CN102432710A - Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst - Google Patents
Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst Download PDFInfo
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- CN102432710A CN102432710A CN2010105027178A CN201010502717A CN102432710A CN 102432710 A CN102432710 A CN 102432710A CN 2010105027178 A CN2010105027178 A CN 2010105027178A CN 201010502717 A CN201010502717 A CN 201010502717A CN 102432710 A CN102432710 A CN 102432710A
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Abstract
The invention discloses a preparation method of an ethylene polymerization catalyst carrier, catalyst components and a catalyst. The ethylene polymerization catalyst carrier is a polymer-doped ball-type carrier. The catalyst components are ethylene polymerization ball-type catalyst components and are prepared from the ethylene polymerization catalyst carrier obtained by the preparation method. The catalyst comprises the ethylene polymerization ball-type catalyst components. A polymer-containing magnesium chloride-alcohol compound is subjected to high-speed stirring emulsification and then is cooled rapidly to form the polymer-doped ball-type carrier. The ethylene polymerization ball-type catalyst components comprise reaction products of the following ingredients of 1, the polymer-doped ball-type carrier subjected to part dealcoholization, 2, one or more titanium compounds, 3, one or more organometallic compounds, and 4, one or more electron donor compounds selected from carboxylates, aliphatic ethers, cyclic aliphatic ethers or aliphatic ketones. Through the catalyst, ball-type polyethylene powder can be prepared. The catalyst has high activity. Polymer powder prepared by the catalyst has high apparent density, wide molecular weight distribution (MWD) and low fine powder content.
Description
Technical field
The present invention relates to that a kind of ethylene homo closes or preparation method, catalyst component and the catalyzer of copolymerization ball shape catalyst carrier, belong to field of olefin polymerisation.
Background technology
The vinyl polymerization ball shape catalyst that contains the Ti/Mg mixture industriallization for many years, this type of catalyzer can be prepared with the catalyzer form similar, has better flowability and tap density, and need not the ball-type polyethylene powder of granulation.The synthetic of ball-type carrier is the precondition of making the vinyl polymerization ball shape catalyst; Prior art uses ethanol and Magnesium Chloride Anhydrous to close at 110-130 degree alcohol usually; Again it being distributed to white oil/silicone oil dispersion medium high speed stirs and generation emulsification; After chilling obtains magnesium chloride alcohol adduct ball-type carrier, CN93102795.0 is said like patent.
But because the physical strength of this type of ball-type carrier is lower, the vinyl polymerization ball shape catalyst that the wherethrough reason obtains is also broken easily, in polymerization, can produce a certain amount of Vilaterm fine powder.Fine powder can be attached to the inwall of reactor drum in industrial production, cause heat transfer inhomogeneous, has increased heat exhaustion; Can in pipeline, deposit again simultaneously, finally cause device to stop; Fine powder possibly have different molecular weight, MWD and the degree of branching with respect to the polyethylene powder of normal size in addition, therefore maybe more difficult uniform mixing in granulation process, cause local defect, and therefore should reduce the generation of fine powder as far as possible.The toughness and the physical strength that strengthen carrier are to avoid catalyst breakage, and then reduce the necessary ways of fine powder content in the industrial production.If in magnesium chloride/monohydroxy-alcohol carrier, introduce polymkeric substance, then polymkeric substance can form network interpenetrating structure (IPN) with carrier, strengthens the anti-breaking capacity of carrier.
The MWD of polyethylene product (MWD) has remarkable influence for the mechanical property of product and the rheological property of melt.The advantage of polyethylene with wide molecular weight distribution product is that its HMW part can be given product mechanical property preferably, like tensile strength and impact-resistance etc.; And its low molecular weight part has been given the product better machining property.Therefore the polyethylene product for preparing wide molecular weight distribution has become the focus of present research.In the prior art, adopt the supported catalyst that has two kinds of active ingredients to prepare the polyethylene product of wide molecular weight distribution usually.In addition, the MWD that other component of doping also can be widened polyethylene product in the carrier of catalyzer.Studied the adulterated effect of Ti/Mg support of the catalyst for 71 pages like synthetic resins and 2007 24 volumes of plastics; The result finds that the maximum effect of doping component is exactly the cloud density that has changed the titanium active site; Make the active site that has same structure but load on the different carriers matrix have different activity, thereby widen the MWD (MWD) of product.If therefore in magnesium chloride/monohydroxy-alcohol carrier, introduce polymeric constituent, then polymkeric substance can play the adulterated effect of carrier, changes the activity that loads to the titanium active site on the polymkeric substance, the MWD (MWD) that therefore can widen product.
Patent like application number 200810102904.X is incorporated into polyethers in magnesium chloride/monohydroxy-alcohol carrier, has obtained a kind of novel ternary component ball-type carrier.Can prepare the ball-type polyolefin catalyst through this carrier, this catalyst applications is when propylene polymerization, and polymeric species is good, and fine powder is few.Yet this ball-type polyolefin catalyst does not possess the function of widening the polyolefin products MWD.In addition, this patent does not comprise the specific embodiment of this catalyst applications in vinyl polymerization.
Patent like application number 200810103228.8 is incorporated into polyester in magnesium chloride/monohydroxy-alcohol carrier, has obtained a kind of novel ternary component ball-type carrier.Can prepare the ball-type polyolefin catalyst through this carrier, this catalyst applications is when propylene polymerization, and activity and degree of isotacticity are higher.Yet not possessing, this ball-type polyolefin catalyst do not widen polyethylene product MWD and the function that reduces fine powder content in the product.
Patent like application number 200910098801.5 adopts processing homogeneous solution after styrol copolymer/silica gel/THF/butyleneglycol mixing.The tetrahydrofuran solution of magnesium chloride is joined in the aforementioned solution, stir and form slurries shape carrier, add hexane again and can form polymer-doped carrier.Can prepare polymer-doped type polyolefin catalyst through this carrier.Because the doping effect of polymkeric substance, this type of catalyzer can be prepared the polyolefin products of MWD broad.Yet because polymkeric substance mainly is distributed in the skin of catalyzer, and middle level and internal layer still are made up of organic molecule and inorganics, therefore do not possess the function that reduces fine powder content in the polymerization product.
Patent like application number 93116992.5 also is incorporated into polyethers in the catalyzer.This catalyst activity is high, and it is few to obtain fine powder, high-bulk-density and high normal polyolefin products.Yet pfpe molecule amount related in this patent is low, more near the category of organic molecule; And this catalyzer does not possess the ball-type form, can't prepare the polyethylene powder of ball-type.
Therefore, need a kind of new method of exploitation to prepare polymer-doped type ball-type polyethylene catalysts, and this new catalyst should have following outstanding characteristics: 1, can produce the ball-type polyethylene powder; 2, the polyethylene powder of preparation should have the characteristics that MWD is wide and fine powder is few.
The inventor finds after deliberation, and polymkeric substance such as TKK 021 and PVA are introduced magnesium chloride alcohol adduct ball-type carrier, can obtain having the polymer-doped type ball-type carrier of anti-breaking capacity.Dealcoholysis through to examples of such carriers is handled with year titanium, can obtain polymer-doped type ball-type polyethylene catalysts.Through this type of catalyzer, can prepare the ball-type polyethylene powder, and polyethylene powder have the wide and few characteristics of fine powder of MWD.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polymer-doped type ball-type carrier of vinyl polymerization ball shape catalyst use, this method is simple to operate, need not conventional equipment is adjusted.
And the vinyl polymerization ball type catalytic component that the polymer-doped type ball-type preparing carriers of this method preparation of a kind of usefulness is provided, its catalyst component and promotor can polymerising ethylenes.This ball shape catalyst has higher anti-breaking capacity, can produce the globular polymer powder, and fine powder is few, and the MWD of polymkeric substance is wide.
A kind of preparation method who is used for the polymer-doped type ball-type carrier of ethylene rolymerization catalyst of the present invention comprises the steps:
(1) under nitrogen protection; Magnesium Chloride Anhydrous/monohydroxy-alcohol/polymkeric substance is joined in the reactor drum that has stirring by a certain percentage; The alcohol that heats up closes the magnesium chloride alcohol adduct melt that obtains containing polymkeric substance; Add emulsifying agent again and further stir, subsequently it is distributed to white oil/silicone oil dispersion agent high speed and stirs to form emulsion, the cool quickly through refrigerant forms ball-type carrier suspension liquid again;
(2) the ball-type carrier suspension liquid that is generated is filtered, with hexane wash for several times, nitrogen dries up and can obtain polymer-doped type ball-type carrier again;
Described monohydroxy-alcohol is a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, octanol or isooctyl alcohol or its mixture; Described polymkeric substance is to have in the polymkeric substance of following functional group one or more ,-OH ,-NH
2,-COOH ,-CN ,-X ,-O-,-CO-,-CO-NH-,-NH-,-Ph ,-SO-,-COOR ,-SH ,-SO
3H ,-Ar ,-ArX, the number-average molecular weight of said polymkeric substance is below 500,000;
The chemical constitution of ball-type carrier is MgCl
2NROHPolymer, n=2.3-3.8 wherein, the mass ratio of polymkeric substance in the ball-type carrier is 1-50%.
Described monohydroxy-alcohol is C
1～C
8Straight or branched alcohol, concrete like methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, octanol, isooctyl alcohol etc.Particular methanol, ethanol, propyl alcohol, isooctyl alcohol.Most preferably be and be ethanol, isooctyl alcohol.Wherein the mol ratio of monohydroxy-alcohol and magnesium chloride is 2.3-3.8.
Dispersant system adopts the nonpolar chemical inert solvent with certain viscosity, like white oil, silicone oil, Yellow Protopet 2A, kerosene etc., is preferably white oil and silicone oil.Refrigerant is the lower varsol of boiling point, like hexane, heptane, decane, sherwood oil etc., and preferred hexane.
The mass ratio of polymkeric substance in the ball-type carrier is 1～50%, and be preferred 10～40%, most preferably 20～30%.The polymkeric substance of introducing in the ball-type carrier is like cellulose derivatives such as FM, CMC 99.5, methylcellulose gum, TKK 021, Natvosol, hydroxypropylcellulose, hydroxypropylcellulose, hypromellose peptide acid esters.Polymethyl acrylic acid, polymethylmethacrylate, polyethyl methacrylate, polypropylmethacryla,es; The methyl butyl polyacrylate, ROHM, polymethyl acrylate, polyethyl acrylate; The ROHM propyl ester, butyl polyacrylate, poly hydroxy ethyl acrylate; The polymethyl acrylic acid hydroxypropyl acrylate, PHEMA, ROHM hydroxypropyl acrylate etc. gathers (methyl) vinylformic acid (ester) analog derivative.PVA, polyvinyl proprionate gathers vinyl butyrate, gathers the valeric acid vinyl acetate, gathers the capric acid vinyl acetate, and the polyoxyethylene lauryl vinyl acetate gathers vinyl cinnamate, gathers Vinyl crotonate, gathers poly carboxylic acid vinyl esters verivates such as NSC 11801.Nylon-6, nylon-66, polymeric amide such as nylon-1010, polyimide, complete fragrant polyamide-based verivate.Starch based verivate and chitosan analog derivative.Polyacrylonitrile, HPMA, maleic anhydride-styrene copolymers, SE, polyvinylidene dichloride, PVF, SEPIGEL 305; Z 150PH, polyvinyl alkyl oxide, polyoxymethylene, resol, terylene; Polycarbonate, unsaturated polyester, Synolac, Polyurethane; Polyureas, polysulfones, urea aldehyde gathers functional polymers such as sulphur and ZGK 5.Preferred, ethyl, PHEMA, PVA and starch.Most preferably TKK 021 and PVA.
Emulsifying agent used in the present invention is the water-in-oil-type tensio-active agent; Comprise the polyvalent alcohol nonionogenic tenside; Like sorbitan fatty acid ester; Commodity are called sapn (span) and polyoxyethylene tensio-active agent, and are concrete like polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan fatty ester, commodity OP by name and tween (Tween).Its HLB (hydrophile-lipophile balance value) value is advisable with 2～8, is preferably 3～6; The consumption of emulsifying agent is advisable with 1～10%wt of dispersion agent, is preferably 1～5%wt.Can use single surfactant, also can use two or more mixed surfactant.
The invention still further relates to a kind of ball type catalytic component that is used for vinyl polymerization, it comprises the reaction product of following component:
(1) the ball-type carrier for preparing among the preparation method of the present invention is through the product of part dealcoholysis;
(2) one or more are like general formula Ti (OR)
nX
4-nShown titanium compound, R is C in the formula
1～C
8Alkyl, X is a halogen atom, 0≤n≤4;
(3) one or more are like general formula AlR '
aX '
bH
cShown organometallic compound, R ' is C in the formula
1～C
14Alkyl, X ' is a halogen, a, b, c are 0～3 integer, and a+b+c=3;
(4) one or more electron donor compounds are selected from carboxylicesters, aliphatic ether, cycloaliphatic ether or alkanone;
The polymer-doped type ball-type carrier of part dealcoholysis described in the component (1) is through with the mode that ball-type carrier of the present invention purges through hot nitrogen or the vacuum shake is taken out, and regulates its pure content.Find through experiment, in 0.1～3.8 moles of alcohol per mole magnesium chloride scope, all can obtain activity catalyzer preferably.Preferable range is in 0.2～2 moles of alcohol per mole magnesium chloride scope.
Titanium compound general formula described in the component (2) is Ti (OR)
nX
4-n, R is C in the formula
1-C
8Alkyl, X is a halogen atom, 0≤n≤4 comprise: TiCl
4, TiBr
4, TiI
4, Ti (OC
2H
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4H
9) Cl
3, Ti (OC
2H
5) Br
3, Ti (OC
2H
5)
2Cl
2, Ti (OCH
3)
2Cl
2, Ti (OCH
3)
2I
2, Ti (OC
2H
5)
3Cl, Ti (OCH
3)
3Cl, Ti (OC
2H
5)
3I, Ti (OC
2H
5)
4, Ti (OC
3H
7)
4, Ti (OC
4H
9)
4Deng.Preferred TiCl
4, Ti (OC
2H
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4H
9) Cl
3, Ti (OC
4H
9)
4With TiCl
4Be the best.These titanium compounds both can use separately, also can make up use more than 2 kinds.
The general formula of the organometallic compound described in the component (3) is AlR '
aX '
bH
cShown organometallic compound, R ' is C in the formula
1～C
14Alkyl, X ' is a halogen, a, b, c are 0～3 integer, and a+b+c=3.Particular compound is like 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) wait alkylaluminium cpd, wherein be preferably Al (CH
2CH
3)
3, Al (n-C
6H
13)
3, Al (i-Bu)
3Most preferably be Al (CH
2CH
3)
3These organometallic compounds both can use separately, also can make up use more than 2 kinds.
Electron donor compound described in the component (4) is selected from carboxylicesters, aliphatic ether, cyclic aliphatic ether or aliphatic ketone, is preferably C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～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 as: methyl-formiate, ETHYLE ACETATE, butylacetate, ether, hexyl ether, THF, acetone and MIBK etc., these electron donor compounds both can use separately, also can make up use more than 2 kinds.
Vinyl polymerization or the copolymerization ball type catalytic component of being used for of the present invention, the ratio between each reactant is in every mole of magnesium in the polymer-doped type ball-type carrier of component (1) part dealcoholysis, 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.
Catalyst component of the present invention can adopt following method preparation:
The described polymer-doped type ball-type carrier of component (1) is dispersed in the inert solvent, obtains suspension-s.Dispersion medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, saturated fatty hydro carbons inert solvent such as hydrogenated gasoline, kerosene.In the presence of component (4) electron donor compound,, above-mentioned polymer-doped type ball-type carrier suspension-s and component (3) organometallic compound are carried out contact reacts at-40 ℃～50 ℃; And mixture slowly is warming up to 20～60 ℃, after the reaction regular hour, remove unreacted reactant and solvent; And adopt inert diluent to wash once or several; And then introduce component (2) titanium compound and react, through the inert diluent washing, promptly obtain catalyst component of the present invention then.
The present invention also provides a kind of ball shape catalyst that is used for vinyl polymerization.
A kind of ball shape catalyst that is used for vinyl polymerization, it comprises the reaction product of following component:
(1) catalyst component of the invention described above;
(2) general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, 0＜n≤3.
Component (2) formula of is AlR
nX
3-nOrgano-aluminium compound, R can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen or carbonatoms in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is like 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) wait alkylaluminium cpd.Be preferably Al (CH
2CH
3)
3, Al (i-Bu)
3Wherein the mol ratio of the middle titanium of aluminium and component (1) is 5～500 in the component (2), preferred 20～200.
Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
Medium comprises during liquid polymerization: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvent such as 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.
Embodiment
Further describe the present invention below in conjunction with embodiment, be not used for limiting scope of the present invention.
Testing method:
The content of titanium in the catalyzer: adopt spectrophotometry.
The mensuration of polymer stacks density: adopt (ASTM D1895) plastics apparent density, the TP of bulkfactor and pouring into property is measured.
Polymer particle size Determination of distribution: adopt standard sieve to sieve.
Embodiment 1
, first reaction kettle of reflux exchanger adds absolute ethyl alcohol 36.5ml in being housed; Magnesium Chloride Anhydrous 21.3g; TKK 021 (EC) 5g, sapn (80) 5ml stirs down and heats up; Treat that magnesium chloride and TKK 021 dissolve white oil/silicone oil mixed solution that the back adds 150ml fully, keep certain hour under 120 ℃.Have in second reaction kettle of high speed agitator at another, add white oil/silicone oil mixed solution of 200ml, and be preheating to 120 ℃; Solution in first reaction kettle is pressed into rapidly, and maintains 120 ℃, with rotating speed 3000rpm high-speed stirring for some time; Under agitation the material in second reactor drum is transferred to and adds the 2000ml hexane in advance, and be cooled in-25 ℃ the 3rd reactor drum, keep the outlet temperature in this reactor drum to be no more than 0 ℃; Suction filtration; With hexane wash for several times, after nitrogen dries up, obtain polymer-doped type ball-type carrier 40g again, the polymer-doped type ball-type of analytical test carrier consist of MgCl
22.5C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 10%.
Embodiment 2
, first reaction kettle of reflux exchanger adds absolute ethyl alcohol 36.5ml in being housed; Magnesium Chloride Anhydrous 14.9g; PVA (PVAc) 10g, sapn (80) 5ml stirs down and heats up; Treat that magnesium chloride and PVA dissolve white oil/silicone oil mixed solution that the back adds 150ml fully, keep certain hour under 120 ℃.Have in second reaction kettle of high speed agitator at another, add white oil/silicone oil mixed solution of 200ml, and be preheating to 120 ℃; Solution in first reaction kettle is pressed into rapidly, and maintains 120 ℃, with rotating speed 3000rpm high-speed stirring for some time; Under agitation the material in second reactor drum is transferred to and adds the 2000ml hexane in advance, and be cooled in-25 ℃ the 3rd reactor drum, keep the outlet temperature in this reactor drum to be no more than 0 ℃; Suction filtration; With hexane wash for several times, after nitrogen dries up, obtain polymer-doped type ball-type carrier 40g again, the polymer-doped type ball-type of analytical test carrier consist of MgCl
23.6C
2H
5OHPVAc, the mass ratio of PVA in the ball-type carrier is 20%.
Embodiment 3
(1) preparation of catalyst component
In the reactor drum of fully replacing through high pure nitrogen, (the ball-type carrier part dealcoholysis by embodiment 1 preparation obtains, and consists of MgCl to add the polymer-doped type ball-type of 6.0g carrier successively
21.4C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 13%), hexane 150ml; Be cooled to 0 ℃ under stirring, drip hexane solution (triethyl aluminum: 0.3M, the isoamyl oxide: 3M) of 27ml triethyl aluminum/isoamyl oxide; Be warming up to 50 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, drips hexane solution (triethyl aluminum: 0.3M, the isoamyl oxide: 3M), be warming up to 40 ℃ then, and keep reaction 1 hour of 27ml triethyl aluminum/isoamyl oxide again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 150ml hexane with hexane, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 2ml, is warming up to 60 ℃ afterwards, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen was fully replaced, adding 1L hexane and 1.0ml concentration was the triethyl aluminum of 1M; Add solid catalyst (containing 0.6 milligram of titanium) again through method for preparing; Be warming up to 75 ℃, feed hydrogen and make the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure); Polymerization is 2 hours under 85 ℃ of conditions, and polymerization result is seen table 2.
Embodiment 4
(1) preparation of catalyst component
In the reactor drum of fully replacing through high pure nitrogen, (the ball-type carrier part dealcoholysis through embodiment 2 preparations obtains, and consists of MgCl to add the polymer-doped type ball-type of 6.0g carrier successively
21.4C
2H
5OHPVAc, the mass ratio of PVA in the ball-type carrier is 29%), hexane 150ml; Be cooled to 0 ℃ under stirring, drip hexane solution (tri-n-hexyl aluminum: 0.3M, the THF: 3M) of 27ml tri-n-hexyl aluminum/THF; Be warming up to 50 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, drips hexane solution (tri-n-hexyl aluminum: 0.3M, the THF: 3M), be warming up to 40 ℃ then, and keep reaction 1 hour of 27ml tri-n-hexyl aluminum/THF again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 150ml hexane with hexane, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 4ml, is warming up to 60 ℃ afterwards, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3, and polymerization result is seen table 2.
Embodiment 5
(1) preparation of catalyst component
In the reactor drum of fully replacing through high pure nitrogen, (the ball-type carrier part dealcoholysis through embodiment 1 preparation obtains, and consists of MgCl to add the polymer-doped type ball-type of 6.0g carrier successively
20.9C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 15%), hexane 150ml; Be cooled to 0 ℃ under stirring, drip hexane solution (tri-n-hexyl aluminum: 0.4M, the THF: 3M) of 17ml tri-n-hexyl aluminum/THF; Be warming up to 40 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, drips hexane solution (tri-n-hexyl aluminum: 0.4M, the THF: 3M), be warming up to 40 ℃ then, and keep reaction 0.5 hour of 17ml tri-n-hexyl aluminum/THF again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 150ml hexane with hexane, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 10ml, is warming up to 60 ℃ afterwards, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3, and polymerization result is seen table 2.
Embodiment 6
(1) preparation of catalyst component
In the reactor drum of fully replacing through high pure nitrogen, (the ball-type carrier part dealcoholysis through embodiment 1 preparation obtains, and consists of MgCl to add the polymer-doped type ball-type of 6.0g carrier successively
20.6C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 16%), hexane 150ml; Be cooled to 0 ℃ under stirring, drip hexane solution (triethyl aluminum: 0.5M, the THF: 2M) of 7ml triethyl aluminum/THF; Be warming up to 40 ℃ then, and keep reaction 1 hour.This system is cooled to 0 ℃, drips hexane solution (triethyl aluminum: 0.5M, the THF: 2M), be warming up to 40 ℃ then, and keep reaction 1 hour of 7ml triethyl aluminum/THF again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 150ml hexane with hexane, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 4ml, is warming up to 60 ℃ afterwards, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3, and polymerization result is seen table 2.
Embodiment 7
(1) preparation of catalyst component
In the reactor drum of fully replacing through high pure nitrogen, (the ball-type carrier part dealcoholysis through embodiment 1 preparation obtains, and consists of MgCl to add the polymer-doped type ball-type of 40.0g carrier successively
21.4C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 13%), hexane 900ml; Be cooled to 0 ℃ under stirring, drip hexane solution (triisobutyl aluminium: 0.3M, the isoamyl oxide: 3M) of 65ml triisobutyl aluminium/isoamyl oxide; Be warming up to 40 ℃ then, and keep reaction 1 hour.This system is cooled to 0 ℃, drips hexane solution (triisobutyl aluminium: 0.3M, the isoamyl oxide: 3M), be warming up to 40 ℃ then, and keep reaction 1 hour of 75ml/ triisobutyl aluminium/isoamyl oxide again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 900ml hexane with hexane, is cooled to 10 ℃ then, slowly drips four titanium butoxide 10ml, is warming up to 60 ℃ afterwards, reacts 3 hours.With system with hexane in room temperature washing twice, add the 900ml hexane, be cooled to 10 ℃ then, slowly drip titanium tetrachloride 20ml.Afterwards solution is warming up to 60 ℃, reacted 3 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3, and polymerization result is seen table 2.
Embodiment 8
(1) preparation of catalyst component
105 milliliters of titanium tetrachlorides are added the preparation still, be cooled to-20 ℃, (the ball-type carrier part dealcoholysis through embodiment 1 preparation obtains, and consists of MgCl to add polymer-doped type ball-type carrier
21.4C
2H
5OHEC, the mass ratio of TKK 021 in the ball-type carrier is 13%) 7 grams, slowly be warming up to 20 ℃, in 2 hours, be warming up to 80 ℃ again, mixing speed 350rpm constant temperature 1 hour; The elimination mother liquor is cooled to room temperature, adds 105 milliliters of titanium tetrachlorides, is warming up to 80 ℃; Constant temperature 2 hours, the elimination mother liquor is cooled to 60 ℃, adds 105 milliliters of titanium tetrachlorides; Be warming up to 120 ℃, constant temperature 2 hours repeatedly washs after drying through hexane, obtains the ball-type solid catalyst.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3, and polymerization result is seen table 2
Embodiment 9
(1) preparation of catalyst component such as embodiment 3.
(2) ethene and hervene copolymer close
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adds hexane 1L; The triethyl aluminum 1.0ml of concentration 1M adds the solid catalyst (containing 0.6 milligram of titanium) of above-mentioned preparation, adds hexene 20ml again; Be warming up to 75 ℃; Feed hydrogen and make the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 1.03Mpa (gauge pressure), polymerization is 2 hours under 85 ℃ of conditions.Obtain ethene-hexene copolymer powder 380g, apparent density (BD) is 0.357g/cm
3, density is 0.935g/cm
3
Comparative Examples 1
(1) preparation of catalyst component
In the reactor drum of fully replacing, add 6.0g magnesium chloride alcohol adduct (MgCl successively through high pure nitrogen
21.4C
2H
5OH, its preparation method is referring to Chinese patent CN93102795.0), hexane 150ml; Be cooled to 0 ℃ under stirring, drip hexane solution (triethyl aluminum: 0.3M, the isoamyl oxide: 3M) of 27ml triethyl aluminum/isoamyl oxide; Be warming up to 50 ℃ then, and keep reaction 0.5 hour.This system is cooled to 0 ℃, drips hexane solution (triethyl aluminum: 0.3M, the isoamyl oxide: 3M), be warming up to 40 ℃ then, and keep reaction 1 hour of 27ml triethyl aluminum/isoamyl oxide again.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, and throw out in room temperature washing twice, adds the 150ml hexane with hexane, is cooled to 0 ℃ then, slowly drips titanium tetrachloride 2ml, is warming up to 60 ℃ afterwards, reacts 2 hours.Stop to stir, leave standstill, the very fast layering of suspension-s extracts supernatant liquid, throw out with twice of hexane wash after, through hexane it is transferred in the chromatography funnel, dry up with high pure nitrogen, obtain the solid ball type catalytic component of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3.Polymerization result is seen table 2.
Comparative Examples 2
(1) preparation of catalyst component (according to the method preparation of introducing among the Chinese patent CN93102795.0 " spherical catalyst of ethylene polymerization ")
105 milliliters of titanium tetrachlorides are added the preparation still, be cooled to-20 ℃, add magnesium chloride alcohol adduct (MgCl
21.4C
2H
5OH) 7 grams slowly were warming up to 20 ℃, in 2 hours, are warming up to 80 ℃ again, mixing speed 350rpm constant temperature 1 hour; The elimination mother liquor is cooled to room temperature, adds 105 milliliters of titanium tetrachlorides, is warming up to 80 ℃; Constant temperature 2 hours, the elimination mother liquor is cooled to 60 ℃, adds 105 milliliters of titanium tetrachlorides; Be warming up to 120 ℃, constant temperature 2 hours repeatedly washs after drying through hexane, obtains the ball-type solid catalyst.The catalyzer composition is seen table 1.
(2) vinyl polymerization is with embodiment 3.Polymerization result is seen table 2.
Table 1 catalyzer is formed
Table 2 polymer performance
Polymerization temperature: 85 ℃; Polymerization pressure: 1.03MPa, H
2/ C
2H
4=0.28/0.75
Relatively can find out from the data of table 2 embodiment and Comparative Examples, go out the ball-type polyethylene powder by the Preparation of Catalyst of gained of the present invention, its catalyst activity is high, resulting polymers has high apparent density and wider molecular weight distribution (MWD), and fine polymer powder is few.
Claims (11)
1. the preparation method of the used polymer-doped type ball-type carrier of an ethylene rolymerization catalyst is characterized in that, comprises the steps:
(1) under nitrogen protection; Magnesium Chloride Anhydrous/monohydroxy-alcohol/polymkeric substance is joined in the reactor drum that has stirring by a certain percentage; The alcohol that heats up closes the magnesium chloride alcohol adduct melt that obtains containing polymkeric substance; Add emulsifying agent again and further stir, subsequently it is distributed to white oil/silicone oil dispersion agent high speed and stirs to form emulsion, the cool quickly through refrigerant forms ball-type carrier suspension liquid again;
(2) the ball-type carrier suspension liquid that is generated is filtered, with hexane wash for several times, nitrogen dries up and can obtain polymer-doped type ball-type carrier again;
Described monohydroxy-alcohol is a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, octanol or isooctyl alcohol or its mixture; Described polymkeric substance is to have in the polymkeric substance of following functional group one or more ,-OH ,-NH
2,-COOH ,-CN ,-X ,-O-,-CO-,-CO-NH-,-NH-,-Ph ,-SO-,-COOR ,-SH ,-SO
3H ,-Ar ,-ArX, the number-average molecular weight of said polymkeric substance is below 500,000;
The chemical constitution of ball-type carrier is MgCl
2NROHPolymer, n=2.3-3.8 wherein, the mass ratio of polymkeric substance in the ball-type carrier is 1-50%.
2. the preparation method of polymer-doped type ball-type carrier according to claim 1 is characterized in that, described polymkeric substance is a cellulose derivative, and the starch based verivate gathers (methyl) vinylformic acid (ester) analog derivative; Poly carboxylic acid vinyl esters verivate, polyamide-based verivate, chitosan analog derivative, polyacrylonitrile, HPMA, maleic anhydride-styrene copolymers, SE; Polyvinylidene dichloride, PVF, SEPIGEL 305, Z 150PH, polyvinyl alkyl oxide; Polyoxymethylene, resol, terylene, polycarbonate, Synolac; Polyurethane, polyureas, polysulfones, urea aldehyde gathers in sulphur and the ZGK 5 one or more.
3. the preparation method of polymer-doped type ball-type carrier according to claim 1; It is characterized in that described polymkeric substance is a TKK 021, PHEMA; In PVA and the starch one or more, the number-average molecular weight of said polymkeric substance is below 100,000.
4. the preparation method of polymer-doped type ball-type carrier according to claim 1 is characterized in that, described polymkeric substance is TKK 021 and/or PVA, and the number-average molecular weight of said polymkeric substance is below 50,000.
5. the preparation method of polymer-doped type ball-type carrier according to claim 1 is characterized in that, the mass ratio of described polymkeric substance in the ball-type carrier is 20-30%.
6. a ball type catalytic component that is used for vinyl polymerization is characterized in that, comprises the reaction product of following component:
(1) the ball-type carrier for preparing among the described preparation method of one of claim 1-5 is through the product of part dealcoholysis;
(2) one or more are by general formula Ti (OR)
nX
4-nShown titanium compound, R is C in the formula
1～C
8Alkyl, X is a halogen atom, 0≤n≤4;
(3) one or more are by general formula AlR '
aX '
bH
cShown organometallic compound, R ' is C in the formula
1～C
14Alkyl, X ' is a halogen, a, b, c are 0～3 integer, and a+b+c=3;
(4) one or more electron donor compounds are selected from carboxylicesters, aliphatic ether, cycloaliphatic ether or alkanone;
Wherein the ratio between each reactant is in every mole of magnesium in the product of the described ball-type carrier part of component (1) dealcoholysis, 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.
7. the ball type catalytic component that is used for vinyl polymerization according to claim 6 is characterized in that, described titanium compound is TiCl
4, Ti (OC
2H
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4H
9) C1
3, Ti (OC
4H
9)
4In one or more.
8. the ball type catalytic component that is used for vinyl polymerization according to claim 6 is characterized in that, described titanium compound is TiCl
4, described organometallic compound is one or more in triethyl aluminum, triisobutyl aluminium, the tri-n-hexyl aluminum.
9. the ball type catalytic component that is used for vinyl polymerization according to claim 6 is characterized in that, described electron donor compound is C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8The alkyl ester of aromatic carboxylic acid, C
2～C
12Aliphatic ether, C
3～C
4Cyclic ethers and C
3～C
6In the saturated fatty ketone one or more.
10. the ball type catalytic component that is used for vinyl polymerization according to claim 6; It is characterized in that described electron donor compound is one or more in methyl-formiate, ETHYLE ACETATE, butylacetate, ether, hexyl ether, isoamyl oxide, THF, acetone, the MIBK.
11. a ball shape catalyst that is used for vinyl polymerization comprises the reaction product of following component:
(1) the described catalyst component of one of claim 6-10;
(2) general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, 0＜n≤3;
Wherein the mol ratio of aluminium in the component (2) and the titanium in the component (1) is 5～500.
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| CN105622790A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Carrier for ethylene homopolymerization or copolymerization, and catalyst thereof |
| CN108219038A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component and preparation method of alkoxyl magnesium particle |
| CN110862472A (en) * | 2018-08-28 | 2020-03-06 | 中国石油化工股份有限公司 | Olefin polymerization reaction catalyst, preparation method and composite catalyst |
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