CN101985360A - Method for preparing magnesiumhalide nano material - Google Patents
Method for preparing magnesiumhalide nano material Download PDFInfo
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- CN101985360A CN101985360A CN 201010571224 CN201010571224A CN101985360A CN 101985360 A CN101985360 A CN 101985360A CN 201010571224 CN201010571224 CN 201010571224 CN 201010571224 A CN201010571224 A CN 201010571224A CN 101985360 A CN101985360 A CN 101985360A
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- magnesium halide
- magnesium
- alcohol
- cooling fluid
- carbon
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims description 117
- 229910052749 magnesium Inorganic materials 0.000 claims description 116
- -1 magnesium halide Chemical class 0.000 claims description 102
- 239000012809 cooling fluid Substances 0.000 claims description 51
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 235000011147 magnesium chloride Nutrition 0.000 claims description 21
- 150000004820 halides Chemical class 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000012442 inert solvent Substances 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 239000004519 grease Substances 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229940099259 vaseline Drugs 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002680 magnesium Chemical class 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 claims description 2
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 claims description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 2
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 229960004217 benzyl alcohol Drugs 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000000110 cooling liquid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229940091250 magnesium supplement Drugs 0.000 description 99
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 229960002337 magnesium chloride Drugs 0.000 description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 8
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 7
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- IUADYGVMSDKSMB-UHFFFAOYSA-N 4-methyl-1-phenylpentan-2-ol Chemical compound CC(C)CC(O)CC1=CC=CC=C1 IUADYGVMSDKSMB-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
The invention provides a method for preparing a magnesiumhalide nano material, belonging to the technical field of nano material preparation. The method for preparing spherical magnesiumhalide nano particles provided by the invention comprises the following steps: mixing a good solvent like alcohol or water with magnesiumhalide based on the molar ratio of (0.1-100):1; heating for reacting to generate a magnesiumhalide alcoholic solution or a magnesiumhalide aqueous solution; transferring the hot magnesiumhalide alcoholic solution or the hot magnesiumhalide aqueous solution to cooling liquid under a stirring state; filtering; cleaning by a poor solvent; and drying to obtain the product. The particles are small in particle size and are evenly distributed, and spherical magnesiumhalide nano particles with the particle size of 20-1000nm can be prepared by adjusting the preparation condition.
Description
Technical field
The invention belongs to field of nanometer material technology and nano material preparation technical field, be specifically related to the preparation method of magnesium halide Nano microsphere.
Background technology
Magnesium chloride has good whiteness, active strong, and the magnesium chloride Nano microsphere also has characteristics such as superfine, can also can improve the fire resistance of paper as filler, the raising paper of whiteness of paper; Magnesium chloride is good fire retardant material, does not burn, does not produce poisonous and hazardous material, and environment is had no side effect; Magnesium chloride adds in the base material as weighting agent, not only plays fire retardation, also can strengthen the physical strength of base material; Spherical MgCl
2Particle can also be used for support of the catalyst, usually the preparation MgCl that adopts
2The method of ball type carrier has spray method (USP4111835, USP4399054), extruding gunite (CN1047302) and high-speed mixing method (CN1103406) etc., but particle size can not reach nano level all at micron order.
Patent CN200510047355.7 has proposed a kind of preparation method of basic magnesium chloride, with magnesium chloride hexahydrate and common light magnesium oxide is raw material, at first prepare the basic magnesium chloride precipitation of gel state, then sedimentation and filtration is also used deionized water wash, precipitate with washed with isopropyl alcohol again, vacuum filters and obtains the magnesium chloride nanometer rod again, and the cross-sectional diameter of rod is about 100 to 200 nanometers, is about 4 to 8 microns.
As far as our knowledge goes, also there is not the preparation of patent and bibliographical information ball shaped nano magnesium halide particulate at present.We are unexpected to find, alcohol or water are mixed by a certain percentage with magnesium halide, after temperature reaction generates magnesium halide alcohol adduct or magnesium halide hydrate soln, directly this magnesium halide alcohol adduct or magnesium halide hydrate soln are transferred in the cooling fluid that is in whipped state while hot, after filtration, obtain ball shaped nano magnesium halide particle after the poor solvent washing, drying; The stir speed (S.S.) of cooling fluid has tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: stir speed (S.S.) is big more, and particle size is more little, and stir speed (S.S.) is the principal element that influences the particle size size; The magnesium halide alcoholic solution or the magnesium halide aqueous solution transfer rate while hot also have tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: the speed of transfer is more little, particle size is more little, and transfer rate is another principal element that influences the particle size size; Grain diameter is little, be evenly distributed.Regulate preparation condition and can prepare the nanometer magnesium halide spheroidal particle of particle diameter between 20nm～1000nm.
Summary of the invention
The object of the present invention is to provide a kind of ball shaped nano magnesium halide particulate preparation method.
Ball shaped nano magnesium halide particulate preparation method provided by the present invention is: for example alcohol or water mix with magnesium halide with good solvent, after temperature reaction generates the magnesium halide alcoholic solution or the magnesium halide aqueous solution, directly the magnesium halide alcoholic solution or the magnesium halide aqueous solution are transferred in the cooling fluid that is whipped state while hot, after filtration, with obtaining ball shaped nano magnesium halide particle after bad organic solvent washing, the drying, grain diameter is little, be evenly distributed, and the conditioned reaction condition can prepare the nanometer magnesium halide spheroidal particle of particle diameter between 20nm～1000nm.
Wherein, magnesium halide is: magnesium halide is: at least a in magnesium dichloride, six water magnesium dichlorides, dibrominated magnesium, two magnesium iodides, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination butoxy magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium or the butyl magnesium chloride, preferred magnesium dichloride or six water magnesium dichlorides.
Described polar solvent is alcohol or water;
Wherein, described alcohol is selected from C
1-C
15Aliphatic alcohols compound, C
3-C
15Cycloalkanol compounds or C
6-C
15At least a in the aromatic alcohol compound specifically comprises: Fatty Alcohol(C12-C14 and C12-C18), as ethanol, methyl alcohol, ethylene glycol, n-propyl alcohol, Virahol, 1, ammediol, butanols, isopropylcarbinol, hexanol, octanol, isooctyl alcohol, decyl alcohol, sorbyl alcohol etc.; Cycloalkanol is as ring propyl alcohol, hexalin, methyl-cyclohexanol; Aromatic alcohol, as benzylalcohol, xylyl alcohol, Isobutyl Benzyl Carbinol etc., preferred fat alcohol, especially at least a in preferred alcohol, propyl alcohol, Virahol, butanols, octanol or the isooctyl alcohol.
Wherein, described water is ortho-water.
Wherein, the mol ratio that described alcohol and magnesium halide feed intake is 0.1-100: 1, be preferably 1-90: 1.
Wherein, the mol ratio that described water and magnesium halide feed intake is 0.1-100: 1, be preferably 1-90: 1.
Wherein, the temperature range that described alcohol or water and magnesium halide reaction generate the magnesium halide alcoholic solution or the magnesium halide aqueous solution is 10 ℃-180 ℃, preferred 30 ℃-150 ℃.
Wherein, described the magnesium halide alcoholic solution or the magnesium halide aqueous solution are transferred in the cooling fluid that is in whipped state while hot, the temperature range of " while hot " is 10 ℃-180 ℃, is preferably 30 ℃-150 ℃.Wherein, described cooling fluid be in-25 ℃ to 60 ℃ with the immiscible inert solvent of magnesium halide or the mixed solution of inert solvent and emulsifying agent, preferred-10 ℃ to 40 ℃ the inert solvent or the mixed solution of inert solvent and emulsifying agent.
Wherein, described inert solvent is selected from a kind of in the aromatic hydrocarbon of the naphthenic hydrocarbon of branched paraffin, a 5-20 carbon of straight-chain paraffin, a 5-20 carbon of 5-20 carbon or 6-20 carbon or their mixture, concrete as: at least a in pentane, hexane, heptane, octane, decane, isohexane, hexanaphthene, toluene or the dimethylbenzene etc. or their mixed solvent, preferred hexane, toluene, heptane or decane.
Wherein, described emulsifying agent is to be selected from vacuum grease, silicone oil, paraffin oil, silicone grease, white oil, Vaseline or polyethylene wax etc., or their mixture.
Wherein, emulsifier concentration is 0g/ml to 0.10g/ml in the mixed solution of described inert solvent and emulsifying agent, preferred 0g/ml to 0.05g/ml.
Wherein, described poor solvent is an organic solvent, be selected from a kind of in the aromatic hydrocarbon of the naphthenic hydrocarbon of branched paraffin, a 5-20 carbon of straight-chain paraffin, a 5-20 carbon of 5-20 carbon or 6-20 carbon or their mixture, specifically be selected from least a in pentane, hexane, heptane, octane, decane, isohexane, hexanaphthene, toluene or the dimethylbenzene etc. or their mixed solvent, preferred hexane, toluene, heptane or decane.
Wherein, the stir speed (S.S.) of described cooling fluid is-8000 rev/mins of 200 commentaries on classics, and preferred 300 change-5000 rev/mins.
Wherein, the 0.1%-100% that the described speed that magnesium halide alcoholic solution or the magnesium halide aqueous solution are shifted while hot is total amount/minute, preferred 1%-50%/minute.
The preparation method of spherical magnesium halide carrier provided by the present invention may further comprise the steps:
1) with polar solvent for example alcohol or water and magnesium halide be 0.1-100 in molar ratio: 1 adds in the encloses container, is warming up to 10 ℃-180 ℃, is stirred to and obtains the transparent magnesium halide alcoholic solution or the magnesium halide aqueous solution;
2) with the magnesium halide alcoholic solution that obtains in the step 1) or the magnesium halide aqueous solution while hot (10 ℃-180 ℃) be transferred in-25 ℃ to 60 ℃ be in whipped state and the mixed solution immiscible inert solvent of magnesium halide or inert solvent and emulsifying agent, produced ball shaped nano magnesium halide alcohol adduct or ball shaped nano magnesium halide hydrate particle in this course;
The stir speed (S.S.) of cooling fluid is-8000 rev/mins of 200 commentaries on classics, and preferred 300 change-5000 rev/mins.The speed that magnesium halide alcohol adduct or magnesium halide hydrate soln shift while hot be total amount 0.1%-100%/minute, preferred 1%-50%/minute.
3) with step 2) in resulting system stir after 10 minutes to 6 hours, leave standstill, filter, with poor solvent organic solvent washing 3-6 time for example, obtain solid spherical nanometer magnesium halide alcohol adduct or solid spherical nanometer magnesium halide hydrate particle after the vacuum-drying.The main technique flow process of preparation nanometer magnesium halide spheroidal particle is seen Fig. 1.
The technology of the present invention special feature is polar solvent, and for example the molar ratio of alcohol or water and magnesium halide is wide, and the molar ratio of alcohol or water and magnesium halide can be at 0.1-100: regulate in 1 scope; Magnesium halide is dissolved in and obtains in alcohol or the water need not to add dispersion agent or emulsifying agent behind the magnesium halide solution; The magnesium halide alcoholic solution directly changes over to while hot and obtains ball shaped nano magnesium halide alcohol adduct or ball shaped nano magnesium halide hydrate particle in the cooling fluid; The stir speed (S.S.) of cooling fluid has tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: stir speed (S.S.) is big more, and particle size is more little; The speed that the magnesium halide alcoholic solution or the magnesium halide aqueous solution shift while hot has tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: the speed of transfer is more little, and particle size is more little; Magnesium halide alcohol adduct or magnesium halide hydrate particle size are little, grain diameter is little, be evenly distributed, regulate the speed that the stir speed (S.S.) of cooling fluid and magnesium halide alcoholic solution or the magnesium halide aqueous solution shifts while hot and can prepare nanometer magnesium halide spheroidal particle, particle diameter can be regulated between 20nm～1000nm, and preparation process is easy and simple to handle.
Beneficial effect:
It is the initiative of this patent that the speed that stir speed (S.S.) by regulating cooling fluid and magnesium halide alcohol adduct or magnesium halide hydrate soln shift while hot prepares magnesium halide nanometer spherical particle.We find that the stir speed (S.S.) of cooling fluid is lower than 200 rev/mins, and when the speed that magnesium halide alcohol adduct or magnesium halide hydrate soln shift while hot is too fast (complete soln shifted in 1 minute), the magnesium halide spherical particle size of preparation is greater than 2 μ m.Therefore, the speed that shifts while hot of stir speed (S.S.) by regulating cooling fluid and magnesium halide alcohol adduct or magnesium halide hydrate soln can obtain beyond thought result.If stir speed (S.S.) is higher than 8000 rev/mins, to the requirement height of equipment, the cost height is unsuitable for industrial production.If the speed that magnesium halide alcohol adduct or magnesium halide hydrate soln shift while hot less than 0.1% of total amount/minute, transfer time is oversize, production time and production cost height are unsuitable for industrial production.Adopt eco-friendly polar solvent for example water or alcohol dissolving magnesium halide, preparation nanometer magnesium halide spheroidal particle, solvent load is few, environmental friendliness; The stir speed (S.S.) of cooling fluid has tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: stir speed (S.S.) is big more, and particle size is more little, and stir speed (S.S.) is the principal element that influences the particle size size; The magnesium halide alcoholic solution or the magnesium halide aqueous solution transfer rate while hot have tangible influence to magnesium halide alcohol adduct or magnesium halide hydrate particle size: transfer rate is more little, particle size is more little, and transfer rate is another principal element that influences the particle size size.Regulate the speed that the stir speed (S.S.) of cooling fluid and magnesium halide alcoholic solution or the magnesium halide aqueous solution shifts while hot and can prepare nanometer magnesium halide spheroidal particle, particle diameter can be regulated between 20nm～1000nm.The stir speed (S.S.) of cooling fluid is controlled at 200 changes-8000 rev/mins, and preferred 300 change-5000 rev/mins; The rate-controlling that magnesium halide alcohol adduct or magnesium halide hydrate soln shift while hot the 0.1%-100% of total amount/minute, preferred 1%-50%/minute, can prepare the nanometer magnesium halide spheroidal particle of particle diameter between 20nm～1000nm.The operating process of the preparation nanometer magnesium halide spheroidal particle that the present invention relates to is simple.
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited only to following embodiment.
Description of drawings
Fig. 1 prepares the main technique schema of nanometer magnesium halide spheroidal particle.1 opening for feed wherein; 2 magnesium halide solutions; 3 magnesium halide solutions are transfer rate controller (under meter) while hot; 4 agitators; 5 cooling fluids.
Fig. 2 is nanometer magnesium halide particle SEM figure.
Embodiment
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, 10ml ethanol stirs, and controlled temperature is reaction 3 hours about 120 ℃, and (120 ℃) go in the mixed emulsion (cooling fluid) of 30 ℃ 0.3g vacuum ester and 50ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 300 rev/mins, MgCl
2The transfer rate of ethanolic soln be 0.5% of total amount/minute.Leave standstill filtration after stirring 20min, wash 3 times, normal hexane with toluene and wash (each 40 milliliters) 3 times, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.5 grams spherical in shape.
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, 20ml ethanol stirs, and controlled temperature is reaction 3 hours about 120 ℃, and (120 ℃) go in the mixed emulsion (cooling fluid) of 30 ℃ 0.2g estersil and 50ml pentane while hot, and the stir speed (S.S.) of cooling fluid is 400 rev/mins, MgCl
2The transfer rate of ethanolic soln be 0.1% of total amount/minute.Leave standstill filtration after stirring 20min, wash 3 times, normal hexane with toluene and wash (each 40 milliliters) 3 times, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.1 grams spherical in shape.
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, the 30ml dehydrated alcohol stirs, and controlled temperature is reaction 3 hours about 60 ℃, and (60 ℃) go in the mixed emulsion (cooling fluid) of-10 ℃ 3.0g white oil and 30ml heptane while hot, and the stir speed (S.S.) of cooling fluid is 600 rev/mins, MgCl
2The transfer rate of ethanolic soln be 5% of total amount/minute.Stir and leave standstill filtration after 5 hours, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains ball shaped nano magnesium chloride alcohol adduct particle 0.9 gram.
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, the 15ml propyl alcohol stirs, and controlled temperature is reaction 3 hours about 120 ℃, and (100 ℃) go in the mixed emulsion (cooling fluid) of 0 ℃ 3.0g Vaseline and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 800 rev/mins, MgCl
2The transfer rate of ethanolic soln be 10% of total amount/minute.Leave standstill filtration after stirring 50min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.5 grams spherical in shape.
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, the 20ml isooctyl alcohol stirs, and controlled temperature is reaction 3 hours about 150 ℃, and (120 ℃) go in 40 ℃ the 30ml hexane solution (cooling fluid) while hot, and the stir speed (S.S.) of cooling fluid is 1500 rev/mins, MgCl
2The transfer rate of ethanolic soln be 50% of total amount/minute.Leave standstill filtration after stirring 90min, wash (each 40 milliliters) 3 times with toluene, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.8 grams spherical in shape.
Embodiment 6
In the reactor of fully replacing through nitrogen, add the anhydrous Mg of 1g (OEt) Cl, the 20ml hexalin, stir, controlled temperature is to react 3 hours about 120 ℃, (120 ℃) go in the mixed emulsion (cooling fluid) of 30 ℃ 6.0g white oil and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 5000 rev/mins, MgCl
2The transfer rate of ethanolic soln be 1% of total amount/minute.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains ball shaped nano magnesium chloride alcohol adduct particle 2.2 grams.
Embodiment 7
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, the 20ml isooctyl alcohol stirs, and controlled temperature is reaction 3 hours about 150 ℃, and (120 ℃) go in 40 ℃ the 0.3g vacuum grease and 30ml heptane mixed emulsion (cooling fluid) while hot, and the stir speed (S.S.) of cooling fluid is 500 rev/mins, MgCl
2The transfer rate of ethanolic soln be 2% of total amount/minute.Leave standstill filtration after stirring 90min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.6 grams spherical in shape.
Embodiment 8
In the reactor of fully replacing, add the anhydrous MgCl of 1g through nitrogen
2, 20ml ethanol stirs, and controlled temperature is reaction 3 hours about 120 ℃, and (90 ℃) go in 40 ℃ the 0.3g vacuum grease and 30ml toluene mixed emulsion (cooling fluid) while hot, and the stir speed (S.S.) of cooling fluid is 450 rev/mins, MgCl
2The transfer rate of ethanolic soln be 100% of total amount/minute.Leave standstill filtration after stirring 90min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains nanometer magnesium chloride alcohol adduct particle 2.8 grams spherical in shape.
Embodiment 9
In the reactor of fully replacing, add the anhydrous MgBr of 1g through nitrogen
2, 20ml ethanol stirs, and controlled temperature is reaction 3 hours about 120 ℃, and (90 ℃) go in 40 ℃ the 0.3g vacuum grease and 30ml toluene mixed emulsion (cooling fluid) while hot, and the stir speed (S.S.) of cooling fluid is 500 rev/mins, MgCl
2The transfer rate of ethanolic soln be 30% of total amount/minute.Leave standstill filtration after stirring 90min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains nanometer MgBr spherical in shape
2Alcohol adduct particle 3.1 grams.
Embodiment 10
In clean reactor, add 2g six water MgCl
2, 20ml water stirs, and controlled temperature is reaction 3 hours about 50 ℃, and (50 ℃) go in the mixed emulsion (cooling fluid) of 30 ℃ 1.0g white oil and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 300 rev/mins, MgCl
2The transfer rate of the aqueous solution be 5% of total amount/minute.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 1.8 grams.
Embodiment 11
In clean reactor, add 50g six water MgCl
2, 300ml water stirs, and controlled temperature is reaction 3 hours about 60 ℃, and (60 ℃) go in the mixed emulsion (cooling fluid) of 20 ℃ 6.0g silicone oil and 300ml pentane while hot, and the stir speed (S.S.) of cooling fluid is 400 rev/mins, MgCl
2The transfer rate of the aqueous solution be 1% of total amount/minute.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with normal hexane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 45 grams.
Embodiment 12
In clean reactor, add the anhydrous MgCl of 1g
2, 20ml ethanol stirs, and controlled temperature is reaction 3 hours about 40 ℃, and (40 ℃) go in the mixed emulsion (cooling fluid) of 20 ℃ 0.3g vacuum grease and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 500 rev/mins, MgCl
2The transfer rate of the aqueous solution be 5% of total amount/minute.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with heptane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 1.8 grams.
Embodiment 13
In clean reactor, add 2g six water MgCl
2, 15ml ethanol stirs, and controlled temperature is reaction 3 hours about 70 ℃, and (50 ℃) go in the mixed emulsion (cooling fluid) of 20 ℃ 0.3g polyethylene wax and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 600 rev/mins, MgCl
2The transfer rate of the aqueous solution be 2% of total amount/minute.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with pentane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 1.9 grams.
Embodiment 14
In clean reactor, add 2g six water MgCl
2, 30ml water stirs, and controlled temperature is reaction 3 hours about 80 ℃, and (50 ℃) go in the mixed emulsion (cooling fluid) of 20 ℃ 2g Vaseline and 30ml toluene while hot, and the stir speed (S.S.) of cooling fluid is 400 rev/mins, MgCl
2The transfer rate of the aqueous solution is that 5% of total amount is 10 ml/min.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with heptane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 1.8 grams.
Embodiment 15
In clean reactor, add 1g MgCl
2, 25ml ethanol stirs, and controlled temperature is reaction 3 hours about 60 ℃, and (60 ℃) go in the mixed emulsion (cooling fluid) of 30 ℃ 0.5g vacuum grease and 30ml hexane while hot, and the stir speed (S.S.) of cooling fluid is 450 rev/mins, MgCl
2The transfer rate of the aqueous solution is that 2% of total amount is 5 ml/min.Leave standstill filtration after stirring 20min, wash (each 40 milliliters) 3 times with hexane, vacuum-drying obtains ball shaped nano magnesium chloride hydrate particle 1.9 grams.
Claims (3)
1. the magnesium halide preparation of nanomaterials is characterized in that, step is as follows:
1) in container, alcohol or water are mixed with magnesium halide, be warming up to 10 ℃-180 ℃, be stirred to and obtain the transparent magnesium halide alcoholic solution or the magnesium halide aqueous solution;
2) with the magnesium halide alcoholic solution that obtains in the step 1) or the magnesium halide aqueous solution while hot, promptly under 10 ℃-180 ℃, be transferred in-25 ℃ to 60 ℃ the cooling fluid that is in whipped state and obtain the magnesium halide mixed system, produced ball shaped nano magnesium halide alcohol adduct or ball shaped nano magnesium halide hydrate particle in this course;
3) with step 2) in resulting system stir after 10 minutes to 6 hours, leave standstill, filter, with organic solvent washing 3-6 time, obtain ball shaped nano magnesium halide alcohol adduct or ball shaped nano magnesium halide hydrate particle after the vacuum-drying;
Described magnesium halide is: at least a in magnesium dichloride, six water magnesium dichlorides, dibrominated magnesium, two magnesium iodides, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination butoxy magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium or the butyl magnesium chloride;
Described alcohol is selected from C
1-C
15Aliphatic alcohols compound, C
3-C
15Cycloalkanol compounds or C
6-C
15At least a in the aromatic alcohol compound;
The mol ratio of described alcohol or water and magnesium halide is 0.1-100: 1;
Wherein, described cooling fluid be in-25 ℃ to 60 ℃ with the immiscible inert solvent of magnesium halide or the mixed solution of inert solvent and emulsifying agent; Described inert solvent is selected from a kind of in the aromatic hydrocarbon of the naphthenic hydrocarbon of branched paraffin, a 5-20 carbon of straight-chain paraffin, a 5-20 carbon of 5-20 carbon or 6-20 carbon or their mixture; Described emulsifying agent is selected from a kind of in vacuum grease, silicone oil, silicone grease, paraffin oil, white oil, Vaseline or the polyethylene wax or their mixture;
Wherein, emulsifier concentration is 0g/ml to 0.10g/ml in the mixed solution of described inert solvent and emulsifying agent;
Wherein, described organic solvent is selected from a kind of in the aromatic hydrocarbon of the naphthenic hydrocarbon of branched paraffin, a 5-20 carbon of straight-chain paraffin, a 5-20 carbon of 5-20 carbon or 6-20 carbon or their mixture;
Wherein, the stir speed (S.S.) of described cooling fluid is-8000 rev/mins of 200 commentaries on classics;
Wherein, the described speed that magnesium halide alcoholic solution or the magnesium halide aqueous solution are shifted the while hot 0.1%-100% that is total amount/minute.
2. preparation method according to claim 1, it is characterized in that, described alcohol is selected from ethanol, propyl alcohol, methyl alcohol, ethylene glycol, n-propyl alcohol, Virahol, 1, ammediol, butanols, isopropylcarbinol, hexanol, enanthol, n-Octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol, sorbyl alcohol, hexalin or benzylalcohol.
3. preparation method according to claim 1 is characterized in that, wherein, the stir speed (S.S.) of described cooling fluid is-5000 rev/mins of 300 commentaries on classics.
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| CN1580136A (en) * | 2003-08-08 | 2005-02-16 | 中国石油化工股份有限公司 | Magnesium halide/alcohol addition compound and its preparing method and use |
| CN101544710A (en) * | 2008-03-28 | 2009-09-30 | 中国石油化工股份有限公司 | Magnesium halide alcohol adduct and preparation method and application thereof |
| CN101579642A (en) * | 2009-05-27 | 2009-11-18 | 中国石油天然气股份有限公司 | Preparation method of magnesium halide supported catalyst |
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| CN101544710A (en) * | 2008-03-28 | 2009-09-30 | 中国石油化工股份有限公司 | Magnesium halide alcohol adduct and preparation method and application thereof |
| CN101579642A (en) * | 2009-05-27 | 2009-11-18 | 中国石油天然气股份有限公司 | Preparation method of magnesium halide supported catalyst |
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| 《山东师大学报(自然科学版)》 20001231 彭安顺 烯丙基型卤化镁的合成及其与醛酮的加成反应 464-466 1-3 第15卷, 第4期 2 * |
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