A method for preparing highly isotactic polybutene-1

Abstract

The present invention belongs to the technical field of polymer preparation and discloses a method for preparing high isotactic polybutene-1, which comprises: preparing butene-1 and optionally C2-C 10 The invention relates to a polymerization reaction of alpha-olefin monomers in the presence of a Ziegler-Natta catalyst system; the catalyst system comprises a solid catalyst component, an organoaluminum compound, and an external electron donor; the solid catalyst component comprises the reaction product of alkoxymagnesium particles, an internal electron donor, and a titanium-containing halide; the internal electron donor comprises an organosilicon compound containing a Si-H functional group, a diether compound, and other types of internal electron donor compounds; the other types of internal electron donor compounds are selected from at least one of carboxylic acid ester compounds, polyol ester compounds, and cyanosuccinate compounds. The invention has high polymerization activity and the resulting polymer has high isotacticity.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer preparation, and in particular relates to a method for preparing highly isotactic polybutene-1. Background Art

[0002] Polybutene-1 is a polymorphic polymer, with the highly isotactic Type I crystal form exhibiting excellent overall physical properties and creep resistance. It is widely used in areas such as easy-open films, hot-melt adhesives, plastic modification, high-end pressure-resistant pipes, and electromechanical components. It holds a particularly high position in the pipe market. However, due to its complex production process and the difficulty in controlling the product structure, its market share has been limited, resulting in a relatively small industry scale.

[0003] Currently, there are three main methods for preparing polybutene-1: gas-phase, slurry, and bulk. The gas-phase method suffers from low polymerization activity. Montel Technologies Co., Ltd.'s patent document 99800235.6 describes a gas-phase polymerization using a ZN catalytic system. Polymerization was performed in a first gas-phase reactor at 60°C for 11 hours, yielding 1.4 kg PB / g catalyst. Polymerization was then continued in a second gas-phase reactor at 70°C for 9 hours, yielding 5 kg PB / g catalyst. This low polymerization activity results in a high ash content in the product, making it of low industrial value.

[0004] Slurry polymerization using inert solvents is widely used in the polyolefin industry. This process allows viscous solubles in the polymer to dissolve in the solvent for further separation and removal, resulting in a high-quality polymer product while also reducing the risk of polymer adhesion. However, polybutene-1 has a high solubility in the inert solvents used in conventional slurry reactions, and at high reaction temperatures, it forms a homogeneous solution system. Patent US5237013 from Idemitsu Corporation of Japan uses n-hexane as a solvent to achieve solution polymerization of butene-1. However, this method has significant drawbacks, including the need for large amounts of solvent recovery, complex process, low efficiency, and high cost.

[0005] Bulk polymerization is currently the predominant method for producing polybutene-1. Qingdao University of Science and Technology has conducted extensive research on the synthesis of polybutene-1. Patent document 200710013587.X provides a bulk precipitation method for the synthesis of highly isotactic polybutene-1. Using a ZN catalyst system, bulk polymerization is performed at 50°C, resulting in a polymer with an isotacticity exceeding 98%, allowing direct production of powdered polybutene-1. However, due to the limited reaction temperature, the polymerization activity is relatively low. Basell's patent document 03800736.3, using a ZN catalyst system, bulk polymerization is performed at 70-75°C, achieving a polymerization activity of 50 kgPB / gcat.·2h and a polymer isotacticity of up to 99%.

[0006] Patent document 201210422461.9 from the Beijing Research Institute of Chemical Industry uses a high-temperature bulk solution method for butene-1 polymerization. The difference is that a ZN catalyst containing a glycol ester is used as the main catalyst. After pretreatment with an alkyl aluminum and an external electron donor, the butene-1 polymerization is carried out. This produces a highly active, highly isotactic polybutene-1 product. The polymerization activity can reach 30 kgPB / gcat.·h, and the polymer isotacticity exceeds 98%. Summary of the Invention

[0007] The inventors of the present invention have discovered through research that a catalyst system consisting of alkoxymagnesium particles prepared by reacting metallic magnesium with a mixed alcohol, a halogenating agent, and a cross-linking agent as a carrier, an organosilicon compound containing Si-H functional groups, a diether compound, and one or more other types of internal electron donor compounds as internal electron donors, combined with an organoaluminum compound and an external electron donor, has the characteristics of high polymerization activity, good hydrogen regulation sensitivity, high isotactic index, and no need for deashing when butene-1 is polymerized under high-temperature bulk conditions. Based on this, the purpose of the present invention is to provide a method for preparing highly isotactic polybutene-1.

[0008] The present invention provides a method for preparing high isotactic polybutene-1, which comprises: preparing butene-1 and optionally C2-C 10 The α-olefin monomers are polymerized under the action of Ziegler-Natta catalyst system;

[0009] The Ziegler-Natta catalyst system comprises a solid catalyst component, an organoaluminum compound and an external electron donor; the solid catalyst component comprises a reaction product of alkoxymagnesium particles, an internal electron donor and a titanium-containing halide; the internal electron donor comprises an organosilicon compound containing a Si-H functional group, a diether compound and other types of internal electron donor compounds, and the other types of internal electron donor compounds are selected from at least one of carboxylic acid ester compounds, polyol ester compounds and cyanosuccinate compounds;

[0010] The polymerization reaction conditions include: a polymerization temperature of 0-150° C., preferably 40-100° C.; and a polymerization pressure higher than the saturated vapor pressure of butene-1 at the corresponding polymerization temperature.

[0011] Compared with the prior art, the present invention has the following beneficial effects:

[0012] The preparation method of the present invention has high polymerization activity, which can reach up to 49.6 kgPB / gcat·h. The obtained polybutene-1 has high isotacticity, which can reach up to 99.3 wt%, good hydrogen adjustment sensitivity, and can produce a polymer with a higher melt flow rate.

[0013] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0014] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0015] According to the present invention, a method for preparing high isotactic polybutene-1 is provided, which comprises: preparing butene-1 and optionally C2-C 10 The α-olefin monomers are polymerized under the action of Ziegler-Natta catalyst system;

[0016] The Ziegler-Natta catalyst system comprises a solid catalyst component, an organoaluminum compound and an external electron donor; the solid catalyst component comprises a reaction product of alkoxymagnesium particles, an internal electron donor and a titanium-containing halide; the internal electron donor comprises an organosilicon compound containing a Si-H functional group, a diether compound and other types of internal electron donor compounds, and the other types of internal electron donor compounds are selected from at least one of carboxylic acid ester compounds, polyol ester compounds and cyanosuccinate compounds;

[0017] The polymerization reaction conditions include: a polymerization temperature of 0-150°C, preferably 40-100°C; and a polymerization pressure higher than the saturated vapor pressure of butene-1 at the corresponding polymerization temperature. It is easy to understand that the polymerization pressure should be lower than the pressure that the equipment can withstand.

[0018] According to the present invention, the alkoxy magnesium particles contain the reaction product of magnesium powder, mixed alcohol, halogenating agent and cross-linking agent, and the specific reaction materials are as follows:

[0019] The magnesium powder has no specific shape restrictions as long as it ensures good reaction performance. To ensure good reaction performance, the magnesium powder is preferably spherical with an average particle size of 360 μm or less. To ensure high reaction speed, the oxide film thickness of the magnesium powder is preferably less than 0.5 μm.

[0020] The mixed alcohol can be a linear or branched monohydric alcohol or polyhydric alcohol, preferably C1-C 10The mixture of alcohols, for example, the mixed alcohol can be selected from methanol, ethanol, n-propyl alcohol, n-butyl alcohol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propyl alcohol, 2-butyl alcohol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3,3,5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, glycerol etc. The mixed alcohol is more preferably a mixture of ethanol and isooctyl alcohol, wherein ethanol accounts for 80-99wt%, and isooctyl alcohol accounts for 1-20wt%. In order to obtain good alkoxy magnesium particles performance, the less moisture content in the raw material, the better. The water content in the alcohol is generally controlled to be below 1000ppm, and preferably the water content is below 200ppm.

[0021] The molar ratio of the mixed alcohol to the magnesium powder is preferably (2-50):1, more preferably (2.5-18):1.

[0022] The halogenating agent can be a halogen element and / or an inorganic halide, preferably selected from at least one of iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide and alkoxymagnesium halide, more preferably selected from at least one of iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halide, particularly preferably a mixture of iodine and magnesium chloride. In addition, iodine or magnesium chloride can be used in the reaction in pure form or in the form of a solution; iodine and magnesium chloride can be added to the reaction system separately, or part or all of them can be mixed together and added to the reaction system.

[0023] The amount of halogenating agent added affects the morphology and particle size of the final alkoxymagnesium particles. When the amount of halogenating agent used is too small, the resulting alkoxymagnesium particles have extremely poor morphology. If the amount of halogenating agent used is too large, not only will the cost of preparing the alkoxymagnesium particles increase, but the size of the alkoxymagnesium particles will also be very uneven, making the reaction difficult to control. The molar ratio of the halogen atoms in the halogenating agent to the magnesium powder can be (0.0002-0.2):1, preferably (0.0025-0.05):1.

[0024] The cross-linking agent is a titanate compound. Specifically, the structure of the titanate compound is shown in Formula I:

[0025] (R5'O) a Ti(OR6) b (OR7') c X d Formula I

[0026] In formula I, R5', R6' and R7' are the same or different and are each selected from H or alkyl, preferably selected from C1-C 10wherein X is selected from alkoxy, carboxyl, chlorine, sulfonic acid, phosphoric acid or sulfate, a, b, c and d are independently integers of 0-4, and a+b+c+d=4.

[0027] The titanate compound is preferably selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate and their isomers; more preferably at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

[0028] The weight ratio of the titanate compound to the magnesium powder is preferably (0.01-5):1, more preferably (0.02-2):1.

[0029] In the present invention, the organosilicon compound containing Si-H functional groups is selected from the organosilicon compounds shown in formula II and / or formula III.

[0030]

[0031] In Formula II, R 1 -R 7 The same or different, each selected from C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl, C3-C 10 Cycloalkyl, C7-C 20 Alkaryl, substituted or unsubstituted C6-C 20 The aromatic hydrocarbon group, the degree of polymerization m is an integer of 2-100; preferably, R 1 is selected from C1-C6 straight chain alkyl, C3-C6 branched chain alkyl, C3-C6 cycloalkyl, aryl, R 2 -R 7 is methyl;

[0032]

[0033] In formula III, R 8 Selected from C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl, C3-C 10 Cycloalkyl, C7-C 20 Alkaryl, substituted or unsubstituted C6-C 20 Aromatic hydrocarbon group, the degree of polymerization n is an integer of 3-20; R 8 Preferably C1-C 12 Straight chain alkyl, C3-C 12 The degree of polymerization n is preferably an integer of 3-8.

[0034] Specific examples of the organosilicon compound represented by Formula II include, but are not limited to, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, and polycyclohexylhydrogensiloxane. These polymethylhydrogensiloxanes, also known as hydrogen-containing silicone oils, have different number average molecular weights and viscosities due to differences in average degree of polymerization (m value), but all possess the functions and effects of the present invention and are preferred examples of the organosilicon compound represented by Formula II of the present invention. For example, polymethylhydrogensiloxanes having a number average molecular weight Mn = 1700-3200 (m = 29-55, viscosity 12-45 cSt, Sigma-Aldrich) and Mn≈390 (m≈6, Sigma-Aldrich) are preferred examples of the organosilicon compound represented by Formula II of the present invention.

[0035] Specific examples of the organosilicon compound represented by Formula III include, but are not limited to, tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane.

[0036] The organosilicon compounds represented by formula II and formula III can be used alone or in combination. The organosilicon compounds represented by formula II and formula III used in the present invention can be commercially obtained or prepared by chemical reactions such as alkylation and condensation of corresponding precursor compounds.

[0037] The molar ratio of the organic silicon compound containing Si—H functional groups to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0038] According to the present invention, the diether compound is selected from 1,3-diether compounds as shown in Formula IV.

[0039]

[0040] In Formula IV, R 1” and R 2” The same or different, each selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl; R 4” and R 5” The same or different, each selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkaryl; R 3” and R 6” the same or different, each selected from hydrogen, C1-C 10 Straight chain alkyl, C3-C10 branched alkyl.

[0041] The diether compounds specifically include but are not limited to: 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-dimethoxy 1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-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-dimethoxy Propane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-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-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-dimethoxymethylfluorene.The diether compound is preferably at least one of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyldimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane and 2,2-diisobutyl-1,3-dimethoxypropane, more preferably 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene.

[0042] The molar ratio of the diether compound to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0043] In the present invention, the carboxylic acid ester compound can be selected from benzoic acid monoester compounds or phthalate compounds as shown in Formula V.

[0044]

[0045] In formula V, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl, C3-C 10 Cycloalkyl or C6-C 20 R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy, preferably, at least three of R3-R6 are hydrogen.

[0046] Specifically, the carboxylic acid ester compound can be selected from ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisobutyl ... At least one of dinonyl phthalate, didecyl phthalate, ethyl methyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethylhexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propylhexyl phthalate, butyl pentyl phthalate, butylhexyl phthalate, pentylhexyl phthalate, and isomers thereof.

[0047] According to the present invention, the polyol ester compound is selected from the diol ester compound having a structure as shown in Formula VI,

[0048]

[0049] In Formula VI, R 1’ and R 2’ the same or different, each selected from substituted or unsubstituted C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkaryl, C7-C 20 Aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused ring aromatic group; R 3’ -R 8’ the same or different, each selected from hydrogen, halogen, substituted or unsubstituted C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkaryl, C7-C 20 Aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused ring aromatic group; or R 3’ -R 6’ At least one of them is related to R 7’ -R 8’ At least one of them forms a ring.

[0050] The diol ester compounds specifically include but are not limited to: 2-ethyl-1,3-propylene glycol dibenzoate, 2-propyl-1,3-propylene glycol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propylene glycol dibenzoate, 1,3-butanediol dimethyl benzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dipivalate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, etc. The diol ester compound is preferably at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate and 2,4-pentanediol dibenzoate.

[0051] The structure of the cyanosuccinate compound is shown in Formula VII.

[0052]

[0053] In formula VII, R1′ and R2′ are the same or different and are independently selected from hydrogen, C1-C 14 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkaryl and C7-C 10 The aralkyl groups are independently selected from hydrogen, C1-C8 straight chain alkyl groups and C3-C8 branched chain alkyl groups; R3′ and R4′ are the same or different and are independently selected from C1-C 14 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkaryl and C7-C 20 The aralkyl groups are each independently preferably selected from C1-C6 straight-chain alkyl groups and C3-C6 branched-chain alkyl groups.

[0054] Specifically, the cyano succinate compound can be selected from at least one of the following compounds: dimethyl 2-cyano-2,3-diisopropylsuccinate, diethyl 2-cyano-2,3-diisopropylsuccinate, diethyl 2-cyano-2,3-dimethylsuccinate, diethyl 2-cyano-2,3-diethylsuccinate, diethyl 2-cyano-2,3-di-n-propylsuccinate, diethyl 2-cyano-2,3-di-n-butylsuccinate, diethyl 2-cyano-2,3-di-n-pentylsuccinate, diethyl 2-cyano-2,3-diisopentylsuccinate, diethyl 2-cyano-2,3-di-n-hexylsuccinate, diethyl 2-cyano-2,3-diisohexylsuccinate, di-n-propyl 2-cyano-2,3-diisopropylsuccinate , diisopropyl 2-cyano-2,3-diisopropylsuccinate, di-n-butyl 2-cyano-2,3-diisopropylsuccinate, diisobutyl 2-cyano-2,3-diisopropylsuccinate, 4-ethyl 1-methyl 2-cyano-2,3-diisopropylsuccinate (R4′=methyl, R3′=ethyl), 4-methyl 1-ethyl 2-cyano-2,3-diisopropylsuccinate (R4′=ethyl, R3′=methyl), 4-ethyl 1-n-butyl 2-cyano-2,3-diisopropylsuccinate (R4′=n-butyl, R3′=ethyl), 4-n-butyl 1-ethyl 2-cyano-2,3-diisopropylsuccinate (R4′=ethyl, R3′=n-butyl), 2-cyano-2,3-diisopropylsuccinate Dimethyl succinate, diethyl 2-cyano-2,3-diisobutylsuccinate, di-n-propyl 2-cyano-2,3-diisobutylsuccinate, diisopropyl 2-cyano-2,3-diisobutylsuccinate, di-n-butyl 2-cyano-2,3-diisobutylsuccinate, diisobutyl 2-cyano-2,3-diisobutylsuccinate, 1-methyl-4-ethyl 2-cyano-2,3-diisobutylsuccinate (R4′=methyl, R3′=ethyl), 1-ethyl-4-methyl 2-isobutyl-2,3-diisobutylsuccinate (R4′=ethyl, R3′=methyl), 1-n-butyl-4-ethyl 2-cyano-2,3-diisobutylsuccinate (R4′=n-butyl, R3′=ethyl), 2-cyano-2,3-diisobutylsuccinate Isobutyl-1-ethyl-4-n-butyl succinate (R4′=ethyl, R3′=n-butyl), dimethyl 2-cyano-2,3-di-sec-butylsuccinate, diethyl 2-cyano-2,3-di-sec-butylsuccinate, di-n-propyl 2-cyano-2,3-di-sec-butylsuccinate, diisopropyl 2-cyano-2,3-di-sec-butylsuccinate, di-n-butyl 2-cyano-2,3-di-sec-butylsuccinate, diisobutyl 2-cyano-2,3-di-sec-butylsuccinate, 4-ethyl 1-methyl 2-cyano-2,3-di-sec-butylsuccinate (R4′=methyl, R3′=ethyl), 4-methyl 1-ethyl 2-cyano-2,3-di-sec-butylsuccinate (R4′=ethyl, R3′=methyl), 2-cyano-2,1-n-butyl-4-ethyl-3-di-sec-butylsuccinate (R4′=n-butyl, R3′=ethyl), 1-ethyl-2-cyano-2,3-di-sec-butylsuccinate-4-n-butyl (R4′=ethyl, R3′=n-butyl), dimethyl 2-cyano-2,3-dicyclopentylsuccinate, diethyl 2-cyano-2,3-dicyclopentylsuccinate, di-n-propyl 2-cyano-2,3-dicyclopentylsuccinate, diisopropyl 2-cyano-2,3-dicyclopentylsuccinate, 2,3-dicyclopentylsuccinic acid di-n-butyl ester, 2-cyano-2,3-dicyclopentylsuccinic acid diisobutyl ester, 2-cyano-2,3-dicyclopentylsuccinic acid-1-methyl-4-ethyl ester (R4′=methyl, R3′=ethyl), 2-cyano-2,3-dicyclopentylsuccinic acid-1-ethyl-4-methyl ester (R4′=ethyl, R3′=methyl), 2-cyano-2,3-dicyclopentylsuccinic acid-1-n-butyl-4-ethyl ester (R4′=n-butyl, R3′=ethyl), 2-cyano-2,3-dicyclopentylsuccinic acid -2,3-dicyclopentylsuccinic acid-1-ethyl-4-n-butyl ester (R4′=ethyl, R3′=n-butyl), 2-cyano-2,3-dicyclohexylsuccinic acid dimethyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diethyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid di-n-propyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diisopropyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid di-n-butyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid diisobutyl ester, 2-cyano-2,3-dicyclohexylsuccinic acid di-n-butyl ester 4-ethyl-1-methyl-2,3-dicyclohexylsuccinate (R4′=methyl, R3′=ethyl), 4-methyl-1-ethyl-2-cyano-2,3-dicyclohexylsuccinate (R4′=ethyl, R3′=methyl), 4-ethyl-1-n-butyl-2-cyano-2,3-dicyclohexylsuccinate (R4′=n-butyl, R3′=ethyl), 4-n-butyl-1-ethyl-2-cyano-2,3-dicyclohexylsuccinate (R4′=ethyl, R3′=n-butyl);

[0055] diethyl 2-cyano-2-methyl-3-ethylsuccinate, diethyl 2-cyano-2-methyl-3-n-propylsuccinate, diethyl 2-cyano-2-methyl-3-isopropylsuccinate, diethyl 2-cyano-2-methyl-3-n-butylsuccinate, diethyl 2-cyano-2-methyl-3-isobutylsuccinate, diethyl 2-cyano-2-methyl-3-n-pentylsuccinate, diethyl 2-cyano-2-methyl-3-isopentylsuccinate, diethyl 2-cyano-2-methyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-methyl-3-n-hexylsuccinate, diethyl 2-cyano-2-methyl-3-isohexylsuccinate;

[0056] Diethyl 2-cyano-2-ethyl-3-methylsuccinate, diethyl 2-cyano-2-ethyl-3-n-propylsuccinate, diethyl 2-cyano-2-ethyl-3-isopropylsuccinate, ethyl 2-cyano-2-ethyl-3-n-butylsuccinate, diethyl 2-cyano-2-ethyl-3-isobutylsuccinate, diethyl 2-cyano-2-ethyl-3-n-pentylsuccinate, diethyl 2-cyano-2-ethyl-3-isopentylsuccinate, diethyl 2-cyano-2-ethyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-ethyl-3-n-hexylsuccinate, diethyl 2-cyano-2-ethyl-3-isohexylsuccinate;

[0057] Diethyl 2-cyano-2-n-propyl-3-methylsuccinate, diethyl 2-cyano-2-n-propyl-3-ethylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-propyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-hexylsuccinate, and diethyl 2-cyano-2-n-propyl-3-isohexylsuccinate;

[0058] Diethyl 2-cyano-2-isopropyl-3-methylsuccinate, ethyl 2-cyano-2-isopropyl-3-ethylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopropyl-3-isobutylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopropyl-3-isopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopropyl-3-isohexylsuccinate;

[0059] diethyl 2-cyano-2-n-butyl-3-methylsuccinate, diethyl 2-cyano-2-n-butyl-3-ethylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-butyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-hexylsuccinate, and diethyl 2-cyano-2-n-butyl-3-isohexylsuccinate;

[0060] Diethyl 2-cyano-2-isobutyl-3-methylsuccinate, diethyl 2-cyano-2-isobutyl-3-ethylsuccinate, monoethyl 2-hydroxy-2-isobutyl-3-n-propylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopropylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-butylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isobutyl-3-isohexylsuccinate;

[0061] Diethyl 2-cyano-2-n-pentyl-3-methylsuccinate, ethyl 2-cyano-2-n-pentyl-3-ethylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isohexylsuccinate;

[0062] diethyl 2-cyano-2-isopentyl-3-methylsuccinate, diethyl 2-cyano-2-isopentyl-3-ethylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopentyl-3-isopropylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopentyl-3-isobutylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopentyl-3-isohexylsuccinate;

[0063] Diethyl 2-cyano-2-cyclopentyl-3-methylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-ethylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopropylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isobutylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isohexylsuccinate;

[0064] Diethyl 2-cyano-2-n-hexyl-3-methylsuccinate, diethyl 2-cyano-2-n-hexyl-3-ethylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-hexyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-hexyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-hexyl-3-cyclopentylsuccinate, and diethyl 2-cyano-2-n-hexyl-3-isohexylsuccinate;

[0065] Diethyl 2-cyano-2-isohexyl-3-methylsuccinate, diethyl 2-cyano-2-isohexyl-3-ethylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-propylsuccinate, diethyl 2-cyano-2-isohexyl-3-isopropylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-butylsuccinate, diethyl 2-cyano-2-isohexyl-3-isobutylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isohexyl-3-isopentylsuccinate, diethyl 2-cyano-2-isohexyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-hexylsuccinate.

[0066] The molar ratio of the other type of internal electron donor compound to the magnesium in the alkoxymagnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0067] According to the present invention, the structure of the titanium-containing halide is shown in Formula VIII,

[0068] TiX 1 e (OR7) 4-e Formula VIII

[0069] In Formula VIII, X 1 is halogen, preferably chlorine, R7 is C1-C 20 The hydrocarbon group is preferably a C1-C5 alkyl group, and e is an integer of 0-4.

[0070] The amount of the titanium-containing halide used can be determined according to prior art and needs.

[0071] In the present invention, the titanium content in the solid catalyst component is 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%; the magnesium atom content is 10wt%-70wt%, preferably 15wt%-40wt%; the halogen atom content is 20wt%-86wt%, preferably 36wt%-80wt%; and the total content of internal electron donors is 2wt%-30wt%, preferably 3wt%-20wt%.

[0072] The preparation of the solid catalyst component of the present invention can be carried out by conventional methods in the prior art, specifically the following method: alkoxymagnesium particles are dispersed with an inert diluent and contacted with an internal electron donor and a titanium-containing halide to obtain a catalyst mother liquor. The solid matter in the mother liquor is filtered, titanium-treated, filtered again, washed, dried, and other treatments to obtain the solid catalyst component. The inert diluent can be at least one of n-hexane, n-heptane, n-octane, n-decane, benzene, toluene, and xylene, and the specific amount thereof is determined according to needs. The contact temperature of each component is generally -40°C to 200°C, preferably -20°C to 150°C, and the contact time is 1 minute to 20 hours, preferably 5 minutes to 8 hours. The number of titanium treatments is 0 to 10 times, preferably 1 to 5 times.

[0073] According to the present invention, the organic aluminum compound can be selected from alkyl aluminum compounds, preferably from trialkyl aluminum, specifically from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexylaluminum, tri-n-butyl aluminum, tri(2-methyl-3-phenyl-butyl) aluminum, tri(2-phenyl-butyl) aluminum, etc.

[0074] The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component may be (10-500):1, preferably (25-100):1.

[0075] In the present invention, the external electron donor can be selected from ethers, esters and silane compounds, and is preferably selected from silane compounds.

[0076] The silane compound can be specifically selected from at least one of tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

[0077] The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1:(1-100), preferably 1:(10-60).

[0078] According to the present invention, before the components of the Ziegler-Natta catalyst system enter the polymerization reactor, they can optionally undergo a pre-complexation treatment, and the solid catalyst component, the organoaluminum compound and the external electron donor undergo a pre-complexation reaction before being sent to the polymerization reactor. The benefit of the pre-complexation treatment is that it can improve the polymerization activity and stereospecificity of the catalyst system. Preferably, the Ziegler-Natta catalyst system is used in the polymerization reaction after the pre-complexation treatment. The temperature of the pre-complexation treatment is -10°C to 60°C, preferably 0-30°C, and the time of the pre-complexation treatment is 0.1-180min, preferably 5-30min. The pre-complexation treatment can be carried out in a continuous stirred tank reactor, or in other containers that can achieve a sufficient mixing effect, such as a loop reactor, a section of pipeline containing a static mixer, or even a section of pipeline where the material is in a turbulent state.

[0079] In the present invention, the polymerization reaction can be carried out in an inert organic solvent or liquid butene-1. Preferably, the polymerization reaction is carried out in liquid butene-1. The inert organic solvent can be a conventional inert organic solvent in the art, specifically n-hexane, isobutane, n-pentane, propane, isopentane, etc.

[0080] The polymerization monomers may be butene-1 and optionally C2-C 10 α-olefin monomers, that is, the polymerization reaction is the homopolymerization of butene-1 or the polymerization of butene-1 with other C2-C 10 Random copolymerization of alpha olefins.

[0081] Additionally, hydrogen can be introduced during the polymerization process as a molecular weight regulator. The partial pressure of hydrogen can be adjusted within the range of 0-2 MPa. As the hydrogen partial pressure increases, the intrinsic viscosity of the polymer decreases, and accordingly, the molecular weight of the polymer also decreases. In addition to regulating the molecular weight of the polymer, an appropriate amount of hydrogen can also enhance polymerization activity and improve the orientation of the active centers, thereby increasing the polymer's isotacticity. However, excessive hydrogen can reduce both activity and isotacticity.

[0082] In the present invention, the polymerization reaction can be carried out continuously or intermittently. Continuous polymerization can be carried out in two or more liquid phase reactors connected in series, and the liquid phase reactor can be a loop reactor or a stirred tank reactor.

[0083] According to the present invention, the preparation method comprises discharging the polymerization reaction product into hot water, introducing steam to remove unreacted monomers, filtering the resulting solid, and drying the solid to obtain polybutene-1. The removed unreacted monomers are then distilled and recycled. The dried polymer can be extruded and granulated. During granulation, additives commonly used in the art, such as antioxidants, light stabilizers, heat stabilizers, colorants, and fillers, are typically added.

[0084] In the present invention, the "high isotacticity" refers to an isotacticity of 95 wt% or more, and particularly 97 wt% or more.

[0085] The materials, equipment and process parameters not limited in the present invention can be selected according to the existing technology and belong to the conventional technical means in this field.

[0086] The present invention will be further described below with reference to the following examples, but is not limited to these examples.

[0087] In the following examples and comparative examples, the relevant data were obtained according to the following test methods:

[0088] 1. Determination of Isotacticity: Place a sample in a vacuum oven at 70°C and dry to remove any residual monomers and moisture. Vacuum dry to constant weight. Accurately weigh 1-2g of sample into a filter paper tube, seal the top with a paper clip, and place in an extractor. Extract with boiling ether for 24 hours. Remove and dry in a vacuum oven to constant weight. The unextractable content is used as the isotacticity of polybutene-1.

[0089] 2. Determination of melt flow rate (MFR): GB / T 3682.1-2018, using CEAST 7026 Melt Flow Indexer, under a load of 2.16 kg and a temperature of 190°C.

[0090] Preparation Example 1

[0091] Preparation of alkoxymagnesium particles: A reflux condenser, thermometer, and burette are installed in a reactor equipped with a stirrer. After sufficient nitrogen displacement, 480 mL of ethanol with a water content of less than 200 ppm and 20 mL of isooctyl alcohol with a water content of less than 200 ppm are added to the reactor, and 1.6 g of elemental iodine and 0.4 g of magnesium chloride are added and dissolved. Then, 32 g of magnesium powder (less than 360 μm) is added. 0.5 g of tetrabutyl titanate is added to the reaction solution to react. After stirring, the temperature is increased until the reflux temperature of the reaction system is reached. The reaction is carried out until completion, that is, no more hydrogen is discharged. The reaction is then washed, separated, and dried.

[0092] Preparation of solid catalyst component: In a 100mL reactor fully replaced with high-purity nitrogen, 10g of the above-prepared alkoxymagnesium particles, 50mL of toluene, 3mL of polymethylhydrogensiloxane (m≈35), and 4.0mL of di-n-butyl phthalate (DNBP) were added, the temperature was raised to 80°C, and the mixture was kept at this temperature for 2 hours to obtain a suspension X1. Simultaneously, in a 300mL reactor fully replaced with high-purity nitrogen, 10mL of toluene and 90mL of titanium tetrachloride were added, the temperature was raised to 80°C, and then the suspension X1 was added. The temperature was slowly raised to 115°C, and 1.0g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added during the heating process. The mixture was kept at this temperature for 2 hours, and then the liquid was filter-pressed. Then, a mixture of 30 mL of titanium tetrachloride and 120 mL of toluene was added, the temperature was raised to 110°C, and the temperature was maintained for 1 hour. The liquid was filtered clean; then, a mixture of 120 mL of titanium tetrachloride and 30 mL of toluene was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated twice, the liquid was filtered off, and the resulting solid was washed four times with 150 mL of hexane at 60°C, the liquid was filtered off, and the mixture was dried to obtain a solid powder, which is the solid catalyst component 1.

[0093] Preparation Example 2

[0094] The difference from Preparation Example 1 is that 1.0 g of 9,9-bis(methoxymethyl)fluorene is used instead of 1.0 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and the rest are the same to obtain solid catalyst component 2.

[0095] Example 1

[0096] Solid catalyst component 1, triisobutylaluminum, and dicyclopentyldimethoxysilane, which had been pre-complexed at room temperature for 2 minutes, were added to a 5L autoclave. Hydrogen was then added, and 2.2L of butene was added to initiate polymerization. The reaction was maintained at 70°C for 1 hour. After completion of the reaction, the polymer was discharged into a discharge container filled with hot water and steam was introduced to remove unreacted monomers. The solid was then filtered and dried to obtain the polymer. Specific process conditions and polymerization results are shown in Table 1.

[0097] Example 2

[0098] The difference from Example 1 is that the amount of hydrogen added is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0099] Example 3

[0100] The difference from Example 1 is that the amount of hydrogen added is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0101] Example 4

[0102] The difference from Example 1 is that the amount of hydrogen added is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0103] Example 5

[0104] The difference from Example 1 is that the amount of hydrogen added is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0105] Example 6

[0106] The difference from Example 1 is that the polymerization reaction temperature is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0107] Example 7

[0108] The difference from Example 1 is that the polymerization reaction temperature is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0109] Example 8

[0110] The difference from Example 1 is that the polymerization reaction temperature is different, and the rest are the same. Specific process conditions and polymerization results are shown in Table 1.

[0111] Example 9

[0112] The difference from Example 1 is that in the catalyst system, solid catalyst component 2 is used instead of solid catalyst component 1, and the rest are the same.

[0113] Comparative Example 1

[0114] The difference from Example 2 is that the solid catalyst component used is the catalyst prepared by the method described in Example 1 of patent document CN93102795, and its Ti content is 2.2 wt %. Specific process conditions and polymerization results are shown in Table 1.

[0115] Table 1

[0116]

[0117] As shown in Table 1, the catalyst system of the present invention exhibits higher polymerization activity than conventional ZN catalysts for butene-1 bulk polymerization, with activity reaching up to 49.6 kgPB / gcat·h. The isotacticity of polybutene-1 is also significantly improved, reaching up to 99.3 wt%. The catalyst system of the present invention exhibits superior hydrogen regulation performance, enabling the production of polybutene-1 products with higher melt flow rates. Examples 1-5 were conducted with polymerization reactions using varying amounts of hydrogen added. The appropriate amount of hydrogen not only acts as a molecular weight regulator but also improves polymerization activity and polymer isotacticity. Examples 6-8 were conducted with polymerization reactions at different temperatures, demonstrating varying catalyst activity and hydrogen regulation performance.

[0118] While various embodiments of the present invention have been described above, the above description is intended to be illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing highly isotactic polybutene-1, characterized in that: The preparation method comprises: butene-1 and optionally C2-C 10 The α-olefin monomers are polymerized under the action of Ziegler-Natta catalyst system; The Ziegler-Natta catalyst system comprises a solid catalyst component, an organoaluminum compound and an external electron donor; the solid catalyst component comprises a reaction product of alkoxymagnesium particles, an internal electron donor and a titanium-containing halide, and the internal electron donor comprises an organosilicon compound containing a Si-H functional group, a diether compound and a carboxylic acid ester compound; The polymerization reaction conditions include: a polymerization temperature of 0-150° C.; and a polymerization pressure higher than the saturated steam pressure of butene-1 at the corresponding polymerization temperature.

2. The method for preparing high isotactic polybutene-1 according to claim 1, wherein The polymerization temperature is 40-100°C.

3. The method for preparing high isotactic polybutene-1 according to claim 1, wherein The alkoxy magnesium particles contain the reaction product of magnesium powder, mixed alcohol, halogenating agent and cross-linking agent; the halogenating agent is a halogen element and / or an inorganic halide, and the cross-linking agent is a titanate compound; The molar ratio of the halogen atoms in the halogenating agent to the magnesium powder is (0.0002-0.2):

1.

4. The method for preparing high isotactic polybutene-1 according to claim 3, wherein: The magnesium powder is spherical magnesium powder particles with an average particle size of less than 360 μm, and the thickness of the oxide film of the magnesium powder is less than 0.5 μm.

5. The method for preparing high isotactic polybutene-1 according to claim 3, wherein: The mixed alcohol is C1-C 10 A mixture of alcohols.

6. The method for preparing high isotactic polybutene-1 according to claim 5, wherein: The mixed alcohol is a mixture of ethanol and isooctyl alcohol, wherein the ethanol accounts for 80-99 wt% and the isooctyl alcohol accounts for 1-20 wt%.

7. The method for preparing high isotactic polybutene-1 according to claim 3, wherein: The halogenating agent is selected from at least one of elemental iodine, elemental bromine, chlorine gas, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide and alkoxy magnesium halide.

8. The method for preparing high isotactic polybutene-1 according to claim 7, wherein: The halogenating agent is selected from at least one of elemental iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halide.

9. The method for preparing high isotactic polybutene-1 according to claim 8, wherein: The halogenating agent is a mixture of elemental iodine and magnesium chloride.

10. The method for preparing high isotactic polybutene-1 according to claim 3, wherein: The structure of the titanate compound is shown in Formula I: (R5’O) a Ti(OR6’) b (OR7’) c X d Formula I In formula I, R5', R6' and R7' are the same or different and are each selected from H or alkyl, X is selected from alkoxy, carboxyl, chloro, sulfonic acid, phosphoric acid or sulfate, a, b, c and d are independently integers of 0-4, and a+b+c+d=4.

11. The method for preparing high isotactic polybutene-1 according to claim 10, wherein: R5', R6' and R7' are each selected from C1-C 10 of alkyl.

12. The method for preparing highly isotactic polybutene-1 according to claim 11, wherein: The titanate compound is at least one selected from tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate and isomers thereof.

13. The method for preparing high isotactic polybutene-1 according to claim 12, wherein: The titanate compound is at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

14. The method for preparing high isotactic polybutene-1 according to claim 3, wherein: The weight ratio of the titanate compound to the magnesium powder is (0.01-5):1; the molar ratio of the mixed alcohol to the magnesium powder is (2-50):1; and the molar ratio of the halogen atoms in the halogenating agent to the magnesium powder is (0.0025-0.05):

1.

15. The method for preparing high isotactic polybutene-1 according to claim 14, wherein: The weight ratio of the titanate compound to the magnesium powder is (0.02-2):1; the molar ratio of the mixed alcohol to the magnesium powder is (2.5-18):

1.

16. The method for preparing high isotactic polybutene-1 according to claim 1, wherein: The organosilicon compound containing Si-H functional groups is selected from the organosilicon compounds shown in formula II and / or formula III. In Formula II, R 1 -R 7 The same or different, each selected from C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl, C3-C 10 Cycloalkyl, C7-C 20 Alkaryl, substituted or unsubstituted C6-C 20 An aromatic hydrocarbon group, wherein the degree of polymerization m is an integer of 2-100; In formula III, R 8 Selected from C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl, C3-C 10 Cycloalkyl, C7-C 20 Alkaryl, substituted or unsubstituted C6-C 20 Aromatic hydrocarbon group, the degree of polymerization n is an integer of 3-20.

17. The method for preparing high isotactic polybutene-1 according to claim 16, wherein: The organosilicon compound containing Si-H functional groups is at least one of 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, polycyclohexylhydrogensiloxane, tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and pentamethylcyclopentasiloxane.

18. The method for preparing high isotactic polybutene-1 according to claim 16, wherein: The molar ratio of the organic silicon compound containing Si—H functional groups to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

19. The method for preparing high isotactic polybutene-1 according to claim 18, wherein: The molar ratio of the organic silicon compound containing Si—H functional groups to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

20. The method for preparing highly isotactic polybutene-1 according to claim 1, wherein: The diether compound is selected from 1,3-diether compounds as shown in Formula IV. In Formula IV, R 1” and R 2” The same or different, each selected from C1-C 10 Straight chain alkyl, C3-C 10 branched alkyl; R 4” and R 5” The same or different, each selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkaryl; R 3” and R 6” the same or different, each selected from hydrogen, C1-C 10 Straight chain alkyl, C3-C 10 branched alkyl; The molar ratio of the diether compound to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

21. The method for preparing highly isotactic polybutene-1 according to claim 20, wherein: The diether compound is at least one of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyldimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane and 2,2-diisobutyl-1,3-dimethoxypropane.

22. The method for preparing highly isotactic polybutene-1 according to claim 21, wherein: The diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene.

23. The method for preparing highly isotactic polybutene-1 according to claim 20, wherein: The molar ratio of the diether compound to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

24. The method for preparing highly isotactic polybutene-1 according to claim 1, wherein: The carboxylic acid ester compound is selected from benzoic acid monoester compounds or phthalate compounds with a structure as shown in Formula V. In formula V, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl, C3-C 10 Cycloalkyl or C6-C 20 R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy; The molar ratio of the carboxylic acid ester compound to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

25. The method for preparing high isotactic polybutene-1 according to claim 24, wherein: At least three of R3-R6 are hydrogen.

26. The method for preparing highly isotactic polybutene-1 according to claim 25, wherein: The carboxylic acid ester compound is selected from ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diisobutyl phthalate, dioctyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n- ...methyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dioctyl phthalate, dimethyl phthalate, dimethyl phthalate, dimethyl phthalate, dimethyl phthalate, dimethyl phthalate, dimethyl phthalate At least one of dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl amyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl amyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl amyl phthalate, propyl hexyl phthalate, butyl amyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate and their isomers.

27. The method for preparing high isotactic polybutene-1 according to claim 24, wherein: The molar ratio of the carboxylic acid ester compound to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

28. The method for preparing high isotactic polybutene-1 according to claim 1, wherein: The structure of the titanium-containing halide is shown in Formula VIII, TiX 1 e (OR7) 4-e Formula VIII In Formula VIII, X 1 is halogen, R7 is C1-C 20 wherein e is an integer of 0-4.

29. The method for preparing high isotactic polybutene-1 according to claim 28, wherein: X 1 For chlorine.

30. The method for preparing high isotactic polybutene-1 according to claim 28, wherein: R7 is a C1-C5 alkyl group.

31. The method for preparing high isotactic polybutene-1 according to claim 1, wherein: The organoaluminum compound is selected from alkyl aluminum compounds; The molar ratio of aluminum in the organic aluminum compound to titanium in the solid catalyst component is (10-500):

1.

32. The method for preparing high isotactic polybutene-1 according to claim 31, wherein: The organoaluminum compound is selected from trialkylaluminum.

33. The method for preparing high isotactic polybutene-1 according to claim 32, wherein: The organoaluminum compound is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, tri(2-methyl-3-phenyl-butyl)aluminum and tri(2-phenyl-butyl)aluminum.

34. The method for preparing high isotactic polybutene-1 according to claim 31, wherein: The molar ratio of aluminum in the organic aluminum compound to titanium in the solid catalyst component is (25-100):

1.

35. The method for preparing high isotactic polybutene-1 according to claim 1, wherein: The external electron donor is selected from ethers, esters and silane compounds; The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1:(1-100).

36. The method for preparing high isotactic polybutene-1 according to claim 35, wherein: The external electron donor is selected from silane compounds.

37. The method for preparing high isotactic polybutene-1 according to claim 36, wherein: The silane compound is selected from at least one of tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

38. The method for preparing high isotactic polybutene-1 according to claim 36, wherein: The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1:(10-60).

39. The method for preparing high isotactic polybutene-1 according to claim 1, wherein: The Ziegler-Natta catalyst system is used in polymerization reaction after pre-complexation treatment. The temperature of the pre-complexation treatment is -10°C to 60°C, and the time of the pre-complexation treatment is 0.1-180 minutes.

40. The method for preparing high isotactic polybutene-1 according to claim 39, wherein: The temperature of the pre-complexation treatment is 0-30° C., and the time of the pre-complexation treatment is 5-30 minutes.

41. The method for preparing highly isotactic polybutene-1 according to claim 1, wherein: The preparation method comprises: discharging the product of the polymerization reaction into hot water, introducing steam to remove unreacted monomers, filtering to obtain a solid, and drying the solid to obtain polybutene-1.

42. The method for preparing high isotactic polybutene-1 according to claim 41, wherein The polymerization reaction is carried out in liquid phase butene-1, and hydrogen is introduced during the polymerization process.

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