CN102898553B - Catalyst component for olefin polymerization, and preparation method and catalyst thereof - Google Patents
Catalyst component for olefin polymerization, and preparation method and catalyst thereof Download PDFInfo
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- CN102898553B CN102898553B CN201110210008.7A CN201110210008A CN102898553B CN 102898553 B CN102898553 B CN 102898553B CN 201110210008 A CN201110210008 A CN 201110210008A CN 102898553 B CN102898553 B CN 102898553B
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Abstract
The invention provides a catalyst component A for olefin polymerization. The catalyst component A is obtained through contacting a solid component a with an Si-H-containing organic silicon compound b having a structure represented by formula (I), wherein the solid component a is composed of magnesium, titanium, a halogen and an internal electron donor compound. The invention also provides a preparation method and a catalyst of the catalyst component. The catalyst component and the catalyst have the advantages of high catalytic activity, good hydrogen response, good stereospecific capability, uniform catalyst activity release, and substantially improved bulk density of obtained polymers. The formula (I) is HSiR<1>nR<2>3-n.
Description
Technical field
The present invention relates to a kind of be all polymerized for alkene or the catalyst component of copolymerization, its preparation method and olefinic polymerization catalyzer.
Background technology
CH is can be used for using magnesium, titanium, halogen and internal electron donor as the ingredient of solid catalyst of basal component
2=CHR olefinic polyreaction has been well known in the art.In polymerization process, above-mentioned ingredient of solid catalyst, promotor alkylaluminium cpd and the silicone compounds as external electron donor together form olefin polymerization catalysis, i.e. Ziegler-Natta (Z-N) catalyzer.As CN1453298 discloses a kind of Z-N catalyzer consisted of the following composition: (1) is using magnesium, titanium, halogen and diol-lipid internal electron donor compound as the ingredient of solid catalyst of basal component; (2) alkylaluminium cpd; (3) organosilicone compounds containing Si-O-C base.This catalyzer has good polymerization activity and orientation property.But possess more high catalytic activity, better stereotaxis ability and better hydrogen response while adding hydrogen amount (identical there is higher melt index), and the catalyzer obtaining the polymkeric substance of high-bulk-density remains the target that this area researchist pursues.
Existing polyolefin often adopts the technical process of two or more reactors in series for continuous processing used, as liquid-phase bulk polymerization reactor and gas-phase polymerization reactor series connection, and two Gas-phase reactor series connection etc.As is well understood in the art, the former has Spheripol technique and Hypol technique, and the latter has Innovene technique and Horizone technique etc.In process of production, control reaction time in each reactor and other parameter according to the performance requriements of specific product and processing condition, the total residence time general control in each reactor is at 2-4 hour; This just needs the release of Z-N catalyzer used energy even in whole polymerization process active.Otherwise the reaction of appearance hyperactivity in early stage is difficult to control, and later stage active not enough problem; This does not even reach its performance requriements by directly causing quality product to decline.As can be seen here, to be on the one hand conducive to stablizing of polymerization process controlled in the even release of Z-N catalyst activity; Be conducive to the adjustment of various parameter in polymerization process on the other hand, to produce the more excellent product of performance.
US20090253874 discloses and ingredient of solid catalyst is contained CH with one under certain condition
2catalyzer can be made to keep active in a long time after the organic silane compound contact of=CH functional group.But this compounds preparation difficulty, expensive.
In the R&D process of Z-N catalyzer and corresponding olefinic polymerization thereof, inevitably encounter serious catalyst activity attenuation problem, namely catalyzer significantly declines reaction is active after 1.5-2 hour, greatly have impact on its result of use.The present inventor is beat all discovery after a large amount of experimental studies, uses a kind of organic silane compound containing Si-H key can significantly improve catalyst activity attenuation problem, catalyst activity even is discharged; Prepared olefin polymer tap density also significantly improves; This catalyzer also has the feature that catalytic activity is high, hydrogen response good, stereotaxis ability is good simultaneously.
Summary of the invention
The object of the present invention is to provide that a kind of catalytic activity is high, hydrogen response good, stereotaxis ability is good, and the more uniform olefin polymerization catalyst components of active release and catalyzer thereof.
Particularly, the invention provides a kind of catalyst component for olefinic polymerization, this catalyst component by a kind of solid constituent a form containing magnesium, titanium, halogen and internal electron donor compound with contact such as formula the silicoorganic compound b containing Si-H functional group shown in (I) after obtain
HSiR
1 nR
2 3-n(I)
In formula (I), R
1, R
2identical or different, be hydrogen atom separately, halogen atom, carbonatoms is the straight or branched saturated alkyl of 1-12, the one in the cycloalkyl of carbonatoms 3-10 and the alkaryl of carbonatoms 6-20, replacement or non-substituted arene base; R
1, R
2be asynchronously hydrogen; N is the integer of 0-3.
According to solid constituent a of the present invention, its preparation method can be by magnesium compound, titanium compound and internal electron donor contact reacts under certain condition; Consumption for the preparation of the titanium compound of described solid ingredient a, magnesium compound and internal electron donor is not particularly limited, and can be all conventional substances and the consumption of this area.
In the preferred case, the magnesium compound of described preparation solid ingredient a can at least one in the alcohol adducts of the magnesium compound shown in the hydrate of the magnesium compound shown in the magnesium compound shown in formula (II), formula (II) and formula (II)
MgR
4R
5(II)
In formula (II), R
4and R
5it is separately halogen, the carbonatoms one that to be the straight or branched alkoxyl group of 1-8 and carbonatoms be in the straight or branched alkyl of 1-8.
The hydrate of the magnesium compound shown in described formula (II) refers to MgR
4r
5pH
2o, wherein, p, within the scope of 0.1-6, is preferably 2-3.5.In the present invention, described alcohol adducts refers to MgR
4r
5qR
6oH, wherein, R
6for carbonatoms is the alkyl of 1-18, being preferably carbonatoms is the alkyl of 1-8, is more preferably methyl, ethyl, n-propyl and sec.-propyl; Q, within the scope of 0.1-6, is preferably 2-3.5.
In the preferred case, described magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-ethyl) hexyloxy magnesium, methoxyl group magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, oxyethyl group magnesium chloride, oxyethyl group magnesium bromide, oxyethyl group magnesium iodide, propoxy-magnesium chloride, propoxy-magnesium bromide, propoxy-magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, methylmagnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated magnesium, diiodinating magnesium, the alcohol adducts of magnesium dichloride, at least one in the alcohol adducts of dibrominated magnesium and the alcohol adducts of diiodinating magnesium.Most preferably, described magnesium compound is alkoxyl magnesium.
In preferred preparation solid ingredient a of the present invention, titanium compound is the compound shown in formula (III),
TiX
m(OR
7)
4-m(III)
In formula (III), X is halogen, R
7for carbonatoms is the alkyl of 1-20, m is the integer of 0-4; Described halogen can be chlorine, bromine or iodine.
In the preferred case, in formula (III), X is halogen, R
7for carbonatoms is the alkyl of 1-5, such as: at least one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
In preferred preparation solid ingredient a of the present invention, internal electron donor compound is selected from one or more in formula (IV),
In formula (IV), R
8and R
9identical or different, be separately one that carbonatoms is in the alkaryl of the straight or branched alkyl of 1-12, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or non-substituted arene base.R
10, R
11, R
12and R
13be all hydrogen; Or wherein three is hydrogen, the straight or branched alkyl that another one is halogen, carbonatoms is 1-4 and carbonatoms are the one in the straight or branched alkoxyl group of 1-4.
In the present invention, carbonatoms is that the example of the straight or branched alkyl of 1-4 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl; Carbonatoms is that the example of the straight or branched alkyl of 1-8 also comprises: n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl and n-octyl; Carbonatoms is that the example of the straight or branched alkyl of 1-10 can also comprise: n-nonyl and positive decyl.
In the present invention, carbonatoms is that the example of the straight or branched alkoxyl group of 1-4 can comprise: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert.-butoxy.
In the present invention, carbonatoms is that the example of the cycloalkyl of 3-10 can comprise: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propyl cyclohexyl and 4-normal-butyl cyclohexyl.
In the present invention, carbonatoms is that the replacement of 6-20 or the example of unsubstituting aromatic yl can comprise: phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-propyl group phenyl, 4-isopropyl phenyl, 4-n-butylphenyl, 4-tert-butyl-phenyl, 4-p-methoxy-phenyl and 4-ethoxyl phenenyl.
The internal electron donor of solid ingredient a of the present invention is preferably diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate.At least one particularly preferably in diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate.
In the present invention, the preparation of solid ingredient a can be undertaken by the method preparing alkene catalyst component of this area routine; Such as prepare solid ingredient a of the present invention by following method.
Alkoxyl magnesium or Alkoxymagnesium halides are suspended in inert diluent and form suspension, then this suspension is mixed with above-mentioned titanium compound, internal electron donor contact to obtain solids dispersion system, be commonly referred to mother liquor.Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is commonly referred to titanium process; Then after filtration, washing can obtain solid ingredient a of the present invention.
The object lesson of above-mentioned alkoxyl magnesium can see in summary of the invention in front described part, the wherein mixture of preferably diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesium.The preparation method of this alkoxyl magnesium compound, can be prepared by method well known in the art, MAGNESIUM METAL and fatty alcohol is prepared under a small amount of iodine exists disclosed in patent CN101906017A.
As above-mentioned Alkoxymagnesium halides object lesson can see in summary of the invention in front described part, wherein preferred oxyethyl group magnesium chloride.The preparation method of this alkoxy magnesium compound can select method well known in the art, prepares oxyethyl group magnesium chloride as Grignard reagent butylmagnesium chloride mixed with purity titanium tetraethoxide and tetraethoxy-silicane.
The inert diluent that in aforesaid method, the formation of mother liquor uses can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.The wherein consumption of each composition that uses of the formation of mother liquor, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; Internal electron donor compound consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Wherein, during the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In the treating processes of titanium described in aforesaid method, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.Wherein, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole.Wherein titanium number of processes is 0-10 time, preferred 1-5 time.And in described titanium treating processes, alternative adds above-mentioned electronic donor compound capable, wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
According to solid ingredient a of the present invention, wherein the content of titanium atom is 1.0-8.0wt%, is preferably 1.6-6.0wt%; The content of magnesium atom is preferably 10-70wt%, is preferably 15-40wt%; The content of halogen atom is 20-86wt%, is preferably 36-80%; Total internal electron donor compound content 2-30wt%, preferred 3-20wt%.
According to olefin polymerization catalyst components of the present invention, wherein silicoorganic compound b can be any compound shown in formula (I), is not particularly limited.Wherein, R
1, R
2be preferably the one in straight or branched saturated alkyl that hydrogen, carbonatoms are 1-12, cycloalkyl and replacement or unsubstituting aromatic yl.
In the preferred case, triethyl silicane, tripropyl silane, tributyl silane, three pentylsilane, three hexyl silanes, tri isopropyl silane, tri-phenyl-silane, diphenyl silane, dipropyl silane, dibutyl silane, diamyl silane, dihexyl silane, diisopropylsilyl, diisobutyl silane, diisoamyl silane, two isohexyl silane etc. can be selected from by the examples of compounds shown in formula (I).Above-claimed cpd can be used alone, and also can mix rear use.The compound shown in formula (I) used in the present invention all can be commercially available, or prepared through alkylated reaction by corresponding precursor compound.
In the present invention, can being undertaken contacting by various method with silicoorganic compound b and prepare alkene catalyst component of solid ingredient a.Such as prepare alkene catalyst component of the present invention by following method.
Method one, silicoorganic compound b and the solid ingredient a contact reacts Kaolinite Preparation of Catalyst component prepared.The solid ingredient a prepared is scattered in inert diluent and carries out contact reacts with silicoorganic compound b.Reaction terminates rear filtration, with inertia alkane solvents as the washing such as hexane, heptane, filtration, drying obtain alkene catalyst component.
In described method one, inert diluent used is not particularly limited, as long as contribute to fully contacting of solid ingredient a and silicoorganic compound b.Described inert diluent is preferably alkane, naphthenic hydrocarbon, aromatic hydrocarbons, halogenated alkane, halogenated aryl hydrocarbon solvent or silicone oil etc., at least one more preferably in hexane, hexanaphthene, heptane, octane, decane, benzene,toluene,xylene, chlorobenzene, dichlorobenzene.The consumption of described inert diluent is not particularly limited, and preferable amount is that every gram of solid ingredient a uses 2-100 milliliter inert diluent, and more preferably every gram of solid ingredient a uses 5-50 milliliter inert diluent.In the method, solid ingredient a can contact at-20 DEG C-150 DEG C with silicoorganic compound b, preferably contacts at-10 DEG C-120 DEG C, more preferably contacts at 0 DEG C-110 DEG C.Duration of contact is 10 minutes-5 hours, is preferably 30 minutes-3 hours.In the method, the usage ratio of solid ingredient a and silicoorganic compound b is not particularly limited.In preferable amount solid ingredient a, the mole number of titanium atom is 1: 0.1-1: 10 with the ratio of the mole number of Si-H functional group in silicoorganic compound b, is preferably 1: 0.2-1: 5.
Method two, in solid ingredient a preparation process, adds silicoorganic compound b and reacts and Kaolinite Preparation of Catalyst component.In solid ingredient a preparation process, add silicoorganic compound b to realize the contact of solid ingredient a and silicoorganic compound b, thus obtain alkene catalyst component.According to the preparation method of aforesaid solid component a, adding of silicoorganic compound b can add any opportunity in solid ingredient preparation process, preferably add on following opportunity: first, in the preparation method of solid ingredient a as previously mentioned, the solids suspension formed after magnesium compound contacts with titanium compound, namely adds silicoorganic compound b and carries out contact reacts in mother liquor.Carry out the titanium process in the preparation method of solid ingredient a as previously mentioned after contact reacts terminates again, filter, washing, drying obtains alkene catalyst component.The second, in the preparation method of solid ingredient a as previously mentioned, carry out adding silicoorganic compound b in the process of titanium process after mother liquor filters, more preferably add silicoorganic compound b in titanium treating processes the last time and carry out contact reacts.Filter after contact reacts terminates, washing, drying obtains alkene catalyst component again.3rd, in the preparation method of solid ingredient a as previously mentioned, add silicoorganic compound b in the washing process after titanium processing reaction terminates and carry out contact reacts and filter, washing, drying obtains alkene catalyst component.
In method two, silicoorganic compound b can carry out contact reacts at-20 DEG C-150 DEG C with solids, preferably contacts at-10 DEG C-120 DEG C, more preferably contacts at 0 DEG C-110 DEG C.Duration of contact is 10 minutes-10 hours, is preferably 30 minutes-5 hours.Wherein, the consumption of silicoorganic compound b is not particularly limited.Preferable amount be the mole number of mole number and the magnesium compound used of Si-H functional group in silicoorganic compound b with it than being 1: 1-1: 100, be preferably 1: 5-1: 50.
According to alkene catalyst component of the present invention, wherein the content of titanium atom is 1.0-8.0wt%, is preferably 1.6-4.0wt%; The content of magnesium atom is 10-70wt%, is preferably 15-40wt%; The content of halogen atom is 20-86wt%, is preferably 36-80%; Silicon atom content is 0.01-2wt%, preferred 0.02-0.5wt%; Total internal electron donor compound content 2-30wt%, preferred 3-20wt%.
According to olefin polymerization catalysis of the present invention, this catalyzer is used for by general formula CH
2the polyreaction of the alkene that=CHR represents, the wherein alkyl of R to be hydrogen or carbonatoms be 1-6.Described catalyzer comprises the reaction product of following material: above-mentioned olefin polymerization catalyst components; As the organo-aluminium compound of promotor; Optionally, external donor compound.
In above-mentioned olefin polymerization catalysis, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst that described organo-aluminium compound can be commonly used for field of olefin polymerisation.In the preferred case, described organo-aluminium compound can be the compound shown in formula (VIII),
AlR′
n′X′
3-n′(VIII)
In formula (VIII), the alkyl that R ' is hydrogen, carbonatoms is 1-20 or carbonatoms are the aryl of 6-20, and X ' is halogen, the integer that n ' is 1-3.The object lesson of described organo-aluminium compound can be at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 5-5000: 1; Preferably, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 20-1000: 1; More preferably, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 50-500: 1.
Kind and the content of the external electron donor in olefin polymerization catalysis of the present invention are not particularly limited.In the preferred case, the mol ratio of the aluminium in described organo-aluminium compound and described external donor compound is 0.1-500: 1, preferred 1-300: 1, more preferably 3-100: 1.
In above-mentioned olefin polymerization catalysis, described external electron donor component can be the silicoorganic compound shown in formula (IX),
R″
m′Si(OR″′)
4-m′(IX)
In formula (IX), R " is halogen, hydrogen atom, the carbonatoms alkyl that is 1-20, the carbonatoms cycloalkyl that is 3-20, the carbonatoms one that to be the aryl of 6-20 and carbonatoms be in the haloalkyl of 1-20; R " ' for carbonatoms is the alkyl of 1-20, carbonatoms is the cycloalkyl of 3-20, carbonatoms is 6-20 aryl and carbonatoms be the one in the haloalkyl of 1-20; The integer that m ' is 1-3.Object lesson as described silicoorganic compound can enumerate trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, Dicyclohexyldimethoxysilane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane and (1, 1, the fluoro-2-propyl group of 1-tri-) at least one in-methyl dimethoxysilane etc.
According to olefine polymerizing process of the present invention, under the method is included in olefin polymerization conditions, make one or more alkene and above-mentioned catalyst exposure, at least one in described alkene is by general formula CH
2the alkene that=CHR represents, the wherein alkyl of R to be hydrogen or carbonatoms be 1-6.
Olefine polymerizing process of the present invention may be used for all polymerizations of alkene, also may be used for multiple alkene to carry out copolymerization.Described by general formula CH
2the specific examples of the alpha-olefin that=CHR represents comprises: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.Preferably, described by general formula CH
2the alkene that=CHR represents is ethene, propylene, 1-butylene.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area.Usually, described olefin polymerization conditions comprises: temperature is 0-150 DEG C, and the time is 0.1-5 hour, and pressure is 0.01-10MPa.Preferably, described olefin polymerization conditions comprises: temperature is 60-130 DEG C, and the time is 0.5-3 hour, and pressure is 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
Embodiment
In further detail the present invention is described below in conjunction with embodiment.Below be only the preferred embodiment of the present invention, protection scope of the present invention is not limited thereto, and any those skilled in the art, in technical scope disclosed by the invention, can be easy to the change carried out or change is all encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Except as otherwise noted, in following embodiment use silicoorganic compound all purchased from ACROS or Sigma-Aldrich company; Anhydrous MgCl
2purchased from Qinghai North Star Science and Technology Ltd.; TiCl
4purchased from Xingtai non-ferrous metals smelting works; Silicoorganic compound as external electron donor and the organo-aluminium compound as promotor are all purchased from Nanjing communications and liaison Chemical Co., Ltd..
In following examples, the titanium atom content in solid ingredient a and olefin polymerization catalyst components A is according to the 721 spectrophotometer tests purchased from An Hemeng (Tianjin) development in science and technology company limited; The melting index of polymkeric substance uses the model purchased from the new experimental instrument and equipment company limited in Changchun to be XRZ-00 fusion index instrument, and measure according to the method specified in GB/T3682-2000.
In following examples, the content of Siliciumatom is measured by following methods: first use Si in Dutch PANalytical company Axios-Advanced type Xray fluorescence spectrometer analysis of catalyst, the relative content of Ti element, the titanium atom content root Ju following formula recycling the test of above-mentioned spectrophotometer calculates and obtains:
Si atom content=(Ti atom content × Si relative content) ÷ Ti relative content.
In following examples, the testing method of polymkeric substance degree of isotacticity comprises: 2 grams of dry polymer samples, is placed in extractor and after 6 hours, residuum is dried to constant weight, by following formulae discovery degree of isotacticity with the extracting of boiling heptane:
Polymer quality/2 × 100 after degree of isotacticity (%)=extracting.
Polymer bulk density: polymer powders is dropped to 100mL cylindrical vessel from funnel, weighs the quality m gram of polymkeric substance in this container, by following formulae discovery polymer bulk density: tap density (BD)=m/100g/cm
3.
Preparation example
The preparation of alkoxyl magnesium:
With in the 1L reactor of agitator, reflux condensing tube, thermometer and drop-burette, after fully replacing, add ethanol 550mL in reactor, 10mL Virahol with nitrogen, iodine 0.68g dissolves.Heat up after opening stirring, until reach the reflux temperature of reaction system; Then magnesium powder 32g is successively added; React to no longer including hydrogen discharge; Then wash, filter and drying, obtain tap density 0.25g/cm
3, the alkoxyl magnesium of median size (D50) 47.0 μm 147 grams.
Embodiment 1
The preparation of solid ingredient a1:
Get 10 grams, alkoxyl magnesium carrier obtained in preparation example, toluene 50mL, n-butyl phthalate 2.5mL, is mixed with suspension; In the reactor repeating the 300mL replaced through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension prepared is added in still, be warming up to 80 DEG C, constant temperature 1 hour is follow-up is continuously warming up to 115 DEG C, constant temperature after 2 hours by clean for liquid (mother liquor) press filtration.Then the mixed solution adding toluene 120mL and titanium tetrachloride 30mL is warming up to 110 DEG C of stir process 1 hour (titanium process), process like this 3 times, elimination liquid, the solid of gained washs 4 times at 50 DEG C with normal hexane 120mL, elimination liquid is also dry, obtains solid ingredient a1 of the present invention.In gained solid ingredient a1, titanium content is 2.4wt%.
The preparation of olefin polymerization catalyst components A1:
Add 10 grams of solid ingredient a1 in 300mL reactor, add 80mL normal heptane and stir formation suspension, be cooled to 0 DEG C, add 3mL triethyl silicane, be warming up to 70 DEG C, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 4 times at 50 DEG C with normal heptane 120mL, elimination liquid dry alkene catalyst component A1.In alkene catalyst component A1, titanium atom content is 2.0wt%, and silicon atom content is 0.080wt%.
Polyolefin is standby:
In 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, the hexane solution (concentration of CHMMS is 0.1mol/L) of 1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A1 prepared of 6-10mg.Close autoclave, introduce the hydrogen of 0.2 standard liter (NL) and the liquid propene of 2L; In under agitation 15 minutes, temperature is risen to 70 DEG C.At 70 DEG C after polyreaction 1-3 hour, stop stirring, remove unpolymerized propylene monomer, collect and obtain polymer P.The polymerization activity of olefin polymerization catalyst components A1, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Wherein the polymerization activity of catalyzer is calculated by following formula: polymerization activity=polymer P quality (Kg)/olefin polymerization catalyst components A1 quality (g).
Comparative example 1
Use solid ingredient a1 in embodiment 1 to replace olefin polymerization catalyst components A1, be polymerized according to process for preparing polyolefins in embodiment 1.The polymerization activity of solid ingredient a1, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 2
The preparation of olefin polymerization catalyst components A2:
Add the solid ingredient a1 of preparation in 10 grams of embodiments 1 in 300mL reactor, add 100mL normal hexane and stir formation suspension, be warming up to 60 DEG C, add 3mL tri isopropyl silane, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 4 times at 50 DEG C with normal hexane 120mL, elimination liquid dry alkene catalyst component A2.In alkene catalyst component A2, titanium atom content is 2.1wt%, and silicon atom content is 0.080wt%.
Polyolefin is standby:
Replace A1 with A2, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A2, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 3
The preparation of olefin polymerization catalyst components A3:
Add the solid ingredient a1 of preparation in 10 grams of embodiments 1 in 300mL reactor, 50mL normal hexane stirs and forms suspension, is warming up to 60 DEG C, adds 3mL tri-hexyl silane, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 4 times at 50 DEG C with normal hexane 120mL, elimination liquid dry olefin polymerization catalyst components A3.In catalyst component A3, titanium atom content is 2.0wt%, and silicon atom content is 0.050wt%.
Polyolefin is standby:
Replace A1 with A3, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A3, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 4
The preparation of olefin polymerization catalyst components A4:
Add the solid ingredient a1 of preparation in 10 grams of embodiments 1 in 300mL reactor, 100mL normal hexane stirs and forms suspension, is cooled to 0 DEG C, adds 3mL diphenyl silane, be warming up to 60 DEG C in 30 minutes, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 4 times at 50 DEG C with normal hexane 120mL, elimination liquid dry alkene catalyst component A4.In alkene catalyst component A4, titanium atom content is 2.1wt%, and silicon atom content is 0.120wt%.
Polyolefin is standby:
Replace A1 with A4, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A4, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 5
The preparation of olefin polymerization catalyst components A5:
Add the solid ingredient a1 of preparation in 10 grams of embodiments 1 in 300mL reactor, 100mL normal hexane stirs and forms suspension, is warming up to 60 DEG C, adds 0.5mL triethyl silicane, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 4 times at 50 DEG C with normal hexane 120mL, elimination liquid dry alkene catalyst component A5.In alkene catalyst component A5, titanium atom content is 2.2wt%, and silicon atom content is 0.040wt%.
Polyolefin is standby:
Replace A1 with A5, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A5, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 6
The preparation of olefin polymerization catalyst components A6:
Get 10 grams, alkoxyl magnesium carrier obtained in preparation example, toluene 50mL, n-butyl phthalate 2.5mL, is mixed with suspension; In the reactor repeating the 300mL replaced through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension prepared is added in still, be warming up to 80 DEG C, 1 hour follow-up continuing of constant temperature is warming up to 115 DEG C, constant temperature 2 hours, then by clean for liquid (mother liquor) press filtration.Then the mixed solution adding toluene 120mL and titanium tetrachloride 30mL is warming up to 110 DEG C of stir process 1 hour, elimination liquid, so process 2 times; The mixed solution adding toluene 120mL and titanium tetrachloride 30mL is again warming up to 110 DEG C, stirs and adds 1.5mL triethyl silicane simultaneously, continues constant temperature stir process 1 hour, elimination liquid.The solid of gained washs 4 times at 50 DEG C with normal hexane 120mL, and elimination liquid is also dry, obtains solid ingredient A6 of the present invention.In gained solid ingredient A6, titanium content is 2.9wt%, silicon atom content 0.210wt%.
Polyolefin is standby:
Replace A1 with A6, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A6, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 7
The preparation of olefin polymerization catalyst components A7:
Get 10 grams, the alkoxyl magnesium carrier that preparation example 1 is obtained, toluene 50mL, n-butyl phthalate 2.5mL, is mixed with suspension; In the reactor repeating the 300mL replaced through high pure nitrogen, add toluene 30mL and titanium tetrachloride 120mL, then the suspension prepared is added in still, be warming up to 80 DEG C, 1 hour follow-up continuing of constant temperature is warming up to 115 DEG C, constant temperature 2 hours, then by clean for liquid (mother liquor) press filtration.Then the mixed solution adding toluene 120mL and titanium tetrachloride 30mL is warming up to 110 DEG C of stir process 1 hour, elimination liquid, so process 3 times.The solid of gained washs 2 times at 50 DEG C with normal hexane 120mL; Then add 120mL hexane, be warming up to 60 DEG C, add 3mL triethyl silicane, constant temperature 2 hours, then by clean for liquid press filtration.Gained solid washs 2 times at 50 DEG C with normal hexane 120mL, elimination liquid dry alkene catalyst component A7.In alkene catalyst component A7, titanium atom content is 2.0wt%, silicon atom content 0.080wt%.
Polyolefin is standby:
Replace A1 with A7, be polymerized by process for preparing polyolefins in embodiment 1.The polymerization activity of olefin polymerization catalyst components A7, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 8
1-butylene liquid-phase bulk polymerization:
In 2 liters of autoclaves, after 1-butylene is fully replaced, at room temperature add the olefin polymerization catalyst components A1 prepared in the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 2mL triethyl aluminum, the hexane solution (concentration is 0.1mmol/mL) of 0.5mL diisopropyl dimethoxy silane, 10mL anhydrous hexane and 10mg embodiment 1.Close autoclave, introduce the hydrogen of 2 standard liters (NL) and the liquid 1-butylene of 350 grams; In under agitation 15 minutes, temperature is risen to 60 DEG C.At 60 DEG C after polyreaction 1-3 hour, stop stirring, remove unpolymerized 1-butylene monomer, collect and obtain polymkeric substance.
The 1-butylene polymerization activity of olefin polymerization catalyst components A1, melt index (MI), result are as shown in table 1.
Comparative example 2
Using solid ingredient a1 in embodiment 1 to replace olefin polymerization catalyst components A1, being polymerized according to preparing process for preparing polyolefins in embodiment 8.1-butylene polymerization activity, polymkeric substance melting means (MI) result of solid ingredient a1 are as shown in table 1.
Table 1
As can be seen from Table 1, the olefin polymerization catalyst components crossed through the silicoorganic compound b contact pairs containing Si-H functional group discharges stable and uniform more than the olefin polymerization catalysis activity prepared by undressed olefin polymerization catalyst components, catalyzer hydrogen response is better, and the gross activity of catalyzer significantly improves, polymer bulk density improves.
Claims (16)
1. the catalyst component for olefinic polymerization, this catalyst component by a kind of solid constituent a form containing magnesium, titanium, halogen and internal electron donor compound with contact such as formula the silicoorganic compound b containing Si-H functional group shown in (I) after obtain
HSiR
1 nR
2 3-n(I)
In formula (I), R
1, R
2identical or different, be hydrogen atom separately, carbonatoms is the straight or branched saturated alkyl of 1-12, the one in the cycloalkyl of carbonatoms 3-10 and the alkaryl of carbonatoms 6-20, replacement or non-substituted arene base; R
1, R
2be asynchronously hydrogen; N is the integer of 0-3;
The described internal electron donor compound preparing solid constituent a is compound shown in formula (IV):
In formula (IV), R
13and R
14identical or different, be separately one that carbonatoms is in the alkaryl of the straight or branched alkyl of 1-12, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or non-substituted arene base; R
15, R
16, R
17and R
18be all hydrogen; Or wherein three is hydrogen, the straight or branched alkyl that another one is halogen, carbonatoms is 1-4, carbonatoms are the one in the straight or branched alkoxyl group of 1-4;
In described catalyst component, the content of titanium atom is 1.0-8.0wt%; The content of magnesium atom is 10-70wt%; The content of halogen atom is 20-86wt%; Silicon atom content is 0.01-2wt%; Internal electron donor compound content is 2-30wt%.
2. catalyst component according to claim 1, is characterized in that, the preparation method of described solid constituent a is by magnesium compound, titanium compound and internal electron donor contact reacts under certain condition.
3. catalyst component according to claim 2, it is characterized in that, at least one in the hydrate that the described magnesium compound preparing solid constituent a is the magnesium compound shown in the magnesium compound shown in formula (II), formula (II) and the alcohol adducts of the magnesium compound shown in formula (II)
MgR
4R
5(II)
In formula (II), R
4and R
5it is separately halogen, the carbonatoms one that to be the straight or branched alkoxyl group of 1-8 and carbonatoms be in the straight or branched alkyl of 1-8.
4. catalyst component according to claim 3, is characterized in that, the described magnesium compound preparing solid constituent a is alkoxyl magnesium.
5. catalyst component according to claim 2, is characterized in that, the described titanium compound of solid constituent a of preparing for the compound shown in formula (III),
TiX
m(OR
7)
4-m(III)
In formula (III), X is halogen, R
7for carbonatoms is the alkyl of 1-20, m is the integer of 0-4; Described halogen is chlorine, bromine or iodine.
6. catalyst component according to claim 5, is characterized in that, described titanium compound is titanium tetrachloride.
7. catalyst component according to claim 1, it is characterized in that, the described internal electron donor compound preparing solid constituent a is at least one in diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate.
8. catalyst component according to claim 1, it is characterized in that, described silicoorganic compound b is at least one in triethyl silicane, tripropyl silane, tributyl silane, three pentylsilane, three hexyl silanes, tri isopropyl silane, tri-phenyl-silane, diphenyl silane, dipropyl silane, dibutyl silane, diamyl silane, dihexyl silane, diisopropylsilyl, diisobutyl silane, diisoamyl silane, two isohexyl silane.
9. catalyst component according to claim 1, is characterized in that, in described catalyst component, the content of titanium atom is 1.6-4.0wt%; The content of magnesium atom is 15-40wt%; The content of halogen atom is 36-80%; Silicon atom content is 0.02-0.5wt%; Internal electron donor compound content is 3-20wt%.
10. as a preparation method for catalyst component as described in any one in claim 1-9, it is characterized in that, silicoorganic compound b forms with the solid ingredient a contact reacts prepared.
11. 1 kinds, as the preparation method of catalyst component as described in any one in claim 1-9, is characterized in that, in solid ingredient a preparation process, add silicoorganic compound b reaction and form; The preparation process of described solid ingredient a is divided into mother liquor formation, titanium treating processes and washing process three step in chronological order successively; Described mother liquor is formed and refers to magnesium compound to be suspended in inert diluent and form suspension, then is mixed with titanium compound, internal electron donor by this suspension and contact to obtain solids dispersion system, namely forms mother liquor; Described titanium treating processes refers to filters described mother liquor, and gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs; Described washing process refers to gained solid matter in filtration, washing previous step, adds described silicoorganic compound b in the washing process after the titanium treating processes in solid ingredient a preparation.
12. 1 kinds of catalyzer for olefinic polymerization, comprise the catalyst component in claim 1-9 described in any one, also comprise the organo-aluminium compound as promotor, and optionally external donor compound.
13. catalyzer according to claim 12, it is characterized in that, described organo-aluminium compound is at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.
14. catalyzer according to claim 12, it is characterized in that, described external donor compound is trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, Dicyclohexyldimethoxysilane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane and (1, 1, the fluoro-2-propyl group of 1-tri-) at least one in-methyl dimethoxysilane.
15. 1 kinds are all polymerized and the application in copolymerization at alkene as the catalyzer in the catalyst component in claim 1-9 as described in any one or claim 12-14 as described in any one, and at least one in described alkene is by general formula CH
2the alkene that=CHR represents, the wherein alkyl of R to be hydrogen or carbonatoms be 1-6.
16. application according to claim 15, described alkene is ethene, propylene or 1-butylene.
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| CN201110210008.7A CN102898553B (en) | 2011-07-26 | 2011-07-26 | Catalyst component for olefin polymerization, and preparation method and catalyst thereof |
| PCT/CN2012/079072 WO2013013611A1 (en) | 2011-07-26 | 2012-07-24 | Catalyst component for olefinic polymerization, preparation method therefor and catalyst thereof |
| US14/235,340 US10150822B2 (en) | 2011-07-26 | 2012-07-24 | Catalyst component for olefin polymerization, preparation method therefor and catalyst thereof |
| KR1020147004921A KR101895826B1 (en) | 2011-07-26 | 2012-07-24 | Catalyst component for olefinic polymerization, preparation method therefor and catalyst thereof |
| BR112014001784A BR112014001784A2 (en) | 2011-07-26 | 2012-07-24 | catalyst component (a) for olefin polymerization, process for preparing catalyst component (a), catalyst for olefin polymerization, and use of catalyst component or catalyst |
| TW101126792A TWI511991B (en) | 2011-07-26 | 2012-07-25 | A catalyst component for olefin polymerization, a process for its preparation and a catalyst |
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| CN1216554A (en) * | 1996-05-07 | 1999-05-12 | 陶氏化学公司 | Improved syndiotactic vinylidene aromatic polymerization process |
| CN1887917A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
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| JPS59221309A (en) * | 1983-05-31 | 1984-12-12 | Toa Nenryo Kogyo Kk | Catalytic component for polymerizing olefin |
| US5093442A (en) * | 1988-10-03 | 1992-03-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing a homopolymer or copolymer of an α-olefin |
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| CN1216554A (en) * | 1996-05-07 | 1999-05-12 | 陶氏化学公司 | Improved syndiotactic vinylidene aromatic polymerization process |
| CN1887917A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
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