CN103772542B - A kind of catalyst component for ethene slurry polymerization and catalyzer thereof - Google Patents
A kind of catalyst component for ethene slurry polymerization and catalyzer thereof Download PDFInfo
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Abstract
The present invention relates to a kind of for the catalyst component of ethene slurry polymerization, the preparation method of catalyst component and its catalyzer.Wherein said catalyst component comprises magnesium alcoholate, titanium compound, organo-aluminium compound, ester compound, the reactant of halogen ester compounds.This catalyzer has higher activity and good copolymerized ability, is applicable to ethene slurry polymerization.
Description
Technical field
The present invention relates to a kind of for the catalyst component of ethene slurry polymerization, the preparation method of this catalyst component and its catalyzer.More particularly, relate to containing two kinds of electron donors for the catalyst component of ethene slurry polymerization, the preparation method of this catalyst component and its catalyzer.
Background technology
The Ziegler-Natta type vinyl polymerization spherical catalyst using magnesium chloride ethanolic vehicle to prepare industrialization for many years, owing to being subject to the restriction of catalyst activity deficiency, this type of catalyzer is mainly used in gas-phase polymerization process at present.If the activity of this type of catalyzer can be significantly improved, ethene slurry polymerization processes can be applied to, then can obtain with catalyzer form similar, there is better mobility and tap density, and can in order to avoid the spherical polyethylene pellet of granulation.
In the prior art, introducing halogenated compound is the common methods improving Ziegler-Natta type polyolefin catalyst polymerization activity.Chinese patent as CN1268520, CN1535286 and CN1551891 discloses, and by introducing halohydrocarbon in the polymerization process of catalyzer, can improve its polymerization activity.Chinese patent as CN1263895 and CN1198751 discloses, in the catalyst component of titaniferous, introduce a certain amount of halohydrocarbon, can significantly improve the polymerization activity of catalyzer.As CN102432712A discloses, generate a certain amount of halogen ester by the catalyst component situ at titaniferous, activity and the hydrogen that can improve catalyzer adjust susceptibility, but its activity is still not enough to be applied to ethene slurry polymerization processes.
In the catalyst component of titaniferous, introduce a certain amount of ester class electron donor is one of common methods improving Ziegler-Natta type polypropylene catalyst activity.But in Ziegler-Natta type polyethylene catalysts, introduce ester class electron donor separately, its polymerization activity can not be significantly improved, but its copolymerization performance can be improved.As CN1726230 discloses, alcohol carrier is carried out physics dealcoholysis, re-use aluminum alkyls subsequently and carry out chemical dealcoholation, re-use the electron donors such as ester, ether, amine, ester and ketone after carrying titanium and aftertreatment is carried out to catalyzer, thus improve the copolymerized ability of catalyzer.As CN1798774 and CN101050248 discloses, alcohol carrier is carried out physics dealcoholysis, re-use titanium tetrachloride subsequently carry out chemical dealcoholation and carry titanium, re-use the electron donors such as ester class and ethers after carrying titanium and aftertreatment is carried out to catalyzer, thus improve the copolymerized ability of catalyzer.
If introduce multiple electron donor and composite electron donor in catalyst component, the synergy between the multiple electron donor of research display can not only significantly improve certain performance of catalyzer, also may give catalyzer multiple character.The present inventor studies discovery, when ester class and halogen ester class electron donor composite after, they significantly improve activity and the copolymerization performance of catalyzer.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst component for ethene slurry polymerization and catalyzer thereof, and this catalyzer has higher activity, makes it be applicable to ethene slurry polymerization processes, also has good copolymerized ability.Specifically, adopt aluminum alkyls as dealcoholysis agent, use ester class and halogen ester class electron donor as composite electron donor, be applied to the spherical catalyst of ethene slurry polymerization.
For a catalyst component for ethene slurry polymerization, this catalyst component comprises the reaction product of following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) organo-aluminium compound;
(4) ester compound;
(5) halogen ester compounds;
Magnesium alcoholate described in component (1) is general formula is MgCl
2the magnesium chloride alcohol adduct of-mROH, wherein R is C
1~ C
4alkyl, m is 0.1 ~ 4.0;
The general formula of the titanium compound 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;
Organo-aluminium compound general formula described in component (3) is AlR "
ax '
bh
c, R in formula " and be C
1~ C
14alkyl, X ' is halogen atom, and a is the integer of 1 ~ 3, and b, c are the integer of 0 ~ 3, and a+b+c=3;
Ester compound general formula described in component (4) is R
1cOOR
2, R in formula
1c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
1~ C
10straight or branched alkyl;
Halogen ester compounds general formula described in component (5) is X
n1r
3cOOR
4x
n2, R in formula
3c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1~ C
10straight or branched alkyl, X is halogen atom, and the value of n1 and n2 is 0,1,2, any one in 3, but be 0 when n1 with n2 is different;
Ratio between each component is in every mole of magnesium in component (1) magnesium chloride alcohol adduct, and component (2) titanium compound is 0.1 ~ 15.0 mole; Component (3) organo-aluminium compound is 0.1 ~ 5.0 mole; Component (4) ester compound is 0.1 ~ 5.0 mole; Component (5) halogen ester compounds is 0.1 ~ 5.0 mole.
Specifically, the general formula described in component (1) is MgCl
2the magnesium chloride alcohol adduct of-mROH is by C
1~ C
4low-carbon alcohol mix for 2.5:1 ~ 4:1 in molar ratio with magnesium chloride, cool rapidly after heating and melting, obtain the spheroidal particle containing 2.5 ~ 4.0 moles of alcohol per mole magnesium chlorides.This patent adopts the magnesium chloride alcohol adduct of non-dealcoholysis, and 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 associated viscera disclosed in it all introduces 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, and 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 etc.Preferred TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3.With TiCl
4for the best.
Organo-aluminium compound general formula described in component (3) is AlR "
ax '
bh
c, R in formula " and be C
1~ C
14alkyl, X ' is halogen atom, and a is the integer of 1 ~ 3, and b, c are the integer of 0 ~ 3, 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 alone, and also can be used in combination.
Ester compound general formula described in component (4) is R
1cOOR
2, R in formula
1c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
1~ C
10straight or branched alkyl.Particular compound, as one in the just own ester of methyl acetate, ethyl acetate, ethyl benzoate, n-butylbenzoate, methyl acrylate, ethyl propenoate, butyl acrylate, n-hexyl acetate, acetic acid n-octyl, 2-ethyl hexyl ethanoate, phenylformic acid, phenylformic acid n-octyl, phenylformic acid ester in the positive last of the ten Heavenly stems, n-octyl or Isooctyl acrylate monomer, is preferably ethyl acetate, acetic acid n-octyl and ethyl benzoate.
Halogen ester compounds general formula described in component (5) is X
n1r
3cOOR
4x
n2, R in formula
3c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1~ C
10straight or branched alkyl, X is halogen atom, and the value of n1 and n2 is 0,1,2, one in 3, but be 0 when n1 with n2 is different.Particular compound, as one in methyl chloroacetate, ethyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, 3-chloropropyl acetic ester, 4-chlorobutyl acetic ester, ethyl difluoro, 4-fluorophenyl acetic ester, benzyl acetate bromide, 4-brombutyl acetic ester, 4-iodine butylacetic acid ester, is preferably ethyl chloroacetate, ethyl dichloroacetate and 4-chlorobutyl acetic ester.
In catalyst component for ethene slurry polymerization of the present invention, the ratio between each reactant is in every mole of magnesium in component (1) magnesium chloride alcohol adduct, and component (2) titanium compound is 0.1 ~ 15.0 mole, is preferably 1.0 ~ 5.0 moles; Component (3) organo-aluminium compound is 0.1 ~ 5.0 mole, is preferably 1.0 ~ 3.0 moles; Component (4) ester compound is 0.1 ~ 5.0 mole, is preferably 0.1 ~ 1.0 mole; Component (5) halogen ester compounds is 0.1 ~ 5.0 mole, is preferably 0.1 ~ 1.0 mole.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
Magnesium chloride alcohol adduct described in component (1) is dispersed in inert solvent, obtains suspension.Inert solvent comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the saturated fatty hydro carbons inert solvent such as hydrogenated gasoline, kerosene.At-40 DEG C ~ 50 DEG C, said mixture and component (3) organo-aluminium compound, component (4) ester compound and (5) halogen ester compounds are carried out contact reacts, and mixture is slowly warming up to 20 ~ 60 DEG C, after the reaction regular hour, removing unreacted reactant and solvent, and adopt inert diluent to wash once or for several times, and then introduce component (2) titanium compound and react, then through inert diluent washing, catalyst component of the present invention is namely obtained.
Present invention also offers a kind of spherical catalyst for ethene slurry polymerization, it comprises the reaction product of following component:
(1) catalyst component of the invention described above;
(2) general formula is AlR " '
dx
3-dorgano-aluminium compound, R in formula " ' for hydrogen or carbonatoms are the alkyl of 1 ~ 20, X is halogen atom, 0<d≤3.
Component (2) formula of is AlR " '
dx
3-dorgano-aluminium compound, R in formula " ' can be the alkyl of 1 ~ 20 for hydrogen or carbonatoms, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; 0<d≤3.Particular compound is as Al (CH
3)
3, Al (CH
2cH
3)
3, Al (i-Bu)
3, AlH (CH
2cH
3)
2, AlH (i-Bu)
2, AlCl (CH
2cH
3)
2, Al
2cl
3(CH
2cH
3)
3, AlCl (CH
2cH
3)
2, AlCl
2(CH
2cH
3) etc. alkylaluminium cpd.Be preferably Al (CH
2cH
3)
3, Al (i-Bu)
3.Wherein aluminium is 5 ~ 500 with the mol ratio of the middle titanium of component (1) in component (2), preferably 20 ~ 200.
Liquid polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the inert solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene.
In order to regulate the molecular weight of final polymkeric substance, hydrogen is adopted to make molecular weight regulator.
The present inventor finds in the preparation process of the catalyst component for ethene slurry polymerization, introduce composite ester class electron donor and halogen ester class electron donor, catalyzer not only can be made to have higher activity, be applicable to ethene slurry polymerization, also there is good copolymerized ability.This catalyzer only uses the aluminum alkyls of small amount in addition, and thus cost is lower and waste liquid is little.
Embodiment
Testing method:
1. the relative weight percents of titanium elements in catalyst system: adopt spectrophotometry;
2. the relative weight percents of ester in catalyst system: adopt high performance liquid chromatography;
3. the mensuration (MI) of melt index: according to ASTMD1238-99.
4. the hexene unit content of polyethylene-hexene copolymerization gained powder: the method adopting nucleus magnetic resonance.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 that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (triethyl aluminum: 1.2M) and the 1ml ethyl acetate of 55ml triethyl aluminum, 1ml ethyl chloroacetate, is then warming up to 50 DEG C, and maintains reaction 4 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with ingredient of solid catalyst (containing 0.6 milligram of titanium) prepared by aforesaid method again, be warming up to 75 DEG C, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa(gauge pressure), be polymerized 2 hours under 80 DEG C of conditions, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with the 1-hexene of ingredient of solid catalyst (containing 0.6 milligram of titanium) prepared by aforesaid method and 15ml again, be warming up to 75 DEG C, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa(gauge pressure), be polymerized 2 hours under 80 DEG C of conditions, polymerization result is in table 2.
Embodiment 2
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
23.0C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (triethyl aluminum: 1.2M) and the 1ml acetic acid n-octyl of 65ml triethyl aluminum, 1ml ethyl dichloroacetate, is then warming up to 50 DEG C, and maintains reaction 4 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 5ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Embodiment 3
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (tri-n-hexyl aluminum: 1.2M) and the 1ml n-octyl of 40ml tri-n-hexyl aluminum, 1ml methyl chloroacetate, is then warming up to 50 DEG C, and maintains reaction 4 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Embodiment 4
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
23.0C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (tri-n-hexyl aluminum: 1.5M) and the 1ml ethyl benzoate of 55ml tri-n-hexyl aluminum, 0.5ml benzyl acetate bromide, is then warming up to 50 DEG C, and maintains reaction 4 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 6ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Embodiment 5
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (triethyl aluminum: 1.2M) and the 1ml ethyl benzoate of 50ml triethyl aluminum, 1ml4-chlorobutyl acetic ester, is then warming up to 50 DEG C, and maintains reaction 3 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Embodiment 6
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, and drip hexane solution (triethyl aluminum: 1.2M) and the just own ester of 1ml phenylformic acid of 55ml triethyl aluminum, 1ml ethyl difluoro, is then warming up to 50 DEG C, and maintains reaction 3 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Comparative example 1
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, drips hexane solution (triethyl aluminum: 1.2M) and the 2ml ethyl benzoate of 50ml triethyl aluminum, be then warming up to 50 DEG C, and maintain reaction 3 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
Comparative example 2
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 5.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 150ml, stir borehole cooling to-10 DEG C, drips hexane solution (tri-n-hexyl aluminum: 1.2M) and the 2ml ethyl chloroacetate of 50ml tri-n-hexyl aluminum, be then warming up to 50 DEG C, and maintain reaction 3 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 8ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow particle size distribution.Catalyzer composition is in table 1.
(2) ethylene polymerization: with embodiment 1, polymerization result is in table 2.
(3) polyethylene-hexene copolymerization: with embodiment 1, polymerization result is in table 2.
The composition of table 1 titanium-containing catalyst component
Table 2 polymer performance
As can be seen from the data of table 2, catalyst activity of the present invention and copolymerized ability significantly improve.
Claims (9)
1., for a catalyst component for ethene slurry polymerization, this catalyst component comprises the reaction product of following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) organo-aluminium compound;
(4) ester compound;
(5) halogen ester compounds;
Magnesium alcoholate described in component (1) is general formula is MgCl
2the magnesium chloride alcohol adduct of-mROH, wherein R is C
1~ C
4alkyl, m is 0.1 ~ 4.0;
The general formula of the titanium compound 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;
Organo-aluminium compound general formula described in component (3) is AlR "
ax '
bh
c, R in formula " and be C
1~ C
14alkyl, X ' is halogen atom, and a is the integer of 1 ~ 3, and b, c are the integer of 0 ~ 3, and a+b+c=3;
Ester compound general formula described in component (4) is R
1cOOR
2, R in formula
1c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
2c
1~ C
10straight or branched alkyl;
Halogen ester compounds general formula described in component (5) is X
n1r
3cOOR
4x
n2, R in formula
3c
1~ C
10straight chain, branched hydrocarbyl, cyclic hydrocarbon radical or aromatic hydrocarbyl, R
4c
1~ C
10straight or branched alkyl, X is halogen atom, and the value of n1 and n2 is 0,1,2, any one in 3, but be 0 when n1 with n2 is different;
Ratio between each component is in every mole of magnesium in component (1) magnesium chloride alcohol adduct, and component (2) titanium compound is 0.1 ~ 15.0 mole; Component (3) organo-aluminium compound is 0.1 ~ 5.0 mole; Component (4) ester compound is 0.1 ~ 5.0 mole; Component (5) halogen ester compounds is 0.1 ~ 5.0 mole.
2. the catalyst component for ethene slurry polymerization according to claim 1, is characterized in that component (4) ester compound is the one in methyl acetate, ethyl acetate, ethyl benzoate, n-butylbenzoate, methyl acrylate, ethyl propenoate or butyl acrylate, 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, n-octyl or Isooctyl acrylate monomer.
3. the catalyst component for ethene slurry polymerization according to claim 1, is characterized in that the halogen ester compounds of described component (5) is the one in methyl chloroacetate, ethyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, 3-chloropropyl acetic ester, 4-chlorobutyl acetic ester, ethyl difluoro, 4-fluorophenyl acetic ester, benzyl acetate bromide, 4-brombutyl acetic ester, 4-iodine butylacetic acid ester.
4. the catalyst component for ethene slurry polymerization according to claim 1, is characterized in that described component (2) titanium compound is TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3in one.
5. the catalyst component for ethene slurry polymerization according to claim 1, is characterized in that the organo-aluminium compound of described component (3) is Al (CH
2cH
3)
3, Al (n-C
6h
13)
3, Al (i-Bu)
3in one.
6. a preparation method for the catalyst component for ethene slurry polymerization according to claim 1, it comprises the following steps:
(1) the magnesium chloride alcohol adduct described in component (1) is dispersed in inert solvent, obtains suspension;
(2) suspension is carried out contact reacts in-40 ~ 50 DEG C with component (3) organo-aluminium compound, component (4) ester compound and component (5) halogen ester compounds;
(3) mixture of step (2) is slowly warming up to 20 ~ 60 DEG C, after the reaction regular hour, removing unreacted reactant, and adopt inert diluent to wash;
(4) add component (2) titanium compound to react, then adopt inert diluent washing, obtain catalyst component of the present invention.
7., for a catalyzer for ethene slurry polymerization, it comprises the reaction product of following component:
(1) catalyst component that one of Claims 1 to 5 is described;
(2) general formula is AlR " '
dx
3-dorgano-aluminium compound, R in formula " ' for hydrogen or carbonatoms are the alkyl of 1 ~ 20, X is halogen atom, 0<d≤3.
8. the catalyzer for ethene slurry polymerization according to claim 7, is characterized in that the mol ratio of aluminium and the middle titanium of component (1) in component (2) is 20 ~ 200.
9. catalyzer described in claim 7 closes the application in reaction or copolymerization at ethylene homo.
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|---|---|---|---|
| CN201210401752.XA CN103772542B (en) | 2012-10-19 | 2012-10-19 | A kind of catalyst component for ethene slurry polymerization and catalyzer thereof |
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| CN110240668A (en) * | 2019-06-24 | 2019-09-17 | 天津科技大学 | The internal electron donor of Ziegler-Natta catalyst, catalytic component, preparation method and applications |
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