CN105482003A - Carrier for ethylene polymerization catalyst and catalyst of carrier - Google Patents
Carrier for ethylene polymerization catalyst and catalyst of carrier Download PDFInfo
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- CN105482003A CN105482003A CN201410532200.1A CN201410532200A CN105482003A CN 105482003 A CN105482003 A CN 105482003A CN 201410532200 A CN201410532200 A CN 201410532200A CN 105482003 A CN105482003 A CN 105482003A
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Abstract
The invention provides a carrier for an ethylene polymerization catalyst and a catalyst of the carrier. The carrier comprises reactants of the following components: magnesium chloride/gallic acid derivatives/epoxy compounds with carbon-carbon double bonds/alcohol compounds/radical initiators. A mixed solution of the components is initiated by the radical initiators in the process of warming, and the carbon-carbon double bonds in a system can generate a polyreaction, so that the carrier with narrow particle size distribution and doped with polymers can be separated out. The polyethylene catalyst prepared through the carrier not only has the characteristic of narrow particle size distribution but also is high in hydrogen adjustment sensibility; the particle size distribution of obtained polymeric powder materials is particularly intensive, and less fine powder is generated.
Description
Technical field
The present invention relates to a kind of polymer-doped type carrier, ingredient of solid catalyst for vinyl polymerization or copolymerization, and containing the Catalysts and its preparation method of this ingredient of solid catalyst.
Background technology
Since Ziegler-Natta type polyolefin catalyst comes out, through the development of nearly 60 years, the resins such as the polyethylene produced by it and polypropylene have become global most important rosin products.In recent years, the common preparation method of one of Ziegler-Natta type polyolefin catalyst is: first prepare magnesium compound (or magnesium compound and electron donor formed the solid complex) carrier with certain particle shape and size distribution, alkoxyl magnesium carrier as described in patent CN102020534A, or the magnesium chloride/ethanolic vehicle etc. described in patent CN1091748A.Again by the method such as dealcoholysis, chlorination, be the skeleton structure of magnesium chloride by vector, complete the preparation process of polyolefin catalyst finally by load titanium chloride.
Modal magnesium compound (or magnesium compound/electron donor) carrier and magnesium chloride/ethanolic vehicle in this area, prior art uses ethanol and Magnesium Chloride Anhydrous to close at 110-130 degree alcohol usually, be distributed to white oil/silicone oil dispersion media high speed again stir and emulsification occurs, magnesium chloride alcohol adduct ball type carrier is obtained, as described in patent CN1091748A finally by chilling.In addition, polymkeric substance can also be introduced in magnesium chloride/ethanolic vehicle, as polyethers (CN101544710A) and polyester (CN101550205A) etc., thus give support/catalyst higher resistant to breakage ability.
In addition, art also discloses the support preparation method compared with multiple types.As CN102020534A and CN101663332A etc. discloses the method preparing alkoxyl magnesium carrier.Magnesium chloride/ethanol/varsol is disclosed and epoxy compounds reacts as WO2011/044761A1, prepare the method for novel ball magnesium compound carrier, its principle is ethanol/react between epoxy chloropropane and magnesium chloride, thus generates the magnesium compound being insoluble to solution system.As CN101554595A discloses the preparation method of the polymer-doped type carrier comprising magnesium chloride/styrol copolymer/silica gel/tetrahydrofuran (THF)/butyleneglycol component.
The physical strength of carrier and catalyzer possesses corresponding relation, if the physical strength of carrier is lower, it is also easily broken that wherethrough manages the catalyzer obtained, and can produce a certain amount of polyethylene fine powder in polymerization.Strengthen the toughness of carrier and physical strength avoids catalyst breakage, and then reduce the necessary ways of fine powder content in industrial production, and in carrier, introduce polymkeric substance be effective means.
In addition, according to the replication of Ziegler-Natta type olefin polymerization catalysis particle, if the size distribution of catalyst particle wider (span value is larger), the polyethylene powder so prepared also will have the wider character of size distribution (span value is larger).The powder of wide distribution usually also comprises a certain amount of comparatively meal material and is less than 190 object fine powders, and this steady running for fluidized-bed is disadvantageous.
Therefore, need a kind of polymer-doped type carrier of preparation and catalyzer, and this catalyst particle size narrow distribution.
The present inventor finds after deliberation, the solution of magnesium chloride/gallic acid-derivate/can be formed in inert hydrocarbon solvent with the epoxy compounds/alcohol compound of carbon-carbon double bond clear, this solution is in temperature-rise period, cause through radical initiator, carbon-carbon double bond in system can polymerization reaction take place, generate the polymkeric substance being insoluble to solution system, and then narrow diameter distribution can be separated out gradually and the carrier of doped polymer.Gallic acid-derivate, in this solution system, not only plays the effect of dissolving dispersion magnesium chloride and derivative thereof, as electron donor, can also be conducive to the hydrogen response improving catalyzer.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the polymer-doped type carrier that a kind of ethylene rolymerization catalyst uses, and the method is simple to operate, without the need to adjusting conventional equipment.And a kind of ethene polymerization catalyst component prepared by polymer-doped type carrier is provided, its catalyst component and promotor can polymerising ethylenes.The polyethylene catalysts prepared by this carrier not only has the feature of narrow diameter distribution, and hydrogen response is high, and the size distribution of gained polymerization powder concentrates especially and fine powder is less.
The polymer-doped type carrier that a kind of ethylene rolymerization catalyst of the present invention is used, this carrier comprises the reaction product of following component:
(1) magnesium compound;
(2) gallic acid-derivate;
(3) with the epoxy compounds of carbon-carbon double bond;
(4) alcohol compound;
(5) radical initiator;
Described magnesium compound be selected from one of them halogen atom in magnesium dihalide, magnesium dihalide molecular formula by-oxyl or halo-oxyl the one in the derivative of replacing, or their mixture;
The general formula of described gallic acid-derivate is
r in formula
1for C
1~ C
8alkyl, R
2for C
1~ C
4alkyl;
The described epoxy compounds with carbon-carbon double bond comprises with at least one in the oxide compound of the aliphatics alkene of carbon-carbon double bond, diolefine, halogenated aliphatic alkene, diolefine, glycidyl ether and inner ether;
Described alcohol compound comprise carbonatoms 1 ~ 18 fatty alcohol or aromatic alcohol at least one;
Described radical initiator comprises azo-initiator and peroxide initiator.
Magnesium compound described in component (1) comprises MgCl
2, MgBr
2, MgI
2, MgCl (OEt) and MgCl (OBu) etc.
Gallic acid-derivate described in component (2) comprises: 3,4,5-tri-butoxybenzoic acid ethyl ester, 3,4,5-tri-butoxybenzoic acid methyl esters, 3,4,5-tri-butoxybenzoic acid propyl ester, 3,4,5-triethoxy ethyl benzoate, 3,4,5-triethoxy methyl benzoate and 3, at least one in the compounds such as 4,5-tri-hexyloxybenzoate ethyl ester.
The epoxy compounds with carbon-carbon double bond described in component (3) comprises glycidyl methacrylate and glycidyl acrylate etc.
Alcohol compound described in component (4) comprises methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the trimethyl carbinol, hexanol, hexalin, octanol, isooctyl alcohol, phenylcarbinol, phenylethyl alcohol etc.
Radical initiator described in component (5) comprises at least one in benzoyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Ratio between each reactant is in every mole of magnesium, and gallic acid-derivate is 0.1 ~ 5.0 mole, and the epoxy compounds with carbon-carbon double bond is 0.1 ~ 5.0 mole, and alcohol compound is 0.1 ~ 5.0 mole, and radical initiator is 0.0001 ~ 0.05 mole.
The preparation method of a kind of polymer-doped type carrier used for ethylene rolymerization catalyst of the present invention, comprises the steps:
(1) magnesium compound described in component (1) is dispersed in hydro carbons inert solvent, obtains suspension;
(2) in suspension, add the gallic acid-derivate described in component (2), the epoxy compounds with carbon-carbon double bond described in component (3) and the alcohol compound described in component (4), after 20 ~ 50 DEG C of reaction regular hours, form homogeneous transparent solution;
(3) at 20 ~ 50 DEG C, the radical initiator described in component (5) is added in the homogeneous transparent solution of step (2), solids is separated out in slow temperature-rise period, after the reaction regular hour, removing unreacted reactant, and adopt inert diluent to wash, obtain polymer-doped type carrier of the present invention.
The invention still further relates to a kind of catalyst component for vinyl polymerization, it comprises the reaction product of following component:
(1) above-mentioned polymer-doped type carrier;
(2) one or more are by general formula Ti (OR
3)
nx
4-nshown titanium compound, R in formula
3for C
1~ C
8alkyl, X is halogen atom, 0≤n≤3;
(3) one or more are by general formula AlR '
ax
bh
cshown organometallic compound, in formula, R ' is C
1~ C
14alkyl, X is halogen, and a, b, c are the integer of 0 ~ 3, and a+b+c=3;
(4) one or more electron donor compounds, are selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and aliphatic ketone;
Ratio wherein between each reactant is in every mole of magnesium in the polymer-doped type carrier described in component (1), and component (2) titanium compound is 0.1 ~ 15.0 mole; Component (3) organometallic compound is 0.1 ~ 5.0 mole; Component (4) electron donor compound is 0.1 ~ 5.0 mole.
Titanium compound general formula described in component (2) is Ti (OR
3)
nx
4-n, R in formula
3for 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.
The general formula of the organometallic compound described in component (3) is AlR '
ax
bh
cshown in, in formula, R ' is C
1~ C
14alkyl, X is halogen, and a, 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 may be used alone, two or more kinds can also be used in combination.
Electron donor compound described in component (4) is selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and aliphatic ketone etc., is preferably C
1~ C
4the alkyl ester of aliphatic saturated monocarboxylic acid, C
1~ C
8the alkyl ester of aromatic carboxylic acid, C
2~ C
12aliphatic ether, C
3~ C
4cyclic ethers, C
3~ C
6saturated fatty ketone.Particular compound is as methyl-formiate, ethyl acetate, butylacetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK) etc., these electron donor compounds both may be used alone, two or more kinds can also be used in combination.
The preparation method of the catalyst component for ethylene polymerization of the present invention, it comprises the following steps:
(1) by the polymer-doped type support dispersion described in component (1) in hydro carbons inert solvent, obtain suspension;
(2) suspension is carried out contact reacts in-40 ~ 50 DEG C and component (3) organo-aluminium compound and one or more electron donor compounds of component (4);
(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.
Present invention also offers a kind of catalyzer for vinyl polymerization or copolymerization, 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, in formula, R is hydrogen or carbonatoms is the alkyl of l ~ 20, and X is halogen atom, 0<d≤3.
Component (2) formula of is AlR
dx
3-dorgano-aluminium compound, in formula, R can be the alkyl of l ~ 20 for hydrogen or carbonatoms, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; 0<d≤3.Particular compound is as Al (CH
3)
3, Al (CH
2cH
3)
3, Al (i-Bu)
3, AlH (CH
2cH
3)
2, AlH (i-Bu)
2, AlCl (CH
2cH
3)
2, Al
2cl
3(CH
2cH
3)
3, AlCl (CH
2cH
3)
2, AlCl
2(CH
2cH
3) etc. alkylaluminium cpd.Be preferably Al (CH
2cH
3)
3, Al (i-Bu)
3.Wherein aluminium is 5 ~ 500 with the mol ratio of the middle titanium of component (1) in component (2), preferably 20 ~ 200.
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 after deliberation, the solution of magnesium chloride/gallic acid-derivate/can be formed in inert hydrocarbon solvent with the epoxy compounds/alcohol compound of carbon-carbon double bond clear, this solution is in temperature-rise period, cause through radical initiator, carbon-carbon double bond in system can polymerization reaction take place, thus can separate out narrow diameter distribution and the carrier of doped polymer.The polyethylene catalysts prepared by this carrier not only has the feature of narrow diameter distribution, and hydrogen response is high, and the size distribution of gained polymerization powder concentrates especially and fine powder is less.
Embodiment
Testing method:
1. the relative weight percents of titanium elements in catalyst system: adopt spectrophotometry;
2. the relative weight percents of polymkeric substance in catalyst system: adopt core magnetic survey;
3, the molecular weight of polymkeric substance in catalyst system, is measured by gel chromatography PL220;
4, the mensuration (MI/2.16Kg) of melt index: according to ASTMD1238-99;
With embodiment, the present invention is described below, but and the unrestricted scope of the invention.
Embodiment 1
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 90ml toluene, 15g3,4,5-tripropoxy methyl benzoate, 8.0ml glycidyl methacrylate, 3ml ethanol join in reactor, under mixing speed 450rpm, temperature are the condition of 40 DEG C, and constant temperature 2 hours.Add Diisopropyl azodicarboxylate 0.08g to system, be slowly warming up to 90 degree, carrier particle is separated out gradually.Constant temperature 1 hour, elimination mother liquor, through inert diluent washing for several times.Transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtain the polymer-doped type carrier of narrow diameter distribution.
Embodiment 2
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 100ml toluene, 25g3,4,5-tri-butoxybenzoic acid ethyl ester, 5.0ml glycidyl acrylate, 6ml ethanol join in reactor, under mixing speed 400rpm, temperature are the condition of 30 DEG C, and constant temperature 2 hours.Add benzoyl peroxide 0.05g to system, be slowly warming up to 90 degree, carrier particle is separated out gradually.Constant temperature 1 hour, elimination mother liquor, through inert diluent washing for several times.Transferred them in chromatography funnel by hexane, dry up with high pure nitrogen, obtain the polymer-doped type carrier of narrow diameter distribution.
Embodiment 3
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add the polymer-doped type carrier of 4.0g (being prepared by embodiment 1) successively, hexane 100ml, stir borehole cooling to-10 DEG C, drip hexane solution (triethyl aluminum: 1.2M) and the 0.5ml ethyl benzoate of 40ml triethyl aluminum, then be warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml 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 ingredient of solid catalyst of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with ingredient of solid catalyst (containing 0.6 milligram of titanium) prepared by aforesaid method again, be warming up to 70 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) polyreaction:
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with ingredient of solid catalyst (containing 1.8 milligrams of titaniums) prepared by aforesaid method again, be warming up to 70 DEG C, pass into hydrogen and make still internal pressure reach 0.58Mpa, then pass into ethene and make stagnation pressure in still reach 0.73Mpa (gauge pressure), be polymerized 2 hours under 80 DEG C of conditions, polymerization result is in table 3.
Embodiment 4
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add the polymer-doped type carrier of 5.0g (being prepared by embodiment 1) successively, hexane 100ml, stir borehole cooling to-10 DEG C, drip hexane solution (triethyl aluminum: 1.2M) and the 0.5ml acetic acid n-octyl of 50ml triethyl aluminum, then be warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml 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 ingredient of solid catalyst of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: 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 the polymer-doped type carrier of 3.0g (being prepared by embodiment 2) successively, hexane 100ml, stir borehole cooling to-10 DEG C, drip hexane solution (tri-n-hexyl aluminum: 1.0M) and the 0.5ml butyl benzoate of 20ml tri-n-hexyl aluminum, then be warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 20ml, 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 ingredient of solid catalyst of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: 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 the polymer-doped type carrier of 3.0g (being prepared by embodiment 2) successively, hexane 100ml, stir borehole cooling to-10 DEG C, drip hexane solution (tri-n-hexyl aluminum: 1.0M) and the 0.5ml tetrahydrofuran (THF) of 20ml tri-n-hexyl aluminum, then be warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 30ml, 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 ingredient of solid catalyst of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2 and table 3.
Comparative example 1
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 4.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexane 100ml, stir borehole cooling to-10 DEG C, drip the hexane solution (triethyl aluminum: 1.2M) of 40ml triethyl aluminum, be then warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml 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.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2 and table 3.
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 100ml, stir borehole cooling to-10 DEG C, drip the hexane solution (tri-n-hexyl aluminum: 1.0M) of 50ml tri-n-hexyl aluminum, ethyl benzoate 2ml, is then warming up to 50 DEG C, and maintains reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexane is room temperature washing twice.Add 100ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 15ml, 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.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
Comparative example 3
By 4.0 grams of magnesium chlorides, 90ml toluene, 15g3,4,5-tripropoxy methyl benzoate, 8.0ml epoxy chloropropane, 3ml ethanol join in reactor, under mixing speed 450rpm, temperature are the condition of 40 DEG C, and constant temperature 2 hours.Slowly be warming up to 90 degree, constant temperature 2 hours.
Experimental phenomena: dissolution system is through 40 DEG C of constant temperature after 2 hours, and magnesium chloride dissolves completely, obtains the solution of clear.But be warming up to 90 degree and constant temperature after 2 hours, system is still the solution of clear, separates out without any solids.As can be seen here, in the solution system temperature-rise period of the embodiment of the present invention 1/2, cause through radical initiator, the carbon-carbon double bond polymerization reaction take place in system, generating the polymkeric substance being insoluble to solution system, is the key that solution system can separate out polymer-doped type carrier gradually.
The composition of table 1 catalyst component
From the data of table 1, very narrow by gained catalyst component size distribution of the present invention, span value is not higher than 0.7.The narrower span value of polymer-doped type carrier comes from its slow precipitation mode.And the span value of comparative example catalyzer is limited to the size distribution of spherical magnesium chloride/ethanolic vehicle.
The size distribution of table 2 catalyst performance and powder
From the data of table 2, the polyethylene powder gone out by gained catalyst preparing of the present invention, melting index is higher, and size distribution is concentrated especially, the powder of more than 70wt% concentrates on 55 orders, and more than 16 orders comparatively meal material content is less than 3wt%, and the fine powder content below 190 orders is less than 0.5wt%.As can be seen here, gained catalyst particle of the present invention is not easily broken in the course of the polymerization process.
The hydrogen response of table 3 catalyzer
As can be seen from the data of table 3, catalyzer hydrogen response of the present invention is good.
Claims (17)
1. the polymer-doped type carrier that ethylene rolymerization catalyst is used, this carrier comprises the reaction product of following component:
(1) magnesium compound;
(2) gallic acid-derivate;
(3) with the epoxy compounds of carbon-carbon double bond;
(4) alcohol compound;
(5) radical initiator;
Described magnesium compound be selected from one of them halogen atom in magnesium dihalide, magnesium dihalide molecular formula by-oxyl or halo-oxyl the one in the derivative of replacing, or their mixture;
The general formula of described gallic acid-derivate is
r in formula
1for C
1~ C
8alkyl, R
2for C
1~ C
4alkyl;
The described epoxy compounds with carbon-carbon double bond comprises with at least one in the oxide compound of the aliphatics alkene of carbon-carbon double bond, diolefine, halogenated aliphatic alkene, diolefine, glycidyl ether and inner ether;
Described alcohol compound comprise carbonatoms 1 ~ 18 fatty alcohol or aromatic alcohol at least one;
Described radical initiator comprises azo-initiator and peroxide initiator.
2. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, it is characterized in that ratio between each reactant is in every mole of magnesium, gallic acid-derivate is 0.1 ~ 5.0 mole, epoxy compounds with carbon-carbon double bond is 0.1 ~ 5.0 mole, alcohol compound is 0.1 ~ 5.0 mole, and radical initiator is 0.0001 ~ 0.05 mole.
3. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, is characterized in that described gallic acid-derivate is 3,4,5-tri-butoxybenzoic acid ethyl ester, 3,4,5-tri-butoxybenzoic acid methyl esters, 3,4,5-tri-butoxybenzoic acid propyl ester, 3,4,5-triethoxy ethyl benzoates, 3,4, at least one in 5-triethoxy methyl benzoate and 3,4,5-tri-hexyloxybenzoate ethyl ester.
4. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, is characterized in that the described epoxy compounds with carbon-carbon double bond is selected from glycidyl methacrylate and glycidyl acrylate.
5. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, is characterized in that described radical initiator is selected from least one in benzoyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, is characterized in that described alcohol compound is selected from least one in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the trimethyl carbinol, hexanol, hexalin, octanol, isooctyl alcohol, phenylcarbinol, phenylethyl alcohol.
7. the polymer-doped type carrier that a kind of ethylene rolymerization catalyst according to claim 1 is used, is characterized in that described magnesium compound is selected from MgCl
2, MgBr
2, MgI
2, MgCl (OEt) and MgCl (OBu).
8., according to the preparation method of the polymer-doped type carrier used of a kind of ethylene rolymerization catalyst one of claim 1-7 Suo Shu, comprise the steps:
(1) magnesium compound is dispersed in hydro carbons inert solvent, obtains suspension;
(2) in suspension, add gallic acid-derivate, with the epoxy compounds of carbon-carbon double bond and alcohol compound, after 20 ~ 50 DEG C of reaction regular hours, form homogeneous transparent solution;
(3) in 20 ~ 50 DEG C of homogeneous transparent solution to step (2), radical initiator is added, solids is separated out in slow temperature-rise period, after the reaction regular hour, removing unreacted reactant, and adopt inert diluent to wash, obtain polymer-doped type carrier.
9., for a catalyst component for ethylene polymerization, it is characterized in that the reaction product comprising following component:
(1) the polymer-doped type carrier that the ethylene rolymerization catalyst that one of claim 1-7 is described is used;
(2) at least one general formula is Ti (OR
3)
nx
4-ntitanium compound, R in formula
3for C
1~ C
8alkyl, X is halogen atom, 0≤n≤3;
(3) at least one is by general formula AlR
a' X
bh
cshown organometallic compound, in formula, R ' is C
1~ C
14alkyl, X is halogen, and a, b, c are the integer of 0 ~ 3, and a+b+c=3;
(4) at least one electron donor compound, is selected from fatty ester/aromatic ester, aliphatic ether/cycloaliphatic ether and aliphatic ketone;
Ratio wherein between each reactant is in every mole of magnesium in described polymer-doped type carrier, and titanium compound is 0.1 ~ 15.0 mole; Organometallic compound is 0.1 ~ 5.0 mole; Electron donor compound is 0.1 ~ 5.0 mole.
10. a kind of catalyst component for ethylene polymerization according to claim 9, is characterized in that size distribution Span is less than or equal to 0.7.
11. a kind of catalyst components for ethylene polymerization according to claim 9, is characterized in that described titanium compound is selected from 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.
12. a kind of catalyst components for ethylene polymerization according to claim 9, is characterized in that described organometallic compound is selected from 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).
13. a kind of catalyst components for ethylene polymerization according to claim 9, is characterized in that described electron donor compound is selected from methyl-formiate, ethyl acetate, butylacetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK).
The preparation method of 14. a kind of catalyst components for ethylene polymerization according to claim 9, it comprises the following steps:
(1) by described polymer-doped type support dispersion in hydro carbons inert solvent, obtain suspension;
(2) suspension is carried out contact reacts in-40 ~ 50 DEG C and organo-aluminium compound and at least one electron donor compound;
(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 titanium compound to react, then adopt inert diluent washing, obtain catalyst component of the present invention.
15. 1 kinds of catalyzer for ethylene polymerization, it comprises the reaction product of following component:
(1) catalyst component according to claim 9;
(2) general formula is AlR "
dx
3-dorgano-aluminium compound, R in formula " for hydrogen or carbonatoms are the alkyl of l ~ 20, X is halogen atom, 0<d≤3.
16. catalyzer for ethylene polymerization according to claim 15, is characterized in that the mol ratio of aluminium and the middle titanium of component (1) in component (2) is 20 ~ 200.
17. catalyzer for ethylene polymerization according to claim 15 close the application in reaction or copolymerization at ethylene homo.
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Cited By (1)
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|---|---|---|---|---|
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