CN112175117B - Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization - Google Patents
Solid catalyst component for olefin polymerization, process for producing the same, catalyst for olefin polymerization, and process for olefin polymerization Download PDFInfo
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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 weight percent polyethylene, from 0.1 to 89 weight percent polyalphaolefin, from 0.1 to 3.5 weight percent titanium, from 1 to 16 weight percent magnesium, from 2 to 50 weight percent chlorine, and from 0.6 to 15 weight percent lewis base; the catalyst component has the advantages of good regularity and less broken particles, and the content of the fine powder of the 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, a preparation method thereof, 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 butene) 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 a prepolymerization unit, such as the SHPERIZONE and SHPERILENE process units, for the production of polypropylene and polyethylene. Although these process units are provided with a prepolymerization operation unit, the catalyst particles and polymer particles are broken up during the production of the resin, resulting in the presence of a certain amount of fines content in the polymer, especially in the production of propylene homopolymers with high melt flow index (MFR), which has a larger fines content, which affects the stability and long-term operation of the unit. Polypropylene units without a prepolymerization unit, such as UNIPOL process units, are not compatible with the use of Ziegler-Natta type spherical catalysts because the catalyst or polymer particles are almost totally broken up during the polymerization process, producing a large amount of fines.
US9453088B2 discloses a prepolymerized catalyst for olefin polymerization, wherein the prepolymerized catalyst has an average particle diameter of less than 30 mu m, a prepolymerization multiple of less than 50g polymer/g catalyst, and a catalyst component containing two electron donors of 1, 3-diether and aromatic ester, and the preparation method comprises the steps of preparing a spherical catalyst containing two electron donors of 1, 3-diether and aromatic ester, and then prepolymerizing with olefin with 2-10 carbon atoms to obtain the prepolymerized catalyst. CN1421468A discloses a process for the polymerization or copolymerization of propylene by prepolymerizing a Ziegler-Natta type catalyst with ethylene or alpha-olefin at a temperature of from-10 ℃ to 80 ℃ followed by propylene polymerization. US7329714B2 discloses a process for the prepolymerization of polypropylene comprising prepolymerizing a Ziegler-Natta type catalyst with propylene or 4-methyl-1-pentene at a temperature of from 0 to 40℃followed by propylene polymerization.
However, in the above-mentioned preparation method of the prepolymerized catalyst, when ethylene is used as a prepolymerized monomer to prepare the prepolymerized catalyst, the catalyst inevitably has a crushing phenomenon, and the content of polymer fine powder is also high when an olefin polymerization reaction is carried out; the prepolymerized catalyst prepared by taking propylene or other alpha-olefins as a prepolymerized monomer has a certain crushing phenomenon, and the activity of the catalyst decays rapidly along with the extension of the storage time, so that the commercial value is low.
Disclosure of Invention
The invention aims to solve the problems that the existing Ziegler-Natta type prepolymerization catalyst has a fragmentation phenomenon in the preparation process and the content of polymer fine powder is high when the prepolymerization catalyst is used for olefin polymerization, and provides a solid catalyst component for olefin polymerization, a preparation method thereof, a catalyst for olefin polymerization and an olefin polymerization method. The solid catalyst component has the advantages of high regularity and few broken particles, and the content of the fine powder of the 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 the polymerization of olefins comprising, 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.
According to a second aspect of the present invention, there is provided a process for the preparation of a solid catalyst component for the polymerization of olefins, the process comprising the steps of:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains titanium, magnesium, chlorine and 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 dosage 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 prepared by the preparation 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 the polymerisation of olefins produced by reacting a solid catalyst component according to the first or third aspect of the present invention with an aluminium 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 for not only olefin polymerization plants with a prepolymerization unit, but also polyolefin plants without a prepolymerization unit. In addition, the olefin polymer obtained by using the solid catalyst component for catalyzing olefin polymerization has better regularity and lower content of fine powder 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 and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention there is provided a solid catalyst component for the polymerization of olefins comprising, 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.
The solid catalyst component of the present invention is spherical solid particles. Preferably, the solid catalyst component has an average particle size (D50) of 20 to 80. Mu.m. 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 one or more selected from polypropylene, polybutene, polyoctene and polyisopentene. 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 selected from at least one of a carboxylic acid ester, a glycol ester compound represented by formula (1), and a 1, 3-diether compound represented by formula (2):
in the formula (1), R 1 -R 6 Each independently selected from hydrogen, C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 10 Alkylaryl or C of (C) 7 -C 10 Aralkyl of R 1 -R 6 Two or more groups of (a) are optionally bonded to each other to form one or more fused ring structures;
R 7 and R is 8 Each independently selected from C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 Wherein the hydrogen on the benzene ring in the aryl, alkylaryl and arylalkyl groups may be optionally substituted with halogen atoms;
in the formula (2), R 9 And R is 10 Each independently selected from hydrogen, C 1 -C 20 Straight or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl group R of (2) 11 And R is 12 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
In the solid catalyst component of the present invention, the glycol ester compound is preferably selected from 1, 3-propylene glycol dibenzoate, 2-methyl-1, 3-propylene glycol dibenzoate, 2-ethyl-1, 3-propylene glycol dibenzoate, 2-dimethyl-1, 3-propylene glycol dibenzoate, 1, 3-diphenyl-1, 3-propylene glycol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propylene glycol dibenzoate, and 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-butylbenzoic acid) ester, 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-methylbenzoic acid) ester, 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-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, and, at least one of 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, 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- (diphenylmethyl) -1, 3-dimethoxypropane 2, 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-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-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 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 at least one selected from the group consisting 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. Wherein the aliphatic carboxylic acid ester is carboxylic acid ester prepared from mono (or dibasic) aliphatic carboxylic acid and aliphatic monohydric alcohol or aromatic monohydric alcohol, and the aromatic carboxylic acid ester is carboxylic acid ester prepared from mono (or dibasic) 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, for example, one or more of methyl benzoate, ethyl benzoate, and n-butyl benzoate.
The phthalate compound may be, for example, one or more selected from diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
The succinate compound may be selected from, for example, one or more of diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate and diethyl 2-ethyl-2-methylsuccinate.
In the present invention, the inclusion of magnesium, titanium, chlorine in the solid catalyst component means inclusion of magnesium element, titanium element, and chlorine element, respectively.
Titanium content was measured by colorimetry. Specifically, 0.2-0.5g of sample is taken with 50mL of 2N H 2 SO 4 Dissolving, filtering the upper layer floating matter, and taking clear liquid for colorimetric; by 2N H 2 SO 4 The solution was used as a blank, the cuvette thickness was 1cm, its absorbance E1 was measured at a wavelength of 410. Mu.m, and then 1 drop of 30% H was dropped 2 O 2 Shaking up, measuring the absorbance E2, and calculating the titanium content Ti (%) according to the following formula:
Ti(％)＝[(E2-E1)×100)/(K·L·W·100)]×100
wherein: w-sample weight (g); l-cuvette thickness (cm); k-ratio extinction coefficient; e1-blank absorbance; e2-absorbance of sample.
The magnesium content was measured by EDTA titration. Specifically, 0.2-0.5g of the sample is put into a 250mL conical flask, and 20-30mL of 2N H is added 2 SO 4 Dissolving the solution, adding 20mL of triethanolamine (1+2) standard solution, adjusting pH to 10 with 20% NaOH solution, shaking, adding 10mL of buffer solution with pH of 10, and adding 6 drops of 30% H 2 O 2 And 30-50mL distilled water, adding a small amount of chrome black T indicator, shaking, titrating with 0.02N EDTA solution until the end point is changed from mauve to blue (disappearance of mauve), and calculating according to the following formulaMagnesium content Mg (%):
Mg(％)＝[(VE·NE×24.31)/(G·1000)]×100
wherein: g—sample mass (G); ve—the amount of EDTA consumed (mL); NE-EDTA solution equivalent; 24.31 atomic weight of magnesium.
Chlorine content was measured according to silver nitrate titration. Specifically, 0.04-0.1g of the sample was weighed into a conical flask, and 20mL of 2N H was added 2 SO 4 The solution is placed for 30 minutes; washing with distilled water for several times, and dripping 20-30mL of 0.1N AgNO 3 Solution, add 1:1HNO 3 Solution 3mL with 0.1N NH 4 CNS standard solution titrates excess AgNO 3 The solution was titrated to the brick red color for two seconds without disappearing as an end point, and the chlorine content Cl (%) was calculated according to the following formula:
Cl(％)＝[(V 1 -V 2 ×D)×N 1 ×35.45/(G·1000)]×100
wherein: v (V) 1 —AgNO 3 Amount of solution (mL); v (V) 2 Consumed NH 4 Amount of CNS solution (mL);
D—AgNO 3 /NH 4 volume ratio of CNS solution; n (N) 1 —AgNO 3 Equivalent concentration of (2); g-mass of sample (G); 35.45 atomic weight of chlorine.
The method for testing the content of polyethylene and poly alpha-olefin in the solid catalyst component comprises the following steps: weighing a certain amount of samples of (M1), dissolving the samples with ethanol and dilute hydrochloric acid, drying insoluble matters in vacuum at 80 ℃ to obtain solid matters (M2), tabletting 0.2g of the solid matters, measuring the polyethylene content (C1) and the poly alpha-olefin content (C2) of the solid matters by using an infrared spectrometer, and respectively calculating the mass percent of polyethylene and poly alpha-olefin in the solid catalyst component according to the following formula:
C A ＝M2×C1/M1
C B ＝M2×C2/M1
wherein C is A And C B The mass percentages of polyethylene and poly-alpha-olefin in the solid catalyst component, M1 and M2 are the mass (g) of the sample and dry solids, respectively, and C1 and C2 are the mass percentages of polyethylene and poly-alpha-olefin in the dry solids, respectively.
The method for testing the Lewis base content in the solid catalyst component comprises the following steps: the sample was dissolved with ethyl acetate and hydrochloric acid solution (concentration 2 mol/L) and extracted to give Lewis base, the content of which was analyzed using a conventional liquid chromatograph.
In the solid catalyst component of the present invention, it is preferable that the polyethylene is contained in an amount of 1 to 50% by weight, the polyalphaolefin is contained in an amount of 1 to 50% by weight, the titanium is contained in an amount of 0.5 to 2% by weight, the magnesium is contained in an amount of 1 to 16% by weight, the chlorine is contained in an amount of 2 to 35% by weight, and the lewis base is contained in an amount of 1 to 10% by weight, based on the total weight of the solid catalyst component.
Preferably, the mass ratio of the poly-alpha-olefin to the polyethylene is 0.1-10:1.
in the solid catalyst component, the solid catalyst component also contains aluminum alkyl and an external electron donor. The types and the contents of the aluminum alkyl and the external electron donor can be selected by referring 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 the polymerization of olefins, comprising:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains titanium, magnesium, chlorine and 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 0-30 ℃, preferably 15-25 ℃; the time may be 5-30min, preferably 10-20min.
In the step (1), the aluminum alkyl and the external electron donor compound may be selected with reference to a conventional olefin prepolymerization catalyst, and the present invention is not particularly limited thereto. The alkyl aluminum may be selected from one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and diethyl aluminum 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. In general, the molar ratio of the aluminum alkyl, the external electron donor compound and the catalyst component a used in terms of elemental titanium may be from 1 to 50:0.2-10:1.
In the preparation method of the present invention, the lewis base may be at least one of a carboxylic acid ester, a glycol ester compound represented by formula (1), and a 1, 3-diether compound represented by formula (2):
in the formula (1), R 1 -R 6 Each independently selected from hydrogen, C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 10 Alkylaryl or C of (C) 7 -C 10 Aralkyl of R 1 -R 6 Two or more groups of (a) are optionally bonded to each other to form one or more fused ring structures;
R 7 and R is 8 Each independently selected from C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 Wherein the hydrogen on the benzene ring in the aryl, alkylaryl and arylalkyl groups may be optionally substituted with halogen atoms;
in the formula (2), R 9 And R is 10 Each independently selected from hydrogen, C 1 -C 20 Straight or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl groups of (a)，R 11 And R is 12 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
In the preparation method of the present invention, specific descriptions of the glycol ester compound, the carboxylic acid ester compound and the 1, 3-diether compound are as described in the first aspect of the present invention, and are not described herein.
In the preparation method of the present invention, the catalyst component a may be prepared according to a conventional method of a main catalyst in an olefin polymerization catalyst in the art, and the present invention is not particularly limited thereto, and may be prepared, for example, by the methods disclosed in patent ZL03153152.0 and ZL 200410062291.3.
According to a preferred embodiment, the catalyst component a is the reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide and the lewis base; the general formula of the spherical magnesium chloride alcohol compound is Mg (R' OH) n (H 2 O) m Wherein 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 alkoxide for 20-120min at the temperature of minus 20 ℃ to 0 ℃ to obtain a mixture I;
2) Heating the mixture I to 100-120 ℃, adding the Lewis base in the heating process, and reacting for 20-200min at 100-120 ℃ to obtain a solid product II;
3) The solid product II was washed with titanium tetrachloride and hexane, respectively, and dried in vacuo.
In the preparation process of the present invention, the inert solvent may be selected with reference to the prior art. In general, 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 may be 5 to 50g/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 0-30 ℃, preferably 15-25 ℃; the time may be 5-30min, preferably 10-20min.
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 0-30 ℃, preferably 15-25 ℃; the time may be 5-30min, preferably 10-20min.
Preferably, after the second polymerization reaction is completed, 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 a solid product; the solid product is then dried under vacuum at 10-80 ℃ to obtain the solid catalyst component.
In the production process of the present invention, the α -olefin is preferably one or more selected from propylene, butene, octene and isoamylene, and further preferably the α -olefin is propylene.
In the preparation method of the invention, the mass ratio of the dosage of the alpha-olefin, the ethylene and 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-Natta type prepolymerization catalyst (i.e. solid catalyst component) with good regularity and less broken particles by sequentially carrying out polymerization reaction on alpha-olefin and ethylene respectively. According to one embodiment, the solid catalyst component produced by the production process 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 the polymerization of olefins, the catalyst being prepared by reacting a solid catalyst component according to the present invention with an aluminium alkyl and optionally an external electron donor compound.
The aluminium alkyl, the external electron donor compound and the respective contents according to the fourth aspect of the invention may all be selected according to the prior art. In general, the alkyl aluminum may be selected from one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and diethyl aluminum monochloride. The ratio of the molar amount of the aluminum alkyl in terms of aluminum element to the molar amount of the solid catalyst component in terms of titanium element may be 1 to 1000:1. the external electron donor compound may be selected from at least one 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 in terms of aluminum element to the molar amount of the external electron donor compound in terms of silicon element is from 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 subjected to a polymerization reaction in the presence of a catalyst for olefin polymerization according to the fourth aspect of the present invention. The conditions for the polymerization reaction may be selected conventionally in the art, for example, a reaction temperature of 0 to 150 ℃, preferably a reaction temperature of 60 to 90 ℃, and a reaction pressure of normal pressure or higher.
In the process of the present invention, the olefin has the general formula CH 2 =chr, R is hydrogen, C 1 -C 6 Alkyl or aryl groups of (a). Preferably, the olefin is selected from one or more of ethylene, propylene, butene, pentene and hexene.
Advantages of the technical solution of the present invention will be described in detail below by means of specific examples.
In the following examples and comparative examples,
the isotactic index of a polymer (polypropylene) refers to the mass percent of polypropylene insoluble in boiling n-heptane under the specified conditions, and is determined by heptane extraction (heptane boiling extraction for 6 hours), i.e., 2g of a dried polymer sample is taken, placed in an extractor and extracted with boiling heptane for 6 hours, after which 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 melt index of the polymer was determined according to the method of ASTM D1238-99.
The particle size distribution of the polymer was screened through a standard sieve to calculate the mass percent of the fraction.
The following examples are presented to illustrate the solid catalyst component of the present invention, its preparation method and the method of olefin polymerization.
Example 1
(1) Preparation of catalyst component A
1.2L of titanium tetrachloride is added into a 3L glass reaction bottle with stirring, and after the temperature is reduced to minus 20 ℃, 100g of magnesium chloride alkoxide spherical carrier [ Mg (C) is added after the temperature is reduced to minus 20 ℃ under the stirring condition 2 H 5 OH) 2.6 ](average particle size d50=45 μm), after 0.5 hour of reaction at-20 ℃, slowly heating to 120 ℃, adding 15g of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane during the heating, then reacting at 120 ℃ for 0.5 hour, filtering off the liquid, adding 1L of titanium tetrachloride, filtering off the liquid after 2 hours at 120 ℃ to obtain a solid product, washing the obtained solid product with hexane 5 times, and finally drying in vacuum to obtain 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 added and reacted at 22℃for 10 minutes; then 6g of propylene was added and reacted at 23℃for 10 minutes, the unreacted propylene was vented; the autoclave was replaced with nitrogen, 3g of ethylene was added, and the reaction was carried out at 15℃for 10 minutes, and unreacted ethylene was vented. After filtering off the liquid in the reaction product, drying under vacuum gave 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) Propylene polymerization
Into 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 charging 1.5NL of hydrogen, 2.0kg of liquid propylene was added; raising the temperature to 70 ℃ under stirring and carrying out polymerization reaction for 1 hour at 70 ℃; the stirring was stopped and the unpolymerized propylene monomer was removed to give polypropylene P-1. The properties of polypropylene P-1 are shown in Table 2.
Example 2
(1) Preparation of catalyst component A
Prepared as in example 1 except that diisobutyl phthalate was used in place of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give catalyst component A2 (average particle size d50=40 μm).
(2) Preparation of solid catalyst component
Prepared as in example 1 except that catalyst component A2 was used in place of catalyst component A1, thereby producing solid catalyst component E-2 (average particle size d50=43 μm). The main component content of E-2 is shown in Table 1.
(3) Propylene polymerization
Polymerization was carried out as in example 1, except that the solid catalyst component was replaced by E-1 to E-2 to obtain polypropylene P-2. The properties of polypropylene P-2 are shown in Table 2.
Example 3
(1) Preparation of catalyst component A
Prepared as in example 1 except 2, 4-pentanediol dibenzoate was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give catalyst component A3 (average particle size d50=40 μm).
(2) Preparation of solid catalyst component
Prepared as in example 1 except that catalyst component A3 was used in place of catalyst component A1, thereby producing solid catalyst component E-3 (average particle size d50=41 μm). The main component content of E-3 is shown in Table 1.
(3) Propylene polymerization
Polymerization was carried out as in example 1, except that the solid catalyst component was replaced by E-1 to E-3 to obtain polypropylene P-3. The properties of polypropylene P-3 are shown in Table 2.
Example 4
(1) Preparation of catalyst component A
As in example 2.
(2) Preparation of solid catalyst component
Prepared as in 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, thereby preparing solid catalyst component E-4. The main component content of E-4 is shown in Table 1.
(3) Propylene polymerization
Polymerization was carried out as in example 2, except that the solid catalyst component was replaced by E-2 with E-4 to give polypropylene P-4. The properties of polypropylene P-4 are shown in Table 2.
Example 5
(1) Preparation of catalyst component A
As in example 2.
(2) Preparation of solid catalyst component
Prepared as in example 2 except that the amount of propylene was adjusted from 6g to 100g to thereby prepare solid catalyst component E-5. The main component content of E-5 is shown in Table 1.
(2) Propylene polymerization
Polymerization was carried out as in example 2, except that the solid catalyst component was replaced by E-5 with E-2 to give polypropylene P-5. The properties of polypropylene P-5 are shown in Table 2.
Example 6
(1) Preparation of catalyst component A
Prepared as in example 1 except that 2, 2-dicyclohexyl-1, 3-dimethoxypropane was used instead of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give catalyst component A4 (average particle size d50=40 μm).
(2) Preparation of solid catalyst component
Prepared as in example 1 except that catalyst component A4 was used in place of catalyst component A1, thereby producing solid catalyst component E-6 (average particle size d50=43 μm). The main component content of E-6 is shown in Table 1.
(3) Propylene polymerization
Polymerization was carried out as in example 1, except that the solid catalyst component was replaced by E-1 with E-6 to give polypropylene P-6. The properties of polypropylene P-6 are shown in Table 2.
Example 7
(1) Preparation of catalyst component A
Prepared as in example 1 except 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was replaced with 2-propyl-1, 3-pentanediol dibenzoate to give catalyst component A5 (average particle size d50=40 μm).
(2) Preparation of solid catalyst component
Prepared as in example 1 except that catalyst component A5 was used in place of catalyst component A1, thereby producing solid catalyst component E-7 (average particle size d50=42 μm). The main component content of E-7 is shown in Table 1,
(3) Propylene polymerization
Polymerization was carried out as in example 1, except that the solid catalyst component was replaced by E-1 to E-7 to obtain polypropylene P-7. The properties of polypropylene P-7 are shown in Table 2.
Comparative example 1
(1) Preparation of catalyst component A
As in example 1.
(2) Preparation of solid catalyst component
Prepared as in example 1 except that the amount of propylene was adjusted from 6g to 0g, i.e., polymerization was carried out without adding propylene, and the amount of ethylene was adjusted from 3g to 9g, thereby obtaining a solid catalyst component DE-1. The main component content of DE-1 is shown in Table 1 and the morphology of the particles is shown in FIG. 2.
(3) Propylene polymerization
Polymerization was carried out as in example 1, except that the solid catalyst component was replaced by DE-1 from E-1, thereby producing polypropylene DP-1. The properties of polypropylene DP-1 are shown in Table 2.
Comparative example 2
(1) Preparation of catalyst component A
As in example 1.
(2) Preparation of solid catalyst component
Prepared as in 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, thereby obtaining solid catalyst component DE-2. The main component content of DE-2 is shown in Table 1.
(3) Propylene polymerization
Polymerization was performed as in example 1, except that the solid catalyst component was replaced with DE-2 from E-1, thereby producing polypropylene DP-2. The properties of polypropylene DP-2 are shown in Table 2.
Comparative example 3
Propylene polymerization was carried out in the same manner as in example 1 except that the solid catalyst component E-1 used was replaced with an equal mass of the catalyst component A1, thereby producing polypropylene DP-3. The properties of polypropylene DP-3 are shown in Table 2.
TABLE 1
Note that: the component content refers to mass percent.
TABLE 2
Comparing fig. 1 and fig. 2, it can be known that the solid catalyst component prepared by the preparation method of the present invention has better regularity and fewer broken particles; as can be seen from Table 2, the polypropylene obtained by the catalytic polymerization using the catalyst containing the solid catalyst component of the present invention has a low content of fine powder and hardly has fine powder having a particle diameter of less than 0.18 mm.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
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 1 to 50% by weight of polyethylene, from 1 to 50% by weight of polyalphaolefin, from 0.5 to 2.3% by weight of titanium, from 1 to 16% by weight of magnesium, from 2 to 35% by weight of chlorine and from 1 to 10% by weight of lewis base;
wherein the mass ratio of the poly alpha-olefin to the polyethylene is 0.1-10:1
The polyalphaolefin is selected from polypropylene and/or polybutene.
2. The solid catalyst component according to claim 1, wherein the solid catalyst component is a spherical solid particle having an average particle size of 20-80 μm.
3. The solid catalyst component according to claim 1 in which the polyalphaolefin is selected from polypropylene.
4. The solid catalyst component according to any one of claims 1 to 3, wherein the lewis base is selected from at least one of a carboxylic acid ester, a glycol ester compound represented by formula (1), and a 1, 3-diether compound represented by formula (2);
in the formula (1), R 1 -R 6 Each independently selected from hydrogen, C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 10 Alkylaryl or C of (C) 7 -C 10 Aralkyl of R 1 -R 6 Two or more groups of (a) are optionally bonded to each other to form one or more fused ring structures;
R 7 and R is 8 Each independently selected from C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 Wherein the hydrogen on the benzene ring in the aryl, alkylaryl and arylalkyl groups may be optionally substituted with halogen atoms;
in the formula (2), R 9 And R is 10 Each independently selected from hydrogen, C 1 -C 20 Straight or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl group R of (2) 11 And R is 12 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
5. The solid catalyst component according to claim 4 in which, the glycol ester compound is selected from 1, 3-propylene glycol dibenzoate, 2-methyl-1, 3-propylene glycol dibenzoate, 2-ethyl-1, 3-propylene glycol dibenzoate, 2-dimethyl-1, 3-propylene glycol dibenzoate, 1, 3-diphenyl-1, 3-propylene glycol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propylene glycol dibenzoate, and 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-butylbenzoic acid) ester, 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-methylbenzoic acid) ester, 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-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, and, at least one of 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, 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, 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-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-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 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, wherein 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.
7. The solid catalyst component according to claim 6, wherein the carboxylic acid ester is one or more of a succinate compound, a benzoate compound, and a phthalate compound;
wherein the succinate compound is selected from one or more of diethyl 2, 3-diisopropyl succinate, diisobutyl 2, 3-diisopropyl succinate, di-n-butyl 2, 3-diisopropyl succinate, dimethyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate;
the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
the phthalate compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
8. A process for preparing a solid catalyst component for olefin polymerization according to any one of claims 1 to 7, comprising:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains titanium, magnesium, chlorine and 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 dosage of the catalyst component A is 0.04-10:0.04-10:1, a step of;
the polyalphaolefin is selected from polypropylene and/or polybutene.
9. The production method according to claim 8, wherein in the step (1), the conditions of the contact reaction include: the temperature is 0-30deg.C, and the time is 5-30min; and/or
In step (2), the conditions of the first polymerization reaction include: the temperature is 0-30deg.C, and the time is 5-30min; and/or
In step (3), the conditions of the second polymerization reaction include: the temperature is 0-30deg.C, and the time is 5-30min.
10. The production method according to claim 9, wherein in the step (1), the conditions of the contact reaction include: the temperature is 15-25deg.C, and the time is 10-20min; and/or
In step (2), the conditions of the first polymerization reaction include: the temperature is 15-25deg.C, and the time is 10-20min; and/or
In step (3), the conditions of the second polymerization reaction include: the temperature is 15-25deg.C, and the time is 10-20min.
11. The process of claim 8, wherein the alpha-olefin is propylene.
12. The production process according to any one of claims 8 to 11, wherein the lewis base is selected from at least one of a carboxylic acid ester, a glycol ester compound represented by formula (1), and a 1, 3-diether compound represented by formula (2);
in the formula (1), R 1 -R 6 Each independently selected from hydrogen, C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C of (2) 7 -C 10 Alkylaryl or C of (C) 7 -C 10 Aralkyl of R 1 -R 6 Two or more groups of (a) are optionally bonded to each other to form one or more fused ring structures;
R 7 and R is 8 Each independently selected from C 1 -C 10 Straight-chain or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Alkylaryl or C of (C) 7 -C 20 Wherein the hydrogen on the benzene ring in the aryl, alkylaryl and arylalkyl groups may be optionally substituted with halogen atoms;
in the formula (2), R 9 And R is 10 Each independently selected from hydrogen, C 1 -C 20 Straight or branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 7 -C 20 Aralkyl or C of (C) 7 -C 20 Alkylaryl group R of (2) 11 And R is 12 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
13. The preparation method according to claim 12, wherein, the glycol ester compound is selected from 1, 3-propylene glycol dibenzoate, 2-methyl-1, 3-propylene glycol dibenzoate, 2-ethyl-1, 3-propylene glycol dibenzoate, 2-dimethyl-1, 3-propylene glycol dibenzoate, 1, 3-diphenyl-1, 3-propylene glycol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propylene glycol diacetate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propylene glycol dibenzoate, and 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-butylbenzoic acid) ester, 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-methylbenzoic acid) ester, 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-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, and, at least one of 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, 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, 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-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-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 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.
14. The production method according to claim 13, wherein the carboxylic acid ester is at least one selected from a group consisting 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.
15. The preparation method of claim 14, wherein the carboxylic acid ester is one or more of a succinate compound, a benzoate compound and a phthalate compound;
wherein the succinate compound is selected from one or more of diethyl 2, 3-diisopropyl succinate, diisobutyl 2, 3-diisopropyl succinate, di-n-butyl 2, 3-diisopropyl succinate, dimethyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate;
the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
the phthalate compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate.
16. The production process according to claim 8, wherein the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the lewis base;
the ballThe general formula of the magnesium chloride alkoxide is Mg (R' OH) n (H 2 O) m Wherein R' is methyl, ethyl, n-propyl or isopropyl, n is 1.5-3.5, and m is 0-0.1.
17. A catalyst for the polymerization of olefins prepared by reacting the solid catalyst component according to any of claims 1 to 7 with an aluminum alkyl and optionally an external electron donor compound.
18. A process for the polymerization of olefins, comprising: polymerizing at least one olefin in the presence of the catalyst for olefin polymerization according to claim 17.
19. The method of claim 18, wherein the olefin has the formula CH 2 =chr, R is hydrogen or C 1 -C 6 Alkyl or aryl of (a);
the temperature of the polymerization reaction is 0-150 ℃.
20. The method of claim 19, wherein the polymerization reaction temperature is 60-90 ℃.
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| 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 |
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| 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 |
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