CN1290875C - System of catalyst for vinyl polymerization or coploymerization and application thereof - Google Patents
System of catalyst for vinyl polymerization or coploymerization and application thereof Download PDFInfo
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- CN1290875C CN1290875C CN 200410082738 CN200410082738A CN1290875C CN 1290875 C CN1290875 C CN 1290875C CN 200410082738 CN200410082738 CN 200410082738 CN 200410082738 A CN200410082738 A CN 200410082738A CN 1290875 C CN1290875 C CN 1290875C
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Abstract
The present invention relates to a loading bimetallic composite catalyst, particularly to a catalyst system for vinyl polymerization or copolymerization, and the application thereof. The catalyst system comprises a titaniferous component, a ferrous component and an aluminum alkyl cocatalyst, wherein the titaniferous component has a general formula of MgTiaXb(OR)c; in the formula, X is F, Cl, Br, I or a mixture thereof, an R group is a fatty hydrocarbon group or an aryl hydrocarbon group with 1 to 20 carbon atoms, and a, b, and c respectively represent 0.01 to 0.9, 1.5 to 3.5 and 0.09 to 2.7; the ferrous component is a diimine coordination compound of ferrum. The present invention has the advantages and the effects that the catalyst shows high activity after being used for the vinyl polymerization by a slurry process, the catalyst system is far higher than a catalyst system in the same type in the prior art by 1.06*10<5> transitional metal per gram, the obtained polyethylene resin has wide molecular weight distribution, and the polyethylene resin with bimodal distribution can be obtained.
Description
Technical field
The present invention relates to a kind of double-metal composite catalyst of load, relate in particular to a kind of catalyst system and application thereof that is used for vinyl polymerization or copolymerization.
Background technology
Bimodal polyethylene is meant that the relative molecular mass distribution curve presents the polyvinyl resin of two peak values, and the distribution of common polythene relative molecular mass has only a peak.The workability of common polythene resin and mechanical property are conflicting, improve molecular weight and can make product have better mechanical property, as intensity height, good toughness etc., but melt flow rate are reduced, and becoming is difficult to processing.And bimodal polyethylene can solve this contradiction well, make product both have better mechanical property, be convenient to processing again, in fields such as film, building materials, pipeline, blow molding materials, injection molding materials, electric wires purposes is widely arranged, therefore the research and development of bimodal molded breadth distribution polyethylene resin are questions of common concern.Present existing preparation method wide or the Bi-modal polyethylene resin can be divided into following three kinds of methods substantially:
(1) the melt-mixing method is meant and adopts reactor production in parallel.The molecular resin quality difference that 2 reactors of this flow process are produced, promptly at the little resin of the first reactor production molecular mass, and at the big resin of the second reactor production molecular mass, according to product needed, according to a certain percentage the resin in 2 reactors is mixed, thereby reach the purpose of controlling molecular weight distribution (MWD).The shortcoming of this method is the cost height, and quality product is difficult to homogeneous.
(2) step reaction method is to adopt the production of cascade reaction still, can realize the production of bimodal resin: a, catalyst concn control method by 2 kinds of approach.The control condition difference of first, second reactor is bigger, and the resin that molecular mass is little forms in first reactor.The lower catalyst concn of control allows a part of polymer molecule proceed transfer reaction in second reactor in second reactor, generates the bigger resin of molecular mass.B, hydrogen are transferred method.In first reactor,, produce the high molecule mass composition, and hang down the composition of molecular mass in the second reactor production at first reactor with very a spot of chain-transfer agent (as hydrogen).Regulate the speed of reaction of 2 reactors by suitable proportion, thereby produce the resin that meets the demands with different MWD.Use cascade reaction still cost height, but operation setting range comparatively flexible, the resin trade mark is big.
(3) one sections reaction methods are to produce resin bimodal or that multimodal distributes in a reactor, thereby can make resin reach the mixing of superparticle level, and this method is the product of catalyst system innovation, and is also the most active in the field of study.Because concrete catalyst system difference, one section reaction method can be divided into 3 kinds again: a, employing 2 kinds or multiple independently homogeneous phase or heterogeneous catalyst hybrid system.Different catalyzer has different active centre, also has different chainpropagations and chain transfer speed naturally, thereby generates bimodal resin.The shortcoming of this method is: 2 kinds of catalyzer influence each other, and the polyethylene particle diameter of generation is inhomogeneous, and easily separated in storage and transportation, and it is more inhomogeneous to cause product cut size to distribute.B, employing contain a catalyst system method of multiple catalytic activity point.Be exactly to prepare this bimetal or multimetallic catalyst in advance, then 2 kinds of catalyzer be stated from on a kind of carrier.Operable system has that Ti system/Ti system, Ti system/Cr system, Ti system/luxuriant system, first kind of luxuriant/second are kind luxuriant, metal ion 1/ metal ion 2/ organic ligand or the like; Also having a kind of method is the preparation binuclear compound, and this compound contains 2 metal centers, though because the kind of these 2 metal centers is different or belong to its residing chemical environment difference of same kind, thereby have different catalytic activitys.C, be two carried catalyst methods.A kind of metallic compound is loaded on the different carriers, forms different active centre, and operable carrier is a lot, as: SiO
2, MgCl
2, Al
2O
3, MgF
2, CaF
2, the methylaluminoxane MAO of modification, polyolefin particles and natural polymer such as Mierocrystalline cellulose etc.One section reaction method does not even need transformation owing to do not need that traditional production device is carried out big transformation, thus easy to implement, and also cost is lower.
Generally believe that it is comparatively desirable feasible polymerization process that the third above-mentioned method of application is developed a kind of many metal active constituents catalyzer.For example: U.S. Pat 5032562, its disclosure is incorporated herein by reference at this special full text, discloses the load olefin Polymerization catalyst compositions that comprises precursor and catalyst activator.In the presence of small quantity of hydrogen, use catalyzer to have the polyolefine of multimodal MWD in single reaction vessel production.Catalyzer comprises the dialkyl magnesium component, zirconium luxuriant and non-metallocene titanium and/or vanadium compound, but consumption is big, and active low, the cost height.
U.S. Pat 6051525, its disclosure is incorporated herein by reference at this special full text, and disclosing in temperature is the SiO of 600 ℃ of following roastings
2With dibutylmagnesium, 1-butanols and titanium tetrachloride and by methylaluminoxane (MAO) and ethyl bridging two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] solution formed, hybrid reaction makes dinuclear catalyst, and in fluidized-bed reactor, gas-phase polymerization ethylene can prepare bimodal molecular mass distribution PE, but its catalyst activity is on the low side.
World patent WO0183498, its disclosure is incorporated herein by reference at this special full text, discloses to adopt to contain chromium and titaniferous mixed catalyst production bimodal molecular mass distribution PE in single reactor.Being used for controlling polymers solution flow rate, density and molecular mass with the different ratios of 2 kinds of catalyzer distributes.The mixed catalyst of high Ti/Gr can be produced the bimodal molecular mass distribution high density polyethylene(HDPE) of high melt flow rate (MFR), cost height.
U.S. Pat 6294500, its disclosure special is incorporated herein by reference in full at this, discloses the patent that one-stage process prepares bimodal polyethylene and adopted bimetallic catalyst.Wherein, first catalyzer is a chromium-based catalysts, and needs the process reduction and reoxidize processing; Second catalyzer also is a chromium-based catalysts, also need pass through activation treatment, carries out fluoridation then in the activation treatment process or after handling, and reduces processing at last.The pore volume difference of first and second catalyzer is at least 0.88cm
3/ g.The polymericular weight that the catalyzer that pore volume is bigger generates is low, MI height, and the polymericular weight height that the less catalyzer of pore volume generates, and MI is low.Adopt this catalyst system can prepare the PE that molecular weight is bimodal distribution, but complicated operation, the cost height.
Chinese patent CN1058601A, its disclosure is incorporated herein by reference at this special full text, a kind of reduction vanadium compound and organic oxygen-containing zirconium compounds of adopting disclosed by being immersed in the catalyst compound on the active carrier material altogether, the ethene polymers that is made by this catalyzer has wide molecular weight distribution, especially distributing more is the higher component of molecular weight, this catalyzer is when being used for vinyl polymerization, activity is: 1.79～2.4 kilograms/mmole (V+Zr) h100psi (3～5 myriagram/gram (V+Zr)), the MI of resin
2.16Be 0.19～0.25, MFR is 120～394, and Mw/Mn is 24.2～40.1, though the polymericular weight of this catalyzer gained than broad, its catalyst activity is on the low side.
Chinese patent CN1292389A, its disclosure is incorporated herein by reference at this special full text, discloses a kind of compounded catalyst that contains metallocene, and the bimetal active centre that this catalyzer had is made up of metallocene catalyst and traditional Titanium series catalyst.The promotor of forming metallocene catalyst is the mixed type alkylaluminoxane, by adjusting the mole consumption of aluminum alkyls more than 2 kinds or 2 kinds when of 2 kinds of metals, can in very large range adjust the molecular weight and the molecular weight distribution of polymkeric substance, thereby obtain the very wide polyolefin resin of molecular weight distribution, but its catalyst activity is also on the low side.
Summary of the invention
A kind of catalyst system and application thereof that is used for vinyl polymerization or copolymerization is provided in order to solve the problems of the technologies described above, purpose is to carry out in single reaction vessel by the double-metal composite catalyst system, make it that higher activity be arranged, and the molecular weight distribution broad of gained polyvinyl resin, and can obtain polyvinyl resin two or that broad peak distributes, make the physicals of polymkeric substance reach optimization.
A kind of catalyzer that is used for vinyl polymerization or copolymerization of the present invention to achieve these goals comprises following component:
A. one kind has formula M gTi
aX
b(OR)
cContain titanium component, X is F, Cl, Br, I or its mixture in the formula, the R base is aliphatic alkyl or the aryl radical with 1～20 carbon atom, a is 0.01～0.9, b is 1.5～3.5, c is 0.09～2.7;
B. an iron content component is a kind of diimine ligand compound of iron, structure specific as follows:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be hydrogen or alkyl, X is a halogen atom; Above-mentioned catalyst cupport is obtained the loading type iron component catalyst to inert solid carrier; Wherein inert solid carrier is silica gel, magnesium chloride, aluminum oxide or clay, and handles through alkylaluminoxane or aluminum alkyls;
C. aluminum alkyl catalyst.
Ratio between described b component and a component is 0.05～50 with the molar ratio computing of iron and titanium, and the molar ratio computing of institute's iron content and titanium is 3～3000 in aluminum alkyls in the c component and the a+b component.
Ratio between described b component and a component is 0.1～10 with the molar ratio computing of iron and titanium, and the molar ratio computing of institute's iron content and titanium is 20～500 in aluminum alkyls in the c component and the a+b component.
The described titanium component MgTi that contains
aX
b(OR)
c, obtain by magnesium compound, Fatty Alcohol(C12-C14 and C12-C18) and titanium compound reaction; The mol ratio of Fatty Alcohol(C12-C14 and C12-C18) and magnesium compound is 0.1～20.0, is preferably 0.1～10; The mol ratio of titanium compound and magnesium compound is 1.0～6.0, is preferably 2.0～4.0; Described magnesium compound is with formula M gX
2Expression, X is F, Cl, Br, I or its mixture; Fatty Alcohol(C12-C14 and C12-C18) is the Fatty Alcohol(C12-C14 and C12-C18) with 1～20 carbon atom; The general formula AlR of described aluminum alkyls
1 gX
3-g, R in the formula
1Be the alkyl of 1～20 carbon, g is 0～3 integer.
Described Fatty Alcohol(C12-C14 and C12-C18) is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, Virahol, the trimethyl carbinol, primary isoamyl alcohol, tertiary amyl alcohol, the 2-Ethylhexyl Alcohol.
Described titanium compound Ti (OR
2)
mX
p, m+p=4 wherein, X is a halogen, R
2For being the aliphatic alkyl of 1～20 carbon atom, or aryl radical or COR ', each R
2Can be identical, also can be different, R ' is aliphatic alkyl or the aryl radical with 1～10 carbon atom.
Described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, purity titanium tetraethoxide, four titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, four phenoxide titaniums, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium.
The catalyzer that is used for vinyl polymerization or copolymerization, the preparation method of described titaniferous component catalyst follows these steps to carry out:
Earlier magnesium compound and Fatty Alcohol(C12-C14 and C12-C18) were reacted 2 hours, make its swelling not destroying under the magnesium compound particulate state, and then react with titanium compound and to obtain above-mentioned titaniferous component catalyst in 6 hours;
The preparation method of described iron content component catalyst follows these steps to carry out:
A, inert support was calcined 6～12 hours under 200～600 ℃ of high temperature, under 110～200 ℃, vacuumized 2～4 hours then;
B, with alkylaluminoxane or aluminum alkyls and through inert support that step a handles in the heptane of deoxidation dehydration, 30～60 ℃ of following stirring reactions 6～12 hours;
C, with the heptane repetitive scrubbing for several times with step b reaction product, vacuum is drained, and preserves under rare gas element;
The carrierization of d, catalyzer: will back transition ferrous metal catalyzer with the inert support of handling through step c in the non-polar solvent of deoxidation dehydration, 30～60 ℃ of following stirring reactions 6～12 hours, use the heptane repetitive scrubbing for several times then, till supernatant liquid becomes colorless, vacuum is drained, and preserves under rare gas element.
Described alkylaluminoxane or aluminum alkyls are methylaluminoxane, ethyl aikyiaiurnirsoxan beta, triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, trimethyl aluminium, tri-propyl aluminum, tri-butyl aluminum, tri-tert aluminium.
The described titanium component MgTi that contains
aX
b(OR)
cIn the R base be preferably: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, sec.-propyl, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-aminomethyl phenyl, right-aminomethyl phenyl, neighbour-sulfonic group phenyl, formyl radical, ethanoyl, benzoyl.
The described titanium component MgTi that contains
aX
b(OR)
cMiddle a is preferably 0.05～0.5; B is preferably 1.7～3; C is preferably 0.10～1.5.
Described non-polar solvent is preferably: one or more in pentane, iso-pentane, Trimethylmethane, hexane, heptane, octane, nonane, decane, hexanaphthene, the pentamethylene.
Application in the polyvinyl resin that this catalyzer is two in preparation or broad peak distributes.
Advantageous effect of the present invention: catalyzer of the present invention has not only shown higher activity after being used for the slurry process vinyl polymerization, generally counts 1.06 * 10 with every gram transition metal
5Be higher than prior art catalyst system of the same type far away, and the molecular weight distribution broad of gained polyvinyl resin, and can obtain the polyvinyl resin of bimodal distribution, its weight-average molecular weight is generally 11～42 (GPC methods) with the ratio of number-average molecular weight, and the preparation of the polyvinyl resin of gained is carried out in single reaction vessel by complex catalyst system, therefore avoided the uneven problem of gained vinyl polymerization, and make the physicals of polymkeric substance reach optimization, therefore have a good application prospect at aspects such as producing film and tubing goods.
Description of drawings
Fig. 1 is the graphic representation of the polymkeric substance GPC of the embodiment of the invention 1.
Fig. 2 is the graphic representation of the polymkeric substance GPC of the embodiment of the invention 5.
Fig. 3 is the graphic representation of the polymkeric substance GPC of the embodiment of the invention 6.
Fig. 4 is the graphic representation of the polymkeric substance GPC of the embodiment of the invention 7.
Embodiment
Catalyzer of the present invention can use on gas phase or liquid phase method poly-unit, is used for the equal polymerization or the copolymerization of alkene.Be specially adapted to the equal polymerization of ethene of slurry process and the copolymerization of ethene and other alpha-olefins.Wherein alpha-olefin adopts in propylene, butylene, amylene, hexene, octene, the 4-methylpentene a kind of.
Can adopt following reaction conditions to carry out vinyl polymerization:
Polymerization temperature: 10～110 ℃, preferred 40～60 ℃
Polymerization pressure: 0.01～10.0Mpa, preferred 0.1～2.0Mpa
Hydrogen/ethylene ratio: 0.001～1mol/mol, preferred 0.01～0.5mol/mol
Embodiment
The test condition of relevant polymkeric substance is as follows in following examples:
MI
2.16: according to the method for ASTMD-1238-98;
R=MI21.6/MI2.16: according to the method for ASTMD-1238-98;
The anti-phase gel chromatography of Mw/Mn:GPC records;
Density: according to ASTMD-1505-98;
Tap density: according to ASTMD1895;
Embodiment 1
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add Magnesium Chloride Anhydrous (MgCl successively
2) 100 milliliters of 2.00 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrachloride (TiCl
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.3Cl
1.9(OCH
2CH
3)
0.7).
The preparation of iron component
At first silicon-dioxide was calcined 10 hours under 400 ℃ of high temperature; under 150 ℃, vacuumized 3 hours then; under nitrogen protection; in having the reaction flask of agitator, add silicon-dioxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration heptane; at room temperature; drip 4.2 milliliters of methylaluminoxane; being warming up to 40 ℃, reacting after 8 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration heptane again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 8 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 5 milliliters of triethyl aluminums (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.002 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.1MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 62 grams, activity is 1.06 * 10
5The gPE/g metal.Gpc analysis is seen accompanying drawing 1, and polymerization result sees Table one.
Embodiment 2
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add anhydrous two magnesium iodide (MgI successively
2) 100 milliliters of 4.00 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped purity titanium tetraethoxide (Ti (OCH
2CH
3)
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.3I
1.9(OCH
2CH
3)
0.7).
The preparation of iron component
At first aluminum oxide was calcined 6 hours under 200 ℃ of high temperature; under 110 ℃, vacuumized 2 hours then; under nitrogen protection; in having the reaction flask of agitator, add aluminum oxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration pentanes; at room temperature; drip 4.2 milliliters of trimethyl aluminiums; being warming up to 30 ℃, reacting after 6 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration pentanes again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 6 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 25 milliliters of triethyl aluminums (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.002 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.1MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 52 grams, activity is 8.8 * 10
4Polymerization result sees Table one.
Embodiment 3
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add anhydrous dibrominated magnesium (MgBr successively
2) 100 milliliters of 1.50 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrabromide (TiBr
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.3Br
1.9(OCH
2CH
3)
0.7).
The preparation of iron component
Under nitrogen protection; in having the reaction flask of agitator, add magnesium chloride (treated) 4.00 grams, 100 milliliters of deoxidation dehydration octanes, at room temperature; drip 4.2 milliliters of aluminium diethyl monochlorides; being warming up to 60 ℃, reacting after 12 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration octanes again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 12 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 10 milliliters of aluminium diethyl monochlorides (hexane solutions of 1.00 mmole/milliliters) add the iron catalyst component of the titanium catalyst component and 0.004 mmole of 0.01 mmole, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.1MPa (gauge pressure), is 1.0MPa (gauge pressure) feeding ethene to the still pressure, and at 50 ℃, polymerization is 2 hours under the 1.0MPa, obtain white polyethylene powder 42 grams, activity is 5.8 * 10
4Polymerization result sees Table one.
Embodiment 4
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add Magnesium Chloride Anhydrous (MgCl successively
2) 100 milliliters of 5.00 grams, deoxidation dehydration heptane, at room temperature, drip anhydrous methanol (CH
3OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrachloride (TiCl
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.01Cl
1.5(OCH
3)
0.09).
The preparation of iron component
At first silicon-dioxide was calcined 12 hours under 600 ℃ of high temperature; under 200 ℃, vacuumized 4 hours then; under nitrogen protection; in having the reaction flask of agitator, add silicon-dioxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration heptane; at room temperature; drip 4.2 milliliters of triisobutyl aluminiums; being warming up to 60 ℃, reacting after 12 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration pentanes again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 12 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 0.045 milliliter of tri-butyl aluminum (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.001 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.1MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 62 grams, activity is 1.06 * 10
5The gPE/g metal.Polymerization result sees Table one.
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add Magnesium Chloride Anhydrous (MgCl successively
2) 100 milliliters of 4.73 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrachloride (TiCl
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.9Cl
3.5(OCH
2CH
3)
2.7).
The preparation of iron component
At first silicon-dioxide was calcined 10 hours under 400 ℃ of high temperature; under 150 ℃, vacuumized 3 hours then; under nitrogen protection; in having the reaction flask of agitator, add silicon-dioxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration pentamethylene; at room temperature; drip 4.2 milliliters of methylaluminoxane; being warming up to 40 ℃, reacting after 4 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration heptane again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 8 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 6.097 milliliters of triethyl aluminums (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.1 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.05MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 87 grams, activity is 1.48 * 10
5The gPE/g metal.Gpc analysis is seen accompanying drawing 2, and polymerization result sees Table one.
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add Magnesium Chloride Anhydrous (MgCl successively
2) 100 milliliters of 10.00 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrachloride (TiCl
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.05Cl
1.7(OCH
2CH
3)
0.1).
The preparation of iron component
At first silicon-dioxide was calcined 10 hours under 400 ℃ of high temperature; under 150 ℃, vacuumized 3 hours then; under nitrogen protection; in having the reaction flask of agitator, add silicon-dioxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration heptane; at room temperature; drip 4.2 milliliters of methylaluminoxane; being warming up to 40 ℃, reacting after 4 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration heptane again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 8 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 12.5 milliliters of triethyl aluminums (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.5 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.2MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 18 grams, activity is 3.0 * 10
4The gPE/g metal.Gpc analysis is seen accompanying drawing 3, and polymerization result sees Table one.
The preparation of titanium component
Under the nitrogen protection, in having the reaction flask of agitator, add Magnesium Chloride Anhydrous (MgCl successively
2) 100 milliliters of 13.00 grams, deoxidation dehydration heptane, at room temperature, drip dehydrated alcohol (CH
3CH
2OH) 2.4 milliliters, be warming up to 98 ℃ of heptane boiling points, alcohol closed reaction after 2 hours, dripped titanium tetrachloride (TiCl
4) 18 milliliters, carry titanium reaction 6 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid catalyst component (MgTi after the drying
0.5Cl
3(OCH
2CH
3)
1.5).
The preparation of iron component
At first silicon-dioxide was calcined 10 hours under 400 ℃ of high temperature; under 150 ℃, vacuumized 3 hours then; under nitrogen protection; in having the reaction flask of agitator, add silicon-dioxide (treated) 4.00 grams successively; 100 milliliters of deoxidation dehydration heptane; at room temperature; drip 4.2 milliliters of triethyl aluminums; being warming up to 40 ℃, reacting after 4 hours, is colourless with hexane wash until supernatant liquid; add 100 milliliters of deoxidation dehydration heptane again; drip 40 milligrams of rear transition metal iron catalysts (being dissolved in 60 milliliters of heptane), carry iron reaction 8 hours, obtain the mazarine slurries.Filtering out mother liquor, is colourless with hexane wash until supernatant liquid, obtains the mazarine ingredient of solid catalyst after the drying.
Polyreaction
In the 2L polymerization reaction kettle, behind nitrogen replacement, drop into 1.0 liters of hexanes successively, 0.243 milliliter of triethyl aluminum (hexane solutions of 1.00 mmole/milliliters), above-mentioned titanium catalyst component (counting 0.01 mmole titanium) with titanium, iron catalyst component (counting 0.0005 mmole iron) with iron, after reaction is warming up to 40 ℃, feed hydrogen to still and press 0.1MPa (gauge pressure), feeding ethene to still pressure is 1.0MPa (gauge pressure), at 50 ℃, 1.0MPa following polymerization 2 hours obtains white polyethylene powder 6.3 grams, activity is 1.06 * 10
4The gPE/g metal.Gpc analysis is seen accompanying drawing 4, and polymerization result sees Table one.
Table one polymerization result
| Embodiment | Fe component (mmol) | Ti component (mmol) | Catalyst efficiency gPE/g metal | Al/ metal (mol) | The polymkeric substance number-average molecular weight | Apparent density (g/cm 3) | Molecular weight distribution |
| 1 | 0.002 | 0.01 | 1.06×10 5 | 410 | 19166 | 0.23 | 34.45 |
| 2 | 0.002 | 0.01 | 8.8×10 4 | 2000 | 27115 | 0.24 | 35.46 |
| 3 | 0.004 | 0.01 | 5.8×10 4 | 360 | 21031 | 0.25 | 28.87 |
| 4 | 0.001 | 0.01 | 4.3×10 4 | 3 | 19677 | 0.23 | 37.74 |
| 5 | 0.01 | 0.01 | 1.48×10 5 | 500 | 19314 | 0.24 | 34.42 |
| 6 | 0.05 | 0.01 | 3.0×10 4 | 3000 | 26995 | 0.24 | 40.51 |
| 7 | 0.0005 | 0.01 | 1.06×10 4 | 20 | 27606 | 0.24 | 14.67 |
Claims (10)
1, a kind of catalyzer that is used for vinyl polymerization or copolymerization comprises following component:
A. one kind has formula M gTi
aX
b(OR)
cContain titanium component, X is F, Cl, Br, I or its mixture in the formula, the R base is aliphatic alkyl or the aryl radical with 1～20 carbon atom, a is 0.01～0.9, b is 1.5～3.5, c is 0.09～2.7;
B. an iron content component is a kind of diimine ligand compound of iron, structure specific as follows:
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Be hydrogen or alkyl, X is a halogen atom; Above-mentioned catalyst cupport is obtained the loading type iron component catalyst to inert solid carrier; Wherein inert solid carrier is silica gel, magnesium chloride, aluminum oxide or clay, and handles through alkylaluminoxane or aluminum alkyls;
C. aluminum alkyl catalyst.
2, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that the ratio between b component and a component is 0.05～50 with the molar ratio computing of iron and titanium, the molar ratio computing of institute's iron content and titanium is 3～3000 in aluminum alkyls in the c component and the a+b component.
3, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 and 2, it is characterized in that, ratio between b component and a component is 0.1～10 with the molar ratio computing of iron and titanium, and the molar ratio computing of institute's iron content and titanium is 20～500 in aluminum alkyls in the c component and the a+b component.
4, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that the described titanium component MgTi that contains
aX
b(OR)
c, obtain by magnesium compound, Fatty Alcohol(C12-C14 and C12-C18) and titanium compound reaction; The mol ratio of Fatty Alcohol(C12-C14 and C12-C18) and magnesium compound is 0.1～20.0, and the mol ratio of titanium compound and magnesium compound is 1.0～6.0; Described magnesium compound is with formula M gX
2Expression, X is F, Cl, Br, I or its mixture; Fatty Alcohol(C12-C14 and C12-C18) is the Fatty Alcohol(C12-C14 and C12-C18) with 1～20 carbon atom; The general formula AlR of described aluminum alkyls
1 gX
3-g, R in the formula
1Be the alkyl of 1～20 carbon, g is 0～3 integer.
5, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 4 is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, Virahol, the trimethyl carbinol, primary isoamyl alcohol, tertiary amyl alcohol, the 2-Ethylhexyl Alcohol.
6, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 4 is characterized in that described titanium compound Ti (OR
2)
mX
p, m+p=4 wherein, X is a halogen, R
2For being the aliphatic alkyl of 1～20 carbon atom, or aryl radical or COR ', each R
2Can be identical, also can be different, R ' is aliphatic alkyl or the aryl radical with 1～10 carbon atom.
7,, it is characterized in that described alkylaluminoxane or aluminum alkyls are methylaluminoxane, ethyl aikyiaiurnirsoxan beta, triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, trimethyl aluminium, tri-propyl aluminum, tri-butyl aluminum, tri-tert aluminium according to claim 1 or the 4 described catalyzer that are used for vinyl polymerization or copolymerization.
8, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, the preparation method who it is characterized in that described titaniferous component catalyst follows these steps to carry out: earlier magnesium compound and Fatty Alcohol(C12-C14 and C12-C18) were reacted 2 hours, make its swelling not destroying under the magnesium compound particulate state, and then react with titanium compound and to obtain above-mentioned titaniferous component catalyst in 6 hours;
The preparation method of described iron content component catalyst follows these steps to carry out:
A, inert support was calcined 6～12 hours under 200～600 ℃ of high temperature, under 110～200 ℃, vacuumized 2～4 hours then;
B, with alkylaluminoxane or aluminum alkyls and through inert support that step a handles in the heptane of deoxidation dehydration, 30～60 ℃ of following stirring reactions 6～12 hours;
C, with the heptane repetitive scrubbing for several times with step b reaction product, vacuum is drained, and preserves under rare gas element;
The carrierization of d, catalyzer: will back transition ferrous metal catalyzer with the inert support of handling through step c in the non-polar solvent of deoxidation dehydration, 30～60 ℃ of following stirring reactions 6～12 hours, use the heptane repetitive scrubbing for several times then, till supernatant liquid becomes colorless, vacuum is drained, and preserves under rare gas element.
9, the catalyzer that is used for vinyl polymerization or copolymerization according to claim 8 is characterized in that described alkylaluminoxane or aluminum alkyls are methylaluminoxane, ethyl aikyiaiurnirsoxan beta, triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, trimethyl aluminium, tri-propyl aluminum, tri-butyl aluminum, tri-tert aluminium; Described inert support is silica gel, magnesium chloride, aluminum oxide or clay; Non-polar solvent is: one or more in pentane, iso-pentane, Trimethylmethane, hexane, heptane, octane, nonane, decane, hexanaphthene, the pentamethylene.
10, the application in the polyvinyl resin that the described catalyzer of a kind of claim 1 is two in preparation or broad peak distributes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410082738 CN1290875C (en) | 2004-11-04 | 2004-11-04 | System of catalyst for vinyl polymerization or coploymerization and application thereof |
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|---|---|---|---|
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| CN101173011B (en) * | 2006-10-31 | 2010-04-14 | 中国石油化工股份有限公司 | Magnesium chloride load non-metallocene schiff base catalyst component, its manufacturing method and application |
| CN101824104B (en) * | 2009-03-05 | 2012-03-07 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization and preparation method thereof |
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