CN101450974A - Improved polyolefin catalyst preparation process - Google Patents
Improved polyolefin catalyst preparation process Download PDFInfo
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- CN101450974A CN101450974A CN 200710178429 CN200710178429A CN101450974A CN 101450974 A CN101450974 A CN 101450974A CN 200710178429 CN200710178429 CN 200710178429 CN 200710178429 A CN200710178429 A CN 200710178429A CN 101450974 A CN101450974 A CN 101450974A
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Abstract
The invention provides an improved process for preparing a polyolefin catalyst. The polyolefin catalyst is prepared from MgCl2, liquid wax, ethanol, diethyl phthalate, butyl acrylate and other raw materials, and waste titanium during catalyst synthesis is treated by use of a compound solvent of ethyl benzene and 1,1-Dichloro-1-fluoroethane. The catalyst obtained in the invention has the advantages of higher activity than the catalyst obtained in the prior art, more uniform particle distribution, stronger anti-interference ability, steadier reaction, sensitive hydrogen regulation and lower production cost.
Description
Technical field
The present invention relates to a kind of improved polyolefin catalyst preparation process.
Background technology
Polyolefin industry technical progress in the world's gives the credit to mainly that the progress of catalyzer---activity of such catalysts obviously improves in decades, and the control device in active centre is obviously improved.China payes attention to development, exploitation and the production domesticization work of polyolefin catalyst always.Catalyst for olefines polymerizing has been obtained fast development, and has become a new branch of science in the polymer science.
The patent No. is that 02120787.9 patent of invention discloses a kind of polyolefin catalyst, is applicable to the homopolymerization and the copolymerization of ethene and alpha-olefin, has higher polymerization activity, the polymericular weight height that makes, molecular weight distribution broad.
The patent No. is that 02120788.7 patent of invention discloses a kind of single metallocene polyolefine catalyst, and this catalyzer cooperates with aluminum alkyls or aluminum alkoxide and is used for olefinic polymerization, can obtain high molecular and than the polymkeric substance of wide molecular weight distribution.
The patent No. is that 97102186.4 patent of invention discloses a kind of method for preparing support of the catalyst, wherein the hydrophilic inorganic oxide compound of the element of the main group II of the periodic table of elements-IV or subgroup IV or their mixture or mixed oxide are dry under 110-800 ℃ temperature, subsequently with aikyiaiurnirsoxan beta or aluminum alkyls reaction, simultaneously with aikyiaiurnirsoxan beta and the reaction of polyfunctionality linking agent.In another stage, support of the catalyst contacts with polyolefin catalyst, obtains supporting polyolefin catalyst, and it can be used for the polyreaction of alkene.
The patent No. is that 97108763.6 patent of invention discloses a kind of method that forms polyolefin catalyst component, comprise: magnesium ethylate is carried out chlorination, handle solid with the electron donor of low donor content earlier then, handle with the titanizing agent again, make catalyst component.Catalyst component activates with aluminum alkyl catalyst.
Can add organic silane compound as the stereoselectivity control agent.Activated catalyzer can be used for the especially polymerization of propylene of alkene, obtains the polymerisate than wide molecular weight distribution.
The patent No. is that 99103281.0 patent of invention discloses a kind of high activity polyolefin Catalysts and its preparation method and the application of this catalyzer in olefinic polymerization of being made up of magnesium, titanium, halogen and alkoxyl group; Mainly comprise magnesium, titanium, halogen and alkoxyl group, can also comprise electron donor, improving agents such as tensio-active agent and halogenated hydrocarbon promotor, overcome catalyzer in the prior art and with the particle thinner problem of the polymkeric substance of this Preparation of Catalyst, and catalyst activity obviously improves, and catalyzer of the present invention can be widely used in olefinic polymerization or the copolymerization.
The patent No. a kind of dual-active component polyolefin catalyst that has been 03149937.6 patent disclosure comprises carrier MgCl
2N (ROH), TiCl
4And the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride, R in the formula (I)
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, be selected from hydrogen, C independently of one another
1～C
6Alkyl or C
7～C
8Aralkyl.This catalyzer has double activity center, is used for olefin polymerization catalysis and can makes the olefin polymer that is bimodal or wide molecular weight distribution, single high-melting-point and high-crystallinity that this polymkeric substance has.
Application number is preparation and the application that 99119984.7 patent application discloses a kind of non-cyclopentadiene titanium polyolefine catalyst.This catalyzer can not only not have sterically hindered alkene by catalyzed polymerization, and can sterically hindered alkene be arranged catalyzed polymerization.This non-luxuriant metalloid catalyzer can also become ethene and styrene copolymerized catalyzer simultaneously.
Application number is that the patent application of 200510080208.X discloses a kind of vanadium non-metallocene catalyst, has formula (I), (II) or (III) described structural formula.Described formula (I) and (II) in R
1Be selected from C
1～C
6Alkyl, R
2And R
3Be selected from hydrogen, C respectively
1～C
6Alkyl, C
1～C
6Alkoxyl group or nitro; R in the formula (III)
4And R
5Be selected from C respectively
1～C
12Alkyl, C
6～C
9Aralkyl or C
1～C
12Perfluoroalkyl; In the formula (I)～(III), X is a halogen, and n is 1 or 2.This catalyzer cooperates with the haloalkyl aluminum cocatalyst and is used for olefinic polymerization, has high polymerization activity.
Application number is that 200610028959.1 patent application discloses the purposes of a class Nonmetallocene polyolefine catalyst in catalyzed ethylene and cyclic olefin copolymerization.This catalyzer is three races's to the 11 group 4 transition metal complexes of a class new tridentate ligand.Under the effect of low consumption promotor, this catalyzer can high reactivity ground catalyzed ethylene and the copolymerization of cyclic olefins such as cyclopentenes, norbornylene.Molecular weight distribution is narrow, and comonomer insertion rate can be adjustable in 0.001-50 mole % scope.
Application number is 200410041606.6 application for a patent for invention, discloses a kind of preparation technology of polyolefin catalyst.
Along with the continuous growth of the market requirement especially high-performance poly olefin product demand, more and more outstanding to the demand and the contradiction between the present situation of polyolefin catalyst technology and high-performance poly olefin product.The polyolefin catalyst that the processing method of foregoing invention prepares, its performance can't satisfy the needs that existing market day by day improves fully.Therefore ｀ develops the catalyzer industrialization technology with independent intellectual property right and just seems particularly important and urgent.The present invention is exactly the improvement of making at above-mentioned prior art, has obtained the polyolefin catalyst that a kind of catalytic is better than prior art.
Summary of the invention
The purpose of this invention is to provide a kind of improved polyolefin catalyst preparation process.
Technical scheme of the present invention is:
A kind of improved polyolefin catalyst preparation process, it may further comprise the steps:
(1) with MgCl
2, liquid wax, ethanol and diethyl phthalate, butyl acrylate be heated to 135-145 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to room temperature (25-28 ℃);
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 20-60 minute; And then after being quickly cooled to-20 ℃, equably with the TiCL that is cooled to-20 ℃
4Mix;
(4) with the said mixture heat temperature raising to 26-28 ℃, stop to stir 30-60 minute;
(5) be rapidly heated to 90-98 ℃, separate out the crystalloid solid;
(6) with the useless titanium in ethylbenzene and the fluorine ethylene dichloride double solvents processing catalyzer building-up process;
(7) dry product.
The inventor finds unexpectedly: the time in each stage, temperature and stirring velocity have a significant impact the performance of catalyzer among alcohol adduct process of cooling and the preparation technology; Preparation technology of the present invention, it is more even to prepare particle, the catalyzer that catalytic performance is more excellent.
The inventor is also unexpected to be found: solvent used in preparation process also has a significant impact the catalyst performance for preparing.The ester compound combination that the present invention selects for use is more excellent than selecting the preparation-obtained catalyst performance of other ester class for use.
The inventor is also unexpected to be found: adopt the double solvents among the present invention, can better handle the useless titanium in the catalyzer building-up process.
Preferred version of the present invention is:
(1) with MgCl
2, liquid wax, ethanol and diethyl phthalate, butyl acrylate be heated to 140 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 25 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, equably with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 28 ℃;
(5) be rapidly heated to 90 ℃, separate out the crystalloid solid;
(6) with the useless titanium in ethylbenzene and the fluorine ethylene dichloride double solvents processing catalyzer building-up process;
(7) dry product.
The more preferably scheme of step of the present invention (1) is:
Stirring velocity is 300-400 rev/min, under best 360 rev/mins, with MgCl
2, liquid wax, ethanol and diethyl phthalate, butyl acrylate be heated to 140 ℃ in autoclave, obtain transparent alcohol adduct; The diethyl phthalate that is adopted, butyl acrylate consumption volume ratio are preferably 1:3;
The more preferably scheme of step of the present invention (4) is:
With said mixture heat temperature raising to 28 ℃, stop and stirred 40 minutes; Stirring velocity is 200-300 rev/min, best 280 rev/mins;
The more preferably scheme of step of the present invention (6) is: use an ethylbenzene and a fluorine ethylene dichloride double solvents at 90-98 ℃, best 90 ℃ of useless titaniums of handling down in the catalyzer building-up process; Wherein an ethylbenzene that is adopted and a fluorine ethylene dichloride consumption volume ratio are preferably 1:3.
Beyond thought effect of the present invention is:
1, the control of the temperature in the catalyst preparation process has a significant impact the prepared catalyst performance, and accident of the present invention has been found each step temperature controlling method in the production process, and method of the present invention can prepare the catalyzer of more excellent performance.
2, in order to promote catalyst activity, improve the performances such as degree of isotacticity of catalyzer, what the past adopted interiorly is generally fragrant monoesters to electron compound, fragrance dibasic acid esters and titanate ester or the like compound a kind of, the present invention is for to aggravate the degree of disorder of support of the catalyst microstructure to improve the performance of catalyzer simultaneously, with compound Ester is the interior electron compound of giving, the present invention finds with the diethyl phthalate of 1:3, butyl acrylate unexpectedly as the interior electronics thing of giving, can enhance productivity greatly, thereby obtain catalyzer more cheaply.
3, the inventor finds unexpectedly, and stirring velocity has very influence to the uniform particles degree of catalyzer in the step of preparation process, and has found the stirring velocity that is fit to.
4, the existence of the invalid titanium in the catalyzer can strengthen the consumption of other cocatalyst in the polymerization process, the performance of impact polymer, even also influence the performance of catalyzer, application number is a compounding mixture solvent selected in 200410041606.6, handle the useless titanium in the catalyzer building-up process, DeGrain.The inventor finds that unexpectedly effect is very obvious with 1:3 ethylbenzene and a fluorine ethylene dichloride useless titanium in can more effective processing building-up process.
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 360 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 140 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 25 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 28 ℃; Stirring velocity is 280 rev/mins;
(5) be rapidly heated to 90 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 90 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 2
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 300 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 135 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 26 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 20 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 30 minutes with said mixture heat temperature raising to 20 ℃; Stirring velocity is 200 rev/mins;
(5) be rapidly heated to 91 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 91 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 3
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 400 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 145 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 28 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 60 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 60 minutes with said mixture heat temperature raising to 26 ℃; Stirring velocity is 300 rev/mins;
(5) be rapidly heated to 98 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 98 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 4
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 380 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 135 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 50 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 50 minutes with said mixture heat temperature raising to 23 ℃; Stirring velocity is 260 rev/mins;
(5) be rapidly heated to 95 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 95 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 5
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 250 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 6
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 360 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 25 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 30 minutes with said mixture heat temperature raising to 22 ℃; Stirring velocity is 260 rev/mins;
(5) be rapidly heated to 97 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 97 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Embodiment 7
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 370 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 142 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 25 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 60 minutes with said mixture heat temperature raising to 27 ℃; Stirring velocity is 260 rev/mins;
(5) be rapidly heated to 94 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 94 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples:
Comparative Examples 1-3 is a common method Comparative Examples in the prior art; Comparative Examples 4-6 is the Comparative Examples with differing temps sequence of control of the present invention; Comparative Examples 7-8 is the Comparative Examples that adopts different stirring velocitys with the present invention; Comparative Examples 9-10 is the Comparative Examples that adopts the different solvents volume ratio with the present invention.
Comparative Examples 1:
Magnesium chloride 10g, liquid wax 100L, monooctyl ester 45L, complex ester (ethyl benzoate: the 5L of dibutyl phthalate=1:6.5), double solvents 50L (No. 250 solvent oils: carbon+cut=2:3)
(1) under nitrogen protection, magnesium chloride, liquid wax, alcohol and compound Ester are stirred and heated to 130 ℃ obtain transparent alcohol adduct in autoclave;
(2) be cooled to room temperature, then equably with the TiCL that is cooled to-20
4Mix;
(3) heat temperature raising to 95 ℃ is separated out crystalline solid;
(4) with compounding mixture solvent useless titanium in the processing catalyzer building-up process under 85-125 ℃;
(5) oven dry obtains product.
Comparative Examples 2
Magnesium chloride 10g, liquid wax 100L, monooctyl ester 45L, complex ester (ethyl benzoate: the 5L of diisobutyl phthalate=1.5:5.5), double solvents 50L (toluene: 97# gasoline=3:5)
(1) under nitrogen protection, magnesium chloride, liquid wax, alcohol and compound Ester are stirred and heated to 130 ℃ obtain transparent alcohol adduct in autoclave;
(2) be cooled to room temperature, then equably with the TiCL that is cooled to-20
4Mix;
(3) heat temperature raising to 95 ℃ is separated out crystalline solid;
(4) with compounding mixture solvent useless titanium in the processing catalyzer building-up process under 85-125 ℃;
(5) oven dry obtains product.
Comparative Examples 3
Magnesium chloride 10g, liquid wax 100L, monooctyl ester 45L, complex ester (ethyl benzoate: diisobutyl phthalate: the 5L of titanic acid ester=1:6.5:1), double solvents 50L (dimethylbenzene: ethane=2:4)
(1) under nitrogen protection, magnesium chloride, liquid wax, alcohol and compound Ester are stirred and heated to 130 ℃ obtain transparent alcohol adduct in autoclave;
(2) be cooled to room temperature, then equably with the TiCL that is cooled to-20
4Mix;
(3) heat temperature raising to 95 ℃ is separated out crystalline solid;
(4) with compounding mixture solvent useless titanium in the processing catalyzer building-up process under 85-125 ℃;
(5) oven dry obtains product.
Comparative Examples 4
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) alcohol adduct that obtains in the step (1) is cooled to-20 ℃;
(3) with above-mentioned-20 ℃ of alcohol adducts uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 250 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 5
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4) with said mixture heat temperature raising to 92 ℃;
(5) stop stirring 40 minutes; Stirring velocity is 250 rev/mins, separates out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 6
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) alcohol adduct that obtains in the step (1) is cooled to-20 ℃;
(3) with above-mentioned alcohol adduct and the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 60 minutes with said mixture heat temperature raising to 60 ℃; Stirring velocity is 280 rev/mins;
(5) be rapidly heated to 90 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 90 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 7
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 200 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 400 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 8
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:3), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:3)
(1) under nitrogen protection, stirring velocity is 500 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 100 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 9
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:1), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:1)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 250 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Comparative Examples 10
Magnesium chloride 10g, liquid wax 100L, ethanol 45L, complex ester (diethyl phthalate: the 5L of butyl acrylate=1:5), double solvents 30L (ethylbenzene: a fluorine ethylene dichloride=1:5)
(1) under nitrogen protection, stirring velocity is 350 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 138 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 27 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 24 ℃; Stirring velocity is 250 rev/mins;
(5) be rapidly heated to 92 ℃, separate out the crystalloid solid;
(6) the useless titaniums in the processing catalyzer building-up process under 92 ℃ with an ethylbenzene and a fluorine ethylene dichloride double solvents;
(7) dry product.
Adopt the measuring method of conventional catalyst performance, the embodiment of the invention and the preparation-obtained catalyzer of Comparative Examples are measured, the every index of the embodiment of the invention all is better than Comparative Examples greatly.
The foregoing description and the contriver did experimental results demonstrate, technical solution of the present invention by among the control preparation technology as alcohol adduct cooling to wait time, temperature and the stirring velocity in each stage to prepare catalytic performance more excellent, unexpected technique effect is arranged.The catalyst activity that the present invention obtains has higher activity than the resulting catalyzer of present prior art; Size distribution is more even; Immunity from interference is stronger; React more steady; Hydrogen is transferred responsive; Production cost is lower.
Claims (11)
1, a kind of improved polyolefin catalyst preparation process, it may further comprise the steps:
(1) with MgCl
2, liquid wax, ethanol and diethyl phthalate, butyl acrylate be heated to 135-145 ℃ in autoclave, obtain transparent alcohol adduct;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to room temperature;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 20-60 minute; And then after being quickly cooled to-20 ℃, equably with the TiCL that is cooled to-20 ℃
4Mix;
(4) with the said mixture heat temperature raising to 26-28 ℃, stop to stir 30-60 minute;
(5) be rapidly heated to 90-98 ℃, separate out the crystalloid solid;
(6) with the useless titanium in ethylbenzene and the fluorine ethylene dichloride double solvents processing catalyzer building-up process;
(7) dry product.
2, polyolefin catalyst preparation process according to claim 1, wherein step (1) is: with MgCl
2, liquid wax, ethanol and diethyl phthalate, butyl acrylate be heated to 140 ℃ in autoclave, obtain transparent alcohol adduct.
3, polyolefin catalyst preparation process according to claim 2, wherein the stirring velocity in the step (1) is 300-400 rev/min.
4, polyolefin catalyst preparation process according to claim 3, the diethyl phthalate, the butyl acrylate consumption volume ratio that are adopted in the step (1) are 1:3.
5, polyolefin catalyst preparation process according to claim 1 and 2, wherein step (2) is: the alcohol adduct that obtains in the step (1) is placed be cooled to 25 ℃.
6, polyolefin catalyst preparation process according to claim 1 and 2, wherein step (3) is: alcohol adduct is cooled to-10 ℃, stops and be quickly cooled to-20 ℃ after 30 minutes again.
7, polyolefin catalyst preparation process according to claim 1 and 2, wherein step (4) is: mixture heating up is warming up to 28 ℃, stops and stirred 40 minutes, stirring velocity is 200-300 rev/min.
8, polyolefin catalyst preparation process according to claim 1 and 2, wherein step (5) is: be rapidly heated to 90 ℃.
9, polyolefin catalyst preparation process according to claim 1 and 2, wherein step (6) is the useless titanium of handling down in the catalyzer building-up process at 90 ℃.
10, an ethylbenzene and a fluorine ethylene dichloride consumption volume ratio are 1:3 in the polyolefin catalyst preparation process according to claim 9, step (6).
11, polyolefin catalyst preparation process according to claim 1 and 2, it is made up of following steps:
(1) under nitrogen protection, stirring velocity is 360 rev/mins, with MgCl
2, liquid wax, ethanol, diethyl phthalate, butyl acrylate is heated to 140 ℃ in autoclave, obtain transparent alcohol adduct; Wherein diethyl phthalate, butyl acrylate volume ratio are 1:3;
(2) the alcohol adduct placement that obtains in the step (1) is cooled to 25 ℃;
(3) above-mentioned alcohol adduct is quickly cooled to-10 ℃, stopped 30 minutes; And then after being quickly cooled to-20 ℃, uniformly with the TiCL that is cooled to-20 ℃
4Mix;
(4), stop and stirred 40 minutes with said mixture heat temperature raising to 28 ℃; Stirring velocity is 280 rev/mins;
(5) be rapidly heated to 90 ℃, separate out the crystalloid solid;
(6) with volume ratio be ethylbenzene and a fluorine ethylene dichloride double solvents useless titaniums in the processing catalyzer building-up process under 90 ℃ of 1:3;
(7) dry product.
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| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
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| RU2153932C2 (en) * | 1995-05-18 | 2000-08-10 | Митсуи Кемикалс, Инк. | Method of preparing solid titanium catalytic component, olefin- polymerization catalyst containing thereof, and olefin polymerization process |
| JP2004527636A (en) * | 2001-05-29 | 2004-09-09 | ユニオン・カーバイド・ケミカルズ・アンド・プラスチックス・テクノロジー・コーポレーション | Olefin polymerization catalyst composition and method for producing the same |
| CN1597713A (en) * | 2004-08-02 | 2005-03-23 | 苏州恒升新材料有限公司 | Preparation process of polyolefin catalyst |
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