CN112175117A - Solid catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization and olefin polymerization method - Google Patents
Solid catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization and olefin polymerization method Download PDFInfo
- Publication number
- CN112175117A CN112175117A CN201910591081.XA CN201910591081A CN112175117A CN 112175117 A CN112175117 A CN 112175117A CN 201910591081 A CN201910591081 A CN 201910591081A CN 112175117 A CN112175117 A CN 112175117A
- Authority
- CN
- China
- Prior art keywords
- dimethoxypropane
- dibenzoate
- methyl
- ethyl
- pentanediol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the field of catalysts for olefin polymerization, and discloses a solid catalyst component for olefin polymerization, a preparation method thereof, a catalyst for olefin polymerization and a method for olefin polymerization. The solid catalyst component comprises, based on the total weight of the solid catalyst component, from 0.1 to 89% by weight of polyethylene, from 0.1 to 89% by weight of polyalphaolefin, from 0.1 to 3.5% by weight of titanium, from 1 to 16% by weight of magnesium, from 2 to 50% by weight of chlorine and from 0.6 to 15% by weight of a lewis base; the catalyst component has the advantages of good regularity and less broken particles, and the content of fine powder of an olefin polymer obtained by catalyzing the olefin catalyst containing the solid catalyst component is lower.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, in particular to a solid catalyst component for olefin polymerization and a preparation method thereof, and a catalyst for olefin polymerization and a method for olefin polymerization.
Background
The Ziegler-Natta type spherical catalyst is widely applied to a loop polypropylene process device, is used for producing propylene homopolymers and propylene/ethylene (or butylene) random copolymers, and has the characteristics of high polymerization activity, high stereospecificity, high polymer particle shape regularity and the like. The spherical catalyst is also applied to gas-phase polypropylene and polyethylene processes with prepolymerization operation units, such as SHPERIZONE and SHPERILENE process units, and is used for the production of polypropylene and polyethylene. Despite the fact that these process units have a prepolymerization unit, there is still a phenomenon of catalyst particles and polymer particle breakage during the production of the resin, resulting in a certain amount of fines content in the polymer, especially in the production of propylene homopolymers having a high melt flow index (MFR), which is high, and which affects the stability and long-term operation of the plant. The use of spherical catalysts of the Ziegler-Natta type is not suitable for polypropylene plants without prepolymerization unit, such as the UNIPOL process plant, because the catalyst or polymer particles are almost completely broken during the polymerization process, resulting in a large amount of fines.
US9453088B2 discloses a prepolymerized catalyst for olefin polymerization, which is a catalyst component containing two electron donors, 1, 3-diether and aromatic ester, having an average particle size of less than 30 μm and a prepolymerization multiple of less than 50g polymer/g catalyst, and is prepared by first preparing a spherical catalyst containing two electron donors, 1, 3-diether and aromatic ester, and then prepolymerizing with an olefin having 2-10 carbon atoms to obtain the prepolymerized catalyst. CN1421468A discloses a propylene polymerization or copolymerization method, which comprises the prepolymerization of a Ziegler-Natta type catalyst with ethylene or an α -olefin at-10 ℃ to 80 ℃, followed by propylene polymerization. US7329714B2 discloses a process comprising prepolymerising a Ziegler-ztta type catalyst with propylene or 4-methyl-1-pentene at 0-40 ℃ followed by propylene polymerisation.
However, in the above method for preparing a prepolymerized catalyst, when ethylene is used as a prepolymerized monomer to prepare a prepolymerized catalyst, the catalyst is inevitably broken, and the content of polymer fine powder is high when an olefin polymerization reaction is carried out; the pre-polymerized catalyst prepared by taking propylene or other alpha-olefin as a pre-polymerized monomer also has a certain crushing phenomenon, and the activity of the catalyst is quickly attenuated along with the prolonging of the storage time, so that the commercial value is low.
Disclosure of Invention
The invention aims to overcome the problems that the prior Ziegler-Zatta type prepolymerization catalyst has a crushing phenomenon in the preparation process and the content of polymer fine powder is high when the prepolymerization catalyst is applied to olefin polymerization, and provides a solid catalyst component for olefin polymerization, a preparation method thereof, a catalyst for olefin polymerization and a method for olefin polymerization. The solid catalyst component has the advantages of high regularity and less broken particles, and the content of fine powder of an olefin polymer obtained by catalyzing the olefin catalyst containing the catalyst component is lower.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization comprising 0.1 to 89% by weight of polyethylene, 0.1 to 89% by weight of polyalphaolefin, 0.1 to 3.5% by weight of titanium, 1 to 16% by weight of magnesium, 2 to 50% by weight of chlorine and 0.6 to 15% by weight of a lewis base, based on the total weight of the solid catalyst component.
According to a second aspect of the present invention, there is provided a process for preparing a solid catalyst component for olefin polymerization, the process comprising the steps of:
(1) in the presence of an inert solvent, carrying out contact reaction on the catalyst component A, alkyl aluminum and an external electron donor compound; the catalyst component A contains titanium, magnesium, chlorine and a Lewis base;
(2) adding alpha-olefin into the reaction system obtained in the step (1) to carry out a first polymerization reaction;
(3) adding ethylene into the reaction system obtained in the step (2) to carry out a second polymerization reaction;
the mass ratio of the alpha-olefin to the ethylene to the amount of the catalyst component A is 0.04-10: 0.04-10: 1.
according to a third aspect of the present invention, there is provided a solid catalyst component produced by the production method according to the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a catalyst for olefin polymerization, which is prepared by reacting the solid catalyst component according to the first or third aspect of the present invention with an aluminum alkyl and optionally an external electron donor compound.
According to a fifth aspect of the present invention, there is provided a process for the polymerisation of olefins, the process comprising: at least one olefin is polymerized in the presence of the catalyst for olefin polymerization.
The solid catalyst component provided by the invention has the advantages of good regularity and less broken particles. The solid catalyst component is suitable not only for an olefin polymerization plant having a prepolymerization operation unit but also for a polyolefin plant having no prepolymerization operation unit. In addition, the olefin polymer obtained by using the solid catalyst component for catalyzing olefin polymerization has better regularity and lower fine powder content in the polymer.
Drawings
FIG. 1 is a photograph of particles of a solid catalyst component prepared in example 1 of the present invention;
fig. 2 is a photograph of particles of the solid catalyst component prepared in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization comprising 0.1 to 89% by weight of polyethylene, 0.1 to 89% by weight of polyalphaolefin, 0.1 to 3.5% by weight of titanium, 1 to 16% by weight of magnesium, 2 to 50% by weight of chlorine and 0.6 to 15% by weight of a lewis base, based on the total weight of the solid catalyst component.
The solid catalyst component of the present invention is a spherical solid particle. Preferably, the solid catalyst component has an average particle size (D50) of 20 to 80 μm. In the present invention, the average particle size (D50) was measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).
In the solid catalyst component of the present invention, the polyalphaolefin is preferably selected from one or more of polypropylene, polybutene, polyoctene and polyisoprene. More preferably, the polyalphaolefin is polypropylene.
In the solid catalyst component of the present invention, the lewis base may be selected from internal electron donors in existing olefin polymerization catalysts. For example, the lewis base may be at least one selected from the group consisting of carboxylic acid esters, glycol ester compounds represented by formula (1), and 1, 3-diether compounds represented by formula (2):
in the formula (1), R1-R6Each independently selected from hydrogen and C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl of (2), R1-R6Two or more of which are optionally bonded to each other to form one or more fused ring structures;
R7and R8Each independently selected from C1-C10Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Wherein hydrogen on the phenyl ring in the aryl, alkaryl and aralkyl groups may be optionally substituted with a halogen atom;
in the formula (2), R9And R10Each independently selected from hydrogen and C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, R11And R12Each independently selected from C1-C10Alkyl group of (1).
In the solid catalyst component of the present invention, the glycol ester compound is preferably selected from the group consisting of 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol diacetate, 1, 3-diisopropyl-1, 3-propanol bis (4-butylbenzoate), 1-phenyl-2-amino-1, 3-propanediol dibenzoate, 1-phenyl-2-methyl-1, 3-butanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (p-methylbenzoate), 2, 4-pentanediol di (p-tert-butylbenzoate), 2, 4-pentanediol di (p-butylbenzoate), 2-methyl-1, 3-pentanediol di (p-methylbenzoate), 2-butyl-1, 3-pentanediol di (p-methylbenzoate), 2-methyl-1, 3-pentanediol di (p-tert-butylbenzoate), 2-methyl-1, 3-pentanediol pivalate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-pentanediol di (p-t-butylbenzoate), 2-methyl-1, 3-pentanediol dibenzoate, 2, 4-pentanediol di (p-butylbenzo, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-4-ethyl-3, at least one of 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, and 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate.
In the solid catalyst component of the present invention, the 1, 3-diether compound is preferably selected from the group consisting of 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2-tert-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-methyl-2-, 2, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
In the solid catalyst component of the present invention, the carboxylic acid ester is an aliphatic carboxylic acid ester and/or an aromatic carboxylic acid ester, and specifically is at least one selected from a monovalent aliphatic carboxylic acid ester, a divalent aliphatic carboxylic acid ester, a monovalent aromatic carboxylic acid ester, and a divalent aromatic carboxylic acid ester. Wherein, the aliphatic carboxylic acid ester is carboxylic acid ester prepared by mono (or di) aliphatic carboxylic acid and aliphatic monohydric alcohol or aromatic monohydric alcohol, and the aromatic carboxylic acid ester is carboxylic acid ester prepared by mono (or di) aromatic carboxylic acid and aliphatic monohydric alcohol or aromatic monohydric alcohol. Preferably, the carboxylic acid ester is selected from one or more of benzoate compounds, phthalate compounds and succinate compounds.
The benzoate compound may be selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate, for example.
The phthalate-based compound may be selected from, for example, one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
The succinate-based compound may be selected from one or more of diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate and diethyl 2-ethyl-2-methylsuccinate, for example.
In the present invention, the solid catalyst component containing magnesium, titanium and chlorine respectively means containing magnesium element, titanium element and chlorine element.
The titanium content was determined by colorimetry. Specifically, 0.2-0.5g of sample is taken and 50mL of 2N H is used2SO4Dissolving, filtering the upper-layer floating matter, taking clear liquid, and carrying out color comparison; with 2N H2SO4The solution was blanked and the absorbance E1 was measured at a wavelength of 410 μm in a cuvette of 1cm thicknessDropping 1 drop of 30% H2O2Shaking up, measuring the absorbance E2, and calculating the titanium content Ti (%):
Ti(％)＝[(E2-E1)×100)/(K·L·W·100)]×100
in the formula: w-weight of sample (g); l-cuvette thickness (cm); k-specific extinction coefficient; e1 — blank absorbance; e2-sample absorbance.
The magnesium content was determined according to EDTA titration. Specifically, 0.2-0.5g of sample is taken and added into 20-30mL of 2N H in a 250mL conical flask2SO4The solution was dissolved, 20mL of triethanolamine (1+2) standard solution was added, the pH was adjusted to 10 with 20% NaOH solution, the mixture was shaken, 10mL of 10 pH buffer solution was added, and 6 drops of 30% H were added2O2And 30-50mL of distilled water, adding a small amount of chrome black T indicator, shaking up, titrating with 0.02N EDTA solution until the purple color changes to blue (purple light disappears), and calculating the magnesium content Mg (%):
Mg(％)＝[(VE·NE×24.31)/(G·1000)]×100
in the formula: g-sample mass (G); VE-amount of EDTA consumed (mL); NE-EDTA solution equivalent number; 24.31-atomic weight of magnesium.
The chlorine content was determined by silver nitrate titration. Specifically, 0.04-0.1g of sample is weighed into an erlenmeyer flask, and 20mL of 2N H is added2SO4Standing the solution for 30 minutes; washing with distilled water for several times, and adding 20-30mL of 0.1N AgNO dropwise3Adding 1:1HNO into the solution33mL of solution in 0.1N NH4CNS standard solution titration of excess AgNO3The solution, titrated to brick red without disappearing for two seconds, was calculated for the chlorine content Cl (%):
Cl(％)＝[(V1-V2×D)×N1×35.45/(G·1000)]×100
in the formula: v1—AgNO3Amount of solution (mL); v2-NH consumed4Amount of CNS solution (mL);
D—AgNO3/NH4volume ratio of CNS solution; n is a radical of1—AgNO3Equivalent concentration of (d); g-mass of sample (G); 35.45 atoms of chlorineAmount of the compound (A).
The method for testing the contents of polyethylene and poly-alpha-olefin in the solid catalyst component comprises the following steps: weighing a certain amount (M1) of sample, dissolving the sample with ethanol and dilute hydrochloric acid, drying insoluble substances at 80 ℃ in vacuum to obtain a solid (M2), taking 0.2g of the solid, tabletting, measuring the polyethylene content (C1) and the poly-alpha-olefin content (C2) of the solid by an infrared spectrometer, and respectively calculating the mass percentages of the polyethylene and the poly-alpha-olefin in the solid catalyst component according to the following formulas:
CA＝M2×C1/M1
CB＝M2×C2/M1
wherein, CAAnd CBRespectively, the mass percentages of polyethylene and polyalphaolefin in the solid catalyst component, M1 and M2 respectively, the mass (g) of the sample and the dry solid, and C1 and C2 respectively, the mass percentages of polyethylene and polyalphaolefin in the dry solid.
The method for testing the content of the Lewis base in the solid catalyst component comprises the following steps: the sample was dissolved with ethyl acetate and a hydrochloric acid solution (concentration 2mol/L) and extracted to obtain a Lewis base, and the content thereof was analyzed using a conventional liquid chromatograph.
In the solid catalyst component of the present invention, it is preferable that the content of the polyethylene is 1 to 50% by weight, the content of the polyalphaolefin is 1 to 50% by weight, the content of titanium is 0.5 to 2% by weight, the content of magnesium is 1 to 16% by weight, the content of chlorine is 2 to 35% by weight, and the content of the lewis base is 1 to 10% by weight, based on the total weight of the solid catalyst component.
Preferably, the mass ratio of the polyalphaolefin to the polyethylene is from 0.1 to 10: 1.
in the solid catalyst component of the present invention, the solid catalyst component further contains an aluminum alkyl and an external electron donor. The types and the contents of the aluminum alkyl and the external electron donor can be selected according to the existing olefin prepolymerization catalyst.
According to a second aspect of the present invention, there is provided a process for preparing a solid catalyst component for olefin polymerization, comprising:
(1) in the presence of an inert solvent, carrying out contact reaction on the catalyst component A, alkyl aluminum and an external electron donor compound; the catalyst component A contains titanium, magnesium, chlorine and a Lewis base;
(2) adding alpha-olefin into the reaction system obtained in the step (1) to carry out a first polymerization reaction;
(3) and (3) adding ethylene into the reaction system obtained in the step (2) to carry out a second polymerization reaction.
In the preparation method of the present invention, in the step (1), the conditions of the contact reaction include: the temperature may be from 0 to 30 ℃, preferably from 15 to 25 ℃; the time can be 5-30min, preferably 10-20 min.
In the step (1), the alkyl aluminum and the external electron donor compound may be selected with reference to an existing olefin prepolymerization catalyst, and the present invention is not particularly limited thereto. The alkyl aluminium may be selected from one or more of triethyl aluminium, triisobutyl aluminium, tri-n-butyl aluminium, tri-n-hexyl aluminium and diethyl aluminium monochloride. The external electron donor compound may be selected from one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, and dicyclopentyldimethoxysilane. Generally, the molar ratio of the aluminum alkyl, the external electron donor compound and the amount of the catalyst component a used, calculated as titanium element, may be from 1 to 50: 0.2-10: 1.
in the production method of the present invention, the lewis base may be at least one of a carboxylic acid ester, a diol ester compound represented by formula (1), and a1, 3-diether compound represented by formula (2):
in the formula (1), R1-R6Each independently selected from hydrogen and C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl of (2), R1-R6Two or more of which are optionally bonded to each other to form one or more fused ring structures;
R7and R8Each independently selected from C1-C10Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Wherein hydrogen on the phenyl ring in the aryl, alkaryl and aralkyl groups may be optionally substituted with a halogen atom;
in the formula (2), R9And R10Each independently selected from hydrogen and C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, R11And R12Each independently selected from C1-C10Alkyl group of (1).
In the preparation method of the present invention, the specific descriptions of the glycol ester compound, the carboxylate and the 1, 3-diether compound are as described in the first aspect of the present invention, and are not repeated herein.
In the preparation method of the present invention, the catalyst component a can be prepared according to the conventional method of main catalyst in olefin polymerization catalyst in the art, and the present invention is not particularly limited thereto, and for example, it can be prepared by the method disclosed in patent ZL03153152.0 and ZL 200410062291.3.
According to a preferred embodiment, said catalyst component a is the reaction product of titanium tetrachloride, a spherical magnesium chloride alcoholate and said lewis base; the general formula of the spherical magnesium chloride alcoholate is Mg (R' OH)n(H2O)mWherein R' is methyl, ethyl, n-propyl or isopropyl, n is 1.5-3.5, and m is 0-0.1. The catalyst component A is prepared by a method comprising the following steps:
1) reacting titanium tetrachloride with the spherical magnesium chloride alcoholate at-20 ℃ to 0 ℃ for 20-120min to obtain a mixture I;
2) heating the mixture I to 100-120 ℃, adding the Lewis base in the heating process, and reacting at the temperature of 100-120 ℃ for 20-200min to obtain a solid product II;
3) the solid product II was washed with titanium tetrachloride and hexane, respectively, and then dried under vacuum.
In the preparation method of the present invention, the inert solvent may be selected with reference to the prior art. Generally, the inert solvent may be selected from one or more of hexane, heptane and decane. The inert solvent is added in an amount such that the mass concentration of the catalyst component A in the inert solvent can be 5 to 50 g/L.
In the preparation method of the present invention, in the step (2), the conditions of the first polymerization reaction include: the temperature may be from 0 to 30 ℃, preferably from 15 to 25 ℃; the time can be 5-30min, preferably 10-20 min.
Preferably, step (2) further comprises removing unreacted α -olefin gas after the first polymerization reaction is completed.
In the preparation method of the present invention, in the step (3), the conditions of the second polymerization reaction include: the temperature may be from 0 to 30 ℃, preferably from 15 to 25 ℃; the time can be 5-30min, preferably 10-20 min.
Preferably, after the second polymerization reaction is finished, step (3) further comprises a post-treatment step, which generally comprises: removing unreacted ethylene gas, filtering to remove liquid or optionally washing with hexane for 1-2 times to obtain solid product; then the solid product is dried under vacuum at 10-80 ℃ to obtain the solid catalyst component.
In the production method of the present invention, the α -olefin is preferably one or more selected from the group consisting of propylene, butene, octene and isopentene, and more preferably the α -olefin is propylene.
In the preparation method of the invention, the mass ratio of the alpha-olefin to the ethylene to the amount of the catalyst component A is 0.04-10: 0.04-10: 1.
according to a third aspect of the present invention there is provided a solid catalyst component obtainable by the process according to the second aspect of the present invention. The method of the invention prepares the Ziegler-Zatta type prepolymerization catalyst (namely a solid catalyst component) with good regularity and less broken particles by respectively carrying out polymerization reaction on alpha-olefin and ethylene in sequence. According to one embodiment, the solid catalyst component obtained by the production method of the present invention is the solid catalyst component according to the first aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a catalyst for olefin polymerization, which is prepared by reacting the solid catalyst component of the present invention with an aluminum alkyl and optionally an external electron donor compound.
The aluminum alkyl, the external electron donor compound and the respective contents of the aluminum alkyl and the external electron donor compound according to the fourth aspect of the present invention can be selected according to the prior art. Generally, the alkyl aluminum may be selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and diethylaluminum monochloride. The ratio of the molar amount of the aluminum alkyl calculated as the aluminum element to the molar amount of the solid catalyst component calculated as the titanium element may be 1 to 1000: 1. the external electron donor compound may be at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and t-hexyltrimethoxysilane. Preferably, the ratio of the molar amount of the aluminum alkyl calculated as the aluminum element to the molar amount of the external electron donor compound calculated as the silicon element is 2 to 1000: 1.
according to a fifth aspect of the present invention, there is provided a process for the polymerisation of olefins, the process comprising: at least one olefin is polymerized in the presence of the catalyst for olefin polymerization according to the fourth aspect of the present invention. The conditions for the polymerization reaction may be conventionally selected in the art, and for example, the reaction temperature is 0 to 150 ℃, preferably the reaction temperature is 60 to 90 ℃, and the reaction pressure is atmospheric pressure or higher.
In the process of the present invention, the olefin has the general formula CH2R is hydrogen or C1-C6Alkyl or aryl of (a). Preferably, the olefin is selected from one or more of ethylene, propylene, butene, pentene and hexene.
The advantages of the technical solution of the present invention will be described in detail by specific embodiments below.
In the following examples and comparative examples,
the isotactic index of the polymer (polypropylene) refers to the mass percent of polypropylene which is insoluble in boiling n-heptane under specified conditions, and is measured by adopting a heptane extraction method (boiling extraction for 6 hours by heptane), namely 2g of a dried polymer sample is placed in an extractor and is extracted for 6 hours by boiling heptane, then the residue is dried to constant weight, and the ratio of the mass (g) of the obtained polymer to 2 is the isotactic index.
The polymer melt index is determined according to the method of ASTM D1238-99.
The particle size distribution of the polymer is calculated as the mass percent of the fraction by standard sieve screening.
The following examples are provided to illustrate the solid catalyst component of the present invention and the process for its preparation and the process for the polymerization of olefins.
Example 1
(1) Preparation of catalyst component A
Adding 1.2L titanium tetrachloride into a 3L glass reaction bottle with stirring, cooling to-20 deg.C, adding 100g magnesium chloride alcohol complex spherical carrier [ Mg (C)2H5OH)2.6](average particle size D50 ═ 45 μm), after reaction at-20 ℃ for 0.5 hour, slowly raising the temperature to 120 ℃, adding 15g of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane during the temperature raising, then reacting at 120 ℃ for 0.5 hour, filtering off the liquid, adding 1L of titanium tetrachloride, filtering off the liquid after maintaining at 120 ℃ for 2 hours to give a solid product, washing the solid product with hexane 5 times, and finally drying under vacuum to give catalyst component a1 (average particle size D50 ═ 40 μm).
(2) Preparation of solid catalyst component
In a 5L autoclave, 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 10.9g of catalyst component A1 were charged and reacted at 22 ℃ for 10 minutes; then 6g of propylene was added, the reaction was carried out at 23 ℃ for 10 minutes, and unreacted propylene was vented; the autoclave was purged with nitrogen, 3g of ethylene was charged, reacted at 15 ℃ for 10 minutes, and unreacted ethylene was vented. After the liquid in the reaction product was filtered off, it was dried under vacuum to obtain a solid catalyst component E-1 (average particle size D50 ═ 43 μm). The main component content of E-1 is shown in Table 1, and the particle morphology is shown in FIG. 1.
(3) Polymerization of propylene
In a 5L autoclave, 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 15mg of solid catalyst component E-1 were charged, and after introducing 1.5NL of hydrogen, 2.0kg of liquid propylene was added; raising the temperature to 70 ℃ under stirring and carrying out polymerization reaction at 70 ℃ for 1 hour; the stirring was stopped, and the unpolymerized propylene monomer was removed to obtain polypropylene P-1. The properties of the polypropylene P-1 are shown in Table 2.
Example 2
(1) Preparation of catalyst component A
Prepared according to the procedure of example 1 except that diisobutylphthalate was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, catalyst component a2 (average particle size D50 ═ 40 μm) was prepared.
(2) Preparation of solid catalyst component
Prepared according to the procedure of example 1 except that the catalyst component a1 was replaced with the catalyst component a2 to obtain a solid catalyst component E-2 (average particle size D50 ═ 43 μm). The main component contents of E-2 are shown in Table 1.
(3) Polymerization of propylene
Polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-2 from E-1 to obtain polypropylene P-2. The properties of the polypropylene P-2 are shown in Table 2.
Example 3
(1) Preparation of catalyst component A
Prepared according to the procedure of example 1 except that 2, 4-pentanediol dibenzoate was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, catalyst component a3 (average particle size D50 ═ 40 μm) was prepared.
(2) Preparation of solid catalyst component
Prepared according to the procedure of example 1 except that the catalyst component a1 was replaced with the catalyst component A3 to obtain a solid catalyst component E-3 (average particle size D50 ═ 41 μm). The main component contents of E-3 are shown in Table 1.
(3) Polymerization of propylene
Polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-3 from E-1 to obtain polypropylene P-3. The properties of the polypropylene P-3 are shown in Table 2.
Example 4
(1) Preparation of catalyst component A
The same as in example 2.
(2) Preparation of solid catalyst component
Prepared according to the method of example 2, except that the amount of propylene was adjusted from 6g to 0.5g and the amount of ethylene was adjusted from 3g to 0.5g, to thereby obtain a solid catalyst component E-4. The main component contents of E-4 are shown in Table 1.
(3) Polymerization of propylene
Polymerization was carried out in the same manner as in example 2 except that the solid catalyst component was replaced with E-4 from E-2 to obtain polypropylene P-4. The properties of the polypropylene P-4 are shown in Table 2.
Example 5
(1) Preparation of catalyst component A
The same as in example 2.
(2) Preparation of solid catalyst component
Prepared by the method of example 2 except that the amount of propylene used was adjusted from 6g to 100g, thereby obtaining solid catalyst component E-5. The main component contents of E-5 are shown in Table 1.
(2) Polymerization of propylene
Polymerization was carried out in the same manner as in example 2 except that the solid catalyst component was replaced with E-5 from E-2 to obtain polypropylene P-5. The properties of the polypropylene P-5 are shown in Table 2.
Example 6
(1) Preparation of catalyst component A
Prepared according to the procedure of example 1, except that 2, 2-dicyclohexyl-1, 3-dimethoxypropane was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, to thereby obtain catalyst component a4 (average particle size D50 ═ 40 μm).
(2) Preparation of solid catalyst component
Prepared according to the procedure of example 1 except that the catalyst component a1 was replaced with the catalyst component a4 to obtain a solid catalyst component E-6 (average particle size D50 ═ 43 μm). The main component contents of E-6 are shown in Table 1.
(3) Polymerization of propylene
Polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-6 from E-1 to obtain polypropylene P-6. The properties of the polypropylene P-6 are shown in Table 2.
Example 7
(1) Preparation of catalyst component A
Prepared according to the procedure of example 1 except that 2-propyl-1, 3-pentanediol dibenzoate was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, to prepare catalyst component a5 (average particle size D50 ═ 40 μm).
(2) Preparation of solid catalyst component
Prepared according to the procedure of example 1 except that the catalyst component a1 was replaced with the catalyst component a5 to obtain a solid catalyst component E-7 (average particle size D50 ═ 42 μm). The main component contents of E-7 are shown in Table 1,
(3) polymerization of propylene
Polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-7 from E-1 to obtain polypropylene P-7. The properties of the polypropylene P-7 are shown in Table 2.
Comparative example 1
(1) Preparation of catalyst component A
The same as in example 1.
(2) Preparation of solid catalyst component
Prepared according to the method of example 1, except that the amount of propylene was adjusted from 6g to 0g, that is, polymerization was carried out without adding propylene, and the amount of ethylene was adjusted from 3g to 9g, to thereby obtain a solid catalyst component DE-1. The main component content of DE-1 is shown in Table 1, and the particle morphology is shown in FIG. 2.
(3) Polymerization of propylene
The polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced from E-1 to DE-1 to thereby obtain polypropylene DP-1. The properties of the polypropylene DP-1 are shown in Table 2.
Comparative example 2
(1) Preparation of catalyst component A
The same as in example 1.
(2) Preparation of solid catalyst component
The preparation was carried out by following the procedure of example 1 except that the amount of propylene was adjusted from 6g to 9g and the amount of ethylene was adjusted from 3g to 0g, i.e., polymerization was carried out without adding ethylene, to thereby obtain a solid catalyst component DE-2. The main component contents of DE-2 are shown in Table 1.
(3) Polymerization of propylene
The polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced from E-1 to DE-2 to thereby obtain polypropylene DP-2. The properties of the polypropylene DP-2 are shown in Table 2.
Comparative example 3
Propylene polymerization was conducted in the same manner as in example 1 except that the solid catalyst component E-1 used was replaced with the catalyst component A1 of an equal mass, thereby obtaining polypropylene DP-3. The properties of the polypropylene DP-3 are shown in Table 2.
TABLE 1
Note: the component contents all refer to mass percentage contents.
TABLE 2
Comparing fig. 1 and fig. 2, the solid catalyst component prepared by the preparation method of the present invention has better regularity and less broken particles; as can be seen from Table 2, the polypropylene obtained by the catalytic polymerization using the catalyst comprising the solid catalyst component of the present invention has a low content of fine powder and almost no fine powder having a particle size of less than 0.18 mm.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A solid catalyst component for the polymerization of olefins, characterized in that it comprises, based on the total weight of the solid catalyst component, from 0.1 to 89% by weight of polyethylene, from 0.1 to 89% by weight of polyalphaolefin, from 0.1 to 3.5% by weight of titanium, from 1 to 16% by weight of magnesium, from 2 to 50% by weight of chlorine and from 0.6 to 15% by weight of lewis base.
2. The solid catalyst component according to claim 1 in which the solid catalyst component is a spherical solid particle with an average particle size of 20-80 μm.
3. The solid catalyst component according to claim 1 or 2 in which the polyalphaolefin is selected from one or more of polypropylene, polybutene, polyoctene and polyisoprene, preferably polypropylene.
4. The solid catalyst component according to any one of claims 1 to 3 in which the Lewis base is selected from at least one of a carboxylic acid ester, a glycol ester-based compound represented by the formula (1) and a1, 3-diether-based compound represented by the formula (2);
in the formula (1), R1-R6Each independently selected from hydrogen and C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl of (2), R1-R6Two or more of which are optionally bonded to each other to form one or more fused ring structures;
R7and R8Each independently selected from C1-C10Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Wherein hydrogen on the phenyl ring in the aryl, alkaryl and aralkyl groups may be optionally substituted with a halogen atom;
in the formula (2), R9And R10Each independently selected from hydrogen and C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, R11And R12Each independently selected from C1-C10Alkyl group of (1).
5. The solid catalyst component according to claim 4, wherein the glycol ester-based compound is selected from the group consisting of 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol diacetate, 1, 3-diisopropyl-1, 3-propanol di (4-butylbenzoate), 1-phenyl-2-amino-1, 3-propanediol dibenzoate, 1-phenyl-2-methyl-1, 3-butanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzo, 3, 3-dimethyl-2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (p-methylbenzoic acid) ester, 2, 4-pentanediol di (p-tert-butylbenzoic acid) ester, 2, 4-pentanediol di (p-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-butyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-tert-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol pivalate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a solvent, At least one of 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, and 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate; and/or
The 1, 3-diether compound is selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-1, 3, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
6. The solid catalyst component according to claim 4 in which the carboxylic acid ester is selected from at least one of a mono aliphatic carboxylic acid ester, a di aliphatic carboxylic acid ester, a mono aromatic carboxylic acid ester and a di aromatic carboxylic acid ester;
preferably, the carboxylic ester is one or more of succinate compounds, benzoate compounds and phthalate compounds;
more preferably, the succinate-based compound is selected from one or more of diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate and diethyl 2-ethyl-2-methylsuccinate;
more preferably, the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
more preferably, the phthalate-based compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
7. The solid catalyst component according to any one of claims 1 to 6 in which the polyethylene is present in an amount of from 1 to 50% by weight, the polyalphaolefin is present in an amount of from 1 to 50% by weight, the titanium is present in an amount of from 0.5 to 2% by weight, the magnesium is present in an amount of from 1 to 16% by weight, the chlorine is present in an amount of from 2 to 35% by weight, and the Lewis base is present in an amount of from 1 to 10% by weight, based on the total weight of the solid catalyst component; preferably the mass ratio of the polyalphaolefin to the polyethylene is from 0.1 to 10: 1.
8. a process for the preparation of a solid catalyst component for the polymerization of olefins, characterized in that it comprises:
(1) in the presence of an inert solvent, carrying out contact reaction on the catalyst component A, alkyl aluminum and an external electron donor compound; the catalyst component A contains titanium, magnesium, chlorine and a Lewis base;
(2) adding alpha-olefin into the reaction system obtained in the step (1) to carry out a first polymerization reaction;
(3) adding ethylene into the reaction system obtained in the step (2) to carry out a second polymerization reaction;
the mass ratio of the alpha-olefin to the ethylene to the amount of the catalyst component A is 0.04-10: 0.04-10: 1.
9. the production method according to claim 8, wherein in the step (1), the conditions of the contact reaction include: the temperature is 0-30 ℃, preferably 15-25 ℃; the time is 5-30min, preferably 10-20 min; and/or
In the step (2), the conditions of the first polymerization reaction include: the temperature is 0-30 ℃, preferably 15-25 ℃; the time is 5-30min, preferably 10-20 min; and/or
In the step (3), the conditions of the second polymerization reaction include: the temperature is 0-30 ℃, preferably 15-25 ℃; the time is 5-30min, preferably 10-20 min.
10. The production method according to claim 8, wherein the α -olefin is one or more selected from propylene, butene, octene and isopentene, preferably propylene.
11. The production process according to any one of claims 8 to 10, wherein the lewis base is at least one selected from a carboxylic acid ester, a glycol ester compound represented by formula (1), and a1, 3-diether compound represented by formula (2);
in the formula (1), R1-R6Each independently selected from hydrogen and C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl or C of7-C10Aralkyl of (2), R1-R6Two or more of which are optionally bonded to each other to form one or more fused ring structures;
R7and R8Each independently selected from C1-C10Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Wherein hydrogen on the phenyl ring in the aryl, alkaryl and aralkyl groups may be optionally substituted with a halogen atom;
in the formula (2), R9And R10Each independently selected from hydrogen and C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl or C7-C20Alkylaryl of, R11And R12Each independently selected from C1-C10Alkyl group of (1).
12. The production process according to claim 11, wherein the glycol ester compound is selected from the group consisting of 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol diacetate, 1, 3-diisopropyl-1, 3-propanol di (4-butylbenzoate), 1-phenyl-2-amino-1, 3-propanediol dibenzoate, 1-phenyl-2-methyl-1, 3-butanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzo, 3, 3-dimethyl-2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (p-methylbenzoic acid) ester, 2, 4-pentanediol di (p-tert-butylbenzoic acid) ester, 2, 4-pentanediol di (p-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-butyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-tert-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol pivalate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a solvent, At least one of 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, and 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate; and/or
The 1, 3-diether compound is selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-1, 3, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
13. The production method according to claim 11, wherein the carboxylic acid ester is at least one selected from a monocarboxylic acid ester, a dicarboxylic acid ester, a monocarboxylic acid ester, and a dicarboxylic acid ester;
preferably, the carboxylic ester is one or more of succinate compounds, benzoate compounds and phthalate compounds;
more preferably, the succinate-based compound is selected from one or more of diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate and diethyl 2-ethyl-2-methylsuccinate;
more preferably, the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
more preferably, the phthalate-based compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
14. The production process according to claim 8, wherein the catalyst component A is a reaction product of titanium tetrachloride, a spherical magnesium chloride alcoholate and the Lewis base;
the general formula of the spherical magnesium chloride alcoholate is Mg (R' OH)n(H2O)mWherein R' is methyl, ethyl, n-propyl or isopropyl, n is 1.5-3.5, and m is 0-0.1.
15. A solid catalyst component produced by the production method according to any one of claims 8 to 14.
16. A catalyst for the polymerization of olefins, characterized in that it is obtained by reacting the solid catalyst component according to any one of claims 1 to 7 and 15 with an aluminum alkyl and optionally an external electron donor compound.
17. A process for the polymerization of olefins, the process comprising: polymerizing at least one olefin in the presence of the catalyst for olefin polymerization according to claim 16;
preferably, the olefin has the formula CH2R is hydrogen or C1-C6Alkyl or aryl of (a);
preferably, the polymerization temperature is from 0 to 150 ℃, more preferably from 60 to 90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591081.XA CN112175117B (en) | 2019-07-02 | 2019-07-02 | Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591081.XA CN112175117B (en) | 2019-07-02 | 2019-07-02 | Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112175117A true CN112175117A (en) | 2021-01-05 |
| CN112175117B CN112175117B (en) | 2023-07-21 |
Family
ID=73915030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910591081.XA Active CN112175117B (en) | 2019-07-02 | 2019-07-02 | Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112175117B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160461A (en) * | 2021-04-02 | 2022-10-11 | 中国石油化工股份有限公司 | Spherical polyethylene powder and preparation method thereof |
| WO2024088298A1 (en) * | 2022-10-26 | 2024-05-02 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, and preparation method therefor and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069034A (en) * | 1991-06-03 | 1993-02-17 | 希蒙特公司 | The gas phase polymerization process of alkene |
| CN1127510A (en) * | 1994-05-12 | 1996-07-24 | 昭和电工株式会社 | Propylene polymer, process for producing the same, composition thereof, polymerization catalyst component, and process for producing the same |
| CN104487463A (en) * | 2012-08-07 | 2015-04-01 | 博里利斯股份公司 | Process for the preparation of polypropylene with improved productivity |
| CN107629155A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | A kind of polypropylene and its preparation method and application |
-
2019
- 2019-07-02 CN CN201910591081.XA patent/CN112175117B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069034A (en) * | 1991-06-03 | 1993-02-17 | 希蒙特公司 | The gas phase polymerization process of alkene |
| CN1127510A (en) * | 1994-05-12 | 1996-07-24 | 昭和电工株式会社 | Propylene polymer, process for producing the same, composition thereof, polymerization catalyst component, and process for producing the same |
| CN104487463A (en) * | 2012-08-07 | 2015-04-01 | 博里利斯股份公司 | Process for the preparation of polypropylene with improved productivity |
| CN107629155A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | A kind of polypropylene and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160461A (en) * | 2021-04-02 | 2022-10-11 | 中国石油化工股份有限公司 | Spherical polyethylene powder and preparation method thereof |
| CN115160461B (en) * | 2021-04-02 | 2024-05-07 | 中国石油化工股份有限公司 | Spherical polyethylene powder and preparation method thereof |
| WO2024088298A1 (en) * | 2022-10-26 | 2024-05-02 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112175117B (en) | 2023-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9809663B2 (en) | Catalyst component for olefin polymerization, preparation method thereof, and catalyst comprising same | |
| RU2489447C2 (en) | Self-limiting catalyst composition with bidentate internal donor | |
| CN103476806B (en) | Catalytic component for olefinic polymerization | |
| US9353197B2 (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| RU2668082C2 (en) | Spherical carriers for olefin polymerisation catalyst, catalyst components, catalyst and preparation methods therefor | |
| US10113012B2 (en) | Catalyst components for the polymerization of olefins | |
| CZ280315B6 (en) | Solid catalytic component for polymerization of olefins and a catalyst containing such component | |
| CN112175115B (en) | Solid catalyst component of olefin polymerization catalyst, preparation method thereof, olefin polymerization catalyst and olefin polymerization method | |
| CN112175117B (en) | Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization | |
| CN112175119B (en) | Solid catalyst component for olefin polymerization, process for producing the same, olefin polymerization catalyst, and process for olefin polymerization | |
| CN107873037A (en) | gas phase process for polymerizing propylene | |
| CN112175118B (en) | Solid catalyst component for olefin polymerization, preparation method thereof, olefin polymerization catalyst and olefin polymerization method | |
| CN106543310B (en) | A kind of olefin polymerization catalyst system and its application | |
| CN117924558A (en) | Solid catalyst component for olefin polymerization, preparation method and application thereof | |
| CN117924557A (en) | Prepolymerized catalyst for olefin polymerization, preparation method and application thereof | |
| CN117924559A (en) | Solid catalyst component for olefin polymerization and application thereof | |
| US20240182606A1 (en) | Method for producing propylene copolymer using catalyst system having improved copolymerization activity | |
| CN116023547B (en) | Catalyst component, catalyst and method for olefin polymerization | |
| CN117924565A (en) | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, preparation method and application thereof | |
| CN114426607A (en) | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer | |
| JP2024062413A (en) | Solid catalyst for propylene-based polymerization, and production method of propylene-based polymer using the same | |
| TW202417529A (en) | Solid catalyst component for olefin polymerization, and preparation method therefor and use thereof | |
| CN114426596A (en) | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer | |
| CN115975079A (en) | Catalyst component for olefin polymerization, catalyst and application | |
| WO2018161854A1 (en) | Solid catalyst component for use in olefin polymerisation, catalyst, and application thereof |
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 |