CN102796130B - Spherical magnesium halide adduct particle and its preparation method and application - Google Patents
Spherical magnesium halide adduct particle and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of preparation method of Spherical magnesium halide adduct particle, the method comprises the following steps: 1) in inert liquid medium, magnesium halide is contacted with one or more lewis base compounds, preparation is containing the mixture of melting adduct of magnesium halides; 2) the above-mentioned mixture containing melting adduct of magnesium halides is formed after emulsion through high shear forces, be transferred to chilling in low-temperature cooling media to be shaped, obtain described adduct of magnesium halides solid particulate, it is characterized in that, in step 1) in contact reacts between magnesium halide and lewis base compound divide the multistage to carry out, and the temperature of reaction of terminal stage is make described adduct of magnesium halides be the temperature of complete molten state.Present invention also offers the Spherical magnesium halide adduct particle and application thereof prepared by the method.By adduct of magnesium halides prepared by method of the present invention, particularly polynary adducts solid particulate particle is regular, without opposite sex material, without the phenomenon such as inter-adhesive.
Description
Technical field
The present invention relates to a kind of preparation method of Spherical magnesium halide adduct particle, the Spherical magnesium halide adduct particle prepared by the method and application thereof.Specifically, relate to and a kind ofly react by magnesium halide and one or more lewis base compounds the preparation method, the Spherical magnesium halide adduct particle prepared by the method that form polynary adducts spheroidal particle and preparing the application in catalyst for olefines polymerizing.
Background technology
Magnesium halide alcohol adduct and magnesium halide alcohol adduct particle are known in this area as the application of carrier in olefin polymerization catalysis preparation.The catalyzer prepared by such carrier has high olefin polymerizating activity, and when these catalyzer comprise electron donor compound, has high stereospecificity.But the form of resulting polymers is copying of catalyzer form, and the form of catalyzer is copying of its carrier form.Therefore, provide a kind of preparation method of well controlled ball type carrier to be very favourable, this carrier is used for the preparation of catalyst component, can give its corresponding catalyst component and the excellent polymerization of catalyzer thereof.
In the prior art, the carrier of magnesium halide containing can be prepared with many diverse ways.Be widely used in the method for the carrier preparing magnesium halide containing, such as, after forming the molten adduct of magnesium halide and Lewis base, spray (spray cooling) in cryogenic inert atmosphere, cause adducts to solidify; Or this adducts in suitable solvent is sprayed in an inert atmosphere, its temperature can make the instantaneous removal of solvent (spraying dry), thus forms solid adduct particle.
Another method being widely used in the ball type carrier preparing magnesium halide containing is above-mentioned adducts is melted in a kind of liquid phase medium not miscible with adducts under stirring, then mixture is transferred to and be down to low temperature in advance and in the heat-eliminating medium that stirred, adducts is insoluble wherein, and this heat-eliminating medium can make adducts solidify the shape of particle spherical in shape very soon.In form and distribution of sizes etc., acquired results depends on parameter selected in method each stage.The various trials that Here it is improves the method generally all relate to the reason of the concrete selection of a series of controling parameters.
US4469648 discloses a kind of method preparing magnesium halide containing ball type carrier.The method comprises (a) and forms the magnesium dichloride-alcohol adducts of molten and the mixture with the immiscible low viscosity inert liq of this adducts, and its ratio makes molten adduct form disperse phase; B () makes mixture through turbulent flow, to obtain emulsion; (c) emulsion is cooled fast, to solidify disperse phase and to collect solid adduct particle.Specifically, emulsion passes through being in control than path length 50-100 in it times by uniform mixture (Reynolds number is greater than 3000) under turbulent-flow conditions.Secondly, the linear velocity of emulsion in pipe and the surface tension between magnesium alkoxide adducts and not miscible inert liq are the determinatives of spherical adduct granular size.The requirement of the method to equipment is higher, and the form of the magnesium chloride alcohol adduct particle of gained is not good enough.
US4399054 discloses the processing method that a kind of high-speed mixing method prepares spherical magnesium dichloride-alcohol adducts particle.Gained adduct particles can be used as the carrier of catalyst component, they utilize high-speed stirring that alcohol adduct melt is distributed in the inert media of certain viscosity with the form of small droplets, after forming emulsion, emulsion is cooled fast, thus adducts is solidified immediately, obtain spherical magnesium chloride alcohol adduct particle.This comparison of processes is simple, but its anti-impurity (being mainly water) ability is more weak, must be could obtain good result raw materials used use after strict process purifying.
US4315874 also reveal that a kind of method preparing magnesium dichloride-alcohol adducts spheroidal particle.The method comprises (a) under the existence of tensio-active agent, forms the emulsion of adducts molten melt drop in liquid medium, and (b) makes this emulsion be entered by transfer pipeline in the heat-eliminating medium cooled in advance, solidifies to make adduct particles.In this preparation method, the good result of particle size dispersion aspect only has under tensio-active agent exists and just can obtain.
CN1580136A discloses and a kind ofly utilizes the high-gravity rotating bed method preparing magnesium dichloride-alcohol adducts spheroidal particle, the method is by the mixture of magnesium dichloride-alcohol adducts melt and inert liquid medium, under super gravity field, high speed rotating is dispersed into uniform drop, then pass into heat-eliminating medium fast setting fast to separate out, obtain the magnesium dichloride-alcohol adducts particle of solid.The mass transfer that the method mainly make use of in super gravity field between reactant can by the characteristic greatly strengthened.The environment of this super gravity field, is realized by a hypergravity swinging bed device.The narrower particle size distribution of solid adduct particle prepared by this technique, but also must be could obtain good result raw materials used use after strict process purifying.
Above in disclosed preparation method, all only disclose the binary adducts system of magnesium chloride and alcohol, and the chemical reaction between magnesium halide and alcohol be all after direct heating to determined temperature constant for some time complete, the ratio of the volume of heat-eliminating medium and the volume discharge rate of the emulsion of magnesium halide containing adduct melt and cooling efficiency are not added yet and define.
Along with the development of olefinic polymerization particularly catalyst for polymerization of propylene, investigator is in order to improve the over-all properties of catalyzer, comprise the fine powder reducing polymkeric substance, improve the stereotaxis ability of catalyzer and improve the hydrogen response etc. of catalyzer, start in the carrier preparation attempting electron donor compound being incorporated in advance magnesium chloride alcohol adduct, but this usually causes the particle form of carrier particle to be deteriorated, as easily occurred, abnormity material is (as oblate spheroid, bar shaped particle etc.), the phenomenons such as carrier particle size instability and carrier particle are clamminess, be unfavorable for the industrial production of carrier and the industrial application (such as propylene polymerization) of catalyzer thereof.
In technology disclosed in CN101050245A, C, C-bis-hydrocarbon oxy compound introduce in carrier, obtained as formula M gX
2-mROH-nE-pH
2ternary Spherical magnesium halide adduct shown in O, wherein said E is C, C-bis--oxyl hydrocarbon compound.By this adducts solid particulate be the catalyzer prepared of carrier for showing good hydrogen response during propylene polymerization, but when preparing solid adduct particle by disclosed preparation method, easily there is bar material, and its broad particle distribution.
The preparation of CN101684165A disclosed in CN101050245A is containing C, a kind of tensio-active agent of polyethenoxy ether class is introduced in the technology of the ternary spherical magnesium halide solid adduct of C-bis--oxyl hydrocarbon compound, overcome and easily occur the defect such as bar material, broad particle distribution, obtain satisfied result.But its good result be also only present in have tensio-active agent exist under just can obtain.
Electron donor compound phthalic ester is introduced in the synthesis of carrier by CN1397568A, defines magnesium dichloride-alcohol-phthalic ester ternary spherical adduct solid particulate.This adducts can be used for the preparation of olefin polymerization catalyst components as carrier, can obtain well spherical propene polymer when gained catalyst component and catalyzer thereof are used for propylene polymerization.But in the preparation process of this adducts carrier, easily there is the phenomenons such as solid adduct granular size instability and particle are clamminess.
In the technology of preparing of the magnesium halide-alcohol disclosed in CN101486722A-o-alkoxyl benzoic ether ternary adducts solid particulate, also there is the phenomenon easily occurring that gained adducts solids are clamminess, strictly must control each operating parameters in preparation process.
Therefore, be starved of a kind of simple and easy to do method preparing adduct of magnesium halides particularly polynary adducts carrier is provided.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Spherical magnesium halide adduct particle, particularly the method for polynary adducts spheroidal particle.This particle can be used for the preparation of olefin polymerization catalysis as carrier.
The present inventor finds in research trial repeatedly, by Spherical magnesium halide adduct prepared by interval (or stage intensification) reaction method, particularly polynary adducts spherical solid particles particle is regular, without opposite sex material, without the phenomenon such as inter-adhesive, and anti-impurity (mainly water) ability of the method is stronger.
The invention provides a kind of preparation method of Spherical magnesium halide adduct particle, the method comprises the following steps:
1) in inert liquid medium, contacted by magnesium halide with one or more lewis base compounds, preparation is containing the mixture of melting adduct of magnesium halides;
2) the above-mentioned mixture containing melting adduct of magnesium halides is formed after emulsion through high shear forces, be transferred to chilling in low-temperature cooling media and be shaped, obtain described adduct of magnesium halides solid particulate;
It is characterized in that, in step 1) in contact reacts between magnesium halide and lewis base compound divide the multistage to carry out, and the temperature of reaction of terminal stage is make described adduct of magnesium halides be the temperature of complete molten state.
The present invention also provides a kind of Spherical magnesium halide adduct particle, it is characterized in that, this adduct particles is prepared by above-mentioned method.
Above-mentioned Spherical magnesium halide adduct particle is as the application of carrier in olefin polymerization catalyst components and catalyzer thereof.
In the present invention, because the contact reacts of magnesium halide and lewis base compound divides the multistage to carry out, and the temperature of reaction of terminal stage is make described adduct of magnesium halides be the temperature of complete molten state, by the Spherical magnesium halide adduct that the method obtains, particularly the spherical solid particles particle of polynary adducts is regular, without opposite sex material, without the phenomenon such as inter-adhesive, and use the method to prepare in the process of Spherical magnesium halide adduct, strict with water treatment without the need to carrying out various raw material, the minor amount of water contained in magnesium halide and alcohol or other lewis base compound can participate in being formed the reaction of adducts, embody good anti-impurity (mainly water) ability.
Particularly, adopt method of the present invention, when not containing the second lewis base compound except alcohol, (D90-D10)/D50 value of the spherical adduct particle obtained can be less than 1.4; When containing multiple Lewis base, (D90-D10)/D50 value of the spherical adduct particle obtained can be less than 1.6.As for the spherical-like morphology of spherical adduct particle, the ratio adopting method of the present invention can obtain maximum diameter and minimum diameter is the particle of 1.5.
Embodiment
The invention provides a kind of preparation method of Spherical magnesium halide adduct particle, the method comprises the following steps:
1) in inert liquid medium, contacted by magnesium halide with one or more lewis base compounds, preparation is containing the mixture of melting adduct of magnesium halides;
2) the above-mentioned mixture containing melting adduct of magnesium halides is formed after emulsion through high shear forces, be transferred to chilling in low-temperature cooling media and be shaped, obtain described adduct of magnesium halides solid particulate;
It is characterized in that, in step 1) in contact reacts between magnesium halide and lewis base compound divide the multistage to carry out, and the temperature of reaction of terminal stage is make described adduct of magnesium halides be the temperature of complete molten state.
The product that method of the present invention obtains especially shows excellent characteristic in size-grade distribution in form, can be used for the preparation of olefin polymerization catalyst components and catalyzer thereof as carrier.In addition, the method shows stronger anti-impurity (being mainly water) ability when the preparation for adduct of magnesium halides.
According to method of the present invention, the contact reacts between described magnesium halide and one or more Lewis bases, normally carries out in the reactor that stirring is housed.Preferably, the contact reacts between magnesium halide and Lewis base is divided into two stages to carry out, and the temperature of reaction of previous stage is lower than the temperature of reaction of the latter half.Usually, the temperature of reaction of first stage is 40-100 DEG C, and the reaction times is 10-60min, and the temperature of reaction of subordinate phase is 105 DEG C-145 DEG C, and the reaction times is 30-300min; More preferably, the temperature of reaction of first stage is 60-90 DEG C, and the reaction times is 20-40min, and the temperature of reaction of subordinate phase is 110-130 DEG C, and the reaction times is 60-180min.
In the inventive method, described magnesium halide can be various halogenated magnesium compound known in the field.Particularly, magnesium halide can be as formula M gX
2shown in one or more in compound, wherein, X is fluorine, chlorine or bromine; Or MgX
2in an X be fluorine, chlorine or bromine, another X is for being selected from C
1-C
14alkyl, aryl, alkoxyl group or aryloxy.Concrete compound can list: magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc.Wherein, magnesium dichloride is particularly preferably.
Described Lewis base be selected from ester, alcohol, ketone, ether, phenol, carboxylic acid, amine and silane one or more, and at least one Lewis base is selected from general formula R (OH)
mshown alcohol, wherein, R is C
1-C
12alkyl or alkylidene group, C
3-C
10cycloalkyl or C
7-C
10aralkyl or arylmethylene alkyl, m is more than or equal to 1.Concrete compound can list; Methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, ethylene glycol, propylene glycol etc.Preferred R is C
1-C
4alkyl, m equals 1.
It is multiple for being more preferably described Lewis base.When described Lewis base is multiple, above-mentioned ester, ketone, ether, phenol, carboxylic acid, amine and silane preferably can be greater than 100 from the molecular weight of its hydrocarbyl portion.Concrete compound can list: 2-sec.-propyl 2-isopentyl 1,3-Propanal dimethyl acetal, diisobutyl phthalate, n-butyl phthalate, ethyl benzoate, o-methoxybenzoic acid ethyl ester, salicylic acid ethyl ester, 2,4-glycol dibenzoate, 4-ethyl-3,4-heptanediol dibenzoate, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 9, two (benzoyloxy methyl) fluorenes of 9-, 9,9-two (methoxymethyl) fluorenes etc.Be particularly preferably in molecular structure containing the ester of aromatic ring, ketone, ether, phenol, carboxylic acid, amine and silane.
According to method of the present invention, described inert liquid medium can be various inert liquid medium known in the field.Particularly, inert liquid medium can be one or more in silicoorganic compound and/or aliphatic hydrocarbon inert solvent.Described silicoorganic compound, such as, comprise methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil, methyl phenyl silicone oil etc.; Described aliphatic hydrocarbon inert solvent, such as, comprise kerosene, paraffin oil, vaseline oil, white oil etc.The present invention is preferably the mixture of methyl-silicone oil or methyl-silicone oil and white oil.When using method of the present invention to prepare Spherical magnesium halide adduct carrier, without the need to removing water treatment through strict before above-mentioned inert liquid medium uses, just particle can be obtained regular, without opposite sex material, solid adduct particle without the phenomenon such as inter-adhesive, embody good anti-impurity (mainly water) ability.
In the present invention, usually, the consumption of magnesium halide is 0.1-1.2mol/L inert liquid medium, and in every mole of magnesium, the consumption of alcohol is 1-6 mole, and one or more the consumption in ester, ketone, ether, phenol, carboxylic acid, amine and silane is 0-1.0 mole.Multiple consumption in described ester, ketone, ether, phenol, carboxylic acid, amine and silane refers to the multiple total consumption in ester, ketone, ether, phenol, carboxylic acid, amine and silane.Normally, the mol ratio of alcohol and magnesium halide changes along with the dissimilar of alcohol, and when use methyl alcohol, ethanol, propyl alcohol and butanols etc., the mol ratio of alcohol and magnesium halide is 2-6, preferred 2.5-4.
Minor amount of water in above-mentioned magnesium halide and alcohol or other Lewis base can participate in the reaction forming adducts.Embody good anti-impurity (mainly water) ability further.
In the preparation process in accordance with the present invention, when preparing the mixture containing melting adduct of magnesium halides, the order of addition(of ingredients) of each raw material can be in no particular order.
According to method of the present invention, after the reaction of magnesium halide and Lewis base completes, the mixture containing melting adduct of magnesium halides forms emulsion through high shear forces.Described high shear forces can adopt conventional method, as high-speed mixing method (see CN1330086A, US4399054), spray method (see US6020279), and higee technology (see CN1580136A) and mulser technology (see CN1463990A) etc.
The above-mentioned emulsion formed through high shear forces is transferred to chilling in low-temperature cooling media be shaped, obtains Spherical magnesium halide adduct solid particulate.In the methods of the invention, preferably make cooling efficiency for being greater than 100s the speed that described emulsion is transferred in heat-eliminating medium; Be more preferably and make cooling efficiency for being greater than 200s the speed that described emulsion is transferred in heat-eliminating medium; More preferably make cooling efficiency for being greater than 500s the speed that described emulsion is transferred in heat-eliminating medium.
In the method for the invention, term " cooling efficiency " means the volume (V of heat-eliminating medium
cold) be transferred to speed (V in heat-eliminating medium with emulsion
breast/ t (s)) ratio, be expressed as with the formula: cooling efficiency=(V
cold)/(V
breast/ t (s)).
Heat-eliminating medium described in the inventive method can adopt the inert hydrocarbon solvent that boiling point is lower, as pentane, hexane, heptane, gasoline or petrol ether etc.Before contacting with material, the temperature of heat-eliminating medium controls at-50 DEG C-0 DEG C, preferably-40 DEG C--and 20 DEG C.
The consumption of above-mentioned heat-eliminating medium has no particular limits, as long as can meet cooling efficiency.Particularly, can be 1-15: 1 for the volume of heat-eliminating medium and the volume ratio of emulsion, be preferably 2-9: 1.
Spherical solid particles obtained above, after inert hydrocarbon solvent washing, drying, obtains spherical adduct particles product.
The described inert hydrocarbon solvent for washing adopts the inert hydrocarbon solvent that boiling point is lower, as sherwood oil, raffinate oil, pentane, hexane, heptane etc., wash temperature adopts room temperature.
According to method of the present invention, when described lewis base compound is alcohol, the size-grade distribution of the spherical adduct particle of acquisition is less than 1.4, even can be less than 1.1; When described lewis base compound be alcohol and other Lewis base of at least one, the size-grade distribution value of the spherical adduct particle obtained is less than 1.6, even can be less than 1.2.
Above-mentioned size-grade distribution calculates by (D90-D10)/D50, and wherein in size distribution curve, D90 is the diameter value that the particle diameter of 90% of whole particle is less than; D10 is the diameter value that the particle diameter of 10% of whole particle is less than, and D50 is the diameter value that the particle diameter of 50% of whole particle is less than.
As for spherical-like morphology, the ratio that method of the present invention can obtain its maximum diameter and minimum diameter is less than 1.5, is even less than the particle of 1.3.
The present invention also provides a kind of Spherical magnesium halide adduct particle, and wherein, this adduct particles is prepared by the above-mentioned method preparing Spherical magnesium halide adduct particle.
The median size of above-mentioned Spherical magnesium halide adduct particle at 10-150 μm, preferred 15-90 μm.
Above-mentioned Spherical magnesium halide adduct particle can be used for the preparation of olefin polymerization catalyst components and catalyzer thereof as carrier.
The synthesis of catalyst component can adopt known synthetic method, as will be described adduct of magnesium halides particle directly and halogenated titanium react, usually according to practical application need optionally add the known internal electron donor compound of some industry.
Below by specific embodiment, the present invention is further detailed, but the present invention is not restricted to following embodiment.
In embodiment, size distribution, melt index and polymkeric substance isotactic index testing method are as follows below:
1, size distribution test: the median size of adduct of magnesium halides particle and size-grade distribution MastersSizer 2000 (being manufactured by Malvern Instruments Ltd) particle size analyzer determination.
2, melt index (M.I): measure according to ASTM D1238-99.
3, polymkeric substance isotactic index (II): adopt heptane extraction process to measure (heptane boiling extracting 6 hours), by 2 grams of dry polymer samples, be placed in extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to the polymer weight (g) of constant weight gained and be isotactic index with the ratio of 2.
Embodiment 1
In the autoclave of 0.5L, add fresh white oil 150ml, magnesium chloride 30g, o-methoxy benzoyl chloride 3ml and ethanol 52ml.Under agitation be warmed up to 80 DEG C, isothermal reaction 30min.Continue afterwards to be warming up to 120 DEG C, and constant temperature stirs 1.5h.Be transferred to by gained mixture in the fresh silicone oil of 300ml of 120 DEG C, high-speed stirring (1600rpm) disperses 30min.Afterwards, be that the discharge rate of 245s is transferred to and is cooled in the 3L hexane of-30 DEG C in advance, form solid particulate, elimination liquid by dispersion gained emulsion with cooling efficiency, with hexanes wash solid five times, vacuum-drying, obtains spherical magnesium chloride adducts solid particulate.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Embodiment 2
Except amount of alcohol added changes 55.5ml into, the other the same as in Example 1.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Embodiment 3
Except the discharge rate by dispersion gained emulsion with cooling efficiency being 982s is transferred to the 3L hexane China and foreign countries being cooled to-30 DEG C in advance, the other the same as in Example 1.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Comparative example 1
In the autoclave of 0.5L, add fresh white oil 150ml, magnesium chloride 30g, o-methoxy benzoyl chloride 3ml and ethanol 52ml.Under agitation directly be warming up to 120 DEG C, and constant temperature stirs 2h.Be transferred to by gained mixture in the fresh silicone oil of 300ml of 120 DEG C, high-speed stirring (1600rpm) disperses 30min.Afterwards, be that the discharge rate of 245s is transferred to and is cooled in the 3L hexane of-30 DEG C in advance with cooling efficiency by dispersion gained emulsion, form solid particulate, elimination liquid, during with hexanes wash solid, gained solid adhesion, in wall, can not obtain spherical magnesium chloride adducts solid particulate.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Embodiment 4
Except not using o-methoxy benzoyl chloride, and ethanol usage quantity changes into outside 50ml, the other the same as in Example 1.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Comparative example 2
Except not using o-methoxy benzoyl chloride, and ethanol usage quantity changes into outside 50ml, and other operation is with comparative example 1.But there is fraction solids particle to stick together in washing process.The characteristic results of its morphological character and size-grade distribution aspect lists in table 1.
Embodiment 5
The preparation of ingredient of solid catalyst
In the 300ml glass reaction bottle that the band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 90ml and the anhydrous hexane of 10ml, be cooled to-20 DEG C, add the solid adduct that 8.0g is prepared by embodiment 1, maintain-20 DEG C and stir 30min.Afterwards, start slowly to be warming up to 110 DEG C, in temperature-rise period, add diisobutyl phthalate (DIBP) 1.5ml, elimination liquid after 110 DEG C of isothermal reaction 30min.Add 80ml titanium tetrachloride, be warming up to 120 DEG C, after maintaining 30min at 120 DEG C, filter liquid; Repeat aforesaid operations once.Finally wash 5 times by hexane 60 DEG C of heat, hexane consumption is 80ml/ time; Vacuum-drying solids, namely obtains spherical catalyst components afterwards.
Propylene polymerization
Liquid phase bulk propylene polymerization carries out in the stainless steel autoclave of 5L.The hexane solution (concentration is 0.5mmol/ml) of 5ml triethyl aluminum, the hexane solution (concentration is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (CHMMS) and the above-mentioned spherical catalyst components of 9mg is added under nitrogen protection successively in reactor.Close autoclave, add the liquid propene of 1.5L hydrogen (standard volume) and 2.3L.Be warming up to 70 DEG C, react 1 hour, cooling, release, discharging, weighs after the drying of gained alfon.Polymerization result is listed in table 2.
Embodiment 6
Except the solid adduct particle used in ingredient of solid catalyst preparation changes the solid adduct that 8.0g prepared by embodiment 2 into, the other the same as in Example 5.Polymerization result is listed in table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Embodiment 4 | Comparative example 2 | |
| Form | Spherical | Spherical | Spherical | Adhesion | Spherical | Residual adhesion |
| Size-grade distribution | 1.5 | 1.3 | 1.1 | - | 1.3 | 2.1 |
Table 2
Claims (10)
1. a preparation method for Spherical magnesium halide adduct particle, the method comprises the following steps:
1) in inert liquid medium, contacted by magnesium halide with one or more lewis base compounds, preparation is containing the mixture of melting adduct of magnesium halides;
2) the above-mentioned mixture containing melting adduct of magnesium halides is formed after emulsion through high shear forces, be transferred to chilling in low-temperature cooling media and be shaped, obtain described adduct of magnesium halides solid particulate;
It is characterized in that, in step 1) in contact reacts between magnesium halide and lewis base compound divide two stages to carry out, and the temperature of reaction of terminal stage is make described adduct of magnesium halides be the temperature of complete molten state, wherein, the temperature of reaction of first stage is 60-90 DEG C, reaction times is 20-40min, and the temperature of reaction of subordinate phase is 110-130 DEG C, and the reaction times is 60-180min.
2. method according to claim 1, wherein, magnesium halide can be as formula M gX
2shown in one or more in compound, in formula, X is fluorine, chlorine or bromine; Or an X in formula is fluorine, chlorine or bromine, and another X is for being selected from C1-C14 alkyl, aryl, alkoxyl group or aryloxy.
3. method according to claim 1, wherein, described lewis base compound be selected from ester, alcohol, ketone, ether, phenol, carboxylic acid, amine and silane one or more.
4. method according to claim 3, wherein, in described lewis base compound, at least one is selected from alcohol, described alcohol is the such as compound shown in general formula R (OH) m, in formula, R is C1-C12 alkyl or alkylidene group, C3-C10 cycloalkyl or C7-C10 aralkyl or arylmethylene alkyl, and m is more than or equal to 1.
5. method according to claim 4, wherein, in described general formula R (OH) m, R is the alkyl of C1-C4, and m equals 1.
6. according to the method in claim 3-5 described in any one, wherein, the molecular weight of the hydrocarbyl portion of described ester, ketone, ether, phenol, carboxylic acid, amine and silane is greater than 100.
7. method according to claim 6, wherein, containing aromatic ring in the molecular structure of described ester, ketone, ether, phenol, carboxylic acid, amine and silane.
8. method according to claim 3, wherein, the consumption of magnesium halide is 0.1-1.2mol/L inert liquid medium, in every mole of magnesium, the consumption of alcohol is 1-6 mole, and one or more the consumption in ester, ketone, ether, phenol, carboxylic acid, amine and silane is 0-1.0 mole.
9. method according to claim 1, wherein, makes cooling efficiency for being greater than 100s the speed that described emulsion is transferred in heat-eliminating medium.
10. method according to claim 9, wherein, makes cooling efficiency for being greater than 200s the speed that described emulsion is transferred in heat-eliminating medium.
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