CN105175587A - Catalyst used for ethylene polymerization, and application thereof - Google Patents
Catalyst used for ethylene polymerization, and application thereof Download PDFInfo
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- CN105175587A CN105175587A CN201410274027.XA CN201410274027A CN105175587A CN 105175587 A CN105175587 A CN 105175587A CN 201410274027 A CN201410274027 A CN 201410274027A CN 105175587 A CN105175587 A CN 105175587A
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Abstract
The invention provides a supported catalyst used for ethylene polymerization, and a composition and a preparation method thereof. The catalyst is composed of a component A, a component B and a component C, wherein the component A is prepared through the following steps: dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and an electron donor compound to form a uniform solution, slowly reacting TiCl4 with the above obtained uniform magnesium halide solution at a low temperature to precipitate catalyst crystals, and carrying out a strictly controlled heating reaction; the component B is an organic aluminum compound; and the component C is a halogenated cycloalkane compound, and the component C can be used in anyone of the following three modes: (1) the component C and the component B are mixed, and the obtained mixture is added to an ethylene polymerization reaction system; (2) the component A, the component B and the component C are respectively added in the polymerization reaction; and (3) the component C is added in the preparation process of the component A. The catalyst has high catalytic activity and improved hydrogen sensitivity in ethylene polymerization.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polymerization particularly vinyl polymerization, and the preparation method of this catalyzer and application.
Background technology
Traditional olefinic polymerization titanium system ziegler natta catalyst, primarily of magnesium compound, titanium compound and the formation such as electron donor and organoaluminum.The method of vinyl polymerization and copolymerization disclosed in Japanese Patent JP49-51378, this catalyzer adopts alkane derivative to make solvent, alcohol compound and magnesium compound contact reacts, due to alcohols and alkane solvents different polarities larger, make magnesium halide can not be formed homogeneous phase solution by dissolving completely, only generate a kind of particulate soliquid or swelling magnesium halide slurries, thus produce some shortcomings relevant with magnesium halide stratiform crystallization property, as: prepared polymkeric substance apparent density is lower, particle form and distribute bad etc.
CN1229092A proposes and a kind ofly to close or the catalyzer of copolymerization and the preparation method of this catalyzer for ethylene homo, wherein catalyzer is dissolved in organic epoxy compound thing, 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 one precipitation additive and transition metals Ti again, be combined with organo-aluminium compound during polymerization.This catalyst dissolution system is owing to having introduced solubility promoter organic epoxy compound thing, organo phosphorous compounds, magnesium chloride can be made to dissolve and form the solution of homogeneous transparent, the catalyzer obtained has good particle form, and catalyst preparation process is simple, very high activity is shown for vinyl polymerization, apparent density is higher, but catalyzer is good not to the susceptibility of hydrogen.
The present inventor finds in catalyst system, introduce halo naphthenic hydrocarbon through large quantity research, not only can improve the activity of catalyzer, and can improve the hydrogen response of catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system for olefinic polymerization, in catalyst system, introduced halo cyclanes compound, not only can improve the activity of catalyzer, and the hydrogen response of catalyzer can be improved.
A kind of catalyst system for vinyl polymerization of the present invention, comprises following component:
(A) ingredient of solid catalyst of titaniferous, it is dissolved in organic epoxy compound thing, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, the halogenide or derivatives thereof of transition metals Ti is slowly added in above-mentioned homogeneous solution, with inert diluent washing, obtain ingredient of solid catalyst;
(B) organo-aluminium compound;
(C) halo cyclanes compound.
Described halo cyclanes compound and the mol ratio of titanium are 200 ~ 0.01, with 30 ~ 0.5 as well.
The general formula of described halo cyclanes compound is C
ch
2c-dx
dwherein X is the halogen of fluorine, chlorine or bromine, c is the integer of 4 ~ 15, d is the integer of 1 ~ 9, and particular compound comprises one or more in a chlorocyclopropane, a chloro tetramethylene, a chlorocyclopentane, Monocyclohexane, a cyclopropane bromide, a bromo tetramethylene, a bromocyclopentane and a bromocyclohexane.
Described halo cyclanes compound can have following several method when using: first organo-aluminium compound and halo cyclanes compound are obtained by reacting mixture in advance during (1) polymerization, its preparation method be by dilution after halo naphthenic hydrocarbon at-10 ~ 60 DEG C, under being top condition with 0 ~ 60 DEG C, slowly be added drop-wise in organo-aluminium compound, rate of addition is 0.1 ~ 0.5ml/min; (2) during polymerization, organo-aluminium compound and halo cyclanes compound are added paradigmatic system respectively; (3) in the preparation process of component A, halo naphthenic hydrocarbon is added.
Magnesium halide described in component (A) comprise one of them halogen atom in complex compound, the magnesium dihalide molecular formula such as water or alcohol of magnesium dihalide, magnesium dihalide by-oxyl or halogen-oxyl the derivative of replacing, above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, diiodinating magnesium.Wherein, be best with magnesium dichloride.
The magnesium halide granularity used is to stir lower easy dissolving as well, and solvent temperature is-10 DEG C ~ 150 DEG C, with 20 DEG C ~ 130 DEG C as well.Can add during dissolving or not with inert diluent as benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.Wherein, benzene,toluene,xylene is good, and toluene, dimethylbenzene are best.
It is the aliphatics alkene of 2 ~ 8, the compound such as oxide compound, glycidyl ether, inner ether of diolefine halogenated aliphatic alkene or diolefine that organic epoxy compound thing described in component (A) comprises carbonatoms.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, 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 described in component (A) 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, ortho-phosphoric acid tri-n-butyl is best.
Electron donor described in component (A) can be selected from C
1~ C
20alcohol or isomery alcohol, such as: 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 component (A) also can add alkyl metal cpd as zinc alkyl(s) and or aluminum alkyls in the process of dissolving formation homogeneous solution.
Can also add silicoorganic compound in component (A), the general formula of silicoorganic compound is R
1 xr
2 ysi (OR
3)
z, wherein R
1and R
2be respectively alkyl or halogen, R
3for alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.Particular compound comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride etc.
Mol ratio in component (A) between each component in every mole of magnesium halide, organic epoxy compound thing 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Organo phosphorous compounds 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Electron donor 0.005 ~ 15 mole, with 0.05 ~ 10 mole as well; Alkyl metal cpd 0 ~ 2 mole, with 0 ~ 0.5 mole as well; The halogenide of transition metals Ti or 0.2 ~ 20 mole, derivative; Silicoorganic compound are 0.05 ~ 1 mole.In component (A), titaniferous amount is 1wt% ~ 8wt%.
The preparation method of component A: under agitation magnesium halide is dissolved in organic epoxy compound thing and organo phosphorous compounds and adds electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, wash, obtain component A solids.
Described component (B) organo-aluminium compound is alkylaluminium cpd, and wherein the molar ratio computing of aluminium and titanium is 100 ~ 0.001, preferably 10 ~ 0.01, be preferably 1 ~ 0.1.
Catalyst A of the present invention, B, component C can directly apply to polymerization system, also can be applied to polymerization system after first pre-complexing.
Catalyzer of the present invention can be used for all polymerizations 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.Polymerization process comprises the following steps: the preparation of (1) component A: be under agitation dissolved in organic epoxy compound thing and organo phosphorous compounds by magnesium halide and add electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, wash, obtain component A solids; (2) in reaction unit, B component organo-aluminium compound, component C halo cyclanes compound mix with component A, carry out vinyl polymerization.
B component organo-aluminium compound in step (2) and component C halo cyclanes compound can also be obtained by reacting mixture in advance, and then mix with component A, carry out vinyl polymerization.
Component C halo cyclanes compound can also add in the preparation process of component A, and then mixes with organo-aluminium compound, carries out vinyl polymerization.
Can liquid polymerization be adopted during polymerization, also can adopt vapour phase polymerization.When carrying out liquid polymerization, propane, hexane, heptane, hexanaphthene, Trimethylmethane, iso-pentane, petroleum naphtha can be used, raffinate oil, the inert solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene makes reaction medium, before polymerization, first can carry out prepolymerization.Polymerization methods can adopt intermittent type, semi continuous or continous way.Polymerization temperature is room temperature ~ 150 DEG C, with 50 DEG C ~ 100 DEG C as well.In order to the molecular weight of telomerized polymer, hydrogen is adopted to make molecular weight regulator.
Due to component A and organo-aluminium compound and the acting in conjunction of halo cyclanes compound in catalyst system, when catalyst system of the present invention is used for vinyl polymerization, not only embodies higher catalytic activity, and the hydrogen response of catalyzer can be improved.
Embodiment
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.Embodiment 1
Prepared by catalyzer (A) component: through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 4.0g successively
2, 50mL toluene, 2.0mL epoxy chloropropane, 3.0mL tributyl phosphate, 50 DEG C are warmed up under stirring, and maintain 15 minutes, add 6.0mL ethanol, continue reaction 15 minutes, this solution is cooled to-5 ~ 0 DEG C, 30mL titanium tetrachloride is added dropwise in above-mentioned magnesium chloride homogeneous solution again, add 5ml tetraethoxy-silicane again, by solution warms to 80 DEG C, removing mother liquor.With hexanes wash 4 times, vacuum-drying, obtains solid catalyst.
Vinyl polymerization 1: volume is that the stainless steel still of 2 liters is through H
2after abundant displacement, add hexane 1000mL wherein, metering containing 0.5mmolTi above-mentioned prepared ingredient of solid catalyst A, triethyl aluminum 1.0mmol.Adding a bromocyclopentane makes itself and catalyzer Ti mol ratio be 5, is warming up to 70 DEG C of hydrogenation 0.26MPa, then passes into ethene and make to reach 0.73MPa (gauge pressure) in still, at 80 DEG C, is polymerized 2 hours.
Embodiment 2
Catalyst component (A), with embodiment 1, only makes the mol ratio of Ti and a bromocyclopentane be 10 by adding a bromocyclopentane in polymerization.
Embodiment 3
Catalyst component (A), with embodiment 1, only makes the mol ratio of Ti and a bromocyclopentane be 3.3 by adding a bromocyclopentane in polymerization.
Embodiment 4
Catalyst component (A), with embodiment 1, will add a chlorocyclopentane in polymerization, make the mol ratio of Ti and Monocyclohexane be 5.
Embodiment 5
Catalyst component (A), with embodiment 1, makes the mol ratio of Ti and Monocyclohexane be 1 by adding a chlorocyclopentane in polymerization.
Embodiment 6
Catalyzer (A) component, with embodiment 1, makes the mol ratio of Ti and Monocyclohexane be 5 by adding a chlorocyclopentane in polymerization
Embodiment 7
Prepared by catalyzer (A) component: through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 4.0g successively
2, 50mL toluene, 2.0mL epoxy chloropropane, 3.0mL tributyl phosphate, 50 DEG C are warmed up under stirring, and maintain 15 minutes, add 6.0mL ethanol, continue reaction 15 minutes, this solution is cooled to-5 ~ 0 DEG C, 30mL titanium tetrachloride is added dropwise in above-mentioned magnesium chloride homogeneous solution again, add 5ml mono-bromocyclopentane again, by solution warms to 80 DEG C, removing mother liquor.With hexanes wash 4 times, vacuum-drying, obtains solid catalyst.
Embodiment 8: with embodiment 7, only changes the amount of the bromocyclopentane added into 3ml.
Embodiment 9: with embodiment 7, only changes the amount of the bromocyclopentane added into 4ml.
Embodiment 10: with embodiment 7, only changes the amount of the bromocyclopentane added into 10ml.
Embodiment 11: with embodiment 7, only changes the amount of the bromocyclopentane added into 2ml.
Embodiment 12: with embodiment 7, be only replaced by the position of the bromocyclopentane added and add Monocyclohexane, consumption is 4ml.
Comparative example: catalyst component synthesizes with embodiment 1 (A) component, vinyl polymerization 1: volume is that the stainless steel still of 2 liters is through H
2after abundant displacement, add hexane 1000mL wherein, metering containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, triethyl aluminum 1.0mmol.Be warming up to 70 DEG C of hydrogenation 0.26MPa (gauge pressure), then pass into ethene and make in still, to reach 0.73MPa (gauge pressure), at 80 DEG C, be polymerized 2 hours.Experimental result is in table 1
Table 1 polymerization result
As can be seen from the data of table 1, when catalyst system of the present invention is used for vinyl polymerization, not only embodies higher catalytic activity, and the hydrogen response of catalyzer can be improved.
Claims (18)
1. the catalyzer for vinyl polymerization, comprise following component: the ingredient of solid catalyst of (A) titaniferous, it is dissolved in organic epoxy compound thing, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, the halogenide or derivatives thereof of transition metals Ti is slowly added in above-mentioned homogeneous solution, with inert diluent washing, obtain the ingredient of solid catalyst of titaniferous; (B) organo-aluminium compound; (C) halo cyclanes compound.
2. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that the general formula of described halo cyclanes compound is C
ch
2c-dx
d, wherein X is the halogen of fluorine, chlorine or bromine, and c is the integer of 4 ~ 15, and d is the integer of 1 ~ 9.
3. a kind of catalyzer for vinyl polymerization according to claim 2, it is characterized in that described halo cyclanes compound is selected from a chlorocyclopropane, a chloro tetramethylene, a chlorocyclopentane, Monocyclohexane, one or more in monobromo cyclopropane, monobromo tetramethylene, monobromo pentamethylene and monobromo hexanaphthene.
4., according to a kind of catalyzer for vinyl polymerization one of claim 1-3 Suo Shu, it is characterized in that the mol ratio of described halo cyclanes compound and titanium is 200 ~ 0.01, the consumption of B component with the molar ratio computing of aluminium and titanium for 100 ~ 0.001.
5., according to a kind of catalyzer for vinyl polymerization one of claim 1-3 Suo Shu, it is characterized in that the mol ratio of described halo cyclanes compound and titanium is 30 ~ 0.5, the consumption of B component with the molar ratio computing of aluminium and titanium for 1 ~ 0.1.
6. a kind of catalyzer for vinyl polymerization according to claim 1, it is characterized in that described component (A) comprises general formula is R
1 xr
2 ysi (OR
3)
zsilicoorganic compound, wherein R
1and R
2be respectively alkyl or halogen, R
3for alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
7. a kind of catalyzer for vinyl polymerization according to claim 6, is characterized in that described silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride.
8. a kind of catalyzer for vinyl polymerization according to claim 1, it is characterized in that described magnesium halide comprise one of them halogen atom in complex compound, the magnesium dihalide molecular formula such as water or alcohol of magnesium dihalide, magnesium dihalide by-oxyl or halogen-oxyl the derivative of replacing.
9. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that described organic epoxy compound thing comprises carbonatoms at the aliphatics alkene of 2 ~ 8, the compound such as oxide compound, glycidyl ether, inner ether of diolefine halogenated aliphatic alkene or diolefine.
10. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that described organo phosphorous compounds comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
11. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that also comprising alkyl metal cpd in described component (A).
12. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that in every mole of magnesium halide, organic epoxy compound thing 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Organo phosphorous compounds 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Electron donor 0.005 ~ 15 mole, with 0.05 ~ 10 mole as well; The halogenide of transition metals Ti or 0.2 ~ 20 mole, derivative.
13. a kind of catalyzer for vinyl polymerization according to claim 1, it is characterized in that the halo cyclanes compound after by dilution is under-10 ~ 60 DEG C of conditions, slowly be added drop-wise in organo-aluminium compound, rate of addition is 0.1 ~ 0.5ml/min, and then with component A contact reacts.
14. a kind of catalyzer for vinyl polymerization according to claim 1, it is characterized in that by organo-aluminium compound and halo cyclanes compound respectively with component A contact reacts.
15. a kind of catalyzer for vinyl polymerization according to claim 1, is characterized in that adding halo cyclanes compound in the preparation process of component A.
16. application of the catalyzer for vinyl polymerization according to claim 1 in polymerization, comprise the following steps: the preparation of (1) component A: under agitation magnesium halide is dissolved in organic epoxy compound thing and organo phosphorous compounds and adds electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, wash, obtain component A solids; (2) in reaction unit, B component organo-aluminium compound, component C halo cyclanes compound mix with component A, carry out vinyl polymerization.
17. application of the catalyzer for vinyl polymerization according to claim 16 in polymerization, it is characterized in that B component organo-aluminium compound in step (2) and component C halo cyclanes compound are obtained by reacting mixture in advance, and then mix with component A, carry out vinyl polymerization.
18. application of the catalyzer for vinyl polymerization according to claim 16 in polymerization, is characterized in that component C halo cyclanes compound can also add in the preparation process of component A.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153740A (en) * | 2016-06-09 | 2019-01-04 | 切弗朗菲利浦化学公司 | The method for improving polymer production rate with halogenated hydrocarbon compound |
| CN112759683A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst used for vinyl polymerizing or copolymerizing and its making method |
| CN102066428A (en) * | 2008-06-13 | 2011-05-18 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst for the polymerization of olefins |
-
2014
- 2014-06-18 CN CN201410274027.XA patent/CN105175587A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst used for vinyl polymerizing or copolymerizing and its making method |
| CN102066428A (en) * | 2008-06-13 | 2011-05-18 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst for the polymerization of olefins |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153740A (en) * | 2016-06-09 | 2019-01-04 | 切弗朗菲利浦化学公司 | The method for improving polymer production rate with halogenated hydrocarbon compound |
| CN109153740B (en) * | 2016-06-09 | 2021-04-02 | 切弗朗菲利浦化学公司 | Process for increasing the production rate of polymers using halogenated hydrocarbon compounds |
| CN112759683A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application |
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