CN105732855B - Main catalyst component and catalyst for olefinic polymerization - Google Patents
Main catalyst component and catalyst for olefinic polymerization Download PDFInfo
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Abstract
The present invention is provided to the main catalyst component of olefinic polymerization and catalyst.Main catalyst component of the invention is prepared by magnesium compound, oxygen-containing titanium compound, chlorine-containing compound, chloride compounds and titanium tetrahalide, has the advantages that particle shape is good, size distribution is uniform.Catalyst of the invention is formulated by main catalyst component, organo-aluminum compound, organosilicon alkyl compound, have the characteristics that catalytic activity is high, particle shape is uniform, narrow particle size distribution, gas-phase polymerization and bulk technique suitable for olefinic polymerization, especially propylene.In the present invention, since the dosage of the titanium tetrachloride in catalyst preparation is reduced, catalyst production cost is remarkably reduced.Also, due to the print effect of particle shape, when using catalyst of the invention, the particle diameter distribution of polymer product also narrows, excessively thick or meticulous in polymer product to tail off.
Description
Technical field
The present invention relates to the main catalyst components and catalyst for olefinic polymerization.In particular, the present invention relates to be used for third
The main catalyst component and the catalyst that is formed by the main catalyst component of alkene polymerization or combined polymerization.
Technical background
Ziegler-Natta catalyst system in olefinic polymerization, in especially polyacrylic industrialized production predominantly
Position, the polymerization activity for focusing on catalyst of theoretical research, the particle shape of catalyst and particle diameter distribution, catalyst it is vertical
Body directionality and copolymerization performance etc..And in polyacrylic actual production, the most pay close attention to the problem of be how to improve it is produced
The particle shape and particle diameter distribution of polypropylene powder.If the particle shape of the polypropylene powder of production is spherical, particle diameter distribution
Narrow, bulk material and fine powder content are few, will greatly reduce viscous wall and caking phenomenon of the polypropylene powder in polymer reactor, simultaneously
Also it can reduce blocking frequency of the polypropylene powder in pipe conveying procedure, so as to effectively extend the steady of process units
Runing time, the product quality of production also can be highly stable.
It is well known that the particle shape of polypropylene powder and particle diameter distribution are mainly by the granulated of catalyst in process units
State and particle diameter distribution control, therefore, preparation is particularly important with the narrow catalyst of good particle shape and particle diameter distribution, this is also
One of the research direction for improving Ziegler-Natta catalyst performance is continuously improved in recent years.
Currently, being generallyd use below several with good particle shape and the narrow catalyst of particle diameter distribution in order to obtain
Method prepares catalyst.First method is fusion method, and this method is that the magnesium compounds such as magnesium chloride are dissolved in alcohol reagent
In, fusant is formed at a certain temperature, then stirs in liquid medium, emulsify fusant, is solidified by the method for quenching
Fusant forms spherical carrier of catalyst.Then, complete the electron donors compound such as phthalic acid ester, titanium compound it is negative
It carries to form catalyst.This preparation method is called low temperature height and stirs method, for example, in US4469648, US4399054 and
Low temperature height is disclosed in WO9844009 stirs method.It is urged in addition it is also possible to which fusant is prepared into spherical shape by the method for misting cooling
Then agent carrier loads other catalyst components again to finally obtain catalyst, this method is documented in patent US5100849
In US4829034.Specific equipment is needed to complete however, preparing ball type carrier by the fusant of magnesium compound, to urging
The preparation of agent brings certain difficulty.
Second method is reaction method, and this method directlys adopt the magnesium chemical combination with certain granules form and size distribution
Object, such as diethoxy magnesium compound are starting material, by being reacted with containing the titanium compound of chlorine or other chlorine-containing compounds,
Then the magnesium chloride for forming nascent state loads the Donor compounds such as phthalic acid ester again, titanium compound forms catalyst.This
Kind method is documented in US5965478.However, in this approach, the particle shape of diethoxy magnesium compound becomes final
The crucial governing factor of catalyst granules form just prepares good particle shape although the method for preparing catalyst is simple
For the technology of diethoxy magnesium compound, grasped by several companies few in number, therefore prepare catalysis in this way
Agent receives certain restrictions.
The third method is solwution method, and this method uses the magnesium compounds such as magnesium chloride or diethoxy magnesium, and selection is suitable
Solvent dissolves magnesium compound, be then added other compounds or change dissolution condition, by the method for precipitating obtain containing magnesium,
The solids of titanium and electron donor, and catalyst particles are obtained after the solids is handled with excessive liquid titanium compound
Grain.This method is documented in CN85100997, CN1099041A, CN1229092.The shortcomings that this method is catalyst granules
Partial size and particle diameter distribution be entirely to be controlled by precipitation process, it is steady due to being the recrystallization process of magnesium carrier ingredient
It qualitatively controls relatively difficult.
Summary of the invention
Problems to be solved by the invention
In view of problem above, the purpose of the present invention is to provide a kind of masters suitable for olefinic polymerization, especially propylene polymerization
Catalytic component and catalyst.The preparation method of the main catalyst component is simple, raw material is easy to get, the requirement to equipment is low, by this
The catalyst that main catalyst component is formed not only has many advantages, such as high polymerization activity, the also good, narrow particle size distribution with particle shape.
The method for solving problem
In view of problem above, present inventor has performed concentrating on studies as a result, solving by the following technical programs above-mentioned
Problem, so as to complete the present invention.That is,
The first aspect of the invention is, provides a kind of main catalyst component for olefinic polymerization, be it is following at
Divide the reaction product of a, ingredient b, ingredient c, ingredient d and ingredient e,
Ingredient a: by formula M g (OR1)nCl2-nThe magnesium compound of expression, in formula, R1It is saturations or undersaturated straight chain, branch
Chain or cricoid C2~C20Alkyl, and 0≤n≤2,
Ingredient b: by general formula Ti (OR2)nCl4-nThe oxygen-containing titanium compound indicated, in formula, R2It is saturated or unsaturated straight
Chain, branch or cricoid C2~C20Alkyl, and 0≤n≤4,
Ingredient c: by formula M ClnThe chlorine-containing compound of expression, in formula, M is metal or nonmetalloid, and 0 n≤4 <,
Ingredient d: by general formula R3(COX)2The acetyl halide compound of expression, in formula, R3For C7~C14Aromatic radical or C3~C8's
Alkyl, X indicate fluorine, bromine, chlorine or iodine atom,
Ingredient e: by general formula TiX4The titanium tetrahalide of expression, in formula, X indicates fluorine, bromine, chlorine or iodine atom,
The method for preparing the main catalyst component includes the following steps 1~step 4,
Step 1: it contacts mentioned component a and ingredient b in 25~200 DEG C of temperature, forms mixed solution,
Step 2: the mixed solution and mentioned component c for obtaining step 1 are contacted in 0~100 DEG C of temperature, and it is outstanding to form solid
Liquid,
Step 3: temperature of the solid suspension for obtaining step 2 with the acetyl halide compound as ingredient d at 0~150 DEG C connects
Touching, obtains solid sediment,
Step 4: in inert organic solvents, under the conditions of 70~150 DEG C of temperature, the solid for obtaining step 3 is settled
Object and titanium tetrahalide as ingredient d come into full contact with, wash, dry after obtain the main catalyst component of solid particulate.
According to the first aspect of aforementioned present invention embodiment, wherein magnesium compound be preferably magnesium chloride or
Diethoxy magnesium.
According to the first aspect of aforementioned present invention embodiment, wherein oxygen-containing titanium compound is preferably oxygen-containing
Or mixtures thereof tetravalent titanium compound, further preferably four titanium n-butoxides.
According to the first aspect of aforementioned present invention embodiment, wherein chlorine-containing compound is preferably selected from four
At least one of silicon chloride, zirconium chloride, boron chloride, phosphorus trichloride, alchlor compound.
According to the first aspect of aforementioned present invention embodiment, wherein acetyl halide compound is preferably selected from third
At least one of diacid chloride, succinyl chloride, o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride compound.
According to the first aspect of aforementioned present invention embodiment, wherein titanium tetrahalide is preferably titanium tetrachloride.
According to the first aspect of aforementioned present invention embodiment, main catalyst component for olefinic polymerization
In preparation method, in terms of every mol composition a, the dosage of ingredient b is 0.01~10 mole, and the dosage of ingredient c is rubbed for 0.01~20
You, the dosage of ingredient d is 0.1~1 mole, and the dosage of ingredient e is 1~5 mole.
Major catalyst according to the first aspect of aforementioned present invention preferred implementation method, for olefinic polymerization
In the preparation method of component, in terms of every mol composition a, the dosage of ingredient b is 0.05~5 mole, the dosage of ingredient c is 0.2~
12 moles, the dosage of ingredient d is 0.1~1 mole, and the dosage of ingredient e is 1~5 mole.
The second aspect of the invention is, provides a kind of catalyst for olefinic polymerization, which is characterized in that the use
It is formulated in the catalyst of olefinic polymerization by following components,
Component a: the main catalyst component for olefinic polymerization of the first aspect of aforementioned present invention,
Component b: by general formula AlR4 nX3-nThe organo-aluminum compound of expression, in formula, R4For hydrogen or C1~C20Alkyl, X indicate
Fluorine, bromine, chlorine or iodine atom, n are the integer of 1 n≤3 <,
Component c: by general formula R5 nSi(OR6)4-nThe organosilicon alkyl compound of expression, in formula, R5For C1~C20Alkyl,
Naphthenic base or aryl, R6For C1~C4Alkyl, n be 1≤n≤3n integer.
According to the second aspect of aforementioned present invention embodiment, wherein organo-aluminum compound and major catalyst
The molar ratio of range of the molar ratio of titanium in component 1~500, organo-aluminum compound and silane compound is 0.1~200
Range.
According to the second aspect of aforementioned present invention embodiment, wherein organo-aluminum compound is selected from three second
At least one of base aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride compound.
According to the second aspect of aforementioned present invention embodiment, wherein organosilicon alkyl compound be selected from
Phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, ring
Hexyl methyl dimethoxysilane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, n-propyl trimethoxy
At least one of silane compound.
Advantageous effect of the invention
1) main catalyst component of the invention has the advantages that particle shape is uniform, narrow particle size distribution.Also, it is led in preparation
When catalytic component, the dosage of titanium tetrahalide greatly reduces, and effectively reduces the production cost of catalyst.
2) preparation method of main catalyst component of the invention has the spy that material composition is easy to get, preparation process is simple and easy to control
Point.
3) catalyst of the invention has the characteristics that catalytic activity is high, particle shape is uniform and particle diameter distribution is narrow, is suitable for alkene
The gas-phase polymerization and bulk technique of polymerized hydrocarbon, especially propylene.Also, due to the print effect of particle shape, using this
When the catalyst of invention, the particle diameter distribution of polymer product also narrows, excessively thick or meticulous in polymer product to tail off.
Specific embodiment
In the present invention, the main catalyst component for olefinic polymerization be following component a, ingredient b, ingredient c, ingredient d and at
Divide the reaction product of e.
In the present invention, ingredient a is by formula M g (OR1)nCl2-nThe magnesium compound of expression, in formula, R1It is saturation or unsaturation
Straight chain, branch or cricoid C2~C20Alkyl, and 0≤n≤2.As the magnesium compound of ingredient a, for example, chlorine can be enumerated
Change the alkoxyl magnesium compound of magnesium, chlorination magnesium ethylate, diethoxy magnesium and long-chain.In an embodiment of the invention, make
Magnesium compound for ingredient a is preferably magnesium chloride, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium or two octyloxy magnesium,
Further preferably magnesium chloride or diethoxy magnesium.
Ingredient b is by general formula Ti (OR2)nCl4-nThe oxygen-containing titanium compound of the liquid of expression, in formula, R2It is saturation or unsaturation
Straight chain, branch or cricoid C2~C20Alkyl, and 0≤n≤4.The oxygen-containing titanium compound of liquid as ingredient d, for example, can
To enumerate titanium tetramethoxide, purity titanium tetraethoxide, four titanium n-butoxides, dimethoxy diethyl titanium, four hexyloxy titaniums, four decyloxies
The oxygen-containing tetravalent titanium compounds such as titanium, benzyloxy-4 titanium or four phenoxide titaniums or their mixture.An implementation of the invention
In mode, the oxygen-containing titanium compound of liquid as ingredient a is preferably four titanium n-butoxides.The oxygen-containing titanium of liquid used in the present invention
It is in a liquid state under compound room temperature, it is good with the compatibility of some common solvents.
Ingredient c is by formula M ClnThe chlorine-containing compound of expression, in formula, M is metal or nonmetalloid, and 0 n≤4 <.
As the chlorine-containing compound of ingredient c, for example, silicon tetrachloride, carbon tetrachloride, zirconium chloride, boron chloride, tri-chlorination can be enumerated
Phosphorus, alchlor or their mixture etc., wherein preferably silicon tetrachloride.
Ingredient d is by general formula R3(COX)2The acetyl halide compound of expression, in formula, R3For C7~C14Aromatic radical or C3~C8
Alkyl, X indicates fluorine, bromine, chlorine or iodine atom.As the acetyl halide compound of ingredient d, for example, malonyl chloride, fourth two can be enumerated
Acyl chlorides, o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or their mixture etc..An implementation of the invention
In mode, the acetyl halide compound as ingredient d is preferably o-phthaloyl chloride.
Ingredient e is by general formula TiX4The titanium tetrahalide of expression, in formula, X indicates fluorine, bromine, chlorine or iodine atom.Of the invention one
In a embodiment, the titanium tetrahalide as ingredient e is preferably titanium tetrachloride.
In the present invention, main catalyst component is by including the following steps prepared by the preparation method of 1~step 4.Wherein,
Step 1 is to contact mentioned component a and ingredient b in 25~200 DEG C of temperature, to form mixed solution.Step 2 is to make step
1 obtained mixed solution and mentioned component c are contacted in 0~100 DEG C of temperature, to form solid suspension.Step 3 is to make step
Temperature of the 2 obtained solid suspensions with the acetyl halide compound as ingredient d at 0~150 DEG C contacts, to obtain solid sedimentation
Object.Step 4 be in inert organic solvents, under the conditions of 70~150 DEG C of temperature, the solid sediment that obtains step 3 and
Titanium tetrahalide as ingredient d comes into full contact with, and washs, dries, to obtain the main catalyst component of solid particulate.
In the present invention, when preparing main catalyst component, the ratio between above-mentioned each ingredient is, in terms of every mol composition a, at
The dosage of b is divided to control at 0.01~10 mole, preferably 0.05~5 mole, the dosage of ingredient c is controlled at 0.01~20 mole,
Preferably 0.2~12 mole, at 0.1~1 mole, the dosage of ingredient e is controlled at 1~5 mole for the dosage control of ingredient d.
In the present invention, when preparing main catalyst component, the Contact Temperature of magnesium compound and oxygen-containing titanium compound in step 1
Depending on the property of reactant, usually in relatively high temperature, but should be dissolved below the decomposition temperature of reactant
And it is brought into contact with.In an embodiment of the invention, the contact of the magnesium compound in step 1 and the oxygen-containing titanium compound of liquid
Range of the temperature at 25~200 DEG C, preferably in 25~150 DEG C of range.Also, the dissolution, time of contact in step 1 depend on
The property and operating condition of reactant, usually on the basis of it can obtain fully transparent solution.In an implementation of the invention
In mode, model of the dissolution, time of contact of magnesium compound and the oxygen-containing titanium compound of liquid in step 1 at 10 minutes~20 hours
It encloses, preferably 4 hours~10 hours ranges.In step 1, when magnesium compound and titanium compound are completely dissolved and are formed
After bright mixture solution (that is, foring transparent magnesium titanium complex solution), can further it be carried out with inert diluent dilute
Release mixing.As inert diluent, for example, it may be selected from benzene,toluene,xylene, iso-butane, pentane, hexane, heptane or
The aliphatic of hexamethylene etc. or aromatic hydrocarbon and their mixture.In an embodiment of the invention, as inertia
Diluent, preferably toluene or hexane.
In the present invention, the step 2 for preparing main catalyst component is chlorination and the step of precipitate.Magnesium is completed in the step 2
The chlorination reaction of titanium complex, that is, replace the alkoxy in magnesium compound and titanium compound with chlorine element, make the magnesium of liquid clear
Titanium complex is precipitated from solution, is precipitated, to form solid suspension.In the present invention, make magnesium titanium complex solution and chloride containing
When conjunction object contacts, magnesium titanium complex solution can be added drop-wise to dropwise for example, can use using any known method progress
Method in chlorine-containing compound solution can also use and chlorine-containing compound solution is added drop-wise to dropwise in magnesium titanium complex solution
Method.Also, rate of addition is also not particularly limited, usually on the basis of the hot-spot for not causing reaction system,
It can be stirred during dropwise addition, so as to the steady progress of reaction.As the reaction temperature of the step 2, can control 0
~100 DEG C of range, preferably 20~80 DEG C of range.For reaction time of the step 2, also there is no particular limitation, as long as
It is capable of forming complete solid suspension.In an embodiment of the invention, the reaction time of the step 2 is 1 minute
~10 hours ranges, preferably 0.5 hour~5 hours ranges.
In an embodiment of the invention, after chlorination, the precipitation reaction of step 2 terminate, preferably centainly reacting
Temperature, further progress maturation process under conditions of certain reaction time.Grain shape of the maturation process for main catalyst component
Control is than advantageous, that is, can make the size distribution narrow of main catalyst component, while can also improve major catalyst particle
Intensity, so as to reduce Fragmentation Phenomena of the major catalyst particle in catalysis propylene polymerization processes.As the maturation process
Treatment temperature is equal to or slightly higher than chlorination, the precipitation reaction temperature of step 2.As the processing time of the maturation process, lead to
Often in 0.5 hour~15 hours ranges, preferably 1 hour~5 hours ranges.
In the present invention, as the step 3 of preparation main catalyst component, one is added in the solid suspension obtained by step 2
Quantitative chloride compounds are reacted, to form solid sediment.The purpose of the step 3 reaction is, makes acyl chlorides chemical combination
Oxyalkylation reaction in object and solid suspension, so that the compounds such as n-butyl phthalate are formed in situ, these chemical combination
Object is the internal electron donor of olefin polymerization, for adjusting the isotacticity of the olefin polymers such as polypropylene.In the present invention
An embodiment in, range of the reaction temperature of step 3 at 0~150 DEG C, preferably 50~130 DEG C of range, step 3
Range of the reaction time at 0.5 minute~5 hours, preferably 30 minutes~1 hour range.
In the present invention, prepare main catalyst component when, step 3 additions chloride compounds after reaction, progress
The reaction of the addition titanium tetrahalide of step 4.According to embodiment of the present invention, titanium tetrahalide used in the step 4 is excellent
It is selected as titanium tetrachloride.In the reaction of the step 4, the desired amount of titanium tetrahalide can be added at one time or repeatedly be added in batches.
If, usually can be in the following ways by the way of be repeatedly added in batches, that is, a batch of four halogenation is added under stiring
Titanium then stops stirring and standing sedimentation for a period of time, after object to be precipitated is deposited to lower layer, upper layer reaction solution is removed, then
The titanium tetrahalide of next batch is added again.In the present invention, using multiple addition titanium tetrahalide in batches in the reaction of the step 4
Mode is more advantageous to the raising of catalyst activity, thus comparing the mode being added at one time is more preferably.According to the present invention
An embodiment, in order to come into full contact with titanium tetrahalide with the solid suspension obtained by step 3, add in the step 4
When entering titanium tetrahalide and range of the reaction temperature condition of subsequent standing sedimentation at 70~150 DEG C, preferably 90~130 DEG C
Range mixes range of the reaction time of sedimentation at 0.5 hour~5 hours, preferably 2 hours~4 hours ranges.
In the present invention, prepare main catalyst component when, step 4 addition titanium tetrahalide after reaction, by washing
The by-product formed in excessive reactant and preparation process is washed away, the master that solid particulate can be obtained then is dried
Catalytic component.In the present invention, cleaning solvent used in the washing step is not particularly limited, can be selected any
A kind of atent solvent, for example, iso-butane, pentane, hexane, heptane, hexamethylene, toluene etc. can be selected as cleaning solvent.
In the present invention, for olefinic polymerization, particularly propylene polymerization or the catalyst of combined polymerization by component a, component b and group
C is divided to be formed, wherein component a is the main catalyst component for olefinic polymerization of the invention, and component b is by general formula AlR4 nX3-nTable
The organo-aluminum compound shown, in formula, R4For hydrogen or C1~C20Alkyl, X indicates that fluorine, bromine, chlorine or iodine atom, n are 1 n≤3 <
Integer, component c are by general formula R5 nSi(OR6)4-nThe organosilicon alkyl compound of expression, in formula, R5For C1~C20Alkyl, ring
Alkyl or aryl, R6For C1~C4Alkyl, n be 1≤n≤3n integer.
In an embodiment of the invention, in the catalyst for olefinic polymerization, particularly propylene polymerization or combined polymerization
In, range of the molar ratio of the titanium in organo-aluminum compound and main catalyst component 1~500, preferably 1~300 range,
Range of the molar ratio of organo-aluminum compound and organosilicon alkyl compound 0.1~200, preferably 1~150 range, into
One step is preferably 3~100 range.
In the present invention, as said components b by general formula AlR4 nX3-nThe organo-aluminum compound of expression, for example, it may be choosing
From at least one of triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride compound.On
State component c, i.e. by general formula R5 nSi(OR6)4-nThe organosilicon alkyl compound of expression is the external electron donor of olefin polymerization,
As this kind of external electron donor being made of organosilicon alkyl compound, for example, it may be being selected from phenyltrimethoxysila,e, benzene
Ethyl triethoxy silicane alkane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, cyclohexyl methyl dimethoxy silicon
At least one of alkane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, n-propyl trimethoxy silane are changed
Close object.
When catalyst of the invention to be used for polymerization or the copolymerization of olefinic polymerization, especially propylene, it can obtain
In high yield, the excellent polymer of the various performances such as high isotactic.In the present invention, for other α-alkene being copolymerized with propylene
There is no particular limitation for hydrocarbon monomer, can be the alpha-olefin of 2~12 carbon atoms, for example, can enumerate ethylene, butylene, amylene,
Hexene, octene, 4-methyl-1-pentene etc..In addition, catalyst of the invention is very suitable for the gas-phase polymerization process and sheet of propylene
Body polymerization technique.In the present invention, as the bulk technique of propylene, for example, liquid monomer can be used according to well-known technique
It carries out, as the gas-phase polymerization process of propylene, for example, can be in one or more fluidized beds or mechanical stirring reactor
It carries out, these polymerization techniques is not particularly limited.
Hereinafter, by example, the present invention will be described in detail.Without saying, the present invention is not by these embodiments more
Limitation.Also, in the range of not departing from general idea of the present invention, change, deformation or variation that these embodiments are done etc.
It belongs in scope of the invention.
Embodiment 1
The preparation of main catalyst component
1) magnesium chloride 10.2g is weighed, four titanium n-butoxides (hereinafter, being also referred to as " butyl titanate ") 78mL is added,
140 DEG C of stirring and dissolvings are down to room temperature up to forming transparent mixed solution, by the mixed solution temperature, and 200mL drying is added
It is spare after hexane dilution.
2) take by above-mentioned steps 1) obtained mixed solution 20mL, at normal temperature, by the mixed solution be slowly dropped to by
In the mixed liquor that 30mL hexane and 20mL silicon tetrachloride are formed.After completion of dropwise addition, successively stirred in the condition that bath temperature is 45 DEG C anti-
It answers 1 hour, is stirred to react 2 hours in the condition that bath temperature is 65 DEG C, to obtain solid suspension.
3) 0.3mL o-phthaloyl chloride is added into the solid suspension obtained by above-mentioned steps 2, is stirred to react 1 at 90 DEG C
After hour, stop stirring, standing settles solids.80 milliliters of toluene are added after removing supernatant, is stirred in 90 DEG C of conditions
After five minutes, stopping stirring, standing settle solids for washing, are washed solids 3 times with toluene repeatedly.
4) solid sediment obtained by above-mentioned steps 3 is resuspended with 80mL toluene, 2.3mL titanium tetrachloride is added, at 110 DEG C
Condition be stirred to react 2 hours.Then, according to above-mentioned steps 3) washing methods successively washed solids 3 times with 80mL toluene,
It is washed solids 3 times with 80mL hexane, temperature when washing is controlled at 60 DEG C.After washing, the condition for being 65 DEG C in bath temperature
Drying is purged with high pure nitrogen, to obtain the main catalyst component of solid particulate.
The preparation and olefinic polymerization of catalyst
In having the polymeric kettle that agitating device and volume are 5L, system atmosphere gas is replaced completely with gas-phase propene, in room
Hexane solution (concentration of triethyl aluminum is 0.5M) 5mL, cyclohexyl methyl dimethoxy silicon of triethyl aluminum is added under the conditions of temperature
The main reminder that the hexane solution (concentration of Cyclohexyl Methyl Dimethoxysilane is for 0.1M) lmL and by above-mentioned steps 4) of alkane obtains
Agent 20~25mg of component, and anhydrous hexane 10mL is added, so as to form the catalyst for olefinic polymerization of the invention.It closes
Polymeric kettle is closed, the hydrogen of 0.1MPa and the propylene liguid monomer of 1.0kg are introduced.Then, while being stirred in 10 minutes
The temperature of system is set to rise to 70 DEG C of polymeric reaction temperature, polymerization reaction carries out timing after starting, after polymerization reaction carries out 1 hour
Discharging.It weighs after polypropylene powder is dry, finds out catalyst activity according to following formula, test the melt index of polypropylene powder,
And it is sieved.
Catalyst activity=polypropylene powder weight (10-4G)/main catalyst component weight (g)
Average grain diameter (D50) and size distribution (Span) measurement
Disperse main catalyst component in hexane, major catalyst group is measured using Malversizer laser particle size analyzer
Average grain diameter (the D divided50) and size distribution (Span).Wherein, size distribution (Span) is found out by following formula.
Size distribution (Span)=(D90-D10)/D50
In formula, D50It is whole particles in the size distribution curve of Malversizer laser particle size analyzer test
50% diameter is lower than the diameter value of the value,
D10It is that 10% diameter of whole particles is lower than the diameter value of the value,
D90It is that 90% diameter of whole particles is lower than the diameter value of the value.
Average grain diameter and size distribution measurement the result shows that, by above step 4) obtained main catalyst component is averaged
Partial size (D50) be 28 μm, breadth of particle size distribution (Span) is 0.6, the screening result of catalyst activity and polypropylene powder be shown in
In the following table 1.
Embodiment 2
Other than the o-phthaloyl chloride dosage in step 3) is adjusted to 0.5 milliliter by 0.3 milliliter, with embodiment 1
It is prepared for main catalyst component in the same manner.
Average grain diameter and size distribution measurement the result shows that, the average grain diameter (D of main catalyst component50) it is 26 μm, grain
Spending the dispersion of distribution (Span) is 0.7, and the screening result of catalyst activity and polypropylene powder is shown in following table 1.
Embodiment 3
It is same as Example 1 other than the titanium tetrachloride dosage in step 4) is adjusted to 1.0 milliliters by 2.3 milliliters
Ground is prepared for main catalyst component.
Average grain diameter and size distribution measurement the result shows that, the average grain diameter (D of main catalyst component50) it is 27 μm, grain
Spending the dispersion of distribution (Span) is 0.7, and the screening result of catalyst activity and polypropylene powder is shown in following table 1.
Embodiment 4
In addition to titanium tetrachloride is not added in step 4), but other than directly being washed, it is prepared for same as Example 1ly
Main catalyst component.
Average grain diameter and size distribution measurement the result shows that, the average grain diameter (D of main catalyst component50) it is 25 μm, grain
Spending the dispersion of distribution (Span) is 0.6, and the screening result of catalyst activity and polypropylene powder is shown in following table 1.
Embodiment 5
Other than the magnesium chloride 10.2g in step 1) is adjusted to diethoxy magnesium 12.7g, same as Example 1ly
It is prepared for main catalyst component.
Average grain diameter and size distribution measurement the result shows that, the average grain diameter (D of main catalyst component50) it is 32 μm, grain
Spending the dispersion of distribution (Span) is 0.9, and the screening result of catalyst activity and polypropylene powder is shown in following table 1.
Comparative example 1
In this comparative example, it is prepared for main catalyst component according to the method for embodiment 1 in United States Patent (USP) US5965478, is had
Production procedure is as follows.Weigh 10g diethoxy magnesium (average grain diameter (D50) be 35 μm, particle diameter distribution width (Span) is 1.1)
Toluene 70mL is added afterwards, system temperature is stablized at 10 DEG C, titanium tetrachloride 30mL and n-butyl phthalate is slowly added dropwise
3.6mL.After completion of dropwise addition, system temperature is risen to 90 DEG C, stops stirring after being persistently stirred to react 2 hours, standing makes solids
Sedimentation.After removing supernatant, toluene 80mL is added, 5 minutes is stirred at 90 DEG C to wash solids, is washed repeatedly with toluene
Solids 3 times.
It adds toluene 70mL and titanium tetrachloride 30mL again into system, so that system temperature is risen to 110 DEG C, persistently stir
Mix reaction 2 hours.It is washed repeatedly with hexane solids 10 times, hexane dosage is 100mL, wash temperature 40 when washing every time
℃.After washing, under conditions of 65 DEG C of bath temperature, drying is purged with high pure nitrogen, to obtain the main reminder of solid particulate
Agent component.
The catalyst for olefinic polymerization has been prepared according to the method for embodiment 1, and to the average grain of main catalyst component
Diameter (D50) and size distribution (Span) be determined.Measurement result shows the average grain diameter (D of main catalyst component50) it is 30
μm, breadth of particle size distribution (Span) is 1.2, is shown in Table 1 below the screening result of catalyst activity and polypropylene powder.
Comparative example 2
Spherical MgC1 is prepared for according to the method for embodiment 1 in United States Patent (USP) US44696482·2.85C2H5OH carrier.?
Under stirring condition, by 5.0g spherical shape MgC12·2.85C2H5OH carrier is added to equipped with 150mL titanium tetrachloride and is cooled to -25 DEG C in advance
In glass reaction bottle, it is gradually warming up to 80 DEG C.Then, 1.1mL internal electron donor n-butyl phthalate is added, in 130
DEG C reaction 2 hours, washed 6 times with n-hexane, main catalyst component obtained after vacuum drying.
The catalyst for olefinic polymerization has been prepared according to the method for embodiment 1, and to the average grain of main catalyst component
Diameter (D50) and size distribution (Span) be determined.Measurement result shows the average grain diameter (D of main catalyst component50) it is 55
μm, breadth of particle size distribution (Span) is 1.3, is shown in Table 1 below the screening result of catalyst activity and polypropylene powder.
Comparative example 3
Preparation main catalyst component is carried out according to the method for embodiment 1 in CN85100997A, specific preparation process is as follows.
In the reactor that environment is sufficiently displaced from high pure nitrogen, anhydrous magnesium chloride 0.05mol, toluene 75mL, ring are sequentially added
Oxygen chloropropane 0.1mol and tributyl phosphate 0.03mol is warming up to 50 DEG C, and maintains 2 hours under stirring.Solids is completely dissolved
Afterwards, phthalic anhydride 0.008mol is added, continues to be stirred 1 hour.Solution is cooled to -25 DEG C, is added dropwise in 1 hour
55 milliliters of titanium tetrachloride, 80 DEG C are then to slowly warm up to, so that solids be made gradually to be precipitated.N-butyl phthalate is added
0.0125mol is stirred to react 1 hour at 80 DEG C, obtains yellow-brown solid sediment.After filtering, solid is washed with 100mL toluene
Sediment is twice.After the completion of washing, toluene 60mL, titanium tetrachloride 40mL is added, is stirred to react at 90 DEG C 2 hours.With 100mL oneself
After alkane washs four times, vacuum drying obtains solid main catalyst component.
The catalyst for olefinic polymerization has been prepared according to the method for embodiment 1, and to the average grain of main catalyst component
Diameter (D50) and size distribution (Span) be determined.Measurement result shows the average grain diameter (D of main catalyst component50) it is 33
μm, breadth of particle size distribution (Span) is 1.3, is shown in Table 1 below the screening result of catalyst activity and polypropylene powder.
The performance evaluation of Examples 1 to 5 and comparative example 1~3
Average grain diameter (the D of the main catalyst component prepared in Examples 1 to 5 and comparative example 1~3 is shown in table 150)、
Size distribution (Span), melt index (MI2.16) and Examples 1 to 5 and comparative example 1~3 in prepare catalyst activity,
The screening result of polypropylene powder.
As shown in Table 1, the narrow particle size distribution of main catalyst component of the invention, range of the Span value 0.6~1.0.
In contrast, range of the Span value of existing catalyst (comparative example 1~3) 1.0~2.0.Due to particle shape print effect,
Under the same polymerization conditions, equally also narrowed using the particle diameter distribution of the resulting polymer of catalyst of the invention, polymer
Middle excessively thick or meticulous particle tails off.
Claims (11)
1. a kind of main catalyst component for olefinic polymerization is following component a, ingredient b, ingredient c, ingredient d and ingredient e
Reaction product,
Ingredient a: by formula M g (OR1)nCl2-nThe magnesium compound of expression, in formula, R1Be saturations or undersaturated straight chain, branch or
Cricoid C2~C20Alkyl, and 0≤n≤2,
Ingredient b: by general formula Ti (OR2)nCl4-nThe oxygen-containing titanium compound indicated, in formula, R2It is saturations or undersaturated straight chain, branch
Chain or cricoid C2~C20Alkyl, and 0≤n≤4,
Ingredient c: by formula M ClnThe chlorine-containing compound of expression, in formula, M is metal or nonmetalloid, and 0 n≤4 <,
The chlorine-containing compound be in silicon tetrachloride, zirconium chloride, boron chloride, phosphorus trichloride, alchlor at least
A kind of compound；
Ingredient d: by general formula R3(COX)2The acetyl halide compound of expression, in formula, R3For C7~C14Aromatic radical or C3~C8Alkane
Base, X indicate fluorine, bromine, chlorine or iodine atom,
Ingredient e: by general formula TiX4The titanium tetrahalide of expression, in formula, X indicates fluorine, bromine, chlorine or iodine atom,
Wherein, in terms of every mol composition a, the dosage of ingredient b is 0.01~10 mole, and the dosage of ingredient c is 0.01~20 mole,
The dosage of ingredient d is 0.1~1 mole, and the dosage of ingredient e is 1~5 mole；
The method for preparing the main catalyst component includes the following steps 1~step 4,
Step 1: it contacts ingredient a and ingredient b in 140~200 DEG C of temperature, forms mixed solution,
Step 2: the mixed solution and ingredient c for obtaining step 1 are contacted in 0~100 DEG C of temperature, form solid suspension,
Step 3: temperature of the solid suspension for obtaining step 2 with the acetyl halide compound as ingredient d at 0~150 DEG C contacts, and obtains
To solid sediment,
Step 4: in inert organic solvents, under the conditions of 70~150 DEG C of temperature, the solid sediment that obtains step 3 and
Titanium tetrahalide as ingredient d comes into full contact with, wash, dry after obtain the main catalyst component of solid particulate.
2. the main catalyst component according to claim 1 for olefinic polymerization, wherein the magnesium compound is chlorination
Magnesium or diethoxy magnesium.
3. the main catalyst component according to claim 1 for olefinic polymerization, wherein the oxygen-containing titanium compound be containing
Or mixtures thereof oxygen tetravalent titanium compound,.
4. the main catalyst component according to claim 3 for olefinic polymerization, wherein the oxygen-containing titanium compound is four
Titanium n-butoxide.
5. the main catalyst component according to claim 1 for olefinic polymerization, wherein the acetyl halide compound be selected from
At least one of malonyl chloride, succinyl chloride, o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride compound.
6. the main catalyst component according to claim 1 for olefinic polymerization, wherein the titanium tetrahalide is four chlorinations
Titanium.
7. the main catalyst component according to claim 1 for olefinic polymerization, wherein in terms of every mol composition a, ingredient
The dosage of b is 0.05~5 mole, and the dosage of ingredient c is 0.2~12 mole, and the dosage of ingredient d is 0.1~1 mole, ingredient e's
Dosage is 1~5 mole.
8. a kind of catalyst for olefinic polymerization, which is characterized in that the catalyst for olefinic polymerization is by following components
It is formed,
Component a: being used for the main catalyst component of olefinic polymerization described in claim 1~7 any one,
Component b: by general formula AlR4 nX3-nThe organo-aluminum compound of expression, in formula, R4For hydrogen or C1~C20Alkyl, X indicate fluorine,
Bromine, chlorine or iodine atom, n are the integer of 1 n≤3 <,
Component c: by general formula R5 nSi(OR6)4-nThe organosilicon alkyl compound of expression, in formula, R5For C1~C20Alkyl, naphthenic base
Or aryl, R6For C1~C4Alkyl, n be 1≤n≤3n integer.
9. being used for the catalyst of olefinic polymerization as claimed in claim 8, wherein the organo-aluminum compound and the main catalytic
Range of the molar ratio of titanium in agent component 1~500, the molar ratio of the organo-aluminum compound and the silane compound
In 0.1~200 range.
10. being used for the catalyst of olefinic polymerization as claimed in claim 8 or 9, wherein the organo-aluminum compound is selected from three
At least one of aluminium ethide, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride compound.
11. being used for the catalyst of olefinic polymerization as claimed in claim 8 or 9, wherein the organosilicon alkyl compound is choosing
From phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane,
Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, n-propyl trimethoxy
At least one of base silane compound.
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