CN102286123A - catalyst component of ethylene polymerization and preparation method thereof - Google Patents
catalyst component of ethylene polymerization and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a supported chromium-based catalyst component for ethylene homopolymerization or alpha-alkene copolymerization, which relates to a supported chromium-based catalyst component modified by aluminium as well as a preparation method and an application of the catalyst component. In the catalyst component, the oxide is adopted as a carrier and an aluminum compound and a chromium compound are mutually supported on the carrier; the aluminum compound is introduced to improve the activity and melt index of the catalyst; wider distribution of molecular weight of polymer is obtained and the distribution width of the molecular weight can be adjusted; and better flowability of the polymer under the stress, which is the property required by multiple extrusion molding processes (such as film formation and blow molding), is obtained so that the catalyst component is suitable for wider machining range.
Description
Technical field
The present invention relates to a kind of supported chrome series catalysts component that is used for ethylene homo or ethene and alpha-olefin copolymer, more particularly, relate to a kind of with the supported chrome series catalysts component of aluminium modification and the preparation method and the application of this catalyst component.
Technical background
Ethene polymers has been widely used in various membrane product resin materials, and has different characteristics according to the different ethene polymerss that require with purpose of film system method.For example, the polymkeric substance with lower molecular weight and narrow molecular weight distributions is applicable to the goods by injection moulding film system.On the other hand, the polymkeric substance with higher molecular weight and wide molecular weight distribution is applicable to the goods by blowing or aerated film method for making film system.To ultra high molecular weight polyethylene, this quasi-polyethylene had enough intensity, has good processing properties simultaneously during (for example pipe applications) needed in many application.
Ethene polymers with wide molecular weight distribution can be by using the chromium-based catalysts preparation, described chromium-based catalysts is calcined in non-reduced atmosphere and is made its activation by loading on chromium cpd on the inorganic oxide carrier, and the chromium atom of partial load is converted into the sexavalent chrome atom.In the art, above-mentioned catalyzer is commonly referred to the Phillips catalyzer.Be immersed on the silicon-dioxide carriers such as (silica gel) with chromic salt, the catalyzer that obtains is removed after the moisture, and with dry air fluidisation activation under 400～1000 ℃ of temperature, this catalyzer is deposited in dry air or in the rare gas element again.This class catalyst component composition generally comprises carrier, active ingredient, is with or without promotor, wherein carrier is an inorganic oxide, active ingredient is the organic or inorganic compound of chromium, promotor is an organometallics, but concrete component concentration of each of catalyzer and preparation method have nothing in common with each other, thereby gained catalyst performance price differs greatly.
The characteristics of chrome catalysts are to have different active centre ratios for chainpropagation in the vinyl polymerization and chain transfer.This catalyzer tends to produce short polymer chain and comonomer is combined with short polymer chain with high frequency, has the comonomer and the side chain of uneven distribution between each macromole of the polymkeric substance that obtains thus.Therefore, the polymkeric substance of making can be wide molecular weight distribution, and this polymkeric substance has good processing properties.But this catalyzer also often has shortcomings such as induction time is long, the product melting index is low, copolymerization performance is poor, hydrogen regulation performance is insensitive.In order to overcome these shortcomings of chrome catalysts, the chromium-based catalysts of many modifications has appearred successively.Generally speaking, before preparation or in the preparation process, add some compounds, as contain the compound of elements such as titanium, fluorine, aluminium, magnesium, zirconium, realization is to the chemical modification of chrome catalysts or carrier, improve catalytic performance (Advances in catalyst 1985, the 33:47 ~ 98M.P.McDaniel) of chromium-based catalysts.
Chinese patent CN1165553C discloses a kind of Preparation of catalysts method that is used for olefinic polymerization.The clear solution of water glass, titanium sulfate and chromium sulphate is mixed preparation silica-titania-chromium gel, and the pH value of regulator solution is neutral, and experience is aging for the first time, and is aging for the second time under the PH of alkalescence condition then, final drying.The catalyzer copolymerization performance of this patented technology gained is improved, and the molecular weight of polymkeric substance reduces, and the melting index of resin increases, and the blowing performance of resin has obtained very big improvement, and the tear resistance of the film of blowing is better.But, all adopt in the patent silicon oxide, titanium, with the co-precipitation or the cogelled method of chromium cpd, the acquisition of carrier need be to co-precipitation or cogelled spraying drying or the azeotropic drying of carrying out, and the gained carrier also need carry out aging for a long time under basic neutral pH value.Such preparation process is very complicated, and the consumption time is long, the less stable of catalyst performance.
U.S. Pat 20040029727 discloses a kind of technology of preparing that is used for the chromium-based catalysts of catalyzed ethylene homopolymerization or copolymerization.At first the high-temperature activation alumina supporter is handled alumina supporter with titan-alkoxide and organoaluminum then, adds organo-chromium compound again, at last with the catalyzer high-temperature activation.The catalyzer of this patented technology gained can obtain the polyethylene of wide molecular weight distribution, but successively introduce the complicacy that titanium and aluminum compound have increased system, and the organoaluminum that uses is methylaluminoxane, because the price of methylaluminoxane is higher, directly increased the Preparation of catalysts cost.
Chinese patent CN101343336 discloses a kind of improved olefin polymerization catalysis and preparation method and application, comprises carrier and bistriphenyl silane chromate activeconstituents.Carrier described in the patent is the complex carrier of aluminum oxide and aluminum chloride, the catalyzer of this patented technology gained can improve ethylene polymerization activity effectively, adjust the hydrogen response and the copolymerization performance of catalyzer, the polyvinyl resin of preparation can be used for producing high-performance polyethylene tubing, coating materials etc.But, disclosed technology is the chromium source with the bistriphenyl silane chromate in this patent, after loading on bistriphenyl silane chromate on the complex carrier, the catalyzer that also will contain chromium with the aluminum alkyls reduction, complicated process of preparation, production cycle is longer, and this catalyzer mainly is applicable to gas-phase polymerization process.
Summary of the invention
The present invention is in order to overcome above-mentioned technical defective, provides that a kind of preparation method is simple, catalyst activity is very high when being used for vinyl polymerization, simultaneously the catalyst component of the ethene polymers of gained with wide molecular weight distribution.
Another object of the present invention has provided the above-mentioned preparation method who is used for the ethylene polymerization catalysts component.Three of purpose has provided a kind of polyvinyl catalyzer that can the production wide molecular weight distribution.
A kind of ethylene polymerization catalysts component that is used for of the present invention, this catalyst component is to be carrier with the oxide compound, and aluminum compound and chromium cpd are carried on the carrier jointly, chromium content is 0.1-10wt% in the catalyzer, preferred 0.1～8.0wt%; Aluminium content is 0.1-12wt%, preferred 0.2～8.0wt%.Described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium dioxide, zinc oxide, boron oxide and the zirconium white or their mixture, preferred silica gel.The general formula of described aluminum compound is: Al
y(OR
1)
m(R
2)
n(X)
z, R wherein
1And R
2Identical or different, be selected from hydrogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, X is a halogen, and wherein y is 1 or 2, and m, n, z are 0,1,2 or 3, and will satisfy m+n+z=3y; Be specially among triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, ethyl diethoxy aluminium, diethylaluminum ethoxide, sesquialter ethyl aluminum chloride, sesquialter methyl aluminum chloride, aluminium diethyl monochloride, a chlorine diethoxy aluminium, ethyl aluminum dichloride, dichloro aluminium isobutyl, dichloro aluminum ethoxide, aluminum chloride, alchlor, aluminium triiodide, methylaluminoxane, ethyl aikyiaiurnirsoxan beta, the sec.-propyl aikyiaiurnirsoxan beta one or more.
Described chromium cpd is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.Water miscible chromium cpd is specially a kind of in chromium trioxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Oil-soluble chromium cpd is tertiary butyl chromate, two luxuriant chromium or Acetyl Acetone acid chromium etc., preferably uses chromium trioxide or chromium nitrate.
Oxide carrier is generally the porous inorganic particulate that contains hydroxyl among the present invention, is good with spheric soild oxide carrier.As a kind of or its mixture in aluminum oxide, silicon-dioxide (silica gel), titanium dioxide, boron oxide, zirconium white, the aluminum phosphate, preferred silica gel is as carrier, and can select specific surface area for use is 245-375m
2The silica-gel carrier of/g, also can select specific surface area for use is 410-620m
2The silica-gel carrier of/g.Along with the carrier specific surface area increases, the hydrogen accent ability of catalyzer reduces; Along with specific surface area reduces, the polymerization activity of catalyzer reduces; Selected carrier silica gel also should have suitable pore volume.Can select pore volume for use is 1.1-1.8cm
3The carrier silica gel of/g, also can select pore volume for use is 2.4-3.7cm
3The carrier silica gel of/g.Along with the pore volume of carrier silica gel reduces, the hydrogen of catalyzer is transferred ability drop, but high pore volume carrier silica gel must prepare by solution extraction, and cost is higher.Can directly adopt the carrier that is purchased, the content of carrier in catalyzer is 70-100wt%, preferred 90-99wt%.
Oxide carrier described in the present invention will carry out drying treatment to remove free-water before load.Drying treatment can be carried out in air, also can carry out in rare gas element, can also finish under vacuum state.The temperature of drying treatment is generally at 100-800 ℃, and the time is 1-10 hour.
The present invention is used for the preparation method of ethylene polymerization catalysts component, and it may further comprise the steps:
(1) 100～800 ℃ of following drying treatment oxide carrier 1～10 hour;
(2) the oxide carrier contact reacts that aluminum compound and chromium cpd and step (1) are obtained, the weight ratio of the aluminum compound of carrier and adding is 10: 1～1000: 1, the weight ratio of the chromium cpd of carrier and adding is 10: 1～1000: 1, the temperature of reaction is-20 ℃～200 ℃, the time of reaction is 0.5～50hr, obtains the pre-catalyst component of load chromium;
(3) the pre-catalyst component of the chromium of load that step (2) is obtained in air, 400～1000 ℃ down calcining obtain catalyst component after 1-10 hour.
The addition sequence of aluminum compound described in the above-mentioned steps (2) and chromium cpd can add aluminum compound and chromium cpd simultaneously in oxide carrier, also can add aluminum compound earlier in oxide carrier, adds chromium cpd again; Also can in oxide carrier, add chromium cpd earlier, add aluminum compound again; Can also earlier aluminum compound and chromium cpd be mixed, then mixture be joined in the oxide carrier.
The carrier catalyst component of being made up of aluminum compound, chromium cpd and oxide carrier must could form the final catalyst component and be used for polymerization by activation.The activatory process is to carry out high-temperature calcination in air, and the incinerating temperature is 400-1000 ℃, preferred 600-800 ℃.Calcining and activating can be in dry air a step finish, also can in air, finish high-temperature activation earlier, with the carbon monoxide reduction, last cool to room temperature seals preservation in atmosphere of inert gases again.
The present invention also provides a kind of ethylene polymerization catalysts that is used for, and comprises following component:
(1) the present invention is above-mentioned is used for the ethylene polymerization catalysts component;
(2) promotor, mixture for one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements, the mol ratio of organometallic compound and chromium is 0.1: 1～100: 1, preferred 0.5: 1～50: 1.
Described promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements.Concrete as n-Butyl Lithium, triethyl-boron, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride and zinc ethyl etc.The C of alkoxide
1-C
10Aluminum alkyls such as oxyethyl group diethyl aluminum, methoxyl group diethyl aluminum etc.In addition, also can use methylaluminoxane, ethyl aikyiaiurnirsoxan beta or butyl aikyiaiurnirsoxan beta etc.
Catalyzer of the present invention can be used for ethylene homo, also can be used for ethene and other olefin-copolymerization.Described other alkene can be to contain C
3-C
20Alpha-olefin, aromatic vinyl compound, alicyclic ring vinyl compound, one or more in the cycloolefin.As propylene, butylene, hexene, 3-methyl-1-butene, 3-ethyl-1-amylene, vinylbenzene, allyl benzene, vinyl cyclohexane, vinyl pentamethylene, tetrahydrobenzene, norbornylene, 5-methyl-2-norbornylene etc.
Catalyzer of the present invention can be used for intermittently or continuous mode production, can be used for solution, gas phase and slurry phase polymerisation technology, is specially adapted to slurry polymerization processes.When using slurry polymerization processes, generally select a kind of inert alkane as thinner, polymer beads can be dispersed in thinner with slurry form, reaction end back is by flash distillation or remove by filter thinner.Common thinner has propane, Trimethylmethane, pentane, hexane, heptane.Typical polymerizing condition be polymerization temperature at 20 ℃-250 ℃, be preferably in 50 ℃-160 ℃; Polymeric pressure is preferably in 5-60atm at 1-100atm.
Vinyl polymerization:
The polyreaction evaluation is carried out in one 2 liters autoclave, and the speed of stirring is 450rmp, and reactor has the stainless steel chuck, and the liquid medium in the chuck is control reaction temperature accurately.After fully replacing with high purity nitrogen, the purifying hexane that adds 1 liter under a little more than atmospheric condition, triethyl aluminium solution of Jia Ruing and ingredient of solid catalyst add an amount of hydrogen then, the temperature of system is raised to 80 ℃, feed ethene at last and make the pressure in the still reach 13.0atm, keep the constant reaction of stagnation pressure one hour, after polymerization finishes, stop to feed ethene, after the slow release of reactor, polyethylene is separated from hexane, carried out at last weighing after the drying.Polymerization activity is per hour used polymkeric substance total amount (gPE/gCat.hr) expression of every gram Catalyst Production.
Testing method:
1, melt index (M.I): measure according to ASTM D1238-99
2, molecular weight distribution index (Mw/Mn): gel gas-chromatography (GPC) is measured
3, ethylene polymerization activity: the weight with every gram catalyzer gained resin is represented
4, the ultimate analysis of Cr/Al in the catalyzer: Xray fluorescence spectrometer is measured
Ethene polymers melting index with catalyst component production of the present invention can be controlled between 0.01g/10min ~ 4000g/10min, and controllable molecular weight distribution is between 10 ~ 40.
Catalyst component preparation method of the present invention is simple, and simultaneously catalyst component is when being used for vinyl polymerization, and activity of such catalysts is very high, and the molecular weight distribution of polymkeric substance is very wide and can adjust.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting the scope of the invention.
Embodiment 1
With model 955 silica gel (W.R.Grace ﹠amp; Co.-Com, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation, be warmed up to 200 ℃ of dryings 4 hours, the silica gel of getting after 10g handles adds 150ml hexane stirring at room formation suspension, in suspension, drip the hexane solution (concentration of Al is 2mmol/ml) of 4ml triethyl aluminum then, at room temperature stirred 2 hours after dripping end, leave standstill except that the 200ml toluene solution that will contain the 1.2g chromium acetylacetonate after desolvating joins in the reactant and flood, the stirring at room reaction is after 4 hours, and removing desolvates obtains containing the pre-catalyst of chromium.Place 1.75 inches silica tubes to activate pre-catalyst, the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 800 ℃ of calcinings 6 hours, obtain the activatory chromium-based catalysts with 300 ℃ speed per hour.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 2
Prepare catalyzer with the method identical with embodiment 1, just the add-on of triethyl aluminium solution becomes 2ml, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 3
With model 955 silica gel (W.R.Grace ﹠amp; Co.-Com, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation, be warmed up to 200 ℃ of dryings 4 hours, the silica gel of getting after 10g handles adds 150ml hexane stirring at room formation suspension, in suspension, drip the hexane solution (concentration of Al is 2mmol/ml) of 4ml triethyl aluminum then, dripping end back rising oil bath temperature stirred 3 hours reaction solution under reflux state, leave standstill except that the 200ml toluene solution that will contain the 1.2g chromium acetylacetonate after desolvating joins in the reactant and flood, the stirring at room reaction is after 4 hours, and removing desolvates obtains containing the pre-catalyst of chromium.Place 1.75 inches silica tubes to activate pre-catalyst, the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 800 ℃ of calcinings 6 hours, obtain the activatory chromium-based catalysts with 300 ℃ speed per hour.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 4
With model 955 silica gel (W.R.Grace ﹠amp; Co.-Com, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation, be warmed up to 200 ℃ of dryings 4 hours, the silica gel of getting after 10g handles adds 150ml hexane stirring at room formation suspension, temperature with suspension drops to 0 ℃ then, drip the hexane solution (concentration of Al is 2mmol/ml) of 4ml triethyl aluminum, make reaction solution continue to stir 3 hours after dripping end at 0 ℃, leave standstill except that the 200ml toluene solution that will contain the 1.2g chromium acetylacetonate after desolvating joins in the reactant and flood, the stirring at room reaction is after 4 hours, and removing desolvates obtains containing the pre-catalyst of chromium.Place 1.75 inches silica tubes to activate pre-catalyst, the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 800 ℃ of calcinings 6 hours, obtain the activatory chromium-based catalysts with 300 ℃ speed per hour.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 5
Dripping the hexane solution (concentration of Al is 2mmol/ml) of 4ml triethyl aluminum in the 200ml of 1.2g chromium acetylacetonate toluene solution, in stirring at room after 2 hours, is 955 silica gel (W.R.Grace﹠amp with model; Co.-Com, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation, being warmed up to 200 ℃ of dryings 4 hours, the silica gel of getting after 10g handles adds in the above-mentioned reaction solution, and the stirring at room reaction is after 4 hours, and removing desolvates obtains containing the pre-catalyst of chromium.Place 1.75 inches silica tubes to activate pre-catalyst, the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 800 ℃ of calcinings 6 hours, obtain the activatory chromium-based catalysts with 300 ℃ speed per hour.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 6
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes aluminium diethyl monochloride, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 7
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes tri-n-hexyl aluminum, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 8
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes the dichloro aluminium isobutyl, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 9
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes ethyl aluminum dichloride, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 10
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes diethylaluminum ethoxide, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 11
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes six water aluminum bromides, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Embodiment 12
Prepare catalyzer with the method identical with embodiment 2, just triethyl aluminium solution becomes sesquialter ethyl aluminum chloride, and other condition is constant.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Comparative Examples 1
With model 955 silica gel (W.R.Grace ﹠amp; Co.-Com, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) being warmed up to 200 ℃ of dryings under the nitrogen fluidisation after 4 hours, the silica gel after getting 10g and handling joins in the 200ml toluene solution that contains the 1.2g chromium acetylacetonate and floods, and react after 4 hours, obtains containing the pre-catalyst of chromium except that desolvating.Place 1.75 inches silica tubes to activate pre-catalyst, the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 800 ℃ of calcinings 6 hours, obtain the activatory chromium-based catalysts with 300 ℃ speed per hour.The content of chromium, aluminium and catalyst vinyl polymerization evaluation result are listed in table 1 in the catalyst component.
Table 1. catalyst performance
| No. | Al | Cr | Active | MI 21.6 | Mw/Mn |
| (wt％) | (wt％) | (gPE/gCat.hr) | (g/10min) | ||
| Embodiment 1 | 2.14 | 0.32 | 995 | 1.43 | |
| Embodiment 2 | 1.15 | 0.52 | 1968 | 1.8 | 21.3 |
| Embodiment 3 | 3.13 | 0.32 | 636 | ||
| Embodiment 4 | 2.28 | 0.34 | 1546 | ||
| Embodiment 5 | 2.02 | 0.37 | 1314 | 1.45 | |
| Embodiment 6 | 1460 | 25.1 | |||
| Embodiment 7 | 1.14 | 0.41 | 2028 | 4.01 | 15.3 |
| Embodiment 8 | 1315 | 23.9 | |||
| Embodiment 9 | 1.08 | 0.59 | 1985 | 0.33 | 25.2 |
| Embodiment 10 | 0.87 | 0.55 | 1810 | 0.79 | 21.4 |
| Embodiment 11 | 1546 | 0.67 | |||
| Embodiment 12 | 1481 | 0.94 | |||
| Comparative Examples 1 | 0 | 0.67 | 916 | 0.47 | 28.8 |
As can be seen from Table 1, the introducing of aluminum compound has improved activity of such catalysts and melting index, the molecular weight distribution broad, and the molecular weight distribution width can be adjusted, polymkeric substance flowing better under stress, and required character in these many just extruding shaping technique (as film forming and blowing), thereby be applicable to the work range of broad.
Claims (9)
1. one kind is used for the ethylene polymerization catalysts component, it is characterized in that, this catalyst component is to be carrier with the oxide compound, and aluminum compound and chromium cpd are carried on the carrier jointly, and chromium content is 0.1-10wt% in the catalyzer, and aluminium content is 0.1-12wt%; Described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium dioxide, zinc oxide, boron oxide and the zirconium white or their mixture; The general formula of described aluminum compound is: Al
y(OR
1)
m(R
2)
n(X)
z, R wherein
1And R
2Identical or different, be selected from hydrogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, X is a halogen, and wherein y is 1 or 2, and m, n, z are 0,1,2 or 3, and will satisfy m+n+z=3y; Described chromium cpd is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.
2. the ethylene polymerization catalysts component that is used for according to claim 1, it is characterized in that described aluminum compound is one or more among triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, ethyl diethoxy aluminium, diethylaluminum ethoxide, sesquialter ethyl aluminum chloride, sesquialter methyl aluminum chloride, aluminium diethyl monochloride, a chlorine diethoxy aluminium, ethyl aluminum dichloride, dichloro aluminium isobutyl, dichloro aluminum ethoxide, aluminum chloride, alchlor, aluminium triiodide, methylaluminoxane, ethyl aikyiaiurnirsoxan beta, the sec.-propyl aikyiaiurnirsoxan beta.
3. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that, described water miscible chromium cpd is a kind of in chromium trioxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Oil-soluble chromium cpd is tertiary butyl chromate, two luxuriant chromium or Acetyl Acetone acid chromium.
4. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described chromium content is 0.1～8.0%, and aluminium content is 0.2～8.0wt%.
5. any one described preparation method who is used for the ethylene polymerization catalysts component of claim 1～4 is characterized in that, may further comprise the steps:
(1) 100～800 ℃ of following drying treatment oxide carrier 1～10 hour;
(2) the oxide carrier contact reacts that aluminum compound and chromium cpd and step (1) are obtained, the weight ratio of the aluminum compound of carrier and adding is 10: 1～1000: 1, the weight ratio of the chromium cpd of carrier and adding is 10: 1～1000: 1, the temperature of reaction is-20 ℃～200 ℃, the time of reaction is 0.5～50hr, obtains the pre-catalyst component of load chromium;
(3) the pre-catalyst component of the chromium of load that step (2) is obtained in air, 400～1000 ℃ down calcining obtain catalyst component after 1-10 hour.
6. the preparation method who is used for the ethylene polymerization catalysts component according to claim 5, wherein the addition sequence of aluminum compound described in the step (2) and chromium cpd randomly adds aluminum compound and chromium cpd simultaneously, adds aluminum compound earlier in oxide carrier in oxide carrier, add chromium cpd again, in oxide carrier, add chromium cpd earlier, add aluminum compound or elder generation again aluminum compound and chromium cpd are mixed, then mixture is joined in the oxide carrier.
7. the preparation method who is used for the ethylene polymerization catalysts component according to claim 5, wherein the calcining temperature in the step (3) is 600～800 ℃.
8. one kind is used for ethylene polymerization catalysts, comprises following component:
A) the described ethylene polymerization catalysts component that is used for of one of claim 1～4;
B) promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements; The mol ratio of organometallic compound and chromium is 0.1: 1～100: 1.
9. the ethylene polymerization catalysts that is used for according to claim 8, wherein the mol ratio of promotor organometallic compound and chromium is 0.5: 1～50: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111013610A (en) * | 2018-10-09 | 2020-04-17 | 中国石油天然气股份有限公司 | Immobilized Lewis acid catalyst, preparation method thereof and α -olefin oligomerization reaction using catalyst |
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| CN108912257A (en) * | 2018-07-13 | 2018-11-30 | 上海弘岸化工有限公司 | A kind of preparation method and applications for the carrier type chromium-series catalyst that aluminium is modified |
| CN111013610A (en) * | 2018-10-09 | 2020-04-17 | 中国石油天然气股份有限公司 | Immobilized Lewis acid catalyst, preparation method thereof and α -olefin oligomerization reaction using catalyst |
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