CN102807632B - Catalyst component applied to vinyl polymerization reaction and catalyst thereof - Google Patents
Catalyst component applied to vinyl polymerization reaction and catalyst thereof Download PDFInfo
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- CN102807632B CN102807632B CN201110148492.5A CN201110148492A CN102807632B CN 102807632 B CN102807632 B CN 102807632B CN 201110148492 A CN201110148492 A CN 201110148492A CN 102807632 B CN102807632 B CN 102807632B
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Abstract
The invention relates to a catalyst component applied to a vinyl polymerization reaction, a preparation method of the catalyst component and a catalyst thereof. The catalyst component comprises a magnesium-alcohol compound, a titanium compound, an alkoxy compound, an organic aluminum compound, a long-carbon-chain monoester compound and a sulfuryl-containing compound. The catalyst has proper activity and very high hydrogen regulation sensitivity; and the piling density of obtained polymer powder is high, and the molecular weight distribution is wide.
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 a kind of ethylene rolymerization catalyst that higher hydrogen is adjusted susceptibility that has, use this catalyzer can prepare the polymkeric substance of high-bulk-density and wide molecular weight distribution.
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 has high-bulk-density.In order to obtain described 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.CN1958620 provides a kind of catalyst component and catalyzer that dissolves precipitation type, owing to having introduced four alkoxyl silicones as electron donor in catalyzer, improve the hydrogen of catalyzer and adjusted susceptibility, also play the effect of precipitation additive simultaneously, but in this patent, do not added ester class electron donor.
Except wishing that catalyzer has good hydrogen response, the polymkeric substance of gained has outside good tap density, and the molecular weight distribution of polymkeric substance is also the focus that people pay close attention to.The polyolefin products of wide molecular weight distribution has good mechanical property and processing characteristics, to introducing some electron donor with special construction in catalyzer, is the common way of widening product molecular weight distribution.CN101880339A has related to a kind of ethylene rolymerization catalyst and preparation method thereof, magnesium chloride/electron donor/the titanium compound of nascent state is loaded on silica supports, through aluminum alkyls, processing, finally carry out complex reaction with electron donor (polar polymer) again, wherein electron donor is selected from aliphatics or aromatic ether, ester, amine or the alcohol that contains 3-8 carbon atom.Gained polymerization catalyst activity is higher, and the molecular weight distribution of producing is wider.CN1769307 relates to a kind of olefin polymerization catalysis of electron donor modification, this catalyzer is by forming by a certain percentage with magnesium compound, titanium compound and electron donor 8-alkoxyl group quinolines, the activity of gained catalyzer is high, adopts this catalyzer to carry out olefinic polymerization resulting polymers molecular weight distribution wider.
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 by containing the compound of sulfuryl for example sulfonates compounds or halogen-containing sulphonating agent introduce in catalyzer, the tap density of resulting polymers powder obtains obviously and improves; Further study and find, by introduce long carbochain monoesters class electron donor in catalyzer, not only to have kept the height of polymer powders to pile close feature, and catalyzer also has very high hydrogen tune susceptibility; In catalyzer, introduce alkoxyl group compounds again, the molecular weight distribution of resulting polymers powder is wider.
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, and this catalyzer has good hydrogen response, and resulting polymers powder tap density is high, and molecular weight distribution is wide.
For a catalyst component for ethylene polymerization, this catalyst component comprises following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) alkoxyl group compounds;
(4) organo-aluminium compound;
(5) grow carbochain monoester class compound;
(6) contain the compound of sulfuryl;
The described magnesium alcoholate of component (1) is that general formula is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH, wherein R
1for 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
2)
nx
4-n, R in formula
2for C
1～C
8alkyl, X is halogen atom, 0≤n≤4;
The general formula of the alkoxyl group compounds that component (3) is described is M (OR
3)
4, R in formula
3for C
1～C
8alkyl, M is Ti or Si;
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
4cOOR
5, R in formula
4c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
5c
6～C
18long carbochain straight or branched alkyl;
General formula described in component (1) is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH 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
2)
nx
4-n, R in formula
2for C
1～C
8alkyl, X is halogen atom, 0≤n≤4, 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.
Alkoxyl group compounds general formula described in component (3) is M (OR
3)
4, R in formula
3for C
1～C
8alkyl, M is Ti or Si, comprising: Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4, Si (OC
2h
5)
4, Si (OC
3h
7)
4, Si (OC
4h
9)
4deng.Preferred Si (OC
4h
9)
4and Ti (OC
4h
9)
4.
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
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, AlCl (CH
2cH
3)
2and Al (n-C
6h
13)
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
4cOOR
5, R in formula
4c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
5c
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 compound containing sulfuryl described in component (6) is that general formula is R
6sO
3r
7sulfonates compounds, R wherein
6that carbonatoms is 1～10 alkyl, R
7for the carbonatoms alkyl that is 1～6.Particular compound is as ethyl benzenesulfonat, the positive butyl ester of Phenylsulfonic acid, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid isopropyl ester etc.The compound containing sulfuryl described in component (4) can also be that general formula is R
6sO
2the sulphonating agent of X, wherein R
6for the alkyl that carbonatoms is 1～10, X is chlorine element or bromo element, and this sulphonating agent obtains above-mentioned sulfonates compounds with corresponding alcohol compound in the reaction of reaction system situ.
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) alkoxyl group compounds 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) is 0.1～5.0 mole containing the compound of sulfuryl.
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.At-40 ℃～50 ℃, said mixture and the long carbochain monoester class compound of component (5), component (6) are carried out to contact reacts containing compound and component (4) organo-aluminium compound of sulfuryl, 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 component (3) alkoxyl group compounds reacts, 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) promotor is that 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.
Promotor is that general formula 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 the mol ratio of the aluminium in promotor and the titanium in catalyst component is 5～500, 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.
Inventor's discovery adds respectively long carbochain monoesters in the preparation process of the catalyst component for vinyl polymerization, contains compound and the alkoxy compound three class electron donors of sulfuryl, not only can make catalyzer there is very high hydrogen response, can also make its gained polyethylene powder there is high-bulk-density and wider molecular weight distribution.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/magnesium/aluminium element in catalyst system: adopt spectrophotometry;
2. the relative weight per-cent of ester in catalyst system: adopt high performance liquid chromatography;
3. the mensuration of polymer bulk density: adopt ASTM D1895;
4. the mensuration of melt index (MI): according to ASTM D1238-99;
5. the mensuration of molecular weight distribution index (MWD): adopt the Waters of Waters company
All iance GPC2000 gel permeation chromatograph is measured, and 1,2,4-trichlorobenzene is solvent, and monodisperse polystyrene is standard.
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 6.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 30ml tri-n-hexyl aluminum (tri-n-hexyl aluminum: 1.2M), with 1ml acetic acid n-octyl, 8ml benzene sulfonyl chloride, is then warming up to 50 ℃, and maintain 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 4ml, slowly drip four titanium butoxide 0.5ml, 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 diameter 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 0.3 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 1.03Mpa (gauge pressure), under 85 ℃ 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 0.3 milligram of titanium) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.50Mpa, then pass into ethene and make stagnation pressure in still reach 1.03Mpa (gauge pressure), under 85 ℃ of conditions, polymerization is 2 hours, and polymerization result is in Table 3.
(4) 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 0.3 milligram of titanium) of preparing by aforesaid method, be warming up to 75 ℃, pass into hydrogen and make still internal pressure reach 0.68Mpa, then pass into ethene and make stagnation pressure in still reach 1.03Mpa (gauge pressure), under 85 ℃ 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 6.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to 0 ℃, the hexane solution of dropping 20ml triethyl aluminum (triethyl aluminum: 1.2M), 1ml acetic acid n-octyl and 10ml benzene sulfonyl chloride, be then warming up to 50 ℃, and maintain 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 4ml, slowly drip four titanium butoxide 0.3ml, 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 diameter distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction: with embodiment 1, polymerization result is in Table 3.
(4) polyreaction: with embodiment 1, polymerization result is in Table 3.
Embodiment 3
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 36.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 750ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 200ml triethyl aluminum (triethyl aluminum: 1.2M), 5ml vinylformic acid n-octyl, and the positive butyl ester of 15ml Phenylsulfonic acid, be then warming up to 50 ℃, and maintain 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 800ml hexane, this system is cooled to 0 ℃, slowly drip titanium tetrachloride 30ml, slowly drip tetraethoxy-silicane 3ml, 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 diameter distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction: with embodiment 1, polymerization result is in Table 3.
(4) polyreaction: with embodiment 1, polymerization result is in Table 3.
Embodiment 4
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 6.0g ball type carrier MgCl
22.5C
2h
5oH, hexane 120ml, stirs borehole cooling to 0 ℃, drips the hexane solution (1.5M) of 20ml aluminium diethyl monochloride, and 1ml vinylformic acid n-octyl and 3ml ethyl benzenesulfonat, be then warming up to 50 ℃, and maintain reaction 2 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 4ml, slowly drip tetraethoxy-silicane 0.5ml, 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 diameter 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 150ml, stirs borehole cooling to-10 ℃, the hexane solution of dropping 50ml tri-n-hexyl aluminum (tri-n-hexyl aluminum: 1.2M), the just own ester of 1ml phenylformic acid and 8ml benzene sulfonyl chloride, be then warming up to 50 ℃, and maintain reaction 4 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 3ml, slowly drip four titanium butoxide 0.5ml, 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 diameter distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
Comparative example 1
(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 150ml, stirs borehole cooling to 0 ℃, drips the hexane solution (triethyl aluminum: 1.2M), be then warming up to 50 ℃, and maintain reaction 3 hours of 20ml 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 4ml, 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 diameter 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 6.0g ball type carrier MgCl
22.6C
2h
5oH, hexane 150ml, stirs borehole cooling to-10 ℃, drips the hexane solution (tri-n-hexyl aluminum: 1.2M), with 8ml benzene sulfonyl chloride, be then warming up to 50 ℃, and maintain reaction 3 hours of 30ml tri-n-hexyl 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 4ml, 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 diameter distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction: with embodiment 1, polymerization result is in Table 3.
(4) polyreaction: with embodiment 1, polymerization result is in Table 3.
Comparative example 3
(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 150ml, stirs borehole cooling to-10 ℃, drips the hexane solution (tri-n-hexyl aluminum: 1.2M), with 1ml acetic acid n-octyl, be then warming up to 50 ℃, and maintain reaction 3 hours of 30ml tri-n-hexyl 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 4ml, slowly drip four titanium butoxide 0.5ml, 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 diameter distribution.Catalyzer forms in Table 1.
(2) polyreaction: with embodiment 1, polymerization result is in Table 2.
(3) polyreaction: with embodiment 1, polymerization result is in Table 3.
(4) polyreaction: with embodiment 1, polymerization result is in Table 3.
Table 1 catalyzer forms
Table 2 polymer performance
From the data of table 1, can find out, gained catalyzer of the present invention contrasts with comparative example 1, and titanium content decreases, and the introducing of ester class electron donor is described, can cause catalyst Ti content suitably to reduce.
From the data of table 2, can find out, though gained polymerization catalyst of the present invention is active, slightly reduce, but still can meet vapour phase polymerization for the requirement of catalyst activity, and the tap density of polymer powders increases substantially, meanwhile, molecular weight distribution is significantly widened, and weight-average molecular weight Mw increases more, so both guaranteed the mechanical property of material, can obtain good processing characteristics again simultaneously.Under the polymerizing condition of low hydrogen ratio, the difference of catalyzer hydrogen regulation performance aspect is also not obvious.
The hydrogen of table 3 catalyzer is adjusted susceptibility
From the data of table 3, can find out, alkoxyl group compounds, long carbochain monoester class compound and jointly introduce after catalyzer containing three kinds of electron donors of compound of sulfuryl, catalyzer hydrogen response obtains significantly and improves.
Claims (12)
1. for a catalyst component for ethylene polymerization, this catalyst component comprises following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) alkoxyl group compounds;
(4) organo-aluminium compound;
(5) grow carbochain monoester class compound;
(6) contain the compound of sulfuryl;
The described magnesium alcoholate of component (1) is that general formula is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH, wherein R
1for 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
2)
nx
4-n, R in formula
2for C
1～C
8alkyl, X is halogen atom, 0≤n≤4;
The general formula of the alkoxyl group compounds that component (3) is described is M (OR
3)
4, R in formula
3for C
1～C
8alkyl, M is Ti or Si;
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
4cOOR
5, R in formula
4c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
5c
6～C
18long carbochain straight or branched alkyl.
2. the catalyst component for ethylene polymerization according to claim 1, is characterized in that the compound containing sulfuryl of described component (6) is that general formula is R
6sO
3r
7sulfonates compounds, R wherein
6and R
7difference representation hydrocarbyl.
3. the catalyst component for ethylene polymerization according to claim 1, is characterized in that the compound containing sulfuryl of described component (6) is that general formula is R
6sO
2the sulphonating agent of X, wherein R
6for alkyl, X is chlorine element or bromo element.
4. the catalyst component for ethylene polymerization according to claim 1, the compound containing sulfuryl that it is characterized in that described component (6) is a kind of in the positive butyl ester of ethyl benzenesulfonat, Phenylsulfonic acid, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid isopropyl ester or benzene sulfonyl chloride.
5. 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, alkoxyl group compounds 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 the compound that contains sulfuryl is 0.1～5.0 mole.
6. the catalyst component for ethylene polymerization according to claim 1, the alkoxyl group compounds that it is characterized in that described component (3) is Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4, Si (OC
2h
5)
4, Si (OC
3h
7)
4or Si (OC
4h
9)
4in a kind of.
7. 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.
8. 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)
3, AlCl (CH
2cH
3)
2or Al (i-Bu)
3in a kind of.
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 with the long carbochain monoester class compound of component (5), component (6) containing compound and component (4) organo-aluminium compound of sulfuryl in-40～50 ℃;
(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 and component (3) alkoxyl group compounds 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) promotor is that 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 aluminium in promotor and the mol ratio of the titanium in catalyst component are 20～200.
Described in 12. claims 10, catalyzer closes the application in reaction or copolymerization at ethylene homo.
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| WO2019060299A1 (en) | 2017-09-22 | 2019-03-28 | Saudi Arabian Oil Company | Inline process to make antifouling agent co-catalyst for ethylene oligomerization |
| CN111072797B (en) * | 2018-10-19 | 2021-07-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application |
| US11440980B2 (en) | 2020-07-22 | 2022-09-13 | Saudi Arabian Oil Company | Methods for forming ultra high molecular weight polyethylenes and methods for reducing contaminant content in such |
| US11623208B2 (en) | 2020-11-30 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems |
| WO2022115754A1 (en) | 2020-11-30 | 2022-06-02 | Saudi Arabian Oil Company | Catalyst systems |
| US11612883B2 (en) | 2020-11-30 | 2023-03-28 | Saudi Arabian Oil Company | Catalyst systems |
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| US11623901B1 (en) | 2022-08-31 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems that include silyl ether moieties |
| US11639321B1 (en) | 2022-08-31 | 2023-05-02 | Saudi Arabian Oil Company | Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands |
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| CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
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| CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
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