CN102807633B - Catalyst component applied to ethylene polymerization reaction and catalyst thereof - Google Patents
Catalyst component applied to ethylene polymerization reaction and catalyst thereof Download PDFInfo
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- CN102807633B CN102807633B CN201110148493.XA CN201110148493A CN102807633B CN 102807633 B CN102807633 B CN 102807633B CN 201110148493 A CN201110148493 A CN 201110148493A CN 102807633 B CN102807633 B CN 102807633B
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Abstract
The invention relates to a catalyst component applied to an ethylene 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 organic aluminum compound, a long-carbon-chain monoester compound and a sulfuryl-containing compound. The catalyst has proper activity and high hydrogen regulation sensitivity, and the piling density of obtained polymer powder is high.
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 the ethylene rolymerization catalyst that a kind of higher hydrogen is adjusted susceptibility, use this catalyzer can prepare the polymkeric substance of high-bulk-density.
Background technology
The existing research more widely of the Ziegler-Natta type vinyl polymerization spherical catalyst prepared by magnesium chloride ethanol carrier, this catalyzer is widely used in liquid phase or ethene (being total to) poly-unit that operates with gas phase.Yet the use of catalyst component itself is not entirely satisfactory.In fact, due to the hyperergy of ethene, the heat release of polyreaction is very high.Therefore, at the starting stage of polymerization catalyzer, bear very strong tension force, this tension force makes catalyzer itself that uncontrolled breaking occur, and this situation is the reason that polymer fine particles forms.The formation of polymer fine particles directly causes the low bulk density of polymkeric substance and the difficulty of operating process.In addition, also require catalyzer to there is stable activity and good hydrogen regulation performance.
For addressing these problems, Basel company has carried out large quantity research.CN1400979A relates to a kind of catalyst component of preparing for ethene (being total to) polymkeric substance, this catalyst component can be produced the polymkeric substance with high bulk density, can avoid the problem of fine powder formation and there is high reactivity, this catalyst component contains the non-three-dimensional ingredient of solid catalyst of selecting, it contains titanium compound and magnesium dihalide, and it is and alpha-olefin CH
2=CHR
1prepolymerized, wherein R is C1-C8 alkyl, but this method complicated process of preparation.
Although part vinyl polymerization spherical catalyst has also been introduced ester class electron donor, their effect is the copolymerized ability that improves catalyzer.As CN1726230 first carries out physics dealcoholysis by alcohol carrier, re-use subsequently aluminum alkyls and carry out chemical dealcoholysis, after year titanium, re-use the electron donors such as ester, ether, amine, ester and ketone catalyzer is carried out to aftertreatment, thereby improved the copolymerized ability of catalyzer.As CN1798774 and CN101050248 first carry out physics dealcoholysis by alcohol carrier, re-using subsequently titanium tetrachloride carries out chemical dealcoholysis and carries titanium, carry and to re-use the electron donors such as ester class and ethers after titanium catalyzer is carried out to aftertreatment, thereby improved the copolymerized ability of catalyzer.
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 adjusted the impact of susceptibility for hydrogen; 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.
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.
For a catalyst component for ethylene polymerization, this catalyst component comprises following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) organo-aluminium compound;
(4) grow carbochain monoester class compound;
(5) 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;
Organo-aluminium compound general formula described in component (3) 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 (4) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
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
2h5
)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 TiC
4for the best.
Organo-aluminium compound general formula described in component (3) 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, AlCl (CH
2cH
3)
2.Most preferably be AlCl (CH
2cH
3)
2, 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 (4) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
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 (5) is that general formula is R
5sO
3r
6sulfonates compounds, R wherein
5that carbonatoms is 1～10 alkyl, R
6for 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 (5) can also be that general formula is R
5sO
2the sulphonating agent of X, wherein R
5for 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) organo-aluminium compound is 0.1～5.0 mole; The long carbochain monoester class compound of component (4) is 0.1～5.0 mole; Component (5) 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 ℃, above-mentioned magnesium chloride ethanol ball-type carrier suspension and the long carbochain monoester class compound of component (4), component (5) are carried out to contact reacts containing compound and component (3) 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.Finally introduce again component (2) titanium compound and react, 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; N is the number of 0 < n≤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.
The inventor finds that the preparation process at the catalyst component for vinyl polymerization adds respectively long carbochain monoesters and containing the compound of sulfuryl, not only can make catalyzer there is applicable activity and very high hydrogen response, can also make its gained polyethylene there is high-bulk-density.This catalyzer is only used aluminum alkyls and the titanium tetrachloride 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 of polymer bulk density: adopt ASTM D1895;
4. 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 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, 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, 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, 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, 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, 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
22.5C
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, 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
The hydrogen of table 3 catalyzer is adjusted susceptibility
From the data of table 1, can find out, relatively, titanium content decreases, and the introducing of ester class electron donor is described, can cause catalyst Ti content suitably to reduce for gained catalyzer of the present invention and comparative example 1.
From the data of table 2, can find out, though catalyst activity slightly reduces in embodiment, still can meet vapour phase polymerization for the requirement of catalyst activity, and polymer powders tap density increase substantially.Under the polymerizing condition of low hydrogen ratio, the difference of catalyzer hydrogen regulation performance aspect is also not obvious.
From the data of table 3, can find out, under different hydrogen ratio condition aggregation tests, due to long carbochain monoester class compound with containing the introducing of the 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) organo-aluminium compound;
(4) grow carbochain monoester class compound;
(5) 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;
Organo-aluminium compound general formula described in component (3) 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 (4) is R
3cOOR
4, R in formula
3c
1～C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
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 (5) is that general formula is R
5sO
3r
6sulfonates compounds, R wherein
5and R
6difference representation hydrocarbyl.
3. the catalyst component for ethylene polymerization according to claim 1, is characterized in that the compound containing sulfuryl of described component (5) is that general formula is R
5sO
2the sulphonating agent of X, wherein R5 is 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 (5) 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, 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 long carbochain monoester class compound that it is characterized in that described component (4) 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.
7. the catalyst component for ethylene polymerization according to claim 1, the titanium compound that it is characterized in that described component (2) is titanium tetrachloride.
8. the catalyst component for ethylene polymerization according to claim 1, the organo-aluminium compound that it is characterized in that described component (3) is Al (CH
2cH
3)
3, AlCl (CH
2cH
3)
2or Al (n-C
6h
13)
3.
9. a preparation method for the described catalyst component for ethylene polymerization of one of claim 1-8, 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 (4), component (5) containing compound and component (3) 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 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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| CN1531558A (en) * | 2000-11-10 | 2004-09-22 | ������ѧ��ʽ���� | Method for producing catalyst for homo-or co-polymerization of ethylene |
| 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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