Summary of the invention
One of the object of the invention is the solid particulate for preparing Ziegler-Natta catalyst in a kind of controlled mode, thereby it is better to obtain form, and such as sphere, the granules of catalyst of narrow size-grade distribution has higher catalytic activity and hydrogen response simultaneously.
Two of the object of the invention is to provide the olefin polymerization catalysis that adopts the inventive method to obtain.
The invention provides a kind of catalyst component for olefinic polymerization and its production and use, it is to comprise at least a organo-magnesium compound, at least a titanium-containing compound, the reaction product of at least a hydroxyl compounds and at least a chloride silicoorganic compound and at least a property-modifying additive.The catalyzer of preparation also has simultaneously good particle form and distribution, thereby more is conducive to the use of catalyzer on the polymerization technique devices such as gas phase, slurry except having good hydrogen regulation performance.
A kind of catalyst component for olefinic polymerization of the present invention, it is to comprise at least a organo-magnesium compound, at least a liquid titanium-containing compound, the reaction product of at least a hydroxyl compounds and at least a chloride silicoorganic compound and at least a property-modifying additive; Wherein:
(1) organo-magnesium compound is by general formula (I) MgR1nCl2-nShown in, R in the formula1C2～C20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2;
(2) titanium-containing compound is by logical formula II Ti (OR2)nCl4-nShown in, R in the formula2C2～C20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤4;
(3) the hydroxyl compounds is such as logical formula III HOR3Shown in, R is C in the formula2～C20Alkyl, optional be saturated or undersaturated straight chain, side chain or closed chain.
(4) chloride silicoorganic compound are such as logical formula IV SiRnCl4-nShown in, R is C in its Chinese style2～C20Alkyl or alkoxyl group, 0≤n in the general formula＜4.
(5) property-modifying additive is polybutadiene block polyethylene oxide base polymer, comprise diblock and three blocks and derivative thereof etc., randomly for linear, that side chain is arranged or star etc. other form, in described polyhutadiene poly-ethylene oxide block analog copolymer, the content of polyhutadiene is 3-97% (wt%).
Described organo-magnesium compound such as general formula (I) MgR1nCl2-nShown in, R is C in the formula2～C20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2.Concrete compound such as MgCl2, MgEtCl, MgBu2, the preferred dibutylmagnesium of the organo-magnesium compound that uses in the reaction, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride are medium.
Described liquid titanium-containing compound is such as logical formula II Ti (OR2)nCl4-nShown in, R is C in the formula2～C20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤n≤4.The preferred tetravalent titanium compound that uses, because they are in a liquid state usually at normal temperatures, and also also fine with the consistency of some solvents under normal conditions.The concrete titanium compound that uses preferably uses tetravalent titanium compound and their mixture in the reaction, and wherein titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate are the most commonly used.
Described hydroxyl compounds is such as logical formula III HOR3Shown in, R is C in the formula2～C20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain.The hydroxyl compounds is Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, preferred propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol, phenylethyl alcohol and composition thereof etc.
Described chloride silicoorganic compound are such as logical formula IV SiRnCl4-nShown in, R is C in its Chinese style2～C20Alkyl or alkoxyl group, 0≤n in the general formula＜4, concrete chloride silicoorganic compound comprise trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine methoxy silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane, silicon tetrachloride, and wherein trichloromethyl silane, trichloroethyl silane, trichlorine methoxy silane, trichlorine Ethoxysilane and silicon tetrachloride are preferred.
Described property-modifying additive is polybutadiene block polyethylene oxide (PB-b-POE) base polymer, comprise diblock and three blocks (PB-b-POE-b-PB, POE-b-PB-b-POE) and derivative thereof etc., can be linear, side chain arranged or star etc. other form.In described polyhutadiene poly-ethylene oxide block analog copolymer, the content of polyhutadiene is 3-97% (wt), preferred 10-90% (wt).
Catalyst component of the present invention preferably adopts the following step to be prepared:
(1) organo-magnesium compound and hydroxyl compounds are reacted, obtain clear solution;
(2) property-modifying additive is dispersed in C4～C20In alkane or the aromatic solvent, formation solution reacts with the clear solution that chloride silicoorganic compound and step (1) obtain again, obtains mixed solution;
(3) titanium-containing compound is joined in the mixed solution that step (2) obtains, obtain catalyst component.
In the preparation process of catalyst component of the present invention, the ratio between the each component is that in every mole of general formula (I) compound, logical formula II compound is controlled at 0.01～10 mole, preferred 0.05～5 mole; Logical formula III compound is controlled at 0.1～20 mole, preferred 0.2～10 mole; Logical formula IV compound amount is controlled at 0.05～50 mole, preferred 0.1～20 mole; The concentration of property-modifying additive in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.
In the first step of Kaolinite Preparation of Catalyst, the temperature of reaction of magnesium compound and alcohols material is typically chosen in carries out comparatively favourablely under the relatively high temperature, and preferably below the boiling temperature of reactant, temperature is not higher than 90 ℃ usually, generally is not higher than 70 ℃.The time of reaction is depended on character and the operational condition of reactant, and required time is generally at 5 minutes to 2 hours, preferred 10 minutes to 1 hour.After magnesium compound and alcohols material reaction, the solution that forms can mix with inert diluent use, inert diluent is selected from aliphatic hydrocarbon usually, for example Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, and general hexane or heptane are proper inert solvents.
In the second step of Kaolinite Preparation of Catalyst, the reaction solution that obtains in a certain amount of property-modifying additive hexane solution for preparing in advance and the first step is fully mixed, kind and different in kind according to property-modifying additive, its hexane solution configuration concentration is controlled at 0.1～100 grams per liter, preferred 1～50 grams per liter, the amount that adds is so that the concentration of property-modifying additive in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.Mixing temperature generally will be lower than the boiling temperature of system, for simplicity, is typically chosen between 0～90 ℃, between preferred 10～50 ℃.Both mixing times are general selects 0.5 minute to 5 hours, preferred 10 minutes to 1 hour.
In the 3rd step of catalyzer preparation, finish rapidly at a certain temperature the even mixing of all substances, the solution system that at first first two steps is obtained is reduced to certain temperature, solution still keeps clear under this temperature, be unlikely to become turbid or precipitate, temperature can be controlled between-90～30 ℃, preferably between-70～0 ℃, then will lead to formula IV compound and logical formula II compound progressively slowly adds successively, usually fully stir the abundant mixing that is beneficial to various materials in reinforced process, feed rate is selected to be as the criterion not cause that significant reaction or system obviously heat up usually.After fully mixing, can adopt any known suitable method to heat up, as slowly, progressively, rapidly or temperature programming, different temperature-rising methods can obtain the totally different catalyzer of performance characteristics, in temperature-rise period, system can change muddiness into by clarification, separate out precipitation, in this precipitin reaction step, the reaction times of settling step should be long enough to obtain completely precipitation, reaction times can be lasted 1 minute to 10 hours, preferred 3 minutes～5 hours.
Experiment finds, after settling step, reacting at a certain temperature for some time, to carry out maturation process more favourable to the particle shape of catalyzer, and it can improve the intensity of catalyst particle, thereby reduces the particle fragmentation phenomenon of catalyzer in polymerization process.The temperature of maturation process generally is equal to or higher than the outlet temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～10 hour, preferred 1～5 hour.
After carrying out maturation process, generally to wash, in order to remove the by product that forms in excessive reactant and the preparation process, any inert solvent all can be used for this washing step, such as selecting Trimethylmethane, pentane, hexane, heptane, hexanaphthene, toluene or various aromatic hydrocarbons and composition thereof etc., usually select in the experiment with after twice of the toluene wash, fully wash oneself with hexane again.After washing, carry out drying under the catalyst suspension nitrogen protection, to obtain catalyst fines.
In addition, the invention still further relates to a kind of catalyzer for olefinic polymerization or copolymerization, it comprises the reaction product of following component:
(a) catalyst component of the invention described above;
(b) at least a general formula is AlR " '3Organo-aluminium compound, R in the formula " ' be identical or not identical C1-8Alkyl, wherein one or two alkyl can be replaced by chlorine.Can select one or more aluminum alkyls to mix use, preferred AlEt3, Al (iso-Bu)3, Al (n-C6H13)3, Al (n-C8H17)3, AlEt2Cl etc.
The catalyzer that the present invention relates to can use according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst, as using with another kind of promotor or electron donor, described catalyzer can also be mixed use with one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst.
Catalyst component of the present invention is applicable to various any alkene that can carry out the polycoordination reaction, comprise a kind of equal polymerization of alkene or the copolymerization of multiple alkene, the alpha-olefins such as optimal ethylene, propylene, butylene in the alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Comonomer is C2-C12 alkene preferably, preferred C4-C10 alkene, such as 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1, diene such as divinyl, Isosorbide-5-Nitrae-hexadiene and 1,7-octadiene, cyclenes such as norbornylene, and their any mixture.
Catalyzer of the present invention can adopt conventional polymerization technique to carry out polyreaction in one or more polymerization reactors, can be gas phase, slurry or bulk polymerization, and polyreaction can be intermittence or continuous polymerization process.
To slurry or bulk reaction device, temperature of reaction is generally at 40-130 ℃, and preferred 60-110 ℃, reactor pressure is generally at 0.2-8MPa, preferred 1-6MPa, and the residence time is generally at 0.2-6 hour, preferred 0.5-3 hour.The general boiling point of selecting uses as thinner at the aliphatic hydrocarbon of-70-100 ℃ scope, and if necessary, polyreaction can be carried out under super critical condition.
For Gas-phase reactor, temperature of reaction is generally at 60-130 ℃, and preferred 70-110 ℃, reactor pressure is generally at 0.5-4MPa, preferred 1-3MPa, and the residence time is generally at 0.5-10 hour, preferred 1-8 hour.If necessary, select suitable aliphatic hydrocarbon to use as thinner, polyreaction can be carried out under the frozen state condition.
Catalyst levels generally depends on character, type of reactor and the operational condition of catalyzer and to the requirement of polymerisate performance, can use the conventional catalyst consumption.
Adopt catalyzer of the present invention, can obtain to have the catalyst system of good form, and catalyzer has higher catalytic activity and hydrogen response preferably, the polymerisate form can copy the particle form of catalyzer preferably, i.e. so-called " print effect ", so this catalyzer has good over-all properties.
Embodiment
Testing method:
1, the size-grade distribution of carrier and catalyzer: MASTERSIZE particles distribution instrument, normal hexane be as dispersion agent, useful range 0.02～2000 μ m.
2, the relative weight per-cent of metal (mainly being titanium, magnesium) in the catalyst system: plasma emission spectrum (ICP).
3, the pattern of catalyzer and polymkeric substance: scanning electron microscope (SEM).
4, the mensuration of melting index: ASTM-D 1238.
5, the mensuration of tap density: DIN-53194.
Embodiment given below is for the present invention is described, rather than limits the invention.
Embodiment 1:
Get successively dibutylmagnesium hexane solution (1M) and the 1.0ml isooctyl alcohol of 30ml hexane, 3.15ml, be warming up to 50 ℃ and keep stirring reaction half an hour, obtain clear solution, then add polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 2ml, be cooled to-10 ℃, add successively 0.36 milliliter of silicon tetrachloride and 0.35ml titanium tetrachloride, add material after, be rapidly heated to 50 ℃ in 10 minutes, and keep reaction 2 hours.The catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times, the consumption of each hexane is 50 milliliters, after washing is finished, the dry mobile powder of brown solid that gets, its median size is 37.4 microns.
Ultimate analysis (ICP): Ti:10.06% (weight), Mg:19.29% (weight).
Vinyl polymerization is estimated A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the hydrogen of disposable adding 0.5MPa, then with ethene the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop to add ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the tap density of test polyethylene powder and the melting index under the 2.16Kg load, the result is as shown in table 1.
Vinyl polymerization is estimated B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in the 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the hydrogen of disposable adding 0.18MPa, then with ethene the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop to add ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the tap density of test polyethylene powder and the melting index under the 2.16Kg load, the result is as shown in table 1.
Embodiment 2
Be rapidly heated to 50 ℃ in 10 minutes in the catalyst preparation process, change temperature programming to 50 in 120 minutes ℃ into, other conditions are with embodiment 1, and its median size is 43.7 microns.
Ultimate analysis (ICP): Ti:6.24% (weight), Mg:13.55% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Embodiment 3
Change the 1.0ml isooctyl alcohol in the catalyst preparation process into the 0.6ml propyl carbinol, change polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 2ml into polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 10ml, other conditions are with embodiment 1, and its median size is 18.7 microns.
Ultimate analysis (ICP): Ti:11.54% (weight), Mg:23.69% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Comparative Examples 1
Adding polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 2ml in the catalyst preparation process is removed, other conditions are with embodiment 1, its median size is 79.46 microns, and size distribution is that wider multimodal distributes.
Ultimate analysis (ICP): Ti:9.73% (weight), Mg:21.06% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result sees Table 1.
Table 1
Can find out from the experimental data of table 1 embodiment and Comparative Examples, in the preparation process of catalyzer, use polybutadiene block polyethylene oxide analog copolymer, the catalyzer that obtains and the particle form of polymkeric substance are good, narrow particle size distribution, (BD) is higher for the tap density of polymer resin, the catalyzer high comprehensive performance.