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CN1177873C - Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof - Google Patents

Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof Download PDF

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Publication number
CN1177873C
CN1177873C CNB011417714A CN01141771A CN1177873C CN 1177873 C CN1177873 C CN 1177873C CN B011417714 A CNB011417714 A CN B011417714A CN 01141771 A CN01141771 A CN 01141771A CN 1177873 C CN1177873 C CN 1177873C
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catalyst component
reaction
catalyst
catalyzer
electron donor
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CN1405191A (en
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罗河宽
吕新平
安京燕
唐瑞国
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention provides a catalyst component for ethylene polymerization or copolymerization, wherein an active component-titanium trichloride is obtained by a way that an organo-magnesium compound is used for reducing titanium tetrachloride on the spot. The catalyst component does not contain an undesirable byproduct, and one of the obtained byproducts is MgCl2 which is one of the active components of the catalyst simultaneously. The MgCl2 can be used on the spot. The other active component-alkyl halide has a certain promotion function on the catalyst component and can be used on the spot. The catalyst component has simple preparation and easy operation. Thus, a reaction product of the catalyst component and an organic aluminum cocatalyst is suitable for the copolymerization reaction of ethylene and high-grade alpha-olefin and is good for reducing the generation of a hexane extract and volatile oil.

Description

The catalyst component and catalyzer and the purposes that are used for vinyl polymerization or copolymerization
Technical field
The present invention relates to a kind of catalyst component that is applicable to vinyl polymerization or copolymerization and preparation method thereof and the catalyzer that comprises this catalyst component, and the application of this catalyzer in olefinic polymerization or copolymerization, the particularly application in ethene gas-phase polymerization, the homopolymer and the multipolymer of production ethene.
Background technology
As everyone knows, adopting gas fluidized bed method production Alathon and multipolymer is one of most important polyethylene production technology, is the key of this production technology and select appropriate catalyst.U.S. Pat 4293673, US4302565, US4302566, having disclosed a kind of among the US4303771 serves as effectively to form the catalyzer that is carried on the silica-gel carrier with titanous chloride/magnesium dichloride/tetrahydrofuran (THF); Having disclosed a kind of among the Chinese patent CN1268520A serves as effectively to form the catalyzer that is carried on the silica-gel carrier with titanous chloride/magnesium dichloride/tetrahydrofuran (THF)/ring-type hydrochloric ether; Having disclosed with titanous chloride/magnesium dichloride/tetrahydrofuran (THF)/halohydrin among the Chinese patent CN1291617A is the catalyzer of effectively forming on the silica-gel carrier of being carried on.These catalyzer all are suitable for the gas phase fluidization bed apparatus and produce polyvinyl resin, are particularly suitable for the production of linear ldpe resin.
The titanous chloride that is adopted in above-mentioned catalyst system is normally produced with metallic aluminium reduction titanium tetrachloride, and this titanous chloride is actually the mixed crystal (TiCl of titanous chloride and aluminum chloride 31/3AlCl 3).Though adopt the catalyzer of this titanous chloride preparation to have high polymerization activity, but still exist two apparent in view defectives.The first is owing to aluminum chloride is mixed in the effective composition of catalyzer, and the limitation of carrier silica gel specific surface area makes its charge capacity be restricted, the existence of aluminum chloride is unfavorable for that catalyzer effectively forms the raising of charge capacity, improves catalyst activity and is restricted thereby make; Its two be since catalyst system in mixed crystal (TiCl 31/3AlCl 3) existence, caused when it is used for ethene and high alpha-olefin such as hexene, octene copolymer, promote to have the generation (in Chinese patent CN1085915A, setting forth to some extent) of unfavorable high-content hexane extractable content and tackifying resin, thereby influenced the stability of gas-phase fluidized-bed production and the raising of producing load.
In order to overcome above-mentioned shortcoming, disclose a kind of magnesium powder that in tetrahydrofuran (THF), adopts among the Chinese patent CN1085915A and reduced the catalyzer that titanium tetrachloride prepares the method for titanous chloride and form thus on the spot, wherein reduction reaction is carried out in the Preparation of catalysts process, the by product MgCl that is produced 2Also be one of active princlple of catalyzer, but in-field use, and by replenishing a certain amount of MgCl 2Make final Mg/Ti mol ratio adjust to needed value.Owing to do not contain undesirable by product---aluminum chloride in the titanous chloride that is generated, so the gained catalyzer overcomes the shortcoming that above-mentioned catalyzer exists.But utilizing the magnesium powder to reduce the reaction of titanium tetrachloride on the spot is a kind of solid-liquid reaction, reaction uniformity is relatively poor, and is restive, and not easy to operate, simultaneously after reaction finishes, unreacted magnesium powder must be removed by filtration unit, otherwise will influence the performance of final catalyzer, because magnesium is more active metal, if the magnesium powder that filters out is not reused, also must carry out inactivation treatment, therefore can bring many inconvenience, be unfavorable for the industrial production of serialization to suitability for industrialized production to it.
Summary of the invention
Therefore, the inventor provides a kind of improved catalyst component by repetition test, active princlple titanous chloride wherein adopts organo-magnesium compound reduction titanium tetrachloride to obtain on the spot, does not only contain undesirable by product, and a kind of of gained by product is MgCl simultaneously 2, be one of active princlple of catalyzer, but in-field use; And another kind of haloalkane has certain promoter action to catalyst component on the contrary, but also in-field use, and also the preparation of catalyst component is simple, processing ease.Therefore the reaction product of catalyst component of the present invention and organoaluminum promotor is highly suitable for the copolymerization of ethene and high alpha-olefin, helps reducing the generation of hexane extractable content and ethereal oil.
The invention provides a kind of catalyst component that is applicable to vinyl polymerization or copolymerization, it comprises a kind of titaniferous active constituent on the carrier substance and reaction product of at least a halides improving agent of being carried on;
Described titaniferous active constituent is in not containing the electron donor solvent of active hydrogen group, passes through MgR 2Or MgRX and titanium tetrachloride contact reacts, make titanium tetrachloride be reduced to titanous chloride after, again with MgX 2Obtain after the reaction;
Described halides improving agent is for having following general formula F-R 1[R 2 bX (3-b)] a compounds, wherein:
F be a kind of can with the oxygen-containing functional group of organo-aluminium compound, titanium compound or hydroxyl generation chemical reaction, R 1Be the C of a divalence 1～C 6Fatty group or aromatic base, it links to each other with Sauerstoffatom among the F of functional group; R 2Be hydrogen, C 1～C 6The C that alkyl, cycloalkyl or aromatic base or halogen replace 1～C 6Alkyl, cycloalkyl aromatic base, b are 0,1 or 2, and X is F, Cl or Br;
In titaniferous catalyst component of the present invention, ratio between each component is counted with every mole of titanium compound: magnesium compound is 0.5～50 mole, preferred 1.5～5 moles, electron donor is 0.5～50 mole, preferred 1～10 mole, the halides improving agent is 0.5～50 mole, preferred 1～10 mole.
The above-mentioned used electron donor that does not contain active hydrogen group (ED) is preferably from following compound: the alkyl ester of aliphatic series or aromatic carboxylic acid, aliphatic ether, cyclic ethers and aliphatic ketone.In these electron donors, preferred C 1～C 4The alkyl ester of saturated aliphatic carboxylic acid, C 7～C 8The alkyl ester of aromatic carboxylic acid, C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6Radical of saturated aliphatic ketone.These electron donors are methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone and methyl iso-butyl ketone (MIBK) most preferably.Electron donor can use separately or several being used.
It is to be noted when the present invention adopts organo-magnesium compound reduction titanium tetrachloride, can produce the by product alkyl chloride, for example with tetrahydrofuran (THF) as the electron donor solvent, quantitative dibutylmagnesium and the following chemical reduction reaction of titanium tetrachloride generation:
Pointed out once in Chinese patent CN1085915A that the formed alkyl chloride of this method is undesirable by product, must separate it before use from the titanous chloride product.And in catalyst component of the present invention, the contriver is surprisingly found out that by repetition test, above-mentioned reaction produce by product---chlorobutane does not only have any detrimentally affect to catalyzer, on the contrary activity of such catalysts is had certain promoter action.Because 107.8 ℃ of the boiling points of chlorobutane, far above the boiling point of tetrahydrofuran (THF) tetrahydrofuran (THF) (66 ℃) and iso-pentane (27.9 ℃), by product needn't be removed, and stays in the catalyzer, will help the performance of catalyst activity.
It is worthy of note and in catalyst component of the present invention, adopt organo-magnesium compound reduction titanium tetrachloride can demonstrate the advantage of following several respects: one, prepared the titanous chloride component on the spot, and do not contain undesirable aluminum chloride in this titanous chloride, help improving the charge capacity that catalyzer is effectively formed on the silica-gel carrier, thereby correspondingly improve activity of such catalysts; Its two, do not contain mixed crystal body (TiCl in the catalyzer 31/3AlCl 3), when the catalyzer of preparation is used for ethene and high-grade alpha-olefin more such as hexene, octene copolymer, help reducing the generation of hexane extractable content and ethereal oil; Its three, the reaction of organic-magnesium and titanium tetrachloride fast and has quantitatively guaranteed the quality of preparation catalyzer, technology is simple, processing ease, and its by product alkyl chloride needn't remove, its existence will help the performance of catalyst activity, simultaneously another by product MgCl 2But also in-field use.
Wherein organo-magnesium compound can adopt alkyl magnesium such as MgR 2Or chloro alkyl magnesium such as MgRX, wherein the R group is C 2～C 10Alkyl, cycloalkyl or aryl, concrete as magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, dioctyl magnesium, butylmagnesium chloride, hexyl magnesium chloride, octyl group magnesium chloride.Be preferably dibutylmagnesium or dioctyl magnesium.
Wherein used formula M gX 2In the magnesium compound, X chooses from Cl, Br, I or its mixture.Specifically can select magnesium dichloride, dibrominated magnesium, two magnesium iodides for use, be preferably magnesium dichloride.
Above-mentioned halides improving agent is for having general formula F-R 1[R 2 bX (3-b)] a compounds, wherein:
F be a kind of can with the functional group of hydroxyl generation chemical reaction on organo-aluminium compound, titanium compound or the silica gel, as aldehyde radical, acyl group, hydroxyl, amino or ester group etc.; R 1Be the C of a divalence 1～C 6Aliphatic group or aromatic group, it links to each other with Sauerstoffatom among the F of functional group; R 2The C that replaces for hydrogen, unsubstituted or halogen 1～C 6Alkyl, C 3～C 6Cycloalkyl or C 6～C 10Aromatic group, b are 0,1 or 2, and X is F, Cl or Br.
When F was hydroxyl, improving agent was a class halohydrin, and particular compound is trichloro-ethyl alcohol (Cl 3CCH 2OH), 2,2-dichlroroethanol (Cl 2CHCH 2OH), ethylene chlorhydrin (ClCH 2CH 2OH), 1,1-dimethyl-trichloro-ethyl alcohol (Cl 3CC (CH 3) 2OH), 4-butylene-chlorohydrin (ClCH 2CH 2CH 2CH 2OH), para-chlorophenol, m-Chlorophenol, ortho chloro phenol and 2-chloro cyclohexanol etc.Preferred trichloro-ethyl alcohol (Cl 3CCH 2OH), 2,2-dichlroroethanol (Cl 2CHCH 2OH), ethylene chlorhydrin (ClCH 2CH 2OH) or 1,1-dimethyl-trichloro-ethyl alcohol (Cl 3CC (CH 3) 2OH).
When F was acyl group, improving agent was a class halogen acyl halide, and particular compound is trichoroacetic chloride, dichloroacetyl chloride, chloroacetyl chloride, o-chlorobenzoyl chloride and 2-chlorine cyclohexyl carbonyl chloride etc.Preferred trichoroacetic chloride, dichloroacetyl chloride or chloroacetyl chloride.
The preparation method of catalyst component of the present invention, generally be method by dipping with active constituent loading on silica-gel carrier, titanium tetrachloride and stoichiometric organic-magnesium are reacted in the electron donor solvent, titanous chloride and the magnesium dichloride produced, form the solubility title complex with this electron donor, then, in this solution, add a certain amount of magnesium dichloride, the Mg/Ti mol ratio is brought up to needed value, obtain desirable catalyst component.Then with solution impregnation in suitable porous support material, by means such as evaporating solvent or spraying dryings catalyzer is effectively formed and to be loaded with on the carrier, obtain the ideal solid catalytic ingredient, constitute olefin polymerization catalysis with the promotor aluminum alkyls.
Above-mentioned porous support material can adopt sphere or class spheric silica gel, and median size 10～100 μ m of this silica gel are preferably: 20～80 μ m, and the best is: 30～60 μ m; Specific surface area 50～1000m 2/ g is preferably: 100～800m 2/ g, the best is: 200～800m 2/ g; Volume of voids is 1.0～6.0ml/g, is preferably: 2.0～5.0ml/g; The hole mean diameter is 5～45nm, is preferably: 10～35nm.Silica gel with dehydration is best, and thermal activation condition that generally can be by control silica gel to be adjusting the content of its surface hydroxyl,
In the above-mentioned thermal activation silica gel process, can also add organo-aluminium compound such as AlEt 3, activators such as MAO or organo-magnesium compound such as dibutyl magnesium.
Preferable embodiment can comprise following reactions steps:
(1) method with routine activates silica-gel carrier, and comparatively preferred condition can adopt at 600 ℃ dewatered 4 hours down;
(2) above-mentioned thermal activation silica gel is added in the lower paraffin hydrocarbons solvent, add alkylaluminium cpd again and boil off solvent after reaction for some time, carry out drying, obtain pressed powder;
(3) titanium tetrachloride compound and organo-magnesium compound are dissolved in the electron donor, add a certain amount of MgX after reaction for some time 2, dissolving is prepared into mother liquor, wherein MgX 2Compound joins time and the restriction that does not have strictness in proper order in the electron donor compound, as long as guarantee that final Mg/Ti mol ratio reaches desirable value;
(4) step (2) activatory carrier is joined in the above-mentioned mother liquor, after the reaction regular hour, it is carried out drying, removing excessive solvent is electron donor, and general control residue content is at 10～21wt%;
(5) solid matter that step (4) is obtained is suspended in the lower paraffin hydrocarbons solvent, reduces processing with one or more alkylaluminium cpds, carries out promptly making final catalyst component after the drying again.
Wherein the lower paraffin hydrocarbons solvent is C described in step (2) and the step (5) 3～C 9Alkane, preferred C 5And C 6Alkane, for example iso-pentane, pentane, hexane etc.;
Wherein used alkylaluminium cpd in step (2) and the step (5) is preferably general formula AlR m' X 3-mCompound, R ' is C identical or inequality in the formula 1-8Alkyl, X are halogen, and m is 1～3 integer.Preferred alkylaluminium cpd is AlEt 3, Al (n-C 6H1 3) 3, AlEt 2Cl etc.
It needs to be noted that halides improving agent of the present invention can be with in any efficient manner introducing catalyst component.For example select in the following method any all can obtain good facilitation effect: i) in above-mentioned silica gel treatment step (2), to introduce, ii) be carried in the step (3) on the silica gel and introduce at above-mentioned catalyst complex, iii) in above-mentioned catalyst reduction step (5), introduce etc., can distinguish or introducing in step (2) or step (3) or step (5) simultaneously.
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, it is the reaction product of above-mentioned catalyst component and alkylaluminium cpd, and the general formula of wherein used alkylaluminium cpd is AlR " 3, R in the formula " and be C identical or inequality 1-8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls to mix use, preferred AlEt 3, Al (iso-Bu) 3, Al (n-C 6H 13) 3, Al (n-C 8H 17) 3, AlEt 2Cl etc.
Catalyzer of the present invention is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefins, and wherein alpha-olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1.Its polymerization technique can adopt vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation particularly gas-phase fluidized-bed condensation technology.
Embodiment
Come the catalyzer that the present invention relates to is done further explanation below by embodiment, obviously catalyzer involved in the present invention is not limited only to following examples.
The testing method of related physical parameter is:
Specific surface area, volume of voids, hole mean diameter: mercury penetration method (Mercury intrusion)
Melting index MI-GB3682-83 (2.16kg)
Melt-flow index FI-GB3682-83 (21.6kg), MFR=FI/MI
Apparent density BD-ASTM-D-1895
Embodiment 1
The preparation of catalyst component
(1) takes by weighing about 12g spherical silica gel (SMR #49-4039, U.S. Grace company produces, and median size is 55 μ m, and specific surface area is 717m 2/ g, volume of voids are that 4.6ml/g, hole mean diameter are 25.7nm) 600 ℃ of activation 4 hours.
(2) under nitrogen protection, in the reaction flask of belt stirrer, be solvent (100ml) with the iso-pentane, add thermal activation silica gel 10g and 6.1mlAlEt in (1) step 3Hexane solution (1mmol/ml), 20～30 ℃ the reaction half an hour, then slowly drip 1.1mlCl 3CCH 2OH adds afterreaction half an hour, purges with high pure nitrogen and is dried to mobile powder.
(3) in the reaction flask of another belt stirrer, add 1.42gMgCl 2And 0.64mlTiCl 4And the 140ml tetrahydrofuran (THF), temperature rising reflux stirred 1 hour, dripped 2.8mlMgBu then 2Solution (1mmol/ml n-heptane solution) refluxed 4 hours again, promptly made the catalyzer mother liquor.
(4) silica gel of handling well in (2) step is mixed with (3) mother liquor that goes on foot preparation, reflux and stirred 1 hour, then purge drying with high pure nitrogen, obtain mobile faint yellow solid powder, wherein the content of tetrahydrofuran (THF) is 14.0wt%.
(5) with the iso-pentane be solvent at room temperature, adopt AlEt 2Cl and Al (n-C 6H 13) 3Reaction product to step (4) gained is carried out prereduction, control AlEt 2The Cl/THF mol ratio is 0.45, Al (n-C 6H 13) 3/ THF is 0.20, and hexane 100ml at first drips 7.0mlAlEt 2The hexane solution of Cl (2.21mmol) drips afterreaction half an hour.Drip 4.5mlAl (n-C again 6H 13) 3Hexane solution (1.5mmol), react again purge with high pure nitrogen after half an hour dry, little yellow solid powder catalyst component.In its catalyst component: Ti%=1.28wt%.
Evaluating catalyst:
The equal polymerization of the slurry of ethene: carry out the slurry evaluation in the 2L stainless steel cauldron, catalyst consumption is 50mg, H 2/ C 2H 4=0.28/0.75MPa, the AlEt of 1ml 3Hexane solution (1mmol/ml), the 1L hexane, 85 ℃ were reacted 2 hours.The polymerization evaluation the results are shown in Table one.
Embodiment 2
The preparation of catalyst component
Except that following difference, other is with embodiment 1.
Difference:
(1) in step (5), Al-(C 6H 12) 3Add reaction and splash into 1.1mlCl after 30 minutes 3CCH 2OH reacts and carried out drying in 30 minutes;
(2) THF% is 17.4wt% in the masterbatch;
(3) Ti% is 1.37wt% in the catalyzer.
The catalyst slurry polymerization is estimated with embodiment 1, and polymerization result sees Table 1.
Embodiment 3
The preparation of catalyst component
Except that following difference, other is identical with embodiment 1.
(1) uses 6.1mlMgBu 2Solution (1mmol/ml n-heptane solution) replaces 6.1mlAlEt 3Solution (1mmol/ml hexane solution) is handled thermal activation SiO 2
(2) THF% is 18.9wt% in the masterbatch;
(3) 1.1mlCl 3CCH 2OH is Al (C in the preactivating catalysts step 6H 12) 3Add reaction and splash into after 30 minutes, react again and carried out drying in 30 minutes;
(4) Ti% is 1.40% in the catalyzer.
The catalyst slurry polymerization is estimated with embodiment 1, and polymerization result sees Table 1.
Embodiment 4
The preparation of catalyst component
(1) (median size is 50 μ m for SYLOPOL948, the production of U.S. Grace company, and specific surface area is 295m to take by weighing about 12g spherical silica gel 2/ g, volume of voids are that 1.7ml/g, hole mean diameter are 23.3nm) 600 ℃ of activation 4 hours.
(2) under nitrogen protection, in the reaction flask of belt stirrer, be solvent (100ml) with the iso-pentane, add thermal activation silica gel 10g and 6.1mlAlEt in (1) step 3Hexane solution (1mmol/ml), 20～30 ℃ of reaction half an hour, then purge and be dried to mobile powder with high pure nitrogen.
(3) in the reaction flask of another belt stirrer, add 0.93gMgCl 2And 0.4mlTiCl 4And the 100ml tetrahydrofuran (THF), temperature rising reflux stirred 1 hour, dripped 1.8mlMgBu then 2Solution (1mmol/ml n-heptane solution) refluxed 4 hours again, promptly made the catalyzer mother liquor.
(4) silica gel of handling well in (2) step is mixed with (3) mother liquor that goes on foot preparation, reflux and stirred 1 hour, then purge drying with high pure nitrogen, obtain mobile faint yellow solid powder, wherein the content of tetrahydrofuran (THF) is 13.3wt%.
(5) with the iso-pentane be solvent at room temperature, adopt AlEt 2Cl and Al (n-C 6H 13) 3Reaction product to step (4) gained is carried out prereduction, control AlEt 2The Cl/THF mol ratio is 0.45, Al (n-C 6H 13) 3/ THF is 0.20, hexane 100ml, at first Dropwise 5 .3mlAlEt 2The hexane solution of Cl (2.21mmol) drips afterreaction half an hour.Drip 3.5mlAl (n-C again 6H 13) 3Hexane solution (1.5mmol), after reaction half an hour, drip 0.71mlCl 3CCH 2OH, react again purge with high pure nitrogen after half an hour dry, little yellow solid powder catalyst component.In its catalyst component: Ti%=1.22wt%.
Evaluating catalyst:
The equal polymerization of the slurry of ethene: carry out the slurry evaluation in the 2L stainless steel cauldron, catalyst consumption is 50mg, H 2/ C 2H 4=0.28/0.75MPa, the AlEt of 1ml 3Hexane solution (1mmol/ml), the 1L hexane, 85 ℃ were reacted 2 hours.Polymerization result sees Table 1.
Comparative Examples 1
The preparation of catalyst component
Except that following difference, other is identical with embodiment 1.
Difference:
(1) with commercially available 1.16gAA level TiCl 3And 1.74gMgCl 2Preparation catalyzer mother liquor, rather than use 2.8mmolMgBu 2Reduction 0.64mlTiCl 4Preparation TiCl 3, add 1.42gMgCl again 2Method prepare the catalyzer mother liquor;
(2) THF% is 17.7wt% in the masterbatch;
(3) Ti% is 1.14wt% in the catalyzer;
The catalyst slurry polymerization is estimated with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 2
The preparation of catalyst component
Except that following difference, other is identical with embodiment 4.
Difference:
(1) with commercially available 0.73gAA level TiCl 3And 1.1gMgCl 2Preparation catalyzer mother liquor, rather than use 1.8mmolMgBu 2Reduction 0.4mlTiCl 4Preparation TiCl 3, add 0.93gMgCl again 2Method prepare the catalyzer mother liquor;
(2) THF% is 14.2wt% in the masterbatch;
(3) Ti% is 0.9wt% in the catalyzer;
The catalyst slurry polymerization is estimated with embodiment 1, and polymerization result sees Table 1.
Table 1. polymerization evaluation result
Embodiment Ti％ Active (gPE/gCat)
Embodiment 1 1.28 5770
Embodiment 2 1.37 5349
Embodiment 3 1.40 4609
Embodiment 4 1.22 3049
Comparative Examples 1 1.14 4955
Comparative Examples 2 0.90 1800
Embodiment 5
Preparation of Catalyst and slurry evaluation are all with embodiment 2.Add chlorobutane at home and abroad in the polymerization evaluation, investigate the influence of chlorobutane and consumption thereof polymerization catalyst and polyvinyl resin.The results are shown in Table 2.
Table 2. adds chlorobutane to catalyst activity and polyvinyl resin Effect on Performance
N-propylcarbinyl chloride/titanium (mol/mol) Active (gPE/gCat) BD (g/cm 3) MI (g/10min) FI (g/10min) MFR
0 5349 0.34 0.39 11.3 29.1
10 5979 0.35 0.50 14.1 28.3
50 5563 0.34 0.31 9.53 30.7
100 4988 0.32 0.30 8.27 27.6
Annotate: stagnation pressure: 1.03MPa; Polymerization temperature: 85 ℃; Reaction times: 2h; Hexane: 1.0L; Aluminum alkyls: 0.1mmol; N-propylcarbinyl chloride is made into the hexane solution of 1mmol/ml.
By embodiment ~ 2 and Comparative Examples 1 contrast, as seen embodiment 4 contrasts with Comparative Examples 2, and the catalyzer that the present invention relates to has the titanium content and the activity of obvious raising; By embodiment 5 as seen, add the small amounts of chlorine butane, help the raising of catalyst activity, also do not observe the influence of the significant adverse of catalyzer and polymkeric substance, proved and utilized MgBu even introduce chlorobutane in a large number 2Reduction TiCl 4Preparation TiCl 3In a spot of by product chlorobutane needn't remove, it has the performance that is beneficial to catalyst activity.

Claims (11)

1, a kind of catalyst component that is applicable to vinyl polymerization or copolymerization, it comprises a kind of titaniferous active constituent on the carrier substance and reaction product of at least a halides improving agent of being carried on;
Described titaniferous active constituent is in not containing the electron donor solvent that has active hydrogen group, passes through MgR 2Or MgRX and titanium tetrachloride contact reacts, make titanium tetrachloride be reduced to titanous chloride after, again with MgX 2Obtain after the reaction, wherein the R group is C 2～C 10Alkyl, cycloalkyl or aryl, X are Cl, Br or I;
Described halides improving agent is for having following general formula F-R 1[R 2 bX (3-b)] a compounds, wherein:
F be a kind of can with the oxygen-containing functional group of organo-aluminium compound, titanium compound or hydroxyl generation chemical reaction, a kind of in aldehyde radical, acyl group, the hydroxyl; R 1Be the C of a divalence 1～C 6Fatty group or aromatic base, it links to each other with Sauerstoffatom among the F of functional group; R 2Be hydrogen, C 1～C 6The C that alkyl, cycloalkyl or aromatic base or halogen replace 1～C 6Alkyl, cycloalkyl or aromatic base, b are 0,1 or 2, and X is F, Cl or Br.
2, catalyst component according to claim 1 is characterized in that, the ratio between the each component is in every mole of titanium: magnesium 0.5-50, electron donor are 0.5-50, and the halides improving agent is 0.5-50.
3, catalyst component according to claim 1 is characterized in that, the F in the described halides improving agent is a kind of in acyl group or the hydroxyl.
4, catalyst component according to claim 1, it is characterized in that, described halides improving agent is selected from one or more in the following halohydrin: 2,2,2-ethapon, 2,2-dichlroroethanol, ethylene chlorhydrin, 1,1-dimethyl-2,2,2-ethapon, 4-butylene-chlorohydrin, para-chlorophenol, m-Chlorophenol, ortho chloro phenol and 2-chloro cyclohexanol.
5, catalyst component according to claim 1 is characterized in that, described MgR 2Be dibutylmagnesium or dioctyl magnesium.
6, catalyst component according to claim 1 is characterized in that, described electron donor compound is selected C for use 1～C 4The alkyl ester of aliphatic saturated monocarboxylic acid, C 7～C 8The alkyl ester of aromatic carboxylic acid, C 2～C 6Aliphatic ether, C 3～C 4Cyclic ethers, C 3～C 6A kind of in the saturated fatty ketone or their mixture.
7, catalyst component according to claim 1 is characterized in that, described carrier substance is that median size is 10～100 μ m, and specific surface area is 50～1000m 2/ g, volume of voids are 1.0～6.0ml/g, and the hole mean diameter is the silica gel of 5～45nm.
8, the preparation method of the described catalyst component of one of claim 1-7 may further comprise the steps:
(1) method with routine activates carrier,
(2) add in the lower paraffin hydrocarbons solvent through the activatory carrier above-mentioned, add alkylaluminium cpd again after reaction for some time, remove and desolvate, obtain pressed powder;
(3) in electron donor, with MgR 2Or MgRX and titanium tetrachloride contact reacts, make titanium tetrachloride be reduced to titanous chloride after, again with MgX 2After the reaction, make mother liquor, final titanium/magnesium mol ratio is 0.5-50;
(4) step (2) activatory carrier is joined in the mother liquor that step (3) obtains, after the reaction regular hour, remove excessive electron donor, control residue electron donor content is at 10～21wt%;
(5) solid matter that step (4) is obtained is suspended in the lower paraffin hydrocarbons solvent, reduces processing with one or more alkylaluminium cpds, carries out promptly making catalyst component after the drying again;
The halides improving agent can be distinguished or introduce in step (2) or step (3) or step (5) simultaneously;
Wherein the lower paraffin hydrocarbons solvent is C described in step (2) and the step (5) 3～C 9Alkane;
Wherein used alkylaluminium cpd is general formula AlR in step (2) and the step (5) m' X 3-mCompound, R ' is C identical or inequality in the formula 1-8Alkyl, X are halogen, and m is 1～3 integer.
9, a kind of catalyzer that is applicable to vinyl polymerization or copolymerization comprises the reaction product of following two components:
(1) the described catalyst component of one of claim 1-7;
(2) organoaluminum component;
Aluminium between component (1) and the component (2)/titanium is than being 50-200.
10, catalyzer according to claim 9 is characterized in that, described component (2) organoaluminum is selected AlEt for use 3, Al (iso-Bu) 3, Al (n-C 6H 13) 3, Al (n-C 8H 17) 3, AlEt 2A kind of among the Cl or their mixture.
11, a kind of claim 9 or the application of 10 described catalyzer in ethene gas phase or slurry polymerization or copolymerization.
CNB011417714A 2001-09-19 2001-09-19 Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof Expired - Lifetime CN1177873C (en)

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CN102020732B (en) * 2009-09-10 2013-02-06 中国石油化工股份有限公司 Catalyst component preparation method and catalyst for vinyl polymerization
CN102050898B (en) * 2009-10-27 2013-11-06 中国石油化工股份有限公司 Method for pretreating polyethylene catalyst
CN104250322B (en) * 2013-06-28 2017-09-29 中国石油化工股份有限公司 A kind of catalytic component and its catalyst for ethylene polymerization
CN112646064B (en) * 2019-10-11 2023-01-03 中国石油化工股份有限公司 Catalyst component for olefin polymerization, preparation method thereof, catalyst and application
CN112724289B (en) * 2019-10-14 2023-02-28 中国石油化工股份有限公司 Titanium-based main catalyst for polymerization, preparation method thereof, catalyst composition containing titanium-based main catalyst and application of catalyst composition
CN112661885B (en) * 2019-10-16 2023-05-12 中国石油化工股份有限公司 Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application
CN112759671B (en) * 2019-10-21 2023-05-09 中国石油化工股份有限公司 Ti-containing solid catalyst component for olefin polymerization, preparation method thereof, catalyst containing Ti-containing solid catalyst component and application of Ti-containing solid catalyst component
CN112707978B (en) * 2019-10-25 2023-05-12 中国石油化工股份有限公司 Magnesium-based catalyst component for olefin polymerization, preparation method thereof, catalyst and application

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