CN102807637B - Catalyst component for ethylene polymerization reaction and catalyst thereof - Google Patents
Catalyst component for ethylene polymerization reaction and catalyst thereof Download PDFInfo
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- CN102807637B CN102807637B CN201110148541.5A CN201110148541A CN102807637B CN 102807637 B CN102807637 B CN 102807637B CN 201110148541 A CN201110148541 A CN 201110148541A CN 102807637 B CN102807637 B CN 102807637B
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Abstract
The invention relates to a catalyst component for ethylene polymerization reaction, a preparation method of the catalyst component and a catalyst of the catalyst component. The catalyst component contains magnesium alcohol complex, titanium compound, borate compound, organic aluminum compound, long-carbon-chain monoester compound, and short-carbon-chain monoester compound. The catalyst has higher hydrogen adjusting sensibility and narrower particle size distribution. The obtained polyethylene powder has high stacking density, particularly centralized particle size distribution, and low contents of rougher powder and fine powder.
Description
Technical field
The present invention relates to a kind of for the catalyst component of ethylene polymerization, the preparation method of this catalyst component and its catalyzer.In particular, relate to contain three kinds of electron donors for the catalyst component of vinyl polymerization, the preparation method of this catalyst component and its catalyzer.
Background technology
In Ziegler-Natta catalyst evolution, electron donor, owing to having the features such as stereoselective that can significantly improve catalyst performance and polymkeric substance, is the hot issue in catalyst research always.A key request of the Z-N type ethylene rolymerization catalyst of preparing for magnesium chloride alcohol adduct carrier is: catalyzer has high hydrogen response, and resulting polymers powder has high-bulk-density.In order to obtain affiliated effect, conventionally in catalyzer, add internal electron donor, as ethers, ester class and amine etc.CN101633704 relates to a kind of catalyst component for ethylene polymerization and catalyzer thereof, wherein said catalyst component comprises magnesium mixture, titanium compound, organic alcohol compound and electron donor boric acid ester, owing to introducing boric acid ester, this catalyzer has good hydrogen response, and the polyethylene powder of gained has good tap density, but the size-grade distribution of polymer powders is concentrated not.
Except wishing that catalyzer has good hydrogen response, the polymkeric substance of gained has outside good tap density, and the size-grade distribution of catalyzer and polymkeric substance is also the focus that people pay close attention to.According to the replication of Ziegler-Natta type olefin polymerization catalysis particle, if the broad particle distribution of catalyst particle (being that span value is larger), resulting polymers powder particles distributes concentratedly not, and the powder that easily produces wide distribution generally includes a certain amount of compared with meal material be less than 190 object fine powders.Thicker powder may deposit in pipeline, results in blockage; And fine powder is easily attached to the inwall of reactor in process of production, cause heat transfer inhomogeneous, increased heat exhaustion, destroy the steady state of fluidized-bed, cause device to stop.Although partial monopoly, as CN1861645 can prepare relatively narrow distribution and the less spherical polyethylene powder of fine powder content, is greater than 20 objects and accounts for overwhelming majority's (> 68%) of powder total mass compared with meal material content in embodiment.Therefore, need to find a kind of raw catalyst component that comprises electron donor, by this component, can obtain polyethylene catalysts that size-grade distribution significantly narrows is the size-grade distribution value that the size-grade distribution value of catalyzer is less than magnesium chloride alcohol adduct ball type carrier.And by the less polyethylene catalysts of this size-grade distribution value, prepare a kind of concentrated especially polyethylene powder of size-grade distribution that has, reduce compared with the generation of meal material and fine powder.
If introducing in catalyst component is composite electron donor more than a kind of electron donor, the synergy between multiple electron donor not only can significantly improve certain performance of catalyzer, also may give catalyzer multiple character.The Patents CN1699433 that is applied to the spherical catalyst of propylene polymerization adopts titanium tetrachloride as dealcoholysis agent, the ester class of using is the composite electron donor of monoesters and di-esters, although significantly improved the activity of catalyzer, author undeclared composite electron donor are for the impact of hydrogen response; This patent is only applied to propylene polymerization in addition.In this patent, owing to using a large amount of titanium tetrachlorides to process, catalyzer cost is higher and gained titaniferous waste liquid is more, has increased the difficulty of production technique aftertreatment.
The inventor adopts aluminum alkyls as dealcoholysis agent, use long carbochain monoesters class, short carbon chain monoesters class and boric acid ester as composite electron donor, be applied to the spherical catalyst of vinyl polymerization, not only can make catalyzer there is very high hydrogen response and narrower size-grade distribution, can also make its gained polyethylene powder there is high-bulk-density and the concentrated especially feature of size-grade distribution, its 70% (wt) above powder concentrates on 55 orders, 16 orders are above is less than 3% compared with meal material content, and the fine powder content below 190 orders is less than 0.5% (wt).
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 and catalyzer thereof, this catalyzer has good hydrogen response and narrower size-grade distribution, resulting polymers tap density is high, and size-grade distribution is concentrated especially, few compared with meal material and fine powder content.
For a catalyst component for ethylene polymerization, this catalyst component comprises following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) boric acid ester compound;
(4) organo-aluminium compound;
(5) grow carbochain monoester class compound;
(6) short carbon chain monoester class compound;
The described magnesium alcoholate of component (1) is that general formula is MgCl
2the magnesium chloride alcohol adduct of-mROH, wherein R is C
1～C
4alkyl, m is 2.5～4.0;
The general formula of the titanium compound that component (2) is described is Ti (OR)
nx
4-n, in formula, R is C
1～C
8alkyl, X is halogen atom, 0≤n≤3;
The general formula of the boric acid ester compound that component (3) is described is B (OR)
3, in formula, R is C
1～C
8alkyl;
Organo-aluminium compound general formula described in component (4) is AlR '
ax '
bh
c, in formula, R ' is C
1～C
14alkyl, X ' is halogen, a, b, c are 0～3 integer, and a+b+c=3;
Long carbochain monoester class compound general formula described in component (5) is R
1cOOR
2, R in formula
1c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
6～C
18long carbochain straight or branched alkyl;
Short carbon chain monoester class compound general formula described in component (6) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1～C
4short carbon chain straight or branched alkyl.
General formula described in component (1) is MgCl
2the magnesium chloride alcohol adduct of-mROH is by C
1～C
4low-carbon alcohol be to mix for 2.5: 1～4: 1 in molar ratio with magnesium chloride, cooling rapidly after heating and melting, obtain the spheroidal particle that contains 2.5～4.0 moles of alcohol per mole magnesium chlorides.This patent adopts the magnesium chloride alcohol adduct of not dealcoholysis.Preferable range is at 2.5～4.0 moles of alcohol per mole magnesium chlorides.Above-mentioned magnesium chloride alcohol adduct is disclosed in Chinese patent CN93102795.0, and its disclosed associated viscera is all introduced the present invention as a reference.
Titanium compound general formula described in component (2) is Ti (OR)
nx
4-n, in formula, R is C
1～C
8alkyl, X is halogen atom, 0≤n≤3, comprising: TiCl
4, TiBr
4, TiI
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
2h
5) Br
3, Ti (OC
2h
5)
2cl
2, Ti (OCH
3)
2cl
2, Ti (OCH
3)
2i
2, Ti (OC
2h
5)
3cl, Ti (OCH
3)
3cl, Ti (OC
2h
5)
3i, Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4deng.Preferred TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
4h
9)
4.With TiCl
4for the best.
Boric acid ester compound general formula described in component (3) is B (OR)
3, in formula, R is C
1-C
8alkyl, comprising: B (OCH
3)
3, B (OC
2h
5)
3, B (OC
3h
7)
3, B (OC
4h
9)
3deng.Preferred B (OC
2h
5)
3.
Organo-aluminium compound general formula described in component (4) is AlR '
ax '
bh
c, in formula, R ' is C
1～C
14alkyl, X ' is halogen, a, b, c are 0～3 integer, and a+b+c=3.Particular compound is as Al (CH
3)
3, Al (CH
2cH
3)
3, Al (i-Bu)
3, Al (n-C
6h
13)
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 wherein preferably Al (CH
2cH
3)
3, Al (n-C
6h
13)
3, Al (i-Bu)
3.Most preferably be Al (CH
2cH
3)
3.These organometallic compounds both can be used separately, also can be used in combination.
The general formula of the long carbochain monoester class compound described in component (5) is R
1cOOR
2, R in formula
1c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
6～C
18long carbochain straight or branched alkyl, this compound is selected from carboxylicesters and aromatic ester.Particular compound is as n-hexyl acetate, acetic acid n-octyl, 2-ethyl hexyl ethanoate, the just own ester of phenylformic acid, phenylformic acid n-octyl, phenylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid n-octyl, Isooctyl acrylate monomer and octadecyl acrylate etc.
The general formula of the short carbon chain monoester class compound described in component (6) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1～C
4short carbon chain straight or branched alkyl, this compound is selected from carboxylicesters and aromatic ester.Particular compound is as methyl acetate, ethyl acetate, ethyl benzoate, the positive butyl ester of phenylformic acid, methyl acrylate, ethyl propenoate and butyl acrylate etc.
Catalyst component for vinyl polymerization of the present invention, the ratio between each reactant is in component (1) every mole of magnesium in dealcoholysis magnesium chloride ethanol ball type carrier not, and component (2) titanium compound is 0.1～15.0 mole; Component (3) boric acid ester compound is 0.1～5.0 mole; Component (4) organo-aluminium compound is 0.1～5.0 mole; The long carbochain monoester class compound of component (5) is 0.1～5.0 mole; Component (6) short carbon chain monoester class compound is 0.1～5.0 mole.
The size-grade distribution Span of the catalyst component for vinyl polymerization of the present invention is lower than 0.7; The powder particles of preparing by this catalyzer distributes concentrated especially, and its 70% (wt) above powder concentrates on 55 orders, and 16 orders are above is less than 3% compared with meal material content, and the fine powder content below 190 orders is less than 0.5% (wt).Wherein Span is defined as follows: [(particle diameter of 90% cumulative particle sizes)-(particle diameter of 10% cumulative particle sizes)]/(particle diameter of 50% cumulative particle sizes), wherein term 90%/10%/50% cumulative particle sizes represents granularity limit value, at the particle of the cumulative amount at limit value place 90%/10%/50%, is all less than this granularity limit value.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
Magnesium chloride alcohol adduct component (1) Suo Shu is dispersed in inert solvent, obtains suspension.Dispersion medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the saturated fatty hydro carbons inert solvent such as hydrogenated gasoline, kerosene.Suspension is carried out to contact reacts in-40～50 ℃ with component (4) organo-aluminium compound, component (3) boric acid ester compound, the long carbochain monoester class compound of component (5) and component (6) short carbon chain monoester class compound.And mixture is slowly warming up to 20～60 ℃, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent to wash once or several, and then introduce component (2) titanium compound and react, then through inert diluent washing, obtain catalyst component of the present invention.
The present invention also provides a kind of spherical catalyst for vinyl polymerization, the reaction product that it comprises following component:
(1) catalyst component of the invention described above;
(2) general formula is AlR "
dx
3-dorgano-aluminium compound, R in formula " be the alkyl that hydrogen or carbonatoms are 1～20, X is halogen, 0 < d≤3.
Component (2) formula of is AlR "
dx
3-dorgano-aluminium compound, R in formula " can be hydrogen or carbonatoms be 1～20 alkyl, particularly alkyl, aralkyl, aryl; X is halogen, 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.
During polymerization, liquid polymerization can be adopted, also vapour phase polymerization can be adopted.
Liquid 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 inventor finds to add respectively long carbochain monoesters, short carbon chain monoesters and the composite electron donor of boric acid ester in the preparation process of the catalyst component for vinyl polymerization, not only can make catalyzer there is very high hydrogen response and narrower size-grade distribution, can also make its gained polyethylene powder there is high-bulk-density, and size-grade distribution is concentrated especially, few compared with meal material and fine powder content.This catalyzer is only used the aluminum alkyls of small amount in addition, thus cost is lower and waste liquid seldom.
Embodiment
Testing method:
1. the relative weight per-cent of titanium elements in catalyst system: adopt spectrophotometry;
2. the relative weight per-cent of ester in catalyst system: adopt high performance liquid chromatography;
3. the mensuration that catalyst grain size distributes: MASTERSIZE particles distribution instrument, normal hexane is as dispersion agent, useful range 0.02～2000 μ m;
4. the mensuration of polymer bulk density: adopt ASTM D1895;
5. the mensuration that polymer particle size distributes: adopt standard sieve to sieve;
6. the mensuration of melt index (MI): according to ASTM D1238-99.
With embodiment, the present invention is described below, but and the unrestricted scope of the invention.
Embodiment 1
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 5.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml triethyl aluminum (triethyl aluminum: 1.2M) with 1ml acetic acid n-octyl, 0.5ml ethyl acetate, 0.5ml triethyl borate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add the triethyl aluminum that 1L hexane and 1.0ml concentration are 1M, add again the ingredient of solid catalyst (containing 0.6 milligram of titanium) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), under 80 ℃ of conditions, polymerization is 2 hours, and polymerization result is in Table 2.
(3) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add the triethyl aluminum that 1L hexane and 1.0ml concentration are 1M, add again the ingredient of solid catalyst (containing 1.8 milligrams of titaniums) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.58Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), under 80 ℃ of conditions, polymerization is 2 hours, and polymerization result is in Table 3.
Embodiment 2
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 4.0g ball type carrier MgCl
23.0C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 40ml triethyl aluminum (triethyl aluminum: 1.2M) with 1ml 2-ethyl hexyl ethanoate, 1ml ethyl acetate, 0.5ml triethyl borate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 6ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Embodiment 3
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 5.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, drip the hexane solution (triethyl aluminum: 1.2M) with 0.5ml octadecyl acrylate of 50ml triethyl aluminum, 0.5ml ethyl benzoate, then 0.5ml tributyl borate is warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Embodiment 4
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 4.0g ball type carrier MgCl
23.0C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml triethyl aluminum (triethyl aluminum: 1.2M), 1ml acetic acid n-octyl, 0.5ml n-butyl acetate, 0.5ml triethyl borate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Embodiment 5
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 6.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 120ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml tri-n-hexyl aluminum (tri-n-hexyl aluminum: 1.2M), 1ml vinylformic acid n-octyl, 1ml methyl acrylate, 0.5ml trimethyl borate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 6ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Embodiment 6
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 5.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml triethyl aluminum (triethyl aluminum: 1.2M), the just own ester of 1ml phenylformic acid, the positive butyl ester of 1ml phenylformic acid, 0.5ml triethyl borate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add the triethyl aluminum that 1L hexane and 1.0ml concentration are 1M, add again the ingredient of solid catalyst (containing 1.8 milligrams of titaniums) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.58Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), under 80 ℃ of conditions, polymerization is 2 hours, and polymerization result is in Table 3.
Comparative example 1
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 5.0g ball type carrier MgCl
23.0C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml triethyl aluminum (triethyl aluminum: 1.2M), 1ml acetic acid n-octyl, 1ml ethyl acetate, is then warming up to 50 ℃, and maintains reaction 3 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Comparative example 2
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 5.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, drips the hexane solution (triethyl aluminum: 1.2M), with 2ml ethyl benzoate, be then warming up to 50 ℃, and maintain reaction 3 hours of 50ml triethyl aluminum.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, throw out with hexane twice of room temperature washing.Add 150ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 8ml, be warming up to afterwards 60 ℃, react 2 hours.Stop stirring, standing, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after twice of hexane washing, transfers them in chromatography funnel by hexane, with high pure nitrogen, dries up, and obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add the triethyl aluminum that 1L hexane and 1.0ml concentration are 1M, add again the ingredient of solid catalyst (containing 1.8 milligrams of titaniums) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.58Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), under 80 ℃ of conditions, polymerization is 2 hours, and polymerization result is in Table 3.
The composition of table 1 catalyst component
From the data of table 1, can find out, by the size-grade distribution of gained catalyst component of the present invention, than magnesium chloride alcohol adduct carrier, significantly be narrowed its size-grade distribution Span≤0.7.
The size-grade distribution of table 2 catalyst performance and powder
From the data of table 2, can find out, the polyethylene powder of being prepared by gained catalyzer of the present invention, its tap density is higher, melting index is higher, and size-grade distribution is concentrated especially, the above powder of 70% (wt) concentrates on 55 orders, and the above fine powder content being less than below 3%, 190 order compared with meal material content of 16 orders is less than 0.5% (wt).
The hydrogen of table 3 catalyzer is adjusted susceptibility
From the data of table 3, can find out, catalyzer hydrogen response of the present invention is good.
Claims (12)
1. for a catalyst component for ethylene polymerization, this catalyst component comprises following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) boric acid ester compound;
(4) organo-aluminium compound;
(5) grow carbochain monoester class compound;
(6) short carbon chain monoester class compound;
The described magnesium alcoholate of component (1) is that general formula is MgCl
2the magnesium chloride alcohol adduct of-mROH, wherein R is C
1～C
4alkyl, m is 2.5～4.0;
The general formula of the titanium compound that component (2) is described is Ti (OR)
nx
4-n, in formula, R is C
1～C
8alkyl, X is halogen atom, 0≤n≤3;
The general formula of the boric acid ester compound that component (3) is described is B (OR)
3, in formula, R is C
1～C
8alkyl;
Organo-aluminium compound general formula described in component (4) is AlR '
ax '
bh
c, in formula, R ' is C
1～C
14alkyl, X ' is halogen, a, b, c are 0～3 integer, and a+b+c=3;
Long carbochain monoester class compound general formula described in component (5) is R
1cOOR
2, R in formula
1c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
6～C
18long carbochain straight or branched alkyl;
Short carbon chain monoester class compound general formula described in component (6) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1～C
4short carbon chain straight or branched alkyl.
2. the catalyst component for ethylene polymerization according to claim 1, it is characterized in that ratio between each reactant is in every mole of magnesium, titanium compound is 0.1～15 mole, boric acid ester compound is 0.1～5.0 mole, organo-aluminium compound is 0.1～5.0 mole, long carbochain monoester class compound is 0.1～5.0 mole, and short carbon chain monoester class compound is 0.1～5.0 mole.
3. the catalyst component for ethylene polymerization according to claim 1, the boric acid ester compound that it is characterized in that described component (3) is B (OCH
3)
3, B (OC
2h
5)
3, B (OC
3h
7)
3or B (OC
4h
9)
3in a kind of.
4. the catalyst component for ethylene polymerization according to claim 1, the boric acid ester compound that it is characterized in that described component (3) is B (OC
2h
5)
3.
5. the catalyst component for ethylene polymerization according to claim 1, the long carbochain monoester class compound that it is characterized in that described component (5) is a kind of in n-hexyl acetate, acetic acid n-octyl, 2-ethyl hexyl ethanoate, the just own ester of phenylformic acid, phenylformic acid n-octyl, phenylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid n-octyl, Isooctyl acrylate monomer or octadecyl acrylate.
6. the catalyst component for ethylene polymerization according to claim 1, the short carbon chain monoester class compound that it is characterized in that described component (6) is a kind of in methyl acetate, ethyl acetate, ethyl benzoate, the positive butyl ester of phenylformic acid, methyl acrylate, ethyl propenoate or butyl acrylate.
7. the catalyst component for ethylene polymerization according to claim 1, the organo-aluminium compound that it is characterized in that described component (4) is Al (CH
2cH
3)
3, Al (n-C
6h
13)
3or Al (i-Bu)
3in a kind of.
8. the catalyst component for ethylene polymerization according to claim 1, is characterized in that its size-grade distribution value≤0.7.
9. a preparation method for the catalyst component for ethylene polymerization claimed in claim 1, it comprises the following steps:
(1) magnesium chloride alcohol adduct component (1) Suo Shu is dispersed in saturated fatty hydro carbons inert solvent, obtains suspension;
(2) suspension is carried out to contact reacts in-40～50 ℃ with component (4) organo-aluminium compound, component (3) boric acid ester compound, the long carbochain monoester class compound of component (5) and component (6) short carbon chain monoester class compound;
(3) mixture of step (2) is slowly warming up to 20～60 ℃, after the reaction regular hour, removes unreacted reactant, and adopt inert diluent washing;
(4) add component (2) titanium compound to react, then adopt inert diluent washing, obtain this catalyst component.
10. for the catalyzer of ethylene polymerization, the reaction product that it comprises following component:
(1) the described catalyst component of one of claim 1-8;
(2) general formula is AlR "
dx
3-dorgano-aluminium compound, R in formula " be the alkyl that hydrogen or carbonatoms are 1～20, X is halogen atom, 0 < d≤3.
11. catalyzer for ethylene polymerization according to claim 10, is characterized in that the mol ratio of titanium in the middle aluminium of component (2) and component (1) is 20～200.
Described in 12. claims 10, catalyzer closes the application in reaction or copolymerization at ethylene homo.
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| CN1531558A (en) * | 2000-11-10 | 2004-09-22 | ������ѧ��ʽ���� | Method for producing catalyst for homo-or co-polymerization of ethylene |
| CN101260165A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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| CN101260165A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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