CN101456924B - Catalyst component for olefin polymerization and catalyst thereof - Google Patents
Catalyst component for olefin polymerization and catalyst thereof Download PDFInfo
- Publication number
- CN101456924B CN101456924B CN2008102273690A CN200810227369A CN101456924B CN 101456924 B CN101456924 B CN 101456924B CN 2008102273690 A CN2008102273690 A CN 2008102273690A CN 200810227369 A CN200810227369 A CN 200810227369A CN 101456924 B CN101456924 B CN 101456924B
- Authority
- CN
- China
- Prior art keywords
- electron donor
- alkyl
- catalyst component
- compound
- general formula
- 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
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst component for olefinic polymerization and a catalyst thereof, which belongs to the field of catalysts. The catalyst component comprises activated MgCl2, a titanic compound, and an ester electron donor compound with the general formula I. The mol ratio of the ester electron donor compound to MgCl2 is 0.01 to 1; and the Ti content in the catalyst component is 1.5to 10 weight percentage. The catalyst component for olefinic polymerization also comprises an organo aluminum compound with the general formula of AlR<5>nX3-n. In the general formula, R<5> is an alkyl with the hydrogen or carbon atom number of 1 to 20, X represents halogen, and N is a number more than 0 and less than or equal to 3. The catalyst component for olefinic polymerization also comprisesan external electron donor compound with the formula of R<2>xR<3>ySi(OR <4>)z. The catalyst component is applied to the polymerization of CH2 being equal to CHR, wherein R is hydrogen or an alkyl with 1 to 15 carbon atoms. Particularly during the polymerization of propylene, the catalyst has high activity and the obtained polymer has high isotacticity.
Description
Technical field
The present invention relates to a kind ofly be used for the catalyst component of olefinic polymerization and the catalyzer that obtains thus, and relate to described catalyzer at alkene CH
2Application in the=CHR polymerization, wherein R is hydrogen or the alkyl with 1-15 carbon atom.The invention particularly relates to the catalyst component that is applicable to the alkene tactic polymerization, it comprises Ti, Mg, halogen and a kind of electronic donor compound capable that is selected from the ester class of general formula I.Described catalyst component is being used for alkene, particularly during propylene polymerization, and catalyst activity height, and the degree of isotacticity height of resulting polymers.
Background technology
In the catalyzer of propylene polymerization, most widely used is the Ziegler-Natta catalyst system.Usually the electron donor that adds in the solid catalyst preparation process is called internal electron donor, the electron donor that adds in propylene polymerization processes is called external electron donor.The electron donor particularly effect of external electron donor in the Ziegler-Natta catalyst system is the very interested problem of worker of catalyzer and field of olefin polymerisation always, its major cause is the performance that electron donor can significantly improve catalyzer, helps suitability for industrialized production.The main effect of electron donor shows: change activity of such catalysts; The degree of isotacticity of impact polypropylene and degree of crystallinity; Other performance of the molecular weight of controlling polymers and molecular weight distribution and polymkeric substance.
If when the preparation effective catalyst, do not add internal electron donor, MgCl
2Because of speed of separating out generates stable, closely packed crystal soon, the catalytic activity and the orientation property of catalyzer are low.
The catalyzer gained polypropylene degree of isotacticity that with monocarboxylic ester is internal electron donor is low, and it is random etc. that product need take off.
Basell (CN 01804636.3) company has developed a series of aliphatic dicarboxylic acid ester that comprises malonic ester, succinate, divinyl acid esters and glutarate.Wherein with succinate---the succinate performance is best, and activity of such catalysts is 40～70kgPP/gcat2h; The molecular weight distribution of polymkeric substance very wide (MWD=10～15).With the succinate compounds is that the catalyzer of internal electron donor has high stereotaxis performance; Maximum characteristics are that the polypropylene that makes has very wide relative molecular mass distribution, can produce the product that to use the multiple reactor explained hereafter in the past with the single reactor operation, product is high rigidity homopolymer and heterophasic copolymer, has expanded the performance of alfon and multipolymer.But internal electron donor succinate compounds add-on height, cost is higher.
The problem that current people pay close attention to is the catalyst component of the polymkeric substance of performance with the Senior Two toluene insoluble that is applicable to the BOPP field, high stereoblock content and wide MWD scope of the polymkeric substance that obtains.
Summary of the invention
The present invention finds that unexpectedly described catalyst component comprises Ti, Mg, halogen and a kind of electronic donor compound capable that is selected from the ester class of general formula I.The objective of the invention is to be used for alkene CH
2=CHR polymerization, comprise Ti, Mg, the catalyst component of the electronic donor compound capable of halogen and a kind of ester class that is selected from general formula I, wherein R is hydrogen or the alkyl with 1-15 carbon atom.
The invention provides a kind of catalyst component that is used for olefinic polymerization, it is characterized in that, comprise the MgCl of active condition
2
General formula is Ti (OR
1)
4-mX
mThe compound of titanium, R in the formula
1Be C
1～C
20Aliphatic group, or aryl radical or COOR`, R` has C
1～C
10Fatty group or aromatic base; X is a halogen atom, and m is 0 to 4 integer;
The ester class electron donor compound of general formula I;
The amount and the MgCl of ester class electron donor compound
2Mol ratio be 0.01 to 1; The content of Ti is 1.5wt%-10wt% in the catalyst component;
The general formula I of above-mentioned ester class electron donor compound is:
Substituent R 3 on the aromatic ring and or the quantity of R4 can be 1 to 5 arbitrary integer, preferred H ,-CH
3,-CH
2CH
3, cyclohexyl, phenyl, benzyl, 2,6-diisopropyl phenyl, 2,6-di-isopropyl benzyl.R5, R6 are selected from identical or different by 1 to 30 alkyl that carbon is formed, cycloalkyl, aryl or their derivative, and be preferred-C
9H
19,-C
8H
17,-C
7H
15,-C
6H
13, benzyl, 2,6-di-isopropyl benzyl.N is selected from 0, or 1 to 10 arbitrary integer, and preferred 0,1,2.
Preferably:
As mentioned above, catalyst component of the present invention also comprises Ti, Mg and halogen except above-mentioned electron donor.Specifically, described catalyst component comprises titanium compound with at least one Ti-halogen bond and the above-mentioned electron donor compound that is carried on the magnesium halide.Described magnesium halide is preferably the MgCl of active condition
2The titanium compound that is used for catalyst component of the present invention is Ti (OR
1)
4-mX
m, R in the formula
1Be C
1～C
20Aliphatic group, or aryl radical or COOR` (R` has C
1～C
10Fatty group or aromatic base), each R
1Can be identical, also can be different; X is a halogen atom, and m is 0 to 4 integer; Preferred TiCl
4And TiCl
3
Can implement the preparation of described ingredient of solid catalyst according to several different methods.According to a kind of method wherein, at MgCl
2Activation takes place please to replenish a little under the activatory condition to be specialized anhydrous MgCl
2, titanium compound and electron compound grind together.Thus obtained product can adopt excessive TiCl under 70 to 130 ℃ temperature
4Handle once or once.Till being washed till no chlorion with varsol again.
According to another kind of method, at 400-600 ℃ of activation MgCl
24-6 hour, then in the presence of the electron donor compound under about 80 to 140 ℃ temperature with excessive TiCl
4Reaction.Repeated using TiCl
4Handle, again with hexane wash till do not have a chlorion.
Another kind method is included in the presence of the electron donor compound, makes-oxyl magnesium or chloro-oxyl magnesium and excessive TiCl under about 80 to 140 ℃ temperature
4React.Above excessive TiCl
4Generally be MgCl
2The 5-50 of mole doubly.
According to a kind of method preferably, described ingredient of solid catalyst can prepare as follows:
Titanium compound is selected from general formula Ti (OR
1)
4-mX
m, X is a halogen atom in the formula, m is 0 to 4 integer, R
1Be C
1～C
20Aliphatic group, or aryl radical or COR`, or COOR` (R` has C
1～C
10Fatty group or aromatic base), each R
1Can be identical, also can be different.R
1Be preferably: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-aminomethyl phenyl, right-aminomethyl phenyl, neighbour-sulfonic group phenyl, formyl radical, ethanoyl, benzoyl or the like.Specifically can select titanium tetrachloride for use, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, one chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, the methoxyl group titanous chloride, the dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, one chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, a kind of in trichlorine one phenoxide titanium or their mixture, described titanium compound should be under application of temperature, completely soluble liquefied compound in the non-polar solvent, the preferred titanium tetrachloride and the preferred self-drifting MgCl that derives
2The magnesium chloride or the MgCl of the adducts of pROH (wherein p is 0.1 to 6, and is preferred 1.8 to 3.2, and R is the alkyl with 1-18 carbon atom)
2React.
Spherical adduct preparation is a prior art, can be as follows: with the immiscible unreactive hydrocarbons of adducts in the presence of, alcohol mixture and magnesium chloride under adducts melt temperature (100-140 ℃) and agitation condition.Make the milk sap quenching then, produce the adducts spheroidal particle.The gained adducts can be directly and the reaction of Ti compound, also can first dealcoholization (80-140 ℃), obtain wherein that the mole number of alcohol is lower than 3, the adducts of preferred 0.1.5 to 2.8.The reaction of adducts and Ti compound can be by following enforcement: adducts is suspended in TiCl
4(being generally 0 ℃); Or adducts is heated to 70-135 ℃, and under this temperature, kept 0.5-4 hour.Can adopt TiCl
4Handle once or once.Can add the electron donor compound at adducts and between the Ti compound reaction period.The electron donor compound can once add, also can be with TiCl
4Repeatedly add.
The another kind of method for preparing catalyst component of the present invention is included under 80-130 ℃ the temperature and adopts TiCl
4Til
4Aromatic hydrocarbon solution (as toluene, dimethylbenzene etc.) and two magnesium alkoxide compounds (as dialkoxy magnesium or two aryloxy magnesium) carry out halogenation.Adopt TiCl
4The processing of aromatic hydrocarbon solution can one or many, during this processing, add the electron donor compound.
Another method for preparing catalyst component of the present invention comprises: magnesium halide is dissolved in the dissolution system that contains organic epoxy compounds and organo phosphorous compounds, in solvent system, add in 30 moles times of above aromatic solvent (toluene of magnesium halide, dimethylbenzene etc.), form homogeneous solution, in the process that forms solution or solution form the back and add organic alcohol compound (doubly) in magnesium halide 0.1-5 mole; In-40～30 ℃, above-mentioned solution and titanium compound are carried out contact reacts, add the electron donor compound during this period, add or do not add silicoorganic compound (doubly) afterwards in magnesium halide 0.01-3 mole, be warming up to 70～130 ℃, in this temperature-rise period, particle is separated out and formed to solids gradually, react after 0.5～24 hour, remove by filter unreacted reactant and solvent, and adopt the inert solvent washing, filter, vacuum (40-80 ℃) dry 3-8 hour obtains ingredient of solid catalyst.
Another method for preparing catalyst component of the present invention comprises: magnesium halide is dissolved in the dissolution system that contains organic epoxy compounds and organo phosphorous compounds, in solvent system, add aromatic solvent (as toluene, dimethylbenzene etc.), add alkane again (as hexane, heptane, octane etc.) solvent forms homogeneous solution, in the process that forms solution or solution form the back and add organic alcohol compound; In-40～30 ℃, above-mentioned solution and titanium compound are carried out contact reacts, add the electron donor compound during this period, add or do not add silicoorganic compound afterwards, be warming up to 70～130 ℃, in this temperature-rise period, particle is separated out and formed to solids gradually, react after 0.5～24 hour, remove by filter unreacted reactant and solvent, and adopt the inert solvent washing, filter, vacuum (40-80 ℃) dry 3-8 hour obtains ingredient of solid catalyst.
Remove unreacted reactant and solvent, and adopt the inert solvent washing, obtain ingredient of solid catalyst.
The surface-area of the ingredient of solid catalyst that obtains according to aforesaid method (measuring by the B.E.T method) is generally 20-500m
2/ g,, overall porosity is greater than 0.2cm
3/ g.
No matter use which kind of preparation method, the amount of described electron donor compound and MgCl
2Mol ratio be 0.01 to 1, preferred 0.05 to 0.5.
According to various known methods, adopt ingredient of solid catalyst of the present invention and organo-aluminium compound to react, be translated into the catalyzer that is used for olefinic polymerization.
Particularly, one of purpose of the present invention is to be used for alkene CH
2=CHR polymeric catalyzer, wherein R is hydrogen or the alkyl with 1-15 carbon atom, described catalyzer comprises the reaction product of following material:
(1) aforesaid ingredient of solid catalyst;
(2) organo-aluminium compound; The general formula of organo-aluminium compound is AlR
5 nX
3-n, R in the formula
5For hydrogen or carbonatoms are that 1～20 alkyl, X are halogen, n is the number of 0＜n≤3; With
(3) external electron donor compound;
The external electron donor compound is preferably from the silicoorganic compound general formula R
2 xR
3 ySi (OR
4)
z, R in the formula
2And R
3Be respectively carbonatoms and be 1～20 alkyl, cycloalkyl, aryl, haloalkyl or halogen, R
4For carbonatoms is 1～15 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
The general formula of organo-aluminium compound of the present invention is AlR
5 nX
3-n, R in the formula
5For hydrogen or carbonatoms are that 1～20 alkyl, X are halogen, n is the number of 0＜n≤3; Relatively exemplary compounds as: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-tert aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter ethyl aluminum chloride etc. are good with triethyl aluminum, triisobutyl aluminium especially wherein; Can use separately, also can several mixing use.The aluminium in the promotor and the mol ratio of the titanium in the catalyst component are 1～500, preferred 20～250.
Suitable external electron donor compound is preferably from the silicoorganic compound general formula R
2 xR
3 ySi (OR
4)
z, R in the formula
2And R
3Be respectively carbonatoms and be 1～20 alkyl, cycloalkyl, aryl, haloalkyl or halogen, R
4For carbonatoms is 1～15 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.The represented silicon compound of above-mentioned general formula comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four decide TMOS, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the isobutyl-triethoxyl silane, the cyclohexyl triethoxyl silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyl dimethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, methylcyclohexyl dimethoxy silane, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, one or more mixing wherein such as two cyclopentyl-methyl methoxy silane and cyclopentyl dimethyl methyl TMOS are used.Preferable methyl cyclohexyl dimethoxy silane, dibutyl dimethoxy silane, tetramethoxy-silicane.
Above-mentioned organic alcohol compound comprises straight chain alcohol, cycloalkanol or the isomery alcohol of C1～C15, and the adding of organic alcohol is transferred extremely important to the hydrogen of polymkeric substance.It comprises: methyl alcohol, ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, ammediol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol etc.; Cycloalkanol, as hexalin, methyl-cyclohexanol; Aromatic alcohol, as Bian alcohol, methyl Bian alcohol, sec.-propyl Bian alcohol etc.Preferred fat alcohol, most preferred ethanol, butanols, 2-Ethylhexyl Alcohol, glycerol.
Described organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbon atom.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane or methyl glycidyl ether, preferred propylene oxide and epoxy chloropropane.
Described organo phosphorous compounds is the hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid three propyl ester, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl, preferred ortho-phosphoric acid tri-n-butyl.
Wherein in every mole of magnesium halide: organic epoxy compounds: 0.1～20mol, preferred 0.5～8mol; Organo phosphorous compounds: 0.1～10mol, preferred 0.3～3mol.
In order to make dissolving more abundant, it is necessary preferably adding aromatic solvent in this solvent system, it comprises that the above-mentioned aromatic solvent of benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof can use separately, use also capable of being combined, add-on is in every mole of magnesium halide, preferred 5～40mol.
The catalyzer that the present invention relates to is applicable to alkene CH
2=CHR polymeric catalyzer, wherein R is hydrogen or the alkyl with 1-15 carbon atom.
Have found that slower reaction process can obtain the catalyst component of better particle form, therefore, preferably lower temperature of reaction.Reaction process among the present invention is generally carried out under about-50 ℃-200 ℃ scope, is preferably-40 ℃-140 ℃.Reaction times also can change in relative broad range, is generally 0.5-24 hour, should make the sufficiently long time of reaction between the component under desired reaction temperature.For further improving the particle form of catalyzer and the tap density of polymerisate, can use slight vacuum, means such as elevated temperature or nitrogen purging in intermediate steps.
The invention provides a kind of spherical polyolefin catalyst.The catalyst activity height, the preparation method is simple, and is low for equipment requirements, and environmental pollution is little, has good hydrogen mediation copolymerization performance.This catalyzer is applicable to substance law, slurry process, gas-phase polymerization process or polymerization mix technology.Adopting slurry polymerization is that the available medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvents such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.
In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen to make molecular weight regulator.
The mensuration of polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): with 2g exsiccant polymer samples, be placed in the extractor with ebullient heptane extracting 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with the ratio of 2g.
The Ti assay of catalyzer: claim 0.5g catalyzer concentrated sulfuric acid dissolution, adopt its content of spectrophotometric determination.
Embodiment
Embodiment is at preference of the present invention, but is not limited to following embodiment when practical application.
Result of implementation is listed in table 1.
Embodiment 1
Under 0C with the TiCl of 125ml
4Add with in the 500ml four neck round-bottomed flasks of nitrogen protection, stir the spherical MgCl of adding 5.0g down
22.6C
2H
5OH, high-speed stirring adds 2.2 mmole internal electron donor compd As simultaneously.Be warming up to 100 ℃, and under this temperature, kept 2 hours, stop to stir, make the solid product standing sedimentation, filter.Add the new TiCl of 125ml again
4, stir, 120 ℃ of reactions 1 hour, leave standstill then, filter, with 60 ℃ anhydrous heptane wash 4 times, vacuum-drying obtains ingredient of solid catalyst.
Ingredient of solid catalyst:
Ti 2.8wt％
Internal electron donor compd A 3.7wt%
Embodiment 2
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compd As, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 4.2wt％
Internal electron donor compd A 12.9wt%
Embodiment 3
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compd Bs, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 4.1wt％
Internal electron donor compd B 11.2wt%
Embodiment 4
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compd Es, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 3.5wt％
Internal electron donor compd E 8.7wt%
Embodiment 5
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compound F 17-hydroxy-corticosterones, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 3.9wt％
Internal electron donor compound F 17-hydroxy-corticosterone 9.8wt%
Embodiment 6
In the reactor of fully replacing, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml through nitrogen, toluene 75ml, hexane 3ml, ethanol 6.2ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compd As, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 3.7wt％
Internal electron donor compd A 7.7wt%
Embodiment 7
In the reactor of fully replacing, add 5.0g dibutoxy magnesium successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml through nitrogen, toluene 75ml, hexane 3ml, 1-octanol 6.2ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds 2.2 mmole internal electron donor compd As, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 4.7wt％
Internal electron donor compd A 11.7wt%
Embodiment 8
In the mill of fully replacing, add 10.0g dichloro magnesium successively, 1.0g TiCl through nitrogen
3, 4.5 mmole internal electron donor compd As, grinding at room temperature 12 hours.Be warming up to 100 ℃ afterwards, adopt 10 moles TiCl
4Handle isothermal reaction 2h.Stop to stir, leave standstill suspension, layering extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 5.3wt％
Internal electron donor compd A 10.5wt%
Embodiment 9
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, methyl glycidyl ether 7.5ml, ortho-phosphoric acid three propyl ester 10.5ml, toluene 75ml, hexanaphthene 3ml, 2-Ethylhexyl Alcohol 6.2ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml trichlorine one ethanolato-titanium adds 2.2 mmole internal electron donor compd As, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Adopt 20 moles TiCl again
4Handle isothermal reaction 2h.Stop to stir, leave standstill suspension, layering extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 4.9wt％
Internal electron donor compd A 12.3wt%
Comparative Examples 1
In the reactor of fully replacing through nitrogen, add the 5.0g magnesium dichloride successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h.Be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride adds two esters of 2.2 mmole internal electron donor compound phthalic acids, reaction 1h, and-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h slowly are warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill suspension, layering is slow, extracts supernatant liquid, toluene wash twice, and hexane wash twice, nitrogen dries up, and obtains the spherical solid catalyst component.
Ingredient of solid catalyst:
Ti 3.5wt％
Two ester 9.8wt% of phthalic acid
Embodiment 10
Olefinic polymerization:
Propylene polymerization
The propylene, the 75ml that lead as going into 30 ℃ in 2 liters of autoclaves of 1 hour of nitrogen replacement of 70 ℃ contain 780mg AlEt
3Anhydrous hexane, mol ratio be that Al/Si is the ingredient of solid catalyst that 20 external electron donor compound methylcyclohexyl dimethoxy silane and 10mg prepare as mentioned above.Close autoclave, add hydrogen 1.5NL, under agitation add the liquid propene of 1.2kg then.Be warming up to 70 ℃ in 5 minutes, unreacted propylene monomer is reclaimed in constant temperature polymerization 2 hours, and collected polymer 60 ℃ of vacuum-dryings 3 hours, is weighed, and carries out the insoluble mensuration of dimethylbenzene.
Embodiment 11
Propylene polymerization: ingredient of solid catalyst adopts the product of embodiment 1-10 preparation respectively
The propylene, the 75ml that lead as going into 30 ℃ in 2 liters of autoclaves of 1 hour of nitrogen replacement of 70 ℃ contain 780mg AlEt
3Anhydrous hexane, mol ratio be that Al/Si is the ingredient of solid catalyst that 20 external electron donor compound tetramethoxy-silicane and 10mg prepare as mentioned above.Close autoclave, add hydrogen 1.5NL, under agitation add the liquid propene of 1.2kg then.Be warming up to 70 ℃ in 5 minutes, unreacted propylene monomer is reclaimed in constant temperature polymerization 2 hours, and collected polymer 60 ℃ of vacuum-dryings 3 hours, is weighed, and carries out the insoluble mensuration of dimethylbenzene.
Embodiment 12
Propylene polymerization: ingredient of solid catalyst adopts the product of embodiment 1-10 preparation respectively
In with 2 liters of autoclaves of 1 hour of nitrogen replacement of 70 ℃, lead and contain 780mg Al (i-Bu) as propylene, the 75ml that goes into 30 ℃
3Anhydrous hexane, mol ratio be that Al/Si is the ingredient of solid catalyst that 20 external electron donor compound tetramethoxy-silicane and 10mg prepare as mentioned above.Close autoclave, add hydrogen 1.5NL, under agitation add the liquid propene of 1.2kg then.Be warming up to 70 ℃ in 5 minutes, unreacted propylene monomer is reclaimed in constant temperature polymerization 2 hours, and collected polymer 60 ℃ of vacuum-dryings 3 hours, is weighed, and carries out the insoluble mensuration of dimethylbenzene.
Embodiment 13
Vinyl polymerization: ingredient of solid catalyst adopts the product of embodiment 1-10 preparation respectively
At 2.0 liters of stainless steel autoclaves, after nitrogen is fully replaced, in still, add above-mentioned synthetic catalyst component (1) 20mg successively, dehydration hexane 200ml, AlEt
3Solution 1.17ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 70 ℃, charges into ethene 0.45MPa, constant voltage isothermal reaction 2h.
Embodiment 14
Ethylene copolymerization: ingredient of solid catalyst adopts the product of embodiment 1-10 preparation respectively
At 2.0 liters of stainless steel autoclaves, after nitrogen is fully replaced, in still, add above-mentioned synthetic catalyst component (1) 20mg successively, dehydration hexane 200ml, AlEt
3Solution 1.17ml (2mmol/ml), 1-hexene 20ml charges into hydrogen 0.28MPa after being warming up to 70 ℃, charges into ethylene, propylene mixed gas (the ethylene/propene mol ratio is 7:3) 0.45MPa, constant voltage isothermal reaction 2h.
Table 1
Claims (1)
1. a catalyst component that is used for olefinic polymerization is characterized in that, comprises
The MgCl of active condition
2
General formula is Ti (OR
1)
4-mX
mThe compound of titanium, R in the formula
1Be C
1～C
20Aliphatic group, or aryl radical or COOR`, R` has C
1～C
10Fatty group or aromatic base; X is a halogen atom, and m is 0 to 4 integer;
The ester class electron donor compound of general formula I;
The amount and the MgCl of ester class electron donor compound
2Mol ratio be 0.01 to 1; The content of Ti is 1.5wt%-10wt% in the catalyst component;
The general formula I of above-mentioned ester class electron donor compound is:
In the general formula I: Y is a bridge linkage group, is selected from alkyl, Si, N, S, P, Se or the O of 1 to 6 carbon; R1, R2 is selected from hydrogen, or by 1 to 20 alkyl that carbon is formed, cycloalkyl, aryl, or the derivative of alkyl, cycloalkyl, aryl; R3, R4 is selected from hydrogen, or by 1 to 20 alkyl that carbon is formed, cycloalkyl, aryl, or the derivative of alkyl, cycloalkyl, aryl, and the quantity of R3 or R4 is less than 5 arbitrary integer more than or equal to 1; R
5, R
6Be selected from the derivative of alkyl, cycloalkyl, aryl or alkyl that 1 to 30 carbon forms, cycloalkyl, aryl; N is selected from 0 to 10 arbitrary integer.
2 are used for the catalyzer of olefinic polymerization, it is characterized in that: comprise the described catalyst component of claim 1, comprise that also general formula is AlR
5 nX
3-nOrgano-aluminium compound, R in the formula
5For hydrogen or carbonatoms are 1～20 alkyl, X is a halogen, and n is the number of 0＜n≤3; Comprise that also general formula is R
2 xR
3 ySi (OR
4)
zThe external electron donor compound, R in the formula
2And R
3Be respectively carbonatoms and be 1～20 alkyl, cycloalkyl, aryl, haloalkyl or halogen, R
4For carbonatoms is 1～15 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102273690A CN101456924B (en) | 2008-11-28 | 2008-11-28 | Catalyst component for olefin polymerization and catalyst thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102273690A CN101456924B (en) | 2008-11-28 | 2008-11-28 | Catalyst component for olefin polymerization and catalyst thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101456924A CN101456924A (en) | 2009-06-17 |
| CN101456924B true CN101456924B (en) | 2010-08-11 |
Family
ID=40768069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102273690A Expired - Fee Related CN101456924B (en) | 2008-11-28 | 2008-11-28 | Catalyst component for olefin polymerization and catalyst thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101456924B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558405B (en) * | 2011-12-30 | 2014-11-05 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application thereof |
| CN107344974B (en) | 2016-05-04 | 2020-06-09 | 中国石油天然气股份有限公司 | Olefin coordination polymerization catalyst, preparation method and application |
| CN108467442B (en) | 2018-02-11 | 2021-06-01 | 中国石油天然气股份有限公司 | Olefin coordination polymerization catalyst and application thereof |
-
2008
- 2008-11-28 CN CN2008102273690A patent/CN101456924B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101456924A (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101407561B (en) | Olefin polymerizing catalyst | |
| CN102958953B (en) | For the catalyst system of olefinic polymerization | |
| US4431568A (en) | Catalyst for polymerization of olefins and polymerization process employing such catalyst | |
| RU2375378C1 (en) | Catalyst component for ethylene polymerisation, production thereof and catalyst containing this component | |
| CN101353385A (en) | Catalyzer for ethylene polymerization and copolymerization and preparing method thereof | |
| US20130196847A1 (en) | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst | |
| CN102603932A (en) | Solid catalyst component and catalyst for olefinic polymerization | |
| CN101456924B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| US5547912A (en) | Solid catalyst component for polymerizing olefins and catalyst containing the same | |
| CN106699933A (en) | Propylene polymerization catalyst, preparation method and application thereof | |
| CN101885793B (en) | Ethylene polymerization catalyst, preparation and application thereof | |
| KR20210080466A (en) | Catalyst components for olefin polymerization, catalysts and uses thereof | |
| CN105199024A (en) | Catalyst component for vinyl polymerization, catalyst and preparation method thereof | |
| CN112661883B (en) | Solid catalyst component for preparing polyolefin, catalyst system and application thereof | |
| CN112661881B (en) | Olefin polymerization catalyst component, catalyst system and olefin polymerization method | |
| WO2008066200A1 (en) | Catalyst component for olefin polymerization, and catalyst and method for producing olefin polymer using the same | |
| KR101928316B1 (en) | Solid catalyst component and catalyst for olefin polymerization | |
| CN112661882B (en) | Application of cyclohexene-1,2-dicarboxylic acid ester compound | |
| CA1248694A (en) | Process for producing poly-1-butene | |
| CN106478844B (en) | Catalyst carrier, catalyst component and catalyst for olefin polymerization | |
| EP0677066A1 (en) | Olefin polymerization catalyst | |
| JP2004503618A (en) | Catalyst for ethylene polymerization and copolymerization | |
| JPH05295025A (en) | Production of polyolefin | |
| JPH03124705A (en) | Ziegler-natta catalyst composition | |
| JP6662781B2 (en) | Method for producing propylene-based block copolymer |
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: 20100811 Termination date: 20101128 |