Process for the preparation of butene-1 based polymers

Abstract

The application belongs to the technical field of polymer preparation, and discloses a preparation method of butene-1 polymer, which comprises the following steps: under the action of a Ziegler-Natta catalyst system, 1-butene and optional C2-C 10 α-olefin monomers are subjected to a polymerization reaction; the polymer solution is fully contacted with a deactivator, and is subjected to pressurization and temperature increase to obtain a supercritical polymer solution; 3) devolatilization treatment is performed to obtain a polymer melt; the Ziegler-Natta catalyst system comprises component A, component B and component C; component A is a solid catalyst component containing Ti and an internal electron donor and loaded with protected alkoxy magnesium particles; component B is a mixture of organic aluminum and an antioxidant, and the molar ratio of the organic aluminum and the antioxidant is 1:(1-100); and component C is an external electron donor. The method has low cost and low energy consumption, and the polymer has excellent performance and good antioxidant performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer preparation technology, specifically, it relates to a method for preparing butene-1 type polymers. Background Technology

[0002] Compared to other polyolefin materials, polybutene-1 exhibits superior creep resistance, environmental stress cracking resistance, and impact resistance, making it highly suitable for use as pipes, such as water supply pipes, hot water pipes, industrial pipes, and building pipes. Adding comonomers can broaden its application areas, improve the balance between toughness and rigidity, and give it good tear resistance and puncture resistance, making it suitable for film products. It can also be used as a polyolefin modifier and adhesive. Currently, polybutene-1 is used in pipes, food and hygiene product packaging, construction, home furnishings, agriculture, and other fields.

[0003] Currently, the main methods for preparing polybutene-1 include gas-phase methods, solution methods, and bulk methods, with the bulk method being the most commonly used. The bulk method includes slurry bulk methods and liquid-phase bulk methods. Patent document CN1590417A introduces an inert gas such as 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, it does not mention polymer processing techniques or improvements to polymer performance. Patent document CN103288993A uses a staged heating method to prepare a spherical 1-butene polymer with a bulk density of 0.30 g / cm³. 3 The isotactic index is greater than 95%, but the first-stage reaction temperature is below 0-20℃, which is not conducive to industrial-scale production control. Patent document CN106893020A uses a multi-stage sequential method to prepare 1-butene polymers with good particle morphology, but this process has a long reaction cycle, low polymerization efficiency, and high ash content in the product, which is not conducive to its use.

[0004] Because the viscosity of the 1-butene polymer / 1-butene polymerization system is between 1000-100000 cp under high-temperature polymerization conditions, the viscosity further increases after the addition of comonomers, causing significant problems for stable material transport and mass and heat transfer efficiency. Patent document CN101233158B adds water to the polymer solution at the upstream inlet of the screw pump to maintain a certain H2O / Al ratio, thus maintaining the screw pump pressure and achieving stable material transport, but it does not address the polymer separation process. Patent document CN103788262B involves transferring the polymer to a sealed container containing hot water after the reaction, with steam introduced at the bottom to deactivate the active centers and remove unreacted monomers. This operation is simple, but the polymer discharge is prone to agglomeration, making subsequent material transport difficult and unsuitable for pilot-scale and industrial-scale plants.

[0005] As is well known, during thermal processing and long-term use, polymers are oxidized by oxygen in the air due to light, heat, or physical stimulation, generating free radicals and peroxide free radicals. This leads to the deterioration of polymer materials, loss of mechanical properties, and damage to their appearance. The addition of antioxidants can effectively capture free radicals to prevent oxidation, decompose unstable hydroperoxides into stable compounds, thereby effectively reducing the auto-oxidation reaction of plastic materials, delaying polymer aging and degradation, and improving the thermal stability of polymers.

[0006] To improve the thermal stability of polymer products, antioxidants are added during processing through blending and other methods, allowing the polymer products to be used for a longer period of time. Among these, hindered phenolic antioxidants are the most widely used, delaying the performance degradation of polymers during use and extending their service life. Commonly used hindered phenolic antioxidants include: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 1330).

[0007] Patent document CN107674361A describes a method of combining a phenolic primary antioxidant with two specific auxiliary antioxidants and mechanically blending it with a polyolefin product to obtain a stabilized polyolefin resin material. Patent documents CN105482250B, CN104419015B, and CN103450379B describe blending a composition formed from hindered phenols, phosphites, stearates, and sodium borohydride with a polyolefin product. This effectively improves the polymer's thermal stability, prevents discoloration by eliminating chromophores, reduces the yellow index, and enhances the product's aesthetics and durability. However, this preparation method occurs during the product processing. Patent document CN103819596B discloses a method for preparing high isotactic poly-1-butene and its in-reactor synthesis. This method employs an in-reactor synthesis method that adds a nucleating agent during the polymerization stage, significantly improving the crystallinity of poly-1-butene, shortening the crystal transformation time, and enhancing its mechanical properties. Summary of the Invention

[0008] In view of the above, the purpose of this invention is to provide a method for preparing butene-1 type polymers. This preparation method adopts a specific catalyst system and process flow, has high polymerization activity, and features high isotactic index, excellent antioxidant properties, adjustable product performance, and easy grade switching. It is also applicable to polybutene-1 / butene-1 or polybutene-1 / inert solvent solution systems, which facilitates the continuous and stable transportation of such high-viscosity materials and simplifies the separation and processing of polymer systems, thereby achieving continuous and stable production.

[0009] This invention provides a method for preparing butene-1 type polymers, the method comprising the following steps:

[0010] 1) Under the action of a Ziegler-Natta type catalyst system, 1-butene and optional C2-C 10 The α-olefin monomers are polymerized in an inert organic solvent or in liquid 1-butene to obtain a polymer solution;

[0011] 2) The polymer solution is brought into full contact with the deactivating agent, and then pressurized and heated to obtain a supercritical polymer solution;

[0012] 3) The supercritical polymer solution is subjected to a devolatification process to obtain a polymer melt;

[0013] The Ziegler-Natta catalyst system contains components A, B, and C; component A is a solid catalyst component containing Ti and an internal electron donor supported on protected alkoxy magnesium particles, wherein the internal electron donor contains carboxylic acid ester compounds and polyol ester compounds; component B is a mixture of organoaluminum and antioxidant, wherein the molar ratio of organoaluminum to antioxidant is 1:(1-100); and component C is an external electron donor.

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

[0015] 1) The catalyst system used in this invention has both antioxidant and catalytic effects. The antioxidant has a better dispersion effect, which can effectively avoid the drawback of uneven dispersion and phase separation during post-processing, reduce the amount of additives, and has high catalytic polymerization activity. The resulting product has a high isotactic index, adjustable product performance, and easy grade switching.

[0016] 2) The preparation method of the present invention can effectively reduce the problems of difficult mass and heat transfer and unstable material conveying in high viscosity systems, reduce the load on conveying equipment and heat exchange devices, reduce gel content, optimize process flow and reduce cost.

[0017] 3) The method of this invention for preparing polyolefins enables in-situ polymerization of antioxidants, resulting in better dispersion in the polymer, thereby reducing the amount of antioxidant required and effectively improving the antioxidant properties of the polymer. It also effectively reduces the difficulty and cost of post-processing of high-viscosity systems, is suitable for both continuous and batch polymerization, and can effectively solve the problem of degradation of powders and high melt index polymers during long-term storage. At the same time, it reduces the load on high-viscosity system dynamic equipment and heat exchange equipment, improves the mass and heat transfer efficiency of polymer solution systems, and reduces the energy consumption of the equipment.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] This invention provides a method for preparing butene-1 type polymers, the method comprising the following steps:

[0021] 1) Under the action of a Ziegler-Natta type catalyst system, 1-butene and optional C2-C 10 The α-olefin monomers are polymerized in an inert organic solvent or in liquid 1-butene to obtain a polymer solution;

[0022] 2) The polymer solution is brought into full contact with the deactivating agent, and then pressurized and heated to obtain a supercritical polymer solution;

[0023] 3) The supercritical polymer solution is subjected to a devolatification process to obtain a polymer melt;

[0024] The Ziegler-Natta catalyst system contains components A, B, and C; component A is a solid catalyst component containing Ti and an internal electron donor supported on protected alkoxy magnesium particles, wherein the internal electron donor contains carboxylic acid ester compounds and polyol ester compounds; component B is a mixture of organoaluminum and antioxidant, wherein the molar ratio of organoaluminum to antioxidant is 1:(1-100); and component C is an external electron donor.

[0025] According to the present invention, the protected alkoxy magnesium particles contain a reaction product of alkoxy magnesium particles and a particle protectant, wherein the particle protectant is a titanate compound and a polysiloxane substance.

[0026] The structure of the alkoxymagnesium particles is shown in Formula I:

[0027] Mg(OR9) 2-p (OR 10 ) p Formula I

[0028] In Equation I, R9 and R 10 Whether the same or different, each is selected from C1-C8 straight-chain alkyl or C3-C8 branched alkyl, 0≤p≤2.

[0029] 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, dihexyloxy magnesium, and di(2-ethyl)hexyloxy magnesium; particularly preferably, the alkoxy magnesium particles are diethoxy magnesium or a mixture of diethoxy magnesium and other alkoxy magnesiums.

[0030] It should also be noted that Formula I only represents the composition and content of each alkoxy group in the alkoxymagnesium particles, and does not represent the specific structure of the alkoxymagnesium particles. Specifically, 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 magnesium diethoxy and magnesium diisopropoxy in a molar ratio of 1, or an ethoxyisopropoxymagnesium compound, or a mixture of all three; it can also be a mixture of alkoxymagnesium compounds with multiple structures in which the total molar ratio of ethoxy to isopropoxy is 1. Wherein Et represents ethyl and iPr represents isopropyl.

[0031] The structure of the titanate compound is shown in Formula II:

[0032] (R1”O) a Ti(OR2”) b (OR3”) c X d Formula II

[0033] In Formula II, R1”, R2” and R3” may be the same or different, and each is selected from H or alkyl groups, preferably from C1-C6. 10 The alkyl group, X is selected from alkoxy, carboxyl, chlorine, sulfonic acid, phosphoric acid or sulfate, a, b, c and d are independent integers from 0 to 4, and a+b+c+d=4.

[0034] The titanate compound may 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.

[0035] The molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles can be (0.01-5):1, preferably (0.02-2):1.

[0036] The structure of the polysiloxane-based substance is shown in Formula III:

[0037] (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

[0038] In Equation III, R 1 -R z Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 10 cycloalkyl, C7-C 20 alkylaryl, substituted or unsubstituted C6-C 20 Aromatic groups, C2-C 12 The chain contains alkenyl, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, cyano, amino, carboxyl, mercapto, carbon functional groups, and polyether chains; the degree of polymerization n+m is an integer from 2 to 100; it should be noted that R y R z To arrange in order in R 8 The following groups, and R z Arranged in R y After that, such as R y Possibly R 11 R z Possibly R 12 R 1 -R z It refers to all the groups in Formula III.

[0039] The polysiloxane material is preferably at least one of polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethylhydrosiloxane, polyhydroxyhydrosiloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyethersiloxane, polycarboxysiloxane, polyol hydroxysiloxane, polyphenol hydroxysiloxane, polythiolsiloxane, and modified forms thereof, more preferably at least one of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyethersiloxane, polycyanosiloxane, and modified forms thereof. The modifier can be a conventional modifier of various polysiloxanes, such as epoxy-modified polymethylsiloxane, polyether-modified polysiloxane, epoxy-modified polysiloxane, and fluoroalkyl-modified polysiloxane.

[0040] The molar ratio of the polysiloxane-based substance to magnesium in the alkoxy magnesium particles can be (0.01-5):1, preferably (0.02-2):1.

[0041] In this invention, the carboxylic acid ester compound may be selected from benzoic acid monoester compounds or phthalic acid ester compounds with structures as shown in Formula IV.

[0042]

[0043] In Formula IV, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy, preferably, at least three of R3-R6 are hydrogen.

[0044] Specifically, the carboxylic acid ester compound may be selected from ethyl benzoate, propyl benzoate, butyl benzoate, amyl 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, and other carboxylic acid esters. Dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate, and at least one of their isomers.

[0045] The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0046] According to the present invention, the polyol ester compound is selected from diol ester compounds with structures as shown in Formula V.

[0047]

[0048] In formula V, R 1’ and R 2’ Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10olefin group, C 10 -C 20 Fused ring aryl group; R 3’ -R 8’ They may be the same or different, each selected from hydrogen, halogen, substituted or unsubstituted C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl; 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.

[0049] The diol ester compounds specifically include, but are not limited to: 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethyl benzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dinepentyl ester, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol cinnamic acid ester, 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.

[0050] The molar ratio of the polyol ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0051] In this invention, the solid catalyst component can be prepared using conventional methods in the prior art, specifically as follows: First, alkoxymagnesium particles are dispersed into a suspension using an inert diluent. A particle protectant is added for treatment. The suspension is then contacted with a titanium-containing halide and an internal electron donor to obtain a catalyst mother liquor. The solid substances in the mother liquor are filtered, treated with titanium, and then filtered again, washed, and dried 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 titanium-containing halide can be titanium tetrachloride, etc. The contact temperature of each component is typically -40℃ to 200℃, preferably -20℃ to 150℃, and the contact time is 1 min to 20 h, preferably 5 min to 8 h. The number of titanium treatments is 0 to 10 times, preferably 1 to 5 times.

[0052] According to the present invention, component B of the catalyst system is a mixture of organoaluminum and antioxidant, and the molar ratio of organoaluminum to antioxidant is controlled at 1:(1-100). The organoaluminum and antioxidant can form a stable and uniform antioxidant shielding structure. This antioxidant shielding structure can both cooperate with the solid catalyst component and external electron donor in the Ziegler-Natta catalyst system to initiate olefin polymerization and improve the oxidation resistance of polyolefins, thereby achieving the purpose of preparing polyolefins with excellent thermal stability. Component B combines the co-catalytic function of organoaluminum with the antioxidant function of antioxidants, and the antioxidant has good dispersion, effectively avoiding the phase separation problem that occurs when antioxidants and polymers are blended during processing. The required amount of antioxidant is less than that used in subsequent processing, resulting in better performance. If the molar ratio of organoaluminum and antioxidant is less than 1:1, the antioxidant content is low and the antioxidant effect is not significant; if it is greater than 1:100, the antioxidant content is too high, which can easily form flocculent precipitates, making the antioxidant dispersion effect worse. During the transportation process, precipitation is likely to occur in the pump, affecting the material transportation.

[0053] The organoaluminum is selected from alkylaluminum compounds and / or alkylaluminoxanes with structures as shown in Formula VI;

[0054] A1R 9’ h X' (3-h) Style VI

[0055] In equation VI, R 9’ Selected from C1-C 20 Alkyl, C7-C 20 Aryl groups, C6-C 20 The aryl group, X' is a halogen, and h is an integer from 0 to 3.

[0056] The alkylaluminum compound shown in Formula VI may be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diisobutylaluminum chloride, tri(2-methyl-3-phenyl-butyl)aluminum, tri(2-phenyl-butyl)aluminum, etc. The aluminum compound of the aluminum oxane may 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.

[0057] The molar ratio of aluminum in the organoaluminum to titanium in the solid catalyst component can be (10-500):1, preferably (25-100):1.

[0058] The antioxidant can be any existing substance suitable for improving the antioxidant properties of polyolefins. For example, the antioxidant can be selected from at least one of phenolic antioxidants, amine antioxidants, phosphite antioxidants, and thioester antioxidants, preferably phenolic antioxidants and / or amine antioxidants. The phenolic antioxidant can be selected from at least one of monophenols, bisphenols, thiobisphenols, and polyphenols.

[0059] In this invention, the external electron donor may be selected from at least one of siloxane compounds, aminosilane compounds, organic amine compounds, and ether compounds.

[0060] The siloxane compound may be selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl tert-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane, and n-propylenetriethoxysilane.

[0061] The aminosilane compound may be selected from at least one of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, piperidinyltriethoxysilane, and pyrrolotriethoxysilane.

[0062] The organic amine compound may be selected from aziridine, aziridine, pyrrolidine, aziridine-heptane, aziridine-octane, 2,3-dimethylaziridine, 2,2-dimethylaziridine, 2,2,3,3-tetramethylaziridine, 2,2,4,4-tetramethylaziridine, 2,2,4,4-tetraethylaziridine, 2,2,3,3-tetramethylaziridine, 2,2,3,3-tetraethylaziridine, 2,2,4,4-tetramethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, 2,2,5,5-tetraethylpyrrolidine, 2,3-dimethylaziridine, 2,2,3,3-tetramethylaziridine, 2,2,3,3-tetraethylaziridine, 2,3-dimethyl ... 2,5,5-Tetra-n-propylpyrrolidine, 2,2,5,5-Tetraisopropylpyrrolidine, 2,2,5,5-Tetraisobutylpyrrolidine, 2,2,6,6-Tetramethylpiperidine, 2,2,6,6-Tetraethylpiperidine, 2,2,6,6-Tetra-n-propylpiperidine, 2,2,6,6-Tetraisopropylpiperidine, 2,2,6,6-Tetraisobutylpiperidine, 2,2,4,4-Tetramethylpiperidine, 2,2,4,4-Tetraethylpiperidine, 2,2,5,5-Tetramethylpiperidine, 2,2,5,5-Tetraethylpiperidine, 2-Methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, 2, 2-Dicyclopentyl-6,6-dimethylpiperidine, 2,2,7,7-tetramethylazacycloheptane, 2,2,7,7-tetraethylazacycloheptane, 2,2,7,7-tetra-n-propylazacycloheptane, 2,2,7,7-tetraisopropylazacycloheptane, 2,2,7,7-tetraisobutylazacycloheptane, 2,2,5,5-tetramethylazacycloheptane, 2,2,5,5-tetraethylazacycloheptane, 3,3,5,5-tetramethylazacycloheptane, 3,3,5,5-tetraethylazacycloheptane, 2-methyl-2-cyclohexyl-7-methyl-7-azacycloheptane, 2, At least one of the following: 2-dicyclopentyl-7,7-dimethylazicycloheptane, 2,2,8,8-tetramethylazicyclooctane, 2,2,8,8-tetraethylazicyclooctane, 2,2,8,8-tetra-n-propylazicyclooctane, 2,2,8,8-tetraisopropylazicyclooctane, 2,2,8,8-tetra-n-butylazicyclooctane, 2,2,8,8-tetraisobutylazicyclooctane, 2,2,7,7-tetramethylazicyclooctane, 2,2,6,6-tetramethylazicyclooctane, 3,3,5,5-tetramethylazicyclooctane, and 3,3,6,6-tetramethylazicyclooctane.

[0063] The ether compound may be selected from at least one of the compounds shown in Formula VII.

[0064]

[0065] In Equation VII, R1' and R2' are each independently selected from C1-C 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20The cycloalkyl group, R3'-R8', is independently selected from hydrogen atoms, halogen atoms, C1-C2 atoms. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aryl alkyl group, wherein any two of R3'-R8' are optionally linked together to form a ring.

[0066] Specific examples of the ether compounds include, but are not limited to: 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-dimethoxypropane, 2,2 - Isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dipropoxypropane, 2-isopropyl-2-isopentyl-1,3-diethoxypropane, 2-isopropyl-2-isopentyl-1,3-dipropoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-diethoxypropane.

[0067] The molar ratio of the external electron donor to the aluminum in the organoaluminum is (0.005-0.5):1, more preferably (0.01-0.4):1.

[0068] According to the present invention, the components of the Ziegler-Natta catalyst system may optionally undergo pre-complexation treatment before entering the polymerization reactor. Components A, B, and C are used in the polymerization reaction after pre-complexation treatment. The advantage of pre-complexation treatment is that it can improve the polymerization activity and stereotactic orientation of the catalyst system. The temperature of pre-complexation treatment is generally 5-30°C, preferably 5-20°C, and the time of pre-complexation treatment is 0.1-180 min, preferably 5-30 min.

[0069] In this invention, C2-C 10The α-olefin monomer is a monoolefin with 2-10 carbon atoms and a double bond at the end of the molecular chain, other than 1-butene, and is particularly preferably selected from at least one of ethylene, propylene, 1-hexene, 1-octene, and 1-decene. When the polymerized olefin is a mixture of 1-butene and α-olefin, it is particularly preferred that the amount of 1-butene is 70-99.9 mol% and the amount of α-olefin is 0.1-30 mol%. The inert organic solvent can be a conventional inert organic solvent in the art, specifically hexane, isobutane, n-pentane, propane, and isopentane, etc.

[0070] The concentration of the organoaluminum in the system is preferably 0.1-10 mol / L, more preferably 0.5-5 mol / L. It can be prepared by dilution with an inert solvent. The inert solvent is at least one selected from n-hexane, heptane, n-octane, and isohexane, preferably n-hexane. At the above concentrations, the organoaluminum and antioxidant can more effectively form a shielding structure, and the reaction between the two is not too vigorous. Furthermore, the amount of the Ziegler-Natta catalyst system is preferably such that the antioxidant component content in the obtained polyolefin is 40 ppm or more, preferably 40-2000 ppm.

[0071] This invention does not particularly limit the conditions of the polymerization reaction, but preferably the obtained polyolefin has a melt index of 0.1-1000 g / 10 min at 190°C and 2.16 kg. Typically, the polymerization reaction temperature is 20-100°C, preferably 30-80°C, more preferably 50-80°C; the polymerization reaction pressure is 1.0-5.0 MPa, preferably 2.0-4.0 MPa; and the polymerization reaction time is 0.5-4 h, preferably 1.5-3.0 h. These can be adjusted according to the process conditions to ensure that the polymer content in the polymer solution is 0-50 wt%, preferably 15-35 wt%.

[0072] The polymerization reaction of the present invention can be carried out in the form of continuous or intermittent polymerization, and can also be carried out in the gas phase, specifically in one or more fluidized or mechanically stirred bed reactors.

[0073] According to the present invention, the polymerization reaction is carried out in one or more polymerization reactors connected in series. Preferably, the number of polymerization reactors is 2-3. The composition of the polymer can be adjusted by controlling the process parameters (such as reactant composition, temperature, and residence time) of each polymerization reactor. The polymerization reactor can be a stirred tank reactor or a loop reactor.

[0074] In addition, hydrogen can be used as a molecular weight regulator in the polymerization process. That is, according to the product requirements, the amount of hydrogen added to each polymerization reactor can be controlled to adjust the average molecular weight, molecular weight distribution and melt mass flow rate of the product. The average molecular weight of the polymer can also be adjusted by controlling the polymerization reaction temperature.

[0075] According to the present invention, the addition of a deactivating agent can deactivate the active centers in the polymer solution, effectively terminating the polymerization reaction and preventing continued polymerization or explosive polymerization in subsequent processing. The deactivating agent can be a conventional deactivating agent in the art, such as water, oxygen, carbon dioxide, carbon monoxide, or alcohols. The alcohols are selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, or glycerol. The amount of the deactivating agent is 0.1%-1.0% of the polymer weight.

[0076] In this invention, the full contact between the polymer solution and the deactivating agent is carried out in a mixer, which can be a stirred tank or a static mixer, preferably a static mixer.

[0077] According to the present invention, the polymer solution reaches a supercritical state under pressure and temperature increases, ensuring that the mixture remains homogeneous and maintaining good heat transfer performance. The pump used in this invention should be suitable for conveying high-viscosity fluids, and can be a gear pump or a screw pump. The polymer solution is pressurized to a pressure above the critical pressure of 1-butene (4.0231 MPa). At this pressure, the polymer solution remains homogeneous during temperature increases, ensuring that 1-butene does not separate due to vaporization during transport, thus preventing the material transport process from becoming extremely difficult. Before entering the devolatilization equipment, the polymer solution is heated to 146.69-250°C, preferably 150-250°C, via a heat exchanger. A static mixer can be selectively installed inside the heat exchanger tubes to enhance heat transfer. Furthermore, at the above temperatures, the polymerization activity of the Ziegler-Natta catalyst system decreases significantly, approaching zero, further deactivating the catalyst system.

[0078] According to the present invention, the devolatilization process achieves effective separation of polymer from unreacted monomers. Preferably, the devolatilization process has at least two stages. Generally, the temperature of the first stage of devolatilization is 100-250°C, and the pressure is 0-4.0 MPaG, preferably 0.5-3.0 MPaG. Subsequent devolatilization processes are operated at near-atmospheric pressure or vacuum, and the final stage of devolatilization is carried out under high vacuum to remove as much unreacted monomer as possible from the polymer. The devolatilization equipment used in the present invention can be a flash tank. Each devolatilization unit is equipped with a heat exchanger to provide the heat required for the devolatilization process. At the same time, a gear pump or screw pump suitable for high-viscosity fluids is installed at the bottom of each devolatilization unit to deliver the polymer solution or polymer melt to downstream equipment.

[0079] In this invention, the volatile matter removal process also yields 1-butene, which is then condensed, purified, and reused. The polymer melt is then granulated. The granulation of the polymer melt and the condensation and purification of the 1-butene can be carried out using conventional methods in the prior art, such as a vacuum exhaust granulator, to further reduce the volatile matter in the polymer. During the granulation process of the polymer melt, additives commonly used in this technical field can be added, such as light stabilizers, antioxidants, colorants, and fillers.

[0080] The substances, equipment, and process parameters not limited in this invention can be selected according to existing technology and are conventional technical means in this field.

[0081] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0082] In the following examples and comparative examples, the data were obtained using the following test methods:

[0083] 1. Melting point (T) m Determination of the crystallinity: The determination was performed using differential scanning calorimetry (DSC) 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 in a nitrogen atmosphere. The temperature was maintained at 180 °C for 5 min to allow all microcrystals to completely melt. The sample was then cooled to -20 °C at a rate of 10 °C / min, and the peak temperature was recorded as the crystallization temperature. After standing at -20 °C for 5 min, the sample was reheated to 180 °C at a rate of 10 °C / min, and the peak temperature was recorded as the melting temperature.

[0084] 2. Determination of melt mass flow rate (melt index, MFR): Determined according to standard ISO 1133, experimental conditions: 2.16 kg, 190℃.

[0085] 3. Molecular weight distribution M w / M nDetermination: Waters GPC 2000 was used for determination. The sample concentration was 0.1 mg / mL, the test temperature was 150℃, and the test flow rate was 1 mL / min. A standard curve was established using the molecular weight of polystyrene as an internal reference. 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 ).

[0086] 4. Determination of isotactic index (II): Weigh about 3g of polymer, dry it in an oven until constant weight, and weigh it again (m1). Extract it with ether in a Soxhlet extractor for 48h, and record the mass of the polymer dried to constant weight (m2). The percentage of insoluble matter by weight after ether extraction (m2 / m1) is the isotactic index of the polymer.

[0087] 5. 13 C-NMR determination of comonomer content: performed in a solution of deuterated o-dichlorobenzene (8-12 wt%) of the polymer at 120 °C. Removal was achieved by using a 90° pulse with a 15-second delay between the pulse and the CPD. 1 H- 13 C-coupling was performed at 120°C using a Bruker AV-600 spectrometer operated in Fourier transform mode at 150 MHz.

[0088] You can refer to the Carbon-13 NMR spectral assignment of five polyolefins determined from the chemical shift calculation and the polymerization mechanism for NMR calculations.

[0089] 6. Oxidation Induction Time (OIT): Tested according to ISO11357 standard at a test temperature of 200℃.

[0090] Preparation Example 1

[0091] Alkoxymagnesium particles were prepared according to the method in Example 6 of patent document CN102453150B: After fully purging a 16L pressure reactor equipped with a stirrer with nitrogen, 10200mL of ethanol and 300mL of 2-ethylhexanol were added to the reactor, along with 6g of iodine and 4g of magnesium chloride to dissolve them. The mixture was stirred and heated until the reflux temperature of the reaction system was reached. Then, 640g of magnesium powder was added sequentially. The reaction was continued until completion, i.e., no more hydrogen gas was emitted. The mixture was then washed, separated, and dried. The resulting diekoxymagnesium support had an average particle size (D50) of 47.0μm, a particle size distribution index of 0.82, and a magnesium isooctoxy content of 1.7wt%.

[0092] Preparation of solid catalyst components: In a 100 mL reactor that has been fully purged with high-purity nitrogen, 10 g of the above-mentioned magnesium alkoxy particles, 50 mL of toluene, 3.0 mL of polymethylsiloxane with a kinematic viscosity of 100 cSt, and 2.0 mL of tetraethyl titanate were added. The mixture was heated to 60 °C and held at that temperature for 8 hours to obtain suspension X1. Simultaneously, in a 300 mL reactor that has been fully purged with high-purity nitrogen, 10 mL of toluene and 90 mL of titanium tetrachloride were added. The mixture was heated to 80 °C, and then suspension X1 was added. The mixture was slowly heated to 115 °C. During the heating process, 3.0 mL of di-n-butyl phthalate (DNBP), 1.0 mL of diethyl phthalate, and 1.0 mL of 3,5-heptanediol dibenzoate were added. The mixture was held at that temperature for 2 hours, and then the liquid was filtered clean. Then, add a mixture of 30 mL titanium tetrachloride and 120 mL toluene, heat to 110 °C, maintain the temperature for 1 hour, and filter the liquid thoroughly. Then, add another mixture of 120 mL titanium tetrachloride and 30 mL toluene, heat to 110 °C, stir for 1 hour, and repeat this process twice. Filter off the liquid, and wash the resulting solid four times with 150 mL hexane at 60 °C. Filter off the liquid and dry to obtain a solid powder, which is solid catalyst component 1.

[0093] Preparation Example 2

[0094] The difference from Preparation Example 1 is that 1.0 mL of 2,4-pentanediol dibenzoate was used instead of 1.0 mL of 3,5-heptanediol dibenzoate, while all other components were the same, to prepare solid catalyst component 2.

[0095] Preparation Example 3

[0096] The difference from Preparation Example 1 is that 3.0 mL of di-n-butyl phthalate was replaced with 3.0 mL of diisobutyl phthalate and 1.0 mL of diisopropyl phthalate was replaced with 1.0 mL of diethyl phthalate, while the rest were the same, to prepare solid catalyst component 3.

[0097] Example 1

[0098] The catalyst system contains solid catalyst component 1, a mixture of triethylaluminum (TEA) and antioxidant AM1 (4,4'-bis(3,5-di-tert-butylbenzoylamino)diphenylmethane) (molar ratio 1:5), and dicyclopentyldimethoxysilane (DCPMS). After pre-contacting at 6°C for 10 min, the components of the catalyst system are continuously fed into the polymerization reactor. The flow rate of the triethylaluminum and antioxidant mixture (calculated as triethylaluminum) is 7.2 g / hr, the flow rate of dicyclopentyldimethoxysilane is 0.24 g / hr, the flow rate of solid catalyst component 1 is 0.4 g / hr, and the molar ratio of TEA to DCPMS is 60:1.

[0099] The polymerization reaction was carried out in two series-connected liquid-phase stirred tank reactors. 1-Butene was fed into the reactors at a rate of 5.9 kg / hr and hydrogen at a 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 time in the two reactors was 90 min and 60 min, respectively.

[0100] After polymerization, the polymer solution is mixed with the deactivator glycerol in a static mixer. The amount of deactivator is 0.5% of the polymer weight. Then, under the action of a booster pump and a heat exchanger, the pressure and temperature are increased to 4.2 MPa and 150 °C to obtain a supercritical polymer solution.

[0101] The supercritical polymer solution is subjected to a devolatilization process. The first-stage devolatilization unit operates at a pressure of 2.6 MPa and a temperature of 130 °C, and then the temperature is raised to 190 °C before entering the second-stage devolatilization unit, which operates at a pressure of 0.5 MPa and a temperature of 170 °C, yielding a polymer melt and 1-butene. The polymer melt is granulated, and the 1-butene is condensed, purified, and returned to the polymerization reactor for reuse.

[0102] Example 2

[0103] The difference from Example 1 is that the hydrogen concentration added to the reactor is 400 ppm, while the rest are the same.

[0104] Example 3

[0105] The difference from Example 1 is that the hydrogen concentration added to the reactor is 1500 ppm, while the rest are the same.

[0106] Example 4

[0107] The difference from Example 1 is that antioxidant AM2 (4,4'-bis(3,5-di-tert-butylbenzoamide)dimethyl ether) was used in place of antioxidant AM1 in the same molar amount, otherwise the same.

[0108] Example 5

[0109] The difference from Example 1 is that antioxidant AO18 (pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionate)) was used instead of antioxidant AM1 in the same molar amount, otherwise the same.

[0110] Example 6

[0111] The difference from Example 1 is that solid catalyst component 2 is used instead of solid catalyst component 1, while the rest are the same.

[0112] Example 7

[0113] The difference from Example 1 is that solid catalyst component 3 is used instead of solid catalyst component 1, while the rest are the same.

[0114] Example 8

[0115] The difference from Example 1 is that ethylene monomer was added to the reaction system, and the ethylene / 1-butene feed ratio was 5.2 wt%.

[0116] Example 9

[0117] The difference from Example 1 is that propylene monomer was added to the reaction system, and the propylene / 1-butene feed ratio was 1.2 wt%.

[0118] Comparative Example 1

[0119] The difference from Example 1 is that no antioxidant is added to the catalyst system, but everything else is the same.

[0120] Comparative Example 2

[0121] The difference from Example 1 is that the molar ratio of triethylaluminum (TEA) and antioxidant AM1 was adjusted to 1:0.5, while all other aspects remained the same.

[0122] Comparative Example 3

[0123] The difference from Example 1 is that the molar ratio of triethylaluminum (TEA) and antioxidant AM1 was adjusted to 1:150, while all other aspects remained the same.

[0124] Comparative Example 4

[0125] The difference from Example 1 is that the polymer solution was heated and pressurized to 130°C and 2.5 MPa, but the rest were the same.

[0126] The polymer powders prepared in each embodiment and comparative example were characterized and analyzed, and the results are shown in Table 1.

[0127] Table 1

[0128]

[0129] As shown in Table 1, the catalyst system of this invention exhibits high polymerization yield, adjustable polymer molecular weight ratio (MFR), narrow molecular weight distribution, and a significantly improved oxidation induction time (OIT), thus enhancing the polymer's antioxidant capacity. When the antioxidant content is low, the polymer has insufficient antioxidant capacity, a slightly higher MFR, and a short OIT time. Conversely, while a high antioxidant content does not affect polymer performance, it causes pump jamming in the alkylaluminum transfer pump and filter, impacting the stable operation of the unit. While maintaining the polymer solution below the supercritical state ensures the final polymer meets performance standards, it significantly increases the total power consumption of the unit's rotating equipment and heat exchangers, which is detrimental to the green and energy-saving production goals of the production unit.

[0130] To further illustrate the effect of adding antioxidants during the polymerization process, the polymer obtained in Comparative Example 1, after adding antioxidants, was compared with the polymer obtained in Example 1 through heat treatment. Specifically, the polymer obtained in Example 1 was cut into small pieces without adding antioxidants, and the MFR was directly tested to obtain specimens; the specimens from the previous step were then cut into smaller pieces again for MFR testing, and this step was repeated 5 times. The polymer obtained in Comparative Example 1 was given the same proportion and type of antioxidant as the polymer obtained in Example 1, then stirred evenly with a stirrer, and the MFR was tested to obtain specimens; the specimens from the previous step were then cut into smaller pieces again for MFR testing, and this step was repeated 5 times. The results are shown in Table 2.

[0131] Table 2

[0132]

[0133] As can be seen from the results in Table 2, under the same conditions of antioxidant type and dosage, the polymer obtained by the method provided by the present invention has better antioxidant capacity and can maintain good thermal stability for a long time. This is because the olefin polymerization reaction carried out by the method provided by the present invention makes it easier for antioxidants to be uniformly dispersed in the polymer, which can avoid the problem of antioxidant aggregation during post-processing.

[0134] In summary, the results in Tables 1 and 2 strongly demonstrate that the method of the present invention is beneficial for improving the antioxidant capacity of polymers and reducing the difficulty and cost of post-processing.

[0135] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they 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 butene-1 type polymer, characterized in that, The preparation method includes the following steps: 1) Under the action of a Ziegler-Natta type catalyst system, 1-butene and optional C2-C 10 The α-olefin monomers are polymerized in an inert organic solvent or in liquid 1-butene to obtain a polymer solution; 2) The polymer solution is brought into full contact with the deactivating agent, and then pressurized and heated to obtain a supercritical polymer solution; the pressurization pressure is above 4.0231 MPa, and the heating temperature is 146.69-250℃; 3) The supercritical polymer solution is subjected to a volatilization treatment to obtain a polymer melt; The Ziegler-Natta catalyst system comprises component A, component B, and component C; component A is a Ti-containing solid catalyst component supported on protected alkoxy magnesium particles, the internal electron donor containing carboxylic acid esters and polyol esters; component B is a mixture of organoaluminum and antioxidant, with a molar ratio of organoaluminum to antioxidant of 1:(1-100); component C is an external electron donor. The protected alkoxy magnesium particles contain the reaction product of alkoxy magnesium particles and a particle protectant, wherein the particle protectant is a titanate compound and a polysiloxane substance.

2. The method for preparing butene-1 type polymers according to claim 1, wherein, The structure of the alkoxymagnesium particles is shown in Formula I: Mg(OR9) 2-p (OR 10 ) p Formula I In Equation I, R9 and R 10 Whether the same or different, each is selected from C1-C8 straight-chain alkyl or C3-C8 branched alkyl, 0≤p≤2.

3. The method for preparing butene-1 type polymers according to claim 2, wherein, R9 and R 10 Similarly, 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, dihexoxy magnesium, and di(2-ethyl)hexoxy magnesium.

4. The method for preparing butene-1 type polymers according to claim 2, wherein, 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'' may be the same or different, 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 independent integers from 0 to 4, and a+b+c+d=4; The structure of the polysiloxane-based substance is shown in Formula III: (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 In Equation III, R 1 -R z Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 10 cycloalkyl, C7-C 20 alkylaryl, substituted or unsubstituted C6-C 20 Aromatic groups, C2-C 12 The chain consists of alkenyl, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, cyano, amino, carboxyl, mercapto, carbon functional groups, and polyether chains; the degree of polymerization n+m is an integer from 2 to 100.

5. The method for preparing butene-1 type polymers according to claim 4, wherein, R1'', R2'', and R3'' are selected from C1-C 10 Alkyl groups.

6. The method for preparing butene-1 type polymers according to claim 5, wherein, The titanate compounds are 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.

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

8. The method for preparing butene-1 type polymers according to claim 4, wherein, The polysiloxanes are selected from at least one of polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethylhydrosiloxane, polyhydroxyhydrosiloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyethersiloxane, polycarboxylic siloxane, polyol hydroxysiloxane, polyphenol hydroxysiloxane, polythiol siloxane, and their modifiers.

9. The method for preparing butene-1 type polymers according to claim 8, wherein, The polysiloxanes are at least one of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyethersiloxane, polycyanosiloxane, and their modifiers.

10. The method for preparing butene-1 type polymers according to claim 4, wherein, The molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; the molar ratio of the polysiloxane substance to magnesium in the alkoxy magnesium particles is (0.01-5):

1.

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

1.

12. The method for preparing butene-1 type polymers according to claim 1, wherein, The carboxylic acid ester compounds are selected from benzoic acid monoester compounds or phthalic acid ester compounds with structures as shown in Formula IV. Formula IV In Formula IV, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy; The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):

1.

13. The method for preparing butene-1 type polymers according to claim 12, wherein, At least three of R3-R6 are hydrogen.

14. The method for preparing butene-1 type polymers according to claim 13, wherein, The carboxylic acid ester compounds are selected from ethyl benzoate, propyl benzoate, butyl benzoate, amyl 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, and phthalic acid esters. Dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate, and at least one of their isomers.

15. The method for preparing butene-1 type polymers according to claim 12, wherein, The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.02-2):

1.

16. The method for preparing butene-1 type polymers according to claim 1, wherein, The polyol ester compound is selected from diol ester compounds with structures as shown in Formula V. Formula V In formula V, R 1’ and R 2’ Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl group; R 3’ -R 8’ They may be the same or different, each selected from hydrogen, halogen, substituted or unsubstituted C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl; 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 polyol ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):

1.

17. The method for preparing butene-1 type polymers according to claim 16, wherein, The diol ester compound is at least one selected from 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dinepentyl ester, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol cinnamic acid ester, 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.

18. The method for preparing butene-1 type polymers according to claim 17, wherein, The diol ester compound is at least one selected from 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2,4-pentanediol dibenzoate.

19. The method for preparing butene-1 type polymers according to claim 16, wherein, The molar ratio of the polyol ester compound to magnesium in the alkoxy magnesium particles is (0.02-2):

1.

20. The method for preparing butene-1 type polymers according to claim 1, wherein, The organoaluminum is selected from alkylaluminum compounds and / or alkylaluminoxanes with structures as shown in Formula VI; AlR 9’ h X' (3-h) Formula VI In equation VI, R 9’ Selected from C1-C 20 Alkyl, C7-C 20 Aryl groups, C6-C 20 The aryl group, X' is a halogen, and h is an integer from 0 to 3; The molar ratio of aluminum in the organoaluminum to titanium in the solid catalyst component is (10-500):1; The antioxidant is selected from at least one of phenolic antioxidants, amine antioxidants, phosphite antioxidants, and thioester antioxidants.

21. The method for preparing butene-1 type polymers according to claim 20, wherein, The organoaluminum is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diisobutylaluminum chloride, 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.

22. The method for preparing butene-1 type polymers according to claim 20, wherein, The molar ratio of aluminum in the organoaluminum to titanium in the solid catalyst component is (25-100):

1.

23. The method for preparing butene-1 type polymers according to claim 20, wherein, The antioxidant is a phenolic antioxidant and / or an amine antioxidant.

24. The method for preparing butene-1 type polymers according to claim 1, wherein, The external electron donor is selected from at least one of siloxane compounds, aminosilane compounds, organic amine compounds, and ether compounds; The molar ratio of the external electron donor to the aluminum in the organoaluminum is (0.005-0.5):

1.

25. The method for preparing butene-1 type polymers according to claim 24, wherein, The siloxane compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl tert-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tetraethoxysilane, and n-propylenetriethoxysilane.

26. The method for preparing butene-1 type polymers according to claim 24, wherein, The aminosilane compound is selected from at least one of diethylaminotriethoxysilane, 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, dimethylaminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, di-n-propylaminomethyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, piperidinyltriethoxysilane, and pyrrolyltriethoxysilane.

27. The method for preparing butene-1 type polymers according to claim 24, wherein, The organic amine compounds are selected from aziridine, aziridine, pyrrolidine, aziridine-heptane, aziridine-octane, 2,3-dimethylaziridine, 2,2-dimethylaziridine, 2,2,3,3-tetramethylaziridine, 2,2,4,4-tetramethylaziridine, 2,2,4,4-tetraethylaziridine, 2,2,3,3-tetramethylaziridine, 2,2,3,3-tetraethylaziridine, 2,2,4,4-tetramethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, 2,2,5,5-tetraethylpyrrolidine, 2,2,3,4-tetramethylpyrrolidine, 2,2,4 ... 5,5-Tetra-n-propylpyrrolidine, 2,2,5,5-Tetraisopropylpyrrolidine, 2,2,5,5-Tetraisobutylpyrrolidine, 2,2,6,6-Tetramethylpiperidine, 2,2,6,6-Tetraethylpiperidine, 2,2,6,6-Tetra-n-propylpiperidine, 2,2,6,6-Tetraisopropylpiperidine, 2,2,6,6-Tetraisobutylpiperidine, 2,2,4,4-Tetramethylpiperidine, 2,2,4,4-Tetraethylpiperidine, 2,2,5,5-Tetramethylpiperidine, 2,2,5,5-Tetraethylpiperidine, 2-Methyl-2-cyclohexyl-6-methyl-6-ethylpiperidine, 2,2 -Dicyclopentyl-6,6-dimethylpiperidine, 2,2,7,7-tetramethylazicycloheptane, 2,2,7,7-tetraethylazicycloheptane, 2,2,7,7-tetra-n-propylazicycloheptane, 2,2,7,7-tetraisopropylazicycloheptane, 2,2,7,7-tetraisobutylazicycloheptane, 2,2,5,5-tetramethylazicycloheptane, 2,2,5,5-tetraethylazicycloheptane, 3,3,5,5-tetramethylazicycloheptane, 3,3,5,5-tetraethylazicycloheptane, 2-methyl-2-cyclohexyl-7-methyl-7-azicycloheptane, 2,2 At least one of the following: dicyclopentyl-7,7-dimethylazicycloheptane, 2,2,8,8-tetramethylazicyclooctane, 2,2,8,8-tetraethylazicyclooctane, 2,2,8,8-tetra-n-propylazicyclooctane, 2,2,8,8-tetraisopropylazicyclooctane, 2,2,8,8-tetra-n-butylazicyclooctane, 2,2,8,8-tetraisobutylazicyclooctane, 2,2,7,7-tetramethylazicyclooctane, 2,2,6,6-tetramethylazicyclooctane, 3,3,5,5-tetramethylazicyclooctane, and 3,3,6,6-tetramethylazicyclooctane.

28. The method for preparing butene-1 type polymers according to claim 24, wherein, The ether compound is selected from at least one of the compounds shown in Formula VII. Equation VII In Equation VII, R1' and R2' are each independently selected from C1-C 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 The cycloalkyl group, R3'-R8', is independently selected from hydrogen atoms, halogen atoms, C1-C2 atoms. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aryl alkyl group, wherein any two of R3'-R8' are optionally linked together to form a ring.

29. The method for preparing butene-1 type polymers according to claim 28, wherein, The ether compounds are 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-phenyl-1,3-dimethoxypropane, 2,2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-dimethoxypropane, and 2,2-isopropyl-1,3-dimethoxypropane. At least one of the following: dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dipropoxypropane, 2-isopropyl-2-isopentyl-1,3-diethoxypropane, 2-isopropyl-2-isopentyl-1,3-dipropoxypropane, and 2,2-bis(cyclohexylmethyl)-1,3-diethoxypropane.

30. The method for preparing butene-1 type polymers according to claim 24, wherein, The molar ratio of the external electron donor to the aluminum in the organoaluminum is (0.01-0.4):

1.

31. The method for preparing butene-1 type polymers according to claim 1, wherein, The Ziegler-Natta catalyst system was pre-complexed before being used in the polymerization reaction. The pre-complexation treatment temperature was 5-30℃ and the pre-complexation treatment time was 0.1-180 min. The polymerization reaction temperature is 20-100℃; the polymerization reaction pressure is 1.0-5.0MPa; and the polymerization reaction time is 0.5-4h.

32. The method for preparing butene-1 type polymers according to claim 31, wherein, The temperature for pre-complexation treatment is 5-20℃, and the time for pre-complexation treatment is 5-30 min.

33. The method for preparing butene-1 type polymers according to claim 31, wherein, The polymerization reaction temperature is 30-80℃; the polymerization reaction pressure is 2.0-4.0MPa.

34. The method for preparing butene-1 type polymers according to claim 1, wherein, The deactivating agent is water, oxygen, carbon dioxide, carbon monoxide, or an alcohol, wherein the alcohol is selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol, or glycerol; the amount of the deactivating agent is 0.1%-1.0% of the polymer weight.

35. The method for preparing butene-1 type polymers according to claim 1, wherein, The temperature for volatile matter removal is 100-250℃, and the pressure is 0-4.0 MPaG. The volatile matter removal process also yields 1-butene. The polymer melt is then granulated, and the 1-butene is reused after condensation and purification.

36. The method for preparing butene-1 type polymers according to claim 35, wherein, The pressure is 0.5-3.0 MPaG.

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