A method and device for preparing 1-butene polymer

Abstract

The present invention belongs to the technical field of polymer preparation and discloses a method and device for preparing a 1-butene polymer. The preparation method comprises: reacting 1-butene and optionally C2-C 10 The invention relates to a method for polymerizing 1-butene monomers; mixing a polymer solution with an antioxidant and a deactivator, pressurizing the mixture and heating the mixture; and devolatilizing the mixture to obtain a polymer melt; wherein 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 a catalyst support, an internal electron donor, and a titanium-containing halide, wherein the internal electron donor comprises a carboxylate compound and a polyol ester compound. The invention can effectively reduce the problem caused by the high viscosity of the 1-butene polymerization system, and the 1-butene polymer has excellent performance.

Description

Technical Field

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

[0002] Compared to other polyolefin materials, polybutene-1 exhibits superior creep resistance, environmental stress cracking resistance, and impact resistance, making it highly suitable for pipes such as water supply pipes, hot water pipes, industrial pipes, and pipes for buildings. The addition of a comonomer broadens its application areas and improves the product's balance between toughness and rigidity, resulting in excellent tear and puncture resistance, making it suitable for film production and as a polyolefin modifier and adhesive. Currently, polybutene-1 has found applications in pipes, food and hygiene product packaging, construction, home furnishings, and agriculture.

[0003] The preparation methods of polybutene-1 mainly include gas phase method, solution method and bulk method, among which the bulk method includes slurry bulk method and liquid phase bulk method.

[0004] Gas-phase processes typically utilize a fluidized bed reactor. Patents such as CN102040693A, CN1140545C, US4503203, US3168484, US3580898, US5241024, and US3922322 all employ Ziegler-Natta catalyst systems to polymerize 1-butene monomer directly in a gas fluidized bed, synthesizing 1-butene polymers with good particle morphology and a controllable melt mass flow rate (MFR) within a certain range and a high isotactic index. However, gas-phase processes, due to low monomer concentration and 1-butene partial pressure, result in low polymerization activity, less than 5.0 kgPB / g·Cat, and result in high ash content in the polymer. Furthermore, the catalysts used in these processes are demanding, placing high demands on technology and equipment, making them difficult for small and medium-sized enterprises to commercialize.

[0005] The synthesis of polybutene-1 mostly adopts the bulk method, among which patent document CN1590417A introduces inert gas CO2 to maintain the polymerization system pressure above the saturated vapor pressure of 1-butene at the corresponding polymerization temperature, thereby improving the polymerization conversion rate. However, there is a problem of separating the raw materials in the later stage after the polymerization is completed, and the process flow is complicated and the cost is high. Patent document CN100488994 adopts the bulk precipitation process to prepare 1-butene polymer, but the particle morphology of the polymer is irregular and very easy to stick together, and the polymer transportation and post-processing are complicated. Patent document CN103288993A adopts the staged heating method to prepare 1-butene polymer with a spherical morphology, with a bulk density of 0.30g / cm 3, the isotactic index is greater than 95%, but the first stage reaction temperature is below 0-20°C, which is not conducive to industrial production control. Patent document CN1294161C uses a bulk method with staged polymerization at a polymerization temperature of 70-75°C to produce a product with an isotactic index of up to 99%, but does not mention the deactivation or killing treatment after the reaction, nor the detailed separation process for removing unreacted monomers from the polymer system. Patent document CN106893020A relates to a method for preparing 1-butene polymers using a composite external electron donor system of alkoxysilane and ether. This method first prepolymerizes propylene at a low temperature to form a polymer with relatively perfect particle morphology, followed by a multi-stage 1-butene polymerization process under the same polymerization process conditions. 1-butene polymers with better particle morphology can be obtained. However, this process has a long reaction cycle, low polymerization conversion rate, and high ash content in the product, making it unsuitable for use. Patent document CN105482009A relates to a continuous polymerization process device for preparing 1-butene polymer. The device uses a 1-butene low-temperature slurry prepolymerization reactor and a gas-phase horizontal reactor reactor in series to prepare 1-butene polymer powder. However, the polymerization activity of this method is not high.

[0006] Since the viscosity of 1-butene polymer / 1-butene polymerization system is 1000-100000cp under high temperature polymerization conditions, the viscosity of the system is further increased after the addition of comonomer. When the monomer is removed, the viscosity of the polymer can reach 20×10 6 cp or above. There are high requirements for stable material transportation. Patent document CN101233158B adds water to the polymer solution at the upstream feed port of the screw pump to maintain a certain ratio of H2O / Al to maintain the screw pump pressure and achieve stable material transportation, but does not involve the polymer separation process. Patent document CN103788262B transfers the polymer to a sealed container containing hot water after the reaction is completed, and steam is introduced into the bottom to deactivate the active center and remove unreacted monomers at the same time. The operation is simple, but the polymer discharge is very easy to agglomerate, and subsequent material transportation is difficult. It is not suitable for pilot and industrial equipment. Summary of the Invention

[0007] In view of the above situation, the purpose of the present invention is to provide a method and apparatus for preparing 1-butene polymers. The preparation method adopts a specific catalyst system and process flow, has high polymerization yield, high product isotactic index, high polymer crystallinity, narrow molecular weight distribution, and is suitable for continuous and stable material transportation of high-viscosity 1-butene polymer / 1-butene solution systems and subsequent polymer separation and processing.

[0008] A first aspect of the present invention provides a method for preparing a 1-butene polymer, the method comprising the following steps:

[0009] 1) Under the action of Ziegler-Natta catalyst system, 1-butene and optional C2-C 10 The α-olefin monomer is polymerized in an inert organic solvent or liquid 1-butene to obtain a polymer solution;

[0010] 2) mixing the polymer solution with an antioxidant and a deactivator, and pressurizing and heating the mixture to obtain a mixture containing supercritical 1-butene;

[0011] 3) devolatilizing the mixture containing supercritical 1-butene to obtain a polymer melt;

[0012] The Ziegler-Natta catalyst system contains a solid catalyst component, an organic aluminum compound and an external electron donor; the solid catalyst component contains a reaction product of a catalyst carrier, an internal electron donor and a titanium-containing halide, and the internal electron donor contains a carboxylic acid ester compound and a polyol ester compound.

[0013] The second aspect of the present invention provides a preparation device for 1-butene polymer, which includes a polymerization reactor, a mixer, a conveying booster pump and a devolatilization device arranged in sequence; the polymerization reactor is provided with one or multiple reactors connected in series; the devolatilization device is provided with at least two reactors connected in series, and a heat exchanger is provided in front of each devolatilization device.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1) Compared with the commonly used catalyst systems in this field, the catalyst system used in the present invention has better catalytic efficiency and higher polymerization yield, which can effectively reduce production costs; the obtained product has a high isotactic index, effectively improves the crystallinity of the polymer, and has a narrower polymer molecular weight distribution, which is more conducive to adjusting the catalyst structure and performance.

[0016] 2) The preparation method of the present invention can effectively reduce the problems caused by the high viscosity of the 1-butene polymerization system under high-temperature polymerization conditions, greatly reduce the load of the delivery pump and heat exchanger, improve the mass transfer and heat transfer efficiency, optimize the process flow, and simplify the equipment.

[0017] 3) The method of the present invention is simple to operate, low in cost, has low technical and equipment requirements, is easy to implement in industrial production, and has high polymerization efficiency; the prepared polymer has excellent properties, and the polymer composition structure and product performance can be adjusted within a wide range according to usage requirements.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1The figure is a schematic diagram of the process flow of the device for preparing 1-butene polymer of the present invention. DETAILED DESCRIPTION

[0020] 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.

[0021] According to a first aspect of the present invention, the present invention provides a method for preparing a 1-butene polymer, the preparation method comprising the following steps:

[0022] 1) Under the action of Ziegler-Natta catalyst system, 1-butene and optional C2-C 10 The α-olefin monomer is polymerized in an inert organic solvent or liquid 1-butene to obtain a polymer solution;

[0023] 2) mixing the polymer solution with an antioxidant and a deactivator, and pressurizing and heating the mixture to obtain a mixture containing supercritical 1-butene;

[0024] 3) devolatilizing the mixture containing supercritical 1-butene to obtain a polymer melt;

[0025] The Ziegler-Natta catalyst system contains a solid catalyst component, an organic aluminum compound and an external electron donor; the solid catalyst component contains a reaction product of a catalyst carrier, an internal electron donor and a titanium-containing halide, and the internal electron donor contains a carboxylic acid ester compound and a polyol ester compound.

[0026] According to the present invention, the catalyst support contains a reaction product of alkoxymagnesium particles and a particle protecting agent, and the particle protecting agent is a titanate compound and a polysiloxane substance.

[0027] The structure of the alkoxy magnesium particles is shown in Formula I:

[0028] Mg(OR9) 2-p (OR 10 ) p Formula I

[0029] In Formula I, R9 and R 10 The same or different, each selected from C1-C8 straight-chain alkyl, C3-C8 branched-chain alkyl, 0≤p≤2.

[0030] Preferably, R9 and R 10 Each is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-hexyl, (2-ethyl) hexyl; More preferably, R9 and R 10Similarly, the alkoxy magnesium particles are selected from at least one of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, diisobutoxy magnesium, dipentoxy magnesium, dihexyl magnesium and di(2-ethyl)hexyl magnesium; particularly preferably, the alkoxy magnesium particles are diethoxy magnesium or a mixture of diethoxy magnesium and other alkoxy magnesiums.

[0031] It should also be noted that Formula I only represents the compositional content of each alkoxy group in the alkoxymagnesium particles and does not represent the specific structure of the alkoxymagnesium particles. Specifically, for example, Mg(OEt)(OiPr) only indicates that the molar ratio of ethoxy to isopropoxy in the alkoxymagnesium particles is 1. It can be a mixture of diethoxymagnesium and diisopropoxymagnesium at a molar ratio of 1, an ethoxyisopropoxymagnesium compound, or a mixture of the three. It can also be a mixture of alkoxymagnesium compounds of various structures in which the total molar ratio of ethoxy to isopropoxy is 1. Et represents an ethyl group, and iPr represents an isopropyl group.

[0032] The structure of the titanate compound is shown in Formula II:

[0033] (R1'O) a Ti(OR2') b (OR3') c X d Formula II

[0034] In formula II, R1', R2' and R3' are the same or different and are each selected from H or alkyl, preferably selected from C1-C 10 wherein 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.

[0035] The titanate compound can be 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; preferably at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

[0036] The molar ratio of the titanate compound to the magnesium in the alkoxy magnesium particles may be (0.01-5):1, preferably (0.02-2):1.

[0037] The structure of the polysiloxane material is shown in Formula III:

[0038] (R 1 R 2 R 3 )SiO[(R 7 R 8)SiO] n …[(R y R z )SiO] m Si(R 4 R 5 R 6 ) Formula III

[0039] In formula III, R 1 -R z the same or different, each selected from substituted or unsubstituted 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 groups, C2-C 12 alkenyl, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, cyano, amino, carboxyl, thiol, carbon functional group, polyether chain; degree of polymerization n+m is an integer of 2-100; it should be noted that R y 、R z To arrange in order in R 8 After the group, and R z Arrange in R y Afterwards, as R y Possibly R 11 、R z Possibly R 12 , R 1 -R z All groups in formula III are referred to.

[0040] The polysiloxane substance is preferably at least one of polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethyl hydrogen siloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethyl hydrogen siloxane, polyhydroxy hydrogen siloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyether siloxane, polycarboxylsiloxane, polyol hydroxy siloxane, polyphenol hydroxy siloxane, polymercaptosiloxane and modified forms thereof, and more preferably at least one of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyether siloxane, polycyanosiloxane and modified forms thereof. The modified product may be a conventional modified product of each polysiloxane, such as epoxy-modified polymethylsiloxane, polyether-modified polysiloxane, epoxy-modified polysiloxane, and fluoroalkyl-modified polysiloxane.

[0041] The molar ratio of the polysiloxane substance to the magnesium in the alkoxy magnesium particles may be (0.01-5):1, preferably (0.02-2):1.

[0042] In the present invention, the carboxylic acid ester compound can be selected from benzoic acid monoester compounds or phthalate compounds as shown in Formula IV.

[0043]

[0044] In formula IV, 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.

[0045] 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.

[0046] The molar ratio of the carboxylic acid ester compound to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

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

[0048]

[0049] In formula V, 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 10The 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 molar ratio of the polyol ester compound to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0052] According to the present invention, the structure of the titanium-containing halide is shown in Formula VI,

[0053] TiX 1 e (OR7) 4-e Formula VI

[0054] In Formula VI, X 1 is halogen, preferably chlorine, R7 is C1-C 20The hydrocarbon group is preferably a C1-C5 alkyl group, and e is an integer of 0-4.

[0055] The amount of the titanium-containing halide used can be determined according to prior art and needs.

[0056] In the present invention, the preparation of the solid catalyst component can be carried out by conventional methods in the prior art, specifically the following method: first, alkoxymagnesium particles are dispersed in an inert diluent to form a suspension, a particle protective agent is added for treatment, and the suspension is contacted with a titanium-containing halide and an internal electron donor to obtain a catalyst mother liquor. The solid matter in the mother liquor is filtered, titanium-treated, and then 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. The amount of the inert diluent is 0.5-100 mol, preferably 1-50 mol. 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 min to 20 h, preferably 5 min to 8 h. The number of titanium treatments is 0-10 times, preferably 1-5 times.

[0057] According to the present invention, the organoaluminum compound is selected from an alkylaluminum compound and / or an aluminum compound of aluminoxane as shown in Formula VII;

[0058] AYR 9’ h X' (3-h) Formula VII

[0059] In Formula VII, R 9’ Selected from C1-C 20 Alkyl, C7-C 20 Aralkyl, C6-C 20 wherein X' is a halogen, and h is an integer of 0-3.

[0060] The alkylaluminum compound shown in Formula VII can be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, monoethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tri(2-methyl-3-phenyl-butyl)aluminum, tri(2-phenyl-butyl)aluminum, etc. The aluminum compound of aluminoxane can be selected from at least one of methylaluminoxane, tetra(isobutyl)aluminoxane, tetra(2,4,4-trimethyl-pentyl)aluminoxane, tetra(2,3-dimethylbutyl)aluminoxane and tetra(2,3,3-trimethylbutyl)aluminoxane.

[0061] 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.

[0062] In the present invention, the external electron donor is selected from at least one of alkoxysilanes, aminosilanes, organic amine compounds and ether compounds. The amount of the external electron donor can be selected from conventional amounts in the art.

[0063] According to the present invention, the components of the Ziegler-Natta catalyst system can optionally undergo a pre-complexation treatment before entering the polymerization reactor. The solid catalyst component, organoaluminum compound, and external electron donor undergo a pre-complexation reaction before being introduced into the polymerization reactor. This pre-complexation treatment can improve the polymerization activity and stereospecificity of the catalyst system. The operating temperature for the pre-complexation treatment is generally 5-30°C, preferably 5-20°C, and the residence time is 5-30 minutes.

[0064] In the present invention, the inert organic solvent may be a conventional inert organic solvent in the art, specifically n-hexane, isobutane, n-pentane, propane, isopentane, and the like.

[0065] Preferably, 1-butene and optionally C2-C 10 The α-olefin monomers are polymerized in liquid 1-butene.

[0066] According to the present invention, the polymerization reaction temperature is 30-100°C, preferably 40-90°C; the polymerization reaction pressure is 1.0-5.0 MPa, preferably 2.0-4.0 MPa. The average residence time (or average reaction time) is 0.5-4 hours, preferably 1.5-3.0 hours, which can be adjusted according to process conditions to ensure that the polymer content in the polymer solution is 0-50wt%, preferably 10-40wt%.

[0067] In addition, hydrogen can be used as a molecular weight regulator in the polymerization process. That is, according to product requirements, the amount of hydrogen added to each polymerization reactor can be controlled to adjust the average molecular weight, molecular weight distribution, melt mass flow rate and other indicators of the product. The polymerization reaction temperature can also be controlled to adjust the average molecular weight of the polymer.

[0068] Among the present invention, can make polymer solution possess high temperature antioxidant ability by adding antioxidant, can effectively reduce or avoid that subsequent high temperature devolatilization handles polymer and occurs obvious or tiny gel, avoid polymer to occur discoloration, degradation, can guarantee product quality stability, avoid outward appearance to cause destruction, prevent gel from remaining in transfer pump and material handling container for a long time and causing the problem of coking simultaneously.Described antioxidant can be selected from at least one of hindered phenol antioxidant, hindered amine antioxidant, phosphite antioxidant and sulfide-containing antioxidant, is preferably hindered phenol antioxidant and phosphite antioxidant.For example, antioxidant can be selected from 1010,168,225,1076,1330,1135 and 235 etc.The consumption of antioxidant can adopt conventional amount, as its consumption is 0.1-1.0% of polymer weight. The antioxidant used in the present invention can be a solid antioxidant or a liquid antioxidant, preferably a liquid antioxidant. Compared with solid antioxidants, liquid antioxidants are easier to mix with polymer solutions and are more fully mixed.

[0069] According to the present invention, the addition of a deactivator can deactivate the active centers in the polymer solution, effectively terminating the polymerization reaction and preventing the problem of continued polymerization or implosion during subsequent processing. The deactivator can be a conventional deactivator in the art, such as water, oxygen, carbon dioxide, carbon monoxide, or an alcohol. The alcohol is selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, or glycerol. The deactivator is used in an amount of 0.1% to 1.0% by weight of the polymer.

[0070] In the present invention, the 1-butene in the mixture reaches a supercritical state under the effects of pressurization and temperature increase, ensuring that the mixture is homogeneous and maintaining a good heat transfer effect. The mixture is pressurized to a pressure above the critical pressure of 1-butene, 4.0231 MPa. At this pressure, the polymer solution remains homogeneous when heated, maintaining a high heat transfer efficiency while also ensuring that the polymer solution does not experience phase separation due to vaporization of the 1-butene during transportation, which would otherwise complicate the material transportation process. Before entering the devolatilization equipment, the mixture is heated to a temperature of 146.69-250°C, preferably 150-250°C. At this temperature, the polymerization activity of the Ziegler-Natta catalyst system is significantly reduced, approaching zero, further deactivating the catalyst system.

[0071] According to the present invention, the devolatilization treatment realizes the effective separation of the polymer and the unreacted monomers. Preferably, the devolatilization treatment is provided with at least two stages. Generally, the temperature of the first stage of the devolatilization treatment is 100-250°C and the pressure is 0-4.0 MPaG, preferably 0-3.0 MPaG. The subsequent devolatilization treatment is operated at close to normal pressure or vacuum, and the last stage of the devolatilization treatment is carried out under high vacuum to remove the unreacted monomers remaining in the polymer as much as possible.

[0072] In the present invention, the devolatilization treatment further produces 1-butene, which is then pelletized into a polymer melt. The 1-butene is then condensed and purified before being reused. The pelletization of the polymer melt and the condensation and purification of the 1-butene can be performed using conventional methods in the prior art. During the pelletization of the polymer melt, additives commonly used in the art, such as light stabilizers, antioxidants, colorants, and fillers, can be added.

[0073] According to the second aspect of the present invention, the present invention provides a preparation device for 1-butene polymer, which comprises a polymerization reactor, a mixer, a conveying booster pump and a devolatilization device arranged in sequence; the polymerization reactor is provided with one or multiple reactors connected in series; the devolatilization device is provided with at least two reactors connected in series, and a heat exchanger is provided in front of each devolatilization device.

[0074] In the present invention, the preparation device of 1-butene polymer also includes a granulation device and a 1-butene recovery device. Along the material flow direction, the polymer melt outlet of the last devolatilization device is connected to the granulation device, and the 1-butene outlet is connected to the 1-butene recovery device. The pellet outlet of the granulation device is connected to a silo, and the 1-butene outlet of the 1-butene recovery device is connected to a polymerization reactor.

[0075] The delivery booster pump used in the present invention should be suitable for transporting high-viscosity fluids and can be either a gear pump or a screw pump. A static mixer can optionally be installed within the heat exchange tubes of the heat exchanger to enhance heat transfer. The devolatilization equipment of the present invention can be a flash tank, each equipped with a heat exchanger to provide the heat required for the devolatilization process. Each devolatilization unit is also equipped with a gear pump or screw pump suitable for high-viscosity fluids at its base to deliver the polymer solution or polymer melt to downstream equipment.

[0076] The granulation equipment of the present invention can be a vacuum exhaust granulator to further reduce the volatile matter in the polymer. The 1-butene recovery equipment includes a condenser and optional conventional purification equipment.

[0077] According to the present invention, adopting multiple polymerization reactors in series not only can increase the production capacity of preparation equipment, improve the utilization rate of catalyst, and be conducive to the regulation and optimization of the composition structure of 1-butene polymer on a large scale. Preferably, the number of polymerization reactors is 2-3, and by controlling the processing parameters (such as reactant composition, temperature and residence time etc.) of each polymerization reactor, the composition of polymer can be regulated. The polymerization reactor can be a stirred tank reactor or a loop reactor.

[0078] The mixer can be a kettle-type device with stirring, or a static mixer, preferably a static mixer.

[0079] 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.

[0080] The present invention will be further described below with reference to the following examples, but is not limited to these examples.

[0081] In the following examples and comparative examples, the relevant data were obtained according to the following test methods:

[0082] 1. Determination of polymer melt mass flow rate (MFR): Determined in accordance with standard ISO 1133, experimental conditions 2.16 kg, 190°C.

[0083] 2. Molecular weight distribution M w / M n Determination of molecular weight: Waters GPC 2000 was used for determination. The sample concentration was 0.1 mg / mL, the test temperature was 150°C, and the test flow rate was 1 mL / min. The molecular weight of polystyrene was used as the internal reference to develop a standard curve. The weight average molecular weight (M) of the sample was calculated based on the elution time. w ), number average molecular weight (M n ) and molecular weight distribution (M w / M n ).

[0084] 3. Determination of isotactic index (II): Weigh about 3 g of polymer, oven-dry to constant weight, then weigh m1. Extract with ether in a Soxhlet extractor for 48 h, and record the mass of the polymer dried to constant weight m2. The weight percentage of insoluble matter after ether extraction (m2 / m1) is the isotactic index of the polymer.

[0085] 4. 13 C-NMR measurements of comonomer content were performed in deuterated o-dichlorobenzene solutions (8-12 wt%) of the polymer at 120 °C. A 90° pulse was used with a 15 s delay between the pulse and CPD to remove the 1 H- 13C coupling, and spectra were acquired at 120°C on a Bruker AV-600 spectrometer operating at 150 MHz in Fourier transform mode.

[0086] Please refer to Carbon-13NMR spectral assignment of five polyolefins determinedfrom the chemical shift calculation and the polymerization mechanism for NMR calculations.

[0087] 5. Determination of melting point and crystallinity: Differential scanning calorimetry was used on a Perkin Elmer DSC-7. 5 ± 1 mg of sample was weighed and heated to 180°C at a rate of 10°C / min. The temperature was maintained for 5 min to ensure complete melting of the crystallites. The sample was then cooled to room temperature at a rate of 10°C / min, allowed to stand for 5 min, and then heated to 180°C again. The peak temperature was taken as the melting point, and the crystallinity was calculated by integrating the peak area.

[0088] Preparation Example 1

[0089] Alkoxymagnesium particles were prepared with reference to the method of Example 6 in patent document CN102453150B: After fully replacing a 16L pressure-resistant reactor with a stirrer with nitrogen, 10200mL of ethanol and 300mL of 2-ethylhexanol were added to the reactor, and 6g of iodine and 4g of magnesium chloride were added to dissolve them. After stirring, the temperature was raised until the reflux temperature of the reaction system was reached. 640g of magnesium powder was then added successively. The reaction was carried out until completion, i.e., no more hydrogen was discharged. It was then washed, separated and dried. The obtained dialkoxymagnesium carrier had an average particle size (D50) of 47.0μm and a particle size distribution index of 0.82, wherein the isooctyl magnesium content was 1.7wt%.

[0090] Preparation of solid catalyst component: In a 100mL reactor fully replaced with high-purity nitrogen, 10g of the above-mentioned alkoxymagnesium particles, 50mL of toluene, 3.0mL of polymethylsiloxane with a kinematic viscosity of 100cSt, and 2.0mL of tetraethyl titanate were added, the mixture was warmed to 60°C and kept at this temperature for 8 hours to obtain a suspension X1. Simultaneously, 10mL of toluene and 90mL of titanium tetrachloride were added to a 300mL reactor fully replaced with high-purity nitrogen, the mixture was warmed to 80°C, the suspension X1 was then added, the temperature was slowly raised to 115°C, 3.0mL of di-n-butyl phthalate (DNBP), 1.0mL of diethyl phthalate, and 1.0mL of 3,5-heptanediol dibenzoate were added during the temperature rise, the mixture was kept at this temperature for 2 hours, and the liquid was then 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.

[0091] Preparation Example 2

[0092] The difference from Preparation Example 1 is that 1.0 mL of 2,4-pentanediol dibenzoate is used instead of 1.0 mL of 3,5-heptanediol dibenzoate. The rest are the same, to obtain solid catalyst component 2.

[0093] Preparation Example 3

[0094] The difference from Preparation Example 1 is that 3.0 mL of diisobutyl phthalate is used instead of 3.0 mL of di-n-butyl phthalate. The rest are the same, and a solid catalyst component 3 is obtained.

[0095] Preparation Example 4

[0096] The difference from Preparation Example 1 is that 3.0 mL of 100 cSt epoxy-modified polymethylsiloxane and 2.0 mL of tetraisopropyl titanate are used instead of 3.0 mL of polymethylsiloxane and 2.0 mL of tetraethyl titanate. The rest are the same, to obtain solid catalyst component 4.

[0097] Example 1

[0098] See also Figure 1 The preparation device used includes a polymerization reactor 1, a mixer 2, a delivery booster pump 3, a devolatilization device 4, a granulation device 6 and a 1-butene recovery device 7 arranged in sequence; the polymerization reactor 1 is provided with two ( Figure 1Only one is shown in the figure); the polymerization reactor is a liquid-phase stirred tank reactor, and two devolatilization devices are provided in series. A heat exchanger 5 is provided in front of each devolatilization device. The devolatilization device 4 is a flash tank. Along the material flow direction, the polymer melt outlet of the last devolatilization device 4 is connected to the granulation device 6, and the 1-butene outlet is connected to the 1-butene recovery device 7. The pellet outlet of the granulation device 6 is connected to the silo 8, and the 1-butene outlet of the 1-butene recovery device 7 is connected to the polymerization reactor 1.

[0099] The preparation method of this embodiment includes: a catalyst system containing a solid catalyst component 1, triethylaluminum and dicyclopentyldimethoxysilane, and the components of the catalyst system are pre-contacted at 6°C for 8 minutes and then continuously introduced into a polymerization reactor. The flow rate of triethylaluminum (TEA) is 6.33 g / hr, the flow rate of dicyclopentyldimethoxysilane (DCPMS) is 0.25 g / hr, the flow rate of solid catalyst component 1 is 0.6 g / hr, and the molar ratio of TEA to DCPMS is 50:1.

[0100] The polymerization reaction was carried out in two liquid-phase stirred tank reactors connected in series. 1-Butene was continuously introduced into the reactor at a feed rate of 5.9 kg / hr and hydrogen was continuously introduced into the reactor at a feed rate of 50 ppm (H2 / 1-butene molar ratio). The polymerization temperature was 70°C and the polymerization pressure was 2.0 MPa. The residence times in the two reactors were 120 min and 60 min, respectively.

[0101] After the polymerization is completed, the polymer solution is mixed with an antioxidant and a deactivator in a mixer 2; the antioxidant is selected from 1010 and 168 (mass ratio 1:1), and the amount used is 0.5% of the weight of the polymer; the deactivator is propylene glycol, and the amount used is 0.5% of the weight of the polymer. The obtained mixture is pressurized to 4.1 MPa and heated to 148° C. to obtain a mixture containing supercritical 1-butene;

[0102] The mixture containing supercritical 1-butene is devolatilized in a first devolatilization device at an operating pressure of 2.6 MPa and a temperature of 130°C, then heated to 190°C and passed into a second devolatilization device for devolatilization at an operating pressure of 0.5 MPa and a temperature of 170°C to obtain a polymer melt and 1-butene. The polymer melt is granulated, and the 1-butene is condensed and purified in a 1-butene recovery device 7 and then returned to the polymerization reactor 1 for reuse.

[0103] Example 2

[0104] The difference from Example 1 is that liquid antioxidant 1135 is selected to replace antioxidants 1010 and 168, and the rest are the same.

[0105] Example 3

[0106] The difference from Example 1 is that the concentration of hydrogen added to the reactor is 50 ppm, and the rest are the same.

[0107] Example 4

[0108] The difference from Example 1 is that the concentration of hydrogen added to the reactor is 400 ppm, and the rest are the same.

[0109] Example 5

[0110] The difference from Example 1 is that the concentration of hydrogen added to the reactor is 1500 ppm, and the rest are the same.

[0111] Example 6

[0112] The difference from Example 1 is that the feed monomers are 1-butene and ethylene, C2 / (C2+C4) is 0.6 mol%, and the rest are the same.

[0113] Example 7

[0114] The difference from Example 1 is that the feed monomers are 1-butene and ethylene, C2 / (C2+C4) is 6.2 mol%, and the rest are the same.

[0115] Example 8

[0116] The difference from Example 1 is that the polymer is pressurized to 4.5 MPa and heated to 160° C. before devolatilization, and the rest are the same.

[0117] Example 9

[0118] The difference from Example 1 is that the polymerization reaction uses n-hexane as solvent to form a n-hexane solution system, and the rest are the same.

[0119] Example 10

[0120] 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.

[0121] Example 11

[0122] The difference from Example 1 is that in the catalyst system, solid catalyst component 3 is used instead of solid catalyst component 1, and the rest are the same.

[0123] Example 12

[0124] The difference from Example 1 is that in the catalyst system, solid catalyst component 4 is used instead of solid catalyst component 1, and the rest are the same.

[0125] Comparative Example 1

[0126] The difference from Example 1 is that no antioxidant and deactivator are added to the mixer after the polymerization is completed, and the rest are the same.

[0127] Comparative Example 2

[0128] The difference from Example 1 is that the mixture is heated to 135° C. before entering the devolatilization equipment, and the rest are the same.

[0129] Comparative Example 3

[0130] The difference from Example 1 is that the catalyst is a commercially available DQ catalyst, and the rest are the same.

[0131] The polymer powders prepared in each embodiment and comparative example were characterized and analyzed. The results are shown in Table 1.

[0132] Table 1

[0133]

[0134] As shown in Table 1, the catalyst system of the present invention has a high polymerization yield, an adjustable polymer MFR, a narrow molecular weight distribution (3.5-5.0), and high crystallinity. Without the addition of antioxidants and deactivators in the mixer, the polymer degrades during the subsequent high-temperature devolatilization process, resulting in an increase in the polymer melt mass flow rate. Lowering the pre-devolatilization heating temperature does not significantly change the properties of the resulting polymer, but can easily cause pipe blockage during device operation. Compared to commercially available DQ-type catalysts, the present invention offers higher yields, a higher isotactic index, a narrower polymer molecular weight distribution, and higher crystallinity.

[0135] 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 a 1-butene polymer, characterized in that: The preparation method comprises the following steps: 1) Under the action of Ziegler-Natta catalyst system, 1-butene and optional C2-C 10 The α-olefin monomer is polymerized in an inert organic solvent or liquid 1-butene to obtain a polymer solution; 2) mixing the polymer solution with an antioxidant and a deactivator, and pressurizing and heating the mixture to obtain a mixture containing supercritical 1-butene; 3) devolatilizing the mixture containing supercritical 1-butene to obtain a polymer melt; 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 a catalyst support, an internal electron donor and a titanium-containing halide, and the internal electron donor comprises a carboxylic acid ester compound and a polyol ester compound; The catalyst carrier contains the reaction product of alkoxy magnesium particles and a particle protective agent, and the particle protective agent is a titanate compound and a polysiloxane substance.

2. The method for preparing a 1-butene polymer according to claim 1, wherein The structure of the alkoxy magnesium particles is shown in Formula I: Mg(OR9) 2-p (OR 10 ) p Formula I In Formula I, R9 and R 10 The same or different, each selected from C1-C8 straight chain alkyl, C3-C8 branched chain alkyl, 0≤p≤2; The structure of the titanate compound is shown in Formula II: (R1'O) a Ti(OR2') b (OR3') c X d Formula II In formula II, R1', R2' and R3' are the same or different and are each selected from H or alkyl, 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; The structure of the polysiloxane material is shown in Formula III: (R 1 R 2 R 3 )SiO[(R 7 R 8 )SiO] n ···[(RyR z )SiO] m Si(R 4 R 5 R 6 ) Formula III In formula III, R 1 -R z the same or different, each selected from substituted or unsubstituted 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 groups, C2-C 12 alkenyl, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, cyano, amino, carboxyl, mercapto, carbon functional group, polyether chain; the degree of polymerization n+m is an integer of 2-100.

3. The method for preparing a 1-butene polymer according to claim 2, wherein R9 and R 10 Similarly, the alkoxymagnesium particles are at least one selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium and di(2-ethyl)hexyloxymagnesium.

4. The method for preparing a 1-butene polymer according to claim 2, wherein R1', R2' and R3' are each selected from C1-C 10 of alkyl.

5. The method for preparing a 1-butene polymer according to claim 4, 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.

6. The method for preparing a 1-butene polymer according to claim 5, wherein The titanate compound is at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

7. The method for preparing a 1-butene polymer according to claim 2, wherein The polysiloxane substance is selected from at least one of polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethyl hydrogen siloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethyl hydrogen siloxane, polyhydroxy hydrogen siloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyether siloxane, polycarboxylsiloxane, polyol hydroxy siloxane, polyphenol hydroxy siloxane, polymercaptosiloxane and modifications thereof.

8. The method for preparing a 1-butene polymer according to claim 7, wherein The polysiloxane substance is at least one of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyethersiloxane, polycyanosiloxane and modified forms thereof.

9. The method for preparing a 1-butene polymer according to claim 2, wherein The molar ratio of the titanate compound to the magnesium in the alkoxy magnesium particles is (0.01-5):1; the molar ratio of the polysiloxane substance to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

10. The method for preparing a 1-butene polymer according to claim 9, wherein The molar ratio of the titanate compound to the magnesium in the alkoxy magnesium particles is (0.02-2):1; the molar ratio of the polysiloxane substance to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

11. The method for preparing a 1-butene polymer according to claim 1, wherein The carboxylic acid ester compound is selected from benzoic acid monoester compounds or phthalate compounds having a structure as shown in Formula IV, In formula IV, 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 polyol ester compound is selected from the diol ester compound having a structure as shown in Formula V, In formula V, 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; The molar ratio of the carboxylic acid ester compound to the magnesium in the alkoxy magnesium particles is (0.01-5):1; the molar ratio of the polyol ester compound to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

12. The method for preparing a 1-butene polymer according to claim 11, wherein At least three of R3-R6 are hydrogen.

13. The method for preparing a 1-butene polymer according to claim 12, 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.

14. The method for preparing a 1-butene polymer according to claim 11, wherein The diol ester compound is at least one of 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 and 2-methyl-3,5-heptanediol dibenzoate.

15. The method for preparing a 1-butene polymer according to claim 14, wherein The diol ester compound is at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate and 2,4-pentanediol dibenzoate.

16. The method for preparing a 1-butene polymer according to claim 11, wherein The molar ratio of the carboxylic acid ester compound to the magnesium in the alkoxy magnesium particles is (0.02-2):1; the molar ratio of the polyol ester compound to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

17. The method for preparing a 1-butene polymer according to claim 1, wherein: The structure of the titanium-containing halide is shown in Formula VI, TiX 1 e (OR7) 4-e Formula VI In Formula VI, X 1 is halogen, R7 is C1-C 20 wherein e is an integer of 0-4.

18. The method for preparing a 1-butene polymer according to claim 17, wherein X 1 is chlorine, and R7 is a C1-C5 alkyl group.

19. The method for preparing a 1-butene polymer according to claim 1, wherein The organoaluminum compound is selected from an alkyl aluminum compound and / or an aluminum compound of aluminoxane as shown in Formula VII; AYR 9’ h X' (3-h) Formula VII In Formula VII, R 9’ Selected from C1-C 20 Alkyl, C7-C 20 Aralkyl, C6-C 20 Aryl, X' is halogen, h is an integer from 0 to 3; The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is (10-500):1; The external electron donor is selected from at least one of alkoxysilanes, aminosilanes, organic amine compounds and ether compounds.

20. The method for preparing a 1-butene polymer according to claim 19, wherein The organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum monochloride, monoethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tri(2-methyl-3-phenyl-butyl)aluminum, tri(2-phenyl-butyl)aluminum, methylaluminoxane, tetra(isobutyl)aluminoxane, tetra(2,4,4-trimethyl-pentyl)aluminoxane, tetra(2,3-dimethylbutyl)aluminoxane and tetra(2,3,3-trimethylbutyl)aluminoxane.

21. The method for preparing a 1-butene polymer according to claim 19, wherein The molar ratio of aluminum in the organic aluminum compound to titanium in the solid catalyst component is (25-100):

1.

22. The method for preparing a 1-butene polymer according to claim 1, wherein 1-butene and optionally C2-C 10 The α-olefin monomer is polymerized in liquid 1-butene; The polymerization reaction temperature is 30-100°C; the polymerization reaction pressure is 1.0-5.0 MPa.

23. The method for preparing a 1-butene polymer according to claim 22, wherein: The polymerization reaction temperature is 40-90°C; the polymerization reaction pressure is 2.0-4.0 MPa.

24. The method for preparing a 1-butene polymer according to claim 1, wherein The antioxidant is selected from at least one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants and sulfide antioxidants; the amount of the antioxidant is 0.1% to 1.0% by weight of the polymer; The deactivator is water, oxygen, carbon dioxide, carbon monoxide or alcohol, and the alcohol is selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol or glycerol; the amount of the deactivator is 0.1%-1.0% by weight of the polymer; The supercharging pressure is higher than the critical pressure of 1-butene, 4.0231 MPa, and the heating temperature is 146.69-250°C.

25. The method for preparing a 1-butene polymer according to claim 24, wherein: The antioxidants are hindered phenol antioxidants and phosphite antioxidants.

26. The method for preparing a 1-butene polymer according to claim 1, wherein The temperature of the devolatilization treatment is 100-250°C and the pressure is 0-4.0 MPaG; The devolatilization treatment also produces 1-butene, which is granulated into polymer melt and reused after condensation and purification.

27. The method for preparing a 1-butene polymer according to claim 26, wherein The pressure is 0-3.0MpaG.

28. The method for preparing a 1-butene polymer according to any one of claims 1 to 27, wherein: The method adopts a 1-butene polymer preparation device, which includes a polymerization reactor, a mixer, a conveying booster pump and a devolatilization device arranged in sequence; the polymerization reactor is provided with one or multiple devices connected in series; the devolatilization device is provided with at least two devices connected in series, and a heat exchanger is provided in front of each devolatilization device.

29. The method for preparing a 1-butene polymer according to claim 28, wherein The device also includes a granulation device and a 1-butene recovery device. Along the material flow direction, the polymer melt outlet of the last devolatilization device is connected to the granulation device, and the 1-butene outlet is connected to the 1-butene recovery device. The pellet outlet of the granulation device is connected to the silo, and the 1-butene outlet of the 1-butene recovery device is connected to the polymerization reactor.

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