个优点:强度、伸长率和韧性之间良好的平衡、极少以至没有挥发性有机组分以及低成本。
当打算将塑料溶胶通过喷枪应用时,它应当附着到基材上并在其上形成光滑的膜。如果塑料溶胶是液体或糊状的,即在它固化前,则应当抑制由于重力而导致的膜的流动和任何移动。这种附着可以通过改变塑料溶胶的流变性质而实现。
但是,由现有技术已知的塑料溶胶并不是在每个方面都令人满意。
当通过喷枪应用于基材时,好的塑料溶胶应当在剪切力低时表现出高的粘性,而在剪切力高时表现出低的粘性。此外,它应当具有以下特征:高的屈服应力和良好的触变性质。
因此,本发明的一个目的是提供一种优于现有技术填料的填料。具体地,该填料应当适合可以通过喷枪应用的塑料溶胶,即包含所述填料的塑料溶胶应当具有高的屈服应力,它应当在剪切力低时表现出高的粘性,而在剪切力高时表现出低的粘性。此外,这些性质应当在一定的时间内是恒定的。
已经令人惊奇地发现,与包含常规碳酸钙颗粒的塑料溶胶相比,当塑料溶胶包含在包覆前比表面积大于50m2g-1并且至少部分地用至少一种包覆剂包覆的碱土金属碳酸盐的颗粒时,其屈服应力会增加五到十倍(或甚至更多)。
包含根据本发明的颗粒的塑料溶胶显示了优良的流变性质特别是高的屈服应力值、良好的粘度和触变性。
根据本发明的颗粒的比表面积在包覆前大于50m2g-1,在包覆前优选大于或等于55m2/g,更优选大于或等于60m2/g,最优选大于或等于65m2/g。特别有利地,在包覆前颗粒的比表面积值大于或等于70m2/g,特别地大于或等于75m2/g,更特别地大于或等于80m2/g。通常,在包覆前颗粒的比表面积小于或等于300m2g-1,更优选小于或等于180m2g-1,最优选小于或等于105m2g-1。
这些沉淀碳酸钙颗粒在现有技术中是已知的,可以通过在试剂例如柠檬酸、聚丙烯酸、二辛基磺化琥珀酸钠和聚天冬氨酸存在下从Ca(OH)2悬浮液中沉淀碳酸钙颗粒来制备。在这方面,可以参考例如WO03/004414,其公开内容并入本文。
为了本说明书的目的,包覆前沉淀碳酸钙颗粒的比表面积定义为根据BET-法(根据Brunnauer-Emmett-Teller(BET)的氮的吸附等温线)确定的表面积。根据BET-法,粉末的表面积可以从在液氮的沸点处观测到的N2-等温线来计算。详细内容可以参考ISO 9277标准(1995-05-15)。
在本发明一个优选的实施方案中,碱土金属碳酸盐的颗粒是碳酸钙或碳酸镁,特别优选碳酸钙。
根据本发明的颗粒用包覆剂包覆。数种包覆剂都适合该目的。
优选地,该包覆剂至少包含选自有机磺酸、烷基硫酸盐、脂肪酸及它们的盐的化合物,所述脂肪酸任选地被羟基取代(即羟基脂肪酸)。
更优选地,该包覆剂至少包含选自有机磺酸、烷基硫酸盐、羟基脂肪酸及它们的盐和脂肪酸的化合物。
仍然更优选地,该包覆剂至少包含选自有机磺酸、烷基硫酸盐、羟基脂肪酸及它们的盐的化合物。
最优选地,该包覆剂至少包含选自有机磺酸、烷基硫酸盐及它们的盐的化合物。
为了本说明书的目的,术语″有机磺酸″包括具有至少一个-SO3H或其盐和至少一个碳原子的任意化合物。因此,有机磺酸可以包含其他的官能团,例如酯。特别地,有机磺酸包括烷基磺化琥珀酸酯例如琥珀酸二辛酯磺酸盐及其钠盐。
为了本说明书的目的,术语″烷基″如果不另有说明,表示的是线型或支化烷基链,优选具有1到30,更优选1到18,最优选1到12,特别是1到6个碳原子,例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基、异辛基、正壬基、异壬基、正癸基、异癸基、正十一烷基、异十一烷基、正十二烷基、异十二烷基等等。
在本发明一个优选的实施方案中,该包覆剂至少包含脂肪酸,其任选被羟基所取代。适当的脂肪酸是线型或支化脂肪族羧酸,优选具有8到22个碳原子,更优选12到18,特别是16到18个碳原子,及其盐。脂肪酸的脂肪链可以是饱和的或不饱和的。优选是饱和的脂肪族脂肪酸。优选地,该包覆剂包含硬脂酸或其盐。更优选硬脂酸。当该包覆剂包含羟基脂肪酸或其盐时,优选是羟基硬脂酸。最优选地,该硬脂酸在12位具有羟基(CH3-(CH2)4-CH2-CHOH-CH2-(CH2)8-CH2-COOH)。
有利地,用脂肪酸或其羟基脂肪酸或用碱金属或其铵盐直接处理包覆前比表面积大于50m2g-1的沉淀碳酸钙颗粒。一般地,为了便于操作和确保最终产品的同质性,利用脂肪酸或羟基脂肪酸的盐的水溶液或悬浮液作为影响对象表面处理的手段。
在本发明另一个优选的实施方案中,该包覆剂至少包含硫有机化合物。优选地,该包覆剂包含选自烷基磺酸、芳基磺酸、烷基芳基磺酸、烷基磺化琥珀酸酯、烷基硫酸盐及它们的盐的化合物。
为了本说明书的目的,术语″芳基″表示的是芳香族单-或二环烃,包含6到10个碳原子,例如苯基和萘基,任选地被卤素取代。
为了本说明书的目的,术语″烷基芳基″表示的是上述定义的″烷基″残基与上述定义的″芳基″残基共价结合,例如-CH2C6H5、-CH2CH2C6H5、-CH2CH2CH2C6H5等等。
在一个优选的实施方案中,该包覆剂包含由通式(I-A)或(I-B)表示的化合物
其中
R1、R7、R9和R10独立地是单键、-O-、-C1-C18-亚烷基-或-C2-C18-亚烯基-(其中在亚烷基-或在亚烯基-链中可以任选地用-O-取代1、2或3个-CH2-基);
R2、R3、R4、R5和R6独立地是-H、-C1-C18-烷基(其中在烷基链中可以任选地用-O-取代1、2或3个-CH2-基)、-OH、-F、-Cl、-CN、-CO2H、-CO-C1-C6-烷基、-CO2-C1-C6-烷基、-O-CO-C1-C6-烷基、-NO2、-NH2、-NH-C1-C6-烷基或-N(C1-C6-烷基)2;
R8是-H或-C1-C6-烷基;和
R11和R12独立地是-H、-C1-C18-烷基(其中在烷基链中可以任选用-O-取代1、2或3个-CH2-基)、-NH2、-NH-C1-C6-烷基或-N(C1-C6-烷基)2。
为了本说明书的目的,术语″亚烷基″表示二价线型或支化亚烷基链,例如-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH(CH3)-、-CH2CH(CH3)-、-CH2CH2CH(CH3)-、-CH2CH(CH3)CH2-等等。
为了本说明书的目的,术语″亚烯基″表示二价线型或支化亚烯基链,例如-CH=CH-、-CH2CH=CH-、-CH2CH2CH=CH-、-CH=C(CH3)-、-CH2CH=C(CH3)-、-CH=C(CH3)CH2-等等。
优选地,在通式(I-A)或(I-B)表示的化合物中,R1、R7、R9和R10独立地是单键或-C1-C6-亚烷基-(其中在亚烷基-链中可以任选用-O-取代1或2个-CH2-基);
R2、R3、R4、R5和R6独立地是-H或-C1-C18-烷基(其中在烷基-链中可以任选用-O-取代1、2或3个-CH2-基);
R8是-H或-C1-C6-烷基;和
R11和R12独立地是-C1-C12-烷基(其中在烷基-链中可以任选用-O-取代1、2或3个-CH2-基)。
更优选地,在通式(I-A)或(I-B)表示的化合物中,
R1和R7是单键;
R2、R3、R5和R6是-H
R4是-H或-C1-C6-烷基;
R8是-H;
R9和R10独立地是单键或-CH2-;和
R11和R12独立地是-C1-C12-烷氧基。
为了本说明书的目的,术语″烷氧基″表示的是上述定义的″烷基″与氧原子共价结合,例如-OCH3、-OCH2CH3等等。
更优选地,该包覆剂包含一种或多种选自苯磺酸、甲苯磺酸、琥珀酸二辛酯磺酸盐及它们的盐的化合物。
本发明的发明者也已经发现,当该包覆剂包含通式(I-A)的化合物,其中R1是单键;R2、R3、R5和R6是-H;和R4是-H或-C1-C10-烷基,优选-H或-C1-C6-烷基时,也可以用包覆前比表面积为50m2g-1或小于50m2g-1的沉淀碳酸钙获得显示优良性质的包覆颗粒。优选地,该包覆剂包含苯磺酸或甲苯磺酸。在该实施方案中,包覆前碳酸钙颗粒的比表面积的优选范围是25到50m2g-1,更优选30到50m2g-1,最优选35到50m2g-1,特别是40到50m2g-1。然而,作为替代地,包覆前比表面积也可以大于50m2g-1,包覆前更优选大于或等于55m2/g,仍然更优选大于或等于60m2/g,最优选大于或等于65m2/g。如上所述,包覆前颗粒的比表面积的值大于或等于70m2/g,特别是大于或等于75m2/g,更特别是大于或等于80m2/g是特别有利的。
优选地,根据本发明的颗粒具有的平均初级粒径范围是0.1到30nm。初级粒径与包覆颗粒和基本上没有团聚体形成的情况相关。初级粒径(dP)可以根据NFX 11601(1974)/11602 NFX(1977)中所述的方法来确定。更特别地,通过Léa和Nurse法(标准NFX11-601,1974)测定初级颗粒的平均粒径。由Léa和Nurse法得到质量面积(SM)来获得dP值,假定所有的颗粒都是球形,没有孔隙,直径相等并忽略颗粒之间的接触面。dP和SM之间的关系如下:
dP=6/(ρSM)
其中ρ是碳酸钙的密度。
更优选地,平均初级粒径范围是1到30nm。
本发明也涉及包含上述包覆颗粒和聚合物的组合物。优选地,该聚合物包含聚氯乙烯。在一个优选的实施方案中,该聚合物的平均分子量Mw范围是5,000到500,000gmol-1,更优选10,000到400,000gmol-1,最优选25,000到250,000gmol-1。
优选地,根据本发明的组合物包含
-根据本发明的包覆颗粒;
-至少一种聚合物,例如聚氯乙烯(PVC),例如Vestolit、Vinolit
-任选至少一种增塑剂,例如邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二异壬酯(DINP)、己二酸酯、癸二酸酯
-任选至少一种溶剂,例如烃类的衍生物
-任选至少一种填料,例如TiO2、SiO2、天然碳酸钙
-任选至少一种促进剂,例如聚胺、聚酰胺
-任选至少一种干燥剂,例如CaO和
-任选的其他添加剂。
根据本发明的组合物的优选实施方案概述如下:
表1:
[wt.-%] | 优选 | 更优选 | 最优选 |
包覆颗粒 | 1-50 | 5-30 | 15-25 |
聚合物 | 5-75 | 15-50 | 25-35 |
增塑剂 | 10-60 | 20-50 | 30-40 |
溶剂 | 0.5-15 | 1-10 | 3-6 |
填料 | 0-30 | 0-20 | 0-16 |
促进剂 | 0-20 | 0-10 | 1-6 |
干燥剂 | 0-20 | 0-10 | 1-2 |
其他添加剂 | 0-15 | 0-10 | 0-5 |
本发明也涉及制备上述包覆颗粒的方法,包括将比表面积大于50m2g-1的未包覆的碱土金属碳酸盐颗粒与包覆剂接触的步骤。
优选地,该包覆剂包含一种或多种如上所述的优选化合物。
在一个优选的实施方案中,该方法包括下列步骤:
(a)在提供大于50m2g-1的比表面积的条件下,从氢氧化钙的悬浮液中沉淀碳酸钙颗粒;和
(b)使从步骤(a)得到的碳酸钙颗粒与包覆剂接触。
本发明也涉及如上所述的包覆颗粒在聚合物组合物中作为填料的用途。
下列的实施例进一步对本发明进行解释说明,但并不能认为是限制其范围。
实施例1:
比表面积范围是41到104m2g-1(包覆前)的碳酸钙颗粒是根据WO03/004414所述的方法获得的。
用选自Marlon、AOT、硬脂酸和羟基硬脂酸甘油酯的包覆剂包覆这些沉淀碳酸钙颗粒。″Marlon″是包含85wt.-%苯磺酸和15wt.-%甲苯磺酸钠盐的混合物,″AOT″是指二辛基磺化琥珀酸钠盐。为了把包覆剂应用到沉淀碳酸钙颗粒上,加入包覆剂的溶液或乳液。当以溶液的形式进行包覆,在室温下向沉淀碳酸钙的浆中加入包覆剂,搅拌30分钟,然后过滤并在干燥箱中干燥。当以乳液的形式进行包覆时,在75-85℃下向沉淀碳酸钙的浆中加入包覆剂,搅拌30分钟,然后过滤并干燥。
颗粒(类型-0到类型-12)的性质总结于下表2中,并与用硬脂酸甘油酯(饱和和不饱和支化脂肪羧酸的混合物,例如Priplus、Edenor、Pristerene、Undesa、Prifrac、Radiacid、Safacid、Cremer)作为包覆剂包覆并在包覆前比表面积为20m2g-1的超细沉淀碳酸钙进行比较。
表2:
颗粒 | 比表面积(包覆前) | 包覆剂 |
对照 | 20m<sup>2</sup>g<sup>-1</sup> | 硬脂酸甘油酯 |
类型-1 | 41m<sup>2</sup>g<sup>-1</sup> | Marlon |
类型-2 | 66m<sup>2</sup>g<sup>-1</sup> | Marlon |
类型-3 | 70m<sup>2</sup>g<sup>-1</sup> | Marlon |
类型-4 | 85m<sup>2</sup>g<sup>-1</sup> | Marlon |
类型-5 | 70m<sup>2</sup>g<sup>-1</sup> | AOT |
类型-6 | 70m<sup>2</sup>g<sup>-1</sup> | AOT |
类型-7 | 85m<sup>2</sup>g<sup>-1</sup> | AOT |
类型-8 | 53m<sup>2</sup>g<sup>-1</sup> | 硬脂酸甘油酯 |
类型-9 | 77m<sup>2</sup>g<sup>-1</sup> | 硬脂酸甘油酯 |
类型-10 | 104m<sup>2</sup>g<sup>-1</sup> | 硬脂酸甘油酯 |
类型-11 | 70m<sup>2</sup>g<sup>-1</sup> | 羟基硬脂酸甘油酯 |
类型-12 | 70m<sup>2</sup>g<sup>-1</sup> | 羟基硬脂酸甘油酯 |
实施例2:
制备两种不同的制剂,包含聚氯乙烯和实施例1的包覆碳酸钙颗粒。所述制剂的组成总结于下表3中。
表3:
实施例3:
根据ISO 3219标准研究实施例2得到的各种制剂的流变性质。在装配有移动式DIN 125圆锥形料筒的UDS 200型流变仪中进行测量。该流变仪测定了剪切力和粘度与强加的速度梯度的关系。所有测定均在25℃下根据下列方法进行:
-将探头在25℃下保持5分钟,直至达到热平衡
-用2分钟从0加速到100s-1,测定120个数据点
-在100s-1保持1分钟,测定20个数据点
-用2分钟从100s-1减速到0,测定120个数据点。
如表2所示,制剂中包覆沉淀碳酸钙颗粒的含量各不相同(100%、75%、65%和50%)。
在制备后1天测试该制剂。流变学测试的实施例总结于下表4到14中:
表4:
表5:
表6:
表7:
表8:
表9:
表10:
表11:
表12:
表13:
表14:
表15:
对照:超细的包覆沉淀碳酸钙
NM:由于粘度太高而不能用料筒测定
Claims (10)
1.一种碱土金属碳酸盐的颗粒,其至少部分用至少一种包覆剂包覆,并且在包覆前的比表面积大于50m2g-1,所述包覆剂由选自被羟基取代的脂肪酸及其盐、有机磺酸及其盐、烷基硫酸盐的至少一种化合物组成。
2.根据权利要求1的颗粒,其特征在于它们在包覆前的比表面积大于65m2g-1。
3.根据权利要求1或2的颗粒,其特征在于该包覆剂由选自有机磺酸及其盐、烷基硫酸盐的至少一种化合物组成。
4.根据权利要求1或2的颗粒,其特征在于该包覆剂由选自被羟基取代的硬脂酸及其盐、苯磺酸及其盐、甲苯磺酸及其盐、琥珀酸二辛酯磺酸盐的至少一种化合物组成。
5.根据权利要求1或2的颗粒,其特征在于它们具有的平均初级粒径范围是从0.1到30nm。
6.一种组合物,其包含根据权利要求1到5中任一项的颗粒和至少一种聚合物。
7.根据权利要求6的组合物,其特征在于该聚合物包含聚氯乙烯。
8.一种制备根据权利要求1到5中任一项的包覆颗粒的方法,所述方法包括将比表面积大于50m2g-1的未包覆的碱土金属碳酸盐颗粒与至少一种包覆剂接触的步骤,其中所述包覆剂由选自被羟基取代的脂肪酸及其盐、有机磺酸及其盐、烷基硫酸盐的至少一种化合物组成。
9.根据权利要求8的方法,包括下列步骤:
(a)在提供大于50m2g-1的比表面积的条件下,从氢氧化钙悬浮液中沉淀碳酸钙颗粒;和
(b)使从步骤(a)得到的碳酸钙颗粒与包覆剂接触。
10.根据权利要求1到5中任一项的颗粒在聚合物组合物中作为填料的用途。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1657278A1 (en) | 2004-11-12 | 2006-05-17 | SOLVAY (Société Anonyme) | Coated particles of calcium carbonate having a high specific surface |
KR20150113210A (ko) | 2004-12-22 | 2015-10-07 | 솔베이(소시에떼아노님) | 알칼리 토금속 카르보네이트의 내산성 입자 |
FR2881957B1 (fr) | 2005-02-16 | 2008-08-08 | Solvay | Comprimes comprenant une substance biologiquement active et un excipient |
EP1746073A1 (en) * | 2005-07-20 | 2007-01-24 | SOLVAY (Société Anonyme) | Process for making a solid compound by precipitation, suspensions of solid in liquids and solids obtained by the process and their use as additives |
WO2008068322A1 (en) * | 2006-12-08 | 2008-06-12 | Solvay (Société Anonyme) | Coated alkaline-earth metal carbonate particles, use of such particles in the production of construction materials and construction materials compositions containing such particles |
CN107075216A (zh) * | 2014-10-01 | 2017-08-18 | 色彩矩阵控股股份有限公司 | 用于聚合物材料的成核剂添加剂组合物 |
EP3124554A1 (en) | 2015-07-30 | 2017-02-01 | Imerys SA | Precipitated calcium carbonate, a method for its manufacture and uses thereof |
GB201514458D0 (en) * | 2015-08-14 | 2015-09-30 | Imerys Minerals Ltd | Coated calcium carbonates and their uses |
CN109399683B (zh) * | 2018-12-06 | 2020-12-01 | 东北大学 | 一种pvc汽车底涂胶屈服增强用纳米碳酸钙的制备方法 |
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2004
- 2004-11-12 EP EP04105748A patent/EP1657278A1/en not_active Withdrawn
-
2005
- 2005-11-09 EP EP05811024.8A patent/EP1812506B1/en not_active Revoked
- 2005-11-09 MY MYPI20055253A patent/MY144938A/en unknown
- 2005-11-09 CN CN2005800386383A patent/CN101056928B/zh not_active Expired - Fee Related
- 2005-11-09 US US11/719,154 patent/US7847002B2/en not_active Expired - Fee Related
- 2005-11-09 JP JP2007540644A patent/JP5192817B2/ja not_active Expired - Fee Related
- 2005-11-09 WO PCT/EP2005/055870 patent/WO2006051087A1/en active Application Filing
- 2005-11-09 KR KR1020077010799A patent/KR101217911B1/ko active IP Right Grant
- 2005-11-11 AR ARP050104757A patent/AR056628A1/es active IP Right Grant
- 2005-11-11 TW TW094139664A patent/TWI389959B/zh not_active IP Right Cessation
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US4927618A (en) * | 1987-11-19 | 1990-05-22 | Pfizer Inc. | Process for the preparation of large surface area, finely divided precipitated calcium carbonate and filled polymeric compositions of matter containing said calcium carbonate |
Also Published As
Publication number | Publication date |
---|---|
JP2008519751A (ja) | 2008-06-12 |
KR101217911B1 (ko) | 2013-01-02 |
EP1812506A1 (en) | 2007-08-01 |
JP5192817B2 (ja) | 2013-05-08 |
US7847002B2 (en) | 2010-12-07 |
TWI389959B (zh) | 2013-03-21 |
CN101056928A (zh) | 2007-10-17 |
MY144938A (en) | 2011-11-30 |
EP1657278A1 (en) | 2006-05-17 |
US20090099285A1 (en) | 2009-04-16 |
AR056628A1 (es) | 2007-10-17 |
KR20070085331A (ko) | 2007-08-27 |
TW200632015A (en) | 2006-09-16 |
EP1812506B1 (en) | 2017-01-18 |
WO2006051087A1 (en) | 2006-05-18 |
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