A preparation process and device for polybutene-1 resin

Abstract

The present invention belongs to the technical field of polymer preparation, and discloses a preparation process and device of polybutene-1 resin, which comprises: reacting 1-butene and optional 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 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 the reaction product of alkoxymagnesium particles, an internal electron donor, and a titanium-containing halide, wherein the internal electron donor comprises a carboxylate compound, a polyol ester compound, and an organosilicon compound containing a Si-H functional group. The invention can effectively reduce the problem caused by the high viscosity of the 1-butene polymerization system, and the 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 preparation process and device for a polybutene-1 resin. Background Art

[0002] Compared to other polyolefin materials, polybutene-1 resins offer superior creep resistance, environmental stress cracking resistance, and impact resistance, making them ideal for pipes such as water supply pipes, hot water pipes, industrial pipes, and pipes for buildings. The addition of comonomers broadens their application areas and improves the product's balance between toughness and rigidity, resulting in excellent tear and puncture resistance, making them suitable for film production. They can also be used as polyolefin modifiers and adhesives. Currently, polybutene-1 resins are being used in pipes, food and hygiene product packaging, construction, home furnishings, and agriculture.

[0003] The preparation methods of polybutene-1 resin 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 resins mostly adopts the bulk method, wherein the 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 preparation process and device for polybutene-1 type resin, which adopts a specific catalyst system and process flow, has high polymerization yield and narrow product molecular weight distribution, and is suitable for continuous and stable material transportation of high-viscosity 1-butene polymer / 1-butene solution system and subsequent polymer separation and treatment.

[0008] A first aspect of the present invention provides a process for preparing a polybutene-1 resin, the process comprising the following steps:

[0009] 1) Under the action of Ziegler-Natta catalyst system, 1-butene and optional C2-C10 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 alkoxy magnesium particles, a reaction product of an internal electron donor and a titanium-containing halide, and the internal electron donor contains a carboxylic acid ester compound, a polyol ester compound and an organic silicon compound containing a Si-H functional group.

[0013] The second aspect of the present invention provides a preparation device for polybutene-1 type resin, 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 higher catalytic efficiency and higher polymerization yield, which can effectively reduce production costs; the molecular weight distribution of the obtained product is narrower and the melt index can be adjusted, which is conducive to adjusting the product structure and performance.

[0016] 2) The preparation process 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 process of the present invention is simple to operate, low in cost, has low technical and equipment requirements, is easy to implement industrial production, and has high polymerization efficiency; the prepared polymer has excellent performance, and the polymer composition structure and product performance can be adjusted 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 1 The figure is a schematic diagram of the process flow of the device for preparing the polybutene-1 type resin 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 process for preparing a polybutene-1 resin, the process 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 alkoxy magnesium particles, a reaction product of an internal electron donor and a titanium-containing halide, and the internal electron donor contains a carboxylic acid ester compound, a polyol ester compound and an organic silicon compound containing a Si-H functional group.

[0026] 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:

[0027] 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.

[0028] 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.

[0029] The molar ratio of the mixed alcohol to the magnesium powder is preferably (2-50):1, more preferably (2.5-18):1.

[0030] 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.

[0031] In order to better control the morphology of the alkoxymagnesium particles, the molar ratio of the halogen atoms in the halogenating agent to the magnesium powder may be (0.0002-0.2):1, preferably (0.0025-0.05):1.

[0032] The cross-linking agent is a titanate compound. Specifically, the structure of the titanate compound is shown in Formula I:

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

[0034] In formula I, 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 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.

[0036] The weight ratio of the titanate compound to the magnesium powder is preferably (0.01-5):1, more preferably (0.02-2):1.

[0037] In the present invention, the carboxylic acid ester compound can be selected from benzoic acid monoester compounds or phthalate compounds as shown in Formula II.

[0038]

[0039] In formula II, 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.

[0040] 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.

[0041] 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.

[0042] According to the present invention, the polyol ester compound is selected from the diol ester compound having a structure as shown in Formula III,

[0043]

[0044] In formula III, R1’ 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.

[0045] 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.

[0046] 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.

[0047] In the present invention, the organosilicon compound containing Si-H functional groups is selected from the organosilicon compounds shown in formula IV and / or formula V.

[0048]

[0049] In Formula IV, 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 or branched alkyl, C3-C6 cycloalkyl, aryl, R 2 -R 7 is methyl;

[0050]

[0051] In formula V, 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 The degree of polymerization n is preferably an integer of 3-8.

[0052] Specific examples of the organosilicon compound represented by Formula IV include, but are not limited to, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, and polycyclohexylhydrogensiloxane. Specific examples of the organosilicon compound represented by Formula V include, but are not limited to, tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane. The organosilicon compounds represented by Formulas IV and V can be used alone or as a mixture.

[0053] 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.

[0054] According to the present invention, the structure of the titanium-containing halide is shown in Formula VI,

[0055] TiX 1e (OR7) 4-e Formula VI

[0056] In Formula VI, 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.

[0057] The amount of the titanium-containing halide used can be determined according to prior art and needs.

[0058] 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%.

[0059] 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.

[0060] 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;

[0061] AYR 9’ h X' (3-h) Formula VII

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] Preferably, 1-butene and optionally C2-C 10 The α-olefin monomers are polymerized in liquid 1-butene.

[0069] 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%.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] According to the second aspect of the present invention, the present invention provides a preparation device for polybutene-1 type resin, 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.

[0077] In the present invention, the preparation device of polybutene-1 type resin 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.

[0078] 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.

[0079] 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.

[0080] According to the present invention, the use of multiple polymerization reactors in series can not only increase the production capacity of the preparation device and improve the utilization rate of the catalyst, but also facilitate the large-scale regulation and optimization of the composition structure of polybutene-1. Preferably, the number of polymerization reactors is 2-3, and the composition of the polymer can be adjusted by controlling the process parameters (such as reactant composition, temperature and residence time, etc.) of each polymerization reactor. The polymerization reactor can be a stirred tank reactor or a loop reactor.

[0081] The mixer can be a kettle-type device with stirring, or a static mixer, preferably a static mixer.

[0082] 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.

[0083] The present invention will be further described below with reference to the following examples, but is not limited to these examples.

[0084] In the following examples and comparative examples, the relevant data were obtained according to the following test methods:

[0085] 1. Determination of polymer melt mass flow rate (MFR): Determined in accordance with standard ISO 1133, experimental conditions 2.16 kg, 190°C.

[0086] 2. Molecular weight distribution M w / M n Determination of molecular weight: Waters GPC2000 was used for determination, with a sample concentration of 0.1 mg / mL, a test temperature of 150°C, and a test flow rate of 1 mL / min. The molecular weight of polystyrene was used as an internal reference to develop a standard curve, and 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 ).

[0087] 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.

[0088] 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.

[0089] Please refer to Carbon-13 NMR spectral assignment of five polyolefins determined from the chemical shift calculation and the polymerization mechanism for NMR calculations.

[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 alkoxymagnesium particles obtained in this preparation example, 50mL of toluene, 3mL of polymethylhydrogensiloxane (m≈35), 2.8mL of di-n-butyl phthalate (DNBP) and 1.2mL of diethyl phthalate 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. At the same time, 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 1.0mL of 3,5-heptanediol dibenzoate 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] Preparation of alkoxymagnesium particles: A reflux condenser, thermometer, and burette are installed in a reactor equipped with a stirrer. After sufficient nitrogen displacement, 500 mL of ethanol with a water content of less than 200 ppm and 10 mL of isooctyl alcohol with a water content of less than 200 ppm are added to the reactor. 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. 5.0 g of tetraethyl 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.

[0095] Preparation of solid catalyst component: Using the alkoxy magnesium particles prepared in this preparation example, the remaining steps were the same as in Preparation Example 1 to obtain solid catalyst component 2.

[0096] Preparation Example 3

[0097] The difference from Preparation Example 1 is that 2.8 mL of diisobutyl phthalate is used instead of 2.8 mL of di-n-butyl phthalate. The rest are the same, and a solid catalyst component 3 is obtained.

[0098] Preparation Example 4

[0099] The difference from Preparation Example 1 is that 3.0 mL of tetramethylcyclotetrasiloxane is used instead of 3 mL of polymethylhydrogensiloxane (n≈35), and the rest are the same, to obtain a solid catalyst component 4.

[0100] Example 1

[0101] 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 1 Only 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.

[0102] The preparation process 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.

[0103] 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.

[0104] 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;

[0105] 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.

[0106] Example 2

[0107] The difference from Example 1 is that liquid antioxidant 1135 is selected to replace antioxidants 1010 and 168, and the rest are the same.

[0108] Example 3

[0109] The difference from Example 1 is that the concentration of hydrogen added to the reactor is 50 ppm, and the rest are the same.

[0110] Example 4

[0111] The difference from Example 1 is that the concentration of hydrogen added to the reactor is 400 ppm, and the rest are the same.

[0112] Example 5

[0113] 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.

[0114] Example 6

[0115] 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.

[0116] Example 7

[0117] 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.

[0118] Example 8

[0119] 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.

[0120] Example 9

[0121] 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.

[0122] Example 10

[0123] 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.

[0124] Example 11

[0125] 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.

[0126] Comparative Example 1

[0127] 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.

[0128] Comparative Example 2

[0129] 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.

[0130] Comparative Example 3

[0131] The difference from Example 1 is that the catalyst is a commercially available DQ catalyst, and the rest are the same.

[0132] The polymer powders prepared in each embodiment and comparative example were characterized and analyzed. The results are shown in Table 1.

[0133] Table 1

[0134]

[0135]

[0136] As shown in Table 1, the catalyst system of the present invention has a high polymerization yield, an adjustable polymer MFR, and a narrow molecular weight distribution (3.5-5.0). 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 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, and a narrower polymer molecular weight distribution.

[0137] 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 process for preparing a polybutene-1 type resin, characterized in that: The preparation process 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 contains a solid catalyst component, an organic aluminum compound and an external electron donor; the solid catalyst component contains alkoxy magnesium particles, a reaction product of an internal electron donor and a titanium-containing halide, and the internal electron donor contains a carboxylic acid ester compound, a polyol ester compound and an organic silicon compound containing a Si-H functional group.

2. The process for preparing the polybutene-1 type resin 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.

3. The process for preparing the polybutene-1 type resin according to claim 2, 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.

4. The process for preparing the polybutene-1 type resin according to claim 2, wherein: The mixed alcohol is C1-C 10 A mixture of alcohols.

5. The process for preparing the polybutene-1 type resin according to claim 4, 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%.

6. The process for preparing the polybutene-1 type resin according to claim 2, 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.

7. The process for preparing the polybutene-1 type resin according to claim 6, wherein: The halogenating agent is selected from at least one of elemental iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halide.

8. The process for preparing the polybutene-1 type resin according to claim 7, wherein: The halogenating agent is a mixture of elemental iodine and magnesium chloride.

9. The process for preparing the polybutene-1 type resin according to claim 2, wherein: The structure of the titanate compound is shown in Formula I: (R1’O) a Ti(OR2’) b (OR3’) c X d Formula I In formula I, 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.

10. The process for preparing the polybutene-1 type resin according to claim 9, wherein: R1', R2' and R3' are selected from C1-C 10 of alkyl.

11. The process for preparing the polybutene-1 type resin according to claim 10, 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.

12. The process for preparing the polybutene-1 type resin according to claim 11, wherein: The titanate compound is at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

13. The process for preparing the polybutene-1 type resin according to claim 2, 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.

14. The process for preparing the polybutene-1 type resin according to claim 13, 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.

15. The process for preparing the polybutene-1 type resin 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 II, In formula II, 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 III, In formula III, 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 organosilicon compound containing Si-H functional groups is selected from the organosilicon compounds shown in formula IV and / or formula V. In Formula IV, 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 V, 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; 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; and the molar ratio of the organosilicon compound containing Si-H functional groups to the magnesium in the alkoxy magnesium particles is (0.01-5):

1.

16. The process for preparing the polybutene-1 type resin according to claim 15, wherein: At least three of R3-R6 are hydrogen.

17. The process for preparing the polybutene-1 type resin according to claim 16, 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.

18. The process for preparing the polybutene-1 type resin according to claim 15, 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.

19. The process for preparing the polybutene-1 type resin according to claim 18, 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.

20. The process for preparing the polybutene-1 type resin according to claim 15, 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.

21. The process for preparing the polybutene-1 type resin according to claim 15, 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; and the molar ratio of the organosilicon compound containing Si-H functional groups to the magnesium in the alkoxy magnesium particles is (0.02-2):

1.

22. The process for preparing the polybutene-1 type resin 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.

23. The process for preparing the polybutene-1 type resin according to claim 22, wherein: X 1 is chlorine, and R7 is a C1-C5 alkyl group.

24. The process for preparing the polybutene-1 type resin 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.

25. The process for preparing the polybutene-1 type resin according to claim 24, 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.

26. The process for preparing the polybutene-1 type resin according to claim 24, wherein: The molar ratio of aluminum in the organic aluminum compound to titanium in the solid catalyst component is (25-100):

1.

27. The process for preparing the polybutene-1 type resin 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.

28. The process for preparing the polybutene-1 type resin according to claim 27, wherein: The polymerization reaction temperature is 40-90°C; the polymerization reaction pressure is 2.0-4.0 MPa.

29. The process for preparing the polybutene-1 type resin 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.

30. The process for preparing the polybutene-1 type resin according to claim 29, wherein: The antioxidants are hindered phenol antioxidants and phosphite antioxidants.

31. The process for preparing the polybutene-1 type resin 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.

32. The process for preparing the polybutene-1 type resin according to claim 31, wherein: The pressure is 0-3.0MpaG.

33. The process for preparing the polybutene-1 type resin according to any one of claims 1 to 32, wherein: The process adopts a preparation device for polybutene-1 type resin, 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.

34. The process for preparing the polybutene-1 type resin according to claim 33, 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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