CN1875037A - Process for the polymerization of olefins - Google Patents
Process for the polymerization of olefins Download PDFInfo
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- CN1875037A CN1875037A CNA2004800320856A CN200480032085A CN1875037A CN 1875037 A CN1875037 A CN 1875037A CN A2004800320856 A CNA2004800320856 A CN A2004800320856A CN 200480032085 A CN200480032085 A CN 200480032085A CN 1875037 A CN1875037 A CN 1875037A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/06—Catalyst characterized by its size
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Abstract
The invention relates to a process for the polymerization of olefins in which at least one olefin is placed in contact with a catalytic system comprising: a) a catalytic solid comprising magnesium, at least on transition metal selected from the group consisting of titanium and zirconium and halogen, prepared by successively: - reacting, in a first step (1), at least one magnesium compound (M) chosen from oxygen-containing organic magnesium compounds with at least on compound (T) selected from the group consisting of oxygen-containing or halogen-containing tetravalent titanium and zirconium compounds, until a liquid complex is obtained; - treating, in a second step (2), the said liquid complex with an electron donor (ED); - treating, in a third step (3), the complex obtained in step (2) with a halogen-containing aluminic compound of formula A1RnX3-n, in which R is a hydrocarbon radical comprising up to 20 carbon atoms, X is halogen and n is less than 3, and B) an organometallic compound of a metal chosen from lithium, magnesium, zinc, aluminum or tin, wherein the complex obtained in step (2) of the preparation of the catalytic solid (a) is a substantially solid complex and the electron donor (ED) is a benzoyl halide.
Description
The present invention relates to the polymerization technique of alkene, relate to the polymerization technique that in the presence of comprising, carries out more precisely based on the catalyst system of the catalytic solid of magnesium, transition metal and halogen and organometallic compound (promotor).
In the Catalytic processes of the various olefinic type monomers of polymerization, have various suitable powder characteristics in order to ensure the product of olefin-based polymer, especially vinyl polymer, catalyst form is most important.In fact, the polymer powder that fines content is high exists serious defective in following link: fines accumulates in the cycling element, the transportation of powder and wrapping process, sampling and the risk of static focus in conveyor and storage tank.These problems have great influence to polymerization and proportioning process usually.The most obvious approach that addresses these problems is to use the catalyzer with suitable particle size: high mean diameter preferably combines with narrow particle size distribution.
With regard to the morphology of the polymkeric substance that reclaimed, some are very effective to comprise based on magnesium, be not entirely satisfactory based on transition metal with based on the catalyst system of the solid catalysis complex compound of halogen (as at described in document EP-A-0 703 247 and the EP-A-0 703 248 those).
In addition, its processing characteristics and/or its mechanical property are had great effect too is well-known to every rheological property of the polymkeric substance that is reclaimed.For this reason, another defective of disclosed described catalyst system is the melt index (MI of institute's synthetic polymkeric substance in the presence of described catalyst system in EP-A-0 703 247
2) value is not best with balance between corresponding dynamic viscosity (μ) value.Yet, the optimum balance between these performances for accurate extrusion swelling, melt strength and relate to the rheology of the olefin-based polymer that is reclaimed and the others of mechanical property for but be key factor.
It has been established that, and the quite special electron donor(ED) that mixes with particular form during preparation is according to the catalyst system of EP-A-0 703 247 can overcome above-mentioned every defective by using a class.
Therefore, main purpose of the present invention is the polymerization technique of alkene, and at least a alkene is contacted with the catalyst system that comprises following material:
(a) comprise magnesium, at least a transition metal of titanium and zirconium and the catalytic solid of halogen of being selected from, be prepared in the following sequence continuously:
-in first step (1), at least a magnesium compound (M) that contains the oxygen organo-magnesium compound that is selected from is reacted, till obtaining liquid complex compound with at least a compound (T) that contains organic titanic of oxygen and zirconium compounds that is selected from;
-in second step (2), (ED) handles described liquid complex compound with electron donor(ED);
-in the 3rd step (3), with halogen-containing formula AlR
nX
3-nAluminum compound handle (wherein, R comprises the most nearly alkyl of 20 carbon atoms, and X is a halogen, and n is less than 3) complex compound of gained in step (2); With
(b) be selected from the organometallic compound of the metal of lithium, magnesium, zinc, aluminium or tin;
Wherein, the complex compound of gained is solid complex substantially in the step (2) of preparation catalytic solid (a), and electron donor(ED) (ED) is acid halide (carboxylic acid halide).
One of principal character of the inventive method is that the electron donor(ED) of acid halide (ED) is joined in the liquid complex compound of gained in the step (1) of preparation catalytic solid, is adopting halogen-containing aluminum compound that it is further handled the precipitation that (step (3)) have caused described liquid complex compound before.
The step of described first known preparation catalytic solid (1) relates to by making at least a magnesium compound (M) that contains the oxygen organo-magnesium compound that is selected from carry out the prepared in reaction liquid complex compound with at least a compound (T) that contains oxygen or halogen-containing titanic and zirconium compounds that is selected from.Certainly use several different compounds (M) simultaneously.Similarly, also can use several different compounds (T) simultaneously, even wherein metal is the several compounds (T) of titanic and zirconium simultaneously.The reaction of first step can be undertaken by any suitable currently known methods, as long as can obtain liquid complex compound.Under the operational condition of reaction, when described compound (M) and/or compound (T) be liquid, require do not have solvent or thinner in the presence of only simply these reactants are mixed in and come together to implement to react.But when the quantity not sufficient of liquid so that reaction is carried out fully or when reactant was solid under the operational condition of reaction, reaction can be carried out in the presence of thinner.Described thinner generally is selected from and preferably comprises liquid aliphatic hydrocarbon, alicyclic hydrocarbon and the aromatic hydrocarbon that reaches 20 carbon atoms at most, be selected from especially various straight chain alkane (as just-butane, just-hexane and just-heptane), branched alkane (as Trimethylmethane, iso-pentane and octane-iso) or cycloalkanes (as pentamethylene and hexanaphthene).Adopt straight chain alkane, especially just-hexane can obtain gratifying result.
The consumption of compound (T) defines with respect to the amount of used compound (M).This amount can change in very wide scope.Generally speaking, every mole of magnesium has 0.01 mole at least in the compound (M), particularly at least 0.02 mole titanium or zirconium are present in the compound (T) preferably at least 0.05 mole, more preferably at least 0.2 mole.In the compound (M) every mole of this amount of magnesium be no more than usually 20 moles titanium or zirconium be present in the compound (T), more preferably no more than 10 moles, especially preferably be no more than 2 moles.
Compound (M) depends on the character of each reactant with the temperature of compound (T) when contacting in the step (1) of preparation catalytic solid, and preferably is lower than the decomposition temperature of each reactant and reaction back gained liquid complex compound.General this temperature is at least-20 ℃, preferably at least 0 ℃, and the temperature that is at least 20 ℃ is the most frequently used.Described temperature is no more than 200 ℃ usually, more preferably no more than 180 ℃, the temperature that is no more than 150 ℃ is favourable, for example about 140 ℃.
The time of the step (1) in the preparation catalytic solid is depended on the character and the operational condition of each reactant, and preferably the time sufficiently long is so that make reacting completely between each reactant.The scope of time was generally 10 minutes to 20 hours, and more preferably 2-15 hour, for example 4-10 hour.
The adding speed of the pressure of step (1) when reacting and each reactant is not key factor.For for simplicity, described technology is generally under atmospheric pressure carried out; General selected adding speed should make not can be owing to the induce reaction unexpected heating of medium of autoacceleration may take place in reaction.Usually during entire reaction the stirring reaction medium so that promote it to homogenize.Reaction can be continuously or mode intermittently carry out.
After the step (1) of preparation catalytic solid finishes, collect the liquid complex compound of compound (M) and compound (T), this liquid complex compound can directly be used in subsequent step, also can choose wantonly to be stored in the thinner (preferred inert diluent) so that use in the presence of thinner subsequently.Usually from above-mentioned disclosed document, select thinner as the possible medium of step (1) reaction.
Select compound (M) the oxygen organo-magnesium compound from various containing.Definition that term " contains the oxygen organo-magnesium compound " be all wherein organic group be bonded to compound on the magnesium by oxygen, also promptly all each magnesium atoms comprise the compound of at least one magnesium-oxygen-organic group bonding sequence.Being bonded to organic group on the magnesium by oxygen generally is selected from and comprises the most nearly 20 carbon atoms, more preferably comprises the most nearly group of 10 carbon atoms.When these groups comprise 2-6 carbon atom, can obtain gratifying result.These groups can be saturated, maybe can be undersaturated, contain side chain or contain straight chain or closed chain.Preferably they are selected from alkyl, particularly are selected from alkyl (straight or branched), thiazolinyl, aryl, cycloalkyl, arylalkyl, alkylaryl and carboxyl groups, and substitutive derivative.
Except be bonded to the organic group on the magnesium by oxygen, compound (M) also can comprise other group.These other group be preferably group-OH ,-(SO
4)
1/2,-NO
3,-(PO
4)
1/3,-(CO
3)
1/2With-ClO
4They also can be to be bonded directly to organic group on the magnesium by carbon.
In the middle of operable compound (M), the hydration carboxylate salt (as acetate and benzoate) that various alkoxide (as ethylate and hexamethylene alkoxide), alkyl alkoxide (as ethyl hexanol salt), hydroxyl alkoxide (as the hydroxyl methylate), phenates (as naphtholate) is arranged and choose wantonly that can mention.They also can be to contain oxygen and nitrogenous organic compound, also promptly comprise magnesium-oxygen-nitrogen-organic group sequence compound (as various oximates, fourth oximate particularly; With the azanol hydrochlorate, the derivative of N-nitroso-group-N-phenyl-azanol particularly); Inner complex, also promptly wherein magnesium have the bonding sequence of at least one normal magnesium-oxygen-organic group type and at least one fit key and comprise magnesium at interior heterocyclic oxygen-containing organic compound (as enolate, particularly acetylacetonate) so that form; And silanol, also promptly comprise the compound (as the tri-phenyl-silane alcoholate) of magnesium-oxygen-silicon-alkyl bonding sequence.Also the example of the compound that can mention (M) has the alkoxide complexes of those compounds (as methyl cellosolve magnesium), magnesium and the another kind of metal that comprise several different organic groups and phenates complex compound (as Mg[Al (OR)
4]
2), and the mixture of two or more compounds (M) as defined above.
In the middle of all suitable compounds (M), preferably use each magnesium atom only to contain magnesium-oxygen-organic group key and without any those compounds of other bonding.Wherein preferred especially magnesium alkoxide.Adopt two magnesium alkoxides, particularly diethyl magnesium alkoxide can obtain optimum.
Compound (T) is selected from and contains organic titanic of oxygen and zirconium compounds.Definition that term " contains organic titanic of oxygen and zirconium compounds " be all wherein organic group be bonded to the compound of titanic or zirconium (the following unified term " transition metal " that is called of described metal) by oxygen, also promptly all each transition metal atoms comprise the compound of at least one transition metal-oxygen-organic group bonding sequence.Described organic group is consistent with above-mentioned definition to compound (compound (M)).Obviously compound (T) can comprise several different organic groups.
Available compound (T) also can comprise transition metal-oxygen-transition metal key or transition metal-halogen-transition metal key.
Compound (T) can be by general formula TX
x(OR ')
4-2xExpression, wherein on behalf of transition metal, X, compound (T) represent oxygen or halogen (being preferably chlorine), and R ' represents organic group as defined above, and x is the numeral that satisfies 0≤x≤3/2.The preferred compound (T) that adopts the satisfied 0≤x of x≤1 in the described formula.
The compound that can mention (T) has various alkoxide (as Ti (O-nC
4H
9)
4), phenates is (as Zr (OC
6H
5)
4), contain the oxygen alkoxide (as TiO (OC
2H
5)
2), the halo alkoxide is (as Ti (OC
2H
5)
2Cl
2Or Zr (OiC
3H
7)
3Cl), the condensed alkoxide is (as Ti
2O (O-iC
3H
7)
6) and enolate (as the acetylacetonate titanium).
Self-evident, can use several compounds (compound (T)) simultaneously.When needs obtain the wide polyolefine of molecular weight distribution, preferably use titanium compound and zirconium compounds.
In the middle of all suitable compounds (compound (T)), preferably use each transition metal atoms only to contain transition metal-oxygen-organic group key and without any those compounds of other bonding.Various alkoxide are suitable for using.Adopt tetrol salt, particularly four butanols titaniums or the four butanols zirconiums of titanium or zirconium can obtain optimum.
During second step (2) of preparation catalytic solid, with the liquid complex compound of gained in electron donor(ED) (ED) treatment step (1), described electron donor(ED) is an acid halide, is preferably the aromatics acid halide.As electron donor(ED) (ED), anyly the liquid complex compound of gained in the step (1) can be converted into the acid halide that is substantially solid complex and can be used for implementing technology of the present invention.
Though do not wish to be entangled in theory, the applicant believes that still acid halide plays the effect of gentle irreducibility halogenating agent to the liquid complex compound of gained in the step (1), has caused magnesium halide, especially MgCl
2Selective precipitation.In reaction process, consumed acid halide and generated ester on the spot.Test has confirmed that these a large amount of esters (being preferably phenylformic acid alkyl ester when using preferred compound (M), (T) and electron donor(ED) (ED)) are attached in the described solid, and the amount of ester reaches as high as gained solid 50% weight after washing and drying operation.Owing to several equilibrated reasons, the magnesium halide of solid form should progressively obtain.
Acid halide (preferred carboxyl acyl chloride) can be derived from monobasic and polycarboxylic acid, preferably derived from monobasic and polynary aromatic carboxylic acid.Derived from monocarboxylic halid example Benzoyl chloride is arranged; Adjacent-,-or right-toluyl chlorine; The halogeno-benzene formyl chloride; Nitrobenzoyl chloride; Amino benzoyl chloride and salycylil chloride.Halid example derived from polycarboxylic acid has phthalyl (phtaloyl) chlorine and dichloro, and derived from m-phthalic acid (isophtalic), terephthalic acid (terephtalic), 1,2,4-benzenetricarboxylic acid, 1,3, the muriate of 5-benzenetricarboxylic acid, hemimellitic acid and prehnitic acid.
Preferably derived from monobasic aromatic carboxylic acid's muriate, wherein Benzoyl chloride can give especially good results.
The processing of adopting electron donor(ED) (ED) to be carried out can be undertaken by any suitable known way.Electron donor(ED) can be joined in the liquid complex compound with pure form, or add as the solution form in the solvent of step (1) reaction acceptable medium to be selected from above-mentioned disclosed thinner usually.Adopt straight chain alkane can obtain gratifying result.Preferred hexane.
The temperature that adopts electron donor(ED) to handle in first kind of variant generally is lower than the decomposition temperature of electron donor(ED) and liquid complex compound.Particularly be at least-20 ℃, more accurately be at least 0 ℃, the value that is at least 20 ℃ is more commonly used.Described temperature is no more than 150 ℃ usually, more preferably no more than 120 ℃, recommends to be no more than 100 ℃ temperature, for example is no more than 70 ℃.
The time of adopting electron donor(ED) to handle in first kind of variant is generally 1 minute to 50 hours, is preferably 45 minutes to 30 hours, for example is 120 minutes to 24 hours.
Pressure when handling is not key factor; Described optimal process under atmospheric pressure carries out.
The amount of used electron donor(ED) (ED) is generally at least 0.01 moles/mole compound used therefor (M), more accurately is at least 0.1 mole, and the value that is at least 0.5 mole is best.The amount of used electron donor(ED) is no more than the used transition metal of 20 moles/mole usually, preferably is no more than 10 moles, and strong recommendation is no more than 5 moles value.The amount of 1-4 mole is suitable especially.
After step (2) finishes, gained is substantially the solid complex compound and can its form in the preparation medium uses, perhaps can after aging step, use, under 0-100 ℃, preferred 25-90 ℃ temperature, stir as the described aging step 1 1-30 hour, preferably carried out in 5-25 hour.Also clathrate separation can be come out and pass through to wash with for example above disclosed thinner, wherein it can be suspended once more is used for preparing the 3rd step of catalytic solid.
When characterizing behind the segregation, the solid that generates during the step (2) shows the particle size distribution of remarkable improvement, compare with the known solid catalysis complex compound that obtains according to EP-A-0703247, its particle size distribution (PSD) is narrower, mean diameter is higher and fines content is lower.
The preparation of solid catalysis complex compound comprises follow-up third step (3), and it mainly act as the valency that reduces transition metal, and makes the halogenation more of magnesium compound and/or transistion metal compound in case of necessity simultaneously.Also promptly replace the alkoxyl group still may be present in magnesium compound and/or the transistion metal compound by halogen, the solid complex compound that is substantially that makes that step (2) obtains changes into catalytic activity throw out as catalytic solid.Adopt halogen-containing aluminum compound to reduce simultaneously and further halogenation, thereby halogen-containing aluminum compound play the effect of reductibility halogenating agent.
In the step (3) of preparation catalytic solid, adopt halogen-containing aluminum compound, can carry out described processing, and preferably halogen-containing organo-aluminium compound is joined gradually in the suspension of the complex compound of gained in the step (2) by any suitable currently known methods.
The amount of used halogen-containing aluminum compound depends on the amount of used magnesium compound and transistion metal compound, and this amount preferably is enough to obtain required reduction ratio and obtains required halogenation rate suitably the time.Adopting in practice greater than the amount that obtains the required minimum of reduction completely and halogenation completely (suitably time) does not have benefit, because excessive use will cause the increase of aluminium concentration in the solid catalysis complex compound, and this is undesirable.Generally speaking, described amount is the used magnesium of at least 0.5 moles, of aluminum per mole of titanium metal/mole, preferably at least 1 mole, and at least 1.5 moles value is the most frequently used; Usually this amount is no more than the used transition metal of 50 moles, of aluminum per mole of titanium metal/moles, particularly is no more than 30 moles, and it is favourable being no more than 20 moles value, especially being no more than 10 moles.Amount by 2-9 moles, of aluminum per mole of titanium metal/mole magnesium can obtain special good result.
It is disclosed to adopt halogen-containing aluminum compound to handle in can be as EP-A-0703248 in step (3), carries out in a step or two successive steps.
Carry out the used temperature of step (3) and be preferably lower than the boiling point of halogen-containing aluminum compound under standard atmosphere pressure.Usually be at least-20 ℃, more preferably be at least 0 ℃, recommendation is at least 20 ℃ temperature.Described temperature is no more than 150 ℃ usually, and more preferably no more than 100 ℃, the temperature that is no more than 80 ℃ is the most frequently used.
What preferred steps (3) was enough grows so that make the solid complex compound that is substantially of step (2) gained realize reduction completely and further halogenation.Its scope can be 1 minute to 10 hours, more accurate be 10 minutes to 8 hours, for example 0.5-5 hour.
The used pressure of step (3) is not key factor.For simplicity, technology is generally under atmospheric pressure carried out.That generally selects enough each reactants of constant adds speed in order to avoid because the possible autoacceleration effect of reaction causes the unexpected heating of reaction medium.General stirring reaction medium is to promote its homogenizing in entire reaction.Reaction can be continuously or mode intermittently carry out.
Described halogen-containing aluminum compound is corresponding to formula AlR
nX
3-n, wherein R comprises to be up to 20 carbon atoms, preferably to be up to the alkyl of 6 carbon atoms.When being alkyl (straight or branched), cycloalkyl, arylalkyl, aryl or alkylaryl, R can obtain gratifying result.When representing the alkyl group of straight or branched, R can obtain optimum.X generally is selected from fluorine, chlorine, bromine and iodine.Suitable especially is chlorine.Preferred n is not more than 1.5, more preferably no more than 1.As the example that can be used for the halogen-containing aluminum compound among the present invention, that can mention has an aluminum chloride [AlCl
3], ethylaluminium dichloride [Al (C
2H
5) Cl
2], sesquialter ethylaluminium chloride [Al
2(C
2H
5)
3Cl
3], diethylaluminum chloride [Al (C
2H
5)
2Cl] and aluminium isobutyl dichloride [Al (iC
4H
9) Cl
2].Preferred aluminium isobutyl dichloride.
After the step (3) of preparation catalytic solid finishes, collect described solid, solid consumes and the precipitation from homogeneous solution (PFHS) thing (co-precipitation goes out each component from liquid complex compound) of the mixture of the various ester resistatess that produce is formed by magnesium halide, transition metal halide and the partial reduction when suitable and/or partially halogenated compound and by electron donor(ED) (ED).These are the complex compounds by the chemical bonding of chemical reaction generation, rather than the result of mixing or adsorption phenomena.In fact, can not be by adopting dissociate any component in these complex compounds of simple physical separation method.
The best follow-up maturation process of step (3) of preparation catalytic solid, its effect are to make it possible to obtain that the uncontrollable fracture of polymerization is had the catalytic solid that improves defensive ability/resistance ability.Described slaking is carried out generally being equal to or higher than under the temperature that step (3) carries out.General its non-critical phase of carrying out is 5 minutes to 12 hours, preferably at least 0.5 hour.
Step (3) also can be follow-up (preferably after optional maturation stage) washing step with remove described catalytic solid still impregnated in wherein excessive reactant and preparation during the by product that may form.Any inert thinner can be used for this washing step, for example above disclosed those thinners as step (1) reaction medium.For example can dry described catalytic solid after the washing by inert gas (, being preferably dry gas) purge as nitrogen.
According to technology of the present invention, and carry out catalyst system that polymeric alkene contacted except containing above-mentioned catalytic solid (a), also can contain as described catalytic solid activator and be commonly referred to the organometallic compound (b) of " promotor ".It is selected from the organometallic compound of lithium, magnesium, zinc, aluminium or tin.Adopt organo-aluminium compound can obtain optimum.
The compound that can use all alkylization is as organometallic compound, wherein said alkyl chain comprises the most nearly 20 carbon atoms, and be straight or branched, for example just-butyllithium, magnesium ethide, zinc ethyl, tin tetraethyl, tetrabutyl tin and various trialkylaluminium.Also can use metal alkylide hydride, wherein said alkyl group also comprises the most nearly 20 carbon atoms, for example diisobutylaluminium hydride and trimethyl tin hydride.Wherein said alkyl group also comprises the alkyl metal halide that reaches 20 carbon atoms most and is fit to too, for example sesquialter ethylaluminium chloride, diethylaluminum chloride and di-isobutyl aluminum chloride.Can also use by making hydrogenation trialkylaluminium or hydrogenation aluminum dialkyl (wherein said group comprises the most nearly 20 carbon atoms) react the organo-aluminium compound that obtains with the diolefine that comprises 4-20 carbon atom, known compound is a prenyl aluminium more specifically.
Generally speaking, preferred trialkylaluminium, particularly wherein alkyl chain is straight chain and comprises the most nearly 18 carbon atoms, more specifically is those trialkylaluminiums of 2-8 carbon atom.Preferred triethyl aluminum and triisobutyl aluminium.
The total amount that is used for polymerization technique organometallic compound of the present invention can change in wide range.Every liter of solvent, thinner or this value of reactant volume are generally the 0.02-50 mmole, be preferably the 0.2-2.5 mmole/liter.
The amount that is used for the solid catalysis complex compound of polymerization technique of the present invention is determined as the function of levels of transition metals in the described complex compound.General this value of selecting makes that described concentration is every liter of solvent, thinner or reactant volume 0.001-2.5 mmole, preferred 0.01-0.25 mmole transition metal.
The total amount that is present in metal in the organometallic compound is at least 1 usually with the mol ratio that is present in the transition metal total amount in the transistion metal compound, and it is favourable being at least 5 value.This ratio generally is no more than 100, recommends to be no more than 50 value.
Polymerization technique of the present invention can in the solution of solvent (can be liquid alkene itself), or carry out in the suspension of hydrocarbon diluent or in gas phase according to any known method.In suspension polymerization, can obtain gratifying result.
By being contacted with the catalyst system that comprises solid catalysis complex compound, organometallic compound and electron donor(ED), alkene carries out described polymerization.
It is optional from the alkene that contains 2-20 carbon atom, preferred 2-6 carbon atom, for example ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene to carry out polymeric alkene.Ethene, 1-butylene and 1-hexene are suitable for using.Special optimal ethylene.Obviously, can use several different alkene simultaneously in order to obtain multipolymer, for example the mixture of two kinds of above-mentioned alkene or one or more these alkene and one or more preferably comprise the mixture of the diolefine of 4-20 carbon atom.These diolefine can be unconjugated aliphatic diolefine hydrocarbon, for example 1, and the 4-hexadiene; The monocycle diolefine, 4 vinyl cyclohexene, 1 for example, 3-divinyl hexanaphthene, cyclopentadiene or 1,5-cyclooctadiene; Alicyclic ring diene with bridged ring bridged bond, for example Dicyclopentadiene (DCPD) or norbornadiene; And conjugated aliphatic diolefine, for example divinyl and isoprene.
Process application of the present invention is in Alathon and contain at least 90% molar ethylene, and effect is good especially in the production of the multipolymer of preferred 95% molar ethylene.
Suspension polymerization is generally carried out in hydrocarbon diluent (as liquid aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbon) and under (the preferably at least 90%) polymkeric substance that generated that makes 80% is insoluble to wherein temperature at least.Preferable absorbent is a straight chain alkane, for example just-and butane, just-hexane and just-heptane; Or branched alkane, for example Trimethylmethane, iso-pentane, octane-iso and 2,2-dimethylpropane; Or cycloalkanes, for example pentamethylene and hexanaphthene; Or its mixture.Adopt hexane and Trimethylmethane can obtain optimum.Polymerization temperature is typically chosen in 20-200 ℃, preferred 50-150 ℃, preferred 65-115 ℃ especially.The dividing potential drop of described alkene is chosen as normal atmosphere-5MPa, preferred 0.2-2MPa, more preferably 0.4-1.5MPa usually.
Polymerization technique of the present invention can be chosen wantonly in the presence of molecular weight regulator (as hydrogen) and carry out.
Polymerization technique of the present invention can be continuously or mode intermittently in single reaction vessel or several reactors that is connected in series, carry out, wherein the polymerizing condition in a reactor (temperature, possible co-monomer content, possible hydrogen richness, the type of polymerisation medium) is different from the condition that is used for other reactor.
Since the morphologic improvement of catalytic solid, feasible particle size distribution and the powder accumulation density that can improve gained polyolefine powder of polymerization technique of the present invention.In addition, polymerization technique of the present invention makes and can also obtain the improved polyolefine of rheological property.
Below each embodiment be used to illustrate the present invention.Be used for the symbolic significance of each embodiment, the method for expressing the unit of described performance and measuring these performances is explained as follows.
Spacing: represent particle size distribution by correlation (D90-D10)/D50, wherein measure by the laser particle size assay method and the meaning of each D of representing with μ m as follows:
D10: the value of collecting 10% volume particles;
D50: the value of collecting 50% volume particles;
D90: the value of collecting 90% volume particles.
MI
2.16: the melt index of polymkeric substance, under 190 ℃ and 2.16 kilograms of load, measure and with expression in g/10 minute according to ASTM standard D 1238 (condition E) (1986).
HLMI: the melt index of polymkeric substance, under 190 ℃ and 21.6 kilograms of load, measure and with expression in g/10 minute according to ASTM standard D 1238.
Density (D): the standard density of polymkeric substance, with kg/m
3Expression is measured according to iso standard 1183 (1987).
SCB: the short-chain branch content of polymkeric substance, by
13C NMR measures.
Tap density (BD): according to the principle that proposes among ASTM standard D 1895 (1979) and the ISO 60 (1977), measure by adopting following method: pouring polymer powder into capacity from hopper is in 50 milliliters the cylindrical container, note not compacting downwards, the lower rim of hopper is placed in 20 millimeters of the tops of upper container edge.Weigh subsequently and loaded the container of powder, deduct tare weight from weight readings, gained result (representing with g) is divided by 50.
μ: the dynamic viscosity of polymkeric substance, represent with dPa.s, at 100s
-1Shearing rate and 190 ℃ measure down.
Fines (%): is the volume % of the polymer beads of feature with mean diameter less than 125 μ m (measuring by the laser particle size assay method).
Embodiment 1
1. the preparation of catalytic solid
Step (1). the preparation of liquid complex compound
Stirring reacted the diethyl magnesium alkoxide and the four butanols titaniums that prepare on the spot by MAGNESIUM METAL and ethanol synthesis in 4 hours under 140 ℃, and the mol ratio of titanium and magnesium equals 1.
Step (2). adopt electron donor(ED) (ED) to handle
60 ℃ and stir under the solution of 16.3 milliliters of Benzoyl chlorides in 50 milliliters of hexanes is joined in the solution of 70 mmole liquid complex compound in 135 milliliters of hexanes.In 45 minutes, finish described adding.Make reaction medium remain on 60 ℃ and stirred 6 hours down, generated white solid.Gained hexane suspension is directly used in the next procedure of preparation catalytic solid.
Step (3). adopt halogen-containing aluminum compound to handle
Aluminium isobutyl dichloride (IBADIC) is joined in the suspension of step (2) gained aluminium under 45 ℃: the mol ratio of titanium is 8: 1.Finished described adding in 135 minutes, temperature rose to 60 ℃ in 60 minutes.The brown solid of decantation gained is also with several parts of hexane wash then.
2. aggregation test
Select present embodiment and following each embodiment to carry out the general operation condition of aggregation test so that obtain ethene polymers, its catalysis productive rate is about 15-20kg polymkeric substance/g catalytic solid.
5 liters of stainless steel autoclaves that mechanical stirrer is housed heat treated under 90 ℃ and nitrogen gas stream is spent the night, and is cooled to room temperature.Add 1.5 liters of hexanes and 2 mmole triethyl aluminums then, heat described autoclave down at 85 ℃.After the pressure-stabilisation, the adding dividing potential drop is that hydrogen and the dividing potential drop of 0.25MPa is the ethene of 0.6MPa.Be suspended in 100 milliliters of catalytic solids in the hexane and begin polyreaction by washing 30 milligrams.By mass flowmeter continuously and automatic gauge ethene with maintenance constant monomer dividing potential drop.After 90 minutes, stop polyreaction and described autoclave is cooled to room temperature (after this being referred to as polymerizing condition I) by quick exhaust.
Embodiment 2
Adopt among the embodiment 1 disclosed catalytic solid and under the same terms described in this embodiment, carry out aggregation test, but the dividing potential drop of hydrogen is set to 0.4MPa (after this being referred to as polymerizing condition II).
Embodiment 3
5 liters of stainless steel autoclaves that mechanical stirrer is housed heat treated under 90 ℃ and nitrogen gas stream is spent the night, and is cooled to room temperature.Add 1.5 liters of hexanes and 2 mmole triethyl aluminums then, heat described autoclave down at 75 ℃.After the pressure-stabilisation, depressing adding ethene and add hydrogen at the branch of 0.4MPa, is 0.003/1 to obtain hydrogen/ethene ratio.
Add 25 gram butylene again.Disclosedly among 30 milligrams of embodiment 1 be suspended in 100 milliliters of catalytic solids in the hexane and begin polyreaction by washing.By mass flowmeter continuously and automatic gauge ethene with maintenance constant monomer dividing potential drop.After 90 minutes, stop polyreaction and described autoclave is cooled to room temperature (after this being referred to as polymerizing condition III) by quick exhaust.
Embodiment 4
Again carry out the preparation of the catalytic solid of embodiment 1, difference is in step (3), and with the aluminium of IBADIC with 6: 1: the titanium mol ratio joins in the slurry of gained in the step (2).Finished described adding in 100 minutes, temperature rose to 60 ℃ in 60 minutes.Decantation gained brown solid is also with several parts of hexane wash then.
Under polymerizing condition I, adopt this catalytic solid to carry out aggregation test.
Embodiment 5
Under polymerizing condition II, adopt the catalytic solid of embodiment 4 to carry out aggregation test.
Embodiment 6
In the preparation that repeats embodiment 1 catalytic solid under the actual conditions of following steps (2) and (3): 30 ℃ and stir under Benzoyl chloride solution in 50 milliliters of hexanes of 16.3 milliliters is joined the liquid complex compound of 70 mmole steps (1) in the solution of 135 milliliters of hexanes.In 45 minutes, finish described adding.Keep stirring 24 hours at 30 ℃ of following reactants, generate white solid.The hexane suspension of gained is directly used in the step (3) of preparation catalytic solid, wherein under 45 ℃ with 3.5: 1 aluminium: the titanium mol ratio joins IBADIC in this suspension.Finished described adding in 60 minutes, temperature kept constant 60 minutes.The brown solid of decantation gained is used hexane wash then.At 45 times, in 40 minutes with 2.5: 1 aluminium: the titanium mol ratio adds IBADIC again.60 ℃ aging 45 minutes down, the Vandyke brown solid of gained is with several parts of hexane wash.
Under polymerizing condition I, adopt this catalytic solid to carry out aggregation test.
Embodiment 7R (being used for contrast)
Again carry out the preparation of embodiment 1 catalytic solid, difference is in step (2), 45 ℃ and stir under will contain 16 milliliters of tetrachloro silicanes and 50 milliliters of hexanes solution join the liquid complex compound of 70 mmole steps (1) in the solution of 80 milliliters of hexanes.Finished described adding in 45 minutes, reactant keeps down stirring 1 hour at 45 ℃.Gained hexane suspension is used directly in the next procedure (3) that carries out under the following actual conditions: under 45 ℃ with 3.5: 1 aluminium: the titanium mol ratio joins IBADIC in the suspension of preparation in the step (2).In 60 minutes, finish described adding, and temperature kept constant 60 minutes.Decantation gained brown solid and use hexane wash then.Then 45 ℃ in following 40 minutes with 2.5: 1 aluminium: the titanium mol ratio adds IBADIC.60 ℃ aging 45 minutes down, gained Vandyke brown solid is with several parts of hexane wash.Under polymerizing condition I, adopt this catalytic solid to carry out aggregation test.
In following table 1, compiled measuring result to the product and the various embodiments described above catalytic solid of step (2).Every physics, morphology and rheologic behavio(u)r in following table 2, have been compiled according to these embodiment resulting polymers.
Embodiment 8R (being used for contrast)
Again carry out the preparation of embodiment 1 catalytic solid, difference is in step (2), will obtain in 19 milliliters ethyl benzoates and the 70 mmole steps (1) and mix with the liquid complex compound that 120 milliliters of hexanes dilute.Then 45 ℃ and stir under drip 3: 1 aluminium: the IBADIC of titanium mol ratio.Finish described adding in 50 minutes, generate white solid.Gained hexane suspension is used directly in the next procedure (3) that carries out under the following actual conditions:
Under 45 ℃ with 4: 1 aluminium: the IBADIC of titanium mol ratio drops in the suspension of preparation in the step (2).Finish described adding in 67 minutes, and temperature kept constant 60 minutes.Wore out 45 minutes down at 60 ℃, with the Vandyke brown solid of several parts of hexane wash gained.
Under polymerizing condition I, adopt this catalytic solid to carry out aggregation test.
In following table 1, compiled measuring result to the product and the various embodiments described above catalytic solid of step (2).Every physics, morphology and rheologic behavio(u)r in following table 2, have been compiled according to these embodiment resulting polymers.
Table 1
| Embodiment | Step (2) solid particle size measurement | The particle size measurement of catalytic solid | ||
| D50 | Spacing | D50 | Spacing | |
| 1 | 16.6 | 1.1 | 22.3 | 1.9 |
| 4 | 16.6 | 1.1 | 22.2 | 2.3 |
| 6 | 14.1 | 1.5 | 20.4 | 1.8 |
| 7R | 7.3 | 1.0 | 8.8 | 1.2 |
| 8R | 14.3 | 2.2 | 9.0 | 1.3 |
This table shown according to the product particle size distribution of step of the present invention (2) and improved (being expressed as lower distance values) (embodiment 1,4 and 6 and 8R contrast), or mean diameter big (being expressed as higher D50 value) (embodiment 1,4 and 6 and 7R contrast).And the mean diameter of catalytic solid of the present invention also big (being expressed as higher D50 value).
Table 2
| Embodiment | Polymerizing condition | The physicals of the polymkeric substance that reclaims | The rheological property of the polymkeric substance that reclaims | ||||
| D | SCB | BD | Fines (%) | MI 2.16 | μ | ||
| 1 | I | 963.2 | - | 355 | 1.1 | 1.0 | 13400 |
| 2 | II | 966.1 | - | 371 | 0.0 | 4.0 | 6600 |
| 3 | III | 929.4 | 4.7 | 360 | 0.0 | 0.49 * | - |
| 4 | I | 961.4 | - | 315 | 0.6 | 1.4 | 13900 |
| 5 | II | 965.3 | - | 331 | 2.6 | 10.4 | 5600 |
| 6 | I | 962.9 | - | 350 | 5.7 | 1.2 | 12520 |
| 7R | I | 958.0 | - | 287 | 10.8 | 0.20 | 29500 |
| 8R | I | 959.0 | - | 318 | 6 | 0.47 | 23000 |
*HLMI
This table has shown that the polymkeric substance that can obtain according to the present invention is in the improvement aspect every physics and the rheological property balance; Under comparable polymerizing condition, reduced the content of fines and increased tap density; In addition, for comparable MI
2,16Value has obtained lower dynamic viscosity, and this balance has been improved the processing characteristics of polymkeric substance.At last, this table has also shown under comparable polymerizing condition, adopts catalyst system of the present invention can obtain higher melt index; This means that its susceptibility to molecular weight regulator (" the hydrogen response " of catalyzer) is higher.
Claims (6)
1. technology that is used for olefinic polymerization wherein makes at least a alkene contact with the catalyst system that comprises following material:
(a) comprise magnesium, at least a transition metal of titanium and zirconium and the catalytic solid of halogen of being selected from, be prepared continuously in the following sequence:
-in first step (1), at least a magnesium compound (M) that contains the oxygen organo-magnesium compound that is selected from is reacted, till obtaining liquid complex compound with at least a compound (T) that contains organic titanic of oxygen and zirconium compounds that is selected from;
-in second step (2), (ED) handles described liquid complex compound with electron donor(ED);
-in the 3rd step (3), with halogen-containing formula AlR
nX
3-nAluminum compound handle the complex compound of gained in step (2), wherein R comprises the alkyl that reaches 20 carbon atoms most, X is a halogen, n is less than 3; With
(b) be selected from the organometallic compound of the metal of lithium, magnesium, zinc, aluminium or tin;
Wherein the complex compound of gained is solid complex substantially in the step (2) of preparation catalytic solid (a), and described electron donor(ED) (ED) is an acid halide.
2. the technology of claim 1, wherein said electron donor(ED) (ED) is the aromatics acid halide.
3. the technology of claim 2, wherein said electron donor(ED) (ED) is derived from the monobasic acid halide.
4. the technology of claim 3, wherein said electron donor(ED) (ED) is a Benzoyl chloride.
5. the technology of claim 1 to 4, the consumption of wherein said electron donor(ED) (ED) is a 1-4 moles/mole compound (M).
6. the technology of claim 1 to 5, wherein at least a alkene is ethene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0320473.2A GB0320473D0 (en) | 2003-09-01 | 2003-09-01 | Process for the polymerization of olefins |
| GB0320473.2 | 2003-09-01 |
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| Publication Number | Publication Date |
|---|---|
| CN1875037A true CN1875037A (en) | 2006-12-06 |
| CN100591701C CN100591701C (en) | 2010-02-24 |
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| CN200480032085A Expired - Fee Related CN100591701C (en) | 2003-09-01 | 2004-08-26 | Process for the polymerization of olefins |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1660546A1 (en) |
| CN (1) | CN100591701C (en) |
| GB (1) | GB0320473D0 (en) |
| WO (1) | WO2005021610A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495523B (en) * | 2006-05-26 | 2011-06-22 | 英尼奥斯制造业比利时有限公司 | Polyolefin powder |
| US8859450B2 (en) | 2007-12-27 | 2014-10-14 | Sumitomo Chemical Company, Limited | Solid catalyst component for olefin polymerization |
| CN105085739A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Alkene polymerization catalyst composition, preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110036043B (en) * | 2016-10-28 | 2021-09-28 | Sabic环球技术有限责任公司 | Method for producing ultra-high molecular weight polyethylene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4935394A (en) * | 1988-08-19 | 1990-06-19 | Exxon Chemical Patents Inc. | Catalyst for olefin polymerization |
| BE1008702A3 (en) * | 1994-09-22 | 1996-07-02 | Solvay | Process for olefin polymerization. |
-
2003
- 2003-09-01 GB GBGB0320473.2A patent/GB0320473D0/en not_active Ceased
-
2004
- 2004-08-26 EP EP04769355A patent/EP1660546A1/en not_active Withdrawn
- 2004-08-26 WO PCT/IB2004/002964 patent/WO2005021610A1/en active Application Filing
- 2004-08-26 CN CN200480032085A patent/CN100591701C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495523B (en) * | 2006-05-26 | 2011-06-22 | 英尼奥斯制造业比利时有限公司 | Polyolefin powder |
| US8859450B2 (en) | 2007-12-27 | 2014-10-14 | Sumitomo Chemical Company, Limited | Solid catalyst component for olefin polymerization |
| CN105085739A (en) * | 2014-04-29 | 2015-11-25 | 中国石油化工股份有限公司 | Alkene polymerization catalyst composition, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1660546A1 (en) | 2006-05-31 |
| WO2005021610A1 (en) | 2005-03-10 |
| GB0320473D0 (en) | 2003-10-01 |
| CN100591701C (en) | 2010-02-24 |
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