CN1931885B - Catalyst for polymerizing olefin and its preparation process - Google Patents
Catalyst for polymerizing olefin and its preparation process Download PDFInfo
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- CN1931885B CN1931885B CN200510103119A CN200510103119A CN1931885B CN 1931885 B CN1931885 B CN 1931885B CN 200510103119 A CN200510103119 A CN 200510103119A CN 200510103119 A CN200510103119 A CN 200510103119A CN 1931885 B CN1931885 B CN 1931885B
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Abstract
The present invention relates to catalyst for polymerization and copolymerization of olefin and its preparation process. The catalyst is obtained through dissolving magnesium halide in homogeneous solution of organic epoxy compound, organophosphorus compound and electron donor compound, and the reaction with the mixture solution of titanium halide or its derivative and liquid co-precipitant. Using the liquid co-precipitant intersoluble with titanium compound can omit the step of dissolving separating assistant, is favorable to the depositing separation of catalyst mother liquid system, raises the yield of the catalyst, avoids the residue of co-precipitant in catalyst product and raises the quality of polymer. The catalyst for polymerization and copolymerization of olefin has high activity and results in good polymer state.
Description
Invention field:
The present invention relates to a kind of catalyzer and method for making thereof that is used for olefinic polymerization or copolymerization.
Background of invention:
Company such as Mitsui petrochemical industry Co., Ltd. succeeds in developing multiple to be the Ti-Mg high-effective carrier catalyst of carrier with the magnesium chloride, to make world's slurry process production polyolefin industry obtain development fast since the seventies.More representational technology is the method for Mitsui oiling disclosed vinyl polymerization and copolymerization in Japanese Patent JP49-51378, and the concrete preparation method of this catalyzer is: magnesium dichloride through grinding in the lam-oil medium and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries are sloughed most of ethanol with aluminium diethyl monochloride generation esterification again, carry the titanium reaction with titanium tetrachloride at last, obtain Ti/MgCl
2High-effective carrier catalyst.This catalyst preparation process is simple, and reaction conditions is not harsh, processing ease, and activity is higher when being used for vinyl polymerization or copolymerization.But in whole catalyst preparation process, because this catalyzer adopts bigger alcohols and the alkane solvents of polarity difference to dissolve magnesium halide, this is a very difficult process, because in this case, even be heated to than higher temperature, for example more than 100 ℃, magnesium halide can not be dissolved fully and generate homogeneous phase solution, only is to generate a kind of particulate soliquid or swollen magnesium halide slurries.So just bring some and the relevant shortcoming of magnesium halide stratiform crystallization property for prepared catalyzer, the irregular sheet form that has formed when the carrier magnesium chloride has kept former grinding substantially in the slurry reaction system causes the Ti/MgCl that finally obtains
2The solid catalyst particle shape is relatively poor, and thickness is inhomogeneous, and fine powder is more.In order to guarantee to obtain the catalyzer of better performances, to close the consumption of alcohol in the reaction be that every mole of magnesium chloride is more than at least four moles to lay special stress on alcohol in the specification sheets of this patent. especially with six moles for well, so the consumption of aluminum alkyls and titanium tetrachloride is all bigger.If pure consumption more after a little while, activity was lower when the catalyzer that obtains was used for vinyl polymerization, and particle shape is relatively poor, and size-grade distribution is inhomogeneous, because the particle shape of polymkeric substance is relatively poor, the concentration of slurry during slurry polymerization is lower, has directly influenced the raising of production equipment production efficiency.
Chinese patent 8510097.2 discloses a kind of catalyst system that is used for equal polymerization of alkene and copolymerization, this catalyst system comprises: (first) contains the ingredient of solid catalyst of Ti, (second) alkylaluminium cpd, (the third) organosilicon, wherein (first) component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide, this solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of compounds such as precipitation additive such as organic acid anhydrides, organic acid, ether, ketone, separates out solids; This solids is handled with the multi-carboxylate, and it is attached on the solids, handles with titanium tetrahalide and inert diluent and obtains.This catalyzer adopts chloride epoxide and organo phosphorous compounds and blended solvent system of toluene composition to replace alcohols and alkane solvent system dissolving magnesium halide.Because the polarity of above-mentioned these components is close.Therefore can make magnesium halide under lower temperature, for example 50 ℃ can dissolve fully, form homogeneous phase solution.This just makes that the shortcoming relevant with magnesium halide stratiform crystalline characteristics is improved in the catalyzer.Particularly improve obviously at aspects such as apparent density, regularity and particle forms.When but this catalyst system was used for propylene polymerization, catalyst activity was higher, and the degree of isotacticity of resulting polymers is higher, and apparent density is also bigger.And when being used for vinyl polymerization, then exist catalyst activity lower, for example disclosed under 85 ℃, the condition of hydrogen pressure 0.25MPa, ethylene pressure 0.75MPa in embodiment 24, vinyl polymerization 2 hours, polymerization activity 537Kg polyethylene/gTi (10.7kgPE/gcat), and hydrogen is transferred responsive inadequately.
Chinese patent 98101108.X has proposed a kind ofly to be used for that ethylene homo closes or the catalyzer of copolymerization and this Preparation of catalysts method, wherein catalyzer is to be dissolved in organic epoxy compounds by magnesium halide, organo phosphorous compounds adds electron donor again and forms homogeneous solution, obtain with the halogenide or derivatives thereof effect of at least a precipitation additive and transition metals Ti again, combining with organo-aluminium compound during polymerization. this catalyst preparation process is simple, be used for vinyl polymerization and shown very high activity, the particle form of resulting polymers is better simultaneously, apparent density is higher, and low-molecular material content is less.
Though being used for olefinic polymerization, the catalyst system of above-mentioned two patents all has preferable performance, the former more biases toward propylene polymerization, the latter is partial to vinyl polymerization, but above-mentioned two kinds of catalyst bodys tie up in the preparation process in order to obtain the catalyst solid thing, all adopted the method for adding precipitation additive, more effective precipitation additive is an organic acid anhydride, organic acid, ether, a kind of in the ketone, when especially adopting Tetra hydro Phthalic anhydride as precipitation additive, better effects if, way is must be earlier with phthalic anhydride dissolving fully in mixed solvent system, and then cooling mixes with titanium compound, because catalyst solid grows out of nothing in the mother liquor system and assembles gradually and grow up in mixing process, in order to obtain good granules of catalyst form, therefore the mixing velocity and the temperature of reaction that need the strict hierarchy of control, and generally all need the long heating-up time, so the use of such precipitation additive is corresponding has prolonged the Preparation of catalysts cycle.In addition, above-mentioned precipitation additive system relative toxicity is bigger, and operational condition is had relatively high expectations, and cost is also higher.
Summary of the invention:
Deficiency at above-mentioned catalyst system existence, the specific inert solvent that the present invention is preferably dissolved each other with used titanium compound as making of coprecipitator success novel titanium polyolefin catalyzer, adopt the catalyzer of this method preparation have with above-mentioned patent catalyzer quite or better properties, and omitted the solubilizing reaction step of precipitation additive, adopt this method also to have following advantage simultaneously: at first the adding of such coprecipitator helps the settlement separate of catalyzer mother liquor system, next adopts this method can improve the catalyzer yield, last such coprecipitator does not residue in the catalyzer finished product, help to reduce the ash of polymerization product, thereby improved resin quality.
The present invention is used for the catalyzer of olefinic polymerization or copolymerization, comprises following component:
A. titaniferous ingredient of solid catalyst, be to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, again with the mixture solution effect of the halogenide or derivatives thereof of liquid coprecipitator and transition metals Ti and obtain, wherein electron donor is selected from a kind of in organic alcohol, the organic ether or their mixture;
B. organo-aluminium compound, its general formula is AlR
nX
3-n, R is a hydrogen in the formula, and carbonatoms is 1～20 alkyl, and X is a halogen, and n is the integer of 0＜n≤3;
Ratio between B component and the component A is 5～1000 with the molar ratio computing of aluminium and titanium.
Magnesium halide described in the catalyst component A of the present invention is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferred magnesium dichloride.
Organic epoxy compounds described in the catalyst component A of the present invention is selected from and comprises the compounds such as oxide compound, glycidyl ether and inner ether of carbonatoms at 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.Wherein, being preferably oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), is best with tetrahydrofuran (THF), epoxy chloropropane.
Organo phosphorous compounds comprises the hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, phosphorous acid benzene methyl etc.Wherein, be preferably ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl and ortho-phosphoric acid tri-n-butyl, the ortho-phosphoric acid tri-n-butyl is best.
Organic alcohol in the electron donor described in the catalyst component A of the present invention comprises C
1～C
12Straight chain alcohol or isomery alcohol, for example: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol are the best with ethanol, butanols, 2-Ethylhexyl Alcohol, glycerol; Organic ether in the described electron donor is a lower aliphatic ether, for example: methyl ether, ether, propyl ether, butyl ether, amyl ether, second diether etc.
Magnesium halide described in the catalyst component A of the present invention forms in the process of homogeneous solution in dissolving, can also add the metal halide conditioning agent, and wherein metal halide is selected a kind of in the halogenide of zinc, vanadium, iron, cobalt or their mixture.The effect that adds metal halide is to make catalyzer be used for ethylene polymerisation process, comes the effect of regulate polymer molecular weight more obvious with hydrogen.
Magnesium halide described in the catalyst component A of the present invention forms in the process of homogeneous solution in dissolving, can also add alkyl metal cpd such as zinc alkyl(s) and/or aluminum alkyls, wherein preferred triethyl aluminum, triisobutyl aluminium and zinc ethyl.
The selected principle of the liquid coprecipitator described in the catalyst component A of the present invention is to be the precipitation agent of magnesium halide solution system when using separately in the chosen temperature scope.Liquid coprecipitator described in the catalyst component A of the present invention is C
1～C
10Aliphatic hydrocarbon, alicyclic hydrocarbon or their mixture, be preferably hexane, heptane, octane, decane and hexanaphthene, with heptane, decane is best.
Can also suitably add inert diluent during the dissolving of magnesium halide described in the catalyst component A of the present invention as benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound, wherein preferred benzene,toluene,xylene is best with toluene, dimethylbenzene.
Its general formula of halogenide or derivatives thereof of the described transition metal Ti of catalyst component A of the present invention is TiX
n(OR)
4-n, wherein, X is a halogen, R is C
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, n is 0～4 integer, concrete as a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture, preferably titanium tetrachloride.
Catalyst component A of the present invention also needs to add the multi-carboxylate after solids is separated out preceding or separated out when being used for propylene polymerization.Described multi-carboxylate comprises aliphatics multi-carboxylate and aromatic series multi-carboxylate, concrete as: diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester etc., preferred n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate.
Mol ratio described in the catalyst component A of the present invention between each component is in every mole of magnesium halide, 0.01～10 mole of organic epoxy compounds, with 0.02～4 mole for well; 0.01～10 mole of organo phosphorous compounds, with 0.02～4 mole for well; 0.005～15 mole of electron donor, with 0.05～10 mole for well; 0～0.2 mole of metal halide, with 0～0.08 mole for well; 0～2 mole of alkyl metal cpd, with 0～0.5 mole for well; 0.2～20 mole in the halogenide of transition metal Ti, 0～2 mole of multi-carboxylate, the halid volume ratio of liquid coprecipitator and Ti is 0.1～10, with 0.5～2.5 for well.
B component is an organo-aluminium compound, and its general formula is AlR
nX
3-n, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, particularly alkyl, aralkyl, aryl etc.; X is halogen, particularly chlorine and bromine; N is the integer of 0＜n≤3.Particular compound is as trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum; Alkyl aluminium hydrides such as one hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum; Alkyl aluminum chlorides such as aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride; Wherein with triethyl aluminum and triisobutyl aluminium for well.
Among the catalyst system component B of the present invention among aluminium and the component A mol ratio of titanium be 5～1000, with 20～800 for well.
Catalyst body of the present invention ties up to when being used for propylene polymerization, also needs to add external electron donor, and its general formula is R
nSi (OR ')
4-nOrganosilane, R and R ' are alkyl of the same race or not of the same race, halo alkyl, 0≤n in the formula≤3.Concrete as: trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, a phenyltrimethoxysila,e, a phenyl triethoxysilane, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane etc.
Among the catalyst system component B of the present invention in aluminium and the external electron donor mol ratio of silicon be 50～0.5.
The preparation method of component A is as follows in the catalyzer of the present invention: under agitation magnesium halide is dissolved in organic epoxy compounds, add electron donor in the organo phosphorous compounds again, also can add metal halide and/or add alkyl metal cpd and form homogeneous transparent solution, under-35～60 ℃ of temperature, best-30～10 ℃, splash into the mixture solution of titanium compound and liquid coprecipitator in the magnesium halide homogeneous solution or magnesium halide solution is splashed in the mixture solution of titanium compound and liquid coprecipitator, when adopting the method that drips halogenated titanium, the dropping time preferably was controlled in 5 hours, when heating up gradually, heat-up rate is per hour to heat up 4～100 ℃ for well; Again with reaction mixture under 0～130 ℃ of temperature, best 20～130 ℃, stirred 1 minute～10 hours, stop to stir, mother liquor is removed in sedimentation, filtration, also can mix B component washing solids therein with toluene and hexane, make titaniferous ingredient of solid catalyst.Catalyst component A of the present invention also needs to add the multi-carboxylate and handles when being used for propylene polymerization after solids is separated out preceding or separated out.
When adopting the B component washing, the consumption of B component is 100～0.001 with the molar ratio computing of aluminium and titanium, is preferably 10～0.01, is preferably 1～0.1.
Gained solid ingredient A of the present invention is the pulverulent solids particulate, and median size is about 2～100 microns, and granular size can be controlled by changing preparation condition.Specific surface is generally at 100 meters
2More than/the gram.
Through above-mentioned steps, made the A component of catalyst system of the present invention, this component can be used with the form of solids or suspension, catalyst A of the present invention, the B component can directly apply to polymerization system, also can be applied to polymerization system after the pre-earlier complexing.
Catalyzer of the present invention can be used for the equal polymerization of ethene, also can be used for the copolymerization of ethene and alpha-olefin, and comonomer can adopt propylene, butylene, amylene, hexene, octene, 4-methyl 1-amylene; Also can be used for the equal polymerization polymerization together of propylene.
Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.When carrying out liquid polymerization, can use propane, hexane, heptane, hexanaphthene, Trimethylmethane, iso-pentane, petroleum naphtha, raffinate oil, inert solvent such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon makes reaction medium, can carry out prepolymerization earlier before the polymerization.Polymerization methods can adopt intermittent type, semi continuous or continous way.
Polymerization temperature is room temperature～150 ℃, with 50 ℃～100 ℃ for well.For the molecular weight of telomerized polymer, adopt hydrogen to make molecular weight regulator.
The present invention compares with prior art, have following obvious advantage: catalyst component A of the present invention select the specific inert solvent that dissolves each other with used titanium compound as making of coprecipitator success novel titanium polyolefin catalyzer, adopt the catalyzer of this method preparation have with the described catalyzer of prior art quite or better properties, and omitted the solubilizing reaction step of precipitation additive, adopt this method also to have following advantage simultaneously: at first the adding of such coprecipitator helps the settlement separate of catalyzer mother liquor system, next adopts this method can improve the catalyzer yield, last such coprecipitator does not residue in the catalyzer finished product, help to reduce the ash of polymerization product, thereby improved the polymeric articles quality.
Embodiment:
(1) Preparation of catalysts
Embodiment 1: through high-purity N
2Fully in the metathetical reactor, add the anhydrous MgCl of 4.0g successively
2, 50ml toluene, 2.0ml epoxy chloropropane, 3.0ml tributyl phosphate, be warmed up to 50 ℃ under stirring, and kept 15 minutes, add 6.0ml ethanol, continue reaction 15 minutes, this solution is cooled to-5 ℃, mixed solution with 30ml titanium tetrachloride and 30ml heptane splashes in it again, is warming up to 40 ℃ then, filters back hexane wash 4 times, vacuum-drying obtains solid catalyst.
Embodiment 2: with embodiment 1, only the intensification terminal temperature is brought up to 105 ℃ by 40 ℃.
Embodiment 3: with embodiment 1, only change the heptane add-on into 20ml.
Embodiment 4: with embodiment 1, only change the heptane add-on into 40ml.
Embodiment 5: with embodiment 1, only change the heptane add-on into 60ml.
Embodiment 6: with embodiment 1, only change heptane into decane, the intensification terminal temperature is brought up to 110 ℃ by 40 ℃.
Embodiment 7: with embodiment 1, only change heptane into hexane.
Embodiment 8: with embodiment 1, only change heptane into hexanaphthene.
Embodiment 9: with embodiment 1, and the only mixed solution washing of triethyl aluminum of increase and hexane after the second time, hexane was washed, wherein the triethyl aluminum consumption is 0.002 mole.
Embodiment 10: with embodiment 9, only when adding Magnesium Chloride Anhydrous, add 0.5 gram Zinc Chloride Anhydrous.
Embodiment 11: through high-purity N
2Fully in the metathetical reactor, add the anhydrous MgCl of 4.0g successively
2, 60ml toluene, 0.08 moles of epichlorohydrin, 0.024 mole of phosphoric acid tri-n-butyl, be warmed up to 50 ℃ under stirring, and kept 120 minutes, this solution is cooled to-25～-20 ℃, mixed solution with 45ml titanium tetrachloride and 45ml heptane splashes in it again, slowly is warming up to 80 ℃ then, adds 0.01 mole of diisobutyl phthalate, under 80 ℃, kept 60 minutes, and filtered back 60 milliliters of washed twice of toluene.Add 60 milliliters of toluene, 40 milliliters of titanium tetrachlorides then, handled 2 hours down at 90 ℃, re-treatment is once again after the filtration.Filter the back and respectively wash 2 times with toluene, hexane, vacuum-drying obtains solid catalyst.
Comparative example 1: through high-purity N
2Fully in the metathetical reactor, add the anhydrous MgCl of 4.0g successively
2, 50ml toluene, 2.0ml epoxy chloropropane, 3.0ml tributyl phosphate, be warmed up to 50 ℃ under stirring, and kept 15 minutes, add 6.0ml ethanol, continue reaction 15 minutes, add Tetra hydro Phthalic anhydride 0.5g then, kept again 30 minutes, this solution is cooled to-5～0 ℃, again the 20mL titanium tetrachloride is splashed in it, slowly be warming up to 40 ℃ then, filter back hexane wash 4 times, vacuum-drying obtains solid catalyst.
Comparative example 2:, only change heptane into toluene with embodiment 1.
Comparative example 3:, only heptane is cancelled with embodiment 1.
Comparative example 4: through high-purity N
2Fully in the metathetical reactor, add the anhydrous MgCl of 4.0g successively
2, 60ml toluene, 0.08 moles of epichlorohydrin, 0.024 mole of phosphoric acid tri-n-butyl, be warmed up to 50 ℃ under stirring, and kept 120 minutes, add 0.0064 mole of Tetra hydro Phthalic anhydride, continue reaction 60 minutes, this solution is cooled to-25～-20 ℃, again the 45ml titanium tetrachloride is splashed in it, slowly be warming up to 80 ℃ then, add 0.01 mole of diisobutyl phthalate, under 80 ℃, kept 60 minutes, and filtered back 60 milliliters of washed twice of toluene.Add 60 milliliters of toluene, 40 milliliters of titanium tetrachlorides then, handled 2 hours down at 90 ℃, re-treatment is once again after the filtration.Filter the back and respectively wash 2 times with toluene, hexane, vacuum-drying obtains solid catalyst.
Comparative example 5: except that not adding the Tetra hydro Phthalic anhydride, all the other are operated with comparative example 4, fail to obtain solid catalyst.
(2) vinyl polymerization: volume is that 2 liters stainless steel still is through H
2Fully after the displacement, add hexane 1000ml therein, triethyl aluminum 1.5ml concentration is the 1mol/L hexane solution, (5～6mg) the above-mentioned prepared ingredients of solid catalyst of metering, be warming up to 70 ℃ of hydrogenation 0.18MPa (gauge pressure), feed ethene again and make and reach 0.73MPa (gauge pressure) in the still, under 80 ℃, polymerization 2 hours, polymerization result sees Table 1.
(3) ethylene copolymerization: volume is that 2 liters stainless steel still is through H
2Fully after the displacement, add hexane 1000ml therein, hexene 10ml, triethyl aluminum 1.5ml (1mol/L hexane solution), metering (ingredient of solid catalyst that 5～6mg) the foregoing descriptions 1 are prepared is warming up to 70 ℃ of hydrogenation 0.18MPa (gauge pressure), feeding ethene again makes and reaches 0.73MPa (gauge pressure) in the still, under 80 ℃, polymerization 2 hours, polymerization result sees Table 1.
(4) propylene polymerization: volume is that 5 liters stainless steel still is after propylene gas is fully replaced, add 0.0008 mole of triethyl aluminum, 0.0001 mole of dimethoxydiphenylsilane therein, (6～8mg) the above-mentioned prepared ingredients of solid catalyst of metering, add 2.5 liters of propylene liquids again, add hydrogen 1.0 standard liters then, be warming up to 70 ℃, polymerization 2 hours, polymerization result sees Table 2.
Table 1:
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Catalyst yield (g) | 4.0 | 6.2 | 6.0 | 5.1 | 6.5 |
| Polymerization activity (ten thousand gPE/gcat) | 3.3 | 4.1 | 4.2 | 4.0 | 4.2 |
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Catalyst yield (g) | 6.3 | 6.5 | 6.4 | 5.6 | 6.3 |
| Polymerization activity (ten thousand gPE/gcat) | 4.1 | 4.0 | 3.3 | 3.6 | 4.0 |
| Embodiment 10 | Comparative example 2 | Comparative example 3 | Copolymerization | ||
| Catalyst yield (g) | 6.2 | 1.2 | 0.8 | 6.2 | |
| Polymerization activity (ten thousand gpE/gcat) | 3.9 | 3.3 | 3.4 | 2.9 |
Table 2:
| Comparative example 4 | Comparative example 5 | Embodiment 11 | |
| Catalyst yield (g) | 5.2 | 0 | 6.5 |
| Polymerization activity (ten thousand gPP/gcat) | 5.4 | ------ | 5.8 |
Claims (15)
1. a catalyzer that is used for olefinic polymerization is characterized in that, comprises following component:
A. titaniferous ingredient of solid catalyst, be to be dissolved in organic epoxy compounds and organo phosphorous compounds by magnesium halide to add electron donor again and form homogeneous solution, again with the mixture solution effect of the halogenide or derivatives thereof of liquid coprecipitator and transition metals Ti and obtain, wherein electron donor is selected from a kind of in organic alcohol, the organic ether or their mixture; Described liquid coprecipitator is selected from hexane, heptane, octane, decane and hexanaphthene;
B. organo-aluminium compound, its general formula is AlR
nX
3-n, R is a hydrogen in the formula, and carbonatoms is 1～20 alkyl, and X is a halogen, and n is the integer of 0＜n≤3;
Ratio between B component and the component A is 5～1000 with the molar ratio computing of aluminium and titanium.
2. the catalyzer that is used for olefinic polymerization according to claim 1, it is characterized in that, the described magnesium halide of component A forms in the process of homogeneous solution in dissolving, add alkyl metal cpd, wherein alkyl metal cpd is meant a kind of in alkylaluminium cpd or the alkyl zinc compound or their mixture.
3. the catalyzer that is used for olefinic polymerization according to claim 2 is characterized in that, the alkyl metal cpd of adding is triethyl aluminum, triisobutyl aluminium or zinc ethyl.
4. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, the organic alcohol in the described electron donor of component A comprises C
1～C
12Straight chain alcohol or isomery alcohol.
5. according to the catalyzer that is used for olefinic polymerization described in the claim 4, it is characterized in that the organic alcohol in the described electron donor of component A is a kind of in methyl alcohol, ethanol, propyl alcohol, butanols, octanol, lauryl alcohol, the glycerol, or their mixture.
6. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, the organic ether in the described electron donor of component A is a kind of in methyl ether, ether, propyl ether, butyl ether, the amyl ether, or their mixture.
7. the catalyzer that is used for olefinic polymerization according to claim 1, it is characterized in that the halogenide or derivatives thereof of the described transition metal Ti of component A is a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture.
8. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, the halid volume ratio of described liquid coprecipitator and Ti is 0.1～10.
9. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, the halid volume ratio of described liquid coprecipitator and Ti is 0.5～2.5.
10. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, the mol ratio of magnesium halide and electron donor compound is 1: 0.005～15 among the described component A.
11. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, when being used for propylene polymerization, also needs to add external electron donor, its general formula is R
nSi (OR ')
4-nOrganosilane, R and R ' are alkyl of the same race or not of the same race, halo alkyl, 0≤n in the formula≤3.
12. the preparation method of component A in the described catalyzer of one of claim 1～10, under agitation magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds and adds electron donor again, randomly add alkyl metal cpd and form homogeneous transparent solution, under-35～60 ℃ of temperature, the mixture solution of the halogenide or derivatives thereof of transition metals Ti and liquid coprecipitator splashed in the magnesium halide homogeneous solution or magnesium halide solution splashed in the mixture solution of the halogenide or derivatives thereof of transition metals Ti and liquid coprecipitator, again reaction mixture was stirred 1 minute～10 hours under 0～130 ℃ of temperature, stop to stir, sedimentation, filter, remove mother liquor, with toluene and hexane wash solids, make titaniferous ingredient of solid catalyst.
13. the preparation method according to the described catalyst component A of claim 12 is characterized in that, stirring, sedimentation, filtration, remove mother liquor after, with toluene and hexane and mix B component therein and wash solids, make titaniferous ingredient of solid catalyst.
14., when being used for propylene polymerization, also needing after solids is separated out preceding or separated out, to add the multi-carboxylate and handle according to the preparation method of the described catalyst component A of claim 12.
15. preparation method according to the described catalyst component A of claim 12, it is characterized in that, in the magnesium halide dissolution process, add alkyl metal cpd ,-30～10 ℃ of mixture solutions with the halogenide or derivatives thereof of transition metals Ti and liquid coprecipitator splash in the magnesium halide homogeneous solution or magnesium halide solution is splashed into the halogenide or derivatives thereof of transition metals Ti and the mixture solution of liquid coprecipitator in.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103087224B (en) * | 2011-10-28 | 2015-03-11 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
| CN104558276B (en) * | 2013-10-10 | 2017-08-25 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application |
| EA034784B9 (en) * | 2015-01-21 | 2020-09-09 | Сабик Глоубл Текнолоджиз Б.В. | Procatalyst for polymerization of olefins |
| CN111057169B (en) * | 2018-10-16 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
| CN111234069B (en) * | 2018-11-29 | 2022-10-21 | 中国石油化工股份有限公司 | Magnesium/titanium-containing solid catalyst component, preparation method thereof, olefin polymerization catalyst and application thereof |
| CN112239238A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid from polyolefin catalyst production |
| CN115975083A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
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