CN101824104A - Catalyst component for vinyl polymerization and preparation method thereof - Google Patents
Catalyst component for vinyl polymerization and preparation method thereof Download PDFInfo
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- CN101824104A CN101824104A CN200910078882A CN200910078882A CN101824104A CN 101824104 A CN101824104 A CN 101824104A CN 200910078882 A CN200910078882 A CN 200910078882A CN 200910078882 A CN200910078882 A CN 200910078882A CN 101824104 A CN101824104 A CN 101824104A
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Abstract
The invention provides a catalyst component for vinyl polymerization and a preparation method thereof. The component uses an oxide as a carrier, and a titanium-magnesium compound and a chromium compound are loaded on the carrier together, wherein the chromium content is between 0.1 and 10 weight percent; the titanium content is between 0.1 and 12 weight percent; the magnesium content is between 0.05 and 10 weight percent; and the titanium-magnesium compound is a compound the molecular formula of which is [Ti2(OR1)2(OR2)2(OR3)2(OR4)2X]2Mg2X2. When the catalyst component is used for the vinyl polymerization, the catalyst has high activity and the prepared vingi ethane polymer also has high melt index.
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 titanium, magnesium-modified supported chrome series catalysts component and the preparation method and the application of this catalyst component.
Technical background
Ethene polymers has been widely used as various membrane product resin materials, and requires ethene polymers to have different characteristics according to film system method and purpose.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, the chromium atom of partial load is converted into the sexavalent chrome atom obtains.In the art, above-mentioned catalyzer is commonly referred to the Phillips catalyzer, and detail operations is referring to Adances in catalyst 1985,33:47～98M.P.McDaniel.Be immersed on the silicon-dioxide carriers such as (silica gel) with chromic salt, the catalyzer that obtains is removed after the moisture, uses dry air fluidized drying and activation under 400～1000 ℃ of temperature again, and this catalyzer is deposited in dry air or in the rare gas element.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 for chainpropagation and chain transfer to have different active centre ratios.This catalyzer tends to produce short polymer chain and comonomer is combined with short polymer chain with high frequency, might have 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, thereby 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, realize chemical modification, improve the catalytic performance of chromium-based catalysts chrome catalysts or carrier.
For example: U.S. Pat 3887494 discloses a kind of Preparation of catalysts method that is used for olefinic polymerization.Titanium compound is mixed with a kind of mineral acid, alkalimetal silicate added in this mixture form hydrogel, be about 6.0 at pH value then, aging this hydrogel in the time of 90 ℃, water then, ammonium salt solution or olefin(e) acid flush away basic metal add a certain amount of water-soluble organic compounds, thereby separation of organic substances and water form xerogel from this mixture.Activate the xerogel that contains chromium down at 482 ℃-982 ℃, be formed for the catalyzer of olefinic polymerization.
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.
Chinese patent CN 1471431A discloses the compound of the silicon oxide-containing that a kind of new magnesium handles, and is suitable as the carrier of chromium base olefin polymerization catalyst system.Make Mg (NO
3)
2.6H
2O and Cr (NO
3)
3.9H
2The O contact generates composition, is that the composition of gained contacts formation magnesium hydroxide, drying composition with alkali.The introducing of magnesium in this catalyzer has increased the surface-area of carrier, has caused the minimizing of long chain branching in the polyvinyl resin, and high molecular partly reduces, and polymkeric substance has good impact property in high molecular weight film is used.
Above-mentioned patent successively uses titanium, magnesium that chromium-based catalysts is carried out modification, the existence of titanium, magnesium has produced remarkable influence to chromium-based catalysts, adding along with titanium, magnesium, the copolymerization performance of catalyzer is improved, the molecular weight of polymkeric substance reduces, 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 the co-precipitation or the cogelled method of silicon oxide, titanium, magnesium and chromium cpd in the patent, begin to prepare chromium-containing catalyst from the silica gel of titaniferous, magnesium, chromium, the acquisition of carrier need be to co-precipitation or cogelled spraying drying or the azeotropic drying of carrying out, the gained carrier also need carry out aging for a long time under basic neutral pH value, even needs to add aperture protective agent.Such preparation process is very complicated, and the consumption time is long, owing to the pore structure generation decisive influence of weathering process to catalyzer, so the less stable of Preparation of Catalyst.
Summary of the invention
One of purpose of the present invention is at the problems referred to above, and a kind of preparation method is provided simple catalyst component, and this catalyst component is when being used for vinyl polymerization, and activity of such catalysts is very high, and the ethene polymers that obtains simultaneously has high fusion index.
Two of purpose of the present invention has provided the above-mentioned preparation method who is used for the ethylene polymerization catalysts component.
Three of purpose of the present invention has provided a kind of catalyzer that can produce the high fusion index olefin polymer.
A kind of ethylene polymerization catalysts component that is used for of the present invention, this component is as carrier with oxide compound, titanium magnesium compound and chromium cpd load on the carrier jointly, wherein chromium content is 0.1-10wt%, titanium content is 0.1-12wt%, Mg content is 0.05-10wt%, and described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium dioxide, boron oxide and the zirconium white or their mixture; The molecular formula of described titanium magnesium compound is [Ti
2(OR
1)
2(OR
2)
2(OR
3)
2(OR
4)
2X]
2Mg
2X
2, substituent R wherein
1, R
2, R
3And R
4Identical or different, be selected from hydrogen, halogen, 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, substituent X is fluorine, chlorine, bromine or iodine; Described chromium cpd is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.
Oxide carrier described in the present invention is generally the porous inorganic particulate that contains hydroxyl, 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, also can finish under vacuum state.The temperature of drying treatment can be 80-280 ℃, and the time is 1-10 hour.
The molecular formula of titanium magnesium compound of the present invention is [Ti
2(OR
1)
2(OR
2)
2(OR
3)
2(OR
4)
2X]
2Mg
2X
2, substituent R wherein
1, R
2, R
3And R
4Can be the same or different, be selected from hydrogen, halogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; Wherein substituent X is for being fluorine, chlorine, bromine or iodine.Concrete titanium magnesium compound is as [Ti
2(OC
2H
5)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
3H
7)
2Cl]
2Mg
2Cl
2, [Ti
2(Oi-C
3H
7)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
4H
9)
2Cl]
2Mg
2Cl
2, [Ti
2(Oi-C
4H
9)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
2H
5)
2Br]
2Mg
2Br
2, [Ti
2(OC
2H
5)
2I]
2Mg
2I
2Deng.This compound can obtain by the following method: alkoxy titanium compound and magnesium compound are reacted formation solution in alkane, carry out recrystallization then, can obtain the titanium magnesium compound, wherein in the alkoxy titanium compound in Ti and the magnesium compound mol ratio of Mg be 1: 1～8: 1, detail operations is referring to Inorganica Chimica Acta.180 (1991) 245-249.
Chromium cpd of the present invention is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.Water miscible chromium cpd such as chromium trioxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Oil-soluble chromium cpd such as tertiary butyl chromate, two luxuriant chromium, Acetyl Acetone acid chromium.In these chromium cpds, preferably use chromium trioxide or chromium nitrate.
The present invention is used for the preparation method of ethylene polymerization catalysts component, and it may further comprise the steps:
(1) 100～250 ℃ of following drying treatment oxide carrier 1-10 hour;
(2) the titanium magnesium compound solution is contacted with the oxide carrier that step (1) obtains with chromium cpd solution, wherein the solvent phase in titanium magnesium compound solution and the chromium cpd solution is same, and solvent is C
4～C
20Alkane or C
1～C
20Alcohol, the weight ratio of carrier and Ti are 10: 1～1000: 1, and the weight ratio of carrier and chromium is 10: 1～1000: 1, remove subsequently and desolvate, and obtain carrying the pre-catalyst of chromium;
What (3) step (2) is obtained carries the chromium pre-catalyst in air, 400～1000 ℃ of following calcinings 1-10 hour.
Solvent described in the step (2) in titanium magnesium compound solution and the chromium cpd solution is selected from and can makes titanium magnesium compound dissolved hydrocarbon or alcohol, and hydro carbons is C
4-C
20Alkane, preferred C
4-C
8Alkane, as Trimethylmethane, iso-pentane, Skellysolve A, normal hexane, normal heptane or octane etc.Alcohols is C
1-C
20Alcohol, preferred C
1-C
8Alcohol, as methyl alcohol, ethanol, propyl alcohol, Virahol, 1-hexanol or isooctyl alcohol etc.
The carried catalyst of being made up of titanium magnesium compound, chromium cpd and silica-gel 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 for example carry out in the carbon monoxide at reducing gas earlier, in air, finish final activation then.Can also be under 300-600 ℃ through the final catalyzer of incinerating, with the carbon monoxide reduction, cool to room temperature seals preservation in atmosphere of inert gases then.
The present invention also provides a kind of ethylene polymerization catalysts that is used for, and comprises following component:
(1) the above-mentioned ethylene polymerization catalysts component that is used for;
(2) 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, 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 phase polymerisation technology.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 5atm-80atm at 1atm-100atm.Can use the melting index and the molecular weight of hydrogen telomerized polymer in the polymerization technique.
Ethene polymers melting index with catalyst component production of the present invention can be controlled between the 0.01g/10min-4000g/10min, and controllable density is built in 0.915-0.975g/cm
3Between.
Catalyst component preparation method of the present invention is very simple, again since titanium and magnesium simultaneously active centre chromium is exerted an influence, make this catalyst component when being used for vinyl polymerization, activity of such catalysts is very high, and can obtain having the ethene polymers than high fusion index.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting the scope of the invention.
Testing method:
1, melt index (M.I): measure according to ASTM D1238-99
2, density: ASTM D-1505 measures
3, molecular weight distribution index (Mw/Mn): gel gas-chromatography (GPC) is measured
4, ethylene polymerization activity: the weight with every gram catalyzer gained resin is represented
Embodiment 1
The preparation of titanium magnesium compound
Add the magnesium chloride of 5g (52.6mmol) and the purity titanium tetraethoxide of 34.3g (150mmol) in the 150ml heptane, three hours postcooling of reflux filter out mother liquor, and then add 100ml heptane recrystallization, obtain the white crystal [Ti of 23.6g
2(OC
2H
5)
2Cl]
2Mg
2Cl
2
The preparation of catalyst component
10g silica gel A (W.R.Grece ﹠amp; Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 2.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol and the aqueous isopropanol that contains the 0.75g chromium acetylacetonate flood, after Virahol is evaporated, obtain 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 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and titanium content is about 5wt%, and Mg content is about 2.8wt%, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 2
The preparation of titanium magnesium compound
Preparation method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
(pore volume is about 2.4-3.7cm to 10g silica gel B for PQ Corporation, MS3050
3/ g, surface-area is about 410-620m
2/ g), successively adding and containing 2.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol and the aqueous isopropanol that contains the 0.75g chromium acetylacetonate flood, after Virahol is evaporated, obtain 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 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 3
The preparation of titanium magnesium compound
Preparation method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
10g silica gel A (W.R.Grece ﹠amp; Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 1.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol and the aqueous isopropanol that contains the 0.38g chromium acetylacetonate flood, after Virahol is evaporated, obtain 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 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.The content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 4
The preparation of titanium magnesium compound
Preparation method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
10g silica gel A (W.R.Grece ﹠amp; Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 1.9g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol and the aqueous isopropanol that contains the 2.38g chromium acetylacetonate flood, after Virahol is evaporated, obtain 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 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.The content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 1
10g silica gel A (W.R.Grece ﹠amp; Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation 200 ℃ of dryings 4 hours, add the aqueous isopropanol that contains the 0.75g chromium acetylacetonate then and flood, after Virahol is evaporated, obtain 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.Catalyzer 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 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 2
(pore volume is about 2.4-3.7cm to 10g silica gel B for PQ Corporation, MS3050
3/ g, surface-area is about 410-620m
2/ g) under the nitrogen fluidisation 200 ℃ of dryings 4 hours, add the aqueous isopropanol that contains the 0.75g chromium acetylacetonate then and flood, after Virahol is evaporated, obtain 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.Catalyzer 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, obtain activatory chromium-based catalysts component with per hour 600 ℃ of calcinings of speed 3 hours of 400 ℃.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 3
The catalyst component preparation method carries out according to embodiment among the Chinese patent CN 1,655,533 1, adopts twice-aged and uses spraying drying, gained catalyst component to use polyreaction evaluation method described in the present invention to estimate.
Comparative Examples 4
The catalyst component preparation method carries out according to embodiment among the Chinese patent CN 1,471,431 3, and by silicon oxide and the cogelled carrier that forms catalyst system of magnesium compound, the gained catalyzer uses polyreaction evaluation method described in the present invention to estimate.
Vinyl polymerization:
The catalyst component of the foregoing description is carried out vinyl polymerization respectively.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 10.0atm, 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.The per hour polymkeric substance total amount (gPE/gCat.hr) of every gram Catalyst Production of polymerization activity, the polymerization result of catalyst component is listed in the table 1.
By above-mentioned polymerization procedure the ingredient of solid catalyst in embodiment and the Comparative Examples is carried out vinyl polymerization respectively, polymerization result is listed in table 2.
The content of Ti, Mg, Cr in table 1. catalyzer
| Catalyzer | ??Ti(wt％) | ??Mg(wt％) | ??Cr(wt％) |
| Embodiment 1 | ??4.2 | ??1.1 | ??1.1 |
| Comparative Examples 1 | ??0 | ??0 | ??1.2 |
| Embodiment 2 | ??4.3 | ??1.2 | ??1.0 |
| Catalyzer | ??Ti(wt％) | ??Mg(wt％) | ??Cr(wt％) |
| Comparative Examples 2 | ??0 | ??0 | ??0.9 |
| Embodiment 3 | ??2.5 | ??0.6 | ??0.5 |
| Embodiment 4 | ??2.2 | ??0.5 | ??3.2 |
| Comparative Examples 3 | ??4.6 | ??0 | ??1.1 |
| Comparative Examples 4 | ??0 | ??4.5 | ??0.9 |
The evaluation result of table 2. catalyzer
| Catalyzer | Active (gPE/gCat.hr) | Density (cm 3/g) | ??MI 2.16??(g/10min) | ??MI 2.16??(g/10min) | ??MI 2.16/MI 2.16 |
| Embodiment 1 | ??523 | ??0.946 | ??0.25 | ??25.3 | ??101 |
| Comparative Examples 1 | ??367 | ??0.951 | ??0.26 | ??22.1 | ??85 |
| Embodiment 2 | ??560 | ??0.948 | ??0.24 | ??28.3 | ??118 |
| Comparative Examples 2 | ??410 | ??0.952 | ??0.19 | ??14.4 | ??76 |
| Embodiment 3 | ??320 | ??0.947 | ??0.23 | ??18.4 | ??80 |
| Embodiment 4 | ??356 | ??0.949 | ??0.23 | ??20.8 | ??90 |
| Comparative Examples 3 | ??420 | ??0.949 | ??0.26 | ??23.7 | ??91 |
| Comparative Examples 4 | ??440 | ??0.952 | ??0.28 | ??23.5 | ??84 |
As can be seen from Table 2, the introducing of titanium magnesium compound has improved activity of such catalysts and melting index, the polyvinyl resin shear loading (HLMI/MI) of preparation is bigger, just show polymkeric substance flowing better under stress, and required character in these many just extruding shaping technique (as film forming and blowing) shows also that simultaneously polymkeric substance has wider molecular weight distribution.The blowing performance of resin has obtained very big improvement, and the tear resistance of the film of blowing is better.
Claims (9)
1. one kind is used for the ethylene polymerization catalysts component, this component is as carrier with oxide compound, titanium magnesium compound and chromium cpd load on the carrier jointly, wherein chromium content is 0.1-10wt%, titanium content is 0.1-12wt%, Mg content is 0.05-10wt%, and described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium dioxide, boron oxide and the zirconium white or their mixture; The molecular formula of described titanium magnesium compound is [Ti
2(OR
1)
2(OR
2)
2(OR
3)
2(OR
4)
2X]
2Mg
2X
2, substituent R wherein
1, R
2, R
3And R
4Identical or different, be selected from hydrogen, halogen, 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, substituent X is fluorine, chlorine, bromine or iodine; 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, wherein said water miscible chromium cpd are 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.
3. the ethylene polymerization catalysts component that is used for according to claim 1, wherein said chromium content is 0.1～2.0wt%, and titanium content is 2.0～8.0wt%, and Mg content is 0.1～6.0wt%.
4. the ethylene polymerization catalysts component that is used for according to claim 1, wherein said oxide carrier is a silicon-dioxide, and described chromium cpd is chromium trioxide or chromium nitrate, and described titanium magnesium compound is that molecular formula is Ti
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Compound.
5. according to any one described preparation method who is used for the ethylene polymerization catalysts component of claim 1～4, it may further comprise the steps:
(1) 100～250 ℃ of following drying treatment oxide carrier 1～10 hour;
(2) the titanium magnesium compound solution is contacted with the oxide carrier that step (1) obtains with chromium cpd solution, wherein the solvent phase in titanium magnesium compound solution and the chromium cpd solution is same, and solvent is C
4～C
20Alkane or C
1～C
20Alcohol, the weight ratio of carrier and Ti are 10: 1～1000: 1, and the weight ratio of carrier and chromium is 10: 1～1000: 1, remove subsequently and desolvate, and obtain the pre-catalyst component of load chromium;
(3) the pre-catalyst component of the chromium of load that step (2) is obtained obtains catalyst component in air, after calcining 1-10 hour under 400～1000 ℃.
6. the preparation method who is used for the ethylene polymerization catalysts component according to claim 5, wherein the solvent described in the step (2) is C
4～C
8Alkane or C
1～C
8Alcohol.
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:
(1) the described ethylene polymerization catalysts component that is used for of one of claim 1～4;
(2) 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. will be according to right with regard to the 8 described ethylene polymerization catalysts that are used for, wherein the mol ratio of promotor organometallic compound and chromium is 0.5: 1～50: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772539A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization, preparation method and application thereof |
| CN103772538A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and preparation method thereof |
| CN106317267A (en) * | 2015-06-16 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation method thereof |
| CN108690151A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363746A (en) * | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
| US4801572A (en) * | 1987-05-28 | 1989-01-31 | Mobil Oil Corporation | Modified chromium-containing catalyst composition for polymerizing alpha-olefins and method of preparing same |
| CN1290875C (en) * | 2004-11-04 | 2006-12-20 | 沈阳化工学院 | System of catalyst for vinyl polymerization or coploymerization and application thereof |
| CN101173013B (en) * | 2006-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
-
2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772539A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization, preparation method and application thereof |
| CN103772538A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and preparation method thereof |
| CN103772538B (en) * | 2012-10-19 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization and preparation method thereof |
| CN106317267A (en) * | 2015-06-16 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation method thereof |
| CN106317267B (en) * | 2015-06-16 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalytic component and preparation method thereof for vinyl polymerization |
| CN108690151A (en) * | 2017-04-07 | 2018-10-23 | 中国石油化工股份有限公司 | A kind of catalyst system and olefine polymerizing process for olefinic polymerization |
| CN108690151B (en) * | 2017-04-07 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
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