CN103130931A - Ball shape ethylene polymerization solid titanium catalytic agent and preparation and application thereof - Google Patents
Ball shape ethylene polymerization solid titanium catalytic agent and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a ball shape ethylene polymerization solid titanium catalytic agent and preparation and application of the ball shape ethylene polymerization solid titanium catalytic agent. A nonionic-type surface active agent is placed in magnesium compound dissolution process, and then magnesium compound micro-emulsion is prepared; and the magnesium compound micro-emulsion reacts with silicane compound, makes contact with liquid state titanium compound, and then solid catalyst components are separated out. The ball shape ethylene polymerization solid titanium catalytic agent has the advantages of being simple in preparation process, ball-shaped in catalyst particles, narrow in particle size distribution, high in catalytic activity when being used for producing ethylene polymers, good in hydrogen regulation sensitive property, good in shapes of polymer particles, and little in fine powder. The ball shape ethylene polymerization solid titanium catalytic agent is suitable for ethylene slurry polymerization process, and especially suitable for ethylene polymerization production process by using a double-reactor to produce wide relative molecular mass distribution.
Description
Technical field
The present invention relates to a kind ofly close or the preparation method of the solid titanium catalyst component that ethene and other alpha-olefin copolymer close for ethylene homo, and the ethylene rolymerization catalyst that forms of this ingredient of solid catalyst and organometallic compound closes or the application in closing of ethene and other alpha-olefin copolymers at ethylene homo.
Background technology
The preparation method of the efficient Ziegler-Natta catalyst of vinyl polymerization is well-known, is mainly by MgCl
2Or SiO
2The halogenide of the titanium of load forms.Preparation method as disclosed vinyl polymerization and copolymerization catalyst in JP 4951378 is: the magnesium dichloride through grinding and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries, then with aluminium diethyl monochloride generation esterification, last and TiCl
4Carry the titanium reaction, obtain MgCl
2Carrier loaded Titanium series catalyst.This method for preparing catalyst is simple, and reaction conditions is gentle, and during the catalyst vinyl polymerization, activity is very high.But this preparation method exists the carrier magnesium chloride can not dissolve in mineral oil, the irregular platy shaped particle that produces when there be former grinding in magnesium chloride in the slurry reaction system, cause the solid catalyst particle form that obtains relatively poor, thickness is inhomogeneous, thereby polymer morphology is also bad, fine powder is more, easily produces static and easy blocking pipe.This catalyzer oligomer in solvent when polymerization mostly is aftertreatment and has brought larger trouble simultaneously.
Patent CN1229092 discloses a kind of catalyst system for vinyl polymerization and copolymerization, and this catalyst system comprises: (1) contains the ingredient of solid catalyst of Ti; (2) alkylaluminium cpd; The ingredient of solid catalyst that wherein contains Ti is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous phase solution by magnesium halide, the magnesium halide that adds Ethanol Treatment to dissolve, then this solution mixes with titanium tetrahalide, under the compounds such as precipitation agent such as organic acid anhydrides, organic acid, ether, ketone exist, separate out solids, obtain solid catalyst.When this catalyst system was used for vinyl polymerization, the resulting polymers fine powder content was more, catalyst activity is lower, hydrogen regulation performance is poor, is unsuitable for preparing bimodal polymers, was difficult to substitute existing high reactivity ethene slurry polymerization catalyzer.The bulk density of polymkeric substance is also a little less than the level that has catalyzer now simultaneously.
Patent CN1112373 discloses a kind of solid titanium catalyst component and preparation technology thereof, mainly adopts low-carbon alcohol to dissolve magnesium halide, and adds alkane diluent and silicane electron donor compound, then with the halogenated titanium effect, separates out solid catalyst.Although this catalyzer can make the ethene polymers with good particle performance when being used for vinyl polymerization, its catalytic activity and oligomer are still unsatisfactory.
patent CN1180712 discloses a kind of Catalysts and its preparation method for vinyl polymerization or copolymerization, added at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more ester groups when magnesium compound and Organic Alcohol reaction formation alcohol adduct slurries, make and just can make magnesium halide and alcohol form the alcohol adduct slurries of swelling at lower temperature in thinner, and need not at high temperature the magnesium halide dissolving be formed solution, also can obtain having the catalyzer of particle form, and reduced pure usage quantity when forming the alcohol adduct slurries, make the preparation technology of catalyzer simple, easy handling, reduced cost.But this catalyzer is when being used for vinyl polymerization, still exists hydrogen to transfer shortcoming insensitive, that morphology is bad, fine powder is many, will be unfavorable for like this polymkeric substance with a kind of Catalyst Production wide molecular weight distribution.
Patent CN1752116A discloses a kind of Catalysts and its preparation method for second polymerization or copolymerization, added at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more ester groups when magnesium compound and Organic Alcohol formation alcohol adduct slurries, solved the hydrogen response problem of catalyzer, but still fail to improve the particle form of catalyzer, when being used for the slurry polymerization processes of ethene like this, still there is the shortcoming that the polymerisate particle form is uneven, fine powder is many.
Summary of the invention
The object of the invention is to adopt the method for microemulsion to prepare spherical ethane polymerization solid titanium catalyst, overcome the deficiencies in the prior art, a kind of ethene slurry polymerization that is very suitable for is provided, be specially adapted to produce the catalyzer of broad molecular weight distribution polymers.This catalyzer compares with existing catalyzer that its advantage is that granules of catalyst is spherical in shape, narrow particle size distribution, fine powder is few, hydrogen response good, more effectively the molecular weight of telomerized polymer and molecular weight distribution.And production technique is simple, production cost is low.
Spherical ethane polymerization solid titanium catalyst of the present invention by:
The ingredient of solid catalyst of A, titaniferous prepares by following component reaction:
(a), a kind of microemulsion of magnesium compound;
(b), a kind of silicoorganic compound of non-activity hydrogen;
(c), a kind of titanium compound;
This solid titanium catalyst component contains magnesium, titanium, silicon and halogen.Each composition for the preparation of solid titanium catalyst component of the present invention is described below:
(a) microemulsion of magnesium compound
In preparation solid titanium catalyst component of the present invention, use the microemulsion of magnesium compound.If magnesium compound is solid-state, should make it before use to change into microemulsion.Magnesium compound is the organo-magnesium compound that is expressed from the next: X
nMgR
2-nWherein, n is the number more than or equal to 0, less than or equal to 2; R is alkyl, aryl or the cycloalkyl of 1～20 carbon atom; When n was 0, two R can be identical or different, as dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl group dibutyl magnesium and ethyl-butyl magnesium; Magnesium alkyl halide is such as a chloroethyl magnesium, a chloropropyl magnesium, a chlorobutyl magnesium, a chlorine amyl group magnesium and a chlorine hexyl magnesium; The alkyl magnesium alkyl oxide is such as butyl magnesium ethylate, ethyl butoxy magnesium and octyl group butoxy magnesium; With other compound, as a hydrogen dibutyl magnesium; Magnesium halide is as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; Alkoxyl magnesium halogenide is such as a chlorine magnesium methylate, a chloroethoxy magnesium, a chlorine isopropoxy magnesium, a chlorine butoxy magnesium and a chlorine octyloxy magnesium; Aryloxy magnesium halogenide is as mono chloro benzene oxygen base magnesium, chloromethyl phenoxy group magnesium; Alkoxyl magnesium is as magnesium ethylate, isopropoxy magnesium, butoxy magnesium, n-octyloxy magnesium and 2-ethyl hexyl oxy magnesium; Aryloxy magnesium is as phenoxy group magnesium, two (methylphenoxy) magnesium; The carboxylate salt of magnesium is as Magnesium monolaurate and Magnesium Stearate; MAGNESIUM METAL and magnesium hydride.X is halogen, as F, Cl, Br and I.In above-claimed cpd, be preferably halogen-containing magnesium compound.Wherein preferably magnesium chloride, a chlorine alkoxyl magnesium and a chlorine aryloxy magnesium.
When being solid-state, this solid-state magnesium compound can make it to change into liquid state by using a kind of solvent when magnesium compound.Described solvent comprises alcohol, phenol, carboxylic acid, aldehyde, amine and metal acid esters.The example of alcohol comprises: Fatty Alcohol(C12-C14 and C12-C18), as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol, 2-Ethylhexyl Alcohol, octanol, decyl alcohol, dodecanol, tetradecanol, Stearyl alcohol, hendecanol, oleyl alcohol and ethylene glycol; Alicyclic ring alcohol is as hexalin and methyl-cyclohexanol; Fragrant and mellow, as phenylcarbinol, methylbenzyl alcohol, isopropyl benzene methyl alcohol, α-methylbenzylalcohol, α, α '-dimethylphenylcarbinol, phenylethyl alcohol, cumic alcohol, phenol, cresols, xylenol, ethylphenol, propylphenol, nonyl phenol and naphthols; The alcohol that contains alkoxyl group is as ethylene glycol-n-butyl ether, glycol-ether, 1-butoxy-2-propyl alcohol; Halogen-containing alcohol is as trichlorine methyl alcohol, ethapon and three Mecorals.Carboxylic acid preferably has the carboxylic acid of seven or more carbon atoms, as sad, 2 ethyl hexanoic acid, n-nonanoic acid and undecylenic acid.Preferably those have the aldehyde of seven or more carbon atoms to aldehyde, as octanal, 2-ethyl hexanal, the undecyl aldehyde, phenyl aldehyde, toluic aldehyde and naphthaldehyde.Amine preferably has the amine of six or more carbon atoms, as heptyl amice, octylame, 2 ethyl hexylamine, nonyl amine, decyl amine, undecylamine and amino dodecane.The example of metal acid esters comprises: purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium butoxide, four hexyloxy titaniums, tetrabutyl zirconate and tetraethoxy zirconium.Wherein, be preferably alcohol, best is has the alcohol of six or more carbon atoms.If use alcohol with six or more carbon atoms as the solvent of liquid magnesium compound processed, alcohol/magnesium mol ratio is not less than 1 usually, is preferably 1～40, preferably 1.0～10.Have five or the alcohol of carbon atom still less if use, its consumption is not less than 1 usually.
When solid-state magnesium compound contacts with alcohol, can use a kind of varsol.The example of this varsol comprises aliphatic hydrocarbon, as pentane, hexane, heptane, octane, decane, dodecane, the tetradecane and kerosene; Alicyclic hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane and cyclooctane; Aromatic hydrocarbon such as benzene,toluene,xylene, ethylbenzene, isopropyl benzene and cymene; Halohydrocarbon is as tetracol phenixin, ethylene dichloride, propylene dichloride, trieline and chlorobenzene etc.If use aromatic hydrocarbons in these solvents, the consumption the during situation of consumption and six of above-mentioned uses or more carbon atom alcohols of alcohol is identical, no matter with the alcohol of which kind of carbonatoms, magnesium compound is solubilized all.When using aliphatic hydrocarbon and/or alicyclic hydrocarbon, the consumption of alcohol is according to carbonatoms and different by above-mentioned.In the present invention, be preferably in make in hydrocarbon solvent solid-state magnesium compound with alcohol contact in hydrocarbon solvent.For solid-state magnesium compound is dissolved in alcohol, the general employing makes solid-state magnesium compound with alcohol in the situation that heated and stirred is reacted, and reacts under the existence that is preferably in hydrocarbon solvent and carries out, and as required it is heated.The temperature of common this contact is 0～300 ℃, is preferably 20～180 ℃, and best is 50～150 ℃, approximately 15 minutes to 5 hours time, preferably approximately 30 minutes to 3 hours.
During preparation magnesium compound microemulsion, also need to add tensio-active agent to make it to become microemulsion in magnesium solution.Tensio-active agent used is the nonionogenic tenside of water-in-oil-type, generally selects polyhydric alcohol fatty acid ester class nonionogenic tenside, and its HLB (hydrophile-lipophile balance value) is advisable with 2～8, is preferably 3～6.Consumption is advisable with 0.1～1.0 ω % of thinner, is preferably 0.4～0.8 ω %.Wherein polyhydric alcohol fatty acid ester class nonionogenic tenside can be selected sucrose fatty ester, sorbitan-fatty acid ester, for example: sorbitan stearate, sorbitol anhydride oleate, sorbitan palm fibre are put acid esters, the two stearates of glycerine, a kind of in Zerol or their mixture.Above-mentioned nonionogenic tenside, in inert diluent, by capillary effect, to swelling the alcohol adduct particle of magnesium compound carry out the particle shape reparation, make it be tending towards spherical and homogenizing, to improve the particle form of final catalyzer.
(b) silicoorganic compound of non-activity hydrogen
Silicoorganic compound at the non-activity hydrogen described in catalyst component of the present invention are selected from silicon tetrachloride, tetraethoxy-silicane, four butoxy silicon, a chlorine triethoxysilicane and dichloro diethoxy silicon.
(c) liquid titanium compound
Liquid titanium compound in the present invention is tetravalent titanium compound preferably.This tetravalent titanium compound can be used following general formula: Ti (OR)
nX
4-nWherein R is C
1～C
10Aliphatic group, alicyclic hydrocarbon radical or aryl, X is halogen, 0≤n≤4.Typical titanium compound comprises: titanium tetrahalide, and as TiCl
4, TiBr
4, TiI
4
The preparation solid titanium catalyst
Catalyst component of the present invention can adopt following method preparation:
(1) preparation magnesium compound microemulsion
Magnesium halide is dissolved in the alcoholic solvent system, adds tensio-active agent in the preferred solvent system, form uniform microemulsion, preferred 50～150 ℃ of solvent temperature; In forming the process of solution or solution add the silicoorganic compound of non-activity hydrogen atom after forming.
(2) preparation solid titanium catalyst
Mentioned solution and titanium compound are carried out contact reacts, the silicoorganic compound of non-activity hydrogen atom also can be in (1) step solution and titanium compound add when carrying out contact reacts, and mixture slowly is warming up to 50～120 ℃, 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 catalyst component of the present invention.
The ratio of each reactant is in every mole of magnesium halide, and organic alcohol compound is: 0.1～10.0 mole, silicoorganic compound are 0.20～0.25 mole, and nonionogenic tenside is 0.005～0.01 mole, and the mol ratio of titanium compound is 1.0～15.0.
The catalyzer that catalyst component A of the present invention and component B consist of is applicable to the equal polymerization of ethene and the copolymerization of ethene and other alpha-olefin, and polymerization methods can adopt slurry process, vapor phase process, solution method etc., wherein take slurry process as best.Above-mentioned alpha-olefin can adopt propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.Catalyst component and general formula that this catalyzer comprises the invention described above are AlR
nX
3-nThe reaction product of organo-aluminium compound, in formula, R can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for carbonatoms; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichlorides, preferred trialkyl aluminium compound wherein, especially with triethyl aluminum, triisobutyl aluminium for well.Wherein the mol ratio of component aluminium and component titanium is 5～500, preferred 20～200.
Solution polymerization, 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.
Polymerization methods can adopt intermittent type, semi continuous or continous way.Polymerization temperature is 0～150 ℃, with 40～100 ℃ for well.In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen as molecular weight regulator.
The present invention compared with prior art has following advantage:
The invention provides a kind of ethene slurry polymerization processes that is very suitable for, be specially adapted to produce broad molecular weight distribution or bimodal distribution polyethylene product, develop high-quality, high value added product.Owing to adopting tensio-active agent to make magnesium compound become the microemulsion state, therefore when preparing, catalyzer is easy to separate out spherical granules of catalyst in catalyst preparation process.And do not need to impel separating out of precipitation with a large amount of titanium tetrachlorides in carrying the titanium process, also do not need repeatedly to process precipitation with titanium tetrachloride, so the add-on of titanium tetrachloride greatly reduces.Tensio-active agent add the particle form that has improved catalyzer, further improved the particle form of polymkeric substance, make the size distribution narrow of polymkeric substance.When this catalyzer is used for vinyl polymerization, show hydrogen response preferably.
Embodiment
Embodiment 1
(1) preparation of catalyst component: lower 4.76 grams of nitrogen protection (50mmol) Magnesium Chloride Anhydrous, 75 milliliters of decane, 0.5 gram sucrose fatty ester and 16.3 grams (125mmol) isooctyl alcohol are heated to 130 ℃; make it stirring reaction 3 hours, and obtained a kind of microemulsion of homogeneous phase magnesium compound.Add the tetraethoxysilane of 12.5mmol and stir 2 hours so that it is dissolved in this solution under 50 ℃ in this microemulsion.Microemulsion obtained above is cooled to room temperature, then was added dropwise to while stirring in 1 hour in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour under 0 ℃, then in 2 hours, temperature is carried to 120 ℃ under whipped state, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With decane and hexane, solid catalyst is fully washed respectively, until inspection does not measure the titanium compound of separating out in scavenging solution, obtain after drying a kind of solid titanium catalyst component.The size distribution of catalyzer and span analytical results see Table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0mL of 1mol/L, the above-mentioned catalyzer that adds accurate weighing with syringe, be warming up to 75 ℃, pass into hydrogen and make the still internal pressure reach 0.28MPa, then pass into ethene and make that stagnation pressure reaches 0.73MPa (gauge pressure) in still, polymerization is 2 hours under 80 ℃ of conditions, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 2
(1) preparation of catalyst component: 4.76 grams (50mmol) Magnesium Chloride Anhydrous, 75 milliliters of decane, 0.5 gram sorbitol anhydride mono-laurate and 16.3 grams (125mmol) isooctyl alcohol are heated to 130 ℃, make it to react 3 hours, obtain a kind of microemulsion of magnesium compound.The microemulsion of magnesium compound obtained above is cooled to room temperature, then was added dropwise to while stirring in 1 hour in the 150mL titanium tetrachloride that temperature remains 0 ℃.Mixture temperature was kept 1 hour under 0 ℃, then add the tetraethoxysilane of 12.5mmol in this solution, keep 1 hour so that tetraethoxysilane is dissolved in this solution system.Then under agitation in 2 hours, temperature is carried to 120 ℃, and this temperature was kept 2 hours.After reaction in 2 hours finishes, the solid that generates is carried out heat filtering separate.With hexane and decane, solid catalyst is fully washed respectively, until inspection does not measure the titanium compound of separating out in scavenging solution, obtain after drying a kind of solid titanium catalyst component.The size distribution of catalyzer and span analytical results see Table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adding hexane 1L and concentration is the triethyl aluminum 1.0mL of 1mol/L, the catalyzer that adds the above-mentioned preparation of accurate weighing with syringe, be warming up to 75 ℃, pass into hydrogen and make the still internal pressure reach 0.28MPa, then pass into ethene and make that stagnation pressure reaches 0.73MPa (gauge pressure) in still, polymerization is 2 hours under 80 ℃ of conditions, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 3
With embodiment 1, difference is that the tensio-active agent that adds is the sorbitol anhydride monopalmitate, and add-on is 0.5 gram.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 4
With embodiment 1, difference is that the tensio-active agent that adds is the sorbitol anhydride single-hard ester acid ester, and add-on is 0.5 gram.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 5
With embodiment 1, difference is that the tensio-active agent that adds is sorbitol anhydride oleate, and add-on is 0.5 gram.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 6
With embodiment 1, difference is that the add-on of sucrose fatty ester is 1.0 grams.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 7
With embodiment 1, difference is that the magnesium compound that adds is a chlorine alkoxyl magnesium.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 8
With embodiment 1, difference is that the magnesium compound that adds is a chlorine aryloxy magnesium.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 9
With embodiment 1, it is sad that difference is that the isooctyl alcohol that adds becomes.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 10
With embodiment 1, difference is that the isooctyl alcohol that adds becomes phenyl aldehyde.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 11
With embodiment 1, difference be to add isooctyl alcohol become 2 ethyl hexylamine.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 12
With embodiment 4, when difference is vinyl polymerization, ethene becomes the gas mixture of ethene and butene-1, and the butene-1 molar content is 3%.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Embodiment 13
With embodiment 1, when being vinyl polymerization, difference adds the 20ml hexene.The size distribution of catalyzer and span analytical results see Table 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Comparative Examples 1
With embodiment 1.Difference is not add tensio-active agent, and the size distribution of catalyzer and span analytical results see Table 1, vinyl polymerization evaluation such as embodiment 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Comparative Examples 2
The synthetic described method of CN1229092 embodiment 1 of pressing of catalyzer prepares.
In the reactor of fully replacing through high pure nitrogen, add successively the anhydrous MgCl of 0.042mol
2(approximately 4g), 60mL toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes solids and dissolve fully, form homogeneous solution, then add Tetra hydro Phthalic anhydride 0.0074mol, kept again 1 hour, this solution is cooled to-25 ℃, again 0.5mol titanium tetrachloride (approximately 55ml) is splashed in it, then slowly be warming up to 80 ℃, reacted 3 hours, wash 3 times with toluene and hexane respectively after filtration, vacuum-drying obtains solid catalyst.
The size distribution of catalyzer and span analytical results see Table 1, vinyl polymerization evaluation such as embodiment 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
Comparative Examples 3
The synthetic described method of JP4951378 embodiment of pressing of catalyzer prepares.
In the reactor of fully replacing through high pure nitrogen, add commercially available anhydrous MgCl
210mol is suspended in the 10L hexane, under room temperature, splashes into 60mol ethanol, stirs 30 minutes.The temperature of maintenance system is no more than under 40 ℃ of conditions and splashes into the 31mol aluminium diethyl monochloride, stirs 30 minutes, adds 5molTiCl
4, system maintains 60 ℃, stirring reaction 6 hours.Through obtaining solid catalyst after filtration, hexane washing.
The size distribution of catalyzer and span analytical results see Table 1.Vinyl polymerization is estimated as embodiment 1, and polymerization activity and polymer bulk density, size-grade distribution the results are shown in Table 2.
The size-grade distribution of table 1 catalyzer and span
Table 2 polymerization activity, polymer bulk density and size-grade distribution result
Claims (10)
1. the preparation method of a spherical ethane polymerization solid titanium catalyst is characterized in that:
(1) preparation magnesium compound microemulsion
Magnesium halide is dissolved in organic alcohol solvent, adds nonionogenic tenside in solvent, form uniform microemulsion, 50～150 ℃ of solvent temperatures; In forming the process of solution or solution add the silicoorganic compound of non-activity hydrogen atom after forming;
(2) preparation solid titanium catalyst
Mentioned solution and titanium compound are carried out contact reacts, mixture slowly is warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after reaction, removes unreacted reactant and solvent, obtains solid titanium catalyst component;
The ratio of each reactant is in every mole of magnesium halide, and organic alcohol compound is: 0.1～10.0 mole, silicoorganic compound are 0.20～0.25 mole, and nonionogenic tenside is 0.005～0.01 mole, and the mol ratio of titanium compound is 1.0～15.0;
Described titanium compound general formula is Ti (OR)
aX
b, in formula, R is C
1～C
10Aliphatic group or aryl, X is halogen, a be 0,1,2 or 3, b be 1 to 4 integer, a+b=3 or 4.
2. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: described magnesium halide is magnesium dihalide, a kind of in the derivative that in the magnesium dihalide molecule, halogen atom is replaced by alkyl or-oxyl or their mixture.
3. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: described organic alcohol compound is that carbonatoms is that alkyl alcohol, cycloalkanol and the carbonatoms of 1～10 straight chain, side chain is that 6～20 fragrant and mellow or aralkyl is pure, and the halides of above-mentioned Organic Alcohol; Described alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol, 2-Ethylhexyl Alcohol, octanol or alcohol.
4. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: the mol ratio of described Organic Alcohol and magnesium compound is 1～10.
5. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: the hydrophile-lipophile balance value HLB of described nonionogenic tenside is 2～8.
6. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: described nonionic surface active agent is selected from a kind of of sucrose stearate, sorbitol anhydride oleate or their mixture.
7. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1, it is characterized in that: the general formula of the silicoorganic compound of described non-activity hydrogen is Si (OR)
nX
4-n, in formula, R is C
1～C
14Alkyl or aralkyl, X is halogen, n is 0～4 integer.
8. the preparation method of spherical ethane polymerization solid titanium catalyst according to claim 1 is characterized in that: described organo-aluminium compound is a kind of of triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter aluminium triethyl or their mixture.
9. a spherical ethane polymerization solid titanium catalyst, is characterized in that: preparation method's preparation of spherical ethane polymerization solid titanium catalyst according to claim 1.
10. the application of a spherical ethane polymerization solid titanium catalyst is characterized in that: the catalyzer that solid titanium catalyst and organo-aluminium compound consist of is used for the equal polymerization of ethene and the copolymerization of ethene and other alpha-olefin;
Organo-aluminium compound, AlR
nX
3-n, in formula, R is that alkyl, X are halogen, n is the integer of 0≤n≤3; Solid titanium catalyst and organo-aluminium compound aluminium titanium mol ratio are 20～200.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558275A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN104710549A (en) * | 2013-12-13 | 2015-06-17 | 陈伟 | Spherical ethylene polymerization solid titanium catalyst prepared through emulsion method, and application thereof |
| CN114426597A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of olefin polymerization catalyst component and prepared olefin polymerization catalyst component |
| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
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| KR20230156389A (en) * | 2021-03-16 | 2023-11-14 | 더블유.알. 그레이스 앤드 캄파니-콘. | Spherical catalyst components for olefin polymerization |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558275A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN104710549A (en) * | 2013-12-13 | 2015-06-17 | 陈伟 | Spherical ethylene polymerization solid titanium catalyst prepared through emulsion method, and application thereof |
| CN104710549B (en) * | 2013-12-13 | 2017-11-14 | 陈伟 | A kind of emulsion process prepares Ball shape ethylene polymerization solid titanium catalytic and its application |
| CN114426597A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of olefin polymerization catalyst component and prepared olefin polymerization catalyst component |
| CN114426597B (en) * | 2020-10-15 | 2023-10-13 | 中国石油化工股份有限公司 | Preparation method of olefin polymerization catalyst component and prepared olefin polymerization catalyst component |
| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
| CN114573739B (en) * | 2020-12-02 | 2023-12-22 | 中国石油天然气股份有限公司 | solid titanium catalyst |
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