CN104558285A - Solid catalyst component for olefin polymerization and catalyst - Google Patents
Solid catalyst component for olefin polymerization and catalyst Download PDFInfo
- Publication number
- CN104558285A CN104558285A CN201310508654.0A CN201310508654A CN104558285A CN 104558285 A CN104558285 A CN 104558285A CN 201310508654 A CN201310508654 A CN 201310508654A CN 104558285 A CN104558285 A CN 104558285A
- Authority
- CN
- China
- Prior art keywords
- cyano group
- succinic acid
- ethyl
- butyl
- ester
- 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.)
- Granted
Links
Abstract
The invention discloses a catalyst solid component for olefin polymerization, which is a reaction product of a magnesium compound, an internal electron donor compound a disclosed as Formula II, an internal electron donor compound b disclosed as Formula III and a titanium compound disclosed as general formula IV. The magnesium compound is alkoxy magnesium or alcoholate thereof disclosed as general formula I, the average particle diameter D50 is 20-100 mu m, and the dispersion index SPAN is less than 1.1. The mole ratio of the internal electron donor compound a to the internal electron donor compound b is 1:4-4:1. The solid catalyst component for olefin polymerization and catalyst have the advantages of high polymerization activity, favorable spatial orientation capacity, favorable hydrogen regulation sensitivity, wide polymer molecular weight distribution and low micropowder content when being used for olefin polymerization; and the polymer is free of phthalate. Mg(OEt)[2-m](OEHA)[m] (I). TiX[n](OR15)[4-n] (IV).
Description
Technical field
The invention belongs to field of olefin polymerisation, be specifically related to a kind of solid catalyst component for olefine polymerization and catalyzer.
Background technology
At present, using magnesium, titanium and electron donor as the catalyst solid constituent of basal component, i.e. Ziegler-Natta(Z-N known in the field) catalyzer, can be used for CH2=CHR olefinic polyreaction, particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atom.Various internal electron donor also has some shortcomings while the corresponding polyolefin products certain features of imparting, thus limits their application.Researchist always wishes the Z-N catalyzer finding a kind of over-all properties more excellent.
Concrete, the now widely used Z-N catalyzer containing phthalic ester internal electron donor has active high, the feature of resin good combination property, but phthalic ester is proved the Fertility that can injure the mankind, thus recently do not become study hotspot containing the Z-N catalyzer of phthalic ester internal electron donor.
Molecular weight distribution (MWD) affects mechanical property and the processing characteristics of polymkeric substance.High molecular weight moieties determines the long term mechanical strength of polymkeric substance to a great extent, and low molecular weight fraction determines its extrusion performance to a great extent.The disclosed Z-N catalyzer containing 1,3-diol ester internal electron donor of CN1213080C has active high, the feature that molecular weight distribution is wide, but its molecular weight distribution prepared is wide not enough, thus limits its application.The Z-N catalyzer of succinate-containing internal electron donor disclosed in EP990201172 and US60999436 has active high, stereotaxis ability is good, the feature that resulting polymers molecular weight distribution is wide, but this catalyzer is bad to molecular weight regulator (hydrogen is the molecular weight regulator the most often adopted) susceptibility, namely, when identical hydrogen usage, the melt flow rate (MFR) (MFR) (or claiming melting index) of polymkeric substance is on the low side; And for meeting injecting products, the especially processing request of thin wall parts, polymkeric substance often needs higher MFR.When production injection moulding homopolymer or anti-impact polymkeric substance, often wish that namely polymkeric substance has high MFR to have wide molecular weight distribution simultaneously.This polymkeric substance is considered to intensity that existing good processing characteristics also had and rigidity.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of catalyst for olefines polymerizing solid ingredient and comprise the catalyzer of described catalyst solid constituent, described catalyzer high comprehensive performance, polymerization activity is high, stereospecificity good and hydrogen response is good, the molecular weight distribution of the polymkeric substance obtained is wide, and not containing phthalic ester in polymkeric substance.
According to an aspect of the present invention, provide a kind of catalyst for olefines polymerizing solid ingredient, it be magnesium compound, the reaction product of the titanium compound shown in the internal electron donor compound b shown in the internal electron donor compound a shown in formula II, formula III and general formula I V; Wherein, the mol ratio of internal electron donor compound a and internal electron donor compound b consumption is 1:4-4:1; Described magnesium compound is the alkoxyl magnesium shown in general formula I or its alcohol adduct, its median size D
50for 20-100um, dispersion index SPAN<1.1,
Mg(OEt)
2-m(OEHA)
m（I）
Wherein, Et is ethyl, and EHA is 2-ethylhexyl, 0.001≤m≤0.5, preferably 0.001≤m≤0.25, more preferably 0.001≤m≤0.1;
In formula II, R
1and R
2can be identical or not identical, be selected from hydrogen, C
1-C
14the alkyl of straight or branched, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl or aralkyl; R3 with R4 can be identical or not identical, is selected from C
1-C
10straight or branched alkyl, C
3-C
10cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl or C
7-C
20aralkyl;
R in formula III
5, R
6group is identical or different, is selected from the C of halogen and substituted or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene and C
10-C
20fused ring aryl; R
7-R
12group is identical or different, is selected from the C of hydrogen, halogen and substituted or unsubstituted straight or branched respectively
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene and C
10-C
20fused ring aryl; R
7-R
12group optionally connects into ring;
TiX
n(OR
15)
4-n（IV）
In formula IV, X is halogen; R
15for C
1-C
20alkyl, n is the integer of 0-4.
In the present invention, SPAN=(D
90-D
10)/D
50, wherein D
90represent that corresponding to cumulative percentage is the particle diameter of 90%, D
10represent that corresponding to cumulative percentage is the particle diameter of 10%, D
50represent that corresponding running summary of the points scored is the particle diameter of 50%.
Alkoxyl magnesium according to formula I of the present invention, its Chinese style I only represents the composition content of described oxyethyl group and 2-ethyl hexyl oxy, not the concrete structure of representation alkoxy magnesium.Concrete, as in Mg (OEt) (OEHA) only expression alkoxyl magnesium compound, the mol ratio of oxyethyl group and 2-ethyl hexyl oxy is 1, the mixture of its both can be mol ratio be diethoxy magnesium and two (2-ethyl hexyl oxygen) magnesium of 1, also can be oxyethyl group (2-ethyl hexyl oxy) magnesium compound, can also be the mixture of three; The mixture that the alkoxyl magnesium compound of its can be the total mole ratio of oxyethyl group and 2-ethyl hexyl oxy be various structures of 1 forms.
According to catalyst solid constituent provided by the present invention, shown in described formula II, internal electron donor compound a can be selected from following compound: 2,3-di-isopropyl-2-cyano group dimethyl succinate, 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl, 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester, 2,3-di-isopropyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-isopropyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-diisobutyl-2-cyano group dimethyl succinate, 2,3-diisobutyl-2-cyano group diethyl succinate, 2,3-diisobutyl-2-cyano group succinic acid di-n-propyl ester, 2,3-diisobutyl-2-cyano group diisopropyl ester amber acid, 2,3-diisobutyl-2-cyano group succinic acid di-n-butyl, 2,3-diisobutyl-2-cyano group succinic acid diisobutyl esters, 2,3-diisobutyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-diisobutyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-di-sec-butyl-2-cyano group dimethyl succinate, 2,3-di-sec-butyl-2-cyano group diethyl succinate, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-sec-butyl-2-cyano group diisopropyl ester amber acid, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-butyl, 2,3-di-sec-butyl-2-cyano group succinic acid diisobutyl esters, 2,3-di-sec-butyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-sec-butyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-bicyclopentyl-2-cyano group dimethyl succinate, 2,3-bicyclopentyl-2-cyano group diethyl succinate, 2,3-bicyclopentyl-2-cyano group succinic acid di-n-propyl ester, 2,3-bicyclopentyl-2-cyano group diisopropyl ester amber acid, 2,3-bicyclopentyl-2-cyano group succinic acid di-n-butyl, 2,3-bicyclopentyl-2-cyano group succinic acid diisobutyl esters, 2,3-bicyclopentyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-bicyclopentyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-dicyclohexyl-2-cyano group dimethyl succinate, 2,3-dicyclohexyl-2-cyano group diethyl succinate, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-propyl ester, 2,3-dicyclohexyl-2-cyano group diisopropyl ester amber acid, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-butyl, 2,3-dicyclohexyl-2-cyano group succinic acid diisobutyl esters, 2,3-dicyclohexyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-dicyclohexyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl) and the positive butyl ester (R of 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl); Be preferably selected from 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl and 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester.
According to catalyst solid constituent provided by the present invention, shown in described formula III, internal electron donor compound b is selected from following compound: 2-sec.-propyl-2-isopentyl-1, 3 propylene glycol dibenzoates, 2, 4-glycol dibenzoate, 3-methyl-2, 4-glycol dibenzoate, 3-ethyl-2, 4-glycol dibenzoate, 2, 2-dimethyl-2, 4-glycol dibenzoate, 3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate and 4-ethyl-3, 5-heptanediol dibenzoate, be preferably selected from 2, 4-glycol dibenzoate, 3, 5 heptanediol dibenzoates and 4-ethyl-3, 5 heptanediol dibenzoates.
To those skilled in the art, can easily reason out, all above-claimed cpd a and b both can use with pure optical isomeric form, also can use with the form of the mixture of the mixture of enantiomer or diastereomer and enantiomer.When using a kind of pure isomer, ordinary skill known in the art or technique is usually adopted to make them be separated.Particularly a part of the compounds of this invention a or compound b can respectively with pure racemize or mesomeric form, or the form of their mixture uses.
According to catalyst solid constituent provided by the present invention, relative to the magnesium in 1mol magnesium compound, total usage quantity of described interior Donor compound a and internal electron donor compound b is 0.005 ~ 10mol, is preferably 0.01-1mol; The mole number of described titanium compound is 0.5-100mol, preferred 1-50mol.
According to a preferred embodiment of catalyst solid constituent provided by the present invention, the mol ratio of described internal electron donor compound a and internal electron donor compound b consumption is 2:3-3:2.
According to alkoxyl magnesium carrier of the present invention, may containing micro-magnesium halide (as MgI
2or MgCl
2) or its alcohol adduct, if but should higher than 90% with the cubage purity of formula I magnesium compound, preferably higher than 95%, more preferably more than 98%.
Importantly, content control overflow 0.001≤m≤0.5 of magnesium ethylate and different octyloxy magnesium in alkoxyl magnesium carrier of the present invention.M value is excessive, and reaction prepared by carrier can become too weak, and size of particles is also difficult to reach OK range of the presently claimed invention; M value is too small, then the reaction that prepared by carrier can too acutely be difficult to control, and the distribution of sizes (SPAN value) of carrier particle also can broaden, and has influence on ultrafine powder content and the tap density of final catalyst activity and prepared polymkeric substance.In a word, if depart from this compositing range, catalyzer prepared by gained carrier is all difficult to show effect of the present invention, not preferably.More preferably 0.001≤m≤0.25, particularly preferably 0.001≤m≤0.1.
Under preferable case, described spherical alkoxyl magnesium carrier median size 25 ~ 80um; Size distribution index SPAN<1.05.
According to alkoxyl magnesium carrier of the present invention, reacted under an inert atmosphere by MAGNESIUM METAL, ethanol, isooctyl alcohol (2-Ethylhexyl Alcohol) and Mixed bittern agent and prepare.Described Mixed bittern agent is the combination of halogen and halogen compounds, and the indefiniteness of described halogen and halogen compounds is selected: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, Repone K, Potassium Bromide, potassiumiodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, oxyethyl group magnesium iodide, methoxyl group magnesium iodide, sec.-propyl magnesium iodide, hydrogenchloride, chloroacetyl chloride etc.
According to the preparation of alkoxyl magnesium carrier of the present invention, the wherein combination of the preferred iodine of Mixed bittern agent and magnesium chloride.The weight ratio of iodine and magnesium chloride is preferably 1:0.05 ~ 0.05:1, is more preferably 0.1:1 ~ 1:0.02.
According to the preparation of alkoxyl magnesium carrier of the present invention, the mol ratio of the halogen atom wherein in MAGNESIUM METAL and Mixed bittern agent is 1:0.0002 ~ 1:0.2, preferred 1:0.001 ~ 1:0.08; The weight ratio of alcohol total amount and magnesium is 4:1 ~ 50:1, preferred 6:1 ~ 25:1; Wherein the mol ratio X of ethanol and isooctyl alcohol is 3 (2-m)/m>X> (2-m)/m.The water-content of the present invention to alcohol used is not particularly limited, and in order to make the alkoxyl magnesium of acquisition have better performance, requires that moisture content is more few better.In alcohol, water-content general control is at below 1000ppm, and preferably water content controls at below 200ppm.
In the present invention, the magnesium used is MAGNESIUM METAL, when its reactivity worth is good, whatsoever shape can, even if can the using of particulate state, silk ribbon shape or the shape such as Powdered.In order to the Average Particle Diameters of the alkoxyl magnesium impelling generation remains in suitable scope, and particle form is excellent, and preferable alloy magnesium is the spheroidal particle of median size 10 ~ 360 μm, more preferably the spheroidal particle of median size 50 ~ 300 μ Μ.In addition, the surface of MAGNESIUM METAL is not particularly limited, but forms the tunicles such as oxyhydroxide on the surface of MAGNESIUM METAL, the total amount of activated carbon can be made to decline, react slack-off, the total content >95% of preferred activated carbon, more preferably the total content >98% of activated carbon.
Inert atmosphere described in the present invention, preferred nitrogen atmosphere, argon atmospher.
According to the preparation of alkoxyl magnesium carrier of the present invention, in preparation process, can alternatively be used inert organic solvents.In the present invention, described inert solvent can be selected from C
6~ C
10alkane or aromatic hydrocarbons at least one, at least one in preferred hexane, heptane, octane, decane, benzene,toluene,xylene or derivatives thereof etc.
According to the preparation of alkoxyl magnesium carrier of the present invention, halogenating agent Adding Way has no particular limits, can be dissolved in alcohol and add, also can directly join in MAGNESIUM METAL and alcohol with solid or liquid form, can also adopt in the process of heating of metal magnesium and alcoholic solution, the method of instillation halogenating agent alcoholic solution, thus be prepared the reaction of carrier.
According to the preparation of alkoxyl magnesium carrier of the present invention, wherein the adding of MAGNESIUM METAL, alcohol, halogenating agent and inert solvent, can, at first by disposable for reactant input, gradation also can be selected to drop into.Gradation drops into the hydrogen that raw material can prevent instantaneous generation a large amount of, and prevents the spittle of alcohol or the halogenating agent caused because instantaneous a large amount of hydrogen produces, and considers, preferred this feed way from the angle of safety perspective and reaction homogeneity.The number of times of segmentation can be determined according to the consumption of the scale of reactor and various material.
According to the preparation of alkoxyl magnesium carrier of the present invention, described temperature of reaction is 30-90 DEG C, preferred 30-80 DEG C, more preferably 50-75 DEG C.The time of described reaction is 2 ~ 30 hours.In actually operating, the discharge of the hydrogen that can be produced by observing response stops judging that reaction terminates.
After having reacted, the final product alkoxyl magnesium carrier obtained can kept dry, in inert diluent used when also can be suspended in the catalyst solid constituent for the preparation of lower step.
According in another preferred embodiment of catalyst solid constituent provided by the invention, in the general formula I V of described titanium compound, X is preferably chlorine, bromine or iodine; R
15be preferably C
1-C
5alkyl, n is the integer of 0-4.Be preferably selected from four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-titan-alkoxide and single halogen titan-alkoxide, be preferably selected from titanium tetrahalide.At least one of described four titan-alkoxides preferably in following compound: tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, four cyclohexyloxy titaniums or four phenoxide titaniums.At least one of described titanium tetrahalide preferably in following compound: titanium tetrachloride, titanium tetrabromide or titanium tetra iodide.At least one of described three halogen titan-alkoxides preferably in following compound: trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide or tribromo ethanolato-titanium.At least one of described dihalo-dialkoxy titanium preferably in following compound: dichloro dimethoxy titanium, dichlorodiethyl oxygen base titanium, dichloro two positive propoxy titanium, dichloro diisopropoxy titanium or dibromo diethoxy titanium.The described at least one of single halogen tri-alkoxy titanium preferably in following compound: a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium or chlorine three titanium isopropoxide.In a specific embodiment, described titanium compound is titanium tetrachloride.
According to catalyst solid constituent of the present invention, described magnesium compound, described electron donor compound a, described electron donor compound b and described titanium compound contact reacts can carry out Kaolinite Preparation of Catalyst solid ingredient by any way.Such as, can prepare by the following method:
Method one:
1. alkoxyl magnesium carrier, electron donor compound a, electron donor compound b and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent, filters; 3. repeat the 2nd step reaction 2-4 time; 3. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method two:
1. the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, filter; 2. the mixture that gained solid substance adds titanium compound, the mixture of inert diluent and all the other electron compound as and electron donor compound b is formed continues reaction, filters; 3. gained solid substance continues the mixture continuation reaction adding titanium compound and inert diluent, filters; 4. repeat the 3rd step reaction 2-4 time; 5. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method three:
1. alkoxyl magnesium carrier and inert diluent are mixed with suspension, the mixture reaction then formed with titanium compound and inert diluents, add electron donor compound a and electron donor compound b, continue reaction, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent formation, filters; 3. repeat the 2nd step reaction 2-4 time; 4. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
Method four:
1. the mixture of alkoxyl magnesium carrier, part electron donor compound a and electron donor compound b and inert diluent are mixed with suspension, then the mixture reaction formed with titanium compound and inert diluents, add the mixture of all the other electron donor compound as and electron donor compound b, continue reaction, filter; 2. gained solid substance adds the mixture continuation reaction of titanium compound and inert diluent formation, filters; 3. repeat the 2nd step reaction 2-4 time; 4. wash above-mentioned solid substance with inert solvent and obtain catalyst solid constituent.
According to the preparation of catalyst solid constituent of the present invention, the consumption of described inert diluent is relative to the mol ratio (0.5-100) of the magnesium in alkoxyl magnesium compound: 1; Preferably (1-50): 1.Preferred inert diluent is toluene.
According to the preparation of catalyst solid constituent of the present invention, alkoxyl magnesium, titanium compound, inert diluent and electron donor compound a and electron donor compound b are preferably according to following conditioned response: temperature of reaction is-40 ~ 200 DEG C, more preferably-20 ~ 150 DEG C; Reaction times is 1 minute ~ 20 hours, is more preferably 5 minutes ~ 8 hours.
According to the preparation of catalyst solid constituent of the present invention, preferred washing inert solvent is hexane.For the method for washing, there is no particular limitation, the modes such as preferred decant, filtration.The usage quantity of inert solvent, washing time, washing times are not particularly limited, and usually use 1 ~ 1000 mole relative to the compound of 1 mole of magnesium, are preferably the solvent of 10 ~ 500 moles, usually wash 1 ~ 24 hour, preferably 6 ~ 10 hours.In addition from the homogeneity of washing and the aspect of detersive efficiency, preferably stir in washing operation.
According to the present invention, each component contained in described catalyst solid constituent content can there is no particular limitation, can be conducive to carrying out olefinic polymerization and obtain high melt flow rate (MFR) and the wide olefin polymer of molecular weight distribution.Under preferable case, with the gross weight of described catalyst solid constituent for benchmark, in described catalyst solid constituent, the content (or claiming in the titanium content of titanium elements) of titanium elements is 1-8%, the content (or claiming in the Mg content of magnesium elements) of magnesium elements is 10-70%, the content (or claiming in the content of halogen of halogens) of halogen is 20-85%, the content of the total amount of described internal electron donor a and internal electron donor b is 2-30%, and wherein the mol ratio of internal electron donor a and internal electron donor b content is 1:4-4:1; Preferably, with the gross weight of described catalyst solid constituent for benchmark, in described catalyst solid constituent, the content (or claiming in the titanium content of titanium elements) of titanium elements is 1.6-6%, the content (or claiming in the Mg content of magnesium elements) of magnesium elements is 15-40%, the content (or claiming in the content of halogen of halogens) of halogen is 30-80%, the content of the total amount of described internal electron donor a and internal electron donor b is 3-20%, and wherein the mol ratio of internal electron donor a and internal electron donor b is 1:3-3.5:1.
According to another aspect of the present invention, present invention also offers a kind of olefin polymerization catalysis, described catalyzer comprises the reaction product of following component:
The catalyst solid constituent that I is above-mentioned;
II promotor organo-aluminium compound;
III optionally, external donor compound.
According to the present invention, describedly optionally show the reaction product that described catalyzer comprises component i and component ii or the reaction product of component i, component ii and component iii.
According to olefin polymerization catalysis of the present invention, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst that the organo-aluminium compound as promotor can be commonly used for field of olefin polymerisation.In the preferred case, described organo-aluminium compound is general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3.At least one of described organo-aluminium compound preferably in following compound: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, more preferably triethyl aluminum and/or triisobutyl aluminium.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.In a specific embodiment, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1.
According to olefin polymerization catalysis of the present invention, described external electron donor component can be various external electron donors known in the industry, is not particularly limited.In the preferred case, the general formula of described external donor compound is R
1'' m''r
2'' n''si (OR
3'')
4-m''-n'', wherein, R
1''and R
2''identical or different, be selected from halogen, hydrogen atom, C independently of one another
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3''be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M'' and n'' is respectively the integer of 0-3, and m''+n''<4.Preferably, silicoorganic compound are selected from least one in following compound: trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes, these silicoorganic compound can individually use, and also two or more can be combinationally used.More preferably, the silicoorganic compound shown in formula VI are selected from least one in following compound: at least one in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane, propyl triethoxy base silane, isobutyl triethoxy silane;
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In a specific embodiment, the mol ratio of the aluminium in described organo-aluminium compound and described external donor compound is 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.This just means, when described external electron donor is silicoorganic compound, the mol ratio of described organo-aluminium compound and silicoorganic compound counts 0.1:1-500:1 with aluminium/silicon, preferred 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the existence of above-mentioned catalyst solid constituent or above-mentioned catalyzer.
Olefine polymerizing process of the present invention may be used for all polymerizations of alkene, also may be used for multiple alkene to carry out copolymerization.The method also can be used for preparing high isotactic, high fusion index polymkeric substance.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions is the temperature of olefinic polymerization is 0-150 DEG C, preferred 60-130 DEG C; Time is 0.1-5 hour, preferred 0.5-4 hour, and pressure is 0.01-10MPa, is preferably 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
Alkene in the present invention, comprises as general formula CH
2alkene shown in=CHR, wherein R is hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl.Described CH
2at least one in the preferred following compound of alkene shown in=CHR: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; More preferably at least one in ethene, propylene and 1-butylene.
In a specific embodiment of olefine polymerizing process in the present invention, the temperature of described polymerization is 85-130 DEG C, preferred 95-110 DEG C.
In the present invention, described catalyst solid constituent, organo-aluminium compound and external donor compound were first carried out pre-contact before contacting olefinic monomer, and then contact with olefinic monomer and carry out polyreaction.In the field of businessly also be referred to as pre-contact or pre-complexing; The time of pre-contact is 0.1-30min, preferred 1-10 minute; The temperature of pre-contact is-20-80 DEG C, preferred 10-50 DEG C.
According to olefine polymerizing process of the present invention (if temperature of reaction is 85-130 DEG C), the reaction of preferred alkenes polymerizing catalyst each component adopts the method for pre-contact to carry out.The time of pre-contact is 0.1-30min, preferred 1-10 minute; The temperature of pre-contact is-20-80 DEG C, preferred 10-50 DEG C.
In addition, olefin polymerization catalysis of the present invention first can also be carried out prepolymerization under the existence of olefinic monomer (on a small quantity), and then the material obtained after prepolymerization is contacted with olefinic monomer further react.This technology is in the field of business is referred to as " prepolymerization " technique, contributes to the raising etc. of polymerization catalyst activity and polymer bulk density.According to olefin high-temperature polymerization method of the present invention, olefin polymerization catalysis can adopt " prepolymerization " technique, also can not adopt " prepolymerization " technique, preferably adopts " prepolymerization " technique.Described prepolymerized multiplying power, the polymkeric substance namely produced and the mass ratio of catalyzer are 2-3000gPP/gCat, preferred 3-2000gPP/gCat; The temperature of " prepolymerization " is-20-80 DEG C, preferred 10-50 DEG C.
In olefine polymerizing process of the present invention, described " pre-contact " technique and " pre-complexing " technique are all alternative to be used.Concrete, can implement to adopt " pre-contact " technique and the polymerization process that do not adopt " pre-complexing " technique; Also can implement not adopt " pre-contact " technique and the polymerization process adopting " pre-complexing " technique; Also can implement both to have adopted " pre-contact " technique, also adopt the polymerization process of " pre-complexing " technique; Can also be each component is joined in olefinic monomer respectively directly carry out polyreaction, namely neither implement " pre-contact " and also do not implement " prepolymerization ".Preferred enforcement both adopted " pre-contact " technique, also adopted the polymerization process of " pre-complexing " technique.
Catalyst solid constituent prepared by the present invention and catalyzer, have excellent over-all properties when it is applied to olefinic polymerization, demonstrates certain synergy, significantly improves the activity of catalyzer; Meanwhile, the vertical structure orientation property of catalyzer is good and hydrogen response is good, and the molecular weight distribution of polymkeric substance is wide, degree of isotacticity good and ultrafine powder content is low; In addition, the safety coefficient of catalyzer high (not containing phthalic ester).Catalyst solid constituent prepared by the present invention and catalyzer, its excellent over-all properties shown is applicable to requiring exploitation that is higher and eco-friendly Polyolefin Resin Grades to mechanical property and processing characteristics.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, but do not form any restriction of the present invention.
In following examples, evaluate and test and carry out by the following method:
1) Breadth parameter of molecular weight distribution Mw/Mn: adopt Polymer Laboratories company of Britain to produce the molecular weight distribution of PL-GPC220 gel permeation chromatograph in conjunction with IR5 type infrared detector working sample, chromatographic column is 3 series connection Plgel10 μm of MIXED-B post, solvent and moving phase are 1,2,4-trichlorobenzene is (containing 0.3g/1000ml oxidation inhibitor 2,6-ditertbutylparacresol), column temperature 150 DEG C, flow velocity 1.0ml/min, adopts PL company EasiCal PS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration.
2) the titanium atom content in catalyst solid constituent is according to the 721 spectrophotometer tests purchased from An Hemeng (Tianjin) development in science and technology company limited.
3) melting index of polymkeric substance is that the model of use purchased from the new experimental instrument and equipment company limited in Changchun is for XRZ-00 fusion index instrument is according to the method mensuration specified in GB/T3682-2000.
4) Malvern Mastersizer
tM2000 normal hexane dispersion agent laser diffractometries measure grain size, size-grade distribution (wherein, the SPAN=(D90-D10)/D50 of alkoxyl magnesium and catalyzer).
5) in olefin polymerization catalyst components, internal electron donor content uses Agilent7890 gas Chromatographic Determination.
6) mensuration of the m value in carrier: get 0.1 gram of carrier, add 10mL1.2mol/L aqueous hydrochloric acid, shakes and makes it decompose in 24 hours, uses gas-chromatography quantitative, be then calculated as follows m value to ethanol wherein and 2-Ethylhexyl Alcohol:
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
7) testing method of polymkeric substance degree of isotacticity comprises: 2 grams of dry polymer samples, is placed in extractor and after 6 hours, residuum is dried to constant weight, by following formulae discovery degree of isotacticity with the extracting of boiling heptane:
Polymer quality/2 × 100 after degree of isotacticity (%)=extracting.
8) fine polymer powder content (%): with 100 eye mesh screen screening resulting polymers, the small particle size powder under sieve accounts for the weight percent of total polymer.
The preparation of alkoxyl magnesium
Alkoxyl magnesium carrier (1) Mg (OEt)
2-m(OEHA)
mpreparation:
After fully replacing the 16L voltage-resistant reactor with agitator with nitrogen, in reactor, add 10L ethanol, 300mL2-ethylhexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder.Stir makes system be warming up to 75 DEG C of back flow reaction simultaneously, till no longer including hydrogen discharge.Stopped reaction, uses 3L washing with alcohol, filtration, drying.The alkoxyl magnesium carrier obtained.Gained alkoxyl magnesium carrier D50=30.2um, Span value 0.81, m value 0.015.
Alkoxyl magnesium carrier (2) Mg (OEt)
2preparation:
Preparation method is identical with alkoxyl magnesium carrier a1, just 300mL2-ethylhexanol is replaced with 300mL ethanol.Gained alkoxyl magnesium carrier D50=37.3um, Span value 1.51, m value is 0.
Embodiment 1
The preparation of catalyst solid constituent A1:
Get 10g alkoxyl magnesium compound (1), 50mL toluene, 1.5mmol2,3-di-isopropyl-2-cyano group diethyl succinate (compound a, preparation method's preparation with reference in CN101811983A) and 6.0mmol3,5-heptanediol dibenzoate (compound b, with reference to preparation method's preparation in CN1213080C) is mixed with suspension.Repeating through high pure nitrogen in the 300mL reactor of replacing, add toluene 40mL and titanium tetrachloride 60mL, be warming up to 80 DEG C, then add in still by the suspension prepared, constant temperature 1 hour, is slowly warming up to 110 DEG C, and constant temperature 2 hours, press filtration obtains solid substance.The mixed solution that gained solid substance adds toluene 78mL and titanium tetrachloride 52mL 110 DEG C of stir process 1 hour, so process 3 times.Press filtration, the solid of gained hexanes wash 4 times, each 150mL, press filtration, drying, obtain catalyst solid constituent.Titanium atom content 4.0wt% in gained catalyst solid constituent A1,2,3-di-isopropyl-2-cyano group diethyl succinate content 2.9wt%, 3,5-heptanediol dibenzoate 6.2wt%.
Olefinic polyreaction
The 5 liters of autoclave gas-phase propenes being connected with catalyst feeder, propylene and hydrogen feed line are fully replaced.In catalyst feeder, add the hexane solution (concentration of triethyl aluminum is 0.5mol/L) of 5mL triethyl aluminum, the hexane solution (concentration of CHMMS is 0.1mol/L) of 1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and the above-mentioned catalyst solid constituent A1 prepared of 10-14mg under room temperature, after mixing 2 minutes (pre-complexing), join autoclave.Close autoclave, introduce the liquid propene of hydrogen (standard liter) and 2.4L; In under agitation 20 minutes, temperature is risen to 70 DEG C.At 70 DEG C, polyreaction is after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collects and obtains polymer P.
Wherein the polymerization activity of catalyzer is calculated by following formula:
Polymerization activity=polymer P quality (kilogram)/alkene catalyst component A1 quality (g)
The polymerization activity of catalyzer, melt index (MI), polymkeric substance degree of isotacticity (II), polymer bulk density (BD), molecular weight distribution (MWD) and weight-average molecular weight (Mw) result as shown in table 2.
Embodiment 2-4, comparative example 1-4:
The preparation method of catalyst solid constituent A2, A3, A4, B1, B2, B3, B4 and polymerization process are with embodiment 1, and difference is the consumption of 2,3-di-isopropyl-2-cyano group diethyl succinate (a) and 3,5-heptanediols dibenzoate (b).Gained catalyst solid constituent and composition are in table 1.
The step of olefinic polyreaction is with embodiment 1, and difference is to use catalyst solid constituent A2, A3, A4, B1, B2, B3, B4 respectively.Data are in table 2.
Comparative example 5
Catalyst solid constituent B5 preparation method is with embodiment 1, and difference is that 2,3-di-isopropyl-2-cyano group diethyl succinate (a) and 3,5-heptanediols dibenzoate (b) all replace with dibutyl phthalate.Gained catalyst solid constituent and composition are in table 1.Olefine polymerizing process is with embodiment 1, and difference is to adopt catalyst solid constituent B5.Data are in table 2.
Comparative example 6
The preparation of catalyst solid constituent B6:
The preparation method of catalyst solid constituent B6 is identical with A1 preparation method in embodiment 1, is just replaced with (2) by alkoxyl magnesium carrier (1).Gained catalyst solid constituent and composition are in table 1.Olefine polymerizing process is with embodiment 1, and difference is to adopt catalyst solid constituent B4.Data are in table 2.
Table 1
Table 2
As can be seen from table 1 and 2 data: under equal conditions, internal electron donor compound b, pure internal electron donor compound a(B1 and the B2 pure with use) compare, according to catalyzer provided by the invention, there is good over-all properties, wider molecular weight distribution, higher tap density, higher isotactic index and good melting index; Especially to be used alone a kind of internal electron donor all high for the polymerization activity ratio of catalyzer, and this also shows to demonstrate certain synergistic effect according to catalyzer provided by the invention.In addition, when exceeding the molar ratio range of internal electron donor compound b of the present invention and a, can not get above-mentioned effect (B3-B4).With adopting the catalyzer of phthalic ester (B5) to compare in prior art, not only increasing the safety coefficient of catalyzer, while maintenance high activity of catalyst and high degree, also greatly having widened the molecular weight distribution of polymkeric substance.In addition, not only catalyst activity is on the low side for the catalyzer using common alkoxyl magnesium carrier to prepare, and etaer micropowders too high levels, be unfavorable for that catalyst application is in the preparation (B6) of polymkeric substance.In a word, alkene catalyst solid ingredient prepared by the present invention is applied to polyolefin polymerization and has excellent over-all properties, demonstrate certain synergy, not only high, the vertical structure orientation property of catalyst activity is good and hydrogen response is good, and the molecular weight distribution of polymkeric substance is wide, degree of isotacticity is high; Meanwhile, the safety coefficient of catalyzer high (not containing phthalic ester).
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (12)
1. a catalyst for olefines polymerizing solid ingredient, it comprises the reaction product of the titanium compound shown in the internal electron donor compound b shown in the internal electron donor compound a shown in magnesium compound, formula II, formula III and general formula I V; Wherein, the mol ratio of described internal electron donor compound a and internal electron donor compound b consumption is 1:4-4:1; Described magnesium compound is the alkoxyl magnesium shown in general formula I or its alcohol adduct, its median size D
50for 20-100um, dispersion index SPAN<1.1,
Mg(OEt)
2-m(OEHA)
m（I）
Wherein, Et is ethyl, and EHA is 2-ethylhexyl, 0.001≤m≤0.5, preferably 0.001≤m≤0.25, more preferably 0.001≤m≤0.1;
In formula II, R
1and R
2can be identical or not identical, be selected from hydrogen, C
1-C
14the alkyl of straight or branched, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10alkaryl or aralkyl; R3 with R4 can be identical or not identical, is selected from C
1-C
10straight or branched alkyl, C
3-C
10cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl or C
7-C
20aralkyl;
In formula III, R
5, R
6group is identical or different, is selected from the C of halogen and substituted or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene and C
10-C
20fused ring aryl; R
7-R
12group is identical or different, is selected from the C of hydrogen, halogen and substituted or unsubstituted straight or branched respectively
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene and C
10-C
20fused ring aryl; R
7-R
12group optionally connects into ring;
TiX
n(OR
15)
4-n（IV）
In formula IV, X is halogen; R
15for C
1-C
20alkyl, n is the integer of 0-4.
2. catalyst solid constituent according to claim 1, it is characterized in that, shown in described formula II, internal electron donor compound a is selected from following compound: 2,3-di-isopropyl-2-cyano group dimethyl succinate, 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl, 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester, 2,3-di-isopropyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-isopropyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-isopropyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-diisobutyl-2-cyano group dimethyl succinate, 2,3-diisobutyl-2-cyano group diethyl succinate, 2,3-diisobutyl-2-cyano group succinic acid di-n-propyl ester, 2,3-diisobutyl-2-cyano group diisopropyl ester amber acid, 2,3-diisobutyl-2-cyano group succinic acid di-n-butyl, 2,3-diisobutyl-2-cyano group succinic acid diisobutyl esters, 2,3-diisobutyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-diisobutyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-diisobutyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-di-sec-butyl-2-cyano group dimethyl succinate, 2,3-di-sec-butyl-2-cyano group diethyl succinate, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-sec-butyl-2-cyano group diisopropyl ester amber acid, 2,3-di-sec-butyl-2-cyano group succinic acid di-n-butyl, 2,3-di-sec-butyl-2-cyano group succinic acid diisobutyl esters, 2,3-di-sec-butyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-di-sec-butyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-di-sec-butyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-bicyclopentyl-2-cyano group dimethyl succinate, 2,3-bicyclopentyl-2-cyano group diethyl succinate, 2,3-bicyclopentyl-2-cyano group succinic acid di-n-propyl ester, 2,3-bicyclopentyl-2-cyano group diisopropyl ester amber acid, 2,3-bicyclopentyl-2-cyano group succinic acid di-n-butyl, 2,3-bicyclopentyl-2-cyano group succinic acid diisobutyl esters, 2,3-bicyclopentyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-bicyclopentyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl), the positive butyl ester (R of 2,3-bicyclopentyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl), 2,3-dicyclohexyl-2-cyano group dimethyl succinate, 2,3-dicyclohexyl-2-cyano group diethyl succinate, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-propyl ester, 2,3-dicyclohexyl-2-cyano group diisopropyl ester amber acid, 2,3-dicyclohexyl-2-cyano group succinic acid di-n-butyl, 2,3-dicyclohexyl-2-cyano group succinic acid diisobutyl esters, 2,3-dicyclohexyl-2-cyano group succinic acid-1-methyl esters-4-ethyl ester (R
1=methyl, R
2=ethyl), 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-methyl esters (R
1=ethyl, R
2=methyl), the positive butyl ester of 2,3-dicyclohexyl-2-cyano group succinic acid-1--4-ethyl ester (R
1=normal-butyl, R
2=ethyl) and the positive butyl ester (R of 2,3-dicyclohexyl-2-cyano group succinic acid-1-ethyl ester-4-
1=ethyl, R
2=normal-butyl); Be preferably selected from 2,3-di-isopropyl-2-cyano group diethyl succinate, 2,3-di-isopropyl-2-cyano group succinic acid di-n-propyl ester, 2,3-di-isopropyl-2-cyano group diisopropyl ester amber acid, 2,3-di-isopropyl-2-cyano group succinic acid di-n-butyl and 2,3-di-isopropyl-2-cyano group succinic acid diisobutyl ester.
3. catalyst solid constituent according to claim 1 and 2, it is characterized in that, shown in described formula III, internal electron donor compound b is selected from following compound: 2-sec.-propyl-2-isopentyl-1, 3 propylene glycol dibenzoates, 2, 4-glycol dibenzoate, 3-methyl-2, 4-glycol dibenzoate, 3-ethyl-2, 4-glycol dibenzoate, 2, 2-dimethyl-2, 4-glycol dibenzoate, 3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate and 4-ethyl-3, 5-heptanediol dibenzoate, be preferably selected from 2, 4-glycol dibenzoate, 3, 5 heptanediol dibenzoates and 4-ethyl-3, 5 heptanediol dibenzoates.
4. according to the ingredient of solid catalyst in claim 1-3 described in any one, it is characterized in that, the mol ratio of described internal electron donor compound a and internal electron donor compound b consumption is 2:3-3:2.
5. according to the ingredient of solid catalyst in claim 1-4 described in any one, it is characterized in that, with the gross weight of described catalyst solid constituent for benchmark, the content of titanium elements is 1-8%, the content of magnesium elements is 10-70%, the content of halogen is 20-85%, the content of the total amount of described internal electron donor a and internal electron donor b is 2-30%, and wherein the mol ratio of internal electron donor a and internal electron donor b content is 1:4-4:1; Preferably, the content of titanium elements is 1.6-6%, the content of magnesium elements is 15-40%, the content of halogen is 30-80%, the content of the total amount of described internal electron donor a and internal electron donor b is 3-20%, and wherein the mol ratio of internal electron donor a and internal electron donor b is 1:3-3.5:1.
6. according to the catalyst solid constituent in claim 1-5 described in any one, it is characterized in that, in the general formula I V of described titanium compound, X is chlorine, bromine or iodine, R
15for C
1-C
5alkyl, preferred described titanium compound is selected from four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-titan-alkoxide and single halogen titan-alkoxide, is more preferably titanium tetrahalide.
7. an olefin polymerization catalysis, comprises the reaction product of following component:
Catalyst solid constituent in I claim 1-6 described in any one;
II promotor organo-aluminium compound;
III optionally, external donor compound.
8. catalyzer according to claim 7, is characterized in that, the general formula of described organo-aluminium compound is AlR'
n'x'
3-n', wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3.
9. the catalyzer according to claim 7 or 8, is characterized in that, described external donor compound is general formula R
1'' m''r
2'' n''si (OR
3'')
4-m''-n''shown silicoorganic compound, wherein, R
1''and R
2''identical or different, be selected from halogen, hydrogen atom, C independently of one another
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3''be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M'' and n'' is respectively the integer of 0-3, and m''+n''<4.
10. according to the catalyzer in claim 7-9 described in any one, it is characterized in that, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1; Aluminium in described organo-aluminium compound and the mol ratio of external electron donor are 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.
11. 1 kinds of olefine polymerizing process, described alkene in claim 1-6 in catalyst solid constituent described in any one or claim 7-10 catalyzer described in any one existence under be polymerized.
12. methods according to claim 11, is characterized in that, the temperature of described polymerization is 85-130 DEG C, preferred 95-110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310508654.0A CN104558285B (en) | 2013-10-24 | 2013-10-24 | Solid catalyst component for olefin polymerization and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310508654.0A CN104558285B (en) | 2013-10-24 | 2013-10-24 | Solid catalyst component for olefin polymerization and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558285A true CN104558285A (en) | 2015-04-29 |
| CN104558285B CN104558285B (en) | 2017-02-15 |
Family
ID=53075431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310508654.0A Active CN104558285B (en) | 2013-10-24 | 2013-10-24 | Solid catalyst component for olefin polymerization and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558285B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608933A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
| CN107033263A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院化学研究所 | One kind prepares wide distribution polyolefin catalyst system and catalyzing and its application |
| CN108219038A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component and preparation method of alkoxyl magnesium particle |
| CN109679005A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN115246898A (en) * | 2021-04-27 | 2022-10-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method thereof, composite catalyst containing catalyst and application |
| CN116041575A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221573C (en) * | 2000-10-13 | 2005-10-05 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for polymerization of olefins |
| CN1948350A (en) * | 2005-10-14 | 2007-04-18 | 中国石油化工股份有限公司 | Solid catalyst composition used for olefine polymerization and catalyst thereof |
| CN102372651A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | 2-cycloalkyl-3-secondary alkyl-2-cyansuccinate compounds, preparation method thereof and application thereof |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
-
2013
- 2013-10-24 CN CN201310508654.0A patent/CN104558285B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221573C (en) * | 2000-10-13 | 2005-10-05 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for polymerization of olefins |
| CN1948350A (en) * | 2005-10-14 | 2007-04-18 | 中国石油化工股份有限公司 | Solid catalyst composition used for olefine polymerization and catalyst thereof |
| CN102372651A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | 2-cycloalkyl-3-secondary alkyl-2-cyansuccinate compounds, preparation method thereof and application thereof |
| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608933A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
| CN106608933B (en) * | 2015-10-27 | 2019-03-26 | 中国石油化工股份有限公司 | Catalytic component and its preparation method and application for olefinic polymerization |
| CN107033263A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院化学研究所 | One kind prepares wide distribution polyolefin catalyst system and catalyzing and its application |
| CN107033263B (en) * | 2016-02-04 | 2020-07-24 | 中国石油化工股份有限公司 | Catalytic system for preparing wide-distribution polyolefin and application thereof |
| CN109679005A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of alkene batch polymerization processes |
| CN108219038A (en) * | 2018-01-09 | 2018-06-29 | 为信（深圳）材料科技有限公司 | The component and preparation method of alkoxyl magnesium particle |
| CN115246898A (en) * | 2021-04-27 | 2022-10-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method thereof, composite catalyst containing catalyst and application |
| CN115246898B (en) * | 2021-04-27 | 2023-08-15 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method thereof, composite catalyst containing catalyst and application of composite catalyst |
| CN116041575A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
| CN116041575B (en) * | 2021-10-28 | 2024-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and olefin polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558285B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101842396B (en) | Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method | |
| CN104558285A (en) | Solid catalyst component for olefin polymerization and catalyst | |
| US9676876B2 (en) | Catalyst for polymerization of olefins and process thereof | |
| CN101107276A (en) | Process for producing olefin polymer and solid titanium catalyst component and catalyst for olefin polymerization | |
| CN103788252A (en) | Catalyst solid ingredient, catalyst containing catalyst solid ingredient and use of catalyst in olefin polymerization | |
| CN106317275B (en) | Prepare catalytic component of fiber polyolefin and its preparation method and application and catalyst system and application and olefine polymerizing process | |
| CN106608933B (en) | Catalytic component and its preparation method and application for olefinic polymerization | |
| CN109111539A (en) | Catalytic component and its catalyst for olefinic polymerization | |
| CN101165073B (en) | Catalyst component used for olefin polymerization reaction and catalyst thereof | |
| CN104558287B (en) | Catalyst component for olefin and catalyst | |
| CN103665204B (en) | A kind of solid catalyst component for olefine polymerization and catalyzer | |
| CN103788237B (en) | Catalyst solid constituent and catalyst thereof with and application in olefinic polymerization | |
| CN104558286A (en) | Catalyst component for olefin polymerization and catalyst | |
| CN105504109A (en) | Catalyst component for alkene polymerization and catalyst thereof | |
| CN104053682B (en) | For the high activity catalyst component and its application method of olefinic polymerization | |
| JP2013515831A (en) | Polyolefin polymerization catalyst and method for producing the same | |
| CN104558312B (en) | The preparation method and its polymer of a kind of olefin polymer | |
| CN106608937B (en) | Catalytic component and its preparation method and application for olefinic polymerization | |
| JP2013515832A (en) | Method for producing polyolefin polymerization catalyst, catalyst produced thereby, and method for producing polyolefin using the same | |
| CN104479055B (en) | A kind of dialkoxy-magnesium support type ingredient of solid catalyst and catalyst | |
| CN107344973A (en) | Catalytic component, catalyst system and its application for olefinic polymerization | |
| CN107344978A (en) | Catalytic component, catalyst system and its application for olefinic polymerization | |
| CN103788255B (en) | A kind of polypropylene product and preparation method thereof | |
| CN106317274B (en) | Prepare catalytic component of fiber polyolefin and its preparation method and application and catalyst system and application and olefine polymerizing process | |
| CN105566520B (en) | A kind of catalytic component and its catalyst for olefinic polymerization |
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 |