CN102585055A - Olefin polymerization catalyst and preparation method and application thereof - Google Patents
Olefin polymerization catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an olefin polymerization catalyst and a preparation method and application thereof. The olefin polymerization catalyst comprises the following main components: magnesium-titanium composite solution with the constitutional formula being MgCl2.xMg(OR<1>)2.yTi(OR2)4, fumed silica, ether compounds, an alkyl aluminium chloride compound with the constitutional formula being R<3>nAlCl(3-n), and a titanium compound with the constitutional formula being Ti(OR<4>)mCl(4-m). The catalyst can be applicable to homopolymerization and copolymerization of ethylene, the specific surface area of catalyst particles is more than or equal to 200m<2>/g, the activity of the catalyst is high, the particle size distribution of the catalyst is concentrated, and fine power is little.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for olefinic polymerization, and this Preparation of catalysts method and the application in vinyl polymerization or copolymerization.
Background technology
Traditional Vilaterm has obtained very big innovation in recent years, and for example gas fluidized-bed process has extensively adopted the condensation operation pattern, makes gas phase process overcome to remove the fatal shortcoming of hot ability, and throughput significantly improves.Therefore the catalyzer that original employing silicon-dioxide is carrier can not adapt to the requirement of novel process because polymerization yield rate is low; The active magnesium chloride of the low or direct employing of dioxide-containing silica is that the new catalyst of carrier constantly occurs, and owing to inert support content reduces the polymerization efficiency of catalyzer is significantly improved.But, originally adopted silica supports can simple realization granules of catalyst morphology Control and also the catalyzer physical strength high, be not easy to produce fine powder in the polymerization.In catalyzer, adopting active magnesium chloride is carrier, or reduces silica supports content significantly the performance of aspects such as granules of catalyst form and physical strength is regulated and control to have brought challenge.
In Chinese invention patent 200910235932; The catalyst Precursors component mainly is magnesium chloride, THF, alcohols, aerosil and titanium tetrachloride; Use through alcohols and THF increases the solubleness of magnesium chloride, utilizes the particle form and the size-grade distribution of spray-dired mode control catalyst, and the catalyzer that obtains contains inert support seldom; Catalyst activity is high, and the fine powder of polymkeric substance is few.But in the Catalyst Production process, need to set up complicated closed cycle spray drying system, not only cost of investment is high, and controls very complicated.
The method that another kind obtains spherical magnesium chloride support derives from the polypropylene catalyst technology of preparing; In Chinese invention patent 200510131969; Promptly adopted the technology of this high speed shear low temperature granulating and forming; Catalyzer contains magnesium active solid component, at least a electron donor and at least a acvator, loads on the nano level silica gel.Make the granules of catalyst size-grade distribution concentrate, polymerization activity is high, and fine polymer powder is few.But high speed shear and low temperature agglomeration technique not only need specific equipment, and it is higher to consume energy, and are unfavorable for the reduction of Catalyst Production cost.
In U.S. patent of invention US4325837; Adopted magnesium chloride and titanate ester to form solution, utilized chlorination alkyl reactive aluminum to separate out solid then, before further reacting with titanium tetrachloride; Must carry out prepolymerization; Utilize prepolymerization to strengthen the granule strength of catalyzer, reduce the fine powder content of catalyzer in polymerization process, and copolymerized ability strengthens.But in the Catalyst Production process, the fluctuation of catalyzer magnesium titanium content all can have influence on the effect of pre-polymerization, makes the control of pre-polymerization degree very difficult, can cause the performance inconsistency of final catalyzer.
In PCT patent of invention WO03/000755; The solution of alkyl magnesium compound and alcohol compound formation is dispersed in the fluorated solvent; Utilize emulsion stabilizer to stir the formation emulsion under certain conditions again; Utilize temperature variation to make the emulsion droplet curing molding at last, finally obtain the granules of catalyst that size-grade distribution is concentrated.But final specific surface area of catalyst is very low, at 20m
2Below/the g, this must cause active ingredient more to load on the particulate surface, can cause the catalyzer initial activity high, the violent difficult control of reaction, and the short shortcoming of catalytic life.
Summary of the invention
The invention provides the preparation method with the prior art different catalyst, preparation technology is simple, and polymerization catalyst is active high, and hydrogen is transferred responsive, and particle size distribution concentrates, and the polymer bulk density that obtains is high, and fine powder content is few.
The present invention is achieved in that
Olefin polymerization catalysis of the present invention comprises body of catalyst component and promotor, described body of catalyst B component ET specific surface area>=200m
2/ g is to get through following method prepared in reaction:
Structural formula is MgCl
2XMg (OR
1)
2YTi (OR
2)
4Magnesium titanium composite solution, described magnesium titanium composite solution is R with structural formula with product that silicon dioxde reaction generates in ether compound again
3 nAlCl
3-nChlorination alkylaluminium cpd reaction, reacted product is Ti (OR with structural formula again
4)
mCl
4-mTitanium compound reaction obtain the body of catalyst component
Wherein, structural formula is MgCl
2XMg (OR
1)
2YTi (OR
2)
4Magnesium titanium composite solution, described R
1, R
2Be the alkyl that contains 1～20 carbon atom, x and y are mole numbers, x=0.1～5, y=0.1～10;
Described structural formula is R
3 nAlCl
3-nThe chlorination alkylaluminium cpd in, R
3Be the alkyl that contains 1～14 carbon atom, n is 1～2;
Described structural formula is Ti (OR
4)
mCl
4-mIn the titanium compound, R
4Be the alkyl that contains 1～10 carbon atom, m is 0～4;
Described silicon-dioxide is content 1～15wt% in final catalyzer;
Described promotor is the organo-aluminium compound of triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium or tri-n-hexyl aluminum; The mol ratio of the titanium in aluminium in the described promotor and the body of catalyst component is Al: Ti=(30～300): 1.
In the body of catalyst component of the present invention, described magnesium titanium composite solution MgCl
2XMg (OR
1)
2YTi (OR
2)
4Be by magnesium chloride, magnesium alkoxide compound Mg (OR
1)
2With titanium ester cpds Ti (OR
2)
4Reaction obtains in alkane solvent.
Magnesium alkoxide compound Mg (OR wherein
1)
2Can be dimethoxy magnesium, diethoxy magnesium, magnesium isopropoxide, tert-butyl alcohol magnesium, two different octyloxy magnesium, dicyclohexyl oxygen base magnesium, two phenoxy magnesium and benzyloxy magnesium etc., preferred Mg (OR
1)
2Be alkoxyl magnesium compound, wherein R
1Be to contain the alkyl of 1～20 carbon atom, preferably contain the alkyl of 2～10 carbon atoms.
Titanium ester cpds Ti (OR wherein
2)
4Can be tetramethoxy titanium, dimethoxy diethoxy titanium, purity titanium tetraethoxide, four titanium n-butoxide, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, Fourth Ring hexyl oxygen base titanium, four phenoxy magnesium, the four pairs of tolyloxy titaniums and benzyloxy-4 titanium etc., preferred Ti (OR
2)
4Be alkoxy titanium compound, R wherein
2Be the alkyl that contains 2～6 carbon atoms, more preferably purity titanium tetraethoxide and four titanium n-butoxide.，
Magnesium chloride, magnesium alkoxide Mg (OR
1)
2With titanium ester Ti (OR
2)
4Compound stirs through mix in alkane solvent, and heating (for example refluxing) reaction just can obtain MgCl
2XMg (OR
1)
2YTi (OR
2)
4Solution.Said alkane solvent comprises normal hexane, normal heptane, octane, n-decane etc., preferred normal hexane and normal heptane.The consumption of alkane solvent is 10～120 milliliters in every gram magnesium chloride, preferred 20～100 milliliters.Temperature of reaction can be selected in the scope of broad, usually at 15～150 ℃, and preferred 50～120 ℃.Reaction times is decided according to dissolving the formation clear solution fully, usually at 2～12 hours.X and y are mole numbers, expression magnesium chloride, Mg (OR
1)
2And Ti (OR
2)
4Deng the additional proportion of 3 kinds of reactants, calculate with the 1mol magnesium chloride, x can be 0.1～5mol, preferred 0.5～4mol, y can be 0.1～10mol, preferred 1～8mol.
In above-mentioned dissolution process, also can adopt some to have the polar solvent, play the hydrotropy effect.Suitable polar solvent comprises oil of mirbane, halogenated alkane (for example methylene dichloride, chlorobenzene, 1,2-ethylene dichloride etc.), saturated alcohols (for example ethanol, propyl carbinol etc.) and saturated rings ethers (for example THF) etc.
In ether compound and under room temperature～60 ℃, with the magnesium titanium composite solution of said acquisition and aerosil reaction 1-5 hour; Wherein the consumption of aerosil is to guarantee that dioxide-containing silica is 1～15wt% in the final catalyzer, preferred 2～11wt%.The consumption of ether compound is 1～30ml/gSiO
2, preferred 2～10ml/gSiO
2
In the body of catalyst component of the present invention, aerosil (fumed silica) is a kind of have minimum particle diameter, bigger serface, highly purified silica gel, and its average particle size range (state of aggregation) is 0.1～0.9 μ m; Specific surface area is 100～500m
2/ g, preferred 150～400m
2/ g.Like
TS-610 of commercially available Cabot company, EH5, M5 etc.
In the body of catalyst component of the present invention; Suitable ether compound comprises various straight chains and cyclic ethers; For example ether, positive propyl ether, n-butyl ether, isopropyl ether, ethyl isobutyl ether, isoamyl oxide, THF, tetrahydropyrans, dioxane, trioxane, crown ether, 2-methyltetrahydrofuran, 2; 5-dimethyl-tetrahydrofuran, tetrahydropyrans-2-methyl alcohol, 2-methyl tetrahydropyrans, 4-methyl tetrahydropyrans, 3-methyl tetrahydropyrans etc. or its mixture; The preferred saturated ethers of ring-type; For example dioxane, trioxane, crown ether, 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetrahydropyrans-2-methyl alcohol, 2-methyl tetrahydropyrans, 4-methyl tetrahydropyrans, 3-methyl tetrahydropyrans etc. or its mixture, preferred especially THF.
In the catalyst preparation process, the interpolation of aerosil and ether compound in no particular order, consumption is to guarantee that dioxide-containing silica is 1～15wt% in the final catalyzer, preferred 2～11wt%.The interpolation of ether compound can promote aerosil good dispersion uniformly in alkane solvents, even particle size distribution when assurance body of catalyst component particles is separated out, and consumption is 1～30ml/gSiO
2, preferred 2～10ml/gSiO
2Remain under 20～90 ℃ stirring reaction 1～7 hour after adding successively.
In the body of catalyst component of the present invention, described chlorination aluminum alkyls can be used formula R
3 nAlCl
3-nExpression, R
3Be the alkyl that contains 1～14 carbon atom, n is 1～2.For example diethyl aluminum chloride, ethylaluminum dichloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, sesquialter ethyl aluminum chloride and composition thereof.Preferred ethylaluminum dichloride and sesquialter ethyl aluminum chloride.
The consumption of chlorination alkylaluminium cpd is R
2 nAlCl
3-nMiddle Al and magnesium titanium composite solution MgCl
2XMg (OR
1)
2YTi (OR
2)
4The mol ratio of middle Mg is Al: Mg=(1.0～3.0): 1.The chlorination aluminum alkyls adopts the method that drips to add, and stirs while adding reaction, and dropping temperature is-30～70 ℃, preferred 0～50 ℃.The dropping time was controlled at 1～10 hour.Along with the adding of chlorination aluminum alkyls, solution is muddy gradually, but solid particulate is not separated out at once.Add the back at 40～120 ℃, preferred 50～100 ℃ were reacted 0.5～20 hour down, and preferred 1～12 hour, along with going deep into of reaction, the white solid particle was separated out gradually.Continue reaction and made that to separate out particle aging in 2～6 hours.
To react the gained solid particulate fully cleans; Warm wash before this, promptly whole cleaning process remains under 50～60 ℃, after the abundant sedimentation of solid particulate, removes supernatant liquid; Add cleaning normal hexane or normal heptane solvent and fully stir, remove clear liquid in abundant sedimentation then.Repeatedly after 2～5 times.Use instead under the room temperature and clean, also adopt aforesaid method to carry out 2～5 times.
Owing to separate out at catalyst solid and to have adopted ether compound in the moulding process, so solid particulate has higher specific surface area, and BET determining adsorption specific surface area reaches 200m
2More than/the g, can not only the more active titanium component of load, and can guarantee the homodisperse of titanium, catalyst life is longer.
The above-mentioned steps product after fully cleaning, with structural formula be Ti (OR
4)
mCl
4-mTitanium compound react, obtain the body of catalyst component after the drying.R in the said titanium compound
4Be the alkyl that contains 1～10 carbon atom, the alkyl of preferred 1～4 carbon atom; M is 0～4; Titanium compound is to choose any one kind of them in titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, butoxy titanous chloride, dibutoxy titanium dichloride, the three butoxy titanium chlorides.The present invention can mix use with two kinds of different titanium compounds, for example contains an OR at least
4The titanium compound of group and titanium tetrachloride mix use, and the present invention preferably only uses a kind of titanium compound, preferred especially titanium tetrachloride.The consumption of described titanium compound is titanium and MgCl
2XMg (OR
1)
2YTi (OR
2)
4The mol ratio of Mg is (0.5～10) in the solution: 1.The method that the employing of titanium compound once adds, then at 50～120 ℃, preferred 50～100 ℃ were reacted preferred 3～8 hours 2～10 hours down.Obtain final catalyst main body component.
React the method for cleaning under the employing room temperature after accomplishing the body of catalyst component particles is fully cleaned, under flowing nitrogen, 70～90 ℃ dry down, obtains good fluidity, and the concentrated body of catalyst component particles of size distribution.
The body of catalyst component contacts with promotor and forms olefin polymerization catalysis of the present invention, and said promotor is an organo-aluminium compound, can select triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, tri-n-hexyl aluminum for use, preferred triethyl aluminum.The mol ratio of described promotor and body of catalyst component is Al in the promotor: Ti=in the body of catalyst component (30～300): 1.
Catalyzer of the present invention can be used for the homopolymerization of ethene, also can be used for ethene and carries out copolymerization with the aliphatics terminal olefin that contains 3～8 carbon atoms.The terminal olefin that is suitable for has propylene, butene-1, amylene-1, hexene-1,4-methylpentene-1, heptene-1 and octene-1.Best terminal olefin is butene-1 and hexene-1.
Polymerizing catalyst can be used for slurry and vapour phase polymerization explained hereafter polymkeric substance.If employing slurry polymerization, polymerization temperature are 60～100 ℃, preferred 80～95 ℃; If employing gas phase polymerization, polymerization temperature are 70～115 ℃, preferred 85～110 ℃.
Polymerization or copolymerization that catalyzer of the present invention is used for ethene compared with prior art have following tangible advantage:
1, polymerization catalyst efficient of the present invention is high, has good hydrogen response.
2, the polymer beads form is good, centralized particle diameter.Therefore the fine powder content of polymkeric substance is few.
Each polymer properties index is measured as follows among the embodiment:
The mensuration of melting index MI: according to ASTM-D1238, condition E, 190 ℃ of following mensuration;
The mensuration of polymer stacks density: measure according to ASTM-D1895;
The mensuration of body of catalyst component particles size distribution: Malven MasterSize2000 particles distribution instrument is measured, and adopts the dry method sampler.
The mensuration of body of catalyst component particles specific surface area: Micromeritics ASAP2020 accelerated surface gathers and the void determination appearance, the BET determination of adsorption method.
Polymer particle size Determination of distribution: sieve with standard sieve.
Description of drawings
Accompanying drawing is the size distribution figure of the body of catalyst component particles that obtains of embodiment 1.
Embodiment
Further set forth the present invention through detailed description below, but the present invention is not limited to these embodiment to specific embodiment of the present invention.
Embodiment 1
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, magnesium ethylate 2.88g and tetrabutyl titanate 12.88g are warmed up under 110 ℃ then, keep reaction 8 hours, obtain lurid magnesium titanium composite solution.Structural formula is MgCl
22Mg (OEt)
23Ti (OBu)
4
Above-mentioned solution is cooled to room temperature, successively adds TS-610 aerosil 1.17g and THF 5ml, be warmed up to 40 ℃ and reacted 1 hour down.
Utilize constant pressure funnel slowly to drip the solution of 9.62g ethyl aluminum dichloride and the formation of 60ml normal hexane, dripped off in 1.5 hours.Rising to 55 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal hexane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal hexane again.
At last, once add titanium tetrachloride 15.07g while stirring, be warming up to 70 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 7.35% in the catalyzer, titanium content 13.12%, aluminium content 2.36%, cl content 46.28%.Granules of catalyst BET specific surface area 233.5m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, add hexane solvent 1000ml respectively, a certain amount of solid catalyst main body component and triethyl aluminum, control Al/Ti=200.Be warming up to 75 ℃, press H
2/ C
2H
4=0.4/0.6 (mol ratio) feeds ethene after adding a certain amount of hydrogen continuously, and keeping the reaction stagnation pressure is 1.0MPa.Continue to be warmed up to 85 ℃, under this temperature, keep reaction 2 hours.After the polymerization, cut off ethene, with reactor drum cooling and exhaust rapidly.Reclaim polymer slurries, from hexane, isolate polyethylene powders.Polymerizing condition and result are summarized in table 1.
Embodiment 2
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, isopropoxy magnesium 1.8g and tetrabutyl titanate 12.88g are warmed up under 100 ℃ then, keep reaction 6 hours, obtain lurid magnesium titanium composite solution.Structural formula is MgCl
2Mg (i-PrO)
23Ti (OBu)
4
Above-mentioned solution is cooled to room temperature, successively adds M-5 aerosil 2.71g and THF 7ml, be warmed up to 40 ℃ and reacted 3 hours down.
The solution that utilizes constant pressure funnel slow Dropwise 5 .13g ethyl aluminum dichloride and 60ml normal hexane to form dripped off in 1.5 hours.Rising to 55 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal hexane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal hexane again.
At last, once add titanium tetrachloride 14.38g while stirring, be warming up to 70 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 4.24% in the catalyzer, titanium content 11.97%, aluminium content 1.93%, cl content 31.86%.Granules of catalyst BET specific surface area 211.4m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, polymerization method is with embodiment 1, and the polymerizing condition and the result data of polymerization catalyst evaluation are seen table 1.
Embodiment 3
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, magnesium ethylate 0.72g and titanium ethanolate 8.64g are warmed up under 110 ℃ then, keep reaction 4 hours, obtain colourless magnesium titanium composite solution.Structural formula is MgCl
20.5Mg (OEt)
23Ti (OEt)
4
Above-mentioned solution is cooled to room temperature, successively adds M-5 aerosil 0.94g and THF 5ml, be warmed up to 60 ℃ and reacted 3 hours down.
Above-mentioned solution is cooled to 0 ℃, utilizes constant pressure funnel slowly to drip the solution of 4.69g sesquialter ethyl aluminum chloride and the formation of 50ml normal hexane, dripped off in 1.0 hours.Rising to 65 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal heptane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal heptane again.
At last, once add titanium tetrachloride 21.57 while stirring, be warming up to 105 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 7.64% in the catalyzer, titanium content 12.95%, aluminium content 1.36%, cl content 41.99%.Granules of catalyst BET specific surface area 249.4m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, polymerization method is with embodiment 1, and the polymerizing condition and the result data of polymerization catalyst evaluation are seen table 1.
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, magnesium ethylate 2.16g and tetrabutyl titanate 8.59g are warmed up under 50 ℃; Stirring reaction 0.5 hour; Add 1,2-ethylene dichloride 19ml is warmed up under 110 ℃ then; Keep reaction 4 hours, obtain lurid magnesium titanium composite solution.Structural formula is MgCl
21.5Mg (OEt)
22Ti (OBu)
4
Above-mentioned solution is cooled to room temperature, successively adds EH-2 aerosil 1.44g and 2-methyl tetrahydropyrans 9ml, be warmed up to 60 ℃ and reacted 2 hours down.
Utilize constant pressure funnel slowly to drip the solution of 12.03g ethyl aluminum dichloride and the formation of 60ml normal hexane, dripped off in 2 hours.Rising to 55 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal hexane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal hexane again.
At last, once add titanium tetrachloride 17.97g while stirring, be warming up to 70 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 9.28% in the catalyzer, titanium content 10.65%, aluminium content 1.52%, cl content 45.35%.Granules of catalyst BET specific surface area 209.7m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, polymerization method is with embodiment 1, and the polymerizing condition and the result data of polymerization catalyst evaluation are seen table 1.
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, tert.-butoxy magnesium 1.08g and tetrabutyl titanate 10.73g, compound is warmed up under 110 ℃ then, keeps reaction 8 hours, obtains lurid magnesium titanium composite solution.Structural formula is MgCl
20.5Mg (t-BuO)
22.5Ti (OBu)
4
Above-mentioned solution is cooled to room temperature, successively adds T-610 aerosil 2.05g and 2,5-dimethyl-tetrahydrofuran 6ml is warmed up to 50 ℃ and reacted 2 hours down.
The solution that utilizes constant pressure funnel slow Dropwise 5 .54g ethyl aluminum dichloride and 50ml normal hexane to form dripped off in 2 hours.Rising to 60 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal hexane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal hexane again.
At last, once add titanium tetrachloride 17.97g while stirring, be warming up to 50 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 6.86% in the catalyzer, titanium content 15.00%, aluminium content 2.08%, cl content 42.46%.Granules of catalyst BET specific surface area 229.0m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, polymerization method is with embodiment 1, and the polymerizing condition and the result data of polymerization catalyst evaluation are seen table 1.
In 250 milliliters of five mouthfuls of glass reaction bottles, add 100 milliliters of normal heptanes, magnesium chloride 1.2g, magnesium ethylate 0.72g and tetrabutyl titanate 12.88g, compound is warmed up under 100 ℃ then, keeps reaction 3 hours, obtains colourless magnesium titanium composite solution.Structural formula is MgCl
20.5Mg (OEt)
23Ti (OBu)
4
Above-mentioned solution is cooled to room temperature, successively adds T-610 aerosil 3.59g and THF 11ml, be warmed up to 50 ℃ and reacted 2 hours down.
The solution that utilizes the slow Dropwise 5 .08g of constant pressure funnel sesquialter ethyl aluminum chloride and 30ml normal hexane to form dripped off in 1.5 hours.Rising to 55 ℃ then reacted 4 hours down.After reaction finishes, remain on and use cleaning normal hexane warm wash 3 times under this temperature, reduce to then under the room temperature and clean 2 times with normal hexane again.
At last, once add titanium tetrachloride 13.16g while stirring, be warming up to 70 ℃ and keep reaction 4 hours down.Reduce under the normal temperature after reaction finishes and clean 4 times with normal hexane.At 60-85 ℃, drying obtained free-pouring body of catalyst component particles under the nitrogen that flows purged.
Mg content 5.14% in the catalyzer, titanium content 15.34%, aluminium content 1.72%, cl content 34.79%.Granules of catalyst BET specific surface area 224.9m
2/ g.
Polymerization is estimated
In 2 liters reaction kettle, carry out the slurry polymerization evaluation, polymerization method is with embodiment 1, and the polymerizing condition and the result data of polymerization catalyst evaluation are seen table 1.
Utilize the catalyzer of embodiment 1 preparation to carry out the polymerization evaluation under the different condition, remove different H
2/ C
2H
4Mol ratio with add different amount hexenes-1 as outside the comonomer, all the other polymerizing conditions are identical with embodiment 1.Polymerization result is listed in table 3, can see that through this embodiment catalyzer of the present invention has good hydrogen response and copolymerized ability.
Table 1
Table 2
Table 3
Claims (10)
1. an olefin polymerization catalysis comprises titanium-containing catalyst main body component and promotor, it is characterized in that, described body of catalyst B component ET specific surface area>=200m
2/ g, be to get through following method prepared in reaction: structural formula is MgCl
2XMg (OR
1)
2YTi (OR
2)
4Magnesium titanium composite solution, described magnesium titanium composite solution is R with structural formula with product that silicon dioxde reaction generates in ether compound again
3 nAlCl
3-nChlorination alkylaluminium cpd reaction, reacted product is Ti (OR with structural formula again
4)
mCl
4-mTitanium compound reaction obtain the body of catalyst component
Wherein, structural formula is MgCl
2XMg (OR
1)
2YTi (OR
2)
4Magnesium titanium composite solution, described R
1, R
2Be the alkyl that contains 1～20 carbon atom, x and y are mole numbers, x=0.1～5, y=0.1～10;
Described structural formula is R
3 nAlCl
3-nThe chlorination alkylaluminium cpd in R
3Be the alkyl that contains 1～14 carbon atom, n is 1～2;
Described structural formula is Ti (OR
4)
mCl
4-mR in the titanium compound
4Be the alkyl that contains 1～10 carbon atom, m is 0～4;
Described silicon-dioxide is content 1～15wt% in final catalyzer;
Described promotor is the organo-aluminium compound of triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium or tri-n-hexyl aluminum;
The mol ratio of the titanium in aluminium in the described promotor and the body of catalyst component is Al: Ti=(30～300): 1.
2. olefin polymerization catalysis according to claim 1 is characterized in that, the R in the described magnesium titanium composite solution
1Be the alkyl that contains 2～10 carbon atoms, R
2Be the alkyl that contains 2～6 carbon atoms, x=0.5～4, y=1～8mol.
3. olefin polymerization catalysis according to claim 1 is characterized in that, the consumption of said aerosil is to guarantee that dioxide-containing silica is 1～15wt% in the final catalyzer.
4. olefin polymerization catalysis according to claim 1; It is characterized in that; Said ether compound is ether, positive propyl ether, n-butyl ether, isopropyl ether, ethyl isobutyl ether, isoamyl oxide, THF, tetrahydropyrans, dioxane, trioxane, crown ether, 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetrahydropyrans-2-methyl alcohol, 2-methyl tetrahydropyrans, 4-methyl tetrahydropyrans, 3-methyl tetrahydropyrans etc. or its mixture.
5. olefin polymerization catalysis according to claim 1; It is characterized in that described chlorination alkylaluminium cpd is to comprise diethyl aluminum chloride, ethylaluminum dichloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, sesquialter ethyl aluminum chloride and composition thereof.
6. olefin polymerization catalysis according to claim 1 is characterized in that, described titanium compound is a titanium tetrachloride.
7. the preparation method of olefin polymerization catalysis according to claim 1 is characterized in that obtaining through following step:
(1), when existing or not having polar solvent, in 15～150 ℃ and the alkane solvent, magnesium chloride, magnesium alkoxide Mg (OR
1)
2With titanium ester Ti (OR
2)
4The compound reaction obtained MgCl in 2～12 hours
2XMg (OR
1)
2YTi (OR
2)
4Solution; Described magnesium chloride, magnesium alkoxide Mg (OR
1)
2With titanium ester Ti (OR
2)
4Mol ratio be 1: (0.1～5): (0.1～10); Said alkane solvent is normal hexane, normal heptane, octane or n-decane, and the consumption of alkane solvent is 10～120 milliliters in every gram magnesium chloride; Wherein said polar solvent is oil of mirbane, halogenated alkane, saturated alcohols or saturated rings ethers;
(2), in ether compound and under room temperature～60 ℃, the magnesium titanium composite solution that (1) is obtained reacted 1-5 hour with aerosil; Wherein the consumption of aerosil is to guarantee that dioxide-containing silica is 1～15wt% in the final catalyzer; The consumption of ether compound is 1～30ml/gSiO
2The average state of aggregation particle diameter of described silicon-dioxide is 0.1～0.9 μ m, and specific surface area is 100～500m
2/ g; Said ether compound is ether, positive propyl ether, n-butyl ether, isopropyl ether, ethyl isobutyl ether, isoamyl oxide, THF, tetrahydropyrans, dioxane, trioxane, crown ether, 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetrahydropyrans-2-methyl alcohol, 2-methyl tetrahydropyrans, 4-methyl tetrahydropyrans, 3-methyl tetrahydropyrans etc. or its mixture;
(3), described structural formula is R
2 nAlCl
3-nThe product reaction of kelene based compound and step (2) 0.5～20 hour, the mol ratio of Mg is Al in Al in the described chlorination alkylaluminium cpd and the magnesium titanium composite solution: Mg=(1.0～3.0): 1;
(4), at 50～120 ℃, the product of step (2) and structural formula are Ti (OR
4)
mCl
4-mTitanium compound react and obtained the body of catalyst component in 2～10 hours; The consumption of described titanium compound is titanium and MgCl
2XMg (OR
1)
2YTi (OR
2)
4The mol ratio of Mg is (0.5～10) in the solution: 1;
Described R
1, R
2, R
1, R
2, n, x and y according to claim 1.
8. method as claimed in claim 7 is characterized in that, the consumption of described chlorination alkylaluminium cpd is R
2 nAlCl
3-nMiddle Al and magnesium titanium composite solution MgCl
2XMg (OR
1)
2YTi (OR
2)
4The mol ratio of middle Mg is Al: Mg=(1.0～3.0): 1.
9. method as claimed in claim 7 is characterized in that, described Ti (OR
4)
mCl
4-mTitanium and MgCl in the titanium compound
2XMg (OR
1)
2YTi (OR
2)
4The mol ratio of Mg is (0.5～10) in the solution: 1.
10. the application of the described olefin polymerization catalysis of claim 1 is characterized in that, described olefin polymerization catalysis is applied to the homopolymerization or the ethene of ethene and contains in the copolymerization of aliphatics terminal olefin of 3～8 carbon atoms.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674385A (en) * | 2015-11-11 | 2017-05-17 | 辽宁鼎际得石化股份有限公司 | Polyolefin catalyst and preparation method and application thereof |
| CN106674389A (en) * | 2015-11-11 | 2017-05-17 | 辽宁鼎际得石化股份有限公司 | Particle size distribution adjustable polyolefin catalyst as well as composition and application thereof |
| CN108503733A (en) * | 2018-04-27 | 2018-09-07 | 上海化工研究院有限公司 | A kind of olefin polymerization catalysis and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339509A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | High activity silica gel carrier catalyst component for ethylene polymerisation or copolymerisation and its catalyst and use of said catalyst |
-
2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339509A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | High activity silica gel carrier catalyst component for ethylene polymerisation or copolymerisation and its catalyst and use of said catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674385A (en) * | 2015-11-11 | 2017-05-17 | 辽宁鼎际得石化股份有限公司 | Polyolefin catalyst and preparation method and application thereof |
| CN106674389A (en) * | 2015-11-11 | 2017-05-17 | 辽宁鼎际得石化股份有限公司 | Particle size distribution adjustable polyolefin catalyst as well as composition and application thereof |
| CN106674389B (en) * | 2015-11-11 | 2019-02-19 | 辽宁鼎际得石化股份有限公司 | A kind of adjustable polyolefin catalyst composition of particle diameter distribution and application |
| CN106674385B (en) * | 2015-11-11 | 2019-05-24 | 辽宁鼎际得石化股份有限公司 | A kind of polyolefin catalyst and the preparation method and application thereof |
| CN108503733A (en) * | 2018-04-27 | 2018-09-07 | 上海化工研究院有限公司 | A kind of olefin polymerization catalysis and preparation method thereof |
| CN108503733B (en) * | 2018-04-27 | 2021-03-09 | 上海化工研究院有限公司 | Olefin polymerization catalyst and preparation method thereof |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee after: Shanghai Chemical Research Institute Co., Ltd. Patentee after: Sinopec Corp. Co-patentee after: China Petrochemical Science and Technology Development Co Ltd Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee before: Shanghai Research Institute of Chemical Industry Patentee before: Sinopec Corp. Co-patentee before: China Petrochemical Science and Technology Development Co Ltd |