CN101173014A - Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same - Google Patents
Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same Download PDFInfo
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Abstract
The invention relates to a solid catalyst component with titanium used for dimethylene polymerization or combined polymerization. An even solution is formed by making halogenation magnesium dissolved in an organic epoxy compound and an orgnophosphorus compound, then an electron donor is added, and then the mixture reacts with the halide of transition metal titanium or the ramification and the mixture solution of a liquid coprecipitator; after the solid catalyst is separated out, an ester type electron donor is added to hold processing and modification to obtain the solid catalyst component. The catalyst used for ethylene polymerization shows high hydrogen response with good activity and high bulk density. Synchronously, the obtained polymer has good particle shape, thereby being more applicable for the catalyst used by the polymerization technique of doublet polyethylene.
Description
Technical field
The present invention relates to a kind of catalyst component that is used for vinyl polymerization or copolymerization and preparation method thereof, and the application in olefinic polymerization or copolymerization.
Background technology
Traditional Z-N catalyzer is begun by the titanium-Al catalysts of classics, has developed into the stage by compound activatings such as magnesium chloride, other various organic compound modifications; And, develop into the performance of improving polymeric articles by the structure of regulating catalyzer by simple raising catalytic activity.
Since the seventies, it is the Ti-Mg high-effective carrier catalyst of carrier with the magnesium chloride that companies such as Mitsui petrochemical industry Co., Ltd. succeed in developing multiple, makes world's slurry process production polyolefin industry obtain development fast.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 the Ti/Mg high-effective carrier catalyst.This catalyst preparation process is simple, and reaction conditions is not harsh, and operation is easier to.But, because this catalyzer adopts bigger alcohols and the alkane solvents of polarity difference to dissolve magnesium halide, 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 can generate a kind of particulate soliquid or swollen magnesium halide slurries.Bring some and the relevant shortcoming of magnesium halide stratiform crystallization property so for prepared catalyzer, as: prepared polymkeric substance apparent density is lower, particle form and distribute bad etc.
Chinese patent 98101108.X has proposed a kind of catalyzer and this Preparation of catalysts method that is used for ethylene homo or copolymerization, wherein catalyzer is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, obtain with the halogenide or derivatives thereof effect of at least a precipitation additive and transition metals Ti again, combine with organo-aluminium compound during polymerization.This catalyst preparation process is simple, is used for vinyl polymerization and has shown very high activity, and the particle form of resulting polymers is better simultaneously, and apparent density is higher, and low-molecular material content is less.But this catalyst body ties up in the preparation process because mother liquor is more sticking, so catalyst solid separates difficulty with mother liquor.
Chinese patent 200510103119.2 has proposed a kind of catalyzer and method for making thereof that is used for olefinic polymerization, it is the deficiency that exists at Chinese patent 98101108.X catalyst system, adopt the inert solvent that dissolves each other with titanium compound to make novel titanium polyolefin catalyzer as coprecipitator, adopt the catalyzer of this method preparation to omit solid precipitation additive dissolving step, and the adding of coprecipitator help the settlement separate of catalyzer mother liquor system.This polymerization catalyst is active high, and catalyst grain size distributes and concentrates, and fine powder is few, but the apparent density of catalyzer still remains to be improved.
Summary of the invention
At the deficiency that above-mentioned catalyst system exists, the invention provides the catalyzer that a kind of polymerization technique that is more suitable for producing bimodal polyethylene uses.The polymerization technique that is fit to the production bimodal polyethylene generally adopts the tandem reactor polymerization methods.The polymerization technique of double-reactor series connection commonly comprises liquid phase-liquid phase process, gas phase-gas phase process and liquid phase-gas phase process.In the double-reactor polymerization technique, mainly be to rely on density of hydrogen, polymeric monomer concentration and the polymerizing condition of regulating in two reactors, make the polyethylene that in different reactor, generates have different molecular weight and performance.This kind polymerization technique requires catalyzer to have good hydrogen response, requires polymkeric substance to have good particle form simultaneously.
The present invention is after solid catalyst is separated out from the magnesium chloride dissolution system, adds ester class electron donor compound, to catalyst modification.It is higher that the catalyzer that adopts this method to prepare has apparent density, and hydrogen response is good, and size-grade distribution is concentrated, and fine powder is few, and catalyzer mother liquor and advantages such as catalyst solid separates well.
A kind of catalyzer that is used for vinyl polymerization or copolymerization of the present invention comprises following component:
A, titaniferous ingredient of solid catalyst, it is 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 and the liquid coprecipitator of transition metals Ti, after catalyst solid is separated out, add again that a kind of of ester class electron donor compound or their mixture are handled and the ingredient of solid catalyst that obtains.Described ester class electron donor compound comprises acrylic acid hydroxy ester or contain-a kind of in the silicon compound of OR base or their mixture; Concrete as methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, the phenylbenzene diethoxy silane, ethyl trimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, the butyl triethoxyl silane, phenyl triethoxysilane, ethyl three isopropoxy silane, vinyl three fourth oxygen TMOSs, tetraethyl silicate, butyl silicate, methyl three aryloxy silanes etc.
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.The magnesium halide granularity of using is dissolved as to stir down easily, and solvent temperature is-10 ℃～150 ℃, with 20 ℃～130 ℃ for well.Can add in dissolution system during dissolving or not with inert diluent, inert diluent can adopt benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound are the best with toluene, dimethylbenzene wherein.
Organic epoxy compounds described in the catalyst A component of the present invention is selected from and comprises that carbonatoms is at the fatty compounds such as oxide compound, glycidyl ether and inner ether of organizing alkene or diolefine of 2～8 aliphatics alkene, diolefine or halo.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.
Organo phosphorous compounds described in the catalyst A component of the present invention is selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, for example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl etc.
The described electron donor of catalyst component of the present invention (A) is C
1～C
12Straight chain alcohol or isomery alcohol, concrete as: a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, glycerol, lauryl alcohol, Bian alcohol, the phenylethyl alcohol, or their mixture, with C
1～C
8Straight chain alcohol be best.
The described liquid coprecipitator of component A of the present invention is aliphatic hydrocarbon and cycloalkane material, and is concrete as a kind of of hexane, heptane, pentane, octane, decane or hexanaphthene or their mixture.In use, generally be that the liquid coprecipitator is mixed mutually with the halogenide or derivatives thereof of transition metals Ti, use behind the formation mixture solution.
The general formula of the halogenide or derivatives thereof of the transition metals Ti described in the catalyst component A of the present invention is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, n is 1 to 4 integer, specifically can select 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 for use, preferred titanium tetrachloride.
The preparation component can also add the metal halide conditioning agent when (A) in forming the homogeneous solution process, it is to be selected from 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.
Mol ratio between described each component of catalyst component of the present invention (A) 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 0.02～0.08 mole for well; 0.2～20 mole in the halogenide of transition metal Ti, the halid volume ratio of liquid coprecipitator and Ti is 0.1～10, with 0.5～2.5 for well; Ester class electron donor compound is 0.01～10 mole, with 0.05～5 mole for well;
The described organo-aluminium compound of catalyst component B of the present invention, its general formula is AlRnX
3-n, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, particularly alkyl, aralkyl, aryl; 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; Aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, wherein with triethyl aluminum and triisobutyl aluminium for well.Ratio between component (B) and the component (A) is 5～1000 with the molar ratio computing of aluminium and titanium, with 20～800 for well.
The preparation method of catalyst component A of the present invention is as follows: under agitation magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds and adds electron donor again, form homogeneous transparent solution, under-30～60 ℃ of temperature, be preferably-30～5 ℃, the mixture solution of the halogenide or derivatives thereof of transition metals Ti and liquid coprecipitator splashed in the magnesium halide homogeneous solution or with magnesium halide solution splash in the titanium compound, after catalyst solid is separated out, under-30～110 ℃ of temperature, be preferably-10～80 ℃, add a kind of of ester class electron donor compound or their mixture, again reaction mixture was stirred 1 minute～10 hours under 80～120 ℃ of temperature, stop to stir sedimentation, filter, remove mother liquor, with toluene and hexane wash solids, vacuum-drying makes titaniferous ingredient of solid catalyst.This solid ingredient titaniferous is in 1～8% scope.
Catalyst A of the present invention, 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 the adoptable alpha-olefin of comonomer is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl 1-amylene etc.
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 following examples and reference example will be further described the present invention.But the present invention is not subjected to the restriction of these embodiment.
Embodiment:
Embodiment:
(1) catalyzer is synthetic:
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-5～0 ℃, mixed solution with 30ml titanium tetrachloride and 30ml heptane splashes in it again, add the 2ml Rocryl 410 then, solution slowly is warming up to 80 ℃, reaction is 2 hours under this temperature.Filter, use hexane wash 4 times, vacuum-drying obtains 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 (1mol/L hexane solution), (5～6mg) the above-mentioned prepared ingredients of solid catalyst of metering, be warming up to 70 ℃ of hydrogenation 0.26MPa, feed ethene again and make and reach 0.73MPa (gauge pressure) in the still, under 80 ℃, polymerization 2 hours, polymerization result sees Table 1.
Embodiment 2 (one) catalyzer are synthetic: with embodiment 1, only change Rocryl 410 into 4ml.
(2) vinyl polymerization is together with embodiment 1.
Embodiment 3:(one) catalyzer is synthetic: with embodiment 1, only change the Rocryl 410 that adds into hydroxyethyl methylacrylate 2ml.
(2) vinyl polymerization is together with embodiment 1.
Embodiment 4:(one) catalyzer is synthetic: with embodiment 1, only change the Rocryl 410 that adds into hydroxyethyl methylacrylate 1ml and silicic acid fat 1ml.
(2) vinyl polymerization is together with embodiment 1.
Embodiment 5:(one) catalyzer is synthetic: with embodiment 1, only change the Rocryl 410 that adds into silicic acid fat 6ml.
(2) vinyl polymerization is together with embodiment 1.
Comparative example 1:
(1) catalyzer is synthetic: 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.
(2) vinyl polymerization is together with embodiment 1.
Comparative example 2:
(1) catalyzer is synthetic: 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-5～0 ℃, 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.
(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 (1mol/L hexane solution), metering (5～6mg) above-mentioned prepared ingredients of solid catalyst are warming up to 70 ℃ of hydrogenation 0.36MPa (gauge pressure),
Feed ethene again and make and reach 0.73MPa (gauge pressure) in the still, under 80 ℃, polymerization 2 hours, polymerization result following table.
Claims (14)
1. catalyzer that is used for vinyl polymerization or copolymerization comprises following component:
A, titaniferous ingredient of solid catalyst, it is 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 and the liquid coprecipitator of transition metals Ti, after catalyst solid is separated out, add again that a kind of of ester class electron donor compound or their mixture are handled and the ingredient of solid catalyst that obtains; Described ester class electron donor compound comprises acrylic acid hydroxy ester or contain-a kind of in the silicon compound of OR base or their mixture;
B, organo-aluminium compound, its general formula are AlRnX
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, the ratio between component (B) and the component (A) is 5～1000 with the molar ratio computing of aluminium and titanium.
2. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, ester class electron donor compound is a vinylformic acid 2-hydroxyl ethyl ester among the component A, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane, the phenylbenzene diethoxy silane, ethyl trimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, the butyl triethoxyl silane, phenyl triethoxysilane, ethyl three isopropoxy silane, vinyl three fourth oxygen TMOSs, tetraethyl silicate, butyl silicate, methyl three aryloxy silanes.
3. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described magnesium halide of component A is a kind of by in-oxyl or the halogen-oxyl institute metathetical derivative of one of them halogen atom in the water of magnesium dihalide, magnesium dihalide or alcohol complex, the magnesium dihalide molecular formula, or their mixture.
4. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described organic epoxy compounds of component A is a kind of in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, the tetrahydrofuran (THF), or their mixture.
5. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described organo phosphorous compounds of component A is a kind of in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, the phosphorous acid benzene methyl, or their mixture.
6. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described electron donor of component A is C
1～C
12Straight chain alcohol or isomery alcohol.
7. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 6, the described electron donor of component A is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, glycerol, lauryl alcohol, Bian alcohol, the phenylethyl alcohol, or their mixture.
8. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described magnesium halide of component A forms in the process of homogeneous solution in dissolving, can also add the metal halide conditioning agent, wherein the metal halide conditioning agent is selected from a kind of in the halogenide of zinc, vanadium, iron, cobalt or their mixture.
9. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the halogenide or derivatives thereof of the described transition metals Ti of component A are 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.
10. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the described liquid coprecipitator of component A are a kind of of hexane, heptane, pentane, octane, decane, hexanaphthene or their mixture.
11. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the mol ratio of described magnesium halide of component A and ester class electron donor compound is 1: 0.05～5.
12. the preparation method according to the described catalyst component A of one of claim 1～10 is as follows: under agitation magnesium halide is dissolved in the solvent system that organic epoxy compounds and organo phosphorous compounds are formed, add electron donor again, form homogeneous transparent solution, under-30～60 ℃ of temperature, the halogenide or derivatives thereof of transition metals Ti and the mixture solution of liquid coprecipitator are splashed in the magnesium halide homogeneous solution, after catalyst solid is separated out, under-30～110 ℃ of temperature, add a kind of of ester class electron donor compound or their mixture, again reaction mixture was stirred 1 minute～10 hours under 80～120 ℃ of temperature, stop to stir, sedimentation, filter, remove mother liquor, with toluene and hexane wash solids, vacuum-drying makes titaniferous ingredient of solid catalyst.
13. according to the preparation method of the described catalyst component A of claim 11, the temperature that adds ester class electron donor compound is controlled at-10～80 ℃.
14. catalyzer the application in vinyl polymerization or copolymerization described according to one of claim 1～11.
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