CN102977235A - Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component - Google Patents
Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component Download PDFInfo
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- CN102977235A CN102977235A CN2011102588300A CN201110258830A CN102977235A CN 102977235 A CN102977235 A CN 102977235A CN 2011102588300 A CN2011102588300 A CN 2011102588300A CN 201110258830 A CN201110258830 A CN 201110258830A CN 102977235 A CN102977235 A CN 102977235A
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Abstract
The invention provides a titanium-containing solid catalyst component for ethylene polymerization and a catalyst system composed of the titanium-containing solid catalyst component. A magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound; the solution is added with an electron donor to form a uniform solution; and the solution reacts with a mixture of a transition metal titanium halide or its derivative, and a halohydrocarbon as an accelerator to produce the titanium-containing solid catalyst component. The catalyst system composed of the titanium-containing solid catalyst component is used for ethylene polymerization or copolymerization and has the characteristics of high activity, high bulk density and good catalyst hydrogen regulation sensitivity.
Description
Technical field
The present invention relates to a kind of for olefinic polymerization particularly catalyst component and the catalyzer of vinyl polymerization, and the preparation method of this catalyzer and application.
Technical background
Traditional olefinic polymerization titanium is ziegler natta catalyst, mainly is made of magnesium compound, titanium compound and electron donor and organoaluminum etc.The method of disclosed vinyl polymerization and copolymerization among the Japanese Patent JP49-51378, this catalyzer adopts alkane derivative to make solvent, alcohol compound and magnesium compound contact reacts, because alcohols and alkane solvents polarity difference are larger, so that magnesium halide can not complete dissolved formation homogeneous phase solution, only be the magnesium halide slurries that generate a kind of particulate soliquid or swelling.Thereby produce some shortcomings relevant with magnesium halide stratiform crystallization property, as: prepared polymkeric substance apparent density is lower, particle form and distribute bad etc.Chinese patent 98101108.X has proposed a kind ofly to close or the catalyzer of copolymerization and the preparation method of this catalyzer for ethylene homo, 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, be combined with organo-aluminium compound during polymerization.This catalyst dissolution system is owing to introduced the organic epoxy compounds of solubility promoter, organo phosphorous compounds, can make the magnesium chloride dissolving and the solution of formation homogeneous transparent, resulting catalyzer has good particle form, and catalyst preparation process is simple, be used for vinyl polymerization and shown very high activity, apparent density is higher, but catalyzer is good not to the susceptibility of hydrogen.
The objective of the invention is provides a kind of catalyst component for olefinic polymerization and copolymerization and preparation method and application thereof in order to overcome the deficiency of above-mentioned catalyzer existence.Specifically, be the crystal formation front introducing halogenated hydrocarbon compound of catalyzer in catalyzer is synthetic, in the halogenide or derivatives thereof of precipitation agent transition metals Ti, add halohydrocarbon according to suitable halohydrocarbon and titanium mol ratio.This catalyzer is used for vinyl polymerization and has shown higher catalyst activity and hydrogen response, and the particle form of resulting polymers is better simultaneously, and apparent density is higher.
Summary of the invention
The present invention synthesizes a kind of novel Z-N catalyzer, is used for vinyl polymerization or copolymerization.
This catalyzer is to introduce halogenated hydrocarbon compound in catalyzer is synthetic in building-up process, in the halogenide or derivatives thereof of precipitation agent transition metals Ti, adds halohydrocarbon according to suitable halohydrocarbon and titanium mol ratio.This catalyzer is used for vinyl polymerization and has shown higher catalyst activity and hydrogen response, and the particle form of resulting polymers is better simultaneously, and apparent density is higher.
A kind of catalyst system for being used for olefinic polymerization of the present invention comprises (A), (B) component:
(A) ingredient of solid catalyst of titaniferous, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor compound formation homogeneous solution again, with the halogenide or derivatives thereof of transition metals Ti by a certain percentage with after the promotor halogenated hydrocarbon compound evenly mixes again with above-mentioned homogeneous solution reaction, add silicoorganic compound, after separating out the catalyzer crystal, wash solids with inert diluent, after the drying, obtain the ingredient of solid catalyst of titaniferous;
Described electron donor compound is at least a in the Organic Alcohol; The halogenated hydrocarbon compound consumption is counted 0.001～20 mole with every mole of magnesium halide; The mol ratio of halogenated hydrocarbon compound and halogenated transition metal titanium is 1: 0.05-100;
(B) organo-aluminium compound;
Ratio between component (B) and the component (A) is take the molar ratio computing of aluminium and titanium as 5～1000.
The detailed description of the invention:
1. the preparation of magnesium halide solution
Magnesium halide solution is that magnesium halide is dissolved in the solvent system of organic epoxy compounds and organo phosphorous compounds composition and the electron donor compound is joined resulting homogeneous solution in the magnesium halide solution, and the solvent system of indication comprises use or do not use inert diluent here.
The described magnesium halide of catalyst component of the present invention (A) comprises the derivative that one of them halogen atom in the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol is replaced by-oxyl or halogen-oxyl, and above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, two magnesium iodides.Wherein, take magnesium dichloride as best.
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 during dissolving or not with inert diluent such as benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.Wherein, benzene,toluene,xylene is preferably, and toluene, dimethylbenzene are best.
Organic epoxy compounds comprises that carbonatoms is at compounds such as the oxide compound of 2～8 aliphatics alkene, diolefine halogenated aliphatic alkene or diolefine, glycidyl ether, inner ethers.Particular compound is such as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.Wherein, be preferably oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), take tetrahydrofuran (THF), epoxy chloropropane as best.
Organo phosphorous compounds comprises 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, take the ortho-phosphoric acid tri-n-butyl as best.
Electron donor compound described in the catalyst component of the present invention (A) is Organic Alcohol, comprises C
1～C
20Straight chain alcohol or isomery alcohol, for example: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol, amylalcohol, decyl alcohol, dodecanol, Stearyl alcohol, Bian alcohol, phenylethyl alcohol, with C
1～C
8Straight chain alcohol be best.
Magnesium halide described in the catalyst component of the present invention (A) forms in the process of homogeneous solution in dissolving, also can add alkyl metal cpd such as zinc alkyl(s) and or aluminum alkyls in the homogeneous solution.
The present invention can add silicoorganic compound after the mixture of the halogenide or derivatives thereof of magnesium halide homogeneous solution and transition metals Ti and promotor halogenated hydrocarbon compound contacts.The general formula of silicoorganic compound is R
1 XR
2 YSi (OR
3)
ZShown compound, wherein R
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and the organosilyl compound of x+y+z=4 comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride etc.
The general formula of the promotor halogenated hydrocarbon compound that the present invention adds is R
m 1X
4-aR
2 nX
4-bR
3 p. R wherein
1, R
2, R
3Be respectively alkyl or aryl, m, n, p represent respectively R
1, R
2, R
3Contained carbon atom number, m, n, p can be 0-10, but are not 0 simultaneously.A, b are 0-4, but a, b are not that 4, X is F simultaneously, Cl, Br.
Consumption between described each component of catalyst component of the present invention (A), 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; 0.2～20 mole in the halogenide of transition metal Ti, with 0.5～2.5 for well; Silicoorganic compound are 0.05～1 mole.
The mol ratio of the halogenide or derivatives thereof of halogenated hydrocarbon compound and halogenated transition metal titanium is 1: 0.05-100, with 1: 0.1-50 is for well.
2. catalyst solid constituent preparation
The magnesium halide solution that above-mentioned steps is obtained and the halogenide or derivatives thereof of transition metals Ti and halogenated hydrocarbon compound be even mixed solution contact reacts by a certain percentage, and the optional silicoorganic compound that add, add temperature-30～110 ℃, to the carried catalyst solid ingredient.
When adopt dripping the method for halogenated titanium, time for adding preferably was controlled in 5 hours, and when heating up gradually, heat-up rate is per hour to heat up 4～100 ℃ for well.
Feature and the chemical ingredients of solid ingredient (A)
Through above-mentioned steps, made (A) component of catalyst system of the present invention, this component can solids or the form of suspension use.
In catalyst system of the present invention, aluminium is 5～1000 with the mol ratio of the middle titanium of component (A) in the component (B), with 20～800 for well.
A kind of preparation method of the component A of catalyzer of the present invention is: under agitation magnesium halide is dissolved in and adds the electron donor compound in organic epoxy compounds and the organo phosphorous compounds again, form homogeneous transparent solution, add or do not add alkyl metal cpd, under-35～60 ℃ of temperature, best-30～10 ℃, halohydrocarbon is mixed with titanium compound with the titanium mol ratio according to suitable halohydrocarbon, after splash into the magnesium halide homogeneous solution, at-30～110 ℃ of adding silicoorganic compound.Filter, remove mother liquor, with toluene and hexane washing solids, in washing composition, also can add a small amount of component (B), to reach the effect of pre-complexing, when adopting the method, the consumption of component (B), take the molar ratio computing of aluminium and titanium as 100～0.001, preferably 10～0.01, be preferably 1～0.1, make the ingredient of solid catalyst of titaniferous.This solid ingredient titaniferous 1～8%.
Catalyst A of the present invention, B component can directly apply to polymerization system, also can be applied to polymerization system after the pre-complexing first.
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, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl 1-amylene.
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, the inert solvent such as the aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon makes reaction medium, can carry out first prepolymerization 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 the invention will be further described.But the present invention is not subjected to the restriction of these embodiment.
Embodiment:
(1) catalyzer is synthetic:
Embodiment 1: through high-purity N
2Fully in the reactor of displacement, add successively the anhydrous MgCl of 4.0g
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 ℃, again the 3ml1.1.2-trichloroethane is evenly mixed with the 30mL titanium tetrachloride, then it is splashed in the above-mentioned magnesium chloride homogeneous solution, add again the 5ml tetraethoxy-silicane, solution is warming up to 80 ℃, removes mother liquor.With hexane washing 4 times, vacuum-drying obtains solid catalyst.
Embodiment 2: embodiment 1, only will add vinyl trichloride 3ml and change 1,2-ethylene dichloride 4ml into.
Embodiment 3: with embodiment 1, only will add vinyl trichloride 3ml and change 6ml into.
Embodiment 4: with embodiment 1, only change 1,2-ethylene dichloride 4ml into 10ml.
Comparative example 1:
Catalyzer is synthetic: through high-purity N
2Fully in the reactor of displacement, add successively the anhydrous MgCl of 4.0g
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, then add Tetra hydro Phthalic anhydride 0.5g, kept again 30 minutes, this solution is cooled to-5～0 ℃, again the 20mL titanium tetrachloride is splashed in it, then slowly be warming up to 40 ℃, wash 4 times with hexane after filtering, vacuum-drying obtains solid catalyst.
(2) vinyl polymerization
1, low hydrogen vinyl polymerization: volume is that 2 liters stainless steel still is through H
2Fully after the displacement, add therein hexane 1000mL, triethyl aluminum 1.5mL (1mol/L hexane solution), the above-mentioned prepared ingredient of solid catalyst of 10mg of metering, be warming up to 70 ℃ of hydrogenation 0.26MPa, pass into again ethene and make and reach 0.73MPa (gauge pressure) in the still, under 80 ℃, polymerization 2 hours.
2, high hydrogen vinyl polymerization: volume is that 2 liters stainless steel still is through H
2Fully after the displacement, add therein hexane 1000mL, triethyl aluminum 1.5mL (1mol/L hexane solution), the above-mentioned prepared ingredient of solid catalyst of 20mg of metering, be warming up to 70 ℃ of hydrogenation 0.50MPa, pass into again ethene and make and reach 1.0MPa (gauge pressure) in the still, under 90 ℃, polymerization 2 hours.
Polymerization result sees Table 1.
Claims (13)
1. a catalyst system that is used for olefinic polymerization is characterized in that, comprises (A), (B) component:
(A) ingredient of solid catalyst of titaniferous, it is to be dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide to add electron donor compound formation homogeneous solution again, with the halogenide or derivatives thereof of transition metals Ti by a certain percentage with after the promotor halogenated hydrocarbon compound evenly mixes again with above-mentioned homogeneous solution reaction, add silicoorganic compound, after separating out the catalyzer crystal, wash solids with inert diluent, after the drying, obtain the ingredient of solid catalyst of titaniferous;
Described electron donor compound is at least a in the Organic Alcohol; The mol ratio of the halogenide or derivatives thereof of halogenated hydrocarbon compound and halogenated transition metal titanium is 1: 0.05-100;
(B) organo-aluminium compound;
Ratio between component (B) and the component (A) is take the molar ratio computing of aluminium and titanium as 5～1000.
2. catalyst system according to claim 1 is characterized in that, the mol ratio of the halogenide or derivatives thereof of the halogenated hydrocarbon compound described in the wherein said component A and halogenated transition metal titanium is 1: 0.1-50.
3. catalyst system according to claim 1 is characterized in that, the Organic Alcohol described in the wherein said component A comprises C
1～C
20Straight chain alcohol or isomery alcohol.
4. catalyst system according to claim 1, it is characterized in that the Organic Alcohol described in the wherein said component A is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol, amylalcohol, decyl alcohol, dodecanol, Stearyl alcohol, Bian alcohol, phenylethyl alcohol.
5. catalyst system according to claim 1 is characterized in that, the Organic Alcohol described in the wherein said component A is C
1～C
8Straight chain alcohol.
6. catalyst system according to claim 1 is characterized in that, promotor halogenated hydrocarbon compound among the wherein said component A, its general formula are R
m 1X
4-aR
2 nX
4-bR
3 p, R wherein
1, R
2, R
3Be respectively alkyl or aryl, m, n, p represent respectively R
1, R
2, R
3Contained carbon atom number, m, n, p are 0-10, but are not 0 simultaneously; A, b are 0-4, but a, b are not that 4, X is F simultaneously, Cl, Br.
7. catalyst system according to claim 1 is characterized in that, the promotor halogenated hydrocarbon compound is 1,2-ethylene dichloride, vinyl trichloride, sym.-tetrachloroethane, 1，1，1-trichloroethane, trichloromethane among the wherein said component A.
8. catalyst system according to claim 1 is characterized in that, the general formula of wherein said silicoorganic compound is R
1 XR
2 YSi (OR
3)
ZShown compound, wherein R
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4, its usage quantity is counted 0.05～1 mole with every mole of magnesium halide.
9. catalyst system according to claim 1 is characterized in that, wherein said silicoorganic compound are a kind of or its mixture in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, the silicon tetrachloride.
10. catalyst system according to claim 1, it is characterized in that the halogenide or derivatives thereof of the described transition metals Ti of component A is a kind of or its mixture 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.
11. the preparation method of component A is as follows in the described catalyst system of one of claim 1～10: under agitation magnesium halide is dissolved in the solvent system that organic epoxy compounds and organo phosphorous compounds form, add again electron donor, form homogeneous transparent solution, with the halogenide or derivatives thereof of transition metals Ti with after the promotor halogenated hydrocarbon compound evenly mixes, under-30～60 ℃ of temperature, splash in the magnesium halide homogeneous solution, under-30～110 ℃ of temperature, add reactive organic silicon compound; Reaction mixture was stirred 1 minute～10 hours under 80～120 ℃ of temperature again, stop to stir, mother liquor is removed in sedimentation, filtration, with toluene and hexane washing solids, vacuum-drying, makes the ingredient of solid catalyst of titaniferous.
12. the preparation method of described catalyst component A according to claim 11, the halogenide or derivatives thereof of transition metals Ti splashes in the magnesium halide homogeneous solution with after the promotor halogenated hydrocarbon compound evenly mixes, and its temperature is controlled at-30～10 ℃.
13. the described catalyst body of one of claim 1～10 ties up to that ethylene homo closes or copolymerization in application.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330770A (en) * | 2014-06-18 | 2016-02-17 | 中国石油化工股份有限公司 | Catalyst used for ethylene slurry polymerization and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189505A (en) * | 1997-01-31 | 1998-08-05 | 台湾聚合化学品股份有限公司 | Ti family catalyst system capable of polymerizing olefines |
| CN1958620A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst components in use for polymerizing ethylene, and catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189505A (en) * | 1997-01-31 | 1998-08-05 | 台湾聚合化学品股份有限公司 | Ti family catalyst system capable of polymerizing olefines |
| CN1958620A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst components in use for polymerizing ethylene, and catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330770A (en) * | 2014-06-18 | 2016-02-17 | 中国石油化工股份有限公司 | Catalyst used for ethylene slurry polymerization and application thereof |
| CN105330770B (en) * | 2014-06-18 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of catalyst and its application for ethylene slurry polymerization |
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