CN103772548B - A kind of Catalysts and its preparation method for ethylene polymerization - Google Patents
A kind of Catalysts and its preparation method for ethylene polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of Catalysts and its preparation method for ethylene polymerization, this catalyzer comprises the ingredient of solid catalyst of the reaction product A. titaniferous of following component: form homogeneous solution by first being reacted with organic alcohol compound by magnesium halide, mix with acetyl halide compound again, then obtain with the mixture solution effect of the halogenide or derivatives thereof of transition metals Ti, the general formula of described acetyl halide compound is R(COX)
a, wherein R to be carbonatoms be 0 ~ 8 aliphatic radical or carbonatoms be the aryl of 6 ~ 10, X is halogen, and a is 1 or 2; B. organo-aluminium compound, does is its general formula Al? R '
nx
3-n, in formula, R ' is hydrogen, carbonatoms is the alkyl of 1 ~ 20, and X is halogen, and n is the integer of 0 < n≤3.This catalyzer has higher activity, and polymkeric substance has higher tap density; The preparation method of this catalyzer is simple, shortens the preparation cycle of catalyzer.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for ethylene polymerization.More particularly, the Catalysts and its preparation method for vinyl polymerization containing acetyl halide compound is related to.
Background technology
In poly evolution, the research of catalyzer is the core of polyethylene study on the synthesis always.Before the eighties in 20th century, the emphasis of polyethylene catalysts research pursues catalyst efficiency, and through the effort of nearly 30 years, the catalytic efficiency of polyethylene catalysts was that the order of magnitude improves, thus simplifies polyolefinic production technique, reduces energy consumption and material consumption.Traditional Z-N catalyzer, by the titanium-Al catalysts of classics, has proceeded to by the stage of the compound activatings such as magnesium chloride, other various organic compound modifications; And by simple raising catalytic activity, develop into the performance by regulating catalyzer to improve polymeric articles.
At present from the development of olefin polymerization catalysis, sum up and mainly contain two aspects: (1) exploitation can prepare the polyolefin resin catalyzer of property or more excellent properties, as metallocene catalyst and non-luxuriant late transition metal catalyst etc.; (2) for the production of general purpose polyolefin resin, improving on the basis of catalyst performance further, simplifying catalyst preparation process, reducing catalyzer cost, develop environment amenable technology, to increase the benefit, enhance the competitiveness.
Chinese patent CN85100997 discloses and is a kind ofly all polymerized the catalyst system with copolymerization for alkene, this catalyst system comprises: (first) is containing ingredient of solid catalyst, (second) alkylaluminium cpd, (third) organosilicon of Ti, wherein (first) component is dissolved in organic epoxy compound thing by magnesium halide and organo phosphorous compounds forms homogeneous solution, this solution mixes with titanium tetrahalide or derivatives thereof, at precipitation additive as under the compound existence such as organic acid anhydride, organic acid, ether, ketone, separate out solids; This solids processes with multi-carboxylate, makes it be attached on solids, then obtains with titanium tetrahalide and inert diluent process.When this catalyst system is used for propylene polymerization, catalyst activity is higher, and the degree of isotacticity of resulting polymers is higher, and apparent density is also comparatively large, but during for vinyl polymerization, then there is the deficiency that catalyst activity is lower, hydrogen adjusts sensitivity not.
Chinese patent 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 catalyzer shows very high activity when being used for vinyl polymerization, and the particle form of resulting polymers is better simultaneously, and apparent density is higher, and low-molecular material content is less.
Although the catalyst system of above-mentioned two sections of patents is used for olefinic polymerization all have good 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 preparation process to obtain catalyst solid thing, all have employed the method for adding precipitation additive, more effective precipitation additive is organic acid anhydride, organic acid, ether, one in ketone, when especially adopting Tetra hydro Phthalic anhydride as precipitation additive, better effects if, way first to be dissolved completely in mixed solvent system by phthalic anhydride, and then cooling mixes with titanium compound, therefore the corresponding preparation cycle extending catalyzer of the use of such precipitation additive.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Catalysts and its preparation method for vinyl polymerization, and this catalyzer has higher activity, and polymkeric substance has higher tap density, and the preparation technology of catalyzer is simple.
For a catalyzer for ethylene polymerization, it is characterized in that, this catalyzer comprises the reaction product of following component:
A. the ingredient of solid catalyst of titaniferous: form homogeneous solution by first being reacted with organic alcohol compound by magnesium halide, mix with acetyl halide compound again, then obtain with the mixture solution effect of the halogenide or derivatives thereof of transition metals Ti, the general formula of described acetyl halide compound is R(COX)
a, wherein R to be carbonatoms be 0 ~ 8 aliphatic radical or carbonatoms be the aryl of 6 ~ 10, X is halogen, and a is 1 or 2;
B. organo-aluminium compound, its general formula is AlR '
nx
3-n, in formula, R ' is hydrogen, carbonatoms is the alkyl of 1 ~ 20, and X is halogen, and n is the integer of 0 < n≤3;
Ratio between B component and component A, with the molar ratio computing of aluminium and titanium for 5 ~ 1000.
Specifically, magnesium halide described in catalyst component A of the present invention is magnesium dihalide, in the complex compound of the water of magnesium dihalide and alcohol, magnesium dihalide molecular formula one of them halogen atom by alkyl or-oxyl the one in the derivative of replacing, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, diiodinating magnesium, preferred magnesium dichloride.
Inert diluent suitably can also be added as benzene,toluene,xylene, 1 when magnesium halide described in catalyst component A of the present invention dissolves, 2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound, so-called inertia here refers to that this thinner should not be participated in reaction and can not produce detrimentally affect to the dissolving of magnesium halide.
Organic Alcohol described in catalyst component A of the present invention comprises C
1~ C
12straight chain alcohol or isomery alcohol, particular compound is as the one in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, or their mixture.With ethanol, butanols, 2-Ethylhexyl Alcohol for the best.
The general formula of the acetyl halide compound described in catalyst component A of the present invention is R(COX)
a, it is the compound formed after hydroxyl in carboxylic acid is replaced by halogen atom, wherein R to be carbonatoms be 0 ~ 8 aliphatic radical or carbonatoms be the aryl of 6 ~ 10, X is halogen, and a is 1 or 2; X is halogen, preferred chlorine element.Particular compound as Acetyl Chloride 98Min., Benzoyl chloride, oxalyl chloride etc., preferred Benzoyl chloride.
Its general formula of halogenide or derivatives thereof of transition metals Ti described in catalyst component A of the present invention is TiX
m(OR ")
4-m, wherein X is halogen, R " and be C
1~ C
14aliphatic hydrocarbyl or aromatic hydrocarbyl, m is the integer of 0 ~ 4, particular compound as a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or their mixture, preferred titanium tetrachloride.
The present invention, in preparation component A process, can also optionally add electron donor compound, such as silicoorganic compound; The feeding quantity of electron donor counts 0 ~ 5 mole with every mole of magnesium halide, with 0 ~ 1 mole as well.
In described component A, the feeding quantity of each component is in every mole of magnesium halide, Organic Alcohol 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; The halogenide or derivatives thereof of transition metals Ti 0.2 ~ 100 mole, with 1.0 ~ 20 moles as well; Acetyl halide compound 0.01 ~ 4.0 mole, with 0.05 ~ 1.0 mole as well.
B component is organo-aluminium compound, and its general formula is AlR '
nx
3-n, in formula, R ' is hydrogen, carbonatoms is the alkyl of 1 ~ 20, 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; The alkyl aluminium hydrides such as one hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum; The alkyl aluminum chlorides such as aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride; Wherein with triethyl aluminum and triisobutyl aluminium as well.
In catalyst system component B of the present invention, in aluminium and component A, the mol ratio of titanium is 5 ~ 1000, with 20 ~ 800 as well.
Component A in catalyzer of the present invention can adopt following methods to prepare: stirring and inert diluent exist under by magnesium halide at 0 ~ 150 DEG C of temperature, best 40 ~ 130 DEG C, react with organic alcohol compound and form homogeneous transparent solution, add acetyl halide compound mixing, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, the halogenide or derivatives thereof of transition metals Ti is instilled in this mixed solution maybe by this mixed solution instillation titanium compound, after first can maintaining for some time after dropping terminates, electron donor such as silicoorganic compound can also be added; Then heat up, heat-up rate with intensification per hour 4 ~ 200 DEG C as well; Again by reaction mixture at 10 ~ 150 DEG C of temperature, best 20 ~ 130 DEG C, stir 1 minute ~ 10 hours, stop stirring, sedimentation, filtration, removing mother liquor, with the varsol such as toluene and hexane washing solids, the ingredient of solid catalyst of obtained titaniferous.
Through above-mentioned steps, obtained the component A of invention catalyst system, this component can use with the form of solids or suspension.Catalyst A of the present invention, B component 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.
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.
The present inventor finds to introduce acetyl halide compound in for the catalyst preparation process of ethylene polymerization, catalyzer not only can be made to have higher activity, polymkeric substance has higher tap density, and shortens the preparation cycle of catalyzer, simplifies the preparation technology of catalyzer.
Embodiment
With embodiment, the present invention is described below, but and the unrestricted scope of the invention.
(1) catalyst preparing
Embodiment 1
Through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 0.042mol successively
2, 0.39mol n-decane, add 0.14mol2-ethylhexanol under stirring, be warmed up to 130 DEG C, maintain 1.5 hours, this solution is cooled to 60 DEG C, adds 0.0026mol Benzoyl chloride, this solution is cooled to-10 DEG C, again 0.36mol titanium tetrachloride is instilled in it, maintain 70 minutes, be then warming up to 110 DEG C, maintain 1 hour, use hexanes wash 4 times after filtering, vacuum-drying, obtains ingredient of solid catalyst.
Embodiment 2
Only change the add-on of n-decane into 0.30mol, the add-on of Benzoyl chloride changes 0.0078mol into, and all the other are with embodiment 1.
Embodiment 3
Only change the add-on of Benzoyl chloride into 0.013mol, all the other are with embodiment 1.
Embodiment 4
Through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 0.042mol successively
2, 0.39mol n-decane, add 0.14mol2-ethylhexanol under stirring, be warmed up to 130 DEG C, maintain 1.5 hours, this solution is cooled to 60 DEG C, adds 0.0026mol Benzoyl chloride, this solution is cooled to-10 DEG C, then 0.36mol titanium tetrachloride is instilled in it, maintain 40 minutes, again 0.013mol tetraethoxy-silicane is instilled in it, maintain 30 minutes, be then warming up to 110 DEG C, maintain 1 hour, use hexanes wash 4 times after filtering, vacuum-drying, obtains ingredient of solid catalyst.
Comparative example 1
Through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 0.042mol successively
2, 0.56mol toluene, add 0.026mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.060mol ethanol under stirring, be warmed up to 65 DEG C, add 0.0081mol phthalic anhydride, maintain 2.5 hours, this solution is cooled to-10 DEG C, 0.54mol titanium tetrachloride is instilled in it, maintain 70 minutes, then be warming up to 85 DEG C, maintain 1 hour, after filtering, use hexanes wash 4 times, vacuum-drying, obtains ingredient of solid catalyst.
Comparative example 2
Through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 0.042mol successively
2, 0.75mol toluene, add 0.089mol epoxy chloropropane, 0.033mol tributyl phosphate under stirring, be warmed up to 50 DEG C, maintain 3.0 hours, add 0.0081mol phthalic anhydride, maintain 2 hours, this solution is cooled to-10 DEG C, 0.36mol titanium tetrachloride is instilled in it, maintains 70 minutes, be then warming up to 85 DEG C, maintain 1 hour, use hexanes wash 4 times after filtering, vacuum-drying, obtains ingredient of solid catalyst.
(2) vinyl polymerization
Volume is that the stainless steel still of 2 liters is through H
2after abundant displacement, add hexane 1000ml wherein, triethyl aluminum 1.0ml(concentration is the hexane solution of 1mol/L), (9 ~ 12mg) above-mentioned prepared ingredient of solid catalyst of metering, be warming up to 70 DEG C of hydrogenation to 0.26MPa(gauge pressure), pass into ethene again to make in still, to reach 0.72MPa(gauge pressure), at 80 DEG C, be polymerized 2 hours.Polymerization result is in table 1.
Table 1 polymerization result
As can be seen from the data of table 1, catalyzer of the present invention has higher activity, and polymkeric substance has higher tap density.
Claims (12)
1. for a catalyzer for ethylene polymerization, it is characterized in that, this catalyzer comprises the reaction product of following component:
A. the ingredient of solid catalyst of titaniferous: inert diluent exist under by magnesium halide at 0 ~ 150 DEG C, react with organic alcohol compound and form homogeneous transparent solution, add acetyl halide compound mixing, at-35 ~ 60 DEG C, by the halogenide or derivatives thereof of transition metals Ti and above-mentioned solution reaction, heat up, then reaction mixture is stirred 1 minute ~ 10 hours at 10 ~ 150 DEG C, stop stirring, sedimentation, filtration, removing mother liquor, washing solids, the ingredient of solid catalyst of obtained titaniferous; The general formula of described acetyl halide compound is R (COX)
a, wherein R to be carbonatoms be 0 ~ 8 aliphatic radical or carbonatoms be the aryl of 6 ~ 10, X is halogen, and a is 1 or 2;
B. organo-aluminium compound, its general formula is AlR '
nx
3-n, in formula, R ' is hydrogen, carbonatoms is the alkyl of 1 ~ 20, and X is halogen, and n is the integer of 0 < n≤3;
Ratio between B component and component A, with the molar ratio computing of aluminium and titanium for 5 ~ 1000.
2. the catalyzer for ethylene polymerization according to claim 1, is characterized in that described acetyl halide compound is chloride compounds.
3. the catalyzer for ethylene polymerization according to claim 1, is characterized in that described acetyl halide compound is Benzoyl chloride.
4. the catalyzer for ethylene polymerization according to claim 1, it is characterized in that the feeding quantity of each component in described component A is in every mole of magnesium halide, Organic Alcohol 0.01 ~ 10 mole, the halogenide or derivatives thereof of transition metals Ti 0.2 ~ 100 mole, acetyl halide compound 0.01 ~ 4.0 mole.
5. the catalyzer for ethylene polymerization according to claim 1, it is characterized in that the magnesium halide described in component A is magnesium dihalide, in the complex compound of the water of magnesium dihalide and alcohol, magnesium dihalide molecular formula one of them halogen atom by alkyl or-oxyl the one in the derivative of replacing, or their mixture.
6. the catalyzer for ethylene polymerization according to claim 1, is characterized in that the magnesium halide described in component A is magnesium dichloride.
7. the catalyzer for ethylene polymerization according to claim 1, is characterized in that the Organic Alcohol described in component A is C
1~ C
12straight chain alcohol or isomery alcohol.
8. the catalyzer for ethylene polymerization according to claim 1, is characterized in that the Organic Alcohol described in component A is selected from least one in ethanol, butanols, 2-Ethylhexyl Alcohol.
9. the catalyzer for ethylene polymerization according to claim 1, is characterized in that the general formula of the halogenide or derivatives thereof of the transition metals Ti described in component A is TiX
m(OR ")
4-m, wherein X is halogen, R " and be C
1~ C
14aliphatic hydrocarbyl or aromatic hydrocarbyl, m is the integer of 0 ~ 4.
10. the catalyzer for ethylene polymerization according to claim 1, is characterized in that the halogenide or derivatives thereof of the transition metals Ti described in component A is a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or their mixture.
11. catalyzer for ethylene polymerization according to claim 1, it is characterized in that adding silicoorganic compound in component A, its feeding quantity counts 0 ~ 5 mole with every mole of magnesium halide.
The application of the described catalyzer of one of 12. claims 1 ~ 11 in vinyl polymerization.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822763A (en) * | 1986-06-18 | 1989-04-18 | Mitsubishi Petrochemical Company Limited | Catalyst component for polymerization of olefin |
| US4970186A (en) * | 1987-12-26 | 1990-11-13 | Toho Titanium Co., Ltd. | Solid catalyst component for the polymerization of olefins and an olefin polymerization catalyst |
| CN102020731A (en) * | 2009-09-10 | 2011-04-20 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and catalyst thereof |
| CN102250266A (en) * | 2010-04-28 | 2011-11-23 | 住友化学株式会社 | Process for producing solid catalyst component for olefin polymerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01292006A (en) * | 1988-05-18 | 1989-11-24 | Showa Denko Kk | Catalyst for polymerizing olefin |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
-
2012
- 2012-10-24 CN CN201210407784.0A patent/CN103772548B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822763A (en) * | 1986-06-18 | 1989-04-18 | Mitsubishi Petrochemical Company Limited | Catalyst component for polymerization of olefin |
| US4970186A (en) * | 1987-12-26 | 1990-11-13 | Toho Titanium Co., Ltd. | Solid catalyst component for the polymerization of olefins and an olefin polymerization catalyst |
| CN102020731A (en) * | 2009-09-10 | 2011-04-20 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and catalyst thereof |
| CN102250266A (en) * | 2010-04-28 | 2011-11-23 | 住友化学株式会社 | Process for producing solid catalyst component for olefin polymerization |
Non-Patent Citations (1)
| Title |
|---|
| 《In situ formation of magnesium chloride support and internal donor during preparation of propylene polymerization catalysts》;Dong Ho Lee;《Ind. Eng. Chem. Res.》;19921231;第31卷(第12期);第2642–2647页 * |
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