CN102898551A - 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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- CN102898551A CN102898551A CN2011102100034A CN201110210003A CN102898551A CN 102898551 A CN102898551 A CN 102898551A CN 2011102100034 A CN2011102100034 A CN 2011102100034A CN 201110210003 A CN201110210003 A CN 201110210003A CN 102898551 A CN102898551 A CN 102898551A
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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.
Description
Technical field
The present invention relates to a kind of catalyzer of catalyst component, its preparation method and the olefinic polymerization for the equal polymerization of alkene or copolymerization.
Background technology
Can be used for CH with 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 consisted of together olefin polymerization catalysis as the silicone compounds of external electron donor, i.e. Ziegler-Natta (Z-N) catalyzer.Disclose a kind of Z-N catalyzer that consists of the following composition such as CN1453298: (1) is with magnesium, titanium, halogen and the diol-lipid internal electron donor compound ingredient of solid catalyst as basal component; (2) alkylaluminium cpd; (3) contain the organosilicone compounds of 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 (having higher melt index during identical hydrogenation amount), and the catalyzer of the polymkeric substance of acquisition high-bulk-density remains the target that this area researchist pursues.
Existing polyolefine prepares the technical process that used continuous processing often adopts two or more reactors in series, such as liquid-phase bulk polymerization reactor and gas-phase polymerization reactor series connection, two Gas-phase reactor series connection etc.As conventionally known to one of skill 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 and other parameter in each reactor according to the performance requriements of specific product and processing condition, the total residence time general control in each reactor was at 2-4 hour; This just needs used Z-N catalyzer can steadily discharge uniformly activity in whole polymerization process.Otherwise hyperactivity reaction in early stage will occur and be difficult to control, and active not enough problem of later stage; This will directly cause quality product to descend even not reach its performance requriements.This shows that it is controlled that the steadily evenly release one side of Z-N catalyst activity is conducive to stablizing of polymerization process; Be conducive on the other hand the adjustment of various parameters in the polymerization process, to produce the more good product of performance.
US20090253874 disclose with ingredient of solid catalyst under certain condition with a kind of CH of containing
2Can make catalyzer keep in a long time active after the organic silane compound contact of=CH functional group.But this compounds preparation difficulty is expensive.
In the R﹠D process of Z-N catalyzer and corresponding olefinic polymerization thereof, can run into inevitably serious catalyst activity attenuation problem, namely catalyzer has affected its result of use greatly in reaction active significantly decline after 1.5-2 hour.The inventor is beat all discovery after a large amount of experimental studies, uses a kind of organic silane compound of the Si-H of containing key can significantly improve the catalyst activity attenuation problem, and catalyst activity is steadily evenly discharged; Prepared olefin polymer tap density also obviously improves; This catalyzer also has catalytic activity height, hydrogen response is good, the stereotaxis ability is good characteristics simultaneously.
Summary of the invention
The object of the present invention is to provide that a kind of catalytic activity is high, hydrogen response is good, the stereotaxis ability is good, and active more uniform olefin polymerization catalyst components and the catalyzer thereof of discharging.
Concrete, the invention provides a kind of catalyst component for olefinic polymerization, this catalyst component is obtained after containing solid constituent a that magnesium, titanium, halogen and internal electron donor compound form and contacting suc as formula the silicoorganic compound b that contains Si-H functional group shown in (I) by a kind of
In the formula (I), R
1For carbonatoms is the straight or branched saturated alkyl of 1-12, the alkaryl of the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or a kind of in the substituted arene base not; R
2, R
3, R
4, R
5Identical or different, the hydrogen of respectively doing for oneself, carbonatoms are the straight or branched saturated alkyl of 1-12, the cycloalkyl of carbonatoms 3-10, the alkaryl of carbonatoms 6-20, replacement or substituted arene base not, a kind of in the alkyl siloxy of the total number of carbon atoms 1-20; R
3, R
4, R
5Be not hydrogen atom simultaneously.
According to solid constituent a of the present invention, its preparation method can be with magnesium compound, titanium compound and internal electron donor contact reacts under certain condition; Consumption for the preparation of titanium compound, magnesium compound and the internal electron donor of described solid ingredient a is not particularly limited, and all can be conventional substances and the consumption of this area.
In the preferred case, what the magnesium compound of described preparation solid ingredient a can be in the alcohol adducts of the hydrate of the magnesium compound shown in the magnesium compound shown in the formula (II), the formula (II) and the magnesium compound shown in the formula (II) is at least a,
MgR
6R
7 (II)
In the formula (II), R
6And R
7Respectively do for oneself halogen, carbonatoms is a kind of in the straight or branched alkoxyl group of 1-5 and the straight or branched alkyl that carbonatoms is 1-5.
The hydrate of the magnesium compound shown in the described formula (II) refers to MgR
6R
7QH
2O, wherein, q is preferably 2-3.5 within the scope of 0.1-6.Among the present invention, described alcohol adducts refers to MgR
6R
7PR
8OH, wherein, R
8For carbonatoms is the alkyl of 1-18, be preferably the alkyl that carbonatoms is 1-8, more preferably methyl, ethyl, n-propyl and sec.-propyl; P is 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 chlorination magnesium, the methoxyl group magnesium bromide, the methoxyl group magnesium iodide, the oxyethyl group magnesium chloride, the oxyethyl group magnesium bromide, the oxyethyl group magnesium iodide, the propoxy-magnesium chloride, the propoxy-magnesium bromide, the propoxy-magnesium iodide, the butoxy magnesium chloride, the butoxy magnesium bromide, the butoxy magnesium iodide, methylmagnesium-chloride, ethylmagnesium chloride, the propyl group magnesium chloride, butylmagnesium chloride, the amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated magnesium, two magnesium iodides, the alcohol adducts of magnesium dichloride, at least a in the alcohol adducts of the alcohol adducts of dibrominated magnesium and two magnesium iodides.Most preferably, described magnesium compound is alkoxyl magnesium.
Be the compound shown in the formula (III) according to titanium compound among the preparation solid ingredient a of the present invention,
TiX
m(OR
9)
4-m (III)
In the formula (III), X is halogen, R
9For 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 the formula (III), X is halogen, R
9For carbonatoms is the alkyl of 1-5, for example: at least a in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
Be selected from compound shown in the formula (IV) according to internal electron donor compound among the preparation solid ingredient a of the present invention,
In the formula (IV), R
10And R
11Identical or different, the carbonatoms of respectively doing for oneself is the alkaryl, replacement of the cycloalkyl of straight or branched alkyl, carbonatoms 3-10 of 1-12 and carbonatoms 6-20 or a kind of in the substituted arene base not; R
12, R
13, R
14And R
15All be hydrogen, perhaps wherein three be hydrogen, another one is that halogen, carbonatoms are a kind of in the straight or branched alkyl of 1-4, the straight or branched alkoxyl group that carbonatoms is 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-ethyl cyclohexyl, 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 at least a in diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, dinoctyl phthalate, the dimixo-octyl phthalate.At least a in diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, the dimixo-octyl phthalate particularly preferably.
In the present invention, the preparation of solid ingredient a can be undertaken by the method for preparing the alkene catalyst component of this area routine; For example can prepare solid ingredient a of the present invention by following method.
Alkoxyl magnesium or alkoxyl group magnesium halide be suspended in form suspension in the inert diluent, this suspension and above-mentioned titanium compound, internal electron donor are mixed contacting to get the solids dispersion system again, be commonly referred to mother liquor.Mother liquor is filtered, and the gained solid matter is suspended in the solution that contains titanium tetrachloride and contacts processing, is commonly referred to titanium and processes; Then after filtration, washing can make solid ingredient a of the present invention.
The object lesson of above-mentioned alkoxyl magnesium can referring in the summary of the invention in front described part, the mixture of preferred diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesium wherein.The preparation method of this alkoxyl magnesium compound can be by method preparation well known in the art, such as the disclosed preparation in the presence of a small amount of iodine with MAGNESIUM METAL and Fatty Alcohol(C12-C14 and C12-C18) among the patent CN101906017A.
As the object lesson of above-mentioned alkoxyl group magnesium halide can referring in the summary of the invention in front described part, preferred oxyethyl group magnesium chloride wherein.The preparation method of this alkoxyl group halogenated magnesium compound can select method well known in the art, as the Grignard reagent butylmagnesium chloride is mixed to prepare the oxyethyl group magnesium chloride with purity titanium tetraethoxide and tetraethoxy-silicane.
The employed inert diluent of the formation of mother liquor can adopt at least a in hexane, heptane, octane, decane, benzene, toluene and the dimethylbenzene in the aforesaid method.The consumption of employed each composition of formation of mother liquor wherein, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound is preferably the 1-50 mole; The usage quantity of inert diluent is generally the 0.5-100 mole, is preferably the 1-50 mole; The internal electron donor compound amount is generally the 0.005-10 mole, is preferably the 0.01-1 mole.Wherein, the Contact Temperature of described each component is generally-40～200 ℃ during the formation of mother liquor, is preferably-20～150 ℃; Be generally 1 minute duration of contact-20 hours, be preferably 5 minutes-8 hours.
In the treating processes of titanium described in the aforesaid method, the alternative inert diluent that adds that uses in the solution that contains titanium tetrachloride, at least a as in hexane, heptane, octane, decane, benzene, toluene and the dimethylbenzene.Wherein, the consumption that contains each composition in the titanium tetrachloride solution that uses, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound is preferably the 1-50 mole; The usage quantity of inert diluent is generally the 0-100 mole, is preferably the 0-50 mole.Wherein the titanium number of processes is 0-10 time, preferred 1-5 time.And in described titanium treating processes, the above-mentioned electronic donor compound capable of alternative adding, wherein the internal electron donor consumption is generally the 0.005-10 mole, is preferably the 0.01-1 mole.The titanium treatment temp is generally 0～200 ℃, is preferably 30～150 ℃; Be generally 1 minute duration of contact-20 hours, 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 compounds content 2-30wt%, preferred 3-20wt%.
The olefin polymerization catalyst components of stating according to the present invention, the silicoorganic compound b that wherein contains Si-H functional group can be any compound shown in the formula (I), is not particularly limited.In its Chinese style (I), R
1Being preferably carbonatoms is the straight or branched saturated alkyl of 1-6; R
2The straight or branched saturated alkyl of preferred carbonatoms 1-6, a kind of in the alkyl siloxy of the total number of carbon atoms 1-12; R
3, R
4, R
5Preferred hydrogen, carbonatoms is the straight or branched saturated alkyl of 1-6, a kind of in the alkyl siloxy of the total number of carbon atoms 2-12.
In the preferred case, can be selected from 1,1,1,3 by the examples of compounds shown in the formula (I), the 3-pentamethyl disiloxane, 1,1,3,3-tetramethyl disiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, four (dimethylsilyl) siloxanes, 1,1,3,3,5,5-hexam ethylcyclotrisiloxane, three (dimethylsilyl bis) methyl-monosilane, 1,1,3,3-tetra isopropyl disiloxane, three (dimethylsilyl bis) phenyl siloxane.Above-claimed cpd can use separately, also can mix rear use.The compound shown in the employed formula (I) all can be commercially available among the present invention, perhaps prepares through chemical reactions such as alkylation, condensations by corresponding precursor compound.
In the present invention, solid ingredient a's can contact to prepare the alkene catalyst component by the whole bag of tricks with silicoorganic compound b.For example can 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 that has prepared.The solid ingredient a for preparing is scattered in the inert diluent carries out contact reacts with silicoorganic compound b.Filter after reaction finishes, obtain the alkene catalyst component with inertia alkane solvents such as the washings such as hexane, heptane, filtration, drying.
In the described method one, used inert diluent is not particularly limited, as long as help 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., more preferably at least a in hexane, hexanaphthene, heptane, octane, decane, benzene,toluene,xylene, chlorobenzene, the dichlorobenzene.The consumption of described inert diluent is not particularly limited, and preferable amount is that every gram solid ingredient a uses 2-100 milliliter inert diluent, and more preferably every gram solid ingredient a uses 5-50 milliliter inert diluent.In the method, solid ingredient a can contact at-20 ℃-150 ℃ with silicoorganic compound b, preferably contacts at-10 ℃-120 ℃, more preferably contacts at 0 ℃-110 ℃.Be 10 minutes-5 hours duration of contact, was preferably 30 minutes-3 hours.In the method, the usage ratio of solid ingredient a and silicoorganic compound b is not particularly limited.Among the preferable amount solid ingredient a among the mole number of titanium atom and the silicoorganic compound b ratio of the mole number of Si-H functional group be 1: 0.1-1: 10, be preferably 1: 0.2-1: 5.
Method two in solid ingredient a preparation process, adds silicoorganic compound b reaction and the Kaolinite Preparation of Catalyst component.In solid ingredient a preparation process, add silicoorganic compound b and realize contacting of solid ingredient a and silicoorganic compound b, thus acquisition alkene catalyst component.Preparation method according to aforementioned solid ingredient a, the adding of silicoorganic compound b can add any opportunity in the solid ingredient preparation process, preferably add on following opportunity: first, in the preparation method of solid ingredient a as previously mentioned, the solids suspension that forms after magnesium compound contacts with titanium compound namely adds silicoorganic compound b and carries out contact reacts in the mother liquor.The titanium that carries out again after contact reacts finishes among the preparation method of solid ingredient a is as previously mentioned processed, filters, and washing, drying obtains the alkene catalyst component.The second, in the preparation method of solid ingredient a as previously mentioned, after filtering, mother liquor carries out adding silicoorganic compound b in the process that titanium processes, and more preferably add silicoorganic compound b in the titanium treating processes the last time and carry out contact reacts.Contact reacts is filtered after finishing again, washing, and drying obtains the alkene catalyst component.The 3rd, in the preparation method of solid ingredient a as previously mentioned, add silicoorganic compound b in the washing process after the titanium processing reaction finishes and carry out contact reacts and filter again, washing, drying obtains the alkene catalyst component.
In the method two, silicoorganic compound b can carry out contact reacts with solids at-20 ℃-150 ℃, preferably contacts at-10 ℃-120 ℃, more preferably contacts at 0 ℃-110 ℃.Be 10 minutes-10 hours duration of contact, was 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 used magnesium compound of Si-H functional group among the 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 compounds 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, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.Described catalyzer comprises the reaction product of following material: above-mentioned olefin polymerization catalyst components; Organo-aluminium compound as promotor; Randomly, external donor compound.
In above-mentioned olefin polymerization catalysis, described organo-aluminium compound can be the field of olefin polymerisation various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst commonly used.In the preferred case, described organo-aluminium compound can be the compound shown in the formula (VIII),
AlR′
n′X′
3-n′ (VIII)
In the formula (VIII), R ' is that hydrogen, carbonatoms are that alkyl or the carbonatoms of 1-20 is the aryl of 6-20, and X ' is halogen, and n ' is the integer of 1-3.The object lesson of described organo-aluminium compound can be 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 ethyl aluminum chloride and the ethyl aluminum dichloride at least a.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, the mol ratio of the aluminium in the described organo-aluminium compound and the titanium in the described catalyzer is 5-5000: 1; Preferably, the mol ratio of the aluminium in the described organo-aluminium compound and the titanium in the described catalyzer is 20-1000: 1; More preferably, the mol ratio of the aluminium in the described organo-aluminium compound and the titanium in the described catalyzer is 50-500: 1.
Kind and the content of the external electron donor in the olefin polymerization catalysis of the present invention are not particularly limited.In the preferred case, the aluminium in the described organo-aluminium compound and the mol ratio of described external donor compound are 0.1-500: 1, and 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 the formula (IX),
R″
m′Si(OR″′)
4-m′ (IX)
In the formula (IX), R " a kind of in the haloalkyl that is 1-20 for halogen, hydrogen atom, carbonatoms are the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms; R " a kind of in the ' haloalkyl that is 1-20 for carbonatoms is the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl and carbonatoms; M ' is the integer of 1-3.Object lesson as described silicoorganic compound can be enumerated the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, Dicyclohexyldimethoxysilane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-at least a in the methyl dimethoxysilane etc.
According to olefine polymerizing process of the present invention, the method is included under the olefinic polymerization condition, and one or more alkene are contacted with above-mentioned catalyzer, and at least a in the described alkene is by general formula CH
2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.
Olefine polymerizing process of the present invention can be used for the equal polymerization of alkene, also can be used for multiple alkene is carried 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 olefinic polymerization condition can be the normal condition of this area.Usually, described olefinic polymerization condition comprises: temperature is 0-150 ℃, and the time is 0.1-5 hour, and pressure is 0.01-10MPa.Preferably, described olefinic polymerization condition comprises: temperature is 60-130 ℃, 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
Below in conjunction with embodiment the present invention is described in further detail.Be preferred implementation of the present invention only below, protection scope of the present invention is not limited to this, and any those skilled in the art can be easy to the change of carrying out or change be encompassed within protection scope of the present invention in technical scope disclosed by the 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 each embodiment the silicoorganic compound that use all available from ACROS or Sigma-Aldrich company; Anhydrous MgCl
2Available from Qinghai North Star Science and Technology Ltd.; TiCl
4Available from Xingtai non-ferrous metals smelting works; As the silicoorganic compound of external electron donor and as the organo-aluminium compound of promotor all available from Nanjing communications and liaison chemical industry company limited.
In following examples, the titanium atom content in solid ingredient a and the olefin polymerization catalyst components is according to the 721 spectrophotometers test available from An Hemeng (Tianjin) development in science and technology company limited; The melting index of polymkeric substance is to use the model available from the new experimental instrument and equipment in Changchun company limited to be the XRZ-00 fusion index instrument, and measures according to the method for stipulating among the GB/T3682-2000.
In following examples, the content of Siliciumatom is measured by following methods: use first Si in the Dutch PANalytical Axios-Advanced of the company type Xray fluorescence spectrometer analysis of catalyst, the relative content of Ti element, the titanium atom content root a tree name following formula that recycles above-mentioned spectrophotometer test calculates and gets:
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: the dry polymer samples of 2 grams, and be placed in the extractor and after 6 hours, residuum be dried to constant weight with the extracting of boiling heptane, calculate degree of isotacticity by following formula:
Polymer quality after degree of isotacticity (%)=extracting/2 * 100.
Polymer bulk density: polymer powders is dropped to the 100mL cylindrical vessel from funnel, and the quality m of polymkeric substance gram calculates polymer bulk density by following formula: tap density (BD)=m/100g/cm in this container of weighing
3
The preparation example
The preparation of alkoxyl magnesium:
In the 1L reactor with agitator, reflux condensing tube, thermometer and drop-burette, after fully replacing with nitrogen, in reactor, add ethanol 550mL, 10mL Virahol, iodine 0.68g dissolving.Heat up after opening stirring, until reach the reflux temperature of reaction system; Then add one by one magnesium powder 32g; Reaction is till no longer include hydrogen and discharge; Then wash, filter and drying, get tap density 0.25g/cm
3, alkoxyl magnesium 147 grams of median size (D50) 47.0 μ m.
Embodiment 1
The preparation of solid ingredient a1:
Get alkoxyl magnesium carrier 10 grams that make in the preparation example, toluene 50mL, n-butyl phthalate 2.5mL is mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension for preparing is added in the still, be warming up to 80 ℃, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature is clean with liquid (mother liquor) press filtration after 2 hours.Then the mixed solution that adds toluene 120mL and titanium tetrachloride 30mL is warming up to 110 ℃ of stir process 1 hour (titanium processing), so process 3 times, elimination liquid, the solid of gained washs 4 times with normal hexane 120mL at 50 ℃, elimination liquid is also dry, namely gets solid ingredient a1 of the present invention.Titanium content is 2.4wt% among the gained solid ingredient a1.
The preparation of olefin polymerization catalyst components A1:
Add 10 gram solid ingredient a1 in the 300mL reactor, add the 80mL normal heptane, be cooled to 0 ℃, add 3mL1,1,3,3-tetramethyl disiloxane stirs and forms suspension, is warming up to 70 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 4 times with normal heptane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component A1 that gets.Titanium atom content is 2.0wt% among the alkene catalyst component A1, and silicon atom content is 0.080wt%.
The polyolefine preparation:
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, hexane solution (concentration of CHMMS is 0.1mol/L), 10mL anhydrous hexane and the above-mentioned olefin polymerization catalyst components A1 for preparing of 6-10mg of 1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS).Close autoclave, introduce the hydrogen of 0.9 standard liter (NL) and the liquid propene of 2L; In under agitation 15 minutes temperature is risen to 70 ℃.After 70 ℃ of lower polyreaction 1-3 hours, 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 (kilogram)/alkene catalyst component A1 quality (g)
Comparative Examples 1
Use solid ingredient a1 replacement olefin polymerization catalyst components A1 among the embodiment 1, carry out polymerization according to process for preparing polyolefins among the 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 among the 10 gram embodiment 1 in the 300mL reactor, the 100mL normal hexane stirs and forms suspension, is warming up to 60 ℃, adds 3mL1,1,1,3,3-pentamethyl disiloxane, constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 4 times with normal hexane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component A2 that gets.Titanium atom content is 2.1wt% among the alkene catalyst component A2, and silicon atom content is 0.055wt%.
The polyolefine preparation:
Replace A1 with A2, carry out polymerization by process for preparing polyolefins among the 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 among the 10 gram embodiment 1 in the 300mL reactor, the 50mL normal hexane is cooled to 0 ℃, adds the stirring of 2mL four (dimethylsilyl) siloxanes and forms suspension, is warming up to 60 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.The gained solid has 50 ℃ with normal hexane 120mL washing 4 times, elimination liquid and dry alkene catalyst component A3.Titanium atom content is 2.0wt% among the alkene catalyst component A3, and silicon atom content is 0.100wt%.
The polyolefine preparation:
Replace A1 with A3, carry out polymerization by process for preparing polyolefins among the 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 among the 10 gram embodiment 1 in the 300mL reactor, the 100mL normal hexane stirs and forms suspension, is cooled to 0 ℃, adds 3mL1,1,1,3,5,5, the 5-heptamethyltrisiloxane is warming up to 60 ℃, and constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 4 times with normal hexane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component A4 that gets.Titanium atom content is 2.1wt% among the alkene catalyst component A4, and silicon atom content is 0.050wt%.
The polyolefine preparation:
Replace A1 with A4, carry out polymerization by process for preparing polyolefins among the 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 among the 10 gram embodiment 1 in the 300mL reactor, the 100mL normal hexane stirs and forms suspension, is warming up to 80 ℃, adds 3mL1,1,3,3,5,5-hexam ethylcyclotrisiloxane, constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 4 times with normal hexane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component A5 that gets.Titanium atom content is 2.0wt% among the alkene catalyst component A5, silicon atom content 0.080wt%.
The polyolefine preparation:
Replace A1 with A5, carry out polymerization by process for preparing polyolefins among the 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:
Add the solid ingredient a1 of preparation among the 10 gram embodiment 1 in the 300mL reactor, the 100mL normal hexane stirs and forms suspension, is warming up to 60 ℃, adds 0.5mL1,1,3,3-tetramethyl disiloxane, constant temperature 3 hours is then clean with the liquid press filtration.The gained solid has 50 ℃ with normal hexane 120mL washing 4 times, elimination liquid and dry alkene catalyst component A6.Titanium atom content is 2.2wt% among the alkene catalyst component A6, and silicon atom content is 0.032wt%.
The polyolefine preparation:
Replace A1 with A6, carry out polymerization by process for preparing polyolefins among the 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 alkoxyl magnesium carrier 10 grams that make in the preparation example, toluene 50mL, n-butyl phthalate 2.5mL is mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension for preparing is added in the still, be warming up to 80 ℃, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with liquid (mother liquor) press filtration.Then the mixed solution that adds toluene 120mL and titanium tetrachloride 30mL is warming up to 110 ℃ of stir process 1 hour, and elimination liquid is so processed 2 times; The mixed solution that adds again 120mL and titanium tetrachloride 30mL is warming up to 110 ℃, stirs to add simultaneously 2.0mL1, and 1,3,3-tetramethyl disiloxane continued the constant temperature stir process 1 hour, elimination liquid.The solid of gained washs 4 times with normal hexane 120mL at 50 ℃, and elimination liquid is also dry, namely gets solid ingredient A7 of the present invention.Titanium content is 3.0wt% among the gained solid ingredient A7, silicon atom content 0.160wt%.
The polyolefine preparation:
Replace A1 with A7, carry out polymerization by process for preparing polyolefins among the 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
The preparation of olefin polymerization catalyst components A8:
Get diethoxy magnesium carrier 10 grams that make in the preparation example, toluene 50mL, n-butyl phthalate 2.5mL is mixed with suspension; In the reactor of the 300mL that repeats to replace through high pure nitrogen, add toluene 30mL and titanium tetrachloride 120mL, then the suspension for preparing is added in the still, be warming up to 80 ℃, 1 hour follow-up continuing of constant temperature is warming up to 115 ℃, and constant temperature 2 hours is then clean with liquid (mother liquor) press filtration.Then the mixed solution that adds toluene 120mL and titanium tetrachloride 30mL is warming up to 110 ℃ of stir process 1 hour, and elimination liquid is so processed 3 times.The solid of gained washs 2 times with normal hexane 120mL at 50 ℃; Then add the 120mL hexane, be warming up to 60 ℃, add 3mL1,1,3,3-tetramethyl disiloxane, constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 2 times with normal hexane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component A8 that gets.Titanium atom content is 2.0wt% among the alkene catalyst component A8, silicon atom content 0.087wt%.
The polyolefine preparation:
Replace A1 with A8, carry out polymerization by process for preparing polyolefins among the embodiment 1.The polymerization activity of olefin polymerization catalyst components A8, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Comparative Examples 2
The preparation of olefin polymerization catalyst components D1:
Add the solid ingredient a1 of preparation among the 10 gram embodiment 1 in the 300mL reactor, the 100mL normal hexane stirs and forms suspension, is warming up to 60 ℃, adds the 3mL hexamethyldisiloxane, and constant temperature 2 hours is then clean with the liquid press filtration.The gained solid washs 4 times with normal hexane 120mL at 50 ℃, elimination liquid and the dry alkene catalyst component D1 that gets.Titanium atom content is 2.3wt% among the alkene catalyst component D1.
The polyolefine preparation:
Replace A1 with D1, carry out polymerization by process for preparing polyolefins among the embodiment 1.The polymerization activity of olefin polymerization catalyst components D1, melt index (MI), polymkeric substance degree of isotacticity (II) and polymer bulk density (BD) result are as shown in table 1.
Embodiment 9
The 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 for preparing among hexane solution (concentration is 0.1mmol/mL), 10mL anhydrous hexane and the 10mg embodiment 1 of hexane solution (concentration of triethyl aluminum is 0.5mmol/mL), 0.5mL diisopropyl dimethoxy silane of 2mL triethyl aluminum.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 ℃.After 60 ℃ of lower polyreaction 1-3 hours, 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 Examples 3
Use solid ingredient a1 replacement olefin polymerization catalyst components A1 among the embodiment 1, carry out polymerization according to preparation process for preparing polyolefins among the embodiment 9.(MI) result is as shown in table 1 for the 1-butylene polymerization activity of solid ingredient a1, the molten finger of polymkeric substance.
Table 1
As can be seen from Table 1, the olefin polymerization catalyst components olefin polymerization catalysis activity more prepared than undressed olefin polymerization catalyst components of processing through the silicoorganic compound b contact that contains Si-H functional group discharges more stable and uniform, the catalyzer hydrogen response is better, and the gross activity of catalyzer significantly improves, and polymer bulk density improves.
Claims (22)
1. catalyst component that is used for olefinic polymerization, this catalyst component is obtained after containing solid constituent a that magnesium, titanium, halogen and internal electron donor compound form and contacting suc as formula the silicoorganic compound b that contains Si-H functional group shown in (I) by a kind of,
In the formula (I), R
1For carbonatoms is the straight or branched saturated alkyl of 1-12, the alkaryl of the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or a kind of in the substituted arene base not; R
2, R
3, R
4, R
5Identical or different, the hydrogen of respectively doing for oneself, carbonatoms are the straight or branched saturated alkyl of 1-12, the cycloalkyl of carbonatoms 3-10, the alkaryl of carbonatoms 6-20, replacement or substituted arene base not, a kind of in the alkyl siloxy of the total number of carbon atoms 1-20; R
3, R
4, R
5Be not hydrogen atom simultaneously.
2. catalyst component according to claim 1 is characterized in that, the preparation method of described solid constituent a is with 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, the magnesium compound of described preparation solid constituent a is at least a in the alcohol adducts of the hydrate of the magnesium compound shown in the magnesium compound shown in the formula (II), the formula (II) and the magnesium compound shown in the formula (II)
MgR
6R
7 (II)
In the formula (II), R
6And R
7Respectively do for oneself halogen, carbonatoms is a kind of in the straight or branched alkoxyl group of 1-8 and the straight or branched alkyl that carbonatoms is 1-8.
4. catalyst component according to claim 3 is characterized in that, described magnesium compound is alkoxyl magnesium.
5. catalyst component according to claim 2 is characterized in that, the titanium compound of described preparation solid constituent a is that titanium compound is the compound shown in the formula (III),
TiX
m(OR
9)
4-m (III)
In the formula (III), X is halogen, R
9For 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 2 is characterized in that, the internal electron donor compound of described preparation solid constituent a is compound shown in the formula (IV):
In the formula (IV), R
13And R
14Identical or different, the carbonatoms of respectively doing for oneself is the alkaryl, replacement of the cycloalkyl of straight or branched alkyl, carbonatoms 3-10 of 1-12 and carbonatoms 6-20 or a kind of in the substituted arene base not; R
15, R
16, R
17And R
18All be hydrogen; Perhaps wherein three be hydrogen, another one is that halogen, carbonatoms are a kind of in the straight or branched alkyl of 1-4, the straight or branched alkoxyl group that carbonatoms is 1-4.
8. catalyst component according to claim 7, it is characterized in that described internal electron donor compound is at least a in diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, the dimixo-octyl phthalate.
9. the described catalyst component of any one in 8 according to claim 1 is characterized in that R among the described silicoorganic compound b
1Be the straight or branched saturated alkyl of 1-6 for carbonatoms; R
2Be the straight or branched saturated alkyl of carbonatoms 1-6, the total number of carbon atoms is a kind of in the alkyl siloxy of 1-12; R
3, R
4, R
5Be hydrogen, carbonatoms is the straight or branched saturated alkyl of 1-6, and the total number of carbon atoms is a kind of in the alkyl siloxy of 2-12.
10. catalyst component according to claim 9 is characterized in that, described silicoorganic compound b is selected from 1,1,1,3, the 3-pentamethyl disiloxane, 1,1,3,3-tetramethyl disiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, four (dimethylsilyl) siloxanes, 1,1,3,3,5,5-hexam ethylcyclotrisiloxane, three (dimethylsilyl bis) methyl-monosilane, 1,1,3,3-tetra isopropyl disiloxane, three (dimethylsilyl bis) phenyl siloxane.
11. the described catalyst component of any one in 8 is characterized in that the content of titanium atom is 1.0-8.0wt% in the described catalyst component according to claim 1; The content of magnesium atom is 10-70wt%; The content of halogen atom is 20-86wt%; Silicon atom content is 0.01-2wt%; The internal electron donor compounds content is 2-30wt%.
12. catalyst component according to claim 11 is characterized in that, the content of titanium atom is 1.6-4.0wt% in the described catalyst component; The content of magnesium atom is 15-40wt%; The content of halogen atom is 36-80%; Silicon atom content is 0.02-0.5wt%; The internal electron donor compounds content is 3-20wt%.
13. the preparation method such as catalyst component as described in any one among the claim 1-12 is characterized in that silicoorganic compound b forms with the solid ingredient a contact reacts that has prepared.
14. the preparation method such as catalyst component as described in any one among the claim 1-12 is characterized in that, in solid ingredient a preparation process, adds silicoorganic compound b reaction and forms; The preparation process of described solid ingredient a is divided into mother liquor formation, titanium treating processes and washing process three steps in chronological order successively; Described mother liquor forms to refer to magnesium compound is suspended in and forms suspension in the inert diluent, again this suspension is contacted to get the solids dispersion system with titanium compound, internal electron donor mixing, namely forms mother liquor; Described titanium treating processes refers to described mother liquor is filtered, and the gained solid matter is suspended in the solution that contains titanium tetrachloride and contacts processing; Described washing process refers to filter, wash gained solid matter in the previous step.
15. a preparation method as claimed in claim 14 is characterized in that, namely adds described silicoorganic compound b before the titanium treating processes after the mother liquor in solid ingredient a preparation forms.
16. a preparation method as claimed in claim 14 is characterized in that, adds described silicoorganic compound b in the titanium treating processes in solid ingredient a preparation.
17. a preparation method as claimed in claim 14 is characterized in that, adds described silicoorganic compound b in the washing process after the titanium in solid ingredient a preparation is processed.
18. a catalyzer that is used for olefinic polymerization comprises the described catalyst component of any one among the claim 1-12, also comprises the organo-aluminium compound as promotor, and external donor compound randomly.
19. catalyzer according to claim 18, it is characterized in that described organo-aluminium compound is at least a 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 ethyl aluminum chloride and the ethyl aluminum dichloride.
20. catalyzer according to claim 18, it is characterized in that, described external donor compound is the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, Dicyclohexyldimethoxysilane, diisopropyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-at least a in the methyl dimethoxysilane.
21. one kind such as the application of the described catalyzer of any one in the equal polymerization of alkene and copolymerization among the described catalyst component of any one or the claim 18-20 among the claim 1-12, at least a in the described alkene is by general formula CH
2The alkene that=CHR represents, wherein R is that hydrogen or carbonatoms are the alkyl of 1-6.
22. application according to claim 21, described alkene are ethene, propylene or 1-butylene.
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