CN105482002A - Catalyst component for polymerization of ethylene, catalyst and preparation method of catalyst component - Google Patents
Catalyst component for polymerization of ethylene, catalyst and preparation method of catalyst component Download PDFInfo
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- CN105482002A CN105482002A CN201410531766.2A CN201410531766A CN105482002A CN 105482002 A CN105482002 A CN 105482002A CN 201410531766 A CN201410531766 A CN 201410531766A CN 105482002 A CN105482002 A CN 105482002A
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Abstract
The invention provides a catalyst component for polymerization of ethylene. The catalyst component comprises reactants of the following components: (1) magnesium compounds; (2) organic acid anhydride; (3) acetic ester compounds; (4) cyclic ketone compounds; and (5) titaniferous compounds. When organic acid anhydride/acetic ester/cyclic ketone compounds are introduced into a system to be used as compounding electron donors, spherical/ellipsoidal magniferous/titaniferous solid particles can be prepared. Through slurry polymerization of ethylene on a catalyst disclosed by the invention, spherical/ellipsoidal powder particles can be obtained, and besides, the powder particles have very high powder bulk density.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polymerization, specifically for the preparation method of the catalyst component of vinyl polymerization, catalyzer and this catalyzer.
Background technology
From the beginning of the fifties in last century, since Ziegler-Natta successively obtains polyethylene and polypropylene by the low-pressure polymerization of Titanium series catalyst, through development for many years, Ziegler-Natta type olefin polymerization catalysis is adjusted in susceptibility, degree of isotacticity, copolymerized ability etc. at active, hydrogen and is achieved breakthrough.On this basis, researchist recognizes that the particle form of Ziegler-Natta type olefin polymerization catalysis is an aspect needing accurately to control equally further, therefore becomes a study hotspot in recent years.
Ziegler-Natta type olefin polymerization catalysis particle has the special ability that their pattern can be copied to polyolefine powder particle prepared by it.As spherical catalyst particles generates spherical powder particles usually, as high porosity catalyst particle generates the powder particles of high porosity usually.In view of this character of Ziegler-Natta type olefin polymerization catalysis, Recent study personnel have prepared spherical polyolefin catalyst.Can be prepared the spherical polyolefine powder with better flowing property by this spherical catalyst, this performance is very favourable for the course of conveying of powder.
Spherical polyolefin catalyst prepares mainly through following several mode: the method 1, be first shaped by emulsification prepares ball type carrier, subsequently ball type carrier (as magnesium chloride ethanolic vehicle) is carried out dealcoholysis and carry titanium process, as described in patent CN1091748A; 2, after magnesium chloride/titanium chloride being dissolved in tetrahydrofuran (THF), prepared by spray-drying process, as described in patent CN1085915A; 3, by the method preparation that emulsification is shaped, as described in patent CN1701081A.The preparation method 1 and 3 of above spherical catalyst all relates to emulsification moulding process, and not only flow process is longer, and needs special reaction reagent; Although and preparation method 2 step is relatively simple, need special spray drying device.Except spherical polyolefin catalyst, the polyolefin catalyst of elliposoidal can give polyolefine powder good mobility too.Therefore, a kind ofly prepare simple and easy method that is spherical or elliposoidal polyolefin catalyst if can find, then there is good industrial prospect, and solution modeling type catalyzer is optimal selection.
As the representative of solution modeling type catalyzer, N-type polypropylene catalyst is in the successful a kind of advanced polyolefin catalyst of research and development in 1985 by Sinopec Beijing Chemical Research Institute.Through the development of nearly 30 years, develop a large amount of derived varietiess now, be widely used in domestic ethene or propylene polymerization field, there is high industrial value.
N series of polyolefins catalyzer belongs to solution modeling type catalyzer, and its preparation process is very simple, and does not need to use special reaction reagent and equipment.Concrete preparation process is dissolved in by magnesium chloride in organic epoxy compound thing, organo phosphorous compounds solvent system, after forming homogeneous solution, mixes under organic acid anhydride existent condition with titanium compound, and precipitation obtains again.This type of catalyst particle size is less than 50 μm usually, and each catalyst particle is assembled by several secondary particle to dozens of μm level and formed.Each secondary particle only comprises an organic centre, and assembled by a large amount of long rod shape aggregate along organic centre's radial growth and form, the length of long rod shape aggregate is close to secondary particle radius (as shown in Figure 1).Because this type of catalyzer is aspherical, so the powder particle of its vinyl polymerization gained is also aspherical (as shown in Figure 2).Aspherical powder particle pile up undertighten, cause it powder tap density be the highest being no more than 0.40g/ml.
Therefore, if the class N-type polyolefin catalyst of spherical/elliposoidal can be prepared, then can not only improve the tap density of powder, the polyolefine powder particle of spherical/elliposoidal can also be obtained.This needs to realize separating out to catalyzer the accurate control be shaped, make to be assembled to dozens of secondary particle the catalyst particle formed and be converted into by several and only obtained by single secondary particles grow, this relates to complicated crystalline growth control techniques, so far there are no bibliographical information.
Existing patent report is crossed and introduce ester class electron donor in class N-type polyolefin catalyst component, as introduced acyloxycarboxylic acid ester and phthalic ester in patent CN1803862A as composite electron donor, as introduced aromatic monocarboxylate's ester and the composite electron donor of aliphatic/aromatic multi-carboxylate in patent CN1955195A.As all introduced aromatic ester/alkoxyl silicone in patent CN103772536A and CN102295717A as composite electron donor.But the present inventor finds after deliberation, the class N-type polyolefin catalyst of spherical/elliposoidal all cannot be prepared by these composite electron donors.
The present inventor finds after deliberation, and the electron donor of some kind is shaped for the precipitation of class N-type polyolefin catalyst and has significant regulating and controlling effect.When particularly introducing organic acid anhydride class/acetate esters/cyclic ketones compounds as composite electron donor in system, then can prepare the solids particle containing magnesium/titanium of spherical/elliposoidal.This solids particle has special physical structure: 1, solids particle is spherical or elliposoidal, and the length-to-diameter ratio of particle is 1:1 ~ 1.5:1 (as Suo Shi Fig. 3/4); 2, each solids particle is only grown by an organic centre and obtains (as Suo Shi Fig. 5/6); 3, solids particle is formed by a large amount of long rod shape aggregate gathering along organic centre's radial growth, and the length of long rod shape aggregate is close to particle radii, and length-to-diameter ratio is 5:1 ~ 100:1.Such catalyzer can obtain the powder particle (as shown in Figure 7) of spherical/elliposoidal after ethene slurry polymerization/copolymerization, and powder tap density is more than 0.43g/ml, and (concrete reaction conditions is hydrogen 2.8 × 10
5pa, ethene 7.5 × 10
5pa, polymerization temperature is 85 DEG C, polymerization time 2h).
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst component for vinyl polymerization, its preparation method and catalyzer thereof.By introducing organic acid anhydride class/acetate esters/cyclic ketones compounds as composite electron donor, then can prepare the solids particle containing magnesium/titanium of spherical/elliposoidal.This type of catalyzer can obtain the powder particle of spherical/elliposoidal through ethene slurry polymerization, and has very high powder tap density.
A kind of catalyst component for vinyl polymerization of the present invention, comprises the reaction product of following component: (1) magnesium mixture; (2) organic acid anhydride; (3) acetate compounds; (4) cyclic ketones compounds; (5) titanium-containing compound.
The general formula of described cyclic ketones compounds is
wherein a, b and c are the integer being more than or equal to 0, and are 0 when a, b are different with c, and wherein 3≤a+b+c≤7, in formula, R is C
1~ C
10straight or branched alkyl, cyclic hydrocarbon radical or aromatic hydrocarbyl.Be specially the one in cyclobutanone, dimethylcyclobutanone, cyclopentanone, 2-methyl-cyclopentanone, pimelinketone, methylcyclohexanone, 2-sec.-butylcyclohexanone, suberone, cyclooctanone.
Described organic acid anhydride is selected from the one in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE;
The general formula of described acetate compounds is CH
3cOOR, in formula, R is C
1~ C
18straight or branched alkyl; Be selected from the one in methyl acetate, ethyl acetate, butylacetate, n-hexyl acetate and acetic acid n-octyl.
The general formula of described titanium compound is Ti (OR
1)
ax
1 b, R in formula
1for aliphatic group or aromatic hydrocarbyl that carbonatoms is 1 ~ 14, X
1for halogen, a be 0,1 or 2, b be 1 to 4 integer, a+b=3 or 4; One in preferred titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, titanous chloride, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or its mixture.
Magnesium mixture of the present invention magnesium halide is dissolved in the mixture formed in the solvent system containing organic epoxy compound thing, organo phosphorous compounds, and this mixture is the solution of a homogeneous transparent, can add the thinner of alkane or aromatic hydrocarbons if desired.Wherein said magnesium halide is selected from the complex compound of the water of magnesium dihalide or magnesium dihalide, alcohol or electron donor.Concrete compound as magnesium dichloride, dibrominated magnesium, bifluoride magnesium, diiodinating magnesium 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 compound 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 compound thing be selected from carbonatoms 2 ~ 8 aliphatics alkene, the oxide compound of diolefine or halogenated aliphatic alkene or diolefine, at least one in glycidyl ether and inner ether.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, trimethyl phosphite, triethyl-phosphite, tributyl phosphate etc.Wherein in every mole of magnesium halide, organic epoxy compound thing: 0.2 ~ 10.0mol, preferably 0.3 ~ 4.0mol; Organo phosphorous compounds: 0.1 ~ 10mol, preferably 0.2 ~ 4.0mol.
In order to make dissolving more abundant, optionally inert diluent is added in this solvent system, usual 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 the straight-chain paraffin of 3 ~ 20 carbon, branched paraffin or naphthenic hydrocarbon or their mixture, and as butane, pentane, hexane, hexanaphthene, heptane etc., as long as can using of contributing to that magnesium halide dissolves.Above-mentioned inert diluent can be used alone, also use capable of being combined.
Described organic acid anhydride, acetate compounds and cyclic ketones compounds form composite electron donor, the halogenide or derivatives thereof hybrid reaction of magnesium mixture and titanium under composite electron donor exists, separate out contain magnesium/titanium spherical/elliposoidal solids particle.
Ratio between each reactant is in every mole of magnesium halide in magnesium mixture, organic epoxy compound thing is 0.2 ~ 10 mole, organo phosphorous compounds is 0.1 ~ 10 mole, organic acid anhydride is 0.03 ~ 1.0 mole, acetate compounds 0.03 ~ 1 mole, cyclic ketones compounds 0.03 ~ 1 mole, titanium compound 0.5 ~ 120 mole.
The solids particle of this catalyst component has special physical structure: 1, solids particle is spherical or elliposoidal, and the length-to-diameter ratio that can calculate particle from electromicroscopic photograph is 1:1 ~ 1.5:1 (as Suo Shi Fig. 3/4); 2, each solids particle is only grown by an organic centre and obtains (as Suo Shi Fig. 5/6); 3, solids particle is formed by a large amount of long rod shape aggregate gathering along organic centre's radial growth, the length of long rod shape aggregate is close to particle radii, and the length-to-diameter ratio that can calculate long rod shape aggregate from electromicroscopic photograph is 5:1 ~ 100:1 (as shown in Figure 5).Such catalyzer can obtain the powder particle (as shown in Figure 7) of spherical/elliposoidal after ethene slurry polymerization/copolymerization, and powder tap density is more than 0.43g/ml, and (concrete reaction conditions is hydrogen 2.8 × 10
5pa, ethene 7.5 × 10
5pa, polymerization temperature is 85 DEG C, polymerization time 2h).
Present invention also offers a kind of preparation method of the catalyst component for vinyl polymerization, magnesium compound is dissolved in the solvent system containing organic epoxy compound thing and organo phosphorous compounds, after forming homogeneous solution, mix with the halogenide or derivatives thereof of titanium under composite electron donor exists, separate out contain magnesium/titanium spherical/elliposoidal solids particle.
Concrete steps comprise:
(1) magnesium halide is dissolved in the solvent system containing organic epoxy compound thing and organo phosphorous compounds and forms homogeneous solution;
(2) above-mentioned solution is added composite electron donor, the reaction regular hour, then carry out contact reacts with titanium compound;
(3) said mixture is removed unreacted reactant and solvent, and adopt inert diluent to wash, obtain ingredient of solid catalyst.
Present invention also offers a kind of catalyzer for vinyl polymerization, comprising: the catalyst component for ethylene polymerization that (1) is described above; (2) general formula is AlR
2 dx
3-dorgano-aluminium compound, R in formula
2for hydrogen or carbonatoms are the alkyl of l ~ 20, X is halogen atom, 0<d≤3.
Component (2) formula of is AlR
2 dx
3-dorgano-aluminium compound, R in formula
2can be the alkyl of l ~ 20 for hydrogen or carbonatoms, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; 0<d≤3.Particular compound is as Al (CH
3)
3, Al (CH
2cH
3)
3, Al (i-Bu)
3, AlH (CH
2cH
3)
2, AlH (i-Bu)
2, AlCl (CH
2cH
3)
2, Al
2cl
3(CH
2cH
3)
3, AlCl (CH
2cH
3)
2, AlCl
2(CH
2cH
3) etc. alkylaluminium cpd.Be preferably Al (CH
2cH
3)
3, Al (i-Bu)
3.Wherein aluminium is 5 ~ 500 with the mol ratio of the middle titanium of component (1) in component (2), preferably 20 ~ 200.
Can slurry polymerization be adopted during polymerization, also can adopt vapour phase polymerization.
Slurry polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the inert solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene.
In order to regulate the molecular weight of final polymkeric substance, hydrogen is adopted to make molecular weight regulator.
Catalyzer of the present invention can obtain the powder particle of spherical/elliposoidal through ethene slurry polymerization, and has very high powder tap density.From accompanying drawing, when introducing organic acid anhydride class/acetate esters/cyclic ketones compounds as composite electron donor in catalyst component, can obtain the catalyst particle of spherical/elliposoidal, and its polymerization gained powder particle replicates the pattern of catalyst particle, is similarly spherical/elliposoidal.And comparative example catalyst particle and the equal aspherical/elliposoidal of polymerization gained powder particle thereof.
Accompanying drawing explanation
Fig. 1 (a) is the electromicroscopic photograph of conventional N-type/class N-type catalyst particle;
Fig. 1 (b) is the electromicroscopic photograph of another conventional N-type/class N-type catalyst particle;
Fig. 2 (a) is the electromicroscopic photograph of Fig. 1 (a) catalyst particle polymerization gained powder;
Fig. 2 (b) is the electromicroscopic photograph of Fig. 1 (b) catalyst particle polymerization gained powder;
Fig. 3 (a) is spherical or the electromicroscopic photograph of the class N-type catalyst particle of elliposoidal;
Fig. 3 (b) is the amplification of Fig. 3 (a);
Fig. 4 (a) is spherical or the electromicroscopic photograph of the class N-type catalyst particle of elliposoidal;
Fig. 4 (b) is the electromicroscopic photograph of the different zones of Fig. 4 (a) catalyst particle;
Fig. 5 (a) is the electromicroscopic photograph of broken spherical or elliposoidal class N-type catalyst particle;
Fig. 5 (b) is the electromicroscopic photograph of the different zones of Fig. 5 (a) catalyst particle;
Fig. 6 (a) is the electromicroscopic photograph of broken spherical or elliposoidal class N-type catalyst particle;
Fig. 6 (b) is the amplification of Fig. 6 (a);
Fig. 7 (a) is spherical or the electromicroscopic photograph of the class N-type catalyst particle of elliposoidal polymerization gained powder;
Fig. 7 (b) is the electromicroscopic photograph of the different zones of Fig. 7 (a) gained powder;
Fig. 8 (a) is the electromicroscopic photograph of comparative example 1 catalyst particle;
Fig. 8 (b) is the electromicroscopic photograph of comparative example 1 catalyst particle polymerization gained powder;
Fig. 9 (a) is the electromicroscopic photograph of comparative example 2 catalyst particle;
Fig. 9 (b) is the electromicroscopic photograph of comparative example 2 catalyst particle polymerization gained powder.
Embodiment
Testing method:
1, the mensuration of scanning electron microscope: adopt FEIXL-30/FEINanoSEM450/HitachiS-4800 type scanning electron microscope;
2, the mensuration (MI) of melt index: according to ASTMD1238-99;
3, the mensuration of polymer stacks density: adopt (ASTMD1895) plastics apparent density, the test method of bulkfactor and pouring into property measures.
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.
Embodiment 1
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 100ml toluene, 9.0ml epoxy chloropropane, 15.0ml TRI N BUTYL PHOSPHATE are joined in reactor, under mixing speed 450rpm, temperature are the condition of 60 DEG C, react 2 hours, add 3g Tetra hydro Phthalic anhydride, 2ml butylacetate and 1ml cyclobutanone, continue constant temperature 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 70ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with ingredient of solid catalyst (containing 0.6 milligram of titanium) prepared by aforesaid method again, be warming up to 75 DEG C, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene and make stagnation pressure in still reach 1.03Mpa (gauge pressure), be polymerized 2 hours under 85 DEG C of conditions, polymerization result is in table 1.
(3) electromicroscopic photograph: catalyzer electromicroscopic photograph is shown in Fig. 3.
Embodiment 2
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 105ml toluene, 7.0ml epoxy chloropropane, 11ml three iso-butyl ester of phosphoric acid are joined in reactor, under mixing speed 450rpm, temperature are the condition of 60 DEG C, react 2 hours, add 2g Tetra hydro Phthalic anhydride, 1ml butylacetate and 1ml cyclopentanone, continue constant temperature 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 75ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: catalyzer electromicroscopic photograph is shown in Fig. 4.
Embodiment 3
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 100ml toluene, 9ml epoxy chloropropane, 10ml three iso-butyl ester of phosphoric acid are joined in reactor, under mixing speed 350rpm, temperature are the condition of 60 DEG C, react 2 hours, add 2g Tetra hydro Phthalic anhydride, 1ml acetic acid n-octyl and 1ml pimelinketone, continue constant temperature 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 30ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
Embodiment 4
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 120ml toluene, 8ml epoxy chloropropane, 18.0ml TRI N BUTYL PHOSPHATE are joined in reactor, under mixing speed 350rpm, temperature are the condition of 60 DEG C, react 2 hours, add 1g Tetra hydro Phthalic anhydride, 2ml acetic acid n-octyl and 1ml2-methyl-cyclopentanone, continue constant temperature 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 80ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: broken catalyzer electromicroscopic photograph is shown in Fig. 5.
Embodiment 5
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 100ml toluene, 7ml epoxy chloropropane, 20ml three iso-butyl ester of phosphoric acid are joined in reactor, under mixing speed 350rpm, temperature are the condition of 60 DEG C, react 2 hours, add 3g Tetra hydro Phthalic anhydride, continue constant temperature 1 hour, be cooled to-40 DEG C, add 1ml acetic acid n-octyl and 1ml pimelinketone, constant temperature 0.5 hour, drips titanium tetrachloride 70ml, is warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: broken catalyzer electromicroscopic photograph is shown in Fig. 6.
Embodiment 6
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 70ml toluene, 7ml epoxy chloropropane, 16.0ml three iso-butyl ester of phosphoric acid are joined in reactor, under mixing speed 350rpm, temperature are the condition of 60 DEG C, react 2 hours, add 3g Tetra hydro Phthalic anhydride, continue constant temperature 1 hour, be cooled to-40 DEG C, add 1ml ethyl acetate and 1ml cyclooctanone, constant temperature 0.5 hour, drips titanium tetrachloride 75ml, is warming up to 95 DEG C gradually, constant temperature 1 hour, elimination mother liquor, dry after inert diluent toluene and organic solvent hexane repeatedly wash, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: powder electromicroscopic photograph is shown in Fig. 7.
Comparative example 1
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 100ml toluene, 10ml epoxy chloropropane, 17.0ml TRI N BUTYL PHOSPHATE are joined in the reactor that nitrogen is fully replaced, under mixing speed 450rpm, temperature are the condition of 60 DEG C, react 2 hours, add 2g Tetra hydro Phthalic anhydride and 1ml diethylene adipate, continue reaction 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 30ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, separates out solids gradually in temperature-rise period, elimination mother liquor, dry after toluene and hexane twice washing, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: the electromicroscopic photograph of catalyzer is as shown in Fig. 8 (a), and the electromicroscopic photograph of polymer particle is as shown in Fig. 8 (b).
Comparative example 2
(1) preparation of catalyst component
4.0 grams of magnesium chlorides, 100ml toluene, 10ml epoxy chloropropane, 17.0ml TRI N BUTYL PHOSPHATE are joined in the reactor that nitrogen is fully replaced, under mixing speed 450rpm, temperature are the condition of 60 DEG C, react 2 hours, add 2g Tetra hydro Phthalic anhydride and 1ml ethyl benzoate, continue reaction 1 hour, be cooled to-40 DEG C, drip titanium tetrachloride 30ml, be warming up to 95 DEG C gradually, constant temperature 1 hour, separates out solids gradually in temperature-rise period, elimination mother liquor, dry after toluene and hexane twice washing, obtain the solids containing magnesium/titanium.
(2) polyreaction: with embodiment 1, polymerization result is in table 1.
(3) electromicroscopic photograph: the electromicroscopic photograph of catalyzer is as shown in Fig. 9 (a), and the electromicroscopic photograph of polymer particle is as shown in Fig. 9 (b).
The polymerization result of table 1 embodiment and comparative example
As shown in Table 1, when introducing organic acid anhydride class/acetate esters/cyclic ketones compounds as composite electron donor in catalyzer, the tap density of its polymerization gained powder is apparently higher than comparative example.
Claims (15)
1. for a catalyst component for vinyl polymerization, comprise the reaction product of following component: (1) magnesium mixture; (2) organic acid anhydride; (3) acetate compounds; (4) cyclic ketones compounds; (5) titanium-containing compound;
The general formula of described acetate compounds is CH
3cOOR, in formula, R is C
1~ C
18straight or branched alkyl;
The general formula of described cyclic ketones compounds is
wherein a, b and c are the integer being more than or equal to 0, and are 0 when a, b are different with c, and wherein 3≤a+b+c≤7, in formula, R is C
1~ C
10straight or branched alkyl, cyclic hydrocarbon radical or aromatic hydrocarbyl;
Described magnesium mixture magnesium halide is dissolved in the mixture formed in the solvent system containing organic epoxy compound thing, organo phosphorous compounds.
2. a kind of catalyst component for vinyl polymerization according to claim 1, it is characterized in that being obtained by following steps: magnesium halide is dissolved in the solvent system containing organic epoxy compounds and organo phosphorous compounds, after forming homogeneous solution, mix with titanium-containing compound under organic acid anhydride, acetate compounds and cyclic ketones compounds exist, separate out containing magnesium/titanium spherical/elliposoidal solids particle, obtain ingredient of solid catalyst.
3. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, it is characterized in that organic epoxy compound thing is 0.2 ~ 10 mole, organo phosphorous compounds is 0.1 ~ 10 mole, organic acid anhydride is 0.03 ~ 1.0 mole, acetate compounds 0.03 ~ 1 mole, cyclic ketones compounds 0.03 ~ 1 mole, titanium-containing compound 0.5 ~ 120 mole.
4. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that described organic acid anhydride is selected from the one in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE.
5. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that described acetate compounds is selected from the one in methyl acetate, ethyl acetate, butylacetate, n-hexyl acetate and acetic acid n-octyl.
6. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that described cyclic ketones compounds is the one in cyclobutanone, dimethylcyclobutanone, cyclopentanone, 2-methyl-cyclopentanone, pimelinketone, methylcyclohexanone, 2-sec.-butylcyclohexanone, suberone, cyclooctanone.
7. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that the general formula of described titanium-containing compound is Ti (OR
1)
ax
1 b, R in formula
1for aliphatic group or aromatic hydrocarbyl that carbonatoms is 1 ~ 14, X
1for halogen, a be 0,1 or 2, b be 1 to 4 integer, a+b=3 or 4.
8. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that described titanium-containing compound comprises one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, titanous chloride, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or its mixture.
9. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, is characterized in that the solids particle of catalyst component is spherical or elliposoidal, and the length-to-diameter ratio of particle is 1:1 ~ 1.5:1.
10. a kind of catalyst component for vinyl polymerization according to claim 1 and 2, it is characterized in that the spherical of catalyst component or elliposoidal solids particle are grown by an organic centre to obtain, and each particle is formed by a large amount of long rod shape aggregate gathering along organic centre's radial growth, the length of long rod shape aggregate is close to particle radii, and length-to-diameter ratio is 5:1 ~ 100:1.
The preparation method of a kind of catalyst component for vinyl polymerization that one of 11. claim 1-10 are described, comprises the following steps:
(1) magnesium halide is dissolved in the solvent system containing organic epoxy compounds and organo phosphorous compounds and forms homogeneous solution;
(2) above-mentioned solution is added organic acid anhydride, acetate compounds and cyclic ketones compounds, the reaction regular hour, then carry out contact reacts with titanium compound;
(3) said mixture is removed unreacted reactant and solvent, and adopt inert diluent to wash, obtain ingredient of solid catalyst.
12. 1 kinds, for the catalyzer of vinyl polymerization, comprising:
(1) catalyst component for vinyl polymerization that one of claim 1-10 is described;
(2) organo-aluminium compound.
13. catalyzer for ethylene polymerization according to claim 12, is characterized in that the mol ratio of aluminium and the middle titanium of component (1) in component (2) is 20 ~ 200.
14. catalyzer for ethylene polymerization according to claim 12 close the application in reaction or copolymerization at ethylene homo.
15. catalyzer for ethylene polymerization according to claim 14 close the application in reaction or copolymerization at ethylene homo, it is characterized in that catalyzer is when ethene slurry polymerization or copolymerization, hydrogen 2.8 × 10
5pa, ethene 7.5 × 10
5pa, polymerization temperature is 85 DEG C, polymerization time 2h, obtain spherical/elliposoidal powder particle, and its tap density is higher than 0.43g/ml.
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