CN106608933B - Catalytic component and its preparation method and application for olefinic polymerization - Google Patents

Catalytic component and its preparation method and application for olefinic polymerization Download PDF

Info

Publication number
CN106608933B
CN106608933B CN201510707980.3A CN201510707980A CN106608933B CN 106608933 B CN106608933 B CN 106608933B CN 201510707980 A CN201510707980 A CN 201510707980A CN 106608933 B CN106608933 B CN 106608933B
Authority
CN
China
Prior art keywords
cyano
diethyl succinate
butyl
succinic acid
diethyl
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.)
Active
Application number
CN201510707980.3A
Other languages
Chinese (zh)
Other versions
CN106608933A (en
Inventor
周奇龙
谭忠
张锐
徐秀东
尹珊珊
宋维玮
李凤奎
于金华
严立安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201510707980.3A priority Critical patent/CN106608933B/en
Publication of CN106608933A publication Critical patent/CN106608933A/en
Application granted granted Critical
Publication of CN106608933B publication Critical patent/CN106608933B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to the preparation method of the catalytic component for olefinic polymerization, the catalytic component obtained by the preparation method, and the catalyst system for olefinic polymerization.In addition, the invention further relates to a kind of polymerizations of tubing polyolefin.The catalytic component and catalyst system particle shape that preparation method through the invention obtains are good, polymerization activity is high, hydrogen tune is insensitive, and without using phthalate compound and, the molecular weight distribution of the catalytic component and catalyst system for corresponding olefinic polymerization resulting polymers is wide.

Description

Catalytic component and its preparation method and application for olefinic polymerization
Technical field
The present invention relates to a kind of preparation methods of catalytic component for olefinic polymerization, are used for alkene by this method preparation The catalytic component of polymerized hydrocarbon and its application.
Background technique
Currently, using magnesium, titanium and electron donor as the catalytic component of basis, i.e., it is known in the field Ziegler-Natta (Z-N) catalyst, can be used for CH2=CHR olefin polymerization especially has 3 carbon or more The polymer of available higher yields and higher stereospecificity in the alpha-olefine polymerizing of atom.Preparation method first is that first Magnesium chloride is prepared into homogeneous solution, then the active component of titaniferous is precipitated and loaded by crystallization.In solution modeling system, only There is the presence of precipitation additive, be possible to obtain even-grained solids, precipitation additive generally uses organic acid anhydride, organic The classes compound such as acid, ketone, ether, ester.
CN85100997A discloses titanium-containing catalyst component, is that organic epoxy compound object and organic phosphorus is dissolved in by magnesium halide Compound forms homogeneous solution, and the solution and titanium tetrahalide or derivatives thereof mixes, in the presence of precipitation additive such as organic acid anhydride, Solids is precipitated；This solids is handled with multi-carboxylate, is attached to it on solids, then with titanium tetrahalide and inert diluents Agent processing obtains.When the catalyst is used for propylene polymerization, catalyst activity is higher, and the isotacticity of resulting polymers is higher, table It is big to see density.But the preparation process of the catalyst is more complicated, and raw materials used many kinds of, reaction process is longer.Meanwhile it is this Method prepares the yield of catalyst and catalyst performance all needs to be further increased.
CN1042156A discloses a kind of catalyst system prepared using the method that is eutectoid out, contains Ti in the catalyst system Ingredient of solid catalyst is that solid magnesium dichloride is dissolved in organic alcohol compound such as 2-Ethylhexyl Alcohol in decane solvent, After organic acid anhydride dissolution is added, precipitating is precipitated under titanium tetrahalide effect, obtains major catalyst using processing such as titanium tetrahalides Component.The catalyst is used for propylene polymerization, and catalyst activity is higher, and morphology is preferable.But the catalyst is synthesizing Used in the process of titanium tetrachloride amount it is larger, polymer isotacticity is slightly lower, and the yield and catalyst performance of catalyst all need into one Step improves.
CN1436766A discloses a kind of polyalcohol ester type compound, which is suitable for the catalyst of olefinic polymerization Preparation.It is all disclosed in CN1436796A, CN1453298A with this special polyalcohol ester type compound as interior electron The polyolefin catalyst active component that body obtains, catalyst activity with higher and preferable stereoselectivity.But the party When method prepares catalyst, because polyol ester is to be carried on catalyst surface after catalyst granules formation, load may not be uniform, Meanwhile preferable catalyst performance in order to obtain, the usage amount of binary alcohol esters is bigger, and this point is from data given in patent Also it is embodied.
CN1763108A discloses a kind of catalytic component and preparation method for olefinic polymerization, solid catalyst containing Ti Component is that solid magnesium dichloride is dissolved in organic alcohol compound such as 2-Ethylhexyl Alcohol in solvent naphtha, and organic acid anhydride is added And after titanate esters dissolution, precipitating is precipitated under titanium tetrahalide effect, obtains main catalyst component using processing such as titanium tetrahalides. The catalyst is used for propylene polymerization, and morphology is preferable.But catalyst titanium tetrachloride amount used in the synthesis process Larger, catalyst activity is slightly lower, and the yield and polymerization of catalyst all need to be further increased.
It is disclosed in CN102276765B and is prepared for particle shape using the precipitation additive system containing glycol ester compounds Well, the catalyst solid constituent that polymerization activity is high and capacity of orientation is strong.There are a certain amount of in above-mentioned catalyst solid constituent Glycol ester compounds.The content of diol-lipid compound > 6 weight % in catalyst.This catalyst solid constituent is used for alkene The polymer prepared when polymerized hydrocarbon has the characteristics that molecular weight distribution is wider.However, such catalyst solid constituent is obtaining more There are still some shortcomings in terms of wide molecular weight distribution polyolefin.
It is well known that homopolymerization or combined polymerization polyolefin pipe material are the very low polyolefin products of a kind of melting means, this requires The Z-N catalyst used in process of production cannot be too sensitive to molecular weight regulator hydrogen, otherwise can make the melting means mistake of product Journey generates difficult；In addition, hydrogen has certain promotion to the activity of Z-N catalyst under a certain concentration, it is too sensitive to hydrogen Z-N catalyst be used to prepare when eutectic refers to product because lower with hydrogen amount, the polymerization activity of catalyst is also relatively low.Molecular weight point The mechanical performance and processing performance of cloth (MWD) influence polymer.High molecular weight moieties largely determine the length of polymer Phase mechanical strength, and low molecular weight fraction largely determines its extrusion performance.In the industry generally, it is considered that molecular weight distribution is wide Polyolefin products for being advantageous as tube material.There are also the polyolefin products of some specific uses, such as high fondant-strengths Polypropylene, it is also desirable to which there is wide molecular weight distribution.To sum up, in the production and preparation of some dedicated polyolefin material, people The Z-N catalyst that is desirable for not only molecular distribution is wide, but also hydrogen tune is insensitive；Certainly, this catalyst should also have height Activity and good capacity of orientation.
But above-mentioned existing catalyst has the following problems when preparing tubing polyolefin:
1) polymer molecular weight distribution is not wide enough, to influence the processing performance and mechanical property of product；
2) catalyst is more sensitive to the hydrogen as molecular weight regulator, is unfavorable for the preparation that eutectic refers to polyolefin.
In addition to this, in view of the conveying of pipe-type polyolefin products hot and cold water is not only possible and direct body contact, also It may directly drink, and the presence of phthalic acid ester (one kind of plasticiser) influences whether male fecundity in polyolefin Development, various countries work out the exceeded plastic products of corresponding regulation limitation phthalic acid ester content in succession and use (range).Therefore it keeps away Exempt to be pursued in the industry in polyolefin catalyst preparation process using phthalic acid ester.
It can be seen that prepare tubing polyolefin, it is desirable to provide particle shape is good, polymerization activity is high, hydrogen tune is unwise Sense, and do not use the catalytic component and catalyst system of phthalate compound, the catalytic component and catalyst Molecular weight distribution of the system for corresponding olefinic polymerization resulting polymers is wide.
Summary of the invention
The first purpose of this invention is to overcome the method for catalytic component of the existing preparation for olefinic polymerization, acquired Catalytic component for catalyst system polymerize when, the narrow molecular weight distribution of prepared polyolefin, thus uncomfortable In being used as tube material, and using the defect of phthalate compound, provide a kind of new urging for olefinic polymerization The preparation method of agent component.
A second object of the present invention is to provide the catalyst groups for olefinic polymerization using the preparation of above-mentioned preparation method Point.
Third object of the present invention is to provide a kind of catalyst systems for olefinic polymerization.
Fourth object of the present invention is to provide a kind of olefine polymerizing process.
The present inventor has found in the research and development that preparation is used for the olefin polymerization catalysis of tube material, in Z-N polyene In hydrocarbon catalyst, the crystalline substance of active magnesium chloride is adsorbed to as the compound of internal electron donor and the titanium as polymerization activity center There is competitive Adsorption relationship to a certain extent in lattice surface.In other words, adsorbance and state of the internal electron donor in chlorination magnesium surface Influence whether the quality and quantity of the titanium as activated centre.In addition, not the higher the better for the total amount of the titanium as activated centre, As the desired catalytic component prepared for tubing with polyolefin of the present invention, it is desirable to which Ti content control is in 2.5-3.5 weight Measure the ideal range of %.If Ti content is excessively high, catalyst is easier to the shakinesses such as temperature fluctuation occur when being applied to continuous polymerization Fixed uncontrollable phenomenon；Also, Ti content is excessively high, and the activated centre of the low capacity of orientation in catalyst is increased, and can reduce final poly- The stereoregularity of olefin product, to reduce properties of product.In addition, the preparation high based on cyano succinic acid ester type compound Cost consideration, it is necessary to improve its service efficiency.Therefore, especially with contain cyano succinic acid ester type compound and diol ester The catalytic component of compound, while controlling titanium atom content in catalyst for preparing there is being used as wide molecular weight distribution to manage The olefin polymer of material has important influence.Furthermore, it is contemplated that the direction of the limitation of regulation and technology development, without using neighbour Phthalates compound, and adjust the preparation of the catalyst.Inventor provides the present invention as a result,.
Provided by the present invention for the preparation method of the catalytic component of olefinic polymerization, comprising the following steps:
1) magnesium halide and alcohol compound are subjected in the presence of hydrocarbon solvent the first haptoreaction, form solution, it is excellent Form slection is at homogeneous solution；
2) in the presence of precipitation additive, the resulting solution of step 1) is carried out second with first part's titanium compound and is contacted Reaction obtains the mixture precipitated containing solid；
3) the resulting mixture of step 2) and first part's internal electron donor are subjected to third haptoreaction, are suspended Liquid；
4) suspension for obtaining step 3) is separated by solid-liquid separation, obtained solid component and second part titanium compound, Second part internal electron donor carries out the 4th haptoreaction, then is separated by solid-liquid separation (such as by filtering or being centrifuged), obtains Solid product；
5) solid product for obtaining step 4) and Part III titanium compound carry out the 5th haptoreaction, obtain described urge Agent component.
The preferred embodiment of preparation method according to the present invention, the precipitation additive include precipitation additive a, wherein described Precipitation additive a is diol-lipid compound shown in formula (I),
In formula (I), R1-R2It may be the same or different, be respectively substituted or unsubstituted C1-C20Straight chained alkyl, substitution or Unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Naphthenic base, substituted or unsubstituted C6-C20Aryl, substitution Or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C2-C10Alkylene or Substituted or unsubstituted C10-C20Fused ring aryl；R3-R8It may be the same or different, be respectively hydrogen, halogen, substituted or unsubstituted C1-C20Straight chained alkyl, substituted or unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Naphthenic base, substitution or Unsubstituted C6-C20Aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, substitution or Unsubstituted C2-C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；Or R3-R6At least one of and R7- R8At least one of cyclization.
The preferred embodiment of preparation method according to the present invention, the precipitation additive include precipitation additive b, wherein described Precipitation additive b is general formula Ti (OR9)nX4-nShown in titanate ester compound, wherein R9For C1-C10Straight chained alkyl, C3-C10Branch Alkyl group or C3-C10Naphthenic base, X is halogen, preferably fluorine, chlorine, bromine or iodine, 1≤n≤4, and n be integer.
The preferred embodiment of preparation method according to the present invention, the precipitation additive include above-mentioned precipitation additive a and upper State precipitation additive b.
The preferred embodiment of preparation method according to the present invention, first part's internal electron donor and second described Dividing one or both of them in internal electron donor includes cyano succinic acid ester type compound shown in formula (II),
In Formula II, R1' and R2' can be identical or not identical, is each independently selected from hydrogen, C1-C14Straight chained alkyl, C3-C14Branched alkane Base, C3-C10Naphthenic base, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl；R3' and R4' can be identical or not identical, respectively It is independently selected from C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Naphthenic base, C6-C20Aryl, C7-C20Alkaryl and C7-C20 Aralkyl.
Preferably, R1' and R2' is each independently selected from hydrogen, C1-C8Straight chained alkyl and C3-C8Branched alkyl.
Preferably, R3' and R4' is each independently selected from C1-C6Straight chained alkyl and C3-C6Branched alkyl.
The preferred embodiment of method produced according to the present invention, precipitation additive a used in step 2) in this method Used in the molar ratio of total internal electron donor be (0.05-0.5): 1, preferably (0.1-0.4): 1, more preferable (0.15- 0.35):1。
The preferred embodiment of method produced according to the present invention, first part's internal electron donor and the second part The molar ratio of internal electron donor is (0.1-10): 1, preferably (0.2-5): 1, more preferably (0.2-1): 1.
The preferred embodiment of method produced according to the present invention, the precipitation additive include the precipitation additive a and described Precipitation additive b, and the molar ratio of the precipitation additive a and precipitation additive b is 1:(0.01-5), preferably 1:(0.5- 3), more preferably 1:(0.5-1.5).
The preferred embodiment of method produced according to the present invention, the titanium compound in terms of titanium elements, the magnesium halide with Magnesium elements meter, alcohol compound, in the method used total titanium compound, in the method total interior electron used The molar ratio of body and magnesium halide is (2-4): (12-160): (0.01-3): 1, preferably (2.5-3.5): (20-140): (0.02-0.3):1。
The preferred embodiment of method produced according to the present invention, it is total used in magnesium halide and step 2) used in step 1) The molar ratio of precipitation additive is 1:(0.025-0.9), preferably 1:(0.03-0.3).
In order to processability it is excellent be suitable for prepare tubing polyolefin catalyst solid component, need strict control glycol The content of ester type compound in the catalyst.Content is too low, then the activity of catalyst will receive a degree of influence.But if Remaining precipitation additive diol-lipid compounds content is higher in catalyst, and the amount of corresponding diester compound is also required to higher. However, the capacity of internal electron donor is limited in catalyst.Gu this, it is necessary to diol-lipid of the control as precipitation additive Close residual quantity of the object in catalyst solid constituent.Therefore, it is necessary to precipitation additive a described in strict control and the internal electron donor Total amount molar ratio.According to the present invention, the molar ratio of the total amount of the precipitation additive a and the internal electron donor is that control exists (0.05-0.5): 1, preferably (0.1-0.4): 1, more preferable (0.15-0.35): 1.
According to the present invention, in the preparation method, the alcohol compound, titanium compound, internal electron donor and the halogen The dosage for changing magnesium, can be properly selected according to the composition of the catalytic component of expected tubing polyolefin.It is preferred that feelings Under condition, the titanium compound in terms of titanium elements, the magnesium halide in terms of magnesium elements, the alcohol compound, titanium compound it is total Amount, the total amount of internal electron donor and the molar ratio of the magnesium halide can be (2-4): (12-160): (0.01-3): 1；Preferably (2.5-3.5):(20-140):(0.02-0.3):1。
In method provided by the invention, titanium compound can be added several times, as first part's titanizing is added in step 2) Object is closed, second part titanium compound is added in step 4), Part III titanium compound etc. is added in step 5).This method can be with It is further added by the step of titanium compound is added as needed, needs the total amount of titanium compound to be offered until meeting preparation method.Separately The additional amount of outer first part's titanium compound can satisfy first part's titanium compound: magnesium halide (in terms of the magnesium elements) rub You are than being 3-40:1, preferably 5-35:1；As long as the amount of the other parts titanium compound of addition can be to make final titanium compound Total amount is added and meets the aforementioned molar ratio between the magnesium halide.Titanium compound, which is added, in substep can preferably control titanium Overall control and good distribution of the active component in catalytic component, improve the service efficiency of internal electron donor, are conducive to make Standby tubing polyolefin is with broader molecular weight distribution and high chain regularity.
According to the present invention, in the step 1) of the preparation method, the first catalytic purpose is described in order to make Magnesium halide, alcohol compound form the adduct (and can be described as magnesium halide alcohol adduct) of magnesium halide and alcohol in the presence of hydrocarbon solvent Homogeneous solution.The present invention does not limit the first haptoreaction of progress specifically with the condition for forming homogeneous solution, Ke Yigen It is determined according to the specific halogenated magnesium compound used.Under preferable case, the first haptoreaction for forming homogeneous solution can be in alcohol It being carried out under the conditions of conjunction, the first catalytic condition usually may include: that the first catalytic temperature is 30-150 DEG C, Preferably 60-140 DEG C；First catalytic time was 0.5-10 hours, preferably 0.5-6 hours.
According to the present invention, the magnesium halide can be magnesium dihalide, the complex compound of the water of magnesium dihalide or alcohol, magnesium dihalide The derivative that one or two of molecular formula halogen atom is replaced by alkyl or halocarbon oxygroup it is one or more.The present invention In, the halogen can be at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine.The specific reality of the magnesium halide Example can be one of magnesium dichloride, magnesium dibromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy or more Kind, preferably anhydrous magnesium dichloride.
According to the present invention, the alcohol compound can be at least one of fatty alcohol, alicyclic ring alcohol and aromatic alcohol.Wherein Fatty alcohol is preferably C1-C10Straight chain or C3-C10Branched fatty alcohol；Alicyclic ring alcohol is preferably C3-C12Alicyclic ring alcohol；Aromatic alcohol is excellent It is selected as C6-C20Aryl alcohol or C7-C20Alkylaryl alcohol.The specific example of alcohol compound can for ethyl alcohol, propyl alcohol, At least one of butanol, 2-Ethylhexyl Alcohol, benzyl alcohol and benzyl carbinol, preferably 2-Ethylhexyl Alcohol.
According to the present invention, in the step 1) of the preparation method, the hydrocarbon solvent used can be commonly used in the art It is various chemically interactive hydrocarbon solvent does not occur with the magnesium halide alcohol adduct, specific example can be alkane, ring One or more, preferably one of decane, benzene,toluene,xylene or a variety of, more preferably toluene of alkane, aromatic hydrocarbon.
According to the present invention, it is not particularly limited in the concrete operations of the step 2) of the preparation method, can refer to existing skill Art carries out, such as first part's titanium compound in step 2) can be individually with the resulting homogeneous solution of step 1) in precipitation additive In the presence of reacted, after first part's titanium compound can also being mixed with inert diluent with the homogeneous solution It is reacted in the presence of precipitation additive.Under preferable case, first part's titanium compound is mixed with inert diluent The second haptoreaction is carried out in the presence of precipitation additive with the homogeneous solution afterwards.Generally, system according to the present invention Preparation Method, the inert diluent can be excellent at least one of for hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene Select toluene.The molar ratio of first part's titanium compound (in terms of titanium elements) and the inert diluent can be 1-20:1, preferably For 2-8:1.
According to the present invention, the described second catalytic condition in step 2) may include: the presence in precipitation additive Under, the resulting homogeneous solution of step 1) and titanium compound are contacted 3-5 hours at a temperature of -40 DEG C to 0 DEG C, then heated to 50-150℃；Preferably, in the presence of precipitation additive, by the resulting homogeneous solution of step 1) and titanium compound -30 DEG C to - It is contacted 3.5-4.5 hours at a temperature of 20 DEG C, then heats to 90-130 DEG C.In step 2), can at a temperature of -40 DEG C to 0 DEG C, The titanium compound is mixed with the mixture of the inert diluent and the homogeneous solution first, it is molten that precipitation additive is then added Liquid contacts 3-5 hours, then heats to 50-150 DEG C, obtains the mixture precipitated containing solid；Or first by precipitation additive solution Be added in the homogeneous solution, then at a temperature of -40 DEG C to 0 DEG C, then with the titanium compound and the inert diluent Mixture contact 3-5 hour after be warming up to 50-150 DEG C, obtain containing solid precipitating mixture；It is preferred that first that precipitation additive is molten Liquid is added in the homogeneous solution, then at a temperature of -40 DEG C to 0 DEG C, with the titanium compound and the inert diluent Mixture contact 3-5 hour after be warming up to 50-150 DEG C, obtain containing solid precipitating mixture；It more preferably will first help precipitation Agent solution is added in the homogeneous solution, then at a temperature of -30 DEG C to -20 DEG C, with the titanium compound and the inertia The mixture of diluent is warming up to 90-130 DEG C after contacting 3.5-4.5 hours, obtains the mixture precipitated containing solid.
According to the present invention, in step 2), the molar ratio of the magnesium halide (in terms of magnesium elements) and the precipitation additive total amount For 1:(0.025-0.9), preferably 1:(0.03-0.3).
In the case of, according to the invention it is preferred to, in step 2), the magnesium halide is in terms of magnesium elements, the magnesium halide and institute The molar ratio for stating precipitation additive a is 1:(0.005-0.3), preferably 1:(0.01-0.05)；The precipitation additive a and help precipitation The molar ratio of agent b can be 1:(0.01-5), preferably 1:(0.5-3), more preferable 1:(0.5-1.5).
According to the present invention, the titanium compound that substep is added in multiple steps can be various titaniums commonly used in the art Compound, under preferable case, the titanium compound can be three halogenated titaniums and/or general formula Ti (OR10)mX4-mShown in titanizing close Object, in the general formula, R10It can be alkyl, preferably C1-C10Alkyl, X can be halogen, such as Cl, Br or I, 0≤m≤3, m are Integer.Preferably, the titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three halogenated titanium of alkoxy, dialkoxy One of dihalide titanium, tri-alkoxy halogenated titanium are a variety of, preferably titanium tetrachloride.
In the case of, according to the invention it is preferred to, the precipitation additive a can for 2- ethyl -1,3-PD dibenzoate, 2- propyl -1,3- propylene glycol dibenzoate, -1,3 propylene glycol dibenzoate of 2- isopropyl -2- isopentyl, 1,3 butylene glycol Mesitylenic acid ester, 2- methyl-1, two m-chlorobenzoic acid ester of 3- butanediol, 2,3- dimethyl -1,3 butylene glycol dibenzoic acid Ester, two pivalate of 1,3- pentanediol, 2,4-PD dibenzoate, 2- methyl-1,3- pentanediol benzoic acid cinnamate, 2,2- dimethyl -1,3- glycol dibenzoate, 2,4- heptandiol dibenzoate, 3,5- heptandiol dibenzoate, 4- At least one of ethyl -3,5- heptandiol dibenzoate and 2- methyl -3,5- heptandiol dibenzoate；Preferably 3,5- At least one in heptandiol dibenzoate, 4- ethyl -3,5- heptandiol dibenzoate and 2,4-PD dibenzoate Kind.
In the case of, according to the invention it is preferred to, the precipitation additive b is general formula Ti (OR9)nX4-nShown in titanate ester chemical combination Object, wherein R9For C1-C10Alkyl or C3-C10Naphthenic base, X is halogen, and 1≤n≤4, n are integer；Preferably, R9Carbon it is former Subnumber is preferably 2-6.
It is highly preferred that the precipitation additive b is tetramethoxy titanate ester, four isopropyl of butyl titanate, tetraethyl titanate and metatitanic acid At least one of ester；Further preferably butyl titanate.
According to the present invention, in step 3), in order to prepare, molecular weight distribution for tube material is wider and regularity is higher Olefin polymer, first part's internal electron donor can be two ester type compounds shown in formula (II).It is other known in the industry Internal electron donor dihydric alcohol ester type compound as shown in formula (I), phthalate, malonic acid esters, 1,3- diether Class compound, glutaric acid esters, pivalate or carbonats compound are because of the polymer molecular weight narrowly distributing of preparation, discomfort In as internal electron donor of the present invention.
According to the present invention, in the step 3) of the preparation method, the catalytic condition of third includes: the temperature of reaction Degree is 20-120 DEG C, preferably 70-110 DEG C；The time of reaction is 0.5-6 hours, preferably 1-4 hours.
The preferred embodiment of method produced according to the present invention, electron phase in electron and second part in first part It is same or different, it is each independently selected from:
2- cyano -2,3- diisopropyl dimethyl succinate, 2- cyano -2,3- diisopropyl diethyl succinate, 2- cyanogen Base -2,3- dimethyl succinic acid diethylester, 2- cyano -2,3- diethyl succinic acid diethylester, 2- cyano -2,3- diη-propyl fourth Diethyl adipate, 2- cyano -2,3- di-n-butyl diethyl succinate, bis- n-pentyl diethyl succinate of 2- cyano -2,3-, 2- Cyano -2,3- diisoamyl diethyl succinate, 2- cyano -2,3- di-n-hexyl diethyl succinate, 2- cyano -2,3- bis- are different Hexyl diethyl succinate, 2- cyano -2,3- diisopropyl succinic acid di-n-propyl ester, 2- cyano -2,3- diisopropyl succinic acid Diisopropyl ester, 2- cyano -2,3- diisopropyl succinic acid di-n-butyl, 2- cyano -2,3- diisopropyl succinic acid diisobutyl ester, 2- cyano -2,3- diisopropyl succinic acid -1- methyl esters -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano -2,3- diisopropyl Succinic acid -1- ethyl ester -4- methyl esters (R4=ethyl, R3=methyl), 2- cyano -2,3- diisopropyl succinic acid -1- N-butyl -4- Ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano -2,3- diisopropyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyano -2,3- diisobutyl dimethyl succinate, 2- cyano -2,3- diisobutyl diethyl succinate, 2- cyano -2,3- diisobutyl succinic acid di-n-propyl ester, 2- cyano -2,3- diisobutyl diisopropyl ester amber acid, cyano -2 2-, 3- diisobutyl succinic acid di-n-butyl, 2- cyano -2,3- diisobutyl succinic acid diisobutyl ester, two isobutyl of 2- cyano -2,3- Base succinic acid -1- methyl esters -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano -2,3- diisobutyl succinic acid -1- ethyl ester -4- Methyl esters (R4=ethyl, R3=methyl), 2- cyano -2,3- diisobutyl succinic acid -1- N-butyl -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano -2,3- diisobutyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyanogen Base -2,3- di-sec-butyl dimethyl succinate, 2- cyano -2,3- di-sec-butyl diethyl succinate, 2- cyano -2,3- di-secondary fourth Base succinic acid di-n-propyl ester, 2- cyano -2,3- di-sec-butyl diisopropyl ester amber acid, 2- cyano -2,3- di-sec-butyl succinic acid Di-n-butyl, 2- cyano -2,3- di-sec-butyl succinic acid diisobutyl ester, 2- cyano -2,3- di-sec-butyl succinic acid -1- methyl esters - 4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano -2,3- di-sec-butyl succinic acid -1- ethyl ester -4- methyl esters (R4=ethyl, R3 =methyl), 2- cyano -2,3- di-sec-butyl succinic acid -1- N-butyl -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano- 2,3- di-sec-butyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyano -2,3- bicyclopentyl fourth Acid dimethyl, 2- cyano -2,3- bicyclopentyl diethyl succinate, 2- cyano -2,3- bicyclopentyl succinic acid di-n-propyl ester, 2- cyano -2,3- bicyclopentyl diisopropyl ester amber acid, 2- cyano -2,3- bicyclopentyl succinic acid di-n-butyl, cyano -2 2-, 3- bicyclopentyl succinic acid diisobutyl ester, 2- cyano -2,3- bicyclopentyl succinic acid -1- methyl esters -4- ethyl ester (R4=methyl, R3= Ethyl), 2- cyano -2,3- bicyclopentyl succinic acid -1- ethyl ester -4- methyl esters (R4=ethyl, R3=methyl), 2- cyano -2,3- two Cyclopenta succinic acid -1- N-butyl -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano -2,3- bicyclopentyl succinic acid -1- Ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyano -2,3- dicyclohexyl dimethyl succinate, 2- cyano -2,3- Dicyclohexyl-succinate, 2- cyano -2,3- dicyclohexyl succinic acid di-n-propyl ester, 2- cyano -2,3- dicyclohexyl fourth Diisopropyl adipate, 2- cyano -2,3- dicyclohexyl succinic acid di-n-butyl, 2- cyano -2,3- dicyclohexyl succinic acid two are different Butyl ester, 2- cyano -2,3- dicyclohexyl succinic acid -1- methyl esters -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano -2,3- two Cyclohexyl succinic acid -1- ethyl ester -4- methyl esters (R4=ethyl, R3=methyl), the positive fourth of 2- cyano -2,3- dicyclohexyl succinic acid -1- Ester -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano -2,3- dicyclohexyl succinic acid -1- ethyl ester -4- N-butyl (R4= Ethyl, R3=normal-butyl)；
2- cyano -2- methyl -3- ethyl succinic acid diethylester, 2- cyano -2- methyl -3- n-propyl diethyl succinate, 2- cyano -2- methyl -3- isopropyl diethyl succinate, 2- cyano -2- methyl -3- normal-butyl diethyl succinate, 2- cyano - 2- methyl -3- isobutyl group diethyl succinate, 2- cyano -2- methyl -3- n-pentyl diethyl succinate, 2- cyano -2- methyl - 3- isopentyl diethyl succinate, 2- cyano -2- methyl -3- cyclopenta diethyl succinate, 2- cyano -2- methyl -3- just oneself Base diethyl succinate, 2- cyano -2- methyl -3- isohesyl diethyl succinate；
2- cyano -2- ethyl -3- diethyl methylsuccinate, 2- cyano -2- ethyl -3- n-propyl diethyl succinate, 2- cyano -2- ethyl -3- isopropyl diethyl succinate, 2- cyano -2- ethyl -3- normal-butyl diethyl succinate, 2- cyano - 2- ethyl -3- isobutyl group diethyl succinate, 2- cyano -2- ethyl -3- n-pentyl diethyl succinate, 2- cyano -2- ethyl - 3- isopentyl diethyl succinate, 2- cyano -2- ethyl -3- cyclopenta diethyl succinate, 2- cyano -2- ethyl -3- just oneself Base diethyl succinate, 2- cyano -2- ethyl -3- isohesyl diethyl succinate；
2- cyano -2- n-propyl -3- diethyl methylsuccinate, 2- cyano -2- n-propyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- n-propyl -3- isopropyl diethyl succinate, 2- cyano -2- n-propyl -3- normal-butyl diethyl succinate, 2- cyano -2- n-propyl -3- isobutyl group diethyl succinate, 2- cyano -2- n-propyl -3- n-pentyl diethyl succinate, 2- Cyano -2- n-propyl -3- isopentyl diethyl succinate, 2- cyano -2- n-propyl -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- n-propyl -3- n-hexyl diethyl succinate, 2- cyano -2- n-propyl -3- isohesyl diethyl succinate；
2- cyano -2- isopropyl -3- diethyl methylsuccinate, 2- cyano -2- isopropyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- isopropyl -3- n-propyl diethyl succinate, 2- cyano -2- isopropyl -3- normal-butyl diethyl succinate, 2- cyano -2- isopropyl -3- isobutyl group diethyl succinate, 2- cyano -2- isopropyl -3- n-pentyl diethyl succinate, 2- Cyano -2- isopropyl -3- isopentyl diethyl succinate, 2- cyano -2- isopropyl -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- isopropyl -3- n-hexyl diethyl succinate, 2- cyano -2- isopropyl -3- isohesyl diethyl succinate；
2- cyano -2- normal-butyl -3- diethyl methylsuccinate, 2- cyano -2- normal-butyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- normal-butyl -3- n-propyl diethyl succinate, 2- cyano -2- normal-butyl -3- isopropyl diethyl succinate, 2- cyano -2- normal-butyl -3- isobutyl group diethyl succinate, 2- cyano -2- normal-butyl -3- n-pentyl diethyl succinate, 2- Cyano -2- normal-butyl -3- isopentyl diethyl succinate, 2- cyano -2- normal-butyl -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- normal-butyl -3- n-hexyl diethyl succinate, 2- cyano -2- normal-butyl -3- isohesyl diethyl succinate；
2- cyano -2- isobutyl group -3- diethyl methylsuccinate, 2- cyano -2- isobutyl group -3- ethyl succinic acid diethyl Ester, 2- cyano -2- isobutyl group -3- n-propyl diethyl succinate, 2- cyano -2- isobutyl group -3- isopropyl diethyl succinate, 2- cyano -2- isobutyl group -3- normal-butyl diethyl succinate, 2- cyano -2- isobutyl group -3- n-pentyl diethyl succinate, 2- Cyano -2- isobutyl group -3- isopentyl diethyl succinate, 2- cyano -2- isobutyl group -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- isobutyl group -3- n-hexyl diethyl succinate, 2- cyano -2- isobutyl group -3- isohesyl diethyl succinate；
2- cyano -2- n-pentyl -3- diethyl methylsuccinate, 2- cyano -2- n-pentyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- n-pentyl -3- n-propyl diethyl succinate, 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate, 2- cyano -2- n-pentyl -3- normal-butyl diethyl succinate, 2- cyano -2- n-pentyl -3- isobutyl group diethyl succinate, 2- Cyano -2- n-pentyl -3- isopentyl diethyl succinate, 2- cyano -2- n-pentyl -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- n-pentyl -3- n-hexyl diethyl succinate, 2- cyano -2- n-pentyl -3- isohesyl diethyl succinate；
2- cyano -2- isopentyl -3- diethyl methylsuccinate, 2- cyano -2- isopentyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- isopentyl -3- n-propyl diethyl succinate, 2- cyano -2- isopentyl -3- isopropyl diethyl succinate, 2- cyano -2- isopentyl -3- normal-butyl diethyl succinate, 2- cyano -2- isopentyl -3- isobutyl group diethyl succinate, 2- Cyano -2- isopentyl -3- n-pentyl diethyl succinate, 2- cyano -2- isopentyl -3- cyclopenta diethyl succinate, 2- cyanogen Base -2- isopentyl -3- n-hexyl diethyl succinate, 2- cyano -2- isopentyl -3- isohesyl diethyl succinate；
2- cyano -2- cyclopenta -3- diethyl methylsuccinate, 2- cyano -2- cyclopenta -3- ethyl succinic acid diethyl Ester, 2- cyano -2- cyclopenta -3- n-propyl diethyl succinate, 2- cyano -2- cyclopenta -3- isopropyl diethyl succinate, 2- cyano -2- cyclopenta -3- normal-butyl diethyl succinate, 2- cyano -2- cyclopenta -3- isobutyl group diethyl succinate, 2- Cyano -2- cyclopenta -3- n-pentyl diethyl succinate, 2- cyano -2- cyclopenta -3- isopentyl diethyl succinate, 2- cyanogen Base -2- cyclopenta -3- n-hexyl diethyl succinate, 2- cyano -2- cyclopenta -3- isohesyl diethyl succinate；
2- cyano -2- n-hexyl -3- diethyl methylsuccinate, 2- cyano -2- n-hexyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- n-hexyl -3- n-propyl diethyl succinate, 2- cyano -2- n-hexyl -3- isopropyl diethyl succinate, 2- cyano -2- n-hexyl -3- normal-butyl diethyl succinate, 2- cyano -2- n-hexyl -3- isobutyl group diethyl succinate, 2- Cyano -2- n-hexyl -3- n-pentyl diethyl succinate, 2- cyano -2- n-hexyl -3- isopentyl diethyl succinate, 2- cyanogen Base -2- n-hexyl -3- cyclopenta diethyl succinate, 2- cyano -2- n-hexyl -3- isohesyl diethyl succinate；And
2- cyano -2- isohesyl -3- diethyl methylsuccinate, 2- cyano -2- isohesyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- isohesyl -3- n-propyl diethyl succinate, 2- cyano -2- isohesyl -3- isopropyl diethyl succinate, 2- cyano -2- isohesyl -3- normal-butyl diethyl succinate, 2- cyano -2- isohesyl -3- isobutyl group diethyl succinate, 2- Cyano -2- isohesyl -3- n-pentyl diethyl succinate, 2- cyano -2- isohesyl -3- isopentyl diethyl succinate, 2- cyanogen Base -2- isohesyl -3- cyclopenta diethyl succinate, in 2- cyano -2- isohesyl -3- n-hexyl diethyl succinate at least It is a kind of；
The preferred embodiment of method produced according to the present invention, electronics in electron and second part in first part Body is identical or different, is each independently selected from:
2- cyano -2,3- diethyl succinic acid diethylester, 2- cyano -2,3- diη-propyl diethyl succinate, 2- cyano - 2,3- diisopropyl diethyl succinates, 2- cyano -2,3- di-n-butyl diethyl succinate, 2- cyano -2,3- diisobutyl Diethyl succinate, bis- n-pentyl diethyl succinate of 2- cyano -2,3-, 2- cyano -2,3- diisoamyl diethyl succinate, 2- cyano -2,3- bicyclopentyl diethyl succinate, 2- cyano -2,3- di-n-hexyl diethyl succinate, 2- cyano -2,3- bis- Isohesyl diethyl succinate；2- cyano -2,3- diisopropyl succinic acid di-n-propyl ester, 2- cyano -2,3- diisopropyl fourth two Sour diisopropyl ester, 2- cyano -2,3- diisopropyl succinic acid di-n-butyl, 2- cyano -2,3- diisopropyl-two isobutyl of succinic acid Ester, 2- cyano -2,3- diisopropyl diethyl succinate, 2- cyano -2- normal-butyl -3- isopropyl diethyl succinate, 2- cyanogen Base -2- isobutyl group -3- isopropyl diethyl succinate, 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate, 2- cyano - At least one in 2- isopentyl -3- isopropyl diethyl succinate and 2- cyano -2- cyclopenta -3- isopropyl diethyl succinate Kind；It is more preferably selected from 2- cyano -2,3- diη-propyl diethyl succinate, 2- cyano -2,3- diisopropyl diethyl succinate, 2- cyano -2,3- di-n-butyl diethyl succinate, 2- cyano -2,3- diisobutyl diethyl succinate, 2- cyano -2,3- bis- N-pentyl diethyl succinate, 2- cyano -2,3- diisoamyl diethyl succinate, 2- cyano -2,3- bicyclopentyl succinic acid Diethylester, 2- cyano -2- normal-butyl -3- isopropyl diethyl succinate, 2- cyano -2- isobutyl group -3- isopropyl succinic acid two Ethyl ester, 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate, 2- cyano -2- isopentyl -3- isopropyl succinic acid diethyl At least one of ester and 2- cyano -2- cyclopenta -3- isopropyl diethyl succinate.
In the present invention, first part's internal electron donor can only be added after solid Precipitation in step 2), preferably in step Rapid 3) middle addition.This is primarily due to, and is added before step 1) or step 2) solid Precipitation, on the one hand influences whether to walk It is rapid 2) in solid precipitating precipitation effect, that is, influence the particle shape of catalytic component, and eventually affect the comprehensive of catalyst Close performance；On the other hand, research shows that internal electron donor is added before solid Precipitation also affects internal electron donor Service efficiency specifically be also difficult to obtain in final catalyst solid constituent even if a large amount of two ester type compound is added Two more ester type compounds make them unsuitable for the use of the preparation of tube material to influence the performance for finally preparing resin.
According to the present invention, in the step 4) of the preparation method, second part internal electron donor is added again.Second part Internal electron donor can be above-mentioned first part's internal electron donor, and the compound of specific choice can be identical or different.It is given by Electron substep is added with special ratios in step 3) and (4), and dosage can be by above-mentioned restriction.
If added respectively relative to all internal electron donors are added in step 3) using in step 3) and step 4) Enter the preparation method of internal electron donor, it can be in the comprehensive performance of the following aspects improvement catalyst: 1, can make to be carried on The internal electron donor of the magnesium halide is more uniform, so that the decay of activity for the catalyst being prepared is changed It is kind.Specifically, the ratio of 2 hours polymerization activities and 1 hour polymerization activities of the catalyst being prepared will increase, show The decay of activity of catalyst is slack-off.This is the target that high performance catalyst is pursued；2, the service efficiency of internal electron donor is improved, The less internal electron donor of total amount is used so that the internal electron donor content in catalyst solid component is identical；3, it effectively drops The content of titanium elements in low catalyst, to reduce unstable activated centre and low capacity of orientation activated centre, reduction are urged Agent temperature of reactor fluctuation risk in polymerization process, and the problem for avoiding the polymer isotactic index generated relatively low.
In the present invention, step 4) and 5) in the use form of titanium compound be not particularly limited, such as in step 4) or (5) Titanium compound individually can directly use, titanium compound can also first be mixed with inert diluent, then again with it is described Solid component carries out the 4th haptoreaction, or carries out the 5th haptoreaction with the solid product.The titanium compound With inert diluent as it was noted above, details are not described herein.
In the present invention, step 4) and 5) in the 4th and the 5th haptoreaction condition can be identical, comprising: reaction temperature Degree is 50-150 DEG C, preferably 80-120 DEG C；Reaction time is 1-6 hours, preferably 2.5-4.5 hours.
The preparation method of the catalytic component provided by the invention for preparing tubing polyolefin can also include completing step 5) after, the liquid in the product that the 5th haptoreaction obtains is filtered out, solid reaction product is obtained, repeats the described 5th Haptoreaction 1-3 times；By washing, drying, the catalytic component of the titaniferous of solid is obtained, to provide the catalytic component of solid As the catalytic component for olefinic polymerization.
Step 4) of the invention and 5) in, the amount of the second part titanium compound of addition, Part III titanium compound, as long as Satisfaction makes the total amount of titanium compound meet the aforementioned and magnesium halide (in terms of magnesium elements) molar ratios, such as can be with second The molar ratio of part titanium compound or Part III titanium compound and magnesium halide can be (3-40): 1, preferably (5-35): 1.
A preferred embodiment of the invention, the catalyst solid constituent of preparation olefinic polymerization provided by the invention Method can carry out in accordance with the following steps:
(1) under hydrocarbon solvent, by anhydrous magnesium chloride and alcohol compound 30-150 DEG C (preferably 60-140 DEG C) into The first haptoreaction of row 0.5-10 hours (preferably 0.5-6 hours), obtain uniform alcohol adduct solution, wherein anhydrous chlorination The molar ratio of magnesium and alcohol compound is 1:(2-4) (preferably 1:(2.5-3.5))；
(2) by diol-lipid compound (precipitation additive a) and general formula Ti (OR9)nX4-nShown in titanate ester compound (help Precipitation agent b) is added in above-mentioned alcohol adduct solution, and the molar ratio of anhydrous magnesium chloride and diol-lipid compound is 1:(0.005- 0.3) (preferably 1:(0.01-0.05)), the molar ratio of precipitation additive a and the additional amount of precipitation additive b is 1:(0.01-5) (excellent It is selected as 1:(0.5-3), more preferable 1:(0.5-1.5))；
By the above-mentioned alcohol adduct solution added with precipitation additive, be added to -40 DEG C to 0 DEG C of first part's titanium compound with it is lazy Property diluent mixture in, reacted under -40 DEG C to 0 DEG C (preferably -30 DEG C to -20 DEG C) by stirring, and at 3-5 hours It is warming up to 50-150 DEG C (preferably 90-130 DEG C) in (preferably 3.5-4.5 hours), solid precipitating is precipitated in temperature-rise period, it is complete At the second haptoreaction, the mixture precipitated containing solid is obtained；Wherein, mole of first part's titanium compound and anhydrous magnesium chloride Than for (3-40): 1, preferably (5-35): 1；
(3) first part's internal electron donor is added in the mixture obtained in above-mentioned (2), is 20-120 DEG C in temperature Third haptoreaction 0.5-6 hours (preferably 1-4 hours) is carried out under (preferably 70-110 DEG C), obtains suspended matter, wherein two The molar ratio of the total amount of alkoxide compound and the internal electron donor of addition is 0.05:1 to less than 0.5:1 (preferably 0.1- 0.4:1, more preferable 0.15-0.35:1)；First part's internal electron donor of addition and subsequent step 4) in the second part that is added Molar ratio between internal electron donor is 0.1-10:1 (preferably 0.2-5:1, more preferable 0.2-1:1)；
(4) suspended matter obtained in above-mentioned (3) be separated by solid-liquid separation and filter out liquid, obtain solid component, and will be to Mixture, the second part internal electron donor of second part titanium compound and inert diluent are added in solid component, in 50- The 4th haptoreaction 1-6 hours (preferably 2.5-4.5 hours) is carried out under 150 DEG C (preferably 80-120 DEG C), after reaction, Liquid is filtered out, solid product is obtained；Wherein, the molar ratio of second part titanium compound and anhydrous magnesium chloride is (3-40): 1, Preferably (5-35): 1；
(5) by solid product obtained in above-mentioned (4), exist with the mixture of Part III titanium compound and inert diluent (preferably 80-120 DEG C) carries out the 5th haptoreaction 1-6 hours (preferably 2.5-4.5 hours) at 50-150 DEG C, is produced Object, wherein the molar ratio of Part III titanium compound and anhydrous magnesium chloride is (3-40): 1, preferably (5-35): 1；
(6) product for obtaining above-mentioned (5), filters out liquid, obtains solid reaction product, and by the solid reaction product Repeat with the mixture of titanium compound and inert diluent the described 5th haptoreaction 1-3 time, it is dry by washing, it obtains To the catalytic component of the titaniferous of solid；Wherein, the molar ratio of the titanium compound and anhydrous magnesium chloride can be (3-40): 1, Preferably (5-35): 1.
In a kind of preferred embodiment of the invention, particularly preferred precipitation additive a is 3,5- heptandiol dibenzoate, interior Electron donor is 2- cyano -2,3- diisopropyl diethyl succinate；The precipitation additive a and total internal electron donor Molar ratio is (0.05-0.5): 1, preferably (0.1-0.4): 1, more preferable (0.15-0.35): 1.In step 3), described first The molar ratio of part internal electron donor and second part internal electron donor is (0.1-10): 1, preferably (0.2-5): 1, more preferably (0.2-1):1.In the application, specific precipitation additive a, internal electron donor can be particularly used, and to electricity in substep addition Daughter and titanium compound, and specific dosage is limited, to better solve technical problems to be solved in this application.
In the present invention, internal electron donor, and strict control are made by using the cyano succinic acid ester type compound of formula (II) Cyano succinic acid ester type compound is with the amount ratio of the diol-lipid compound of the formula (I) as precipitation additive a and by specific Internal electron donor is added in ratio substep, to be prepared for high comprehensive performance, catalyst suitable for preparing tube material polyolefin Solid component.The particle of the catalyst solid constituent can it is good in the form of, polymerization activity is high, capacity of orientation is good, obtain polyene The distribution of hydrocarbon molecule amount is wider.
The present invention also provides a kind of catalytic component for olefinic polymerization, the preparation that can be provided through the invention Method obtains.
The catalytic component provided according to the present invention contains 1-3.5 weight % based on the total weight of the catalytic component Titanium, the internal electron donor of precipitation additive a, the 6-15 weight % of 1-3.5 weight %, and precipitation additive a and internal electron donor Molar ratio is 0.05:1-0.5:1；It is highly preferred that the titanium containing 1.8-3.2 weight %, the precipitation additive a, 7- of 1.5-3 weight % The internal electron donor of 11 weight %, and the molar ratio of precipitation additive a and internal electron donor is (0.1-0.3): 1.
In catalytic component provided by the invention, it is preferable that the total weight based on the catalytic component contains 1-3.5 The titanium of weight %, the glycol ester compounds of 1-3.5 weight %, two ester type compounds of 6-15 weight %, and glycol ester compounds Molar ratio with bis- ester type compound of 1,3- is 0.05:1 to less than 0.5:1；It is highly preferred that based on the total of the catalytic component Weight, the titanium containing 1.8-3.2 weight %, the glycol ester compounds of 1.5-3 weight %, the two esters chemical combination of 7-11 weight % Object, and the molar ratio of glycol ester compounds and two ester type compounds is (0.1-0.3): 1.
Catalyst the present invention also provides the above-mentioned catalytic component for olefinic polymerization in preparation for olefinic polymerization Application in system.
Therefore, the present invention also provides a kind of for olefinic polymerization in particular for the caltalyst of preparation polyolefin System, the catalyst system contain: (1) catalytic component of the present invention；(2) alkyl aluminum compound；And (3) optional outer is given Electron compound.
According to the present invention, the olefinic polymerization refers to general formula CH2The polymerization reaction for the alkene that=CHR is indicated, wherein R is hydrogen Or C1-C6Alkyl (preferably hydrogen or methyl).
According to the present invention, the dosage of the alkyl aluminum compound can be the conventional amount used of this field.Under preferable case, institute Alkyl aluminum compound is stated in terms of aluminium, the catalytic component is in terms of titanium, the alkyl aluminum compound and the catalytic component Molar ratio is (5-5000): 1；Preferably, the molar ratio of the alkyl aluminum compound and the catalytic component is 20-1000: 1.It is highly preferred that the molar ratio of the alkyl aluminum compound and the catalytic component is 50-500:1.
In the present invention, in the catalyst system for preparing tubing polyolefin, the alkyl aluminum compound can be alkene The alkyl aluminum compound of the common various co-catalysts that can be used as Ziegler-natta catalyst of polymerization field.Preferably In the case of, the alkyl aluminum compound can be formula (III) compound represented,
AlR'n'X'3-n'(III),
In formula (III), R' is hydrogen, C1-C20Alkyl or C6-C20Aryl, X' is halogen, and n' is the integer of 1-3.It is preferred that Ground, the specific example of the alkyl aluminum compound for example can for trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, One hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and dichloro At least one of aluminium ethide.
According to the present invention, in the catalyst system for preparing tubing polyolefin, the kind of the external donor compound Class and content are not particularly limited.The alkyl aluminum compound and the external electron donor chemical combination under preferable case, in terms of aluminium The molar ratio of object is 0.1-500:1, preferably 1-300:1, more preferably 3-100:1.
According to the present invention, the external donor compound can be used as together for field of olefin polymerisation is commonly various The external donor compound of Ge Le-Natta catalyst co-catalyst.Under preferable case, the external donor compound It can be organo-silicon compound shown in formula (IV),
R1”m”R2”n”Si(OR3”)4-m”-n”(IV),
In formula (IV), it is respectively halogen, hydrogen atom, C that R1 " and R2 ", which can be identical or different,1-C20Alkyl, C3-C20Naphthenic base, C6-C20Aryl and C1-C20One of halogenated alkyl；R3 " is C1-C20Alkyl, C3-C20Ring Alkyl, C6-C20Aryl and C1-C20One of halogenated alkyl；M " and n " is respectively the integer of 0-3, and m "+n " < 4.Make Trimethylmethoxysilane, trimethylethoxysilane, three can be enumerated for the specific example of the external donor compound Methylphenoxy triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, dimethyldimethoxysil,ne, dimethyl diethoxy It is silane, ethylisopropyl base dimethoxysilane, propyl iso-propyl dimethoxysilane, diisopropyl dimethoxy silane, two different Butyldimethoxysilane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl diformazan Oxysilane, t-butylethyl dimethoxysilane, tert-butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxy silicon Alkane, tert-butyl butyldimethoxysilane, tert-butyl isobutyl group dimethoxysilane, tert-butyl (sec-butyl) dimethoxy silicon Alkane, t-butyl amyl dimethoxysilane, tert-butyl nonyl dimethoxysilane, tert-butyl hexyl dimethoxysilane, tertiary fourth Base heptyl dimethoxysilane, tert-butyl octyl dimethoxysilane, tert-butyl decyl dimethyl oxysilane, methyl tertbutyl two Methoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl-ethyl dimethoxysilane, Cyclohexylpropyl dimethoxy silicon Alkane, cyclohexyl isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl t-butyldimethoxysilane, ring Phenyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclopentylpropyi dimethoxysilane, the tertiary fourth of cyclopenta Base dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, bis- (2- methylcyclopentyls) Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyl trimethoxy Oxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, Isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxysilane, trimethoxysilane, tertiary fourth Base trimethoxy silane, sec-butyl trimethoxy silane, amyltrimethoxysilane, isopentyl trimethoxy silane, cyclopenta Trimethoxy silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl three Methoxy silane, phenyl triethoxysilane, n-propyl trimethoxy silane, vinyltrimethoxysilane, tetramethoxy-silicane Alkane, tetraethoxysilane, four butoxy silanes, 2- ethyl piperidine base -2- t-butyldimethoxysilane, (the fluoro- 2- of 1,1,1- tri- Propyl) in -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- propyl of 1,1,1- tri-)-methyl dimethoxysilane at least It is a kind of.It is highly preferred that the external donor compound can be dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy Silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane and tetramethyl At least one of oxysilane.
The present invention also provides a kind of polymerizations of tubing polyolefin, this method comprises: under olefin polymerization conditions, Contact one or more alkene with catalyst system provided by the invention, at least one of described alkene is by general formula CH2 The alkene that=CHR is indicated, wherein R is hydrogen or C1-C6Alkyl.The polymerization of tubing polyolefin provided by the invention can be with For the homopolymerization of alkene, can be used for a variety of alkene carrying out combined polymerization.The alkene can with specific example include: second At least one of alkene, propylene, 1- n-butene, 1- n-pentene, 1- n-hexylene, the positive octene of 1- and 4-methyl-1-pentene.It is preferred that Ground, the alkene can be at least one of ethylene, propylene, 1- n-butene, 4-methyl-1-pentene and 1- n-hexylene.It is more excellent Selection of land, the alkene are propylene.
According to the present invention, the catalyst solid component is applied in polyolefin preparing tubing, prepares tubing polyene The component of the catalyst system of hydrocarbon, i.e., catalyst solid constituent provided by the invention, the organo-aluminum compound as co-catalyst Can first be contacted before contacting olefinic monomer with as external donor compound, it is in the field of business be referred to as " pre-contact " or " pre- complexing "；Can also three components be added separately in olefinic monomer carry out polymerization reaction again, i.e., do not implement " pre-contact ". The olefine polymerizing process provided according to the present invention, each component in preferred alkenes polymerisation catalyst system using " pre-contact " side Method.The time of " pre-contact " be 0.1-30min, preferably 1-10 minutes；The temperature of " pre-contact " is -20 DEG C to 80 DEG C, preferably 10- 50℃。
The catalyst system is first carried out in the presence of a small amount of olefinic monomer to a degree of polymerization and obtains prepolymerization Catalyst, then pre-polymerized catalyst is further contacted with olefinic monomer and is reacted to obtain olefin polymer.This technology exists It is referred to as " prepolymerization " technique in the industry, facilitates polymerization catalyst activity and raising of polymer bulk density etc..According to this hair The olefine polymerizing process of bright offer can use " prepolymerization " technique, can not also use " prepolymerization " technique, it is preferred to use " prepolymerization " technique.The multiplying power of " prepolymerization " is 5-1000gPP/gCat when olefinic monomer is propylene, preferably 10-500gPP/ gCat；The temperature of " prepolymerization " is -20 DEG C to 80 DEG C, preferably 10-50 DEG C.
The polymerization according to the present invention for preparing tubing polyolefin, the polymerizing condition can be the routine of this field Condition.The dosage of catalyst can be the dosage of the various catalyst of the prior art.
Specific embodiment
The present invention will be described in detail with reference to embodiments, but is not intended to limit the invention.
In following embodiment, the test method being related to is as follows:
1, the yield (%) of catalytic component=(gained catalyst quality/magnesium chloride used quality) × 100%；
2,721 spectrophotometric determinations the Ti content in catalytic component: are used；
3, the size distribution of the solid of catalytic component: 2000 laser particle size analyzer of Malvern is used, according to n-hexane The measurement of dispersing agent laser diffractometry；
4, (diester contains the content of precipitation additive a compounds content (diol ester) and internal electron donor in catalytic component Amount): Waters 600E liquid chromatogram is measured；
5, it melt index (MI): is measured according to GB/T3682-2000；
6, acrylic polymers isotacticity index (II): measured using heptane extraction process: 2g dry polymer samples are placed on It is after being extracted 6 hours in extractor with boiling heptane, residue is dry to the resulting polymer weight (g) of constant weight and 2 (g) ratio Value is isotacticity；
7, polymer molecular weight distribution MWD (MWD=Mw/Mn): PL-GPC220 is used, using trichloro-benzenes as solvent, 150 (standard specimen: polystyrene, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um MlxED-B 300x7.5nm) is measured at DEG C.
8, activity calculates: catalyst activity=(the polyolefin quality of preparation)/(catalyst solid component quality) g/g
9, sedimentating density measuring: will prepare resulting polymer powders in funnel from 10cm height freely falling body to In 100mL container, polymer powders weight is Mg in weighing container, then polymer bulk density is M/100g/cm3。
Preparation example 1
The preparation of 2- cyano -2,3- diisopropyl diethyl succinate: in 1000mL round-bottomed flask, the tertiary fourth of 48.1g is added Sodium alkoxide and 300mLDMF.Temperature rising reflux.It stirs while 81.5g cyano ethyl isovalerate is added dropwise.80 DEG C are warming up to flow back 2 hours. The mixed solution of 99.6g bromo ethyl isovalerate and 100mLDMF is added dropwise.100 DEG C are continuously heating to react 20 hours.Stop anti- It answers, cooling, filtering.Washing of Filter Cake.Filtrate rotary evaporation removes solvent.Saturated ammonium chloride solution washing, liquid separation is added.It is organic relevant Dry, filtering is spin-dried for solvent.Obtain crude product.Rectification under vacuum obtains product 94.2g, (8mbar, 123-127 DEG C).1H-NMR(CDCl3/ TMS, 300MHz) (δ ppm): 0.99-1.04 (m, 8H), 1.08-1.38 (m, 10H), 2.12-2.16 (m, 1H), 2.28-2.37 (m, 1H), 2.97-3.02 (m, 1H), 4.14-4.30 (m, 4H).
Preparation example 2
The preparation of 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate: 1 method of preparation example is used, by cyano isovaleric acid Ethyl ester is changed to cyano enanthic ether and 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate is prepared, and rectification under vacuum obtains Product 53.7g (8mbar, 145-148 DEG C).1H NMR(CDCl3/TMS,300MHz)δ(ppm):0.85-0.91(t,3H), 0.97-1.10(m,6H),1.21-1.37(t,6H,m,4H),1.56-1.64(m,2H),1.73-1.82(t,2H),2.15- 2.22(m,1H),2.81-2.83(d,1H),4.14-4.30(m,4H)。
Embodiment 1-3 is for illustrating that catalyst component for olefin polymerization of the invention, olefin polymerization catalysis and alkene are poly- Conjunction method.
Embodiment 1
(1) preparation of catalytic component A1
(1) it is repeating to sequentially add the anhydrous chlorination of 3.150mol (300.0g) in displaced reaction kettle by High Purity Nitrogen Magnesium, the toluene of 19.68mol (2.1L), 8.4mol (1.1L) 2-Ethylhexyl Alcohol, speed of agitator 450rpm, temperature be 115 DEG C Under conditions of, it reacts 3.0 hours, obtains the alcohol adduct solution of stable and uniform；
(2) 3,5- heptandiol dibenzoate 124mmol (42ml) and four fourth of metatitanic acid are added in Xiang Shangshu alcohol adduct solution Ester 132mmol (45ml) is stirred 60 minutes, is cooled to room temperature, obtains homogeneous solution；Above-mentioned homogeneous solution is added to through nitrogen It is sufficiently displaced from and is equipped in the reactor of the titanium tetrachloride of -20 DEG C of 60mol (6.6L) and the toluene of 11.4mol (1.2L), lead to Crossing stirring comes into full contact with them at -20 DEG C, after 5 hours, is warming up to 100 DEG C, and solid precipitating is precipitated in temperature-rise period, obtains To the mixture precipitated containing solid；
(3) it is above-mentioned heavy containing solid 2- cyano -2,3- diisopropyl diethyl succinate 123.5mmol (35g) to be added It is reacted 1 hour in the mixture in shallow lake, after reaction, filters out liquid；
(4) then by toluene, the 26.2mol (2.88L) of the solid component being obtained by filtration in (3) and 40.8mol (4.32L) Titanium tetrachloride and the 2- cyano -2,3- diisopropyl diethyl succinate of 247.0mmol (70g) that 1.5 are contacted at 100 DEG C is small When, after reaction, filter out liquid；
(5) then by the toluene and 26.2mol of the solid product being obtained by filtration in (4) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) obtained product is reacted in filtering (5), by the solid reaction product being obtained by filtration 40.8mol (4.32L) toluene And that haptoreaction is carried out at 110 DEG C is primary for 26.2mol (2.88L) titanium tetrachloride；Finally obtained solids is used 55.14mol (7.2L) hexane washs 5 times, then dries, obtains the catalytic component A1 for olefinic polymerization.
For the Ti content of catalytic component A1 of olefinic polymerization, the content of precipitation additive a, internal electron donor content with And the results are shown in Table 1 for the size distribution of the catalytic component A1 for olefinic polymerization.
(2) olefin polymerization
The examination of polymerization in (1) 1 hour: it in 5 liters of autoclaves, after gas-phase propene is sufficiently displaced from, is added at room temperature The cyclohexyl methyl dimethoxy silicon of the hexane solution (concentration of triethyl aluminum be 0.5mmol/ml) of the triethyl aluminum of 5ml, lml The catalytic component of the hexane solution (concentration of CHMMS be 0.1mmol/ml) of alkane (CHMMS), the anhydrous hexane of 10ml and 10mg A1.Autoclave is closed, the hydrogen of 0.18mol and the liquid propene of 2.4L are introduced；Under agitation, by temperature liter in 10 minutes To 70 DEG C.70 DEG C polymerization reaction 60 minutes, stop to stir after reaction, remove unpolymerized propylene monomer, collected polymer, It is dried in vacuo 1 hour at 70 DEG C, weighing calculates catalyst activity.
The examination of polymerization in (2) 2 hours: it is examined with polymerization in above-mentioned 1 hour, catalyst charge amount is only reduced to 8mg, hydrogen Dosage is reduced to 0.02mol, while polymerization reaction time was increased to 2 hours by 1 hour.
The performance parameter of polymerization activity and polymer that the caltalyst of the A1 containing catalytic component ties up in propylene polymerization is shown In table 2.
Comparative example 1
(1) preparation of catalytic component D1
(1) repeated in displaced reaction kettle by High Purity Nitrogen, sequentially add 3.150mol (300.0g) anhydrous magnesium chloride, 19.68mol (2.1L) toluene, 8.4mol (1.1L) 2-Ethylhexyl Alcohol, in speed of agitator 450rpm, the condition that temperature is 110 DEG C Under, it reacts 3.0 hours, obtains the alcohol adduct solution of stable and uniform；
(2) 3,5- heptandiol dibenzoate 124mmol (42ml), butyl titanate are added in Xiang Shangshu alcohol adduct solution 132mmol (45ml) is stirred 60 minutes, is cooled to room temperature, obtains homogeneous solution；Above-mentioned homogeneous solution is added to and is filled through nitrogen It splits and changes and be equipped in -20 DEG C of 60mol (6.6L) titanium tetrachloride and the reactor of 11.4mol (1.2L) toluene, pass through stirring It comes into full contact with them at -20 DEG C, after 5 hours, is warming up to 110 DEG C, solid precipitating is precipitated in temperature-rise period, is contained The mixture of solid precipitating；
(3) 2- cyano -2,3- diisopropyl diethyl succinate 425.0mmol (120.4g) is added and above-mentioned contains solid It is reacted 1 hour in the mixture of precipitating, after reaction, filters out liquid；
(4) then by the toluene and 26.2mol of the solid component being obtained by filtration in (3) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) contacts 1 hour at 110 DEG C, filtering；
(5) then again by the solid product being obtained by filtration in (4) and 40.8mol (4.32L) toluene and 26.2mol (2.88L) titanium tetrachloride contacts 0.5 hour at 110 DEG C；
(6) obtained product is reacted in filtering (5), by the solid reaction product being obtained by filtration 55.14mol (7.2L) hexane Washing 5 times, then dries, obtains the catalytic component D1 for olefinic polymerization.
For the Ti content of catalytic component D1 of olefinic polymerization, the content of precipitation additive a, internal electron donor content with And the results are shown in Table 1 for the size distribution of the catalytic component D1 for olefinic polymerization.
(2) olefin polymerization:
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with D1 substitution A1.
The performance parameter of polymerization activity and polymer that the caltalyst of the D1 containing catalytic component ties up in propylene polymerization is shown In table 2.
Embodiment 2
(1) preparation of catalytic component A2
(1) it is repeating to sequentially add the anhydrous chlorination of 3.150mol (300.0g) in displaced reaction kettle by High Purity Nitrogen Magnesium, the toluene of 19.68mol (2.1L), 8.4mol (1.1L) 2-Ethylhexyl Alcohol, speed of agitator 450rpm, temperature be 115 DEG C Under conditions of, it reacts 3.0 hours, obtains the alcohol adduct solution of stable and uniform；
(2) 3,5- heptandiol dibenzoate 124mmol (42ml) and four fourth of metatitanic acid are added in Xiang Shangshu alcohol adduct solution Ester 132mmol (45ml) is stirred 60 minutes, is cooled to room temperature, obtains homogeneous solution；Above-mentioned homogeneous solution is added to through nitrogen It is sufficiently displaced from and is equipped in the reactor of the titanium tetrachloride of -20 DEG C of 60mol (6.6L) and the toluene of 11.4mol (1.2L), lead to Crossing stirring comes into full contact with them at -20 DEG C, after 5 hours, is warming up to 110 DEG C, and solid precipitating is precipitated in temperature-rise period, obtains To the mixture precipitated containing solid；
(3) by 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate 112.4mmol (35.0g) be added it is above-mentioned containing It is reacted 1 hour in the mixture of solid precipitating, after reaction, filters out liquid；
(4) then by toluene, the 26.2mol (2.88L) of the solid component being obtained by filtration in (3) and 40.8mol (4.32L) Titanium tetrachloride and 224.8mmol (70.0g) 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate at 100 DEG C Lower contact 1.5 hours, after reaction, filters out liquid；
(5) then by the toluene and 26.2mol of the solid product being obtained by filtration in (4) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) contacts 0.5 hour at 110 DEG C；
(6) obtained product is reacted in filtering (5), by the solid reaction product being obtained by filtration 40.8mol (4.32L) toluene And that haptoreaction is carried out at 110 DEG C is primary for 26.2mol (2.88L) titanium tetrachloride；Finally obtained solids is used 55.14mol (7.2L) hexane washs 5 times, then dries, obtains the catalytic component A2 for olefinic polymerization.
For the Ti content of catalytic component A2 of olefinic polymerization, the content of precipitation additive a, internal electron donor content with And the results are shown in Table 1 for the size distribution of the catalytic component A2 for olefinic polymerization.
(2) olefin polymerization
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with A2 substitution A1.
The performance parameter of polymerization activity and polymer that the caltalyst of the A2 containing catalytic component ties up in propylene polymerization is shown In table 2.
Embodiment 3
(1) preparation of catalytic component A3
(1) it is repeating to sequentially add the anhydrous chlorination of 3.150mol (300.0g) in displaced reaction kettle by High Purity Nitrogen Magnesium, the toluene of 19.68mol (2.1L), 8.4mol (1.1L) 2-Ethylhexyl Alcohol, speed of agitator 450rpm, temperature be 115 DEG C Under conditions of, it reacts 3.0 hours, obtains the alcohol adduct solution of stable and uniform；
(2) 3,5- heptandiol dibenzoate 124mmol (42ml) and four fourth of metatitanic acid are added in Xiang Shangshu alcohol adduct solution Ester 132mmol (45ml) is stirred 60 minutes, is cooled to room temperature, obtains homogeneous solution；Above-mentioned homogeneous solution is added to through nitrogen It is sufficiently displaced from and is equipped in the reactor of the titanium tetrachloride of -20 DEG C of 60mol (6.6L) and the toluene of 11.4mol (1.2L), lead to Crossing stirring comes into full contact with them at -20 DEG C, after 5 hours, is warming up to 100 DEG C, and solid precipitating is precipitated in temperature-rise period, obtains To the mixture precipitated containing solid；
(3) it is above-mentioned heavy containing solid 2- cyano -2,3- diisopropyl diethyl succinate 123.5mmol (35g) to be added It is reacted 1 hour in the mixture in shallow lake, after reaction, filters out liquid；
(4) then by toluene, the 26.2mol (2.88L) of the solid component being obtained by filtration in (3) and 40.8mol (4.32L) Titanium tetrachloride and 2, the 3- diisopropyl -2- cyano diethyl succinate of 300.0mmol (85g) contacted at 100 DEG C 1.5 hours, after reaction, filter out liquid；
(5) then by the toluene and 26.2mol of the solid product being obtained by filtration in (4) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) obtained product is reacted in filtering (5), by the solid reaction product being obtained by filtration 40.8mol (4.32L) toluene And that haptoreaction is carried out at 110 DEG C is primary for 26.2mol (2.88L) titanium tetrachloride；Finally obtained solids is used 55.14mol (7.2L) hexane washs 5 times, then dries, obtains the catalytic component A3 for olefinic polymerization.
For the Ti content of catalytic component A3 of olefinic polymerization, the content of precipitation additive a, internal electron donor content with And the results are shown in Table 1 for the size distribution of the catalytic component A3 for olefinic polymerization.
(2) olefin polymerization
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with A3 substitution A1.
The performance parameter of polymerization activity and polymer that the caltalyst of the A3 containing catalytic component ties up in propylene polymerization is shown In table 2.
Embodiment 4
As described in Example 1, unlike, the Cyclohexyl Methyl Dimethoxysilane of 1ml is added without in (1) of (two) (CHMMS) hexane solution.
The performance parameter of polymerization activity and polymer is shown in Table 2.
Comparative example 2
(1) preparation of catalytic component D2
According to the method for (one) in comparative example 1, the difference is that, " diisobutyl phthalate of 95g " is used in step (3) It replaces " the 2- cyano -2,3- diisopropyl diethyl succinate of 120.4g ".
Obtain catalytic component D2.
The result of the size distribution of the Ti content of catalytic component D2, the content of precipitation additive a and catalytic component D2 As shown in table 1.
The content of diisobutyl phthalate is 8.8 weight % in D2.
(2) olefin polymerization
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with D2 substitution A1.
The performance parameter of polymerization activity and polymer that the caltalyst of the D2 containing catalytic component ties up in propylene polymerization is shown In table 2.
Comparative example 3
(1) preparation of catalytic component D3
(1) it is repeating to sequentially add the anhydrous chlorination of 3.150mol (300.0g) in displaced reaction kettle by High Purity Nitrogen Magnesium, the toluene of 19.68mol (2.1L), 8.4mol (1.1L) 2-Ethylhexyl Alcohol, speed of agitator 450rpm, temperature be 110 DEG C Under conditions of, it reacts 3.0 hours, obtains the alcohol adduct solution of stable and uniform；
(2) 3,5- heptandiol dibenzoate 124mmol (42ml), cyano -2 2- are added in Xiang Shangshu alcohol adduct solution, 3- diisopropyl diethyl succinate 148.2mmol (42g), butyl titanate 132mmol (45ml) are stirred 60 minutes, cooling To room temperature, homogeneous solution is obtained；Above-mentioned homogeneous solution is added to and is sufficiently displaced from through nitrogen, equipped with -20 DEG C of 60mol (6.6L) Titanium tetrachloride and 11.4mol (1.2L) toluene reactor in, by stirring come into full contact with them at -20 DEG C, through 5 After hour, 110 DEG C are warming up to, solid precipitating is precipitated in temperature-rise period, obtains the mixture precipitated containing solid；
(3) dibutyl phthalate 336mmol (90.0ml) is added anti-in the above-mentioned mixture containing solid precipitating After answering 1 hour, liquid is filtered out；
(4) then by the toluene and 26.2mol of the solid component being obtained by filtration in (3) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) contacts 1 hour at 110 DEG C, after reaction, filters out liquid；
(5) then by the toluene and 26.2mol of the solid product being obtained by filtration in (4) and 40.8mol (4.32L) The titanium tetrachloride of (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) obtained product is reacted in filtering (5), by the solid reaction product being obtained by filtration 55.14mol (7.2L) hexane Washing 5 times, then dries, obtains catalytic component D3.
The Ti content of catalytic component D3, the content of precipitation additive a, internal electron donor content and catalytic component D3 The results are shown in Table 1 for size distribution.
(2) olefin polymerization
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with D3 substitution A1.
Caltalyst containing catalytic component D3 ties up to the performance parameter of polymerization activity and polymer in propylene polymerization It is shown in Table 2.
Comparative example 4
(1) preparation of catalytic component D4
According to the method for (one) in comparative example 1, the difference is that, " 2- cyano -2,3- diisopropyl fourth of 90.0g is used in (3) Diethyl adipate " substitution " the 2- cyano -2,3- diisopropyl diethyl succinate of 120.4g ".
Obtain catalytic component D4.
The Ti content of catalytic component D4, the content of precipitation additive a, internal electron donor content and catalytic component D4 The results are shown in Table 1 for size distribution.
(2) olefin polymerization
According to the method in embodiment 1 in (two), the difference is that, it is polymerize with D4 substitution A1.
The performance parameter of polymerization activity and polymer that the caltalyst of the D4 containing catalytic component ties up in propylene polymerization is shown In table 2.
Table 1
Note: d (10) is indicated: the cumulative particle sizes distribution number of a sample reaches partial size corresponding when 10%.Its physics Meaning is that partial size is less than its particle and accounts for 10%；
D (50) is indicated: the cumulative particle sizes percentile of a sample reaches partial size corresponding when 50%.Its physics Meaning is that partial size is greater than its particle and accounts for 50%, also accounts for 50%, D50 less than its particle and is also meso-position radius or median particle diameter.D50 It is commonly used to indicate the average particle size of powder；
D (90) is indicated: the cumulative particle sizes distribution number of a sample reaches partial size corresponding when 90%.Its physical significance It is that partial size is less than its particle and accounts for 90%；
Span is indicated: (D90-D10)/D50, for indicating particle diameter distribution.
Table 2
Note: the ratio of the polymerization activity of damped expoential i.e. 2 hour and 1 hour polymerization activity.
It can be seen that catalytic component obtained by the present invention in composition, particle shape, polymerization from the data of table 1, table 2 Performance etc. has more preferable performance.Compared with comparative example 1 (internal electron donor is added without substep): 1, being esterified and close in the present invention The service efficiency of object is higher, i.e., has just reached 13.4 weight % using two ester contents in catalyst using the diester total amount of 105g (embodiment 1), and the diester reserves in the final catalyst of diester in comparative example 1 using 120.4g also only reach 8.9 weight %； 2, total Ti content in catalyst solid constituent of the present invention is lower, is conducive to raising (the polymer isotactic of catalyst capacity of orientation Index it is higher indicate catalyst capacity of orientation it is higher) and catalyst decay of activity speed reduce, while also reduce alkene gather The unstable risks happened such as the temperature fluctuation during symphysis production.(the interior of no two ester type compound gives electricity with comparative example 2 Daughter) and comparative example 3 (two ester type compounds being added before solid Precipitation, diester compound content is low in catalytic component) It compares, when prepared catalytic component is used for olefinic polymerization in embodiment, hydrogen tune is more insensitive (equally have been used when hydrogen amount and polymerize Object melt flow rate (MFR) is lower, becomes apparent from when 0.18mol is polymerize with hydrogen amount), and prepared polymer molecular weight distribution Width, the raising of these parameters are conducive to the preparation of special material for tube.In addition, containing when the diester compound in catalytic component When measuring lower (comparative example 4), the hydrogen response of catalyst, the molecular weight and catalyst activity damped expoential of polymer, It is unfavorable for the production of special material for tube.

Claims (18)

1. a kind of preparation method of the catalytic component for olefinic polymerization, comprising the following steps:
1) magnesium halide and alcohol compound are subjected in the presence of hydrocarbon solvent the first haptoreaction, form solution；
2) in the presence of precipitation additive, the resulting solution of step 1) is carried out second with first part's titanium compound and is contacted instead It answers, obtains the mixture precipitated containing solid；
3) the resulting mixture of step 2) and first part's internal electron donor are subjected to third haptoreaction, obtain suspension；
4) suspension for obtaining step 3) is separated by solid-liquid separation, obtained solid component and second part titanium compound, second Part internal electron donor carries out the 4th haptoreaction, then is separated by solid-liquid separation, and solid product is obtained；
5) solid product for obtaining step 4) and Part III titanium compound carry out the 5th haptoreaction, obtain the catalyst Component；
The precipitation additive includes precipitation additive a and optional precipitation additive b, the precipitation additive a are glycol shown in formula (I) Ester type compound,
In formula (I), R1-R2It is identical or different, respectively substituted or unsubstituted C1-C20It is straight chained alkyl, substituted or unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Naphthenic base, substituted or unsubstituted C6-C20It is aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C2-C10Alkylene or substitution or not Substituted C10-C20Fused ring aryl；R3-R8It is identical or different, it is respectively hydrogen, halogen, substituted or unsubstituted C1-C20Straight chain Alkyl, substituted or unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Naphthenic base, substituted or unsubstituted C6- C20Aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, substituted or unsubstituted C2- C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；Or R3-R6At least one of and R7-R8In at least One cyclization；
The precipitation additive b is general formula Ti (OR9)nX4-nShown in titanate ester compound, wherein R9For C1-C10Straight chained alkyl, C3-C10Branched alkyl or C3-C10Naphthenic base, X be halogen, 1≤n≤4, and n be integer；
One or both of them includes formula in first part's internal electron donor and the second part internal electron donor (II) cyano succinic acid ester type compound shown in,
In Formula II, R1' and R2' is identical or not identical, is each independently selected from hydrogen, C1-C14Straight chained alkyl, C3-C14Branched alkyl, C3- C10Naphthenic base, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl；R3' and R4' is identical or not identical, is each independently selected from C1-C10Straight chained alkyl, C3-C10Branched alkyl, C3-C10Naphthenic base, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aralkyl；
Precipitation additive a and the molar ratio of internal electron donor total used in the preparation method used in step 2) be (0.05-0.5):1；The molar ratio of first part's internal electron donor and the second part internal electron donor is (0.1- 10):1。
2. preparation method according to claim 1, which is characterized in that precipitation additive a used in step 2) at this The molar ratio of total internal electron donor used in preparation method is (0.1-0.4): 1.
3. preparation method according to claim 1, which is characterized in that precipitation additive a used in step 2) at this The molar ratio of total internal electron donor used in preparation method is (0.15-0.35): 1.
4. preparation method according to claim 3, which is characterized in that first part's internal electron donor and described second The molar ratio of part internal electron donor is (0.2-5): 1.
5. preparation method according to claim 3, which is characterized in that first part's internal electron donor and described second The molar ratio of part internal electron donor is more preferably (0.2-1): 1.
6. preparation method according to any one of claims 1-5, which is characterized in that the precipitation additive includes described helps The precipitation agent a and precipitation additive b, and the molar ratio of the precipitation additive a and precipitation additive b is 1:(0.01-5).
7. preparation method according to claim 6, which is characterized in that the precipitation additive a and precipitation additive b's rubs You are than being 1:(0.5-3).
8. preparation method according to claim 6, which is characterized in that the precipitation additive a and precipitation additive b's rubs You are than being 1:(0.5-1.5).
9. preparation method according to any one of claims 1-5, which is characterized in that the titanium compound is with titanium elements Meter, the magnesium halide is in terms of magnesium elements, alcohol compound, in the method used total titanium compound, in the method institute The molar ratio of total internal electron donor and magnesium halide is (2-4): (12-160): (0.01-3): 1.
10. preparation method according to claim 9, which is characterized in that alcohol compound, used total in the method The molar ratio of titanium compound, in the method used total internal electron donor and magnesium halide is (2.5-3.5): (20- 140):(0.02-0.3):1。
11. preparation method according to any one of claims 1-5, which is characterized in that magnesium halide used in step 1) with The molar ratio of total precipitation additive used in step 2) is 1:(0.025-0.9).
12. preparation method according to claim 11, which is characterized in that magnesium halide used in step 1) is made with step 2) The molar ratio of total precipitation additive is 1:(0.03-0.3).
13. preparation method according to any one of claims 1-5, which is characterized in that precipitation additive a is selected from 2- ethyl- 1,3- propylene glycol dibenzoate, 2- propyl -1,3- propylene glycol dibenzoate, -1,3 propylene glycol of 2- isopropyl -2- isopentyl Dibenzoate, 1,3 butylene glycol mesitylenic acid ester, 2- methyl-1, two m-chlorobenzoic acid ester of 3- butanediol, 2,3- diformazan Base -1,3 butylene glycol dibenzoate, two pivalate of 1,3- pentanediol, 2,4-PD dibenzoate, 2- methyl-1,3- Pentanediol benzoic ether, 2,2- dimethyl -1,3- glycol dibenzoate, 2,4- heptandiol dibenzoate, 3,5- heptan two In alcohol dibenzoate, 4- ethyl -3,5- heptandiol dibenzoate and 2- methyl -3,5- heptandiol dibenzoate at least It is a kind of；
Precipitation additive b is selected from least one of tetramethoxy titanate ester, butyl titanate, tetraethyl titanate and tetraisopropyl titanate.
14. preparation method according to any one of claims 1-5, which is characterized in that electron and in first part Electron is identical or different in two parts, is respectively selected from 2- cyano -2,3- diisopropyl dimethyl succinate, 2- cyano -2,3- Diisopropyl diethyl succinate, 2- cyano -2,3- dimethyl succinic acid diethylester, 2- cyano -2,3- diethyl succinic acid two Ethyl ester, 2- cyano -2,3- diη-propyl diethyl succinate, 2- cyano -2,3- di-n-butyl diethyl succinate, 2- cyano - Bis- n-pentyl diethyl succinate of 2,3-, 2- cyano -2,3- diisoamyl diethyl succinate, 2- cyano -2,3- di-n-hexyl Diethyl succinate, two isohesyl diethyl succinate of 2- cyano -2,3-, 2- cyano -2,3- diisopropyl succinic acid two positive third Ester, 2- cyano -2,3- diisopropyl diisopropyl ester amber acid, 2- cyano -2,3- diisopropyl succinic acid di-n-butyl, 2- cyanogen Base -2,3- diisopropyl succinic acid diisobutyl ester, 2- cyano -2,3- diisopropyl succinic acid -1- methyl esters -4- ethyl ester, 2- cyano - 2,3- diisopropyl succinic acid -1- ethyl ester -4- methyl esters, 2- cyano -2,3- diisopropyl succinic acid -1- N-butyl -4- ethyl ester, 2- Cyano -2,3- diisopropyl succinic acid -1- ethyl ester -4- N-butyl, 2- cyano -2,3- diisobutyl dimethyl succinate, 2- cyanogen Base -2,3- diisobutyl diethyl succinate, 2- cyano -2,3- diisobutyl succinic acid di-n-propyl ester, 2- cyano -2,3- two are different Butyl diisopropyl ester amber acid, 2- cyano -2,3- diisobutyl succinic acid di-n-butyl, 2- cyano -2,3- diisobutyl fourth two Sour diisobutyl ester, 2- cyano -2,3- diisobutyl succinic acid -1- methyl esters -4- ethyl ester, 2- cyano -2,3- diisobutyl succinic acid - 1- ethyl ester -4- methyl esters, 2- cyano -2,3- diisobutyl succinic acid -1- N-butyl -4- ethyl ester, 2- cyano -2,3- diisobutyl fourth Diacid -1- ethyl ester -4- N-butyl, 2- cyano -2,3- di-sec-butyl dimethyl succinate, 2- cyano -2,3- di-sec-butyl fourth two Diethyl phthalate, 2- cyano -2,3- di-sec-butyl succinic acid di-n-propyl ester, 2- cyano -2,3- di-sec-butyl diisopropyl ester amber acid, 2- cyano -2,3- di-sec-butyl succinic acid di-n-butyl, 2- cyano -2,3- di-sec-butyl succinic acid diisobutyl ester, cyano -2 2-, 3- di-sec-butyl succinic acid -1- methyl esters -4- ethyl ester, 2- cyano -2,3- di-sec-butyl succinic acid -1- ethyl ester -4- methyl esters, 2- cyanogen Base -2,3- di-sec-butyl succinic acid -1- N-butyl -4- ethyl ester, the positive fourth of 2- cyano -2,3- di-sec-butyl succinic acid -1- ethyl ester -4- Ester, 2- cyano -2,3- bicyclopentyl dimethyl succinate, 2- cyano -2,3- bicyclopentyl diethyl succinate, cyano -2 2-, 3- bicyclopentyl succinic acid di-n-propyl ester, 2- cyano -2,3- bicyclopentyl diisopropyl ester amber acid, two ring penta of 2- cyano -2,3- Base succinic acid di-n-butyl, 2- cyano -2,3- bicyclopentyl succinic acid diisobutyl ester, 2- cyano -2,3- bicyclopentyl succinic acid - 1- methyl esters -4- ethyl ester, 2- cyano -2,3- bicyclopentyl succinic acid -1- ethyl ester -4- methyl esters, 2- cyano -2,3- bicyclopentyl fourth two Acid -1- N-butyl -4- ethyl ester, 2- cyano -2,3- bicyclopentyl succinic acid -1- ethyl ester -4- N-butyl, two ring of 2- cyano -2,3- Hexyl dimethyl succinate, 2- cyano -2,3- dicyclohexyl-succinate, 2- cyano -2,3- dicyclohexyl succinic acid two N-propyl, 2- cyano -2,3- dicyclohexyl diisopropyl ester amber acid, 2- cyano -2,3- dicyclohexyl succinic acid di-n-butyl, 2- Cyano -2,3- dicyclohexyl succinic acid diisobutyl ester, 2- cyano -2,3- dicyclohexyl succinic acid -1- methyl esters -4- ethyl ester, 2- cyanogen Base -2,3- dicyclohexyl succinic acid -1- ethyl ester -4- methyl esters, 2- cyano -2,3- dicyclohexyl succinic acid -1- N-butyl -4- second Ester, 2- cyano -2,3- dicyclohexyl succinic acid -1- ethyl ester -4- N-butyl, 2- cyano -2- methyl -3- ethyl succinic acid diethyl Ester, 2- cyano -2- methyl -3- n-propyl diethyl succinate, 2- cyano -2- methyl -3- isopropyl diethyl succinate, 2- cyanogen Base -2- methyl -3- normal-butyl diethyl succinate, 2- cyano -2- methyl -3- isobutyl group diethyl succinate, 2- cyano -2- first Base -3- n-pentyl diethyl succinate, 2- cyano -2- methyl -3- isopentyl diethyl succinate, 2- cyano -2- methyl -3- ring Amyl diethyl succinate, 2- cyano -2- methyl -3- n-hexyl diethyl succinate, 2- cyano -2- methyl -3- isohesyl fourth Diethyl adipate, 2- cyano -2- ethyl -3- diethyl methylsuccinate, 2- cyano -2- ethyl -3- n-propyl succinic acid diethyl Ester, 2- cyano -2- ethyl -3- isopropyl diethyl succinate, 2- cyano -2- ethyl -3- normal-butyl diethyl succinate, 2- cyanogen Base -2- ethyl -3- isobutyl group diethyl succinate, 2- cyano -2- ethyl -3- n-pentyl diethyl succinate, 2- cyano -2- second Base -3- isopentyl diethyl succinate, 2- cyano -2- ethyl -3- cyclopenta diethyl succinate, 2- cyano -2- ethyl -3- are just Hexyl diethyl succinate, 2- cyano -2- ethyl -3- isohesyl diethyl succinate, 2- cyano -2- n-propyl -3- methyl fourth Diethyl adipate, 2- cyano -2- n-propyl -3- ethyl succinic acid diethylester, 2- cyano -2- n-propyl -3- isopropyl succinic acid Diethylester, 2- cyano -2- n-propyl -3- normal-butyl diethyl succinate, 2- cyano -2- n-propyl -3- isobutyl group succinic acid two Ethyl ester, 2- cyano -2- n-propyl -3- n-pentyl diethyl succinate, 2- cyano -2- n-propyl -3- isopentyl succinic acid diethyl Ester, 2- cyano -2- n-propyl -3- cyclopenta diethyl succinate, 2- cyano -2- n-propyl -3- n-hexyl diethyl succinate, 2- cyano -2- n-propyl -3- isohesyl diethyl succinate, 2- cyano -2- isopropyl -3- diethyl methylsuccinate, 2- cyanogen Base -2- isopropyl -3- ethyl succinic acid diethylester, 2- cyano -2- isopropyl -3- n-propyl diethyl succinate, 2- cyano -2- Isopropyl -3- normal-butyl diethyl succinate, 2- cyano -2- isopropyl -3- isobutyl group diethyl succinate, 2- cyano -2- are different Propyl -3- n-pentyl diethyl succinate, 2- cyano -2- isopropyl -3- isopentyl diethyl succinate, 2- cyano -2- isopropyl Base -3- cyclopenta diethyl succinate, 2- cyano -2- isopropyl -3- n-hexyl diethyl succinate, 2- cyano -2- isopropyl - 3- isohesyl diethyl succinate, 2- cyano -2- normal-butyl -3- diethyl methylsuccinate, 2- cyano -2- normal-butyl -3- second Base diethyl succinate, 2- cyano -2- normal-butyl -3- n-propyl diethyl succinate, 2- cyano -2- normal-butyl -3- isopropyl Diethyl succinate, 2- cyano -2- normal-butyl -3- isobutyl group diethyl succinate, 2- cyano -2- normal-butyl -3- n-pentyl fourth Diethyl adipate, 2- cyano -2- normal-butyl -3- isopentyl diethyl succinate, 2- cyano -2- normal-butyl -3- cyclopenta fourth two Diethyl phthalate, 2- cyano -2- normal-butyl -3- n-hexyl diethyl succinate, 2- cyano -2- normal-butyl -3- isohesyl succinic acid Diethylester, 2- cyano -2- isobutyl group -3- diethyl methylsuccinate, 2- cyano -2- isobutyl group -3- ethyl succinic acid diethylester, 2- cyano -2- isobutyl group -3- n-propyl diethyl succinate, 2- cyano -2- isobutyl group -3- isopropyl diethyl succinate, 2- Cyano -2- isobutyl group -3- normal-butyl diethyl succinate, 2- cyano -2- isobutyl group -3- n-pentyl diethyl succinate, 2- cyanogen Base -2- isobutyl group -3- isopentyl diethyl succinate, 2- cyano -2- isobutyl group -3- cyclopenta diethyl succinate, 2- cyano - 2- isobutyl group -3- n-hexyl diethyl succinate, 2- cyano -2- isobutyl group -3- isohesyl diethyl succinate, 2- cyano -2- N-pentyl -3- diethyl methylsuccinate, 2- cyano -2- n-pentyl -3- ethyl succinic acid diethylester, 2- cyano -2- n-pentyl - 3- n-propyl diethyl succinate, 2- cyano -2- n-pentyl -3- isopropyl diethyl succinate, 2- cyano -2- n-pentyl -3- Normal-butyl diethyl succinate, 2- cyano -2- n-pentyl -3- isobutyl group diethyl succinate, 2- cyano -2- n-pentyl -3- are different Amyl diethyl succinate, 2- cyano -2- n-pentyl -3- cyclopenta diethyl succinate, 2- cyano -2- n-pentyl -3- just oneself Base diethyl succinate, 2- cyano -2- n-pentyl -3- isohesyl diethyl succinate, 2- cyano -2- isopentyl -3- methyl fourth Diethyl adipate, 2- cyano -2- isopentyl -3- ethyl succinic acid diethylester, 2- cyano -2- isopentyl -3- n-propyl succinic acid Diethylester, 2- cyano -2- isopentyl -3- isopropyl diethyl succinate, 2- cyano -2- isopentyl -3- normal-butyl succinic acid two Ethyl ester, 2- cyano -2- isopentyl -3- isobutyl group diethyl succinate, 2- cyano -2- isopentyl -3- n-pentyl succinic acid diethyl Ester, 2- cyano -2- isopentyl -3- cyclopenta diethyl succinate, 2- cyano -2- isopentyl -3- n-hexyl diethyl succinate, 2- cyano -2- isopentyl -3- isohesyl diethyl succinate, 2- cyano -2- cyclopenta -3- diethyl methylsuccinate, 2- cyanogen Base -2- cyclopenta -3- ethyl succinic acid diethylester, 2- cyano -2- cyclopenta -3- n-propyl diethyl succinate, 2- cyano -2- Cyclopenta -3- isopropyl diethyl succinate, 2- cyano -2- cyclopenta -3- normal-butyl diethyl succinate, 2- cyano -2- ring Amyl -3- isobutyl group diethyl succinate, 2- cyano -2- cyclopenta -3- n-pentyl diethyl succinate, 2- cyano -2- ring penta Base -3- isopentyl diethyl succinate, 2- cyano -2- cyclopenta -3- n-hexyl diethyl succinate, 2- cyano -2- cyclopenta - 3- isohesyl diethyl succinate, 2- cyano -2- n-hexyl -3- diethyl methylsuccinate, 2- cyano -2- n-hexyl -3- second Base diethyl succinate, 2- cyano -2- n-hexyl -3- n-propyl diethyl succinate, 2- cyano -2- n-hexyl -3- isopropyl Diethyl succinate, 2- cyano -2- n-hexyl -3- normal-butyl diethyl succinate, 2- cyano -2- n-hexyl -3- isobutyl group fourth Diethyl adipate, 2- cyano -2- n-hexyl -3- n-pentyl diethyl succinate, 2- cyano -2- n-hexyl -3- isopentyl fourth two Diethyl phthalate, 2- cyano -2- n-hexyl -3- cyclopenta diethyl succinate, 2- cyano -2- n-hexyl -3- isohesyl succinic acid Diethylester, 2- cyano -2- isohesyl -3- diethyl methylsuccinate, 2- cyano -2- isohesyl -3- ethyl succinic acid diethylester, 2- cyano -2- isohesyl -3- n-propyl diethyl succinate, 2- cyano -2- isohesyl -3- isopropyl diethyl succinate, 2- Cyano -2- isohesyl -3- normal-butyl diethyl succinate, 2- cyano -2- isohesyl -3- isobutyl group diethyl succinate, 2- cyanogen Base -2- isohesyl -3- n-pentyl diethyl succinate, 2- cyano -2- isohesyl -3- isopentyl diethyl succinate, 2- cyano - At least one in 2- isohesyl -3- cyclopenta diethyl succinate and 2- cyano -2- isohesyl -3- n-hexyl diethyl succinate Kind.
15. the catalytic component for olefinic polymerization that preparation method according to any one of claims 1-5 obtains, It is characterized in that, based on the total weight of the catalytic component, the titanium containing 1-3.5 weight %, the precipitation additive of 1-3.5 weight % The internal electron donor of a, 6-15 weight %, and the molar ratio of precipitation additive a and internal electron donor is 0.05:1 to less than 0.5:1.
16. the catalytic component for olefinic polymerization that preparation method according to claim 15 obtains, which is characterized in that Titanium containing 1.8-3.2 weight %, the internal electron donor of precipitation additive a, the 7-11 weight % of 1.5-3 weight %, and help precipitation The molar ratio of agent a and internal electron donor is 0.1-0.3:1.
17. a kind of catalyst system for olefinic polymerization, comprising:
A catalysis described in the catalytic component or claim 16 that) preparation method described in any one of claim 1-15 obtains Agent component；
B) alkyl aluminum compound；And
C) optional external donor compound.
18. a kind of olefine polymerizing process, this method comprises: wanting one or more alkene with right under olefin polymerization conditions The contact of catalyst system described in asking 17, at least one of described alkene are by general formula CH2The alkene that=CHR is indicated, wherein R It is hydrogen or C1-C6Alkyl.
CN201510707980.3A 2015-10-27 2015-10-27 Catalytic component and its preparation method and application for olefinic polymerization Active CN106608933B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510707980.3A CN106608933B (en) 2015-10-27 2015-10-27 Catalytic component and its preparation method and application for olefinic polymerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510707980.3A CN106608933B (en) 2015-10-27 2015-10-27 Catalytic component and its preparation method and application for olefinic polymerization

Publications (2)

Publication Number Publication Date
CN106608933A CN106608933A (en) 2017-05-03
CN106608933B true CN106608933B (en) 2019-03-26

Family

ID=58614701

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510707980.3A Active CN106608933B (en) 2015-10-27 2015-10-27 Catalytic component and its preparation method and application for olefinic polymerization

Country Status (1)

Country Link
CN (1) CN106608933B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109111535B (en) * 2017-06-23 2021-03-16 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
CN109111538B (en) * 2017-06-23 2021-02-05 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
CN110511301B (en) * 2018-05-21 2020-10-20 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
CN110511302B (en) * 2018-05-21 2020-10-23 中国石油化工股份有限公司 Catalyst component for olefin polymerization and catalyst thereof
EP3798241A4 (en) * 2018-05-21 2022-06-22 China Petroleum & Chemical Corporation Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558285A (en) * 2013-10-24 2015-04-29 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization and catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558285A (en) * 2013-10-24 2015-04-29 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization and catalyst

Also Published As

Publication number Publication date
CN106608933A (en) 2017-05-03

Similar Documents

Publication Publication Date Title
CN106608933B (en) Catalytic component and its preparation method and application for olefinic polymerization
CN103012625B (en) Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method
CN103788259B (en) A kind of molecular weight narrow ditribution polypropylene
CN106317275B (en) Prepare catalytic component of fiber polyolefin and its preparation method and application and catalyst system and application and olefine polymerizing process
CN103012627B (en) Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method
CN104558285B (en) Solid catalyst component for olefin polymerization and catalyst
CN109111539A (en) Catalytic component and its catalyst for olefinic polymerization
CN107629156A (en) Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application
CN106608937B (en) Catalytic component and its preparation method and application for olefinic polymerization
CN103012626B (en) For catalyst component and preparation method thereof and the catalyst system of olefinic polymerization and application and olefine polymerizing process
CN104558286B (en) A kind of catalyst component for olefin and catalyst
CN104558287B (en) Catalyst component for olefin and catalyst
CN110511301A (en) A kind of catalytic component and its catalyst for olefinic polymerization
CN104558288B (en) A kind of olefin polymer and preparation method thereof
CN104558312B (en) The preparation method and its polymer of a kind of olefin polymer
CN107629154A (en) Catalyst for olefinic polymerization and its preparation method and application
CN106317274B (en) Prepare catalytic component of fiber polyolefin and its preparation method and application and catalyst system and application and olefine polymerizing process
CN105777953B (en) The main catalyst component and preparation method of propylene polymerization
CN103012631B (en) Preparation method of propylene polymer
CN107344973A (en) Catalytic component, catalyst system and its application for olefinic polymerization
CN107344978A (en) Catalytic component, catalyst system and its application for olefinic polymerization
CN103788258B (en) A kind of polymerization of propylene
CN104558289B (en) Olefin polymerization catalysis and its application and polypropylene and its polymerization
CN110511302A (en) A kind of catalytic component and its catalyst for olefinic polymerization
CN110511303A (en) A kind of catalytic component and its catalyst for olefinic polymerization

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant