CN101113182A - Catalyst component, catalyst, preparation method and its application - Google Patents
Catalyst component, catalyst, preparation method and its application Download PDFInfo
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- CN101113182A CN101113182A CN 200610107651 CN200610107651A CN101113182A CN 101113182 A CN101113182 A CN 101113182A CN 200610107651 CN200610107651 CN 200610107651 CN 200610107651 A CN200610107651 A CN 200610107651A CN 101113182 A CN101113182 A CN 101113182A
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Abstract
The invention relates to supported Ziegler-Natta catalyst components based on water-bearing silica gel (water content 0.5-8.0wt percent), which comprises the supported Ziegler-Natta catalyst and catalyst components of the supported Ziegler-Natta catalyst components, and a preparation method of the catalyst. The supported Ziegler-Natta catalyst is applied to homopolymerization of catalytic olefin and copolymerization of two or more than two different olefins. The supported Ziegler-Natta catalyst of the invention has low production cost, stable and easily controllable kinetic curve when being used in homopolymerization and copolymerization of catalytic olefin and stable active release; besides, polymers produced by the invention have low contend of fine powder and oligomer of the polymer and narrow particle size distribution of the polymer.
Description
Technical field
The present invention is about a kind of loading type Ziegler-Natta catalyst component based on water-containing column, the loading type Ziegler-Natta catalyst that comprises this loading type Ziegler-Natta catalyst component, this catalyst component and this Preparation of catalysts method, and the application in the copolyreaction carried out between the homopolymerization of catalyzed alkene and two or more different alkene of this loading type Ziegler-Natta catalyst.
Background technology
The kind of used olefin polymerization catalysis mainly comprised Ziegler-natta catalyst, single-site catalysts when ethylene homo closed with copolymerization production polyvinyl resin, or both composite catalysts.Wherein single-site catalysts also comprises metallocene catalyst, non-metallocene catalyst and late transition metal catalyst etc.
The Ziegler-Natta type polymerization catalyzer is the title complex that is formed by the halogenide of transition metal (as titanium or vanadium) and metal hydride and/or metal alkyls (normally organo-aluminium compound) as promotor basically, and the loading type Ziegler-Natta catalyst generally by load on magnesium compound that aluminum alkyl catalyst cooperates on titanium halide constitute.The most commonly used is to adopt magnesium chloride or basic magnesium chloride as carrier, when being used for slurry or vapour phase polymerization, also adopts the formed complex carrier of silica gel and magnesium chloride as carrier sometimes.
The high efficiency load type Ziegler-Natta catalyst has been widely used in the copolymerization of the equal polymerization of ethene, propylene and they and other alpha-olefin.In disclosed patented technology, the high efficiency load type Ziegler-Natta catalyst usually with magnesium chloride as single carrier, in order to improve catalytic activity, at first take different physics or chemical process to prepare magnesium chloride support, then transistion metal compound and electron donor compound and form catalyst active center in the load.In now disclosed many patents, magnesium chloride load on porous inorganic oxide carriers such as silica gel, and then with halogen titanium compound and electron donor compound treatment, is finally obtained olefin polymerization catalysis.
With titanium compound and magnesium compound is catalyst component, with the electron donor solvent is ligand, with the aluminum compound is activating component, and is the loading type Ziegler-Natta catalyst of carrier with silica gel, and its preparation generally comprises four steps: (1) contains the preparation of the solution of magnesium-Ti-base catalyst component; (2) preparation of silica gel impregnated carrier; (3) preparation of catalyst precursor; (4) preparation of pre-activated catalyst.Wherein the solution of titaniferous-magnesium-base catalyst component is with titanium aluminum chloride (3TiCl
3AlCl
3) and MgCl
2Be dissolved in the ether solvents such as tetrahydrofuran (THF), remove by filter insolubles then and make.But broken phenomenon when being used for equal polymerization of catalyzed alkene or copolymerization, it often takes place easily, the fine powder amount that produces is more, will influence the steady running of poly-unit, and oligomer is higher during copolymerization, bring many problems for the subsequent disposal of polymkeric substance, plugging easily.
When this type of catalyzer is used for gas-phase fluidized bed polymerization process,, normally above-mentioned catalyst component is carried on the silica gel for the form that guarantees granules of catalyst and size-grade distribution are more suitable for operation in fluidized state.As US4302565, US4379759 and CN1064870A be disclosed to be used for gas-phase fluidized-bed catalyst for reaction, be to be immersed in by the precursor components of titanium compound, magnesium compound and electron donor compound on the carrier substance such as silica gel, handle with active compound again and flooded the carrier of precursor components and prepare.But this method is difficult to the uniform distribution of control catalyst active principle on support of the catalyst, and the repetition stability of catalyst preparation process is relatively poor, so the particle form of catalytic efficiency and resulting polymers and size-grade distribution are unsatisfactory.
The catalyzer that U.S. Pat 5290745 is announced consists of MgCl
2TiCl
3(THF)
4.5NSiO
2It is with through the silica gel of 10～80 microns of high temperature dehydration and surface treatments as carrier, with Primary Catalysts TiCl
3, promotor MgCl
2, the electron donor tetrahydrofuran (THF) is configured to mother liquor and is carried on this silica-gel carrier, and the parent that makes is handled with TnHAl, to remove thinner after reducing with aluminium diethyl monochloride (DC) again.
Patent CN1145530 has announced and has been used for that ethylene homo closes or the preparation process of the loading type Ziegler-Natta catalyst of copolymerization.It is by silica gel that makes the belt surface hydroxyl in the hydro carbons slurries and dialkyl magnesium compound reaction, make product and carbon tetrachloride reaction, make products therefrom and titanium tetrachloride reaction again, use this product and dimethylaluminum chloride to react then and prepare the catalyzer that is used for equal polymerization or copolymerization.
Patent CN1216081C discloses a class ethylene homo and has closed and the preparation method of copolymerization with titanium-magnesium series catalysts, comprises following four steps: the preparation of (1) titaniferous-magnesium base catalyst component solution; (2) preparation of silica gel impregnated carrier; (3) preparation of catalyst precursor; (4) preparation of pre-activated catalyst.Being main reductive agent with metallic aluminium or aluminum magnesium alloy in ether solvent, is assistant reducing agent with the MAGNESIUM METAL, makes TiCl
4Basically be reduced into 3TiCl fully
3AlCl
3With a small amount of TiCl
3, add MgCl
2Solvent obtains the catalyst based component solution of Ti-Mg, makes reduction accelerator with iodine, is used for vapour phase polymerization, and activity can be brought up to 4～8,000 times.
The catalyst component that patent CN1218971C provides a kind of complex carrier and adopted this complex carrier to obtain, described complex carrier is magnesium halide to be contacted with one or more electron donor compounds form solution, mix with the anhydrous silica gel of mean particle size then less than 30 microns, spray-dried and the spherical granules that makes, this complex carrier again with Ti (OR)
4-mX
mCatalyzer is made in (R is an alkyl, and X is a halogen) reaction, and it is particularly suitable for propylene polymerization.
English Patent GB2028347 provides the method that a kind of preparation is loaded in porous inorganic oxide supported catalyst component, promptly uses MgCl
2The solution impregnation silica-gel carrier makes solvent evaporation afterwards, the solid product that obtains again with particularly titanium compound reaction of transistion metal compound.
Many patents were all described the technology by immersion process for preparing complex carrier type catalyzer, as US5559071, US5625015, WO94/14855, WO94/14856, WO95/11263, WO/15216, WO95/12622, WO96/16903, WO96/05236, WO97/23518, WO98/01481, WO99/46306, WO00/22011, WO00/40623, WO00/05277, EP0295312C etc., the silica gel mean particle size that these patents adopted is 50 microns, limited the charge capacity of active ingredient, made final activity of such catalysts not high.
Patent CN1181105C discloses and a kind ofly has been applicable to that ethylene homo closes or the high activity silica gel loaded catalyst component and the catalyzer of copolymerization, this catalyst component is that the reaction product with titanium compound, magnesium compound and electron donor loads on and has than on the silica gel of bigger serface and preparation, can also add the halogenide improving agent in addition, it is particularly useful for the gas fluidised bed polymerisation of ethene.
Above-mentioned cited loading type Z-N olefin polymerization catalysis all requires carrier process thermal activation treatment to remove moisture contained in the carrier, perhaps requires support material itself not moisture.In the other technical literature, moisture contained in the carrier is also removed by the mode of chemical activation processing carrier sometimes.Why must remove moisture contained in the carrier, be because generally believe that the existence of water is disadvantageous in this area for the activity of prepared loading type Ziegler-Natta catalyst.Therefore, handle carrier,, become this area conventional steps necessary that adopts when using this class loading type Ziegler-Natta catalyst of the aqueous preparing carriers of possibility to remove the moisture that wherein exists by thermal activation or chemical activation.
Because the thermal activation and the chemical activating process of carrier all need special equipment, and, the chemical activation of carrier also needs to use expensive chemical activating agent, in addition, owing to increased the carrier activation step, it is numerous and diverse that the Preparation of catalysts method will become, and therefore, can increase the manufacturing cost of this class loading type Ziegler-Natta catalyst so greatly.Moreover the loading type Ziegler-Natta catalyst that adopts this process activatory preparing carriers is when being used for vinyl polymerization, and its kinetic curve is decay property, heat transmission or control when being unfavorable for industrial production.
And, adopt magnesium chloride existence form in the prepared Ziegler-Natta catalyst of silica gel and magnesium chloride complex carrier to have influence on fine powder content and oligomer in the final polymkeric substance, and the polymkeric substance particle diameter distributes, this is for producing restriction separating of polymkeric substance in the industrial production and solvent, too much fine powder content and oligomer, and the distribution of the polymkeric substance particle diameter of broad will cause the obstruction of centrifugal separation equipment and have to carry out unplanned parking.
Therefore, a kind of loading type Ziegler-Natta catalyst of urgent hope exploitation, its low cost of manufacture, and when being used for catalyzed alkene homopolymerization or copolymerization, its kinetic curve is easily control steadily, activity of such catalysts discharges steadily, and fine powder content and oligomer are low in the polymkeric substance of being produced, and narrow grain size distribution of polymers.
Summary of the invention
For this reason, the present invention carries out in order to overcome these problems of existence of the prior art, its objective is a kind of loading type Ziegler-Natta catalyst based on water-containing column is provided on the basis of existing technology, its low cost of manufacture, and when being used for catalyzed alkene homopolymerization or copolymerization, its kinetic curve is easily control steadily, and activity of such catalysts discharges steadily, and fine powder content and oligomer are low in the polymkeric substance of being produced, and narrow grain size distribution of polymers.
The inventor is surprised to find that through diligent research, by the water content as the silica gel of carrier is in certain scope, but not remove wherein contained whole moisture like that as far as possible according to prior art, and the silica gel that uses this specified moisture content prepares the loading type Ziegler-Natta catalyst, just can realize above-mentioned purpose, finish the present invention thus.
That is to say that the present invention relates to a kind of loading type Ziegler-Natta catalyst component in first aspect, it is characterized in that, this catalyst component can be represented with following general formula:
(S·M)·T
Wherein, S representative is as the water-containing column of carrier, M representative and this water-containing column bonded alcohol magnesium compound, and the T representative loads on by described S and described M by in conjunction with the halogenated titanium as the Ziegler-Natta catalyst active ingredient on the complex carrier that constitutes.
The present invention relates to a kind of loading type Ziegler-Natta catalyst in second aspect, it is characterized in that, this catalyzer by with the loading type Ziegler-Natta catalyst component of first aspect present invention as Primary Catalysts, constitute as promotor with alkylaluminoxane or aluminum alkyls.
The present invention relates to a kind of preparation method of loading type Ziegler-Natta catalyst component in the third aspect, it is the preparation method of the loading type Ziegler-Natta catalyst component of first aspect present invention, it is characterized in that, comprise following steps: magnesium compound is dissolved in the tetrahydrofuran (THF) under the condition that alcohol exists, to prepare uniform solution, adding water-containing column then in this solution reacts it, follow solid-liquid separation and the dry solidliquid mixture that is obtained, with the preparation complex carrier, in this complex carrier, add halogenated titanium then, thereby make loading type Ziegler-Natta catalyst component of the present invention as the Ziegler-Natta catalyst active ingredient.
The present invention relates to a kind of preparation method of loading type Ziegler-Natta catalyst in fourth aspect, it is the preparation method of the loading type Ziegler-Natta catalyst of second aspect present invention, it is characterized in that, comprise following steps: the loading type Ziegler-Natta catalyst component that makes with the method by third aspect present invention or the loading type Ziegler-Natta catalyst component of first aspect present invention are Primary Catalysts, add alkylaluminoxane or aluminum alkyls therein as promotor, make this loading type Ziegler-Natta catalyst thus.
The present invention relates to a kind of catalysis homopolymerization or copolymerization process of alkene aspect the 5th, it is characterized in that, may further comprise the steps:
Adopt the loading type Ziegler-Natta catalyst of the method manufacturing of passing through fourth aspect present invention or the loading type Ziegler-Natta catalyst of second aspect present invention, under polymeric reaction condition, in polymerization reactor, introduce polymerization single polymerization monomer and/or copolymerization monomer, carry out equal polymerization of alkene and/or copolymerization.
Description of drawings
Fig. 1 is the grain size distribution curve figure of the polymer product that obtained when adopting Primary Catalysts CAT-1 of the present invention and CAT-1-J to carry out polyreaction.
Fig. 2 is the polymerization kinetics curve when carrying out polyreaction among embodiment 1-A and the comparative example 1-1.
Embodiment
At first, the present invention relates to a kind of loading type Ziegler-Natta catalyst component, it is characterized in that this catalyst component can be represented with following general formula:
(S·M)·T
Wherein, S representative is as the water-containing column of carrier, M representative and this water-containing column bonded alcohol magnesium compound, and the T representative loads on by described S and described M by in conjunction with the halogenated titanium as the Ziegler-Natta catalyst active ingredient on the complex carrier that constitutes.
In the context of the invention, described term " water-containing column " is for the anhydrous silica gel of using always as carrier in the prior art (comprising the silica gel that process thermal activation or drying treatment are crossed).Carrier component when in the present invention, this water-containing column is as preparation catalyst component or catalyzer is used.
For this water-containing column without any special qualification, as long as its water content is 0.5～8wt%, can adopt any conventional silica gel that satisfies this water content condition. it is to be noted, this water content can be the water content that the silica gel itself without any processing is showed, also can be that water content is not in silica gel in the specialized range of the present invention through after the wetting or drying treatment, thereby make its water content satisfy the silica gel of requirement of the present invention, but preferably this water content is the water content that the silica gel itself without any processing is showed, because can save the vehicle treated step like this, thus the manufacturing cost of reduction catalyst component and catalyzer.
The preferred water content of this water-containing column is 2～6wt%, more preferably 3.5～4.5wt%.The moisture determination of this water-containing column can adopt methods such as thermogravimetry to carry out.As long as water content satisfies regulation of the present invention, suitable silica-gel carrier can be the commerical prod that can buy arbitrarily.There is no particular limitation to the surface-area (BET method mensuration) of this water-containing column, but preferred 10～1000m
2/ g, more preferably 100～600m
2/ g.Preferred 0.1～the 4cm of carrier hole volume (determination of nitrogen adsorption)
3/ g, more preferably 0.2～2cm
3/ g.Preferred 1～500 μ m of the mean particle size of carrier (laser particle analyzer mensuration), more preferably 1～100 μ m.This used water-containing column carrier of the present invention can be a form arbitrarily, such as granular, spherical, aggregate or other form.The commerical prod that can buy is such as enumerating Grace 955, and Grace 952, and Grace 948, GraceSP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES70Y, ES757, Aerosil812, CS-2133 and MS-3040 etc.
Described pure magnesium compound refers to formed compound when making magnesium compound be dissolved in the tetrahydrofuran solvent under the condition that alcohol exists.This compound reacts when contacting in solution with water-containing column of the present invention and chemistry and/or physically be combined on this water-containing column, through washing and dry and form complex carrier of the present invention.
Under situation not bound by theory, think that physics and/or chemical reaction that this alcohol magnesium compound and water-containing column are carried out are to carry out in the hole of described water-containing column.That is, be subjected under capillary action and the surface action of silica gel duct, pure magnesium compound preferentially enters in the silica gel hole, and pure thus magnesium compound is higher than concentration outside the silica gel hole in the intrapore concentration of silica gel.Exist an amount of moisture to help more pure magnesium compound to be combined on this silica-gel carrier in the water-containing column of the present invention, finally should be present in the silica gel hole by the alcohol magnesium compound, rather than depend on the silica gel surface in a large number.Simultaneously, this moisture also is fixed on silica-gel carrier inside by reacting, thereby increases the oxygen level of final catalyst component that obtains and catalyzer, has unexpectedly obtained the present invention's described excellent effect before thus.This fixed moisture can be because of follow-up drying and other steps break away from from carrier, and contains at silica gel under the condition of certain water gaging and can not produce any adverse influence to the performance of prepared catalyzer yet.
Described magnesium compound is selected from magnesium halide, alkoxyl group magnesium halide, or alkoxyl magnesium, preferred magnesium halide, most preferably magnesium chloride.Described magnesium compound is preferably not moisture, promptly preferred anhydrous magnesium compound.
Described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18), cyclic alcohol or aromatic alcohol, and preferred fat alcohol is as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, octanol and isooctyl alcohol etc., more preferably ethanol or butanols.
Described halogenated titanium as the Ziegler-Natta catalyst active ingredient can be selected from the halogenated titanium active ingredient that this area is used always when the preparation Ziegler-Natta catalyst, as titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide etc., but preferred titanium tetrachloride.
Loading type Ziegler-Natta catalyst component of the present invention is a kind of white or little yellow and runny pressed powder.
In one embodiment, the invention still further relates to a kind of loading type Ziegler-Natta catalyst, it be by with loading type Ziegler-Natta catalyst component of the present invention as Primary Catalysts, constitute as promotor with alkylaluminoxane or aluminum alkyls.
Can adopt the linear alkyl aikyiaiurnirsoxan beta of formula (I) as the described alkylaluminoxane of promotor use:
(R just
2-(Al (R)-O)
n-AlR
2)
And/or the ring-type type alkylaluminoxane of formula (II):
(just-(Al (R)-O-)
N+2).
In formula (I) with (II), the R group can be identical or different, is selected from C
1-C
8Alkyl, preferable methyl, ethyl, isobutyl-or normal-butyl.Preferred R group is identical, and is selected from methyl, ethyl or isobutyl-, most preferable.In the formula, n is the integer of 1-50, preferred 10～30.Described alkylaluminoxane is such as enumerating methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO) and isobutyl aluminium alkoxide (IBAO) etc.
The described aluminum alkyls that uses as promotor is the compound with following general formula (III):
Al(R)
3 (III)
In the formula (III), each radicals R is identical or different, is selected from C
1-C
8Alkyl.Its specific examples can be enumerated trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopentyl aluminium, three n-pentyl aluminium, triisopentyl aluminium, three hexyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum or three amyl group aluminium etc.
In a further embodiment, the present invention relates to a kind of preparation method of loading type Ziegler-Natta catalyst component, it is the preparation method of loading type Ziegler-Natta catalyst component of the present invention, it is characterized in that, comprises following steps:
(1) magnesium compound is dissolved in the tetrahydrofuran (THF) under the condition that alcohol exists, preparing uniform solution,
(2) in this solution, add water-containing column it reacted,
(3) solid-liquid separation and the dry solidliquid mixture that is obtained are with the preparation complex carrier, then
(4) in this complex carrier, add halogenated titanium, thereby make this loading type Ziegler-Natta catalyst component as the Ziegler-Natta catalyst active ingredient.
Specifically, the preparation process of this loading type Ziegler-Natta catalyst component is as follows:
Take by weighing a certain amount of magnesium compound, add tetrahydrofuran (THF) and alcohol or its mixed solvent, being stirred to magnesium compound under 20～60 ℃ of liquid temperature dissolves fully, form uniform solution, then to wherein adding water-containing column, continue to stir, and keep this temperature regular hour it is reacted, solid-liquid separation is also dry then, thereby makes complex carrier.Then, in described complex carrier, under agitation add halogenated titanium or its solution as the Ziegler-Natta catalyst active ingredient, drying after the optional solid-liquid separation, thus make loading type Ziegler-Natta catalyst component of the present invention.
In the step (1) of the inventive method, when the solution temperature of selecting is low, can adopt long dissolution time, and when the solution temperature of selecting is higher, can adopt short dissolution time.The dissolution time of described magnesium compound in tetrahydrofuran (THF) and alcohol was generally 0.5～24 hour.For example, when dissolving under 60 ℃ temperature, dissolution time may be selected to be 0.5～4 hour, and when the solution temperature was 20 ℃, dissolution time may be selected to be 4～24 hours.Can utilize during dissolving to stir and shorten dissolution time.This stirring can be adopted any type of stirring, and the rotating speed during stirring is generally 10～1000 rev/mins.
In described step (1), by the mole number of magnesium elements and alcoholic extract hydroxyl group for, the mol ratio of described magnesium compound and described alcohol is 1: 1～20, preferred 1: 2～6.The consumption of tetrahydrofuran (THF) is that every mole of magnesium compound adds 0.12～5 liter of tetrahydrofuran (THF), preferred 1.2～2.5 liters.
In step (2), the described reaction times, there is no particular limitation, but be generally 0.1～8 hour, preferred 0.5～4 hour.And the addition of described water-containing column will make that the proportioning of this water-containing column and described magnesium compound is 1: 0.2～4, preferred 1: 0.5～1 by mass.
In step (3), described solid-liquid separation and drying can select for use one of following mode to carry out: mode (1): add varsol (precipitation solvent) in the solidliquid mixture that step (2) obtains, thereby the described pure magnesium compound that exists in the solution is precipitate on the described water-containing column, filter then, wash and the dry solid matter that is obtained, thereby obtain described complex carrier; Mode (2): the solidliquid mixture that filtration step (2) obtains, wash then and the dry solid matter that is obtained, thereby obtain described complex carrier; Perhaps mode (3): the solidliquid mixture that drying step (2) obtains, thus obtain described complex carrier.In the method for the invention, described solid-liquid separation and dry preferred employing mode (1) are carried out.
When employing mode (1) is carried out described solid-liquid separation and drying, described varsol is selected from tetrahydrofuran (THF) and dissolves each other, but can not dissolve the aliphatic hydrocarbon or the aromatic hydrocarbon of described pure magnesium compound or described magnesium compound, the preferred fat hydrocarbon, such as butane, Skellysolve A, iso-pentane, hexane, heptane, octane, octane-iso, decane and hexanaphthene etc., further preferred Skellysolve A, iso-pentane, hexane and, decane, more preferably Skellysolve A and hexane.
Described filtration, washing and the dry mode of routine that can all adopt are carried out.Such as, when washing, can add cleaning solvent earlier, stirred then 5～60 minutes, skim supernatant liquor then, or add cleaning solvent earlier, stirred then 5～60 minutes, then conventional filtration.Washing times is generally 2～8 times, preferred 3～6 times.Drying then can adopt heating method, heating, vacuum desiccating method or hot inert gas desiccating method etc. are not carried out, preferably not heating, vacuum desiccating method or hot inert gas desiccating method, and the Heating temperature of this moment can suitably be selected, but preferably is lower than solvent boiling point below 5 ℃.The rare gas element here refers to the gas that nitrogen or argon gas etc. do not react with heated material.Described cleaning solvent can adopt varsol, and described varsol can be from carrying out the described solid-liquid separation of step (3) at employing mode (1) and selecting the cited varsol when dry before.
In step (4), in the complex carrier that step (3) is obtained, under agitation add halogenated titanium or its solution as the Ziegler-Natta catalyst active ingredient, drying after the optional solid-liquid separation, thus make loading type Ziegler-Natta catalyst component of the present invention.
Described halogenated titanium as the Ziegler-Natta catalyst active ingredient can be selected from conventional those halogenated titaniums that use in this area, such as enumerating titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide, titanium tetra iodide etc., preferred titanium tetrachloride.
Described halogenated titanium or its solution can adopt any way to add in the described complex carrier, but preferably drip mode, and described stirring also can be undertaken by the usual manner of this area.
The solvent that is adopted when the described halogenated titanium solution of preparation can be from carrying out the described solid-liquid separation of step (3) before at employing mode (1) and selecting the cited varsol when dry, as long as it can dissolve halogenated titanium of the present invention with the solubleness of regulation.
After adding described halogenated titanium, described halogenated titanium and described complex carrier reacted 0.5～24 hour, drying then, thus make loading type Ziegler-Natta catalyst component of the present invention.When the form of solution adds described halogenated titanium, make described halogenated titanium solution and described complex carrier reaction 0.5～24 hour, the solidliquid mixture of solid-liquid separation gained afterwards, drying then, thus make loading type Ziegler-Natta catalyst component of the present invention.Described solid-liquid separation can be carried out according to the filtration washing mode of routine.Carry out cleaning solvent that described washing the time adopted and can adopt solvent identical when preparing this solution, washing times is generally 1～8 time, preferred 2～6 times.
Dry can adopt the mode of this area routine to carry out, such as adopting heating method, not heating, vacuum desiccating method or hot inert gas desiccating method, preferably not heating, vacuum desiccating method or hot inert gas desiccating method.Heating temperature can suitably be selected, but preferably is lower than solvent boiling point below 5 ℃.The rare gas element here refers to the gas that nitrogen or argon gas etc. do not react with heated material.
In described step (4), by the mole number of magnesium elements and titanium elements for, the proportioning of described complex carrier and described halogenated titanium is 1: 0.4～4, preferred 1: 0.5～1.5.
In addition, when carrying out described step (4) since the halogenated titanium that adopted easily and water or oxygen-containing gas etc. react, so, under inert atmosphere, carry out as this step 1, this is known in those skilled in the art.
After having obtained loading type Ziegler-Natta catalyst component of the present invention, itself and promotor are combined, can obtain loading type Ziegler-Natta catalyst of the present invention.
Described promotor generally is selected from aluminum alkyls or alkylaluminoxane, and it is described that it is specified the literary composition that sees before.
When constituting loading type Ziegler-Natta catalyst of the present invention, mole number in the titanium elements in aluminium element in the described promotor and the loading type Ziegler-Natta catalyst component of the present invention (Primary Catalysts) is, the proportioning of described Primary Catalysts and described promotor is 20～1000, preferred 30～500, more preferably 50～200.
As previously mentioned, loading type Ziegler-Natta catalyst of the present invention can be used for the copolyreaction carried out between the homopolymerization of catalyzed alkene and two or more different alkene.
Therefore, another object of the present invention is the equal polymerization of catalysis of adopting loading type Ziegler-Natta catalyst of the present invention to carry out alkene, the copolymerization of carrying out between the perhaps catalysis different alkene.
In this further embodiment, technical scheme involved in the present invention is: a kind of catalysis homopolymerization or copolymerization process of alkene, it is characterized in that, may further comprise the steps: adopt loading type Ziegler-Natta catalyst of the present invention, under polymeric reaction condition, in polymerization reactor, introduce polymerization single polymerization monomer and/or copolymerization monomer, carry out equal polymerization of alkene and/or copolymerization.
Here said alkene is selected from C
2～C
10Alkene, diolefin or cycloolefin, as ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene or vinylbenzene, 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1,7-octadiene etc.The said equal polymerization of the present invention is meant the polyreaction that single alkene, diolefin or the cycloolefin that contains two keys carries out, and copolymerization is meant the polymerization process of being carried out between two kinds or two or more alkene, diolefin or the cycloolefin.
The catalysis homopolymerization of alkene of the present invention or copolymerization process can adopt variety of way to carry out, such as enumerating slurry process, emulsion method, solution method, substance law and vapor phase process, and wherein preferred vapor phase process and slurry process, special preferred slurries method.
When need adopting solvent, used polyreaction can be the solvent that this area is used always when carrying out this class olefinic polymerization or copolymerization with solvent in equal polymerization of alkene of the present invention or the copolymerization.Typical solvent is the varsol of 5 to 12 carbon atoms, or the varsol of 5 to 12 carbon atoms that replaced by the chlorine atom, such as methylene dichloride, or the ether solvent, such as ether or tetrahydrofuran (THF).Described solvent optimization aromatic solvent is such as toluene and dimethylbenzene; The aliphatic solvent of 6 to 10 carbon atoms is such as hexane, heptane, octane, nonane, decane or their isomer; The cycloaliphatic solvent of 6 to 12 carbon atoms is as hexane; Or their mixture.Most preferably hexane is as polyreaction solvent of the present invention.
Loading type Ziegler-Natta catalyst preferred concentration range is 0.001～1 gram loaded catalyst/rise polyreaction solvent in the catalyst system, most preferably 0.005～0.2 restrains loaded catalyst/rise polyreaction solvent.
When carrying out equal polymerization of alkene of the present invention or copolymerization, if reaction needed is carried out under certain pressure, then polymerization pressure is the conventional pressure of this area when carrying out this class reaction, generally between 0.1～10MPa, preferred 0.3～4.0MPa, most preferably 0.5～3.0MPa.
In olefinic polymerization of the present invention and process for copolymerization, conditions of polymerization temperature vary is the normal condition in this area, is generally-40 ℃～200 ℃, preferred 10 ℃～150 ℃, and most preferably 40 ℃～90 ℃.
In equal polymerization of alkene of the present invention or copolymerization, the form that comonomer is incorporated in the polymerization container can be intermittently, also can be continuous uninterrupted.According to the needs to copolymerized product after the polymerization, the introducing amount of comonomer can be 0.01～50% (for the polymerization product total amount).
In equal polymerization of alkene of the present invention or copolymerization, when reaction needed stirs, can adopt conventional alr mode, stir speed (S.S.) generally is 1～2000 rev/min, preferred 20～300 rev/mins.
Equal polymerization of alkene of the present invention or copolymerization can be carried out under the condition that hydrogen exists, and also can carry out under the condition that does not have hydrogen to exist.If desired, then the dividing potential drop of hydrogen can be 0.01%～99% of a polymerization pressure, and preferred hydrogen partial pressure accounts for 0.01%～50% of polymerization pressure.
As previously mentioned, loading type Ziegler-Natta catalyst of the present invention is particularly suitable for the slurry polymerization reaction.
Therefore, also purpose of the present invention provides a kind of slurry phase polymerisation process, and this method has adopted loading type Ziegler-Natta catalyst of the present invention.
Except concrete regulation, other item with before the explanation done at the equal polymerization of alkene or copolymerization.
Loading type Ziegler-Natta catalyst preferred concentration range is 0.001～1 gram loaded catalyst/rise polyreaction solvent, most preferably 0.005～0.2 restrains loaded catalyst/rise polyreaction solvent.
The polymerization temperature that adopts in the slurry phase polymerisation process of the present invention is the conventional temperature of this area, is generally 10～100 ℃, and preferred 10～95 ℃, more preferably 30～95 ℃, polymerization pressure is 0.1～3.0MPa, preferred 0.5～2.0MPa.
Slurry polymerization form of the present invention comprises: ethylene homo, ethene and C
3-C
12Alpha-olefinic copolymerization, or in the presence of hydrogen ethylene homo, ethene and C
3-C
12Alpha-olefinic copolymerization.Wherein, C
3-C
12Can be propylene, butene-1, amylene-1, hexene-1,4-methyl-amylene-1, heptene-1, octene-1, or norbornylene etc.Wherein, preferred propylene, butene-1, hexene-1, octene-1 and norbornylene, most preferably propylene, butene-1, hexene-1.
For the melting index of telomerized polymer, in slurry polymerization process of the present invention, use hydrogen usually as chain-transfer agent.The amounts of hydrogen of using can account for 0.01～0.99 (volume ratio) of total gas volume, preferred 0.01～0.50 (volume ratio).
When adopting loading type Ziegler-Natta catalyst provided by the present invention to carry out polymerization process, the polymkeric substance that is obtained will duplicate the grain size of Primary Catalysts, be to be template in the polymerization process, and to form thereon with the Primary Catalysts be the polymer beads of core with the Primary Catalysts.
The invention effect
When preparation loading type Ziegler-Natta catalyst of the present invention, silica-gel carrier did not need thermal activation or chemical activation before using, therefore can simplify the preparation method, thereby reduced the manufacturing cost of catalyzer.
The present invention finds, by adopting loading type Ziegler-Natta catalyst component of the present invention, only need fewer methylaluminoxane or triethyl aluminum consumption just can obtain the active loading type Ziegler-Natta catalyst that improves of olefinic polymerization catalysis as Primary Catalysts; And polymkeric substance such as resulting polyethylene has the tap density of raising thus.
The size distribution that adopts loading type Ziegler-Natta catalyst size distribution of the present invention to duplicate water-containing column, and the activity of such catalysts that is obtained does not have obvious variation because adopting the water-containing column of different-grain diameter distribution.
The size distribution that the polymkeric substance particle diameter that adopts loading type Ziegler-Natta catalyst of the present invention to obtain by polymerization process distributes and duplicated loading type Z-N Primary Catalysts, be template with the Primary Catalysts in the polymerization process, and to form thereon with the Primary Catalysts be the polymer beads of core, under the close condition of activity, polymkeric substance particle diameter equal proportion increases.
The polymkeric substance that adopts loading type Ziegler-Natta catalyst of the present invention to be obtained, even particle size distribution, and narrow particle size distribution, fine powder amount (granularity less than 75 microns polymkeric substance) reduces, and when carrying out copolymerization, the amount of the oligopolymer that is generated (the leachable thing of solvent) reduces.
The present invention finds, when the equal polymerization of catalysis of adopting loading type Ziegler-Natta catalyst of the present invention to carry out alkene or copolymerization, with adopt thermal activation after silica gel and the loading type Ziegler-Natta catalyst of the same type that obtains is compared, the kinetics of polyreaction is easily control steadily, and activity of such catalysts discharges steadily.
And, the present invention also finds, loading type Ziegler-Natta catalyst of the present invention is in catalyzed ethylene and butylene copolymerization, or shows the copolymerization effect when catalyzed ethylene and hervene copolymer, that is, the specific activity catalyzed ethylene homopolymerization that this moment, catalyzer showed is fashionable higher.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the invention is not restricted to these embodiment.
Polymer stacks density measurement reference standard GB 1636-79 carries out.
The moisture determination of water-containing column adopts thermogravimetry to carry out.
Active metallic content mensuration reference standard Q/SH105502-2003 carries out in the Primary Catalysts.
Polymerization kinetics is measured to adopt under certain stagnation pressure condition and is carried out in the mode of the online detection ethene of mass flowmeter consumption.
The size-grade distribution of Primary Catalysts and polymkeric substance adopts the polymer particle size distributional analysis to carry out on Beckman Coulter LS230 type laser particle size analyzer, and its particle size measurement scope is 0.04～2000 micron.
Catalyst activity calculates in accordance with the following methods: after polyreaction finishes, the polymerisate in the reactor is filtered and drying, the quality of this polymerisate of weighing is represented catalyst activity with this polymerisate quality divided by the ratio of Primary Catalysts quality then.
The oligomer test is calculated in accordance with the following methods: the slurry after polyreaction is finished is measured 1 liter of solution through after the sedimentation, and polymer solvent is evaporated back weighing residuum weight (g) fully, is oligomer (g/L).
Fine powder content is by carrying out on the Beckman Coulter LS230 type laser particle size analyzer, calculates granularity less than 75 microns polymer content.
Carrier adopts silica gel, and model is ES757 (Ineos company product, 25 microns of median sizes, specific surface area 300m
2/ g, mean pore size 19.5nm, pore volume 1.6ml/g), without activation, its water-content is 4.09%.
Take by weighing the 3.4g Magnesium Chloride Anhydrous, add 75ml tetrahydrofuran (THF) and 8.5ml ethanol, being stirred to Magnesium Chloride Anhydrous under 60 ℃ dissolves fully, add the described silica gel of 4.0g, continue stirring reaction 4h. down at 60 ℃ and be cooled to 32 ℃, add 45ml hexane (precipitation solvent), this moment, slurry temp was 25 ℃, filter then, adopt 45ml * 2 hexane wash, under 80 ℃, vacuumize drying and obtain powder solid.
Take by weighing above-mentioned powder solid, the hexane solution (concentration is 5% volume ratio) that adds the 50ml titanium tetrachloride, 60 ℃ are stirred 5h down, filter then, adopt 45ml * 2 hexane wash, under 60 ℃, vacuumize drying and obtain white solid particulate Primary Catalysts (being loading type Ziegler-Natta catalyst component), be designated as CAT-1.Ti content is 3.02% in the Primary Catalysts.
In the preparation process, water-containing column and magnesium compound quality proportioning are 1: 0.85, and magnesium compound is 1: 4.13 with the mol ratio of alcohol, and magnesium compound and titanium tetrachloride mol ratio are 1: 0.64.
Embodiment 1-A
Take by weighing 44mgCAT-1, the hexane solution that adds 3.1ml promotor triethyl aluminum (abbreviates AT as, concentration 0.88mol/L), the aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 98.5, obtain loading type Ziegler-Natta catalyst of the present invention.
This catalyzer is joined 2 risings presses in the reactor, add the 1L hexane again, open and stir, rotating speed is 250 rev/mins, feeds hydrogen to 0.11MPa, be warmed up to 85 ℃ after, feed ethene continuously, control reactor total pressure is 0.8MPa, emptying behind the reaction 2h. weighing is 370g after the taking-up polymkeric substance drying, and tap density is 0.35g/cm
3. oligomer 0.14g/L.Fine powder content 1.77%.
Embodiment 1-B
Process is with embodiment 1-A, but just like following change:
Use 20mgCAT-1, the hexane solution (concentration 0.88mol/L) of 3.0ml promotor triethyl aluminum is formed loading type Ziegler-Natta catalyst of the present invention.Wherein, the aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 211, and do not add hydrogen before polyreaction.
Weighing is 632g after the polymkeric substance drying, and tap density is 0.32g/cm
3. oligomer 0.27g/L.
Embodiment 1-C
Process is with embodiment 1-A, but just like following change:
Use 50mgCAT-1, the hexane solution (concentration 0.88mol/L) of 16.0ml promotor triethyl aluminum is formed loading type Ziegler-Natta catalyst of the present invention.Wherein, the mol ratio of aluminium element in the promotor and the titanium elements in the Primary Catalysts is 450.After feeding ethene 5min, adding 150g hexene-1.
Weighing is 475g after the polymkeric substance drying, and tap density is 0.33g/cm
3Oligomer 1.34g/L.
Embodiment 1-D
Process is with embodiment 1-A, but just like following change:
Use 50mgCAT-1, the hexane solution (concentration 0.88mol/L) of 35.5ml promotor triethyl aluminum is formed loading type Ziegler-Natta catalyst of the present invention.Wherein, the aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 1000, behind the feeding ethene 5min, add the 60g butene-1.
Weighing is 540g after the polymkeric substance drying, and tap density is 0.26g/cm
3Oligomer 1.67g/L.
Embodiment 1-E
Basic identical with embodiment 1-A, but following change is arranged:
The CAT-1 add-on is 37mg, and promotor changes methylaluminoxane (MAO, concentration is 10wt%, toluene solution, aluminium content 4.64wt%) into, forms loading type Ziegler-Natta catalyst of the present invention.Wherein, the mol ratio of aluminium element in the promotor and the titanium elements in the Primary Catalysts is 236.
After feeding ethene 5min, add the 50g octene-1.
Weighing is 437g after the polymkeric substance drying, and tap density is 0.35g/cm
3
Embodiment 1-F
Basic identical with embodiment 1-A, but following change is arranged:
Promotor changes trimethyl aluminium into;
Polymerization changes pentane into solvent;
After feeding ethene 5min, add the 30g norbornylene.
60 ℃ of polymerization temperatures, polymerization pressure 1.0MPa, hydrogen partial pressure 0.3MPa.
The aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 147.
Embodiment 1-G
Basic identical with embodiment 1-A, but following change is arranged:
Promotor changes triisobutyl aluminium into;
Polymerization changes decane into solvent;
After feeding ethene 5min, add 1,4-divinyl 50g.
120 ℃ of polymerization temperatures, polymerization pressure 1.6MPa, hydrogen partial pressure 0.8MPa.
The aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 426.
Embodiment 1-H
Basic identical with embodiment 1-A, but following change is arranged:
Promotor changes triethyl alumina alkane into;
Polymerization changes toluene into solvent;
After feeding ethene 5min, add 50g vinylbenzene.
95 ℃ of polymerization temperatures, polymerization pressure 1.2MPa, hydrogen partial pressure 0.5MPa.
The aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 20.
Embodiment 1-I
Basic identical with embodiment 1-A, but following change is arranged:
Promotor changes triisobutyl alumina alkane into;
Polymerization changes ethylbenzene into solvent;
After feeding ethene 5min, add the 100g propylene.
60 ℃ of polymerization temperatures, polymerization pressure 2.0MPa, hydrogen partial pressure 0.5MPa.
The aluminium element in the promotor and the mol ratio of the titanium elements in the Primary Catalysts are 771.
Embodiment 1-J
Basic identical with embodiment 1-A, but following change is arranged:
Silica gel adopts ES70 (Ineos company product, 38 microns of median sizes, specific surface area 300m
2/ g, mean pore size 19.5nm, pore volume 1.6ml/g, silica gel water content 4.09%).
Primary Catalysts is designated as CAT-1-J.
Polymerization process is also identical with embodiment 1-A.
By table 1 as seen, adopt the water-containing column carrier particle diameter of the same water content of different-grain diameter that polymerization activity is not obviously influenced.
In order to compare, adopt the Primary Catalysts CAT-1-J of embodiment 1-J acquisition and the Primary Catalysts CAT-1 of embodiment 1 acquisition to carry out polyreaction according to the method for embodiment 1-A, resulting polymkeric substance grain size distribution curve separately is shown among Fig. 1.From this figure as seen, owing to adopt the silica-gel carrier of greater particle size, the Primary Catalysts particle diameter is equal proportion increase thereupon also.Can prove thus, adopt method for preparing catalyst provided by the present invention, physics and/or chemical reaction that alcohol magnesium compound and water-containing column are carried out carry out in the silica gel hole, this alcohol magnesium compound finally is present in the silica gel hole, rather than depends on silica gel surface (otherwise the Primary Catalysts particle diameter can increase more than the water-containing column particle diameter) in a large number.This also is by one of good reason of catalyzer form provided by the present invention.
From the contrast of Fig. 1 also as can be known, the polymer replication that is obtained the grain size of Primary Catalysts, in polymerization process, be template, and to form thereon with the Primary Catalysts be the polymer beads of core with the Primary Catalysts, under the close condition of activity, the particle diameter equal proportion of polymkeric substance increases.This also is one of catalyzer provided by the present invention reason of obtaining the good polymer beads of form when being used for polymerization.
Comparative example 1-1
Substantially the same manner as Example 1, but following change is arranged:
Silica gel is at 650 ℃ of following constant temperature fluidisation 6h of nitrogen atmosphere, and by thermal activation treatment, the final water content 0.38wt% of silica gel.
The Primary Catalysts that is obtained is designated as CAT-1-1.
Polymerization process is also identical with embodiment 1-A.
Its polymerization kinetics curve is seen accompanying drawing 1.
Oligomer 2.62g/L. fine powder content 4.53%.
Thus example as seen, fashionable in the catalyzed ethylene homopolymerization by the prepared catalyzer of silica gel after activating, oligomer and fine powder amount all are higher than the catalyzer that the present invention makes.
Fig. 2 is the polymerization kinetics curve when carrying out polyreaction among embodiment 1-A and the comparative example 1-1.As shown in the drawing, adopt the loading type Ziegler-Natta catalyst of the silica gel of process thermal activation treatment as preparing carriers, polymerization kinetics presented decay when it was used for catalysis in olefine polymerization, and promptly the prolongation polymerization activity with polymerization time reduces gradually.Has the silica gel of certain water content as the prepared loading type Ziegler-Natta catalyst of the present invention of carrier and adopt without heat treated, polymerization kinetics presented stability when it was used for catalysis in olefine polymerization, and promptly the prolongation polymerization activity with polymerization time can keep not changing substantially.
Embodiment 1-A1
Basic identical with embodiment 1-A, but following change is arranged:
After feeding ethene 5min, add the 50g butene-1.
Weighing is 447g after the taking-up polymkeric substance drying, and tap density is 0.34g/cm
3
Thus embodiment as can be known, catalyzer of the present invention is when the copolymerization of catalyzed ethylene and butene-1, its catalytic activity is higher than the fashionable activity of catalyzed ethylene homopolymerization, has shown second fourth copolymerization effect.Oligomer 1.42g/L.
Embodiment 1-A2
Basic identical with embodiment 1-A, but following change is arranged:
After feeding ethene 5min, add 50g hexene-1.
Weighing is 412g after the taking-up polymkeric substance drying, and tap density is 0.36g/cm
3
Thus embodiment as can be known, catalyzer of the present invention is when the copolymerization of catalyzed ethylene and hexene-1, its activity is higher than the fashionable activity of catalyzed ethylene homopolymerization, has shown the own copolymerization effect of second.Oligomer 1.07g/L.
Substantially the same manner as Example 1, but just like following change:
The silica gel water-content is 0.50%;
Water-containing column and magnesium compound quality proportioning are 1: 0.52, and magnesium compound and alcoholic extract hydroxyl group mol ratio are 1: 2.5, and magnesium compound and titanium tetrachloride mol ratio are 1: 1, and cleaning solvent adopts Skellysolve A.
Primary Catalysts is designated as CAT-2.
Polymerization process is also identical with embodiment 1-A.
Substantially the same manner as Example 1, but just like following change:
The silica gel water-content is 2.70%.
Water-containing column and magnesium compound quality proportioning are 1: 1, and magnesium compound and alcoholic extract hydroxyl group mol ratio are 1: 5.4, and magnesium compound and titanium tetrachloride mol ratio are 1: 1.5, and cleaning solvent adopts pentane.
Primary Catalysts is designated as CAT-3.
Polymerization process is also identical with embodiment 1-A.
Embodiment 4
Substantially the same manner as Example 1, but just like following change:
The silica gel water-content is 6.30%.
Water-containing column and magnesium compound quality proportioning are 1: 4, and magnesium compound and alcoholic extract hydroxyl group mol ratio are 1: 20, and magnesium compound and titanium tetrachloride mol ratio are 1: 4, and cleaning solvent adopts hexanaphthene.Primary Catalysts is designated as CAT-4.
Polymerization process is also identical with embodiment 1-A.
Substantially the same manner as Example 1, but just like following change:
The silica gel water-content is 8.00%.
Water-containing column and magnesium compound quality proportioning are 1: 2, and magnesium compound and alcoholic extract hydroxyl group mol ratio are 1: 2, and magnesium compound and titanium tetrachloride mol ratio are 1: 1.5, and cleaning solvent adopts toluene.
Primary Catalysts is designated as CAT-5.
Polymerization process is also identical with embodiment 1-A.
Embodiment 6
Substantially the same manner as Example 1, but just like following change:
The employing model is the silica gel of Grace955 (Grace davison company product, water content is 0.83%).
Anhydrous magnesium nitride changes MgClOCH into
3
Ethanol changes hexalin into.
Primary Catalysts is designated as CAT-6.
Polymerization process is also identical with embodiment 1-A.
Substantially the same manner as Example 1, but just like following change:
The employing model is CS-2133 (Pq Corp.'s product, water content are a 1.70%) silica gel.
Magnesium Chloride Anhydrous changes MgClOCH into
2CH
3
Ethanol changes propyl alcohol into;
Primary Catalysts is designated as CAT-7.
Polymerization process is also identical with embodiment 1-A.
Substantially the same manner as Example 1, but just like following change:
The employing model is MS-3040 (Pq Corp.'s product, water content are a 2.40%) silica gel.
Magnesium Chloride Anhydrous changes MgBrOC into
2H
5
Ethanol changes butanols into;
Primary Catalysts is designated as CAT-8.
Polymerization process is also identical with embodiment 1-A.
Embodiment 9
Substantially the same manner as Example 1, but just like following change:
The employing model is ES70 (Ineos company product, water content are a 4.95%) silica gel.
Magnesium Chloride Anhydrous changes Mg (OC into
4H
9)
2
Ethanol changes butanols into;
Primary Catalysts is designated as CAT-9.
Polymerization process is also identical with embodiment 1-A.
Substantially the same manner as Example 1, but just like following change:
Adopting model is Grace SP9-485 (Grace davison company product, water content is 6.74%) silica gel.
Magnesium Chloride Anhydrous changes MgBr into
2
Ethanol changes ethylene glycol into;
Primary Catalysts is designated as CAT-10.
Polymerization process is also identical with embodiment 1-A.
Embodiment 11
Substantially the same manner as Example 1, but just like following change:
The employing model is ES70 (Ineos company product, water content are a 3.37%) silica gel.
Magnesium Chloride Anhydrous changes MgBr into
2
Ethanol changes phenylcarbinol into;
Primary Catalysts is designated as CAT-11.
Polymerization process is also identical with embodiment 1-A.
The effect table look-up of table 1 loading type Ziegler-Natta catalyst of the present invention in catalyzed alkene homopolymerization/copolyreaction
| Embodiment | The Primary Catalysts kind | The silica gel water content, wt% | The Primary Catalysts consumption, mg | The promotor kind | Al/ Ti, mol ratio | The polymerization solvent | Polymerization temperature ℃ | The comonomer kind | The comonomer add-on, g | The polymerization total pressure, MPa | Hydrogen partial pressure, MPa | Catalyst activity, kgPE/gCat | Polymer stacks density, g/cm 3 | The oligopolymer amount, g/L |
| Embodiment 1-A | CAT-1 | 4.09 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 8.41 | 0.35 | 0.14 | ||
| Embodiment 1-B | CAT-1 | 4.09 | 20 | Triethyl aluminum | 211 | Hexane | 85 | 0.8 | 31.60 | 0.32 | 0.27 | |||
| Embodiment 1-C | CAT-1 | 4.09 | 50 | Triethyl aluminum | 450 | Hexane | 85 | Hexene-1 | 150 | 0.8 | 0.11 | 9.50 | 0.33 | 1.34 |
| Embodiment 1-D | CAT-1 | 4.09 | 50 | Triethyl aluminum | 1000 | Hexane | 85 | Butene-1 | 60 | 0.8 | 0.11 | 10.80 | 0.26 | 1.67 |
| Embodiment 1-E | CAT-1 | 4.09 | 37 | Methylaluminoxane | 236 | Hexane | 85 | Octene-1 | 50 | 0.8 | 0.11 | 11.81 | 0.35 | 0.22 |
| Embodiment 1-F | CAT-1 | 4.09 | 44 | Trimethyl aluminium | 147 | Pentane | 60 | Norbornylene | 30 | 1.0 | 0.30 | 2.46 | 0.30 | 0.11 |
| Embodiment 1-G | CAT-1 | 4.09 | 44 | Triisobutyl aluminium | 426 | Decane | 120 | 1, the 4-divinyl | 50 | 1.6 | 0.8 | 16.44 | 0.30 | 2.47 |
| Embodiment 1-H | CAT-1 | 4.09 | 44 | Triethyl alumina alkane | 20 | Toluene | 95 | Vinylbenzene | 50 | 1.2 | 0.5 | 13.40 | 0.29 | 1.94 |
| Embodiment 1-I | CAT-1 | 4.09 | 44 | Triisobutyl alumina alkane | 771 | Ethylbenzene | 60 | Propylene | 100 | 2.0 | 0.5 | 27.66 | 0.34 | 3.52 |
| Embodiment 1-J | CAT-1-J | 4.09 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 8.39 | 0.35 | 0.13 | ||
| Comparative example 1-1 | CAT-1-1 | 0.38 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 6.67 | 0.30 | 2.62 | ||
| Embodiment 1-A1 | CAT-1 | 4.09 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | Butene-1 | 50 | 0.8 | 0.11 | 10.16 | 0.34 | 1.42 |
| Embodiment 1-A2 | CAT-1 | 4.09 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | Hexene-1 | 50 | 0.8 | 0.11 | 9.36 | 0.36 | 1.07 |
| Embodiment 2 | CAT-2 | 0.50 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 6.94 | 0.32 | 2.24 | ||
| Embodiment 3 | CAT-3 | 2.70 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 7.57 | 0.31 | 0.55 |
Annotate: 2 liters of polymerization autoclaves have been adopted in homopolymerization/copolymerization, and the polyreaction form is a slurry polymerization, and polymerization reaction time is 2 hours.
The effect table look-up (continue) of table 1 loading type Ziegler-Natta catalyst of the present invention in catalyzed alkene homopolymerization/copolyreaction
| Embodiment | The Primary Catalysts kind | The silica gel water content, wt% | The Primary Catalysts consumption, mg | The promotor kind | Al/ Ti, mol ratio | The polymerization solvent | Polymerization temperature ℃ | The comonomer kind | The comonomer add-on, g | The polymerization total pressure, MPa | Hydrogen partial pressure, MPa | Catalyst activity, kgPE/gCat | Polymer stacks density, g/cm 3 | The oligopolymer amount, g/L |
| Embodiment 4 | CAT-4 | 6.30 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 7.96 | 0.26 | 0.94 | ||
| |
CAT-5 | 8.00 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 5.27 | 0.25 | 0.35 | ||
| Embodiment 6 | CAT-6 | 0.83 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 8.03 | 0.30 | 1.61 | ||
| |
CAT-7 | 1.70 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 7.88 | 0.31 | 1.17 | ||
| |
CAT-8 | 2.40 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 7.67 | 0.29 | 0.86 | ||
| Embodiment 9 | CAT-9 | 4.95 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 7.55 | 0.31 | 0.18 | ||
| |
CAT-10 | 6.74 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 6.84 | 0.30 | 0.21 | ||
| Embodiment 11 | CAT-11 | 3.37 | 44 | Triethyl aluminum | 98.5 | Hexane | 85 | 0.8 | 0.11 | 4.47 | 0.29 | 0.34 |
Annotate: 2 liters of polymerization autoclaves have been adopted in homopolymerization/copolymerization, and the polyreaction form is a slurry polymerization, and polymerization reaction time is 2 hours.
Claims (39)
1. loading type Ziegler-Natta catalyst component is characterized in that this catalyst component is represented with following formula:
(S·M)·T
Wherein, the S representative is as the water-containing column of carrier, M representative and this water-containing column bonded alcohol magnesium compound, and the T representative loads on by described S and described M by in conjunction with the halogenated titanium as the Ziegler-Natta catalyst active ingredient on the complex carrier that constitutes.
2. according to the described loading type Ziegler-Natta catalyst of claim 1 component, it is characterized in that the water content of described water-containing column is 0.5～8 weight %.
3. according to the described loading type Ziegler-Natta catalyst of claim 2 component, it is characterized in that the water content of described water-containing column is 2～6 weight %.
4. according to the described loading type Ziegler-Natta catalyst of claim 3 component, it is characterized in that the water content of described water-containing column is 3.5～4.5 weight %.
5. according to the described loading type Ziegler-Natta catalyst of claim 1 component, it is characterized in that described pure magnesium compound is a formed compound when making magnesium compound be dissolved in the tetrahydrofuran solvent under the condition that alcohol exists.
6. according to the described loading type Ziegler-Natta catalyst of claim 1 component, it is characterized in that described magnesium compound is selected from magnesium halide, alkoxyl group magnesium halide and alkoxyl magnesium.
7. according to the described loading type Ziegler-Natta catalyst of claim 6 component, it is characterized in that described magnesium compound is selected from magnesium halide.
8. according to the described loading type Ziegler-Natta catalyst of claim 7 component, it is characterized in that described magnesium compound is selected from magnesium chloride.
9. according to the described loading type Ziegler-Natta catalyst of claim 1 component, it is characterized in that described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18), cyclic alcohol or aromatic alcohol.
10. according to the described loading type Ziegler-Natta catalyst of claim 9 component, it is characterized in that described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
11., it is characterized in that described alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, octanol and isooctyl alcohol according to the described loading type Ziegler-Natta catalyst of claim 9 component.
12., it is characterized in that described alcohol is selected from ethanol and butanols according to the described loading type Ziegler-Natta catalyst of claim 9 component.
13., it is characterized in that described halogenated titanium is selected from one or more in titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tribromide and the titanium tetra iodide according to the described loading type Ziegler-Natta catalyst of claim 1 component.
14., it is characterized in that described halogenated titanium is selected from titanium tetrachloride according to the described loading type Ziegler-Natta catalyst of claim 13 component.
15. a loading type Ziegler-Natta catalyst is characterized in that, this catalyzer by according to each described loading type Ziegler-Natta catalyst component of claim 1-14 as Primary Catalysts, alkylaluminoxane or aluminum alkyls constitute as promotor.
16., it is characterized in that described alkylaluminoxane is selected from the linear alkyl aikyiaiurnirsoxan beta of formula (I) according to the described loading type Ziegler-Natta catalyst of claim 15:
And the ring-type type alkylaluminoxane of formula (II):
In formula (I) with (II), radicals R is identical or different, is selected from C
1-C
8Alkyl, n are the integer of 1-50.
17., it is characterized in that in formula (I) with (II), described R group is identical, and is selected from methyl, ethyl or isobutyl-according to the described loading type Ziegler-Natta catalyst of claim 16, n is 10～30 integer.
18., it is characterized in that described R group is a methyl according to the described loading type Ziegler-Natta catalyst of claim 17.
19., it is characterized in that described aluminum alkyls is selected from the compound of following formula (III) according to the described loading type Ziegler-Natta catalyst of claim 15:
Al(R)
3 (III)
In the formula (III), each radicals R is identical or different, is selected from C
1-C
8Alkyl.
20. according to the described loading type Ziegler-Natta catalyst of claim 19, it is characterized in that described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopentyl aluminium, three n-pentyl aluminium, triisopentyl aluminium, three hexyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum and three amyl group aluminium.
21. the preparation method of a loading type Ziegler-Natta catalyst component, it is according to the preparation method of each described loading type Ziegler-Natta catalyst component of claim 1-14, it is characterized in that, comprises following steps:
(1) magnesium compound is dissolved in the tetrahydrofuran (THF) under the condition that alcohol exists, preparing uniform solution,
(2) in this solution, add water-containing column it reacted,
(3) solid-liquid separation and the dry solidliquid mixture that is obtained, with the preparation complex carrier and
(4) in this complex carrier, add halogenated titanium, thereby make this loading type Ziegler-Natta catalyst component as the Ziegler-Natta catalyst active ingredient.
22. according to the described preparation method of claim 21, it is characterized in that, in described step (1), by the mole number of magnesium elements and alcoholic extract hydroxyl group for, the mol ratio of described magnesium compound and described alcohol is 1: 1～20.
23., it is characterized in that the mol ratio of described magnesium compound and described alcohol is 1: 2～6 according to the described preparation method of claim 22.
24., it is characterized in that in step (2), the proportioning of described water-containing column and described magnesium compound is 1: 0.2～4 by mass according to the described preparation method of claim 21.
25., it is characterized in that the proportioning of described water-containing column and described magnesium compound is 1: 0.5～1 by mass according to the described preparation method of claim 24.
26. according to the described preparation method of claim 21, it is characterized in that, in step (3), in order to carry out described solid-liquid separation and drying, in the solidliquid mixture that step (2) obtains, add varsol, the described pure magnesium compound that exists in the solution is precipitate on the described water-containing column, filter then, wash and the dry solid matter that is obtained.
27., it is characterized in that described varsol is selected from aliphatic hydrocarbon or aromatic hydrocarbon according to the described preparation method of claim 26.
28., it is characterized in that described varsol is selected from Skellysolve A, iso-pentane, hexane and decane according to the described preparation method of claim 27.
29., it is characterized in that described varsol is selected from Skellysolve A and hexane according to the described preparation method of claim 28.
30. according to the described preparation method of claim 21, it is characterized in that, in described step (4), by the mole number of magnesium elements and titanium elements for, the proportioning of described complex carrier and described halogenated titanium be 1: 0.4～4.
31., it is characterized in that the proportioning of described complex carrier and described halogenated titanium is 1: 0.5～1.5 according to the described preparation method of claim 30.
32. the preparation method of a loading type Ziegler-Natta catalyst, it is according to the preparation method of each described loading type Ziegler-Natta catalyst of claim 15-20, it is characterized in that, comprises following steps:
With according to each described loading type Ziegler-Natta catalyst component of claim 1-14 as Primary Catalysts, add described alkylaluminoxane or aluminum alkyls therein as promotor, make this loading type Ziegler-Natta catalyst thus.
33., it is characterized in that, be that the proportioning of described Primary Catalysts and described promotor is 20～1000 in the mole number of the titanium elements in aluminium element in the described promotor and the described Primary Catalysts according to the described preparation method of claim 32.
34., it is characterized in that the proportioning of described Primary Catalysts and described promotor is 30～500 according to the described preparation method of claim 33.
35., it is characterized in that the proportioning of described Primary Catalysts and described promotor is 50～200 according to the described preparation method of claim 34.
36. the catalysis homopolymerization or the copolymerization process of an alkene is characterized in that, may further comprise the steps:
With according to each described loading type Ziegler-Natta catalyst of claim 15-20, perhaps according to the loading type Ziegler-Natta catalyst of each described preparation method preparation of claim 32-35 as catalyzer, carry out the homopolymerization or the copolymerization of described alkene.
37. catalysis homopolymerization or copolymerization process according to the described alkene of claim 36 is characterized in that described alkene is selected from C
2～C
10Alkene, diolefin and cycloolefin.
38. catalysis homopolymerization or copolymerization process according to the described alkene of claim 37, it is characterized in that, described alkene is selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene, vinylbenzene, 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1, the 7-octadiene.
39. catalysis homopolymerization or copolymerization process according to the described alkene of claim 36 is characterized in that described homopolymerization or copolymerization are carried out according to slurry process.
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| CN103044585A (en) * | 2012-12-26 | 2013-04-17 | 任丘市利和科技发展有限公司 | Method for preparing olefinic polymerization solid catalyst and carrier thereof |
| CN103071538A (en) * | 2013-01-31 | 2013-05-01 | 苏州瀚海高分子有限公司 | Catalyst for catalyzing cyclization trimerization reaction of butadiene and use method of catalyst |
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| IT1245250B (en) * | 1991-03-27 | 1994-09-13 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| CN1281634C (en) * | 2003-10-29 | 2006-10-25 | 扬子石油化工股份有限公司 | Loaded method of Non-metallocene catalyst loaded by composite carrier and polymerizing application |
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| CN112759679B (en) * | 2019-11-01 | 2023-02-28 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation and application thereof |
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