CN102875707A - Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof - Google Patents
Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst component for ethylene polymerization or copolymerization and a catalyst thereof. The method comprises the following steps: (1) at a temperature of 50-90DEG, dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution; adding an organic alcohol compound during or after the solution formation and leaving them to react for certain time so as to obtain a reaction solution; (2) in the presence of an organic titanium compound and at a temperature of -30DEG C-0DEG C, subjecting the solution and a titanium compound to a contact reaction, or adding the organic titanium compound after the contact reaction of the solution obtained in step (1) and the titanium compound, and raising the temperature of the mixture slowly to 50-120DEG C, leaving solids to precipitate gradually and form particles, after certain period of reaction, removing the unreacted material and the solvent, and conducting washing with an inert diluent so as to obtain a solid component; and (3) suspending the solid component in certain amount of the inert diluent, performing a contact reaction with an organic aluminium compound under a temperature of 0DEG C-50DEG C, and after certain reaction time, removing the inert diluent, thus obtaining the catalyst component. The catalyst provided in the invention has high catalytic activity and good hydrogen response.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyst component for vinyl polymerization or copolymerization and the catalyzer of this catalyst component.
Background technology
As everyone knows, the catalyst body that contains the Ti/Mg mixture ties up in the polyolefinic suitability for industrialized production occupies an leading position, and its research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance etc.And in the slurry polymerization processes of ethene, except requiring catalyzer should have the higher catalytic activity, polyvinyl size and size distribution that control is produced are very important.In olefinic polymerization, particularly in the slurry polymerization process of ethene, be easy to produce thinner polymer particle, this fine powder easily produces static, causes " airborne dust " phenomenon, sometimes also easily lumps, and causes the obstruction of equipment pipe.And the effective means of the control size of polymkeric substance and size distribution is particle diameter and the size distribution of control catalyzer.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to come Kaolinite Preparation of Catalyst usually.
The first is the magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent, and then with this solution and titanium compound and randomly electron donor mix, method by precipitation obtains containing the solids of magnesium, titanium and optional electron donor, and obtains granules of catalyst after this solids processed with excessive liquid titanium compound.Such as disclosed among Chinese patent CN1099041A, the CN1229092 etc.The shortcoming of this traditional method is that the particle diameter of granules of catalyst and size distribution are to be that the recrystallization process of magnesium carrier composition is controlled the relatively more difficult control of its stability by precipitation process fully.
The second is that the catalyst activity component directly is carried on inert support such as the silica gel etc., and owing to the particle diameter of silica gel is easily controlled, and particle form is better, therefore can obtain evengranular catalyst particle.But because the charge capacity of active ingredient is restricted on the carrier, therefore titanium content is lower in the catalyzer that makes of this method, and polymerization activity is not high.For example: in patent CN1268520, take magnesium chloride, silicon-dioxide as carrier, titanium tetrachloride is active ingredient, and the preparation method of catalyzer is as follows: with MgCl
2In tetrahydrofuran THF with TiCl
4Reaction is again with the SiO that processed through aluminum alkyls
2Mix, make catalyst component after removing tetrahydrofuran THF.When being used for vinyl polymerization, because the titanium content in the catalyzer is lower, thereby polymerization activity is lower.Therefore, although this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethene, because lower catalytic activity is difficult to be applicable in the slurry polymerization processes of ethene.
As everyone knows, in the slurry polymerization processes of ethene, except requiring catalyzer should have higher catalytic activity and preferably the size distribution, in order to produce Alathon or the multipolymer with better performance, also require catalyzer should have preferably hydrogen response, the melting index of namely regulating final polymkeric substance by hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of the catalyst system that above-mentioned two kinds of methods make is also unsatisfactory.
Chinese patent CN1958620A improves the catalyzer of above-mentioned two kinds of methods preparation, discloses a kind of catalyzer that is applicable to the ethene slurry polymerization, its have high reactivity, particle diameter evenly, narrow diameter distribution, the preferably characteristics such as hydrogen response.It is take magnesium chloride as carrier, and titanium tetrachloride is active ingredient, and the preparation method of catalyzer is as follows: first with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then at low temperatures precipitation additive silicon ester compound and TiCl
4Reactivity is separated out solid catalyst by slow intensification.When the catalyst component that makes was used for vinyl polymerization, the catalytic activity of catalyzer was higher, and is more although its hydrogen response also improves than the catalyzer among the Chinese patent CN1229092A, still can not satisfy industrial demand fully.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method and catalyzer thereof of the catalyst component for vinyl polymerization or copolymerization, and this catalyzer has higher catalytic activity and hydrogen response preferably.
A kind of preparation method of the catalyst component for vinyl polymerization or copolymerization, it may further comprise the steps:
(1) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds forms homogeneous solution, solvent temperature is 50～90 ℃; In forming the process of solution or solution add organic alcohol compound after forming, the reaction regular hour, obtain reaction soln;
(2) in the presence of organic titanic compound, at-30 ℃～0 ℃, mentioned solution and titanium compound are carried out contact reacts, organic titanic compound also can solution and titanium compound in step (1) carry out adding after the contact reacts, and mixture slowly is warming up to 50～120 ℃, and particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain solid ingredient;
(3) above-mentioned solid ingredient is suspended in a certain amount of inert diluent, carries out contact reacts with organo-aluminium compound, temperature is 0 ℃～50 ℃, removes inert diluent behind the reaction certain hour, obtains catalyst component of the present invention; Described magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
The general formula of described titanium compound is Ti (OR
1)
aX
1 b, R in the formula
11～14 aliphatic group or aromatic hydrocarbyl for carbonatoms, X
1Be halogen, a be 0,1 or 2, b be 1 to 4 integer, a+b=3 or 4;
Described organic alcohol compound is that carbonatoms is that the alcohol of 1～10 straight chain, side chain or cycloalkyl or carbonatoms are 6～20 to contain the alcohol of aryl;
The general formula of described organic titanic compound is Ti (OR
2)
aX
2 b, R wherein
2Be 1～14 aliphatic alkyl or aromatic hydrocarbyl for carbonatoms, X
2Be halogen, a be 1,2,3 or 4, b be 0,1,2,3, a+b=4;
The general formula of described organo-aluminium compound is AlR
3 nX
3 3-n, R in the formula
3Be 1～20 alkyl for hydrogen or carbonatoms, X
3Be halogen, n is the integer of 0＜n≤3.
Magnesium mixture of the present invention is that magnesium halide is dissolved in formed mixture in the solvent system of organic epoxy compounds, organo phosphorous compounds, and this mixture is the solution of a homogeneous transparent.Wherein said magnesium halide is selected from the complex compound of water, alcohol or the electron donor of magnesium dihalide or magnesium dihalide.Concrete compound is such as magnesium dichloride, dibrominated magnesium, bifluoride magnesium, two magnesium iodides etc., wherein preferred magnesium dichloride; The complex compound of the water of described magnesium dihalide, alcohol or electron donor comprises the complex compound of the compounds such as magnesium dihalide and water, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, isooctyl alcohol, ammonia, hydroxyl ammonia, ether, ester; Described magnesium halide can be used alone or as a mixture.
Described organic epoxy compounds is selected from least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether etc.
Described organo phosphorous compounds is hydrocarbyl carbonate or the halo 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, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl etc.Wherein in every mole of magnesium halide, organic epoxy compounds: 0.2～10.0mol, preferred 0.3～4.0mol; Organo phosphorous compounds: 0.1～10.0mol, preferred 0.2～4.0mol.
In order to make dissolving more abundant, in this solvent system, optionally add inert diluent, common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture, such as butane, and pentane, hexane, hexanaphthene, heptane etc. are as long as help can using of magnesium halide dissolving.Above-mentioned inert diluent can use separately, also use capable of being combined.
Described organic alcohol compound comprises that carbonatoms is that the alcohol of 1～10 straight chain, side chain or cycloalkyl or carbonatoms are 6～20 to contain the alcohol of aryl.The example of alcohol comprises Fatty Alcohol(C12-C14 and C12-C18): methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, decyl alcohol etc.; Cycloalkanol is such as hexalin, methyl-cyclohexanol etc.; Aromatic alcohol, such as phenylcarbinol, methylbenzyl alcohol, α-methylbenzylalcohol, α, alpha-alpha-dimethyl phenylcarbinol etc.Wherein preferred alcohol, butanols, 2-Ethylhexyl Alcohol, glycerol.Each pure ratio in the alcohol composition is had no particular limits.
Described titanium compound 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, titanous chloride, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
Described organic titanic compound is four titan-alkoxides, comprising: four titanium butoxide, purity titanium tetraethoxide, tetramethoxy titanium, preferred four titanium butoxide.Among the present invention, organic titanic compound should contain the organic titanic compound of q.s to improve the over-all properties of catalyzer in the solid titanium catalyst component that finally obtains except using as precipitation additive.
Described organo-aluminium compound comprises triethyl aluminum, aluminium diethyl monochloride, dichloro one aluminium triethyl, sesquialter aluminium triethyl, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine di-isopropyl aluminium, chloromethyl n-propyl aluminium, a chlorodiphenyl base aluminium etc.Preferred sesquialter aluminium triethyl wherein, aluminium diethyl monochloride, dichloro one aluminium triethyl.
In the preparation method of the catalyst component for vinyl polymerization or copolymerization of the present invention, the ratio between each reactant is in every mole of magnesium halide in the magnesium mixture, and the consumption of Organic Alcohol is generally 0～6 mole, preferred 0～2 mole; The consumption of titanium compound is generally 1～20 mole, preferred 1～15 mole; The consumption of organic titanic compound is generally 0.1～2 mole, preferred 0.1～1 mole; The consumption of organo-aluminium compound is generally 0～5 mole.
The present invention also provides a kind of and has closed the catalyzer of reaction for ethene and alpha-olefin copolymer, and alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.This catalyzer comprises the catalyst component that the above-mentioned the present invention of component (1) obtains; Component (2) general formula is AlR
3 nX
3 3-nThe reaction product of organo-aluminium compound, R in the formula
3Be 1～20 alkyl for hydrogen or carbonatoms, these groups can be the same or different, X
3Being halogen, can be that the same halogen atom also can be different halogen atom, and n is the integer of 0＜n≤3.Particular compound is such as triethyl aluminum, aluminium diethyl monochloride, dichloro one aluminium triethyl, sesquialter aluminium triethyl, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine di-isopropyl aluminium, chloromethyl n-propyl aluminium, a chlorodiphenyl base aluminium etc.Preferred triethyl aluminum wherein.Wherein the mol ratio of the middle titanium of aluminium and component (1) is 5～500 in the component (2), preferred 20～200.
Slurry polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
The slurry polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the inert solvent such as the aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.
In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen to make molecular weight regulator.
The present invention is owing to adding organo-aluminium compound after carrying titanium, catalyzer has the advantages such as higher catalytic activity, hydrogen response and narrow grain size distribution of polymers, fine powder content be few preferably, is highly suitable for the slurry polymerization processes of ethene and needs in the polymerization mix technique of high hydrogen response catalyzer.
Embodiment
The below illustrates the present invention with embodiment, but and unrestricted invention scope.
Embodiment 1
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add successively the 4.0g magnesium dichloride, toluene 90ml, epoxy chloropropane 2.0ml, tributyl phosphate 6.0ml, ethanol 3.4ml, stir and to be warming up to 65 ℃ down, dissolve 65 ℃ of lower reactions 2 hours behind the solution that forms homogeneous when solid fully.This system is cooled to-8 ℃, slowly drips the 60ml titanium tetrachloride, then add four titanium butoxide 4.7ml, reacted 0.5 hour.Slowly be warming up to 85 ℃, reacted 2 hours.Being cooled to the 0 ℃ of slow 12.5ml of dropping concentration is the n-heptane solution of the ethyl aluminum dichloride of 0.9M, reacts 0.5 hour, is warming up to 35 ℃ of reactions 1 hour.High pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds the solid catalyst of above-mentioned preparation, is warming up to 80 ℃, passing into hydrogen makes the still internal pressure reach 0.60Mpa, pass into ethene again and make the interior stagnation pressure of still reach 1.0Mpa (gauge pressure), polymerization is 2 hours under 90 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Just ethyl aluminum dichloride changes the dichloro aluminium isobutyl into.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 1.Just ethyl aluminum dichloride changes aluminium diethyl monochloride into.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 4
(1) catalyzer is synthetic with embodiment 1.Just ethyl aluminum dichloride changes the sesquialter aluminium triethyl into.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 1, does not just add ethyl aluminum dichloride.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 6
(1) catalyzer is synthetic with embodiment 1, and just the ethyl aluminum dichloride consumption is 10.8ml.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 7
(1) catalyzer is synthetic with embodiment 1, and just the ethyl aluminum dichloride consumption is 14.2ml.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Comparative Examples 1
(1) the synthetic CN1958620A embodiment 1 described method of pressing of catalyst component prepares.
(2) the vinyl polymerization condition is with embodiment 1, and polymerization result sees Table 1.
Table 1 polymer performance
Can find out from the data of table 1, under same polymerizing condition, catalyzer of the present invention has higher catalytic activity, and preferably hydrogen response is arranged.
Claims (8)
1. preparation method who is used for the catalyst component of vinyl polymerization or copolymerization, it may further comprise the steps:
(1) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds forms homogeneous solution, solvent temperature is 50～90 ℃; In forming the process of solution or solution add organic alcohol compound after forming, the reaction regular hour, obtain reaction soln;
(2) in the presence of organic titanic compound, at-30 ℃～0 ℃, mentioned solution and titanium compound are carried out contact reacts, organic titanic compound also can solution and titanium compound in step (1) carry out adding after the contact reacts, and mixture slowly is warming up to 50～120 ℃, and particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain solid ingredient;
(3) above-mentioned solid ingredient is suspended in a certain amount of inert diluent, carries out contact reacts with organo-aluminium compound, temperature is 0 ℃～50 ℃, removes inert diluent behind the reaction certain hour, obtains catalyst component of the present invention;
Described magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
The general formula of described titanium compound is Ti (OR
1)
aX
1 b, R in the formula
11～14 aliphatic group or aromatic hydrocarbyl for carbonatoms, X
1Be halogen, a be 0,1 or 2, b be 1 to 4 integer, a+b=3 or 4;
Described organic alcohol compound is that carbonatoms is that the alcohol of 1～10 straight chain, side chain or cycloalkyl or carbonatoms are 6～20 to contain the alcohol of aryl;
The general formula of described organic titanic compound is Ti (OR
2)
aX
2 b, R wherein
2Be 1～14 aliphatic alkyl or aromatic hydrocarbyl for carbonatoms, X
2Be halogen, a be 1,2,3 or 4, b be 0,1,2,3, a+b=4;
The general formula of described organo-aluminium compound is AlR
3 nX
3 3-n, R in the formula
3Be 1～20 alkyl for hydrogen or carbonatoms, X
3Be halogen, n is the integer of 0＜n≤3.
2. the preparation method of the catalyst component for vinyl polymerization or copolymerization according to claim 1 is characterized in that described organic titanic compound is four titan-alkoxides.
3. the preparation method of the catalyst component for vinyl polymerization or copolymerization according to claim 1 is characterized in that described organic titanic compound is four titanium butoxide.
4. the preparation method of described catalyst component for vinyl polymerization or copolymerization one of according to claim 1～3, it is characterized in that in every mole of magnesium halide, the consumption of organic alcohol compound is 0～6 mole, the consumption of titanium compound is 1～20 mole, the consumption of organic titanic compound is 0.1～1 mole, and the consumption of organo-aluminium compound is 0～5 mole.
5. the preparation method of described catalyst component for vinyl polymerization or copolymerization one of according to claim 1～3, it is characterized in that described solvent system is in every mole of magnesium halide, organic epoxy compounds is 0.2～10.0mol, and organo phosphorous compounds is 0.1～10.0mol.
6. catalyzer that is used for vinyl polymerization or copolymerization, it comprises the reaction product of following component:
(1) catalyst component that obtains of preparation method claimed in claim 1;
(2) general formula is AlR
3 nX
3 3-nOrgano-aluminium compound, R in the formula
3Be 1～20 alkyl for hydrogen or carbonatoms, X
3Be halogen, n is the integer of 0＜n≤3.
7. the catalyzer for vinyl polymerization or copolymerization according to claim 6, the mol ratio that it is characterized in that aluminium and titanium is 20～200.
The described catalyzer of claim 6 ethylene homo close the reaction or copolymerization in application.
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| CN106589173A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization reaction and preparation method thereof |
| CN112724287A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation method and application thereof |
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