CN112175115B - Solid catalyst component of olefin polymerization catalyst, preparation method thereof, olefin polymerization catalyst and olefin polymerization method - Google Patents
Solid catalyst component of olefin polymerization catalyst, preparation method thereof, olefin polymerization catalyst and olefin polymerization method Download PDFInfo
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Abstract
The invention relates to the field of olefin polymerization, and discloses a solid catalyst component of an olefin polymerization catalyst, a preparation method thereof, the olefin polymerization catalyst and an olefin polymerization method. The solid catalyst component comprises polyethylene, polyalphaolefin, titanium, magnesium, chlorine, and an internal electron donor compound; the polyethylene is 0.1 to 89 wt%, the poly alpha-olefin is 0.1 to 89 wt%, the titanium is 0.1 to 3.5 wt%, the magnesium is 1 to 16 wt%, the chlorine is 2 to 50 wt%, and the internal electron donor compound is 0.6 to 15 wt%, based on the total weight of the solid catalyst component; the internal electron donor compound comprises a 1, 3-diether compound shown in a formula (1). The solid catalyst component of the olefin polymerization catalyst has higher regularity and fewer broken particles, and the content of the fine powder of the polyolefin prepared by the catalysis of the olefin catalyst containing the catalyst component is also lower.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a solid catalyst component of an olefin polymerization catalyst, a preparation method thereof, the olefin polymerization catalyst and an olefin polymerization method.
Background
The preparation of Ziegler Natta (Ziegler-Natta) catalysts by supporting a titanium compound on a magnesium halide in active form is well known in the art. In general, the active magnesium halide often employs an adduct of magnesium halide with an alcohol, which is reacted as a support with titanium halide and an electron donor compound to give a spherical catalyst. Currently, a wide variety of internal electron donor compounds have been disclosed, such as polycarboxylic acids, mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyether, alcohols, amines and the like and derivatives thereof, of which dibasic aromatic carboxylic acid esters, such as di-n-butyl phthalate or di-isobutyl phthalate and the like, are more commonly used (see CN85100997 a).
When the spherical catalyst is used for olefin polymerization (especially propylene polymerization), the spherical catalyst has higher polymerization activity and stereospecificity, and the obtained polymer has better particle morphology. Spherical catalysts are widely used in loop polypropylene process units for the production of propylene homopolymers, propylene/ethylene (or butene) random copolymers. Spherical catalysts are also used in, for example, the SHPERIZONE and SHPERILENE process units with prepolymerization units for the production of polypropylene and polyethylene. Although the process devices are provided with a prepolymerization operation unit, catalyst particles and polymer particles are still broken in the polyolefin production process, and the obtained polyolefin product fine powder has high content, so that problems of kettle sticking, kettle hanging, pipeline blocking and the like in the production are caused, and the polyolefin production benefit is greatly influenced.
CN1421468A discloses a method for polymerizing or copolymerizing propylene, which comprises the steps of prepolymerizing a Ziegler-Natta catalyst with ethylene or alpha-olefin at-10 ℃ to 80 ℃, controlling the prepolymerization multiple to 6-50000 times, and then carrying out propylene polymerization.
CN101400710a discloses a process for polymerizing propylene comprising a prepolymerization step, which comprises prepolymerizing a catalyst of the Ziegler-natta type with propylene or 4-methyl-1-pentene at 0-40 ℃ followed by propylene polymerization.
The method disclosed in the above patent document can improve the stereoregularity, polymerization activity and hydrogen sensitization of the polymer, but when the prepolymerized catalyst is prepared by using the prepolymerized monomer, the catalyst is broken, and when the olefin polymerization reaction is carried out, the content of polymer fine powder is higher; and the pre-polymerized catalyst prepared by taking alpha-olefin such as propylene and the like as a pre-polymerized monomer has quicker activity decay along with the extension of the storage time, and lacks commercial value.
Disclosure of Invention
In order to solve the problems of the existing olefin polymerization catalyst, the invention provides a solid catalyst component of the olefin polymerization catalyst, a preparation method thereof, the olefin polymerization catalyst and an olefin polymerization method. The solid catalyst component has higher regularity and fewer broken particles, and the content of the fine powder of polyolefin prepared by catalyzing an olefin catalyst containing the solid catalyst component is also lower.
According to a first aspect of the present invention there is provided a solid catalyst component of an olefin polymerization catalyst, the solid catalyst component comprising polyethylene, polyalphaolefin, titanium, magnesium, chlorine and an internal electron donor compound; the polyethylene is 0.1 to 89 wt%, the poly alpha-olefin is 0.1 to 89 wt%, the titanium is 0.1 to 3.5 wt%, the magnesium is 1 to 16 wt%, the chlorine is 2 to 50 wt%, and the internal electron donor compound is 0.6 to 15 wt%, based on the total weight of the solid catalyst component; the internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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) 3 And R is 4 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
According to a second aspect of the present invention, there is provided a process for preparing a solid catalyst component of an olefin polymerization catalyst, the process 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 an internal electron donor compound;
The internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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 and C of (C) 7 -C 20 Is one of alkylaryl groups, R 3 And R is 4 Each independently selected from C 1 -C 10 Alkyl of (a);
(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 0.1-10:0.1-10:1.
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 an olefin polymerisation catalyst prepared by reacting a solid catalyst component according to the first or third aspect of the present invention, an alkyl aluminium 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 olefin polymerization catalyst.
The solid catalyst component provided by the invention is a prepolymerized catalyst and has the advantages of good regularity and less broken particles, so that the solid catalyst component can be applied to an olefin polymerization device with a prepolymerized operation unit or a polyolefin device without the prepolymerized operation unit. Further, the solid catalyst component is used for catalyzing the olefin polymerization to obtain a polymer with lower content of fine powder and better regularity.
Drawings
FIG. 1 is a photograph showing particles of a solid catalyst component prepared in example 1 of the present invention;
FIG. 2 is a photograph showing 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 of an olefin polymerization catalyst, the solid catalyst component comprising polyethylene, polyalphaolefin, titanium, magnesium, chlorine and an internal electron donor compound; the polyethylene is 0.1 to 89 wt%, the poly alpha-olefin is 0.1 to 89 wt%, the titanium is 0.1 to 3.5 wt%, the magnesium is 1 to 16 wt%, the chlorine is 2 to 50 wt%, and the internal electron donor compound is 0.6 to 15 wt%, based on the total weight of the solid catalyst component.
In the solid catalyst component of the present invention, the polyalphaolefin is preferably one or more of polypropylene, polybutene, polyoctene and polyisopentene. More preferably, the polyalphaolefin is polypropylene.
In the solid catalyst component, the internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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) 3 And R is 4 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
Preferably, the method comprises the steps of, 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.
In the solid catalyst component of the present invention, the internal electron donor compound may further include a carboxylate or phosphate compound.
The carboxylic acid ester is aliphatic carboxylic acid ester and/or aromatic carboxylic acid ester, and is specifically at least one selected from mono-aliphatic carboxylic acid ester, di-aliphatic carboxylic acid ester, mono-aromatic carboxylic acid ester and 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.
The structure of the phosphate compound is shown as a formula (2):
wherein R is 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
Preferably, the phosphate compound is at least one selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate and o-tolyl p-di-t-butylphenyl phosphate.
In the present invention, for convenience of description, the 1, 3-diether compound is also referred to as an internal electron donor a, and the carboxylate and phosphate compounds are collectively referred to as an internal electron donor b.
In the solid catalyst component of the present invention, in the case where the internal electron donor compound further includes the internal electron donor b, the ratio of the internal electron donors a and b may be selected within a wide range, for example, the mass ratio of the internal electron donor a to the internal electron donor b may be 0.1 to 1000:1.
the solid catalyst component of the present invention is spherical solid particles, preferably spherical solid particles having 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, preferably, the polyethylene is present in an amount of 1 to 50% by weight, the polyalphaolefin is present in an amount of 1 to 50% by weight, the titanium is present in an amount of 0.5 to 2% by weight, the magnesium is present in an amount of 1 to 16% by weight, the chlorine is present in an amount of 2 to 35% by weight, and the internal electron donor compound is present 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 present invention, the inclusion of titanium, magnesium and chlorine in the solid catalyst component means inclusion of magnesium element, titanium element and chlorine element, respectively. The content of each component in the solid catalyst component was measured as follows.
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; taking 2N H2SO4 solution as blank, measuring absorbance E1 of the cuvette with a thickness of 1cm at 410 μm wavelength, and dripping 1 drop of 30% H 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 of distilled water, adding a small amount of chrome black T indicator, shaking uniformly, titrating with 0.02N EDTA solution until the end point is changed from purple red to blue (purple light disappears), and calculating the magnesium content Mg (%) according to the following formula:
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
in the middle of：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.
Polyethylene, poly alpha-olefin content test method: 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 content of the internal electron donor compound comprises the following steps: the sample was dissolved with ethyl acetate and hydrochloric acid solution (concentration: 2 mol/L), and extracted to obtain an internal electron donor compound, the content of which was analyzed using a conventional liquid chromatograph.
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 of an olefin polymerization catalyst, the process 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 an internal electron donor compound;
(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 invention, the internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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) 3 And R is 4 Each independently selected from C 1 -C 10 Is a hydrocarbon group.
In the preparation method of the invention, the internal electron donor compound comprises carboxylic acid ester or phosphate ester compounds besides the 1, 3-diether compounds.
The structure of the phosphate compound is shown as a formula (2):
wherein R is 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
In the preparation method of the present invention, the specific descriptions of the 1, 3-diether compound, the carboxylic acid ester and the phosphate compound are as described in the first aspect of the present invention, and are not described herein.
In the production method of the present invention, 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. Typically, 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 process of the present invention, in the step (1), 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 used in such an amount that the mass concentration of the catalyst component A can be 5 to 50g/L.
In step (1), the conditions of the contact reaction include: the temperature may be 0-30deg.C, preferably 10-25deg.C; the time may be 5-30min, preferably 10-20min.
In the production method of the present invention, in the step (2), a polyalphaolefin can be obtained by the first polymerization reaction. The alpha-olefin is preferably one or more of propylene, butene, octene and isoamylene, and more preferably the alpha-olefin is propylene.
The conditions of the first polymerization reaction include: the temperature may be 0-30deg.C, preferably 10-25deg.C; the time may be 5-60min, preferably 10-20min. Preferably, step (2) further comprises removing unreacted α -olefin gas after the first polymerization reaction is completed.
In the production method of the present invention, in the step (3), polyethylene can be obtained by the second polymerization reaction.
The conditions of the second polymerization reaction include: the temperature may be 0-30deg.C, preferably 10-25deg.C; the time may be 5-60min, preferably 10-20min. Preferably, step (3) further comprises a post-treatment step after the second polymerization reaction is completed. The post-treatment step 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 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.
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 internal electron donor compound. 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 an internal electron donor compound 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.
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 an olefin polymerization catalyst prepared by reacting a solid catalyst component according to the present invention, an alkyl aluminium 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. The ratio of the molar amount of the aluminum alkyl to the molar amount of the external electron donor compound to the silicon element may be 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 olefin polymerization catalyst.
The general formula of the olefin is 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.
In the present invention, the conditions of the polymerization reaction may be selected conventionally in the art, for example, the reaction temperature is 0 to 150 ℃, preferably 60 to 90 ℃, and the reaction pressure is normal pressure or higher.
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 refers to the mass percent of the polymer 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 preparation examples are given to illustrate the preparation of catalyst component A.
Preparation example 1
Into a 3L glass reaction flask with stirring, 1.1L titanium tetrachloride was added and cooled to-20deg.C, and then 100g of magnesium chloride alkoxide spherical carrier [ Mg (C) was added under stirring 2 H 5 OH) 2.6 ](average particle size d50=45 μm, the same applies hereinafter), after reacting at-20 ℃ for 0.5 hours, slowly heating to 120 ℃, adding 15g of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and 0.6g of tributyl phosphate during the heating, then reacting at 120 ℃ for 0.5 hours, filtering off the liquid, adding 1L of titanium tetrachloride, filtering off the liquid after maintaining at 120 ℃ for 2 hours to obtain a solid product, washing the obtained solid product with hexane for 5 times, and finally drying in vacuo to obtain a catalyst component a (average particle size d50=40 μm), denoted as A1.
Preparation example 2
Into a 3L glass reaction flask with stirring, 1.2L titanium tetrachloride was added and cooled to-20deg.C, and then 100g of magnesium chloride alkoxide spherical carrier [ Mg (C) was added under stirring 2 H 5 OH) 2.6 ]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 for 0.5 hour at 120 ℃, filtering off liquid, adding 1L of titanium tetrachloride, and maintaining at 120 DEG C After 2 hours the liquid was filtered off to give a solid product, which was washed 5 times with hexane and finally dried in vacuo to give catalyst component a (average particle size d50=40 μm), designated A2.
Preparation example 3
Catalyst component A was prepared by following the procedure of preparation example 1, except that tributyl phosphate was replaced with an equal mass of diethyl 2, 3-diisopropylsuccinate, thereby producing catalyst component A, designated A3.
Preparation example 4
Into a 3L glass reaction flask with stirring, 1.2L titanium tetrachloride was added and cooled to-20deg.C, and then 100g of magnesium chloride alkoxide spherical carrier [ Mg (C) was added under stirring 2 H 5 OH) 2.6 ]After 0.5 hour of reaction at-20 ℃, 17g of 2, 2-diethyl-1, 3-dimethoxypropane and 2g of n-butyl benzoate were added during the temperature rise, then the reaction was carried out at 120 ℃ for 1 hour, the liquid was filtered off, 1L of titanium tetrachloride was added, after 2 hours at 120 ℃, the liquid was filtered off to obtain a solid product, the obtained solid product was washed 5 times with hexane, and finally dried under vacuum at 40 ℃ to obtain a catalyst component a (average particle size d50=41 μm), denoted as A4.
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 solid catalyst component
In a 5L autoclave, 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 10.0g of catalyst component A1 were added and reacted at 12℃for 10 minutes; then 16g of propylene was added and reacted at 12℃for 10 minutes, the unreacted propylene was vented; the autoclave was replaced with nitrogen, 10g of ethylene was added, and the reaction was carried out at 12℃for 10 minutes, followed by purging of unreacted ethylene. After filtering off the liquid in the reaction product, drying under vacuum gave solid catalyst component E-1 (average particle size d50=42 μm). The main component content of E-1 is shown in Table 1, and the particle morphology is shown in FIG. 1.
(2) Propylene polymerization
Into a 5L autoclave, 2.5mmol of triethylaluminum, 0.1mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 12mg 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 solid catalyst component
In a 5L autoclave, 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 10.9g of catalyst component A2 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-2 (average particle size d50=43 μm). The main component content of E-2 is shown in Table 1.
(2) Propylene polymerization
Into a 5L autoclave, 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 15mg of solid catalyst component E-2 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-2. The properties of polypropylene P-2 are shown in Table 2.
Example 3
(1) Preparation of solid catalyst component
A solid catalyst component was produced in the same manner as in example 1 except that the amount of propylene was adjusted from 16g to 10g and the amount of ethylene was adjusted from 10g to 16g, thereby producing solid catalyst component E-3. The main component content of E-3 is shown in Table 1.
(2) Propylene polymerization
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 polypropylene P-3 are shown in Table 2.
Example 4
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the amount of propylene was adjusted from 16g to 0.5g and the amount of ethylene was adjusted from 10g to 0.5g, thereby obtaining solid catalyst component E-4. The main component content of E-4 is shown in Table 1.
(2) Propylene polymerization
Propylene polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-4 from E-1 to obtain polypropylene P-4. The properties of polypropylene P-4 are shown in Table 2.
Example 5
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the amount of propylene was adjusted from 16g to 100g, thereby obtaining solid catalyst component E-5. The main component content of E-5 is shown in Table 1.
(2) Propylene polymerization
Propylene polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with E-5 from E-1 to obtain polypropylene P-5. The properties of polypropylene P-5 are shown in Table 2.
Example 6
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the catalyst component A1 was replaced with an equal mass of the catalyst component A3, thereby producing a solid catalyst component E-6. The main component content of E-6 is shown in Table 1.
(2) Propylene polymerization
Propylene polymerization was conducted in the same manner as in example 1 except that the solid catalyst component was replaced with E-6 from E-1, thereby producing polypropylene P-6. The properties of polypropylene P-6 are shown in Table 2.
Example 7
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the catalyst component A1 was replaced with an equal mass of the catalyst component A4, thereby producing a solid catalyst component E-7. The main component content of E-7 is shown in Table 1.
(2) Propylene polymerization
Propylene polymerization was conducted in the same manner as in example 1 except that the solid catalyst component was replaced with E-7 from E-1, thereby obtaining polypropylene P-7. The properties of polypropylene P-7 are shown in Table 2.
Comparative example 1
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the amount of propylene was adjusted from 16g to 0g, that is, polymerization was carried out without adding propylene, and the amount of ethylene was adjusted from 10g to 26g, 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.
(2) Propylene polymerization
Propylene polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with DE-1 from E-1, thereby obtaining polypropylene DP-1. The properties of polypropylene DP-1 are shown in Table 2.
Comparative example 2
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the amount of propylene was adjusted from 16g to 26g and the amount of ethylene was adjusted from 10g to 0g, i.e., polymerization was carried out without adding ethylene, to thereby obtain a solid catalyst component DE-2. The main component content of DE-2 is shown in Table 1.
(2) Propylene polymerization
Propylene polymerization was carried out in the same manner as in example 1 except that the solid catalyst component was replaced with DE-2 from E-1, thereby obtaining 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 contents refer to mass percent.
TABLE 2
Comparing fig. 1 and fig. 2, it can be seen that the solid catalyst component provided by the invention has significantly better regularity and less broken particles. As can be seen from Table 2, the olefin polymerization catalyst containing the solid catalyst component gave a polypropylene having a low content of fine powder obtained by catalyzing propylene polymerization, and hardly had fine powder having a particle diameter of less than 0.18 mm. In addition, although the product of comparative example 2 has a small content of fine powder, the activity of the catalyst is too low to meet the requirements for industrial production.
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 (33)
1. A solid catalyst component for an olefin polymerization catalyst, characterized in that the solid catalyst component comprises polyethylene, poly-alpha-olefin, titanium, magnesium, chlorine and an internal electron donor compound; based on the total weight of the solid catalyst component, the polyethylene accounts for 1-50 wt%, the poly alpha-olefin accounts for 1-50 wt%, the titanium accounts for 0.5-2.2 wt%, the magnesium accounts for 1-18 wt%, the chlorine accounts for 2-35 wt%, and the internal electron donor compound accounts for 1-10.5 wt%; the internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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) 3 And R is 4 Each independently selected from C 1 -C 10 Alkyl of (a);
the mass ratio of the poly alpha-olefin to the polyethylene is 0.1-10:1, a step of;
the poly alpha-olefin is polypropylene and/or polybutene.
2. The solid catalyst component according to claim 1 in which the polyalphaolefin is polypropylene.
3. The solid catalyst component according to claim 1 or 2, wherein, 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, 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-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-sec-butyl-2-isopropyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-sec-butyl-isopropyl-1, 3-dimethoxypropane, at least one of 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.
4. The solid catalyst component according to claim 1 or 2, wherein the internal electron donor compound further comprises a carboxylate or phosphate compound; the structure of the phosphate compound is shown as a formula (2):
in the formula (2), R 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
5. The solid catalyst component according to claim 4 in which the phosphate compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate and o-tolyl p-di-t-butylphenyl phosphate; and/or
The carboxylic acid ester is 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.
6. The solid catalyst component according to claim 5, wherein the carboxylic acid ester is one or more of benzoate, succinate and phthalate;
wherein the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
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, 3-diisopropyl succinate, diisobutyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate;
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.
7. The solid catalyst component according to claim 3 in which the internal electron donor compound further comprises a carboxylate or phosphate compound; the structure of the phosphate compound is shown as a formula (2):
In the formula (2), R 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
8. The solid catalyst component according to claim 7 in which the phosphate compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate and o-tolyl p-di-t-butylphenyl phosphate; and/or
The carboxylic acid ester is 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.
9. The solid catalyst component according to claim 8, wherein the carboxylic acid ester is one or more of benzoate, succinate and phthalate;
Wherein the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
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, 3-diisopropyl succinate, diisobutyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate;
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.
10. The solid catalyst component according to any one of claims 1-2, 5-9, wherein the solid catalyst component is a spherical solid particle having an average particle size of 20-80 μm.
11. A solid catalyst component according to claim 3, wherein the solid catalyst component is a spherical solid particle having an average particle size of 20-80 μm.
12. The solid catalyst component according to claim 4, wherein the solid catalyst component is spherical solid particles having an average particle size of 20 to 80 μm.
13. A process for preparing a solid catalyst component for an olefin polymerization catalyst according to any one of claims 1 to 12, characterized in that the process comprises:
(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 an internal electron donor compound;
the internal electron donor compound comprises a 1, 3-diether compound, and the structure of the 1, 3-diether compound is shown as a formula (1):
wherein R is 1 And R is 2 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) 3 And R is 4 Each independently selected from C 1 -C 10 Alkyl of (a);
(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 poly alpha-olefin is polypropylene and/or polybutene.
14. The process of claim 13, wherein the alpha-olefin is propylene.
15. The production method according to claim 13 or 14, 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 5-60min; and/or
In step (3), the conditions of the second polymerization reaction include: the temperature is 0-30deg.C, and the time is 5-60min.
16. The production method according to claim 15, wherein in the step (1), the conditions of the contact reaction include: the temperature is 10-25deg.C, and the time is 10-20min; and/or
In step (2), the conditions of the first polymerization reaction include: the temperature is 10-25deg.C, and the time is 10-20min; and/or
In step (3), the conditions of the second polymerization reaction include: the temperature is 10-25deg.C, and the time is 10-20min.
17. The process according to any one of claims 13 to 14, 16, wherein, 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, 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-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-sec-butyl-2-isopropyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-sec-butyl-isopropyl-1, 3-dimethoxypropane, at least one of 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.
18. The process according to claim 15, wherein, 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, 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-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-sec-butyl-2-isopropyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-sec-butyl-isopropyl-1, 3-dimethoxypropane, at least one of 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.
19. The production method according to any one of claims 13 to 14, 16, 18, wherein the internal electron donor compound further comprises a carboxylic acid ester or a phosphoric acid ester compound; the structure of the phosphate compound is shown as a formula (2):
in the formula (2), R 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
20. The production method according to claim 19, wherein the phosphate compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate, and o-tolyl p-di-t-butylphenyl phosphate; and/or
The carboxylic acid ester is 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.
21. The preparation method of claim 20, wherein the carboxylic acid ester is one or more of benzoate, succinate and phthalate;
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.
22. The preparation method of claim 15, wherein the internal electron donor compound further comprises a carboxylate or phosphate compound; the structure of the phosphate compound is shown as a formula (2):
In the formula (2), R 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
23. The production method according to claim 22, wherein the phosphate compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate, and o-tolyl p-di-t-butylphenyl phosphate; and/or
The carboxylic acid ester is 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.
24. The preparation method of claim 23, wherein the carboxylic acid ester is one or more of benzoate, succinate and phthalate;
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.
25. The preparation method of claim 17, wherein the internal electron donor compound further comprises a carboxylate or phosphate compound; the structure of the phosphate compound is shown as a formula (2):
in the formula (2), R 5 、R 6 And R is 7 Each independently selected from C 1 -C 4 Straight 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 An aralkyl group of (a).
26. The production method according to claim 25, wherein the phosphate compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropyl phenyl dimethyl phosphate, isopropyl phenyl diethyl phosphate, isopropyl phenyl dibutyl phosphate, phenyl xylene phosphate, phenyl diisopropyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropyl phenyl dimethyl phosphate, p-isopropyl phenyl diethyl phosphate, p-t-butylphenyl dimethyl phosphate, and o-tolyl p-di-t-butylphenyl phosphate; and/or
The carboxylic acid ester is 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.
27. The preparation method of claim 26, wherein the carboxylic acid ester is one or more of benzoate, succinate and phthalate;
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.
28. The production method according to any one of claims 13 to 14, 16, 18, 20 to 27, wherein the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the internal electron donor compound.
29. The method of preparing according to claim 15, wherein the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the internal electron donor compound.
30. The method of preparing according to claim 17, wherein the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the internal electron donor compound.
31. The method of claim 19, wherein the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the internal electron donor compound.
32. An olefin polymerization catalyst prepared by reacting the solid catalyst component of any one of claims 1-12, an alkyl aluminum and optionally an external electron donor compound.
33. A process for the polymerization of olefins, comprising: polymerizing at least one olefin in the presence of the olefin polymerization catalyst of claim 32.
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