CN100362026C - Process for producing catalyst for olefin polymerization and process for producing olefin polymer - Google Patents

Process for producing catalyst for olefin polymerization and process for producing olefin polymer Download PDF

Info

Publication number
CN100362026C
CN100362026C CNB2005100765470A CN200510076547A CN100362026C CN 100362026 C CN100362026 C CN 100362026C CN B2005100765470 A CNB2005100765470 A CN B2005100765470A CN 200510076547 A CN200510076547 A CN 200510076547A CN 100362026 C CN100362026 C CN 100362026C
Authority
CN
China
Prior art keywords
compound
solid catalyst
ingredient
titanium
polymkeric substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100765470A
Other languages
Chinese (zh)
Other versions
CN1690091A (en
Inventor
熊本伸一
佐藤淳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN1690091A publication Critical patent/CN1690091A/en
Application granted granted Critical
Publication of CN100362026C publication Critical patent/CN100362026C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

There are disclosed: (1) a process for producing a catalyst for olefin polymerization, which comprises the step of contacting with one another: (i) a solid catalyst component containing at least titanium, magnesium and halogen atoms, (ii) an organoaluminum compound, and (iii) a compound selected from the group consisting of (a) an oxygen-containing compound having a structure wherein at least two hydrocarbyloxy groups are bound to the same carbon atom, and (b) a cyclic ketone compound, and (2) a process for producing an olefin polymer, which comprises the step of polymerizing an olefin in the presence of the above-mentioned catalyst.

Description

The preparation method of catalyst for olefines polymerizing and the preparation method of olefin polymer
The present patent application is that application number is the dividing an application of application for a patent for invention of CN01116488.3 (applying date is March 28 calendar year 2001).
Invention field
The present invention relates to a kind of preparation method and a kind of method for preparing olefin polymer of catalyst for olefines polymerizing.
Background technology
From for example angle consideration of light transmission, shock resistance and anti stick of performance by the prepared film of ethene polymers, people wish to obtain a kind of ethene polymers with lower molecular weight component of low levels.
Just has the polymerizing catalyst of good catalytic efficiency, known catalyzer (for example contains (i) a kind of ingredient of solid catalyst that is made by the composition of specific magnesium compound and (ii) a kind of specific titanium compound, can be referring to JP-B46034092, JP-B47-41676, JP-B55-23561 and JP-B57-24361).But, consider that from the anti stick angle it is unsafty adopting the resulting ethene polymers of this class catalyzer.
And, just be used for preparing the polymerizing catalyst of highly crystalline propene polymer, known catalyzer contains a kind of positro that contains of a kind of employing (for example gives the prepared ingredient of solid catalyst of body as the inherence for body such as ester, can be referring to JP-B52-39431, JP-B52-36786, JP-B1-28049 and JP-B3-43283).But, consider that from the anti stick angle multipolymer that adopts resulting ethene of this class catalyzer and alpha-olefin also is unsafty.
In addition, JP-A11-80234 and JP-A11-322833 disclose a kind of ethylene polymerization catalyzer, and it can prepare the ethene polymers of the lower molecular weight component with low levels.But, consider that from the angle that improves the vinyl polymerization amount people expect a kind of more ethene polymers of the lower molecular weight component of low levels that has.
Summary of the invention
An object of the present invention is to provide a kind of preparation method of catalyst for olefines polymerizing, it can make the olefin polymer of the lower molecular weight component with low levels.
Another object of the present invention provides a kind of preparation method of olefin polymer of the lower molecular weight component with low levels.
The invention provides a kind of preparation method of catalyst for olefines polymerizing, it comprises the step that is in contact with one another of following substances:
(i) a kind of ingredient of solid catalyst that contains titanium, magnesium and halogen atom at least,
(ii) a kind of organo-aluminium compound and
(iii) a kind of compound is selected from and contains oxygenatedchemicals that at least two-oxyls are connected with same carbon atom and (b) a kind of cyclic ketones compound in (a) a kind of its structural formula.
The present invention also provides a kind of method for preparing olefin polymer, and it comprises the steps:
(1) following material is in contact with one another, (i) a kind of ingredient of solid catalyst that contains titanium, magnesium and halogen atom at least, (ii) a kind of organo-aluminium compound, (iii) a kind of compound, be selected from and contain oxygenatedchemicals that at least two-oxyls are connected with same carbon atom and (b) a kind of cyclic ketones compound in (a) a kind of its structural formula, thereby make olefin polymerization catalysis and
(2) in the presence of resulting olefin polymerization catalysis, carry out olefinic polymerization, make olefin polymer.
Embodiment
Oxygenatedchemicals
" oxygenatedchemicals " that is adopted among the present invention is meant and contains the compound that at least two-oxyls are connected with same carbon atom in its structural formula.The preferred embodiment of described-oxyl is alkoxyl group, aralkoxy and aryloxy.In these groups, be more preferably alkoxyl group, be preferably methoxyl group especially.Preferred oxygenatedchemicals is for having the compound that two above-mentioned-oxyls of mentioning are connected with same carbon atom in its structural formula.
More preferred oxygenatedchemicals can be represented with following structural formula:
Figure C20051007654700051
Wherein, R 1And R 2Each is hydrogen atom or the alkyl with 1-20 carbon atom independently, R 1And R 2Can be interconnected to form is a ring, R 3And R 4Each is independently for having the alkyl of 1-20 carbon atom.
For R 1, R 2, R 3And R 4, alkyl, aryl and aralkyl are preferred.
The specific examples of described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, isobutyl-, n-pentyl, neo-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, Pentadecane base, NSC 62789 base, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and suberyl.In these groups, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, cyclopentyl and cyclohexyl are preferred.
The above-mentioned alkyl of mentioning can be replaced by halogen atom such as fluorine, chlorine, bromine and iodine atom.The specific examples of the described alkyl that is replaced by halogen atom has the fluoro methyl, difluoromethyl, trifluoromethyl, the chloro methyl, dichloromethyl, trichloromethyl, bromomethyl, two brooethyls, trisbromomethyl, iodo-methyl, diiodomethyl, three iodomethyls, the fluoro ethyl, two fluoro ethyls, trifluoroethyl, the tetrafluoro ethyl, pentafluoroethyl group, the chloro ethyl, Dichloroethyl, three chloroethyls, the tetrachloro ethyl, the pentachloro-ethyl, bromoethyl, two bromotrifluoromethanes, three bromomethyl, the tetrabromo ethyl, the pentabromo-ethyl, perfluoro propyl, perfluoro butyl, the perfluor amyl group, perfluoro hexyl, perfluoro capryl, the perfluor dodecyl, the perfluor pentadecyl, the perfluor eicosyl, the perchloro-propyl group, the perchloro-butyl, the perchloro-amyl group, the perchloro-hexyl, the perchloro-octyl group, the perchloro-dodecyl, the perchloro-pentadecyl, the perchloro-eicosyl, the perbromo-propyl group, the perbromo-butyl, the perbromo-amyl group, the perbromo-hexyl, the perbromo-octyl group, the perbromo-dodecyl, perbromo-pentadecyl and perbromo-eicosyl.
With regard to the above-mentioned aryl of mentioning, be preferably aryl with 6-20 carbon atom.The specific examples of described aryl is a phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 3-xylyl, 2, the 4-xylyl, 2, the 5-xylyl, 2, the 6-xylyl, 3, the 4-xylyl, 3, the 5-xylyl, 2,3, the 4-trimethylphenyl, 2,3, the 5-trimethylphenyl, 2,3, the 6-trimethylphenyl, 2,4, the 6-trimethylphenyl, 3,4, the 5-trimethylphenyl, 2,3,4, the 5-tetramethylphenyl, 2,3,4, the 6-tetramethylphenyl, 2,3,5, the 6-tetramethylphenyl, the penta-methyl benzene base, the ethylbenzene base, the n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, the n-pentyl phenyl, the neo-pentyl phenyl, the n-hexyl phenyl, the n-octyl phenyl, positive decyl phenyl, the dodecyl phenyl, n-tetradecane base phenyl, naphthyl and anthryl.In these groups, phenyl is more preferred.
Described aryl can partly be replaced by halogen atom such as fluorine, chlorine, bromine and iodine atom.
With regard to the above-mentioned aralkyl of mentioning, preferably has the aralkyl of 7-20 carbon atom.The specific examples of these aralkyl has phenmethyl, (2-tolyl) methyl, (3-tolyl) methyl, (4-tolyl) methyl, (2, the 3-xylyl) methyl, (2, the 4-xylyl) methyl, (2, the 5-xylyl) methyl, (2, the 6-xylyl) methyl, (3, the 4-xylyl) methyl, (3, the 5-xylyl) methyl, (2,3, the 4-trimethylphenyl) methyl, (2,3, the 5-trimethylphenyl) methyl, (2,3, the 6-trimethylphenyl) methyl, (3,4, the 5-trimethylphenyl) methyl, (2,4, the 6-trimethylphenyl) methyl, (2,3,4, the 5-trimethylphenyl) methyl, (2,3,4, the 6-trimethylphenyl) methyl, (2,3,5, the 6-trimethylphenyl) methyl, (penta-methyl benzene base) methyl, (ethylbenzene base) methyl, (n-propyl phenyl) methyl, (isopropyl phenyl) methyl, (n-butylphenyl) methyl, (secondary butyl phenenyl) methyl, (tert-butyl-phenyl) methyl, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, (n-tetradecane base phenyl) methyl, menaphthyl, the anthracene methyl.In these groups, phenmethyl is more preferred.
Described aralkyl can partly be replaced by halogen atom such as fluorine, chlorine, bromine and iodine atom.
With regard to R 1And R 2, hydrogen atom and methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclopentyl and cyclohexyl are preferred.
Work as R 1And R 2When being interconnected to form ring, preferred ring structure is suberane ring structure or cyclohexane ring structure.
With regard to R 3And R 4, methyl and hexyl are preferred, and methyl is particularly preferred.
The example of oxygenatedchemicals has Methylal(dimethoxymethane), methylene diethyl ether, two (positive propoxy) methane, two (isopropoxy) methane, two (n-butoxy) methane, hexichol oxygen methylmethane, 1, the 1-glycol dimethyl ether, 1, the 1-Propanal dimethyl acetal, 1, the 1-dimethoxy-butane, the propionic aldehyde dimethylacetal, the 2-methyl isophthalic acid, the 1-Propanal dimethyl acetal, 2,2-dimethyl-1, the 1-Propanal dimethyl acetal, the 3-methyl isophthalic acid, the 1-Propanal dimethyl acetal, 3,3-dimethyl-1, the 1-Propanal dimethyl acetal, 1, the 1-dimethoxy-butane, 1,1-dimethoxy pentane, the n-octaldehyde dimethylacetal, the phenyl aldehyde dimethylacetal, the phenylacetic aldehyde dimethylacetal, 2, the 2-Propanal dimethyl acetal, 2, the 2-dimethoxy-butane, 3-methyl-2, the 2-dimethoxy-butane, 3,3-dimethyl-2, the 2-dimethoxy-butane, 2,2-dimethoxy pentane, 2,2-dimethoxy octane, 2,2-dimethoxy decane, 3,3-dimethoxy pentane, 4-methyl-3,3-dimethoxy pentane, 4,4-dimethyl-3,3-dimethoxy pentane, 2,4-dimethyl-3,3-dimethoxy pentane, 2,2,4,4-tetramethyl--3,3-dimethoxy pentane, 3,3-dimethoxy hexane, 5-methyl-3,3-dimethoxy hexane, 5,5-dimethyl-3,3-dimethoxy hexane, 3,3-dimethoxy pentane, 3,3-dimethoxy decane, the phenylbenzene Methylal(dimethoxymethane), dicyclopentyl dimethoxyl methane, the dicyclohexyl Methylal(dimethoxymethane), 1-phenyl-1, the 1-glycol dimethyl ether, 1-cyclopentyl-1, the 1-glycol dimethyl ether, 1-cyclohexyl-1, the 1-glycol dimethyl ether, 1-cyclohexyl-1, the 1-Propanal dimethyl acetal, 1-cyclohexyl-2-methyl isophthalic acid, the 1-Propanal dimethyl acetal, 1-cyclohexyl-2,2-dimethyl-1, the 1-Propanal dimethyl acetal, trimethoxy-methane, 1,1, the 1-trimethoxy-ethane, 1,1, the 2-trimethoxy-ethane, 1,1,1-trimethoxy propane, 1,1,2-trimethoxy propane, 1,1,3-trimethoxy propane, 1,1,1-trimethoxy pentane, 1,1,2,2-tetramethoxy ethane, 1,1,3, the 3-tetramethoxy propane, the 2-methyl isophthalic acid, 1,3, the 3-tetramethoxy propane, 2,2-dimethyl-1,1,3, the 3-tetramethoxy propane, 1,1-dimethoxy tetramethylene, 1,1-dimethoxy pentamethylene, 1,1-dimethoxy hexanaphthene, 1,1,2-trimethoxy hexanaphthene, 1,1,2,2-tetramethoxy hexanaphthene and 1,1,3,3-tetramethoxy hexanaphthene.
With regard to described oxygenatedchemicals, radical of saturated aliphatic ketone and be more preferred by radical of saturated aliphatic aldehyde and pure resulting acetal.In these compounds, radical of saturated aliphatic ketone and be particularly preferred by radical of saturated aliphatic aldehyde and the resulting acetal of methyl alcohol.Especially, Methylal(dimethoxymethane), 1,1-glycol dimethyl ether, propionic aldehyde dimethylacetal, n-octaldehyde dimethylacetal, 2,2-Propanal dimethyl acetal, 3,3-dimethoxy hexane and 1,1-dimethoxy hexanaphthene is preferred.
The consumption of described oxygenatedchemicals with respect to every mole titanium atom meter in the ingredient of solid catalyst, is generally the 1-2000 mole, is preferably the 5-1000 mole especially.And with respect to every moles, of aluminum per mole of titanium metal atom meter in the organo-aluminium compound, the consumption of described oxygenatedchemicals is generally the 0.001-10 mole, is preferably the 0.01-5 mole especially.
The cyclic ketones compound
" the cyclic ketones compound " that adopted among the present invention is meant the compound that contains carbonyl in its carbocyclic ring.Described ring can be saturated or the unsaturated aliphatic ring, also can be saturated or unsaturated aromatic ring.Described ring can be monocycle, also can be many rings.3-10 unit ring is preferred, and 5-8 unit ring is more preferred.
The specific examples of described cyclic ketones compound can be represented with following structural formula.
Figure C20051007654700091
In above-mentioned structural formula, X is hydrogen atom, alkyl,-oxyl or the amino that replaced by two alkyl.Each X in the molecular formula can interconnect.Another replacement scheme is, can be those be selected from the above-mentioned compound of mentioning that compound obtains at their the mutual bonding in X position by two or more to described cyclic ketones compound.
Particularly preferred cyclic ketones compound is 1,4-cyclohexanedione, hydroresorcinol, 1,2-cyclohexanedione and 1,4-benzoquinones.
The consumption of described cyclic ketones compound with respect to every mole titanium atom meter in the ingredient of solid catalyst, is generally the 1-2000 mole, is preferably the 5-1000 mole especially.And, described cyclic ketones compound, with respect to every moles, of aluminum per mole of titanium metal atom meter in the organo-aluminium compound, its consumption is generally the 0.001-10 mole, is preferably the 0.01-5 mole especially.
Ingredient of solid catalyst
Be used for ingredient of solid catalyst of the present invention, can be any contain titanium, magnesium and halogen atom oneself know ingredient of solid catalyst.
The example is for being disclosed in JP-B 46-34092, JP-B 47-41676, JP-B 55-23561, JP-B 57-24361, JP-B 52-39431, JP-B 52-36786, JP-B 1-28049, JP-B 3-43283, JP-A 4-80044, JP-A 55-52309, JP-A 58-21405, JP-A 61-181807, JP-A 63-142008, JP-A 5-339319, JP-A 54-148093, JP-A 4-227604, JP-A 6-2933, JP-A 64-6006, JP-A 6-179720, JP-B7-116252, JP-A 8-134124, JP-A 9-31119, JP-A 11-228628, those among JP-A 11-80234 and the JP-A11-322833.
With regard to described ingredient of solid catalyst, be preferably those also contain electron donor(ED) except titanium, magnesium and halogen atom catalyst component.
With regard to the preparation method of described ingredient of solid catalyst, as an example, can list following method (1)-(5):
Method (1) comprises the step that a kind of halogenated magnesium compound and a kind of titanium compound are in contact with one another;
Method (2) comprises the step that a kind of halogenated magnesium compound, a kind of electron donor(ED) and a kind of titanium compound are in contact with one another;
Method (3) is included in a kind of electron donor(ED) solvent a kind of halogenated magnesium compound of dissolving and a kind of titanium compound obtaining a kind of solution, and adopts the step of this solution impregnating carrier;
Method (4) comprises the step that a kind of dialkoxy magnesium compound and a kind of halogenated titanium compound are in contact with one another; With
Method (5) comprises making that (a) a kind of solid catalyst component precursor, (b) that contains magnesium atom, titanium atom and-oxyl is a kind of to have the halogenated compound of halogenation ability and (c) step that is in contact with one another of a kind of electron donor(ED).
In these methods, method (5) is preferred.
Preferred solid catalyst component precursor is the following solid phase prod of mentioning (1) and (2):
(1) by in the presence of a kind of silicoorganic compound with Si-O key, the resulting solid phase prod of titanium compound that adopts the organo-magnesium compound reduction to represent with following structural formula,
Ti(OR 1) aX 4-a
Wherein, R 1For having the alkyl of 1-20 carbon atom, X is a halogen atom, " a " for the numerical value (referring to JP-A 11-80234) that satisfies 0＜a≤4 and
(2) by in the presence of a kind of silicoorganic compound and porous support with Si-O key, the resulting solid phase prod of titanium compound (referring to JP-B 4-57685) that adopts the organo-magnesium compound reduction to represent with above-mentioned structural formula.
R in the said structure formula 1Example alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, heptyl, octyl group, decyl and dodecyl are arranged; Aryl such as phenyl, tolyl, xylyl and naphthyl; Cycloalkyl such as cyclohexyl and cyclopentyl; Thiazolinyl such as allyl group; With aralkyl such as phenmethyl.In these groups, the aryl that has the alkyl of 2-18 carbon atom and have a 6-18 carbon atom is preferably, and the straight chained alkyl with 2-18 carbon atom is particularly preferred.When " a " in the said structure formula is that titanium compound can be a kind of two or more (OR that differ from one another that have when satisfying the numerical value of 2≤a≤4 1) basic compound.
X in the said structure formula as an example, can be chlorine atom, bromine atoms and iodine atom.In these atoms, the chlorine atom is particularly preferred.
" a " in the said structure formula is preferably the numerical value that satisfies 2≤a≤4, and particularly preferred " a " is 4.
The titanium compound of representing with above-mentioned structural formula can prepare according to traditional method, and for example, method (i) comprises making Ti (OR 1) 4With TiX 4Step of reacting with predetermined proportion and method (ii) comprise making correspondent alcohol such as R 1OH and TiX 4The step of reacting with predetermined proportion.
With regard to the above-mentioned silicoorganic compound of mentioning with Si-O key, the compound that preferably can be represented by the formula:
Si(OR 3) bR 4 4-b，
R 5(R 6 2SiO) cSiR 7 3Or
(R 8 2SiO) d
In following formula, R 3For having the alkyl of 1-20 carbon atom, R 4, R 5, R 6, R 7And R 8For having the alkyl or the hydrogen atom of 1-20 carbon atom, " b " for satisfying the numerical value of 0＜b≤4, " c " is an integer among the 1-1000 by oneself for each, and " d " is an integer among the 2-1000.
The specific examples of the silicoorganic compound of being represented by following formula has tetramethoxy-silicane, dimethyldimethoxysil,ne, tetraethoxysilane, triethoxy ethyl silane, the diethoxy diethylsilane, ethoxy triethyl silane, tetraisopropoxysilan, diisopropoxy di-isopropyl silane, tetrapropoxysilane, dipropoxy dipropyl silane, four butoxy silanes, dibutoxy dibutyl silane, two cyclopentyloxy diethylsilanes, the diethoxy diphenyl silane, the cyclohexyloxy trimethyl silane, the benzyloxy trimethyl silane, tetraphenoxy-silicane alkane, triethoxyphenylsilan, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, the octaethyl trisiloxanes, dimethyl polysiloxane, the phenylbenzene polysiloxane, hydrogenated methyl polysiloxane and phenyl hydrogenation polysiloxane.
In these silicoorganic compound of representing by following formula, more preferably can be by general formula Si (OR 3) bR 4 4-bThe alkoxysilane compound containing trialkylsilyl group in molecular structure of expression.In the formula, " b " is preferably the numerical value that satisfies 1≤b≤4.In these compounds, the tetraalkoxysilane compounds during b=4 is particularly preferred.
With regard to the above-mentioned organo-magnesium compound of mentioning, the organo-magnesium compound with magnesium-carbon bond of any kind all can adopt.Grignard compound that is expressed from the next and the dialkyl magnesium compound that is expressed from the next are particularly preferred.
R 9MgX
R 10R 11Mg
In following formula, Mg is a magnesium atom, R 9For having the alkyl of 1-20 carbon atom, X is a halogen atom, R 10And R 11Each is independently for having the alkyl of 1-20 carbon atom, R 10And R 11Each other can be identical, also can be different.
R 9, R 10And R 11Specific examples for all having alkyl, aryl, aralkyl and the thiazolinyl of 1-20 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isopentyl, hexyl, octyl group, 2-ethylhexyl, phenyl and phenmethyl.Consider the Grignard compound that special recommendation adopts the following formula of the form that is its ethereal solution to represent from the catalyst efficiency angle.
Above-mentioned organo-magnesium compound also can be used to and a kind of organometallic compound combination, forms a kind of title complex that dissolves in hydrocarbon.The example of described organometallic compound has Li, Be, B, the compound of Al or Zn.
Above-mentioned porous support can be traditional carrier.The example of described porous support is porous inorganic oxide such as SiO 2, Al 2O 3, MgO, TiO 2And ZrO 2With organic porous polymer such as polystyrene, styrene diethylene benzene copoly mer, vinylbenzene-ethylene glycol-methyl methacrylate multipolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinyl benzene copolymer, polymethylmethacrylate, methyl methacrylate-divinyl benzene copolymer, polyacrylonitrile, vinyl cyanide-divinyl benzene copolymer, polyvinyl chloride, polyethylene and polypropylene.In these materials, organic porous polymer is preferred, and styrene diethylene benzene copoly mer and vinyl cyanide-divinyl benzene copolymer are particularly preferred.
About described porous support, (i) volume of the micropore of radius between the 200-2000 dust is preferably 0.3cc/g or bigger, 0.4cc/g or bigger more preferably, if (ii) the amount of the micropore of radius between the 35-75000 dust is 100%, then the amount of the micropore of radius between the 200-2000 dust is preferably 35% or bigger, and more preferably 40% or bigger.Do not recommend to adopt porous support, because catalyst component can not load on this carrier effectively with too small micropore volume.Simultaneously, even a kind of porous support has 0.3cc/g or bigger micropore volume, if but this porous support does not satisfy its pore radius between the 200-2000 dust, and catalyst component can not load on this carrier effectively.
As for the method that adopts organo-magnesium compound reduction titanium compound, method as an example has; Method (1) comprises the step that is added dropwise to organo-magnesium compound in the mixture of described titanium compound and silicoorganic compound; Method (2) comprises the step that dropwise adds the mixture of titanium compound and silicoorganic compound in described organo-magnesium compound.In these methods, porous support can adopt simultaneously.
Described titanium compound and silicoorganic compound are preferably dissolved in a kind of solvent or with solvent and dilute.The example of described solvent has aliphatic hydrocrbon such as hexane, heptane, octane and decane; Aromatic hydrocarbons such as toluene and dimethylbenzene; Alicyclic hydrocarbon such as hexanaphthene, methylcyclohexane and naphthalane; With ether compound such as Anaesthetie Ether, dibutyl ether, diisoamyl ether and tetrahydrofuran (THF).
Reduction reaction temperature is usually between-50 to 70 ℃, preferably at-30 to 50 ℃, particularly preferably in-25 to 35 ℃.The dropping time is unqualified, and it is usually between 30 minutes to 6 hours.After under described temperature, reacting, can allow under 20 to 120 ℃ temperature, further to carry out afterreaction.
The consumption of described silicoorganic compound represents that with the Si/Ti atomic ratio (being the Siliciumatom in the silicoorganic compound and the ratio of the titanium atom in the titanium compound) is generally 1-500, is preferably 1-300, is preferably 3-100 especially.
The consumption of described organo-magnesium compound, represent that with (Si+Ti)/Mg atomic ratio (being the titanium atom in the titanium compound and the summation of the Siliciumatom in the silicoorganic compound and the ratio of the magnesium atom in the organo-magnesium compound) is generally 0.1-10, be preferably 0.2-5.0, be preferably 0.5-2.0 especially.
Each plant demand of the titanium compound that adopts, silicoorganic compound and organo-magnesium compound, should make the Mg/Ti atomic ratio in the ingredient of solid catalyst is 1-51, is preferably 2-31, is preferably 4-26 especially.
By the resulting solid phase prod of reduction reaction, normally separate and carry out isolatingly by solid-liquid, and it is done repeatedly washing with a kind of inert hydrocarbon solvent such as hexane and heptane.Contain titanous atom, magnesium atom and-oxyl through this solid phase prod that obtains, it generally shows amorphous or ultralow crystal property.Consider that from the catalyst efficiency angle solid phase prod with amorphous structure is particularly preferred.
As for described halogenated compound, be preferably the compound that those can replace the-oxyl of solid catalyst precursor with halogen atom with halogenation ability.Particularly preferably, be the halogenated compound of the 4th family's element, the halogenated compound of the 13rd family's element and the halogenated compound of the 14th family's element.
With regard to described the 4th family's element halogenated compound, be preferably the halogenated compound of titanium.Its concrete example has halogenated titanium, halo titanium oxide and halo titanium acid amides (titanium amide).
With regard to the described the 13rd or 14 family's element halogenated compounds, be preferably the compound that those can be expressed from the next:
MR m-aX a
Wherein, M is a kind of atom that belongs to the 13rd or the 14th family, and R is a kind of alkyl with 1-20 carbon atom, and X is a kind of halogen atom, and m is the valency of M, and " a " is for satisfying the numerical value of 0＜a≤m.
The example that belongs to the 13rd family's atom is B, Al, Ga, In and Tl.In these atoms, B and Al are preferred, and Al is more preferred.The example that belongs to the 14th family's atom is C, Si, Ge, Sn and Pb.In these atoms, Si, Ge and Sn are preferred, and Si and Sn are more preferred.When M was Si, m was 4, and " a " is preferably 3 or 4.
X is F, Cl, and Br and I, in these atoms, Cl is preferred.
The example of R has alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, isopentyl, hexyl, heptyl, octyl group, decyl and dodecyl; Aryl such as phenyl, tolyl, cresyl, xylyl and naphthyl; Cycloalkyl such as cyclohexyl and cyclopentyl; Thiazolinyl such as allyl group; With aralkyl such as phenmethyl.
Preferred R is an alkyl or aryl in the following formula, and particularly preferred R is methyl, ethyl, n-propyl, amyl group or p-methylphenyl.
The specific examples of the chlorinated compound of the 13rd family's element is a boron trichloride, methyl dichloro boron, ethyl dichloride boron, phenyl dichloride boron, cyclohexyl dichloride boron, dimethyl chlorination boron, the methylethyl boron chloride, aluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, the phenyl al dichloride, the cyclohexyl al dichloride, dimethylaluminum chloride, diethyl aluminum chloride, methylethyl aluminum chloride, the sesquialter ethylaluminium chloride, gallium chloride, gallium dichloride, gallium trichloride, the methyl dichloro gallium, the ethyl gallium dichloride, the phenyl gallium dichloride, the cyclohexyl gallium dichloride, dimethyl chlorination gallium, the methylethyl gallium chloride, indium chloride, Indium-111 chloride, the dichloromethyl indium, the dichlorophenyl indium, chlorination dimethyl indium, thallium chloride, thallium trichloride, the dichloromethyl thallium, dichlorophenyl thallium and chlorination dimethyl thallium; The compound of being named with substituting by F, Br or I by chlorine in the above-mentioned given compound.
The specific examples of the chlorinated compound of the 14th family's element has tetrachloromethane, trichloromethane, methylene dichloride, monochloro methane, 1,1, the 1-trichloroethane, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1,2, the 2-tetrachloroethane, tetrachloro silicane, trichlorosilane, METHYL TRICHLORO SILANE, ethyl trichlorosilane, n-propyltrichlorosilan, the normal-butyl trichlorosilane, phenyl-trichloro-silicane, the phenmethyl trichlorosilane, the p-methylphenyl trichlorosilane, the cyclohexyl trichlorosilane, dichlorosilane, dimethyl dichlorosilane (DMCS), ethyl dichlorosilane, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, the methylethyl dichlorosilane, one chlorosilane, trimethylchlorosilane, tri-phenyl chloride, the tetrachloro germane, the trichlorine germane, methyl trichlorine germane, ethyl trichlorine germane, phenyl trichlorine germane, the dichloro germane, dimethyl dichloro germane, diethyl dichloro germane, phenylbenzene dichloro germane, one chlorine germane, trimethylammonium chlorine germane, triethyl chlorine germane, three n-butyl chloride germanes, tin tetrachloride, the methyl tin trichloride, the normal-butyl tin trichloride, dimethyltin chloride, di-n-butyl tin dichloride, the diisobutyl tindichloride, the phenylbenzene tindichloride, the divinyl tindichloride, the methyl tin trichloride, the phenyl tin trichloride, lead dichloride, methyl lead chloride and phenyl lead chloride; The compound of being named with substituting by F, Br or I by chlorine in the above-mentioned given compound.
With regard to described halogenated compound, consider that from the polymerization activity angle titanium tetrachloride, methylaluminum dichloride, ethylaluminum dichloride, tetrachloro silicane, phenyl-trichloro-silicane, METHYL TRICHLORO SILANE, ethyl trichlorosilane, n-propyltrichlorosilan and tin tetrachloride are particularly preferred.
With regard to described halogenated compound, above-mentioned given compound can singlely use, but also two or more are used in combination.
With regard to described electron donor(ED), have as an example: oxygenatedchemicals is as alcohol, phenol, ketone, aldehyde, carboxylic acid, organic acid acetic, inorganic acid ester, ether, acid amides and acid anhydrides; With nitrogenous compound such as ammonia, amine, nitrile and isocyanic ester.In these compounds, organic acid acetic and ether are preferred.
With regard to described organic acid acetic, single carboxylicesters and polycarboxylate are preferred.The example of described carboxylicesters has saturated aliphatic carboxylic acid ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid ester.
Described carboxylicesters specific examples has: methyl acetate, ethyl acetate, the acetate phenylester, methyl propionate, the propionic acid ethyl ester, the butyric acid ethyl ester, the valeric acid ethyl ester, methyl acrylate, the vinylformic acid ethyl ester, methyl methacrylate, the phenylformic acid ethyl ester, the phenylformic acid butyl ester, the toluic acid methyl ester, the toluic acid ethyl ester, the anisic acid ethyl ester, the Succinic Acid diethyl ester, Succinic Acid dibutyl ester, the propanedioic acid diethyl ester, propanedioic acid dibutyl ester, the toxilic acid dimethyl esters, toxilic acid dibutyl ester, the methylene-succinic acid diethyl ester, methylene-succinic acid dibutyl ester, phthalic acid list ethyl ester, the phthalic acid dimethyl esters, phthalic acid methylethyl ester, the phthalic acid diethyl ester, phthalic acid di ester, the phthalic acid diisopropyl ester, phthalic acid di-n-butyl ester, phthalic acid diisobutyl ester, phthalic acid two (2-ethylhexyl) ester, phthalic acid di-n-octyl ester and phthalic acid diphenyl.
With regard to preferred ether, have as an example: dialkyl ether and the diether compounds that is expressed from the next:
Wherein, R 22-R 25Each is alone to have all nearly alkyl, the aryl or aralkyl of 20 carbon atoms, and R 22And R 23Can be alone hydrogen atom.
The specific examples of described ether has: dimethyl ether, Anaesthetie Ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methylcyclohexyl ether, 2,2-dimethyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-di-n-butyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2-ethyl-2-butyl-1, the 3-Propanal dimethyl acetal, 2-n-propyl-2-cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dimethyl-1,3-di ethyl propyl ether and 2-n-propyl-2-cyclohexyl-1,3-di ethyl propyl ether.
Especially, with regard to described electron donor(ED), organic acid acetic is preferred, and the aromatic dicarboxylic acid dialkyl is particularly preferred, and the phthalic acid dialkyl is highly preferred.
Above-mentioned given compound can use separately also can two or more combinations be used as electron donor(ED).
Described solid catalyst component precursor, halogenated compound and electron donor(ED) can traditional method be in contact with one another, for example the mechanical crushing method of slurry process and employing ball mill.But this mechanical crushing method is considered to be unworthy recommending from the industrial production angle, and this is because may make many ultrafine powder, thereby makes the size-grade distribution of resulting ingredient of solid catalyst broaden.Therefore, recommendation is in the presence of the following medium of mentioning they to be in contact with one another.
Described medium is preferably a kind ofly has pending component to be the inert compound for above-mentioned.The example of described medium has: aliphatic hydrocarbon such as pentane, hexane, heptane and octane; Aromatic hydrocarbons such as benzene, toluene and dimethylbenzene; Alicyclic hydro carbons such as hexanaphthene and pentamethylene; With halohydrocarbon as 1,2-ethylene dichloride and monochloro benzene.Especially, consider that from resulting polymerization catalyst reactive behavior angle aliphatic hydrocarbon is preferred.
Consumption for described medium is not done special qualification.But, consider from the production efficiency angle of catalyzer, adopt excessive medium and inadvisable.With respect to every gram solid catalyst component precursor meter, its consumption is generally 0.1-1000ml, is preferably 0.5-20ml, is preferably 1-5ml especially.
But be used for follow-up processing via the solid former state ground that described contact action obtains.But, is to adopt a kind of washing composition that it is carried out the washing of arbitrary number of times be worth recommending, thereby removes the impurity that is contained among the solid.
With regard to described washing composition, those remain to be washed solid to be the inert material are preferred described, and those also can adopt to above-mentioned enumerating as the similar material of the compound of medium.
Its consumption of described washing composition with respect to every gram solid catalyst component precursor meter, is generally 0.1-1000ml, is preferably 1-100ml.
Described contact and washing are normally carried out under-50-150 ℃ temperature, and preferred temperature is 0-140 ℃, more preferably 60-135 ℃.To not being particularly limited duration of contact.Be preferably 0.5-8 hour, more preferably 1-6 hour.Washing time is not particularly limited yet.Be preferably 1-120 minute, more preferably 2-60 minute.
How to contact as for described solid catalyst component precursor, halogenated compound and electron donor(ED), do not limit.As its example, can exemplify following method (1) and (2):
Method (1), comprise make step that described solid catalyst component precursor, halogenated compound and electron donor(ED) contact simultaneously mutually and
Method (2) comprises the step that described halogenated compound and electron donor(ED) are contacted with described solid catalyst component precursor one by one.
When stating method (1) on the implementation, as example can exemplify following method (i) to method (v), method wherein (i) is preferred:
Method (i) comprises that the mixture that adds halogenated compound and electron donor(ED) in described solid catalyst component precursor is to realize their step that contacts.
Method (ii) comprises described solid catalyst component precursor is joined the mixture of halogenated compound and electron donor(ED) to realize their step that contacts.
Method (iii) comprises adding halogenated compound and electron donor(ED) successively to realize their step that contacts in described solid catalyst component precursor.
Method (iv) comprises adding electron donor(ED) and halogenated compound successively to realize their step that contacts in described solid catalyst component precursor.
Method (v), comprises and adds halogenated compound and electron donor(ED) simultaneously to realize their step that contacts in described solid catalyst component precursor.
During the method for stating on the implementation (2),, can exemplify following method (i) and method (ii) as example:
Method (i) may further comprise the steps: in described solid catalyst component precursor, adds halogenated compound, obtains a kind of contact product, wash this product, then add electron donor(ED) in the contact product after washing, thus complete operation; With
Method (ii) may further comprise the steps: in described solid catalyst component precursor, adds electron donor(ED), obtains a kind of contact product, wash this product, then add halogenated compound in the contact product after washing, thus complete operation.
Another kind of replacement scheme is, can adopt and implement described contact in such a way, described solid catalyst component precursor, halogenated compound and electron donor(ED) are in contact with one another, make at least a contact the in resulting contact product and halogenated compound and the electron donor(ED) then.
With regard to the special preferred method that described solid catalyst component precursor, halogenated compound and electron donor(ED) are contacted, can list following method (1) to method (8):
Method (1) may further comprise the steps: succeedingly adds halogenated compound and electron donor(ED) in described solid catalyst component precursor, washs resulting product, adds described halogenated compound in the contact product after washing then, thereby realizes contact,
Method (2) may further comprise the steps: add the mixture of halogenated compound and electron donor(ED) in described solid catalyst component precursor, wash resulting product, add described halogenated compound in the contact product after washing then, thereby realize contact;
Method (3), may further comprise the steps: succeedingly adds halogenated compound and electron donor(ED) in described solid catalyst component precursor, wash resulting product, succeedingly adds described halogenated compound and electron donor(ED) in the contact product after washing then, thereby realizes contact;
Method (4), may further comprise the steps: the mixture that in described solid catalyst component precursor, adds described halogenated compound and electron donor(ED), wash resulting product, add the mixture of described halogenated compound and electron donor(ED) then in the contact product after washing, thereby realize contact;
Method (5) may further comprise the steps: succeedingly adds halogenated compound and electron donor(ED) in described solid catalyst component precursor, thereby realizes contact;
Method (6) may further comprise the steps: add halogenated compound in described solid catalyst component precursor, wash resulting product, add described electron donor(ED) in the contact product after washing then, thereby realize contact;
Method (7), may further comprise the steps: in described solid catalyst component precursor, add electron donor(ED), wash resulting product, succeedingly adds described halogenated compound and electron donor(ED) in the contact product after washing then, washing gained contact product, succeedingly adds described halogenated compound and electron donor(ED) in the contact product after washing then, thus realize contact and
Method (8), may further comprise the steps: in described solid catalyst component precursor, add electron donor(ED), wash resulting product, the mixture that adds described halogenated compound and electron donor(ED) then in the contact product after washing, wash resulting contact product, add the mixture of described halogenated compound and electron donor(ED) then in the contact product after washing, thereby realize contact.
In above-mentioned some method, wherein said halogenated compound and electron donor(ED) are used for more than one step, allow respectively and use described halogenated compound and the electron donor(ED) that is same to each other or different to each other.
The consumption of the each contact of described halogenated compound with respect to every gram solid catalyst component precursor meter, is generally 0.1-1000mmol, is preferably 0.3-500mmol, is preferably 0.5-300mmol especially.
The consumption of the each contact of described electron donor(ED) with respect to every gram solid catalyst component precursor meter, is generally 0.1-1000mmol, is preferably 0.3-500mmol, is preferably 0.5-300mmol especially.
In the above-mentioned contact of mentioning, the mol ratio of electron donor(ED) and halogenated compound is preferably 0.01-200, more preferably 0.1-100.
Resulting ingredient of solid catalyst when being used for polyreaction, can combining with a kind of inert diluent and form slurry, and perhaps drying obtains the mobile powder.
Prepolymerization is handled
In the present invention, but described ingredient of solid catalyst former state ground be used among the polyreaction, this polyreaction is called " actual polyreaction " hereinafter.Another kind of replacement scheme is, described ingredient of solid catalyst can carry out prepolymerization to be handled, thereby obtains a kind of pre-polymerized catalyst components, and it can be then used in actual polymerization.When the described prepolymerization of enforcement was reacted, as example, described ingredient of solid catalyst contacted with a kind of alkene with a kind of organo-aluminium compound.The described alkene example that is used for the prepolymerization reaction has ethene, propylene and butene-1.The prepolymerization reaction can be homopolymerization or copolyreaction.
React resulting prepolymer for what obtain highly crystalline by prepolymerization, when prepolymerization is handled, can adopt electron donor(ED) commonly used or hydrogen simultaneously.Preferred electron donor(ED) is a kind of organic compound with Si-OR key, and R wherein is a kind of alkyl with 1-20 carbon atom.
When prepolymerization was handled, adopting a kind of solvent was recommendable to make the slurry that contains ingredient of solid catalyst.The example of described solvent has aliphatic hydrocarbon such as butane, pentane, hexane, heptane and aromatic hydrocarbons such as toluene and dimethylbenzene.
Slurry concentration is generally 0.001-0.5 gram ingredient of solid catalyst/milliliter solvent, is preferably 0.01-0.3 gram ingredient of solid catalyst/milliliter solvent especially.Described organo-aluminium compound consumption is represented with the Al/Ti atomic ratio, and promptly the atomic ratio of Ti atom in Al atom and the solid catalyst in the organo-aluminium compound is preferably 0.1-100, is preferably 0.5-50 especially.
The prepolymerization treatment temp is generally-30 to 80 ℃, is preferably-10 to 50 ℃ especially.The yield of prepolymer with respect to every gram ingredient of solid catalyst meter, is generally 0.1-300g, is preferably 0.5-50g especially.
Resulting prepolymerized solid catalyst component when being used for actual polyreaction, can mix forming slurry with a kind of inert diluent, but also drying obtains a kind of mobile powder.
Organo-aluminium compound
Used " organo-aluminium compound " of the present invention is meant the compound that contains at least one Al-C key in molecular formula.Its typical example is the material that available following structural formula is represented:
R 12 rAlY 3-rWith
R 13R 14Al-(O-AlR 15) dR 16
Wherein, R 12, R 13, R 14, R 15And R 16Each represents to have the alkyl of 1-8 carbon atom independently, and Y is halogen atom, hydrogen atom or alkoxyl group, and r is for satisfying the numeral of 2≤r≤3, and d is for satisfying the numeral of 1≤d≤30.
The specific examples of described compound has trialkylaluminium such as triethyl aluminum, three n-butylaluminum, triisobutyl aluminium and three hexyl aluminium; Dialkyl group aluminum hydride such as ADEH, di-n-butyl aluminum hydride and diisobutyl aluminium hydride; Alkyl dihalide aluminium such as ethylaluminum dichloride, normal-butyl al dichloride and isobutyl-al dichloride; Dialkylaluminum halides such as diethyl aluminum chloride, di-n-butyl aluminum chloride and diisobutyl aluminum chloride; The mixture of trialkylaluminium and dialkylaluminum halides; With alkylaluminoxane such as tetraethyl-two aikyiaiurnirsoxan beta and the tetrabutyl two aikyiaiurnirsoxan beta, poly-methylaluminoxane and poly-ethyl aikyiaiurnirsoxan beta.
In these materials, trialkylaluminium, trialkylaluminium and dialkylaluminum halides mixture and alkylaluminoxane are preferred.The mixture and tetraethyl-two aikyiaiurnirsoxan beta of triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, three hexyl aluminium, triethyl aluminum and diethyl aluminum chloride are particularly preferred.
The consumption of described organo-aluminium compound with respect to every mole in ingredient of solid catalyst titanium atom meter, is generally the 1-10000 mole, is preferably the 5-5000 mole especially.
But described organo-aluminium compound former state ground uses, and perhaps adopts with the solution form that is made by inert diluent and uses.
The preparation of olefin polymer
The catalyzer that is used for olefinic polyreaction of the present invention can adopt following method preparation, and it comprises contacts above-mentioned three kinds of components mentioning mutually, that is:
(i) the described ingredient of solid catalyst that contains titanium, magnesium and halogen atom at least,
(ii) described organo-aluminium compound and
(iii) a kind of compound is selected from (a) a kind of its structural formula oxygenatedchemicals that at least two-oxyls are connected with same carbon atom and (b) a kind of cyclic ketones compound.
Described three kinds of components are not limiting of how contacting, as long as can make needed catalyzer.
The method that just is used for their contacts can exemplify following method (1) as an example to method (3):
Method (1) may further comprise the steps: each of the described three kinds of components of usefulness solvent cut, and the product behind the mixed diluting is implemented contact, then this product of contact is input to polymerization reactor;
Method (2) may further comprise the steps: make describedly not to be mixed with each other through three kinds of components of solvent cut, thereby implement contact, then this product of contact is input to polymerization reactor; With
Method (3) may further comprise the steps: described three kinds of components are input in the polymerization reactor respectively by oneself, thereby implement contact in polymerization reactor.
What be worth recommendation ground is that under anhydrous existence condition, employing rare gas element such as nitrogen and argon gas, hydrogen and olefin gas are input to described three kinds of components in the polymerization reactor as carrier gas.Described three kinds of components can be input in the polymerization reactor respectively by oneself.At least two kinds of components in described three kinds of components are contacted, and then the product after will contacting is input in the polymerization reactor.
Do not limit for polymerisation process.For example, polyreaction can be carried out according to traditional method, as gas phase polymerization process and slurry phase polymerisation process.The temperature of polyreaction is generally the temperature that resulting polymkeric substance can not melt, and preferably is not higher than 130 ℃, more preferably between 20-110 ℃, particularly preferably in 40-100 ℃.Polymerization pressure preferably at normal atmosphere between the 5MPa.In order to control polymers obtained melt flow rate (MFR), polyreaction can be carried out under as the condition of molecular weight regulator adding hydrogen.Described polyreaction can be carried out in a continuous manner, also can carry out by intermittent mode.
According to the method that is used for preparing olefin polymer of the present invention, may further comprise the steps: prepare aforesaid olefinic polyreaction catalyzer, in the presence of described catalyzer, carry out olefinic polymerization to obtain a kind of olefin polymer.
" olefin polymer " of the present invention is meant olefin homo or carries out the resulting olefin copolymer of polymerization by at least two kinds of alkene.The example of olefin copolymer has: ethylene-propylene copolymer, ethene-butyl multipolymer, ethene-pentene copolymer, ethene-hexene copolymer, ethene-4 methyl 1 pentene copolymer, ethylene-octene copolymer, propene-1-butene copolymer, propylene-hexene copolymer, propylene-4 methyl 1 pentene copolymer, ethylene-propylene-butylene copolymer and ethylene-propylene-hexene copolymer.In these multipolymers, preferred multipolymer is the multipolymer of ethene and a kind of alpha-olefin, as linear low density polyethylene (L-LDPE) with polyethylene crystalline texture, this analog copolymer contains in mole and is not less than 50% and comes from the structural unit of ethene and be not less than 0.3% structural unit that comes from described alpha-olefin in mole.Come from the content of the structural unit of alpha-olefin, be preferably 0.5-30 mole %, more preferably 1-20 mole %.At this, the summation of described acetate unit content and described alpha-olefin unit content is 100 moles of %.
The example of described alpha-olefin has propylene, 1-butylene, 1-amylene, 1-hexene, 3-Methyl-1-pentene and 4-methyl-1-pentene.In these alkene, 1-butylene, 1-hexene and 4-methyl-1-pentene are preferred.
Embodiment
Following embodiment will be described in more detail the present invention, and still, they only are illustrative, and can not be interpreted as limitation of the scope of the invention.
The analysis of described polymkeric substance, solid catalyst component precursor and ingredient of solid catalyst, and the mensuration of their physical propertiess adopts following method to carry out.
1. compositional analysis
Coming from the structural unit content of alpha-olefin in the ethene-alpha-olefin copolymer, is that wherein SCB is obtained by calibration curve with the expression of the short-chain branch number (SCB) among per 1000 C (carbon atom number is 1000); Described calibration curve is prepared by the feature absorption of ethene and described alpha-olefin; Described feature absorption is to be measured by a kind of infrared spectrometer (Series 1600, made by Perkin ElmerLtd.).
2. flow rate (FR)
Under 190 ℃, measure according to ASTM D1238 method.
3. flow rate is than (FRR)
Flow rate is the measure that is used for representing fluidity of molten than (FRR).FRR represents that with the ratio of the flow rate separately (FR) of the above-mentioned measuring method gained of mentioning wherein the load of being adopted is respectively 21.60kg and 2.160kg, that is:
FRR=(flow rate when load is 21.60kg) ÷ (flow rate when load is 2.160kg)
As everyone knows, the FRR value can improve along with the raising of molecular weight distribution usually.
4. the content of lower molecular weight component (CXS)
Be to evaluate by the quantity that dissolves in the material of dimethylbenzene 25 ℃ the time, amount (wt%) (CXS) by weight percentage.Usually, the SCB value is big more, and then the CXS value also can be big more.
5. the content of titanium
Adopt dilute sulphuric acid to decompose solid ingredient, and in the product of decomposition reaction, add excessive aqueous hydrogen peroxide solution, obtain a kind of liquid sample.Adopt dual beam spectrophotometer U-2001 (by Hitachi Co., Ltd makes), measure the characteristic absorbance of resulting liquid sample, adopt cut-and-dried calibration curve to calculate the content of Ti then at the 410nm place.
6. alkoxy group content
After obtaining a kind of liquid sample with the water decomposition solid ingredient, employing marker method gas chromatography is measured the pure content corresponding to alkoxyl group in the liquid sample that is obtained, and then it is scaled alkoxy group content.
Embodiment 1
(1) preparation of solid catalyst component precursor
With nitrogen a reactor of being furnished with agitator is purged, afterwards,, obtain a kind of mixture through stirring to wherein feeding 800l hexane, 349kg tetraethoxysilane and 38kg four titanium butoxide.Then, (the dibutyl ether solution of the butylmagnesium chloride of concentration=2.1mol/l) was added drop-wise in 5 hours in this mixture, kept temperature of reactor simultaneously at 5 ℃ with 852 l.After dripping end of processing, under 8 ℃, stirred the mixture 1 hour, and under 20 ℃, stirred in addition again 1 hour.Afterwards, filter reaction mixture, resulting solid are at every turn with 1100 l toluene wash 3 times.Add toluene in the solid after washing and obtain a kind of slurry.Take out this slurry sample of 50 milliliters, removing desolvates obtains the solid catalyst component precursor of 8.15g.
Contain Ti:2.09wt%, oxyethyl group: 38.8wt% and butoxy: 2.9wt% in this solid catalyst component precursor after measured.
(2) preparation of ingredient of solid catalyst
With nitrogen 200 ml flasks of being furnished with agitator are purged.In flask the feeding contain the 21.0g solid catalyst component precursor, in above-mentioned (1) resulting slurry.Adopt a Glass tubing that wherein has the formed filtering layer of sintered glass, remove solvent in the slurry by suction.Each heptane with 100ml is to the solids wash in the flask 3 times.Described washing step and other washing cited below are carried out by this way, and the solvent that will be used for washing is fed into this flask and it is stirred, and desolvate by adopting the above-mentioned Glass tubing suction of mentioning to remove then.Add heptane in the solid after washing, obtaining cumulative volume is the heptane slurry of 122ml.
With nitrogen 400 milliliters of potheaters being furnished with agitator are purged, afterwards, the heptane slurry of above-mentioned solid catalyst component precursor all is moved into wherein.And by following order to the tetrachloro silicane and 16.1ml phthalic acid (2-ethylhexyl) ester that wherein add 11.0 milliliters, stirred 3 hours down at 105 ℃, obtain a kind of mixture.Cool off potheater then to room temperature, this mixture is transferred in the flask behind nitrogen purging of a 200ml afterwards.Resulting mixture is through the solid-liquid separating treatment, separates the solid that obtains 105 ℃ of each toluene wash with 105ml 3 times, adds the toluene of 105ml then in the solid after washing.After improving temperature to 70 ℃,, and stirred the gained mixtures 1 hour down at 105 ℃ to the titanium tetrachloride that wherein adds 10.5ml.Afterwards, through the solid-liquid separation solid is separated from mixture after being mixed, the gained solid washs 6 times down at 105 ℃ with 105ml toluene at every turn, and at room temperature washs 2 times with the 105ml hexane in addition at every turn.Solid drying under reduced pressure after the washing obtains ingredient of solid catalyst.Ingredient of solid catalyst contains Ti:1.0wt% after measured.
(3) polyreaction
3 liters of potheaters that dispose agitator are through thoroughly in dry and be evacuated.Place 400 gram butane and 350 gram 1-butylene therein, then improve temperature to 70 ℃.Then, to wherein introducing hydrogen and ethene, make its dividing potential drop be respectively 0.4MPa and 1.2MPa.5.7 3 of mmole triethyl aluminum, 0.57mmol, 3-dimethoxy hexane and 17.4mg be resulting ingredient of solid catalyst in above-mentioned (2), adopts argon to be pressed into wherein, with initiated polymerization.This polyreaction was carried out under 70 ℃ 3 hours, infeeded ethene simultaneously continuously and stablized to keep stagnation pressure.
After polyreaction finishes, remove all unreacted monomers, obtain the polymkeric substance that 160 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 9200g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:21.0, FR:0.56, FRR:22.7 and CXS:10.3wt%.
Embodiment 2
Repeat embodiment 1, difference is with 3 among the embodiment 1 (3), 3-dimethoxy hexane changes 2 of 0.57mmol into, the 2-Propanal dimethyl acetal, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 14.1mg, like this, obtain the polymkeric substance that 24 grams have gratifying powder property.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 1700g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:21.1, FR:0.36, FRR:24.3 and CXS:9.0wt%.
Embodiment 3
Repeat embodiment 1, difference is that 3-dimethoxy hexane changes 1 of 0.57mmol into 3 among the embodiment 1 (3), 1-dimethoxy hexanaphthene, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 11.1mg, like this, obtain the polymkeric substance that 53 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 4800g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:21.5, FR:0.46, FRR:19.9 and CXS:9.7wt%.
Embodiment 4
Repeat embodiment 1, difference is that 3-dimethoxy hexane changes 1 of 0.57mmol into 3 among the embodiment 1 (3), the 1-glycol dimethyl ether, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 21.3mg, like this, obtain the polymkeric substance that 66 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 3100g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:19.1, FR:0.61, FRR:22.3 and CXS:7.4wt%.
Embodiment 5
Repeat embodiment 1, difference is that 3-dimethoxy hexane changes the propionic aldehyde dimethylacetal of 0.57mmol into 3 among the embodiment 1 (3), and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 16.6mg, like this, obtain the polymkeric substance that 108 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 6500g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:16.0, FR:0.78, FRR:21.5 and CXS:.4.2wt%.
Embodiment 6
Repeat embodiment 1, difference is that 3-dimethoxy hexane changes the n-octaldehyde dimethylacetal of 0.57mmol into 3 among the embodiment 1 (3), and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 17.2mg, like this, obtain the polymkeric substance that 103 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 5990g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:17.3, FR:0.87, FRR:21.7 and CXS:5.9wt%.
Embodiment 7
Repeat embodiment 1, difference is that 3-dimethoxy hexane changes the phenyl aldehyde dimethylacetal of 0.057mmol into 3 among the embodiment 1 (3), and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 11.5mg, like this, obtain the polymkeric substance that 54.7 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 4760g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:15.9, FR:0.67, FRR:21.8 and CXS:4.3wt%.
Comparative Examples 1
Repeat embodiment 1, difference is not use 3 among the embodiment 1 (3), 3-dimethoxy hexane, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 9.8mg, like this, obtain the polymkeric substance that 140 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 14000g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:20.9, FR:1.12, FRR:23.0 and CXS:11.1wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 2
Repeat embodiment 1, difference is that the consumption of butane among the embodiment 1 (3) and 1-butylene changes 380 grams and 370 respectively into and restrains, do not use 3 among the embodiment 1 (3), 3-dimethoxy hexane, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 11.2mg, like this, obtain the polymkeric substance that 222 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 19800g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:12.3, FR:1.27, FRR:24.5 and CXS:13wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 3
Repeat embodiment 1, difference is that the consumption of butane among the embodiment 1 (3) and 1-butylene changes 450 grams and 300 respectively into and restrains, do not use 3 among the embodiment 1 (3), 3-dimethoxy hexane, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 14.3mg, like this, obtain the polymkeric substance that 245 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 17100g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:19.1, FR:1.34, FRR:24.5 and CXS:9.1wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 4
Repeat embodiment 1, difference is that the consumption of butane among the embodiment 1 (3) and 1-butylene changes 480 grams and 270 respectively into and restrains, do not use 3 among the embodiment 1 (3), 3-dimethoxy hexane, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 7.1mg, like this, obtain the polymkeric substance that 105 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 15000g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:15.9, FR:0.69, FRR:25.5 and CXS:5.4wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 5
Repeat embodiment 1, difference is 3 among the embodiment 1 (3), and 3-dimethoxy hexane changes 0.57mmol n-propyl methyl dimethoxysilane into, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 16.1mg, like this, obtain the polymkeric substance that 71 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 4100g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:13.6, FR:0.96, FRR:22.0 and CXS:5.9wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 6
Repeat embodiment 1, difference is 3 among the embodiment 1 (3), and 3-dimethoxy hexane changes 0.57mmol dimethoxy-methyl silane into, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 26.5mg, like this, obtain the polymkeric substance that 33 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 1300g polymkeric substance/g ingredient of solid catalyst.The discovery polymkeric substance has: SCB:17.5, FR:0.58, FRR:20.8 and CXS:7.3 wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Comparative Examples 7
Repeat embodiment 1, difference is 3 among the embodiment 1 (3), 3-dimethoxy hexane changes 0.57mmol 2 into, 2-diisobutyl-1, the 3-Propanal dimethyl acetal, and, change the ingredient of solid catalyst consumption among the embodiment 1 (3) into 16.5mg, like this, obtain the polymkeric substance that 71 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 4300g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:22.2, FR:1.68, FRR:23.4 and CXS:16.0wt%.Compare with the situation that adopts oxygenatedchemicals, it is bigger to observe relative SCB CXS value.
Embodiment 8
(1) preparation of solid catalyst component precursor
With nitrogen a reactor of being furnished with agitator is purged, afterwards,, obtain a kind of mixture through stirring to wherein feeding 800 l hexanes, 349kg tetraethoxysilane and 38kg four titanium butoxide.Then, (the dibutyl ether solution of the butylmagnesium chloride of concentration=2.1mol/l) was added drop-wise in 5 hours in this mixture, kept temperature of reactor simultaneously at 5 ℃ with 852 l.After dripping end of processing, under 8 ℃, stirred the mixture 1 hour, and under 20 ℃, stirred in addition again 1 hour.Afterwards, filter reaction mixture, resulting solid are used the 1100l toluene wash 3 times at every turn.Add toluene in the solid after washing and obtain a kind of slurry.Take out this slurry sample of 50 milliliters, removing desolvates obtains the solid catalyst component precursor of 8.15g.
Contain Ti:2.09wt%, oxyethyl group: 38.8wt% and butoxy: 2.9wt% in this solid catalyst component precursor after measured.
(2) preparation of ingredient of solid catalyst
With nitrogen 200 ml flasks of being furnished with agitator are purged.In flask the feeding contain 21.0g solid catalytic component precursor, in above-mentioned (1) resulting slurry.Adopt a Glass tubing that wherein has the formed filtering layer of sintered glass, remove solvent in the slurry by suction.Each heptane with 100ml is to the solids wash in the flask 3 times.Add heptane in the solid after washing, obtaining cumulative volume is the heptane slurry of 122ml.
With nitrogen 400 milliliters of potheaters being furnished with agitator are purged, afterwards, the heptane slurry of above-mentioned solid catalyst component precursor all is moved into wherein.And by following order to the tetrachloro silicane and 16.1ml phthalic acid (2-ethylhexyl) ester that wherein add 11.0 milliliters, stirred 3 hours down at 105 ℃, obtain a kind of mixture.Cool off potheater then to room temperature, this mixture is transferred in the flask behind nitrogen purging of a 200ml afterwards.Resulting mixture separates the solid that obtains through the solid-liquid separating treatment, 105 ℃ of each toluene wash with 105ml 3 times, adds the toluene of 105ml then in the solid after washing.After improving temperature to 70 ℃,, and stirred the gained mixtures 1 hour down at 105 ℃ to the titanium tetrachloride that wherein adds 10.5ml.Afterwards, through the solid-liquid separation solid is separated from mixture after being mixed, the gained solid washs 6 times down at 105 ℃ with 105ml toluene at every turn, and at room temperature washs 2 times with the 105ml hexane in addition at every turn.Solid drying under reduced pressure after the washing obtains ingredient of solid catalyst.Ingredient of solid catalyst contains Ti:1.0wt% after measured.
(3) polyreaction
3 liters of potheaters that dispose agitator are through thoroughly in dry and be evacuated.Place 400 gram butane and 350 gram 1-butylene therein, then improve temperature to 70 ℃.Then, to wherein introducing hydrogen and ethene, make its dividing potential drop be respectively 0.4MPa and 1.2MPa.5.7 1 of mmole triethyl aluminum, 0.57mmol, 4-cyclohexanedione and 20.6mg be resulting ingredient of solid catalyst in above-mentioned (2), adopts argon to be pressed into wherein, with initiated polymerization.This polyreaction was carried out under 70 ℃ 3 hours, infeeded ethene simultaneously continuously and stablized to keep stagnation pressure.
After polyreaction finishes, remove all unreacted monomers, obtain the polymkeric substance that 148 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 7180g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:19.4, FR:1.01, FRR:23.1 and CXS:8.2wt%.
Embodiment 9
Repeat embodiment 8, difference is that the 4-cyclohexanedione changes 1 of 0.57mmol into 1 among the embodiment 8 (3), hydroresorcinol, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 19.7mg, like this, obtain the polymkeric substance that 215 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 10900g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:20.8, FR:0.88, FRR:22.4 and CXS:9.8wt%.
Embodiment 10
Repeat embodiment 8, difference is that the 4-cyclohexanedione changes 1 of 0.57mmol into 1 among the embodiment 8 (3), the 2-cyclohexanedione, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 11.6mg, like this, obtain the polymkeric substance that 111 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 9570g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:21.2, FR:0.86, FRR:23.0 and CXS:10.2wt%.
Embodiment 11
Repeat embodiment 8, difference is that the 4-cyclohexanedione changes 1 of 0.57mmol into 1 among the embodiment 8 (3), the 4-benzoquinones, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 18.2mg, like this, obtain the polymkeric substance that 189 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 10400g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:22.3, FR:1.31, FRR:21.8 and CXS:11.7wt%.
Comparative Examples 8
Repeat embodiment 8, difference is not use 1 among the embodiment 8 (3), the 4-cyclohexanedione, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 9.8mg, like this, obtain the polymkeric substance that 140 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 14000g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:20.9, FR:1.12, FRR:23.0 and CXS:11.1wt%.Compare with the situation that adopts the cyclic ketones compound, it is bigger to observe relative SCB CXS value.
Comparative Examples 9
Repeat embodiment 8, difference is that butane and the 1-butylene consumption among the embodiment 8 (3) changes 380 grams and 370 grams respectively into, do not use 1 among the embodiment 8 (3), the 4-cyclohexanedione, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 11.2mg, like this, obtain the polymkeric substance that 222 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 19800g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:12.3, FR:1.27, FRR:24.5 and CXS:13wt%.Compare with the situation that adopts the cyclic ketones compound, it is bigger to observe relative SCB CXS value.
Comparative Examples 10
Repeat embodiment 8, difference is that butane and the 1-butylene consumption among the embodiment 8 (3) changes 450 grams and 300 grams respectively into, do not use 1 among the embodiment 8 (3), the 4-cyclohexanedione, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 14.3mg, like this, obtain the polymkeric substance that 245 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 17100g polymkeric substance/g ingredient of solid catalyst.Find that polymkeric substance has SCB:19.1, FR:1.34, FRR:24.5 and CXS:9.1wt%.Compare with the situation that adopts the cyclic ketones compound, it is bigger to observe relative SCB CXS value.
Comparative Examples 11
Repeat embodiment 8, difference is that butane and the 1-butylene consumption among the embodiment 8 (3) changes 480 grams and 270 grams respectively into, do not use 1 among the embodiment 8 (3), the 4-cyclohexanedione, and, change the ingredient of solid catalyst consumption among the embodiment 8 (3) into 7.1mg, like this, obtain the polymkeric substance that 105 grams have the good powder performance.Find that this polymkeric substance almost do not adhere on potheater inwall and agitator.
The polymer yield (polymerization activity) of per unit quantity catalyzer is 15000g polymkeric substance/g ingredient of solid catalyst.The discovery polymkeric substance has: SCB:15.9, FR:0.69, FRR:25.5 and CXS:5.4wt%.Compare with the situation that adopts the cyclic ketones compound, it is bigger to observe relative SCB CXS value.

Claims (6)

1. the preparation method of a catalyst for olefines polymerizing, it comprises the step that is in contact with one another of following substances:
(i) contain the ingredient of solid catalyst of titanium, magnesium and halogen atom at least,
(ii) organo-aluminium compound, the consumption of described organo-aluminium compound, with respect to every mole in ingredient of solid catalyst titanium atom meter, be 1 mole-10000 moles and
(iii) cyclic ketones compound, it comprises 3 yuan-10 yuan cyclic ketones, the consumption of described cyclic ketones compound with respect to every mole titanium atom meter in the ingredient of solid catalyst, is 1 mole-2000 moles,
Wherein component (i) is to make by the method that may further comprise the steps:
-in the presence of a kind of silicoorganic compound with Si-O key, the titanium compound that adopts the organo-magnesium compound reduction to represent with following structural formula, thus obtain solid catalyst component precursor,
Ti(OR 1) aX 4-a
Wherein, R 1For having the alkyl of 1-20 carbon atom, X is a halogen atom, a for the numerical value that satisfies 0＜a≤4 and
-make (a) described solid catalyst component precursor, (b) have the halogenated compound of halogenation ability and (c) electron donor(ED) be in contact with one another.
2. the preparation method of the described catalyst for olefines polymerizing of claim 1, wherein said cyclic ketones compound is included in the compound that has at least two carbonyls on its ring.
3. the preparation method of the described catalyst for olefines polymerizing of claim 1, wherein said ingredient of solid catalyst also contains electron donor(ED).
4. the preparation method of the described catalyst for olefines polymerizing of claim 3, wherein said electron donor(ED) contains organic acid acetic.
5. method that is used for preparing olefin polymer, it comprises the steps:
(1) thus following material is in contact with one another makes catalyst for olefines polymerizing: the ingredient of solid catalyst that (i) contains titanium, magnesium and halogen atom at least, (ii) organo-aluminium compound, the consumption of described organo-aluminium compound, with respect to every mole in ingredient of solid catalyst titanium atom meter, it is 1 mole-10000 moles, the cyclic ketones compound that (iii) comprises 3 yuan of-10 yuan of cyclic ketones, the consumption of described cyclic ketones compound, with respect to every mole titanium atom meter in the ingredient of solid catalyst, it is 1 mole-2000 moles; With
(2) in the presence of resulting olefin polymerization catalysis, carry out olefinic polymerization, make olefin polymer,
Wherein component (i) is to make by the method that may further comprise the steps:
-in the presence of a kind of silicoorganic compound with Si-O key, the titanium compound that adopts the organo-magnesium compound reduction to represent with following structural formula, thus obtain solid catalyst component precursor,
Ti(OR 1) aX 4-a
Wherein, R 1For having the alkyl of 1-20 carbon atom, X is a halogen atom, a for the numerical value that satisfies 0＜a≤4 and
-make (a) described solid catalyst component precursor, (b) have the halogenated compound of halogenation ability and (c) electron donor(ED) be in contact with one another.
6. the described method for preparing olefin polymer of claim 5, wherein said olefin polymer contains the multipolymer of ethene and alpha-olefin.
CNB2005100765470A 2000-03-30 2001-03-28 Process for producing catalyst for olefin polymerization and process for producing olefin polymer Expired - Fee Related CN100362026C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP93949/00 2000-03-30
JP93955/00 2000-03-30
JP2000093955 2000-03-30

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNB011164883A Division CN1232544C (en) 2000-03-30 2001-03-28 Method of preparing catalyst for olefines polymerizing and preparation method of olefin polymer

Publications (2)

Publication Number Publication Date
CN1690091A CN1690091A (en) 2005-11-02
CN100362026C true CN100362026C (en) 2008-01-16

Family

ID=35345877

Family Applications (2)

Application Number Title Priority Date Filing Date
CN 200510118073 Pending CN1772771A (en) 2000-03-30 2001-03-28 Process for producing catalyst for olefin polymerization and process for producing olefin polymer
CNB2005100765470A Expired - Fee Related CN100362026C (en) 2000-03-30 2001-03-28 Process for producing catalyst for olefin polymerization and process for producing olefin polymer

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN 200510118073 Pending CN1772771A (en) 2000-03-30 2001-03-28 Process for producing catalyst for olefin polymerization and process for producing olefin polymer

Country Status (1)

Country Link
CN (2) CN1772771A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG172665A1 (en) 2007-12-27 2011-07-28 Sumitomo Chemical Co Production process of olefin polymerization catalyst component, of olefin polymerization catalyst, and of olefin polymer

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2130225A (en) * 1982-09-24 1984-05-31 Nippon Oil Co Ltd Ziegler catalysed olefin polymerization
JPS61231008A (en) * 1985-04-05 1986-10-15 Mitsubishi Petrochem Co Ltd Production of olefin polymer
US4701505A (en) * 1984-09-26 1987-10-20 Mitsubishi Petrochemical Company Limited Process for production of olefin polymers
US4762898A (en) * 1985-03-08 1988-08-09 Mitsubishi Petrochemical Company Limited Process for polymerizing ethylene
CN1057656A (en) * 1990-04-13 1992-01-08 三井石油化学工业株式会社 The solid titanium catalyst component that is used for olefinic polymerization, olefin polymerization catalysis, the catalyzer of prepolymerized polyolefi-ncontaining and the method for olefinic polymerization
CN1105671A (en) * 1993-10-01 1995-07-26 希蒙特公司 Components and catalysts for the polymerization of olefins
CN1149878A (en) * 1994-05-31 1997-05-14 博雷里斯控股公司 Stereospecific catalyst system for polymerization of olefines
CN1230552A (en) * 1998-03-11 1999-10-06 住友化学工业株式会社 Solid catalyst component and catalyst for olefin polymerization, and process for producing olefin polymer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2130225A (en) * 1982-09-24 1984-05-31 Nippon Oil Co Ltd Ziegler catalysed olefin polymerization
US4701505A (en) * 1984-09-26 1987-10-20 Mitsubishi Petrochemical Company Limited Process for production of olefin polymers
US4762898A (en) * 1985-03-08 1988-08-09 Mitsubishi Petrochemical Company Limited Process for polymerizing ethylene
JPS61231008A (en) * 1985-04-05 1986-10-15 Mitsubishi Petrochem Co Ltd Production of olefin polymer
CN1057656A (en) * 1990-04-13 1992-01-08 三井石油化学工业株式会社 The solid titanium catalyst component that is used for olefinic polymerization, olefin polymerization catalysis, the catalyzer of prepolymerized polyolefi-ncontaining and the method for olefinic polymerization
CN1105671A (en) * 1993-10-01 1995-07-26 希蒙特公司 Components and catalysts for the polymerization of olefins
CN1149878A (en) * 1994-05-31 1997-05-14 博雷里斯控股公司 Stereospecific catalyst system for polymerization of olefines
CN1230552A (en) * 1998-03-11 1999-10-06 住友化学工业株式会社 Solid catalyst component and catalyst for olefin polymerization, and process for producing olefin polymer

Also Published As

Publication number Publication date
CN1690091A (en) 2005-11-02
CN1772771A (en) 2006-05-17

Similar Documents

Publication Publication Date Title
CN100537613C (en) Solid catalyst component and catalyst for olefin polymerization, and process for producing olefin polymer
CN101469036B (en) Production process of olefin polymerization catalyst component, of olefin polymerization catalyst, and of olefin polymer
CN102762602B (en) New internal and external donor compounds for olefin polymerization catalysts
CN104583219A (en) Multi component mixture of magnesiumcoholates, magnesiumhalides and alcohol, processes to make them and their use in processes to make olefin polymerization catalyst
CN1235917C (en) Method for producing catalyst for homo-or co-polymerization of ethylene
CN104662027A (en) Precursor for catalyst, process for preparing the same and its use thereof
CN101715461A (en) Super high molecular weight ethylene-alpha-olefin copolymer powder
CN107207657A (en) The method for preparing the spherical polymerization catalyst component for olefinic polyreaction
CN101268105A (en) Supported ziegler-natta catalyst for olefin polymerization
CN104583244B (en) Catalyst for olefines polymerizing and preparation method thereof
CN101838353A (en) Catalyst component for vinyl polymerization and catalyst thereof
CN102234341A (en) Components and catalysts for the polymerization of olefins
CN102295717A (en) Catalyst compound used for vinyl polymerization reaction and catalyst thereof
CN102875707A (en) Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof
CN103130931B (en) A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof
CN102040686B (en) Catalyst component and catalyst for vinyl polymerization
CN1316442A (en) Method of preparing catalyst for olefines polymerizing and preparation method of olefin polymer
CN104710549B (en) A kind of emulsion process prepares Ball shape ethylene polymerization solid titanium catalytic and its application
CN100362026C (en) Process for producing catalyst for olefin polymerization and process for producing olefin polymer
CN100506851C (en) Catalysts for polymerization and copolymerization of ethylene
CN102206295B (en) Olefin polymerization catalyst component and production process thereof, and production process of olefin polymerization catalyst and olefin polymer
CN102329400B (en) Olefin polymerization catalyst containing silane compound, preparation and application thereof
CN101565474A (en) Process for producing catalyst for ethylene polymerization and process for producing ethylene polymer
CN101374868B (en) Process for polymerization or copolymerization of ethylene
CN104755515A (en) Mixed compatible Ziegler-Natta/chromium catalysts for improved polymer products

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080116

Termination date: 20140328