CN103030718A - Method for preparing solid catalyst for olefinic polymerization and carrier of solid catalyst - Google Patents
Method for preparing solid catalyst for olefinic polymerization and carrier of solid catalyst Download PDFInfo
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- CN103030718A CN103030718A CN201210575900XA CN201210575900A CN103030718A CN 103030718 A CN103030718 A CN 103030718A CN 201210575900X A CN201210575900X A CN 201210575900XA CN 201210575900 A CN201210575900 A CN 201210575900A CN 103030718 A CN103030718 A CN 103030718A
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Abstract
The invention provides a method for preparing a solid catalyst for an olefinic polymerization and a carrier of the solid catalyst. The method comprises the steps that magnesium (a component a), alcohol (a component b), halogen or a halogen compound (a component c) and titanium halide (a component d) are prepared to form the carrier (a component e) for the solid catalyst for the olefinic polymerization; the component e is further contacted with an inert solvent (a component f), titanium halide (the component d), an electron donor compound (a component g), and the like; and then the solid catalyst for the olefinic polymerization is synthesized. Then solid catalyst for the olefinic polymerizatio prepared by the method is higher in activity.
Description
Technical field
The present invention relates to a kind of method for preparing olefin polymerization solid catalyst, specifically, the present invention relates to a kind of method for preparing olefin polymerization solid catalyst and used carrier thereof.
Background technology
Along with the development of polypropylene industry, the preparation method of olefin polymerization catalysis has also obtained fast development.The present preparation method of a lot of business-like polyolefin catalysts adopts the carrier of first synthesis of polyolefins catalyzer and then the method for synthesis of polyolefins catalyzer.The carrier of the polyolefin catalyst of traditional method preparation is mainly the solid particulates such as the alcohol adduct of magnesium chloride or alkoxyl magnesium.
Application number is that CN201010279310.3 discloses a kind of method for preparing carrier and the catalyzer of magnesium halide alcohol adduct.Its step is mainly: be that 2 ~ 100:1 adds in the encloses container in molar ratio with alcohol and magnesium halide, be warming up to 60 ~ 180 ℃ of stirring reaction certain hours, the solution that obtains is transferred to while hot in the mixed system of-25 ℃ to 30 ℃ the inert solvent that is in flow state or inert solvent and emulsifying agent, stir, with organic solvent washing 3 ~ 6 times, vacuum-drying obtains the pure and mild composition granule of solid spherical magnesium halide, and diameter of carrier is little, be evenly distributed, and diameter of carrier is between 2 ~ 3 μ m.Carrier is dispersed in the organic solvent, at-30 ℃ to 30 ℃ lower and titanium compound reactions, the Primary Catalysts that obtains.The feature of the Primary Catalysts of its invention is: granules of catalyst is spherical in shape; Carry titanium amount high (4.0 ~ 9.76wt/%); The catalytic efficiency of polymerization or copolymerization is high, and polyolefinic molecular weight in very large range can be regulated.
Application number is 200510109095.1 to disclose a kind of method for preparing solid catalyst in olefin polymerization catalyst, and the dialkoxy magnesium of its temperature by reducing the dialkoxy magnesium compound and contact with titanium compound, employing high-bulk-density or the dripping quantity of raising titanium compound improve the tap density of polymkeric substance.
The present inventor adopts component a(MAGNESIUM METAL), the halogenide of components b (alcohols), amount of component b (halogen or halogen compounds), component d(titanium) carrier of synthetic component e(solid catalyst for olefin polymerization), then with component e and component f(inert solvent), the halogenide of component d(titanium) with component g(to electron compound) etc. contact and synthesize solid catalyst for olefin polymerization.
Summary of the invention
The object of the present invention is to provide a kind of method of the carrier for the preparation of olefin polymerization solid catalyst.
Another object of the present invention is to provide the solid catalyst carrier by the method preparation.
A further object of the present invention is to provide a kind of method for preparing olefin polymerization solid catalyst.
An also purpose of the present invention is to provide the thus solid catalyst of method acquisition.
In order to realize the object of the invention, a kind of olefin polymerization solid catalyst of the present invention is with the preparation method of carrier, and it adopts, and (component a), the halogenide (component d) of alcohols (components b), halogen or halogen compounds (amount of component b), titanium prepares olefin polymerization solid catalyst with carrier (component e) with MAGNESIUM METAL.
Wherein, component a is MAGNESIUM METAL, can be magnesium rod, magnesium grain, magnesium chips or magnesium powder.Recommendation magnesium powder, the particle diameter of magnesium powder be at 5～400 orders, preferred 40～200 orders.
Components b is that a kind of room temperature is liquid alcohol compound, can be monohydroxy-alcohol, polyvalent alcohol or these pure mixtures.The alcohol of recommending comprises: a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or the trimethyl carbinol etc., particular methanol, ethanol or the trimethyl carbinol, take ethanol as best, the consumption of alcohol is that every mol magnesium powder needs 1～30mol alcohol, and the best is that every mol magnesium powder needs 3～10mol alcohol.Temperature of reaction is 0 ℃～200 ℃, preferred 20 ℃～80 ℃.
The amount of component b halogen be or/and halogen compounds can be chlorine, bromine, elemental iodine or magnesium chloride, magnesium bromide, magnesium iodide, the most handy elemental iodine and magnesium chloride in these are used.The consumption of iodine is that every mol magnesium powder needs 1～500mmol, and the best is that every mol magnesium powder needs 10～100mmol.
Component d is the halogenide of titanium, comprise titanium tetrachloride, titanium tetrabromide and titanium tetra iodide, alkoxyl group halogenated titanium such as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, three n-Butoxyl titanium-chlorides.Preferred titanium tetrachloride in these halogenated titaniums.Can use one or more in these halogenated titaniums and mix use.
Wherein, each amounts of components is as follows:
The mol ratio of components b and component a is 1～30, preferred 3～10;
The mol ratio of amount of component b and component a is 0.001～0.5, preferred 0.01～0.1;
The mol ratio of component d and component a is 0.001～0.5, preferred 0.05～0.1.
In the preparation process of solid catalyst of the present invention with carrier component e, the order of addition(of ingredients) of each component or mode are arbitrarily, preferably component a is joined in the mixing solutions of components b and amount of component b, and then adding component d, reaction is carried out drying after finishing, and obtains olefin polymerization solid catalyst carrier (component e) powder.
Particularly preferably, olefin polymerization solid catalyst of the present invention with the preparation method of carrier is: amount of component b is dissolved in the part components b first, then add part component a and heat up and mix, continue again to add component a and components b, add at last component d and react and form.
By the olefin polymerization solid catalyst of aforesaid method preparation with the performance perameter of carrier be: titanium content is 0.1 ~ 10(wt) %, and cl content is 0.1 ~ 15(wt) %, and Mg content is 15 ~ 25(wt) %, and oxyethyl group content is 50 ~ 80(wt) %.
Olefin polymerization solid catalyst of the present invention can further react the acquisition olefin polymerization solid catalyst with carrier.
In order to realize another object of the present invention, the preparation method of olefin polymerization solid catalyst of the present invention, employing with olefin polymerization solid catalyst with carrier component e at component f(inert solvent) under, with the halogenide of component d(titanium) and component g(electron donor compound) react and form.
Wherein, component f inert solvent is to be liquid hydro carbons or aromatic hydroxy compound, preferred toluene, hexane, heptane etc., particularly preferably toluene, hexane under the normal temperature.
Component g is the electron donor compound, is the compounds such as the ester class of phenols, ketone, aldehydes, carboxylic acid, propanedioic acid, organic acid or mineral acid, monoether, diether, polyethers.Wherein the multi-carboxylate is preferred, the aromatic polycarboxylic acid ester be preferred, consider that from the polymerization activity aspect aromatic binary carboxylic acid monoesters, diester or diether are particularly preferred.The diester class of aromatic carboxylic acid wherein, comprise Bisphthalate or bis--terephthalate, Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, the Methyl Benzene-o-dicarboxylate ethyl ester, the Methyl Benzene-o-dicarboxylate isopropyl ester, the Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), the ethyl phthalate(DEP) isobutyl ester, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2,2-dimethyl hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2,2-dimethyl heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can use in independent or multiple mixing.
The bis--terephthalate comprises: dimethyl terephthalate (DMT), diethyl terephthalate, the terephthalic acid di-n-propyl ester, the terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutyl ester), terephthalic acid two n-pentyl esters, the terephthalic acid diisoamyl ester, the terephthalic acid dihexyl, terephthalic acid two positive heptyl esters, the terephthalic acid di-n-octyl, terephthalic acid two different n-octyls, terephthalic acid two (2,2-dimethyl hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, the terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester), with terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can use in independent or multiple mixing.
Preferred diethyl phthalate in these diester, the dipropyl phthalic butyl ester, the terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, the terephthalic acid di-n-octyl, the terephthalic acid di-isooctyl, the mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or the Di Iso Decyl Phthalate.
Two ethers are such as alkyl two ethers: dme, second diether, the first and second diether, glycol dimethyl ether, diethyl ether, 2,2-diisobutyl-1,3-methoxy propane etc.; Aryl two ethers: dibenzyl ether, ethylbenzene diether, n-proplbenzene diether, isopropyl benzene diether, n-butylbenzene diether, isobutyl-benzene diether, triphen diether, two (methoxymethyl) fluorenes of 9,9-, 2-methoxymethyl cumarone, bis-phenol diether etc.
The proportional range of the amount of each component is as follows in the solid catalyst preparation process:
The mass ratio of component d and component e is 1～100, preferred 3～20;
The mass ratio of component f and component e is 1～100, preferred 3～20;
The mass ratio of component g and component e is 0.01～1, preferred 0.15～0.5.
In the process of the present invention by the solid catalyst component for olefine polymerization A of component e preparation, engagement sequence or the mode of carrier e and component d, component f, component g are arbitrarily, and preferred version is:
Support of the catalyst e contacts with component f, component d first, and then contact with component g, the gained solid part contacts through one or many with mixture or the component d of component d and component f again, then the gained solid contacts one or many with component f again, carries out at last dry solid catalyst component for olefine polymerization A.
The Contact Temperature of carrier e and component f, component d, component g is-50 to 200 ℃, preferred-20 to 130 ℃.
The solid catalyst of gained of the present invention can be used for preparing olefin polymerization catalysis, and described olefin polymerization catalysis comprises following component:
(A) ingredient of solid catalyst of the present invention (being called for short component A)
(B) a kind of organo-aluminium compound (abbreviation B component), the general molecular formula is as follows: R
2 PAlQ
3-P(R
2Refer to C
1-4Alkyl; Q refers to hydrogen atom or halogen atom (such as chlorine, bromine, iodine), and the value of P is 0-3)
(C) a kind of silicoorganic compound (being called for short component C), the general molecular formula is as follows: R
3 qSi(OR
4)
4-q(R
3And R
4Refer to C
1-12Alkyl, C
1-12Cycloalkyl, phenyl, allyl group, aralkyl, vinyl, these groups can be the same or different, the value of q is: 1-3).
Wherein: B component is preferably triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, diethyl aluminum bromide or ADEH.The organism of these aluminium can use separately or two or more simultaneously use.What effect was best is triethyl aluminum and triisobutyl aluminium.
Component C specifically can be: the trimethylammonium methoxy silane, trimethylethoxysilane, three n-propyl methoxy silane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silane, the triisobutyl Ethoxysilane, the thricyclohexyl methyl-monosilane, the thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, the diη-propyl diethoxy silane, the di-isopropyl diethoxy silane, the di-n-butyl diethoxy silane, the diisobutyl diethoxy silane, di-t-butyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, the di-t-butyl diethoxy silane, the di-n-butyl diethoxy silane, n-butylmethyldimethoxyforane, two (2-ethylhexyl) dimethoxy silane, two (2-ethylhexyl) diethoxy silane, Dicyclohexyldimethoxysilane, the dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexyl Methyl Dimethoxysilane, the cyclohexyl methyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclohexyl n-propyl dimethoxy silane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silane, the amyl group methyl dimethoxysilane, the amyl group methyldiethoxysilane, amyl group ethyl dimethoxy silane, amyl group ethyl diethoxy silane, cyclohexyl dimethyl methyl TMOS, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl Ethoxysilane, 2-ethylhexyl Trimethoxy silane, cyclohexyl dimethoxy silane, the cyclohexyl diethoxy silane, 2-ethylhexyl triethoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, the isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, the cyclopentyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-ethylhexyl Trimethoxy silane, 2-ethylhexyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane, 3,5-Dimethylcyclohexyl cyclopentyl dimethoxy silane, 3-methylcyclohexyl cyclohexyl dimethoxy silane, two (3-methylcyclohexyl) dimethoxy silane, 4-methylcyclohexyl cyclohexyl dimethoxy silane, two (4-methylcyclohexyl) dimethoxy silane, 3,5-Dimethylcyclohexyl cyclohexyl dimethoxy silane, two (3,5-Dimethylcyclohexyl) dimethoxy silane, tetrapropoxysilane, four butoxy silanes.First-selected in these silicoorganic compound: diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, the di-n-butyl diethoxy silane, tert-butyl trimethoxy silane, Dicyclohexyldimethoxysilane, the dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl ethyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, the cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane and 3,5-dimethylcyclopentyl dimethoxy silane etc.These compound component C can use separately or mix use.
The catalyzer of using among the present invention carries out olefinic polymerization, and homopolymerization and copolymerization can be used above-mentioned by component A, B component, the prepared catalyzer of component C.Usually the mol ratio of B component and component A be 1～1000(wherein component A in the amount of titanium atom among the component A), be preferably 50～800; The mol ratio of component C and B component is 0.002～10, is preferably 0.01～2, is preferably 0.01～0.5.
The order of addition(of ingredients) of each component is arbitrarily, joins at first in the paradigmatic system with B component, then adds component C, and it is good adding at last component A.
Polymerization technique among the present invention can carry out in the situation of solvent solvent being arranged or do not have.Olefinic monomer can be gas phase or liquid phase.Further add hydrogen and can be used as molecular weight regulator.Certainly polymerization also can be carried out in the situation of molecular weight regulator not having.Polymerization temperature is not higher than 200 ℃, had better not be above 100 ℃.Polymerization pressure does not surpass 10MPa, had better not surpass 5MPa.Successive polymerization or batchwise polymerization technique can be used.And polyreaction can divide a step, two steps or multistep to carry out.
Use the alkene that catalyzer of the present invention carries out homopolymerization or copolymerization and comprise normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is such as 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is such as divinyl, vinyl cyclopentenes and vinyl cyclohexene.Catalyzer of the present invention preferably is applied in polyethylene and the polypropylene.These alkene can use in independent or multiple mixing.
Use the polymerization (referring to the main body polymerization here) of the alkene that catalyst component A of the present invention, B component, component C carry out, recommend to carry out the degree of isotacticity, particle properties of the reactive polymer of the incompatible increase catalyzer of pre-polymerization etc.This prepolymerization technology can be used for the vinylbenzene homopolymerization equally.
The order of addition(of ingredients) of each component and monomer is arbitrarily in prepolymerization technology.Preferably first B component is joined and contain inertia and maybe will carry out in the alkene gas of polymerization, then after adding component A, add one or more alkene of wanting polymerization.In using the prepolymerized process of alkene of organosilane, suggestion joins B component in the prepolymerization system of olefin gas that rare gas element maybe will carry out polymerization, then adds component C, then adds component A, adds at last alkene again.
Olefin polymerization solid catalyst of the present invention is good with the particle shape of carrier, particle intensity is high, distribution is concentrated, specific surface area is high, and is high, difficult broken by catalyst activity height, the particle intensity of carrier preparation of the present invention.
Embodiment
The below further describes the present invention with embodiment, is conducive to the understanding to the present invention and advantage thereof, better effects if, but described embodiment only is used for explanation the present invention rather than restriction the present invention.
Testing method:
1. titanium content is measured with 721 spectrophotometer colorimetrys;
2. the mensuration of oxyethyl group adopts the GC7890A of Agilent Technologies gas chromatograph for determination;
3. the mensuration of Mg content adopts EDTA complexometric titration;
4. chloride content determination adopts A
gNO
3-NH
4The anti-method of dripping of CNS;
5. polymer bulk density (BD) is with reference to the GB/T1636-1989 standard test;
6. particles distribution instrument is according to the optical diffraction Principle Method based on one-wavelength laser, with Ma Erwen laser particle analyzer Mastersizer2000 tester.
The comparative example 1
1, the preparation of support of the catalyst (preparation of spherical magnesium ethylate)
In the four-hole boiling flask of agitator is housed, install back to connect on the flow condenser and accumulate the moulded coal gas meter, whole reaction unit adds dehydrated alcohol 70.8ml in container after fully replacing through nitrogen, and iodine 1.26g makes it dissolving.Then add the 6g MAGNESIUM METAL, be warming up to the reflux temperature of ethanol under agitation condition, beginning adds dehydrated alcohol 47ml, magnesium powder 6g, totally 3 times every 10min from refluxing.About 1～2h liquid viscosity begins rapid rising (can calculate reactivity by the amount of the hydrogen of generation this moment is about 85%) after adding is finished for the third time, at this moment in reactive system, add ethanol 259ml again, continue reaction until the reaction termination no longer produces till the hydrogen, about about 6h of whole reaction times.Then with the remaining liq press filtration and drain, get the white solid powder, be the spherical magnesium ethylate of polyolefin catalyst carrier.
2, the preparation of catalyzer
The magnesium ethylate of getting the above-mentioned preparation of 10g is added in the 80ml20 ℃ of toluene that is stirring, then add titanium tetrachloride 20ml, heating makes reaction solution be warming up to 80 ℃ of adding dibutyl phthalate 3.6ml, continue to be warming up to 110 ℃ of reaction 2h, then the liquid press filtration is clean, and with 100ml toluene 80 ℃ the washing 2 times, then the gained solid being divided with volume ratio is that 20% titanium tetrachloride toluene solution 100ml processes 60min in 110 ℃, then with 40 ℃ of washings of 100ml hexane 5 times, with the gained solid drying, both got solid catalyst.
The ingredient of solid catalyst of gained by analysis, titanium content is 2.83(wt) %.
3, propylene polymerization (polymerization appreciation condition)
At the 5L stainless steel cauldron after nitrogen is fully replaced, adding 5ml concentration is that triethyl aluminum hexane solution and the 1ml concentration of 0.5mol/L is the catalyzer 10mg of 1mol/L Cyclohexylmethyldimethoxysilane (CMMS) hexane solution and above-mentioned preparation, then add 10ml hexane flushing charge line, add again 2LH
2(mark attitude) and 2.5L make with extra care propylene, and the control reaction is warming up to 70 ℃, polyreaction 1h under this temperature at 20 ℃ of pre-polymerization 5min.After reaction finished, with the reactor cooling and stop to stir and discharge reaction product, drying obtained polypropylene powder 41000g.Catalyst activity is 41000g/g(polypropylene/catalyzer), polymer bulk density is 0.42g/cm
3
Embodiment 1
1, the preparation of support of the catalyst
500ml through nitrogen fully replace with 5 mouthfuls of flasks that stir in, the dehydrated alcohol and the iodine 1.1g that add 120ml, make its dissolve complete, then add magnesium powder 12g and heat up and high-speed stirring, again to wherein adding magnesium powder 18g and dehydrated alcohol 160ml reaction, again to wherein dripping titanium tetrachloride 10ml and constantly stirring, then continue to wherein adding dehydrated alcohol to 320ml, isothermal reaction 2.5h is with the product drying of preparation, the pressed powder that obtains is the support of the catalyst e among the present invention.
The gained solid ingredient by analysis, titanium content is 1.1(wt) %, cl content is 2.72(wt) %, Mg content is 19.75(wt) %, oxyethyl group content is 76.41(wt) %.Tap density 0.29g/ml.
Gained ball type carrier size-grade distribution is component D10:18 micron after tested; Component D50:39 micron; Component D90:50 micron.
2, the preparation of catalyzer
Except the support of the catalyst e with the aforesaid method preparation, the preparation method of all the other catalyzer obtains solid catalyst 9.6g with comparative example 1, contains Ti2.82(wt) %.
3, propylene polymerization (polymerization appreciation condition)
Polypropylene powder 45100g.Catalyst activity is 43100g/g(polypropylene/catalyzer), polymer bulk density is 0.45g/cm
3
Embodiment 2
1, the preparation of support of the catalyst
500ml through nitrogen fully replace with 5 mouthfuls of flasks that stir in, the dehydrated alcohol and the iodine 1.1g that add 120ml, it is dissolved fully, then add magnesium powder 12g and heat up and high-speed stirring, again to wherein adding magnesium powder 18g and dehydrated alcohol 160ml reaction, then to wherein adding dehydrated alcohol to 320ml, drip titanium tetrachloride 10ml and constantly stirring, isothermal reaction 2.5h is dry with the product of preparation, the pressed powder that obtains is the support of the catalyst e among the present invention.
The gained solid ingredient by analysis, titanium content is 1.09(wt) %, cl content is 3.28(wt) %, Mg content is 20.14(wt) %, oxyethyl group content is 75.49(wt) %.Tap density 0.27g/ml.
2, the preparation of catalyzer
Except the support of the catalyst e with the aforesaid method preparation, the preparation method of all the other catalyzer obtains solid catalyst 9.7g with comparative example 1, contains Ti2.87(wt) %.
3, propylene polymerization (polymerization appreciation condition)
Polypropylene powder 38500g.Catalyst activity is 46500g/g(polypropylene/catalyzer), polymer bulk density is 0.416g/cm
3
Embodiment 3
1, the preparation of support of the catalyst
500ml through nitrogen fully replace with 5 mouthfuls of flasks that stir in, the dehydrated alcohol and the iodine 1.1g that add 120ml, it is dissolved fully, add titanium tetrachloride 5ml, adding 12g magnesium powder after titration is complete heats up and high-speed stirring 30min again, again to wherein adding magnesium powder 18g and dehydrated alcohol 150ml, accelerate to stir and add dehydrated alcohol to 320ml after adding above-mentioned substance, again to wherein adding titanium tetrachloride 5ml and constantly stirring, isothermal reaction 2.5h, the product of preparation is dry, and the pressed powder that obtains is the support of the catalyst e among the present invention.
The gained solid ingredient by analysis, titanium content is 1.23(wt) %, cl content is 2.23(wt) %, Mg content is 19.94(wt) %, oxyethyl group content is 76.6(wt) %.Tap density 0.29g/ml.
2, the preparation of catalyzer
Except the support of the catalyst e with the aforesaid method preparation, the preparation method of all the other catalyzer obtains solid catalyst 9.8g with comparative example 1, contains Ti2.95(wt) %.
3, propylene polymerization (polymerization appreciation condition)
Polypropylene powder 45300g.Catalyst activity is 45300g/g(polypropylene/catalyzer), polymer bulk density is 0.44g/cm
3
Table 1: the close data of activity, polymer stacks that adopt the catalyzer of different methods preparation
| ? | Catalyst activity gpp/gcat | The close g/cm of polymer stacks 3 |
| The comparative example 1 | 41000 | 0.42 |
| Embodiment 1 | 45100 | 0.45 |
| Embodiment 2 | 46500 | 0.42 |
| Embodiment 3 | 45300 | 0.44 |
Can draw by comparison sheet 1 data, adopt the catalyst activity of the inventive method preparation higher.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. one kind prepares olefin polymerization solid catalyst with the method for carrier, it is characterized in that it adopts the halogenide with MAGNESIUM METAL, alcohols, halogen or halogen compounds, titanium to prepare the olefin polymerization solid catalyst carrier.
2. method according to claim 1 is characterized in that, described alcohols is that a kind of room temperature is liquid alcohol compound, is monohydroxy-alcohol, polyvalent alcohol or these pure mixtures; Comprise: a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or the trimethyl carbinol, particular methanol, ethanol or the trimethyl carbinol are take ethanol as best; The consumption of alcohol is that every mol magnesium powder needs 1～30mol alcohol, and the best is that every mol magnesium powder needs 3～10mol alcohol.
3. method according to claim 1 and 2 is characterized in that, described halogen is or/and halogen compounds is chlorine, bromine, elemental iodine or magnesium chloride, magnesium bromide, magnesium iodide, preferred elemental iodine and magnesium chloride; Consumption is that every mol magnesium powder needs 1～500mmol, and the best is that every mol magnesium powder needs 10～100mmol.
4. the described method of any one according to claim 1-3, it is characterized in that, the halogenide of described titanium, comprise titanium tetrachloride, titanium tetrabromide and titanium tetra iodide, one or more mixing in alkoxyl group halogenated titanium such as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, three n-Butoxyl titanium-chlorides; Preferred titanium tetrachloride; The mol ratio of the halogenide of titanium and magnesium powder is 0.001～0.5, preferred 0.05～0.1.
5. any one described method is characterized in that according to claim 1-4, and the temperature of reaction of described method is 0 ℃～200 ℃, preferred 20 ℃～80 ℃.
6. any one described method is characterized in that according to claim 1-5, and described method adopts is reacted by MAGNESIUM METAL, halogen or halogen compounds and alcohols first, and then reacts to the halogenide that wherein adds titanium and to form.
7. the olefin polymerization solid catalyst carrier that is prepared by any one described method among the claim 1-6.
8. a method for preparing olefin polymerization solid catalyst is characterized in that, adopt with the described olefin polymerization solid catalyst of claim 1-6 any one with carrier under inert solvent, form with halogenide and the reaction of electron donor compound of titanium.
9. method according to claim 8, it is characterized in that, described method adopts described olefin polymerization solid catalyst is contacted with the halogenide of inert solvent, titanium first with carrier, and then contact with the electron donor compound, the gained solid part contacts through one or many with halogenide and the mixture of inert solvent or the halogenide of titanium of titanium again, then the gained solid contacts one or many with inert solvent again, carries out at last drying and forms.
10. the olefin polymerization solid catalyst that is prepared by claim 8 or 9 described methods.
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| CN111848837A (en) * | 2020-07-16 | 2020-10-30 | 国家能源集团宁夏煤业有限责任公司 | Ziegler-Natta catalyst, preparation method, application and system thereof |
| WO2020237772A1 (en) | 2019-05-28 | 2020-12-03 | 国家能源集团宁夏煤业有限责任公司 | Industrial preparation method for ziegler-natta catalyst |
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| CN111848837A (en) * | 2020-07-16 | 2020-10-30 | 国家能源集团宁夏煤业有限责任公司 | Ziegler-Natta catalyst, preparation method, application and system thereof |
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