CN116769089B - Preparation process and device of polybutene-1 resin - Google Patents
Preparation process and device of polybutene-1 resinInfo
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- CN116769089B CN116769089B CN202210243905.6A CN202210243905A CN116769089B CN 116769089 B CN116769089 B CN 116769089B CN 202210243905 A CN202210243905 A CN 202210243905A CN 116769089 B CN116769089 B CN 116769089B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
本发明属于聚合物制备技术领域，公开了一种聚丁烯‑1类树脂的制备工艺和装置，该制备工艺包括：在Ziegler‑Natta类催化剂体系的作用下，1‑丁烯和任选的C2‑C10的α‑烯烃单体进行聚合反应；将聚合物溶液与抗氧化剂、减活剂进行混合，混合物增压、升温；将混合物进行脱挥发分处理，得到聚合物熔体；Ziegler‑Natta类催化剂体系含有固体催化剂组分、有机铝化合物和外给电子体；固体催化剂组分含有烷氧基镁颗粒、内给电子体和含钛的卤化物的反应产物，内给电子体含有羧酸酯类化合物、多元醇酯化合物和含Si‑H官能团的有机硅化合物。本发明可有效降低1‑丁烯聚合体系粘度大引起的问题，聚合物的性能优良。
The invention belongs to the technical field of polymer preparation, discloses a kind of preparation process and device of polybutene-1 type resin, the preparation process includes：Under the action of Ziegler-Natta type catalyst system, 1-butene and optional C 2 -C 10 alpha-olefin monomers are polymerized；The polymer solution is mixed with antioxidant and deactivator, and the mixture is pressurized and heated；The mixture is devolatilized to obtain a polymer melt；Ziegler-Natta type catalyst system contains solid catalyst component, organoaluminum compound and external electron donor；Solid catalyst component contains the reaction product of alkoxy magnesium particles, internal electron donor and titanium-containing halide, and internal electron donor contains carboxylic acid ester compound, polyol ester compound and organosilicon compound containing Si-H functional group.The present invention can effectively reduce the problems caused by the large viscosity of 1-butene polymerization system, and the performance of polymer is excellent.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a preparation process and a preparation device of polybutene-1 resin.
Background
Compared with other polyolefin materials, the polybutene-1 resin has excellent creep resistance, environmental stress cracking resistance and impact resistance, is very suitable for being used as a pipe, such as a water supply pipe, a hot water pipe, an industrial pipe, a building pipe and the like, and can widen the application field, improve the balance between the toughness and the rigidity of a product by adding a comonomer, so that the polybutene-1 resin has good tearing performance and puncture resistance, is suitable for being used as a film product, and can be also used as a polyolefin modifier and an adhesive. At present, polybutene-1 resins have been used in the fields of pipe materials, food and sanitary product packaging, construction, home furnishings, agriculture and the like.
The preparation method of polybutene-1 resin mainly comprises a gas phase method, a solution method and a bulk method, wherein the bulk method comprises a slurry bulk method and a liquid phase bulk method.
The gas phase process generally employs a fluidized bed gas phase reactor, and patent documents CN102040693A, CN1140545C, US4503203, US3168484, US3580898, US5241024 and US3922322 all relate to the use of Ziegler-Natta catalyst systems, so that the 1-butene monomer is directly polymerized in a gas fluidized bed to synthesize and prepare the 1-butene polymer with better particle morphology and controllable high isotactic index of melt mass flow rate in a certain range. However, the gas phase method has low polymerization activity, which is lower than 5.0 KgPB/g.Cat due to low monomer concentration and low 1-butene monomer partial pressure, and the ash content in the polymer is higher, and the catalyst used by the gas phase method has higher requirements on technology and equipment, so that industrialization is difficult to realize for common small and medium enterprises.
Most of the synthesis of polybutene-1 resins adopts a bulk method, wherein the pressure of a polymerization system is maintained above the saturated vapor pressure of 1-butene at the corresponding polymerization temperature by introducing inert gas CO 2 and the like into a patent document CN1590417A, so that the polymerization conversion rate is improved, but the problem of separating raw materials in the later period after the polymerization is finished is solved, the process flow is complex, and the cost is high. In patent document CN100488994, a bulk precipitation method is adopted to prepare the 1-butene polymer, but the particle morphology of the polymer is irregular, the polymer is extremely easy to adhere, and the polymer is complex to convey and post-treat. In the patent document CN103288993A, a sectional heating mode is adopted to prepare the 1-butene polymer with a spherical form, the bulk density is 0.30g/cm 3, the isotactic index is more than 95%, but the reaction temperature in the first stage is lower than 0-20 ℃, which is not beneficial to the control production of an industrial device. In patent document CN1294161C, a product with an isotactic index of up to 99% can be prepared by a bulk polymerization at a polymerization temperature of 70-75 ℃ in stages, but no mention is made of deactivation or deactivation after the end of the reaction and detailed separation of the polymer system to remove unreacted monomers. Patent document CN106893020A relates to a method for preparing a 1-butene polymer by using an alkoxy silane and ether composite external electron donor system, wherein the method comprises the steps of pre-polymerizing propylene at low temperature to form a polymer with relatively perfect particle morphology, and then carrying out multistage 1-butene polymerization process under the same polymerization process conditions to obtain the 1-butene polymer with relatively good particle morphology, but the process has long reaction period, low polymerization conversion rate, high product ash content and no benefit for use. Patent document CN105482009a relates to a continuous polymerization process device for preparing 1-butene polymer, the device adopts a 1-butene low-temperature slurry prepolymerization reactor and a gas phase horizontal reactor to realize the preparation of 1-butene polymer powder in series, but the polymerization activity of the method is not high.
Because the viscosity of the 1-butene polymer/1-butene polymerization system is 1000-100000cp under the high-temperature polymerization condition, after the comonomer is added, the viscosity of the system is further improved, and after the monomer is removed, the viscosity of the polymer can reach more than 20 multiplied by 10 6 cp. The patent document CN101233158B adds water into the polymer solution at the upstream feed inlet of the screw pump, so that the H 2 O/Al ratio is kept in a certain proportion, the screw pump pressure can be maintained, and stable material conveying is realized, but the process of polymer separation treatment is not involved. In patent document CN103788262B, the polymer is transferred into a closed container containing hot water after the reaction is finished, steam is introduced into the bottom to inactivate the active center, and simultaneously, unreacted monomers are removed, the operation is simple, but the polymer is easy to agglomerate during discharging, and the subsequent material is difficult to convey, so that the method is not suitable for pilot-scale tests and industrialized devices.
Disclosure of Invention
Aiming at the situation, the invention aims to provide a preparation process and a device of polybutene-1 resin, wherein the preparation process adopts a specific catalyst system and a specific process flow, has high polymerization yield and narrow molecular weight distribution of products, and is suitable for continuous and stable material conveying of a high-viscosity system 1-butene polymer/1-butene solution system and subsequent polymer separation treatment.
The first aspect of the present invention provides a process for preparing polybutene-1-based resins, comprising the steps of:
1) Under the action of a Ziegler-Natta catalyst system, carrying out polymerization reaction on 1-butene and optional C 2-C10 alpha-olefin monomers 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 the supercritical 1-butene to obtain a polymer melt;
the Ziegler-Natta catalyst system comprises a solid catalyst component, an organic aluminum compound and an external electron donor, wherein the solid catalyst component comprises reaction products of alkoxy magnesium particles, an internal electron donor and a titanium-containing halide, and the internal electron donor comprises a carboxylate compound, a polyol ester compound and an organosilicon compound containing Si-H functional groups.
The second aspect of the invention provides a preparation device of polybutene-1 resin, which comprises a polymerization reactor, a mixer, a conveying booster pump and devolatilization devices which are sequentially arranged, wherein one or more polymerization reactors are arranged in series, at least two devolatilization devices are arranged in series, and a heat exchanger is arranged in front of each devolatilization device.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with the catalyst system commonly used in the field, the catalyst system used in the invention has higher catalytic efficiency and higher polymerization yield, can effectively reduce the production cost, has narrower molecular weight distribution and adjustable melt index, and is beneficial to adjusting the structural performance of the product.
2) The preparation process can effectively reduce the problems caused by the high viscosity of the 1-butene polymerization system under the high-temperature polymerization condition, greatly reduce the load of a conveying pump and a heat exchanger, improve the mass transfer and heat transfer efficiency, optimize the process flow and simplify the device equipment.
3) The preparation method has the advantages of simple and convenient process operation, low cost, low technical and equipment requirements, easy realization of industrial production and high polymerization efficiency, and the prepared polymer has excellent performance, and the polymer composition structure and the product performance can be adjusted according to the use requirement.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic process flow diagram of a device for preparing polybutene-1 resin according to the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention, there is provided a process for preparing polybutene-1-based resins, the process comprising the steps of:
1) Under the action of a Ziegler-Natta catalyst system, carrying out polymerization reaction on 1-butene and optional C 2-C10 alpha-olefin monomers 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 the supercritical 1-butene to obtain a polymer melt;
the Ziegler-Natta catalyst system comprises a solid catalyst component, an organic aluminum compound and an external electron donor, wherein the solid catalyst component comprises reaction products of alkoxy magnesium particles, an internal electron donor and a titanium-containing halide, and the internal electron donor comprises a carboxylate compound, a polyol ester compound and an organosilicon compound containing Si-H functional groups.
According to the invention, the alkoxy magnesium particles contain the reaction product of magnesium powder, mixed alcohol, halogenating agent and cross-linking agent, and the following reaction materials are adopted:
the magnesium powder has no specific limitation on shape and the like under the condition of ensuring good reaction performance. In order to ensure good reactivity, the magnesium powder is preferably spherical magnesium powder particles with an average particle size of 360 μm or less. In order to ensure the reaction rate, the oxide film thickness of the magnesium powder is preferably 0.5 μm or less.
The mixed alcohol may be a linear or branched monohydric or polyhydric alcohol, preferably a mixture of alcohols of C 1-C10, for example, the mixed alcohol may be selected from methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3, 5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, glycerol, and the like. The mixed alcohol is more preferably a mixture of ethanol and isooctanol wherein ethanol comprises 80-99wt% and isooctanol comprises 1-20wt%. In order to obtain good performance of the magnesium alkoxide particles, the lower the water content in the raw material, the better, and the water content in the alcohol is generally controlled to 1000ppm or less, preferably 200ppm or less.
The molar ratio of the mixed alcohol to the magnesium powder is preferably (2-50) to 1, and more preferably (2.5-18) to 1.
The halogenating agent may be a halogen element and/or an inorganic halide, preferably at least one selected from the group consisting of an iodine element, a bromine element, chlorine gas, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide and an alkoxymagnesium halide, more preferably at least one selected from the group consisting of an iodine element, magnesium iodide, magnesium chloride and an alkoxymagnesium halide, and particularly preferably a mixture of an iodine element and magnesium chloride. In addition, the iodine simple substance or the magnesium chloride can be applied to the reaction in a pure state or in a solution form, and the iodine simple substance and the magnesium chloride can be added into the reaction system respectively or can be mixed together partially or completely to be added into the reaction system.
In order to better control the morphology of the alkoxy magnesium particles, the molar ratio of the halogen atoms in the halogenating agent to the magnesium powder can be (0.0002-0.2) to 1, preferably (0.0025-0.05) to 1.
The cross-linking agent is a titanate compound, and specifically, the structure of the titanate compound is shown as a formula I:
(R 1'O)aTi(OR2')b(OR3')cXd formula I
In formula I, R 1'、R2 'and R 3', which are identical or different, are each selected from H or alkyl, preferably from C 1-C10 alkyl, X is selected from alkoxy, carboxyl, chloro, sulfonic, phosphoric or sulfuric, a, b, C and d are independently integers from 0 to 4, and a+b+c+d=4.
The titanate compound is preferably at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapropyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate and isomers thereof, more preferably at least one selected from the group consisting of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.
The weight ratio of the titanate compound to the magnesium powder is preferably (0.01-5) to 1, and more preferably (0.02-2) to 1.
In the invention, the carboxylic ester compound can be selected from benzoic acid monoester compounds or phthalic acid ester compounds with the structure shown in the formula II,
In formula II, R 1 and R 2 are independently selected from substituted or unsubstituted C 1-C8 alkyl, C 3-C10 cycloalkyl or C 6-C20 aryl, R 3-R6 is independently selected from hydrogen, halogen, C 1-C4 alkyl or C 1-C4 alkoxy, preferably at least three of R 3-R6 are hydrogen.
Specifically, the carboxylic acid ester compound may be selected from at least one of 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, dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, valyl phthalate, propyl hexyl phthalate, ding Wuzhi, ding Ji phthalate, pentyl hexyl phthalate, and isomers thereof.
The molar ratio of the carboxylic ester compound to magnesium in the alkoxy magnesium particles is (0.01-5) to 1, preferably (0.02-2) to 1.
According to the present invention, the polyol ester compound is selected from the group consisting of a glycol ester compound having a structure represented by formula III,
In formula III, R 1' and R 2' are identical or different and are each selected from the group consisting of substituted or unsubstituted C 1-C20 linear alkyl, C 3-C20 branched alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, C 7-C20 arylalkyl, C 2-C10 alkylene, C 10-C20 condensed ring aryl, R 3'-R8' are the same or different and are each selected from hydrogen, halogen, substituted or unsubstituted C 1-C20 straight-chain alkyl, C 3-C20 branched-chain alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, C 7-C20 arylalkyl, C 2-C10 alkylene, C 10-C20, or at least one of R 3'-R6' is cyclic with at least one of R 7'-R8'.
The glycol ester compound specifically includes, but is 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 dimethylbenzoate, 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 cinnamic acid ester, 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, and the like. The glycol ester compound is preferably at least one of 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and 2, 4-pentanediol dibenzoate.
The molar ratio of the polyol ester compound to magnesium in the alkoxy magnesium particles is (0.01-5) to 1, preferably (0.02-2) to 1.
In the invention, the organosilicon compound containing Si-H functional groups is selected from organosilicon compounds with structures shown in formula IV and/or formula V,
In formula IV, R 1-R7, which are identical or different, are each selected from the group consisting of C 1-C12 straight-chain alkyl, C 3-C12 branched-chain alkyl, C 3-C10 cycloalkyl, C 7-C20 alkylaryl, substituted or unsubstituted C 6-C20 aryl, the degree of polymerization m being an integer from 2 to 100, preferably R 1 is selected from the group consisting of C 1-C6 straight-chain or branched-chain alkyl, C 3-C6 cycloalkyl, aryl, R 2-R7 is methyl;
In the formula V, R 8 is selected from the group consisting of C 1-C12 straight-chain alkyl, C 3-C12 branched-chain alkyl, C 3-C10 cycloalkyl, C 7-C20 alkylaryl, substituted or unsubstituted C 6-C20 aryl hydrocarbon, the polymerization degree n is an integer from 3 to 20, R 8 is preferably C 1-C12 straight-chain or branched-chain alkyl, and the polymerization degree n is preferably an integer from 3 to 8.
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, polymethylhydrosiloxane, polyethylhydrosiloxane, polyphenylhydrosiloxane, polycyclohexylhydrosiloxane. Specific examples of the organosilicon compound represented by formula V include, but are not limited to, tetraethyl cyclotetrasiloxane, tetramethyl cyclotetrasiloxane, pentamethyl cyclopentasiloxane. The organosilicon compounds of the formulae IV and V may be used alone or in combination.
The molar ratio of the organosilicon compound containing Si-H functional groups to magnesium in the alkoxy magnesium particles is (0.01-5) to 1, preferably (0.02-2) to 1.
According to the invention, the structure of the titanium-containing halide is shown in a formula VI,
TiX 1 e(OR7)4-e VI
In formula VI, X 1 is halogen, preferably chlorine, R 7 is a C 1-C20 hydrocarbon radical, preferably a C 1-C5 alkyl radical, and e is an integer from 0 to 4.
The amount of the titanium-containing halide may be as desired and referred to in the art.
In the present invention, the content of titanium in the solid catalyst component is 1.0wt% to 8.0wt%, preferably 1.6wt% to 6.0wt%, the content of magnesium atoms is 10wt% to 70wt%, preferably 15wt% to 40wt%, the content of halogen atoms is 20wt% to 86wt%, preferably 36wt% to 80wt%, and the total content of the internal electron donor is 2wt% to 30wt%, preferably 3wt% to 20wt%.
The preparation of the solid catalyst component can be carried out by adopting a conventional method in the prior art, and concretely, the preparation method can be adopted by adopting a method that magnesium alkoxide particles are dispersed by using an inert diluent and are contacted with an internal electron donor and a halide containing titanium to obtain a catalyst mother solution, and solid matters in the mother solution are subjected to filtration, titanium treatment, filtration, washing, drying and other treatments to obtain the solid catalyst component. Wherein, the inert diluent can be at least one of n-hexane, n-heptane, n-octane, n-decane, benzene, toluene and xylene, and the specific dosage is determined according to the needs. The contact temperature of the components is generally from-40 ℃ to 200 ℃, preferably from-20 ℃ to 150 ℃, and the contact time is from 1min to 20h, preferably from 5min to 8h. The number of titanium treatments is 0 to 10, preferably 1 to 5.
According to the present invention, the organoaluminum compound is selected from aluminum alkyl compounds and/or aluminum aluminoxane compounds having the structure shown in formula VII;
AlR 9' hX'(3-h) A VII
In formula VII, R 9' is selected from C 1-C20 alkyl, C 7-C20 aralkyl, C 6-C20 aryl, X' is halogen, and h is an integer from 0 to 3.
The alkylaluminum compound represented by formula VII may be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum chloride, diethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum, tris (2-phenyl-butyl) aluminum and the like. The aluminum compound of the aluminoxane may be at least one selected from the group consisting of methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2, 4-trimethyl-pentyl) aluminoxane, tetra (2, 3-dimethylbutyl) aluminoxane and tetra (2, 3-trimethylbutyl) aluminoxane.
The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component may be (10-500) to 1, preferably (25-100) to 1.
In the invention, the external electron donor is at least one selected from alkoxy silane, amino silane, organic amine compound and ether compound. The external electron donor may be used in an amount conventional in the art.
According to the invention, the components of the Ziegler-Natta type catalyst system are optionally pre-complexed before entering the polymerization reactor, and the solid catalyst component, the organoaluminum compound and the external electron donor are pre-complexed before being fed to the polymerization reactor. The benefits of the pre-complexation treatment are that the polymerization activity and stereotacticity of the catalyst system can be improved. The operating temperature of the pre-complexation treatment is generally in the range of 5-30 ℃, preferably 5-20 ℃, and the residence time is in the range of 5-30min.
In the present invention, the inert organic solvent may be a conventional inert organic solvent in the art, and specifically may be n-hexane, isobutane, n-pentane, propane, isopentane, etc.
Preferably, the 1-butene and optionally the C 2-C10 alpha-olefin monomers are polymerized in liquid 1-butene.
According to the invention, the polymerization temperature is 30-100 ℃, preferably 40-90 ℃, and the polymerization pressure is 1.0-5.0MPa, preferably 2.0-4.0MPa. The average residence time (or average reaction time) is from 0.5 to 4 hours, preferably from 1.5 to 3.0 hours, and can be adjusted in particular according to the process conditions so that the polymer content in the polymer solution is from 0 to 50% by weight, preferably from 10 to 40% by weight.
In addition, hydrogen can be used as a molecular weight regulator in the polymerization process in the polymerization reaction, namely, the addition amount of hydrogen in each polymerization reactor is controlled according to the product requirement, indexes such as average molecular weight, molecular weight distribution, melt mass flow rate and the like of the product are regulated, and the average molecular weight of the polymer can be regulated by controlling the polymerization reaction temperature.
According to the invention, the polymer solution has high-temperature oxidation resistance by adding the antioxidant, so that obvious or tiny gel of the polymer in the subsequent high-temperature devolatilization treatment can be effectively reduced or avoided, the polymer is prevented from being discolored and degraded, the product quality is ensured to be stable, the damage to the appearance is avoided, and the problem of coking caused by long-term residue of the gel in the conveying pump and the material treatment container is prevented. The antioxidant may be at least one selected from hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants and sulfide-containing antioxidants, and is preferably a hindered phenol antioxidant and a phosphite antioxidant. For example, the antioxidants may be 1010, 168, 225, 1076, 1330, 1135, 235, etc. The antioxidants may be used in conventional amounts, for example in amounts of from 0.1 to 1.0% by weight based on the weight of the polymer. The antioxidant selected by the invention can be a solid antioxidant or a liquid antioxidant, preferably a liquid antioxidant, and compared with the solid antioxidant, the liquid antioxidant and the polymer solution are easier to mix and more fully mixed.
According to the invention, the addition of the deactivator can deactivate active centers in the polymer solution, effectively stop the polymerization reaction, and prevent the problem of continuous polymerization or explosion polymerization in the subsequent treatment process. The deactivation agent may be a conventional deactivation agent in the art, for example, water, oxygen, carbon dioxide, carbon monoxide or alcohols. The alcohol is selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol or glycerol. The amount of the deactivation agent is 0.1% -1.0% of the weight of the polymer.
In the invention, 1-butene in the mixture reaches a supercritical state under the actions of pressurization and temperature rise, so that the mixture is ensured to be in a homogeneous state, and the material has a good heat transfer effect. The pressure of pressurizing the mixture is above the critical pressure 4.0231MPa of 1-butene, and at the pressure, the polymer solution can keep homogeneous phase when the temperature is raised, so that the higher heat transfer efficiency can be kept, the situation that the 1-butene is separated due to vaporization in the process of conveying the polymer solution can be avoided, and the conveying process of materials is very difficult. The mixture is heated to a temperature of 146.69 to 250 ℃, preferably 150 to 250 ℃, before entering the devolatilization apparatus, at which the polymerization activity of the Ziegler-Natta type catalyst system is greatly reduced, close to zero, and the catalyst system can be further deactivated.
According to the invention, the devolatilization process achieves an effective separation of the polymer from the unreacted monomers, preferably the devolatilization process is provided with at least two stages, typically at a temperature of 100-250 ℃, a pressure of 0-4.0MPaG, preferably 0-3.0MPaG, the subsequent devolatilization process being operated at approximately atmospheric pressure or vacuum, and the final stage devolatilization process being carried out under high vacuum to remove as much unreacted monomers remaining in the polymer as possible.
In the invention, 1-butene is obtained from the devolatilization treatment, the polymer melt is granulated, and the 1-butene is reused after condensation and purification. The pelletization of the polymer melt and the condensation and purification of 1-butene can be carried out in a manner customary in the art. Additives commonly used in the art, such as light stabilizers, antioxidants, colorants, fillers, etc., may be added during the pelletization of the polymer melt.
According to a second aspect of the invention, the invention provides a preparation device of polybutene-1 resin, which comprises a polymerization reactor, a mixer, a conveying booster pump and devolatilization devices which are sequentially arranged, wherein one or more polymerization reactors are arranged in series, the devolatilization devices are provided with at least two connected in series, and a heat exchanger is arranged in front of each devolatilization device.
In the invention, the preparation device of the polybutene-1 resin also comprises a granulating device and a 1-butene recovery device, wherein the polymer melt outlet of the last devolatilization device is connected with the granulating device, the 1-butene outlet is connected with the 1-butene recovery device, the granule outlet of the granulating device is connected with a storage bin, and the 1-butene outlet of the 1-butene recovery device is connected with a polymerization reactor along the material flow direction.
The delivery booster pump selected in the present invention is a pump suitable for delivering a fluid with high viscosity, and may be a gear pump or a screw pump. A static mixer can be selectively arranged in the heat exchange tube of the selected heat exchanger so as to achieve the effect of enhancing heat transfer. The devolatilization apparatuses of the present invention may be flash tanks, each of which is provided with a heat exchanger to provide heat required for the devolatilization process, and a gear pump or screw pump suitable for high viscosity fluid is installed at the bottom of each devolatilization apparatus to send the polymer solution or polymer melt to downstream equipment.
The granulating equipment can be a vacuum exhaust type granulator, so that the volatile matters in the polymer are further reduced. The 1-butene recovery unit comprises a condenser and optionally conventional purification units.
According to the invention, the use of a plurality of polymerization reactors connected 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 from 2 to 3, and the composition of the polymer can be adjusted by controlling the process parameters of each polymerization reactor (e.g., reactant composition, temperature, residence time, etc.). The polymerization reactor may be a stirred tank reactor or a loop reactor.
The mixer may be a tank-type device with stirring, or may be a static mixer, preferably a static mixer.
The substances, equipment and process parameters not limited in the invention can be selected according to the prior art, and belong to the conventional technical means in the field.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples, the data were obtained as follows:
1. Determination of the Polymer melt Mass Flow Rate (MFR) according to Standard ISO 1133, test conditions 2.16kg,190 ℃.
2. Determination of molecular weight distribution M w/Mn A standard curve was prepared by using WATERS GPC2000, the mass concentration of the sample was 0.1mg/mL, the test temperature was 150℃and the test flow rate was 1mL/min, and the weight average molecular weight (M w), the number average molecular weight (M n) and the molecular weight distribution (M w/Mn) of the sample were calculated from the outflow time by using the molecular weight of polystyrene as an internal reference.
3. Measuring an isotactic index (I.I.), namely weighing about 3g of polymer, weighing m 1 after baking until the weight is constant, extracting the polymer for 48 hours by using diethyl ether in a Soxhlet extractor, recording the mass m 2 of the polymer after baking until the weight is constant, and obtaining the isotactic index of the polymer by the insoluble substance m 2/m1 after diethyl ether extraction.
4. 13 C-NMR measurement of comonomer content was carried out in deuterated o-dichlorobenzene solution (8-12% by weight) of the polymer at 120 ℃. By using a 90 pulse, a 15s delay between pulse and CPD was used to remove 1H-13 C coupling, and a spectrum was obtained on a Bruker AV-600 spectrometer operating in a Fourier transform mode at 120℃at 150 MHz.
The nuclear magnetic calculations may be performed with reference to Carbon-13 NMR spectral assignment of five polyolefins determined from the chemical shift calculation and the polymerization mechanism.
Preparation example 1
Preparation of magnesium alkoxide pellets in a reactor with a stirrer, a reflux condenser, a thermometer and a burette were installed. After sufficient displacement with nitrogen, 480mL of ethanol having a water content of less than 200ppm and 20mL of isooctanol having a water content of less than 200ppm were added to the reactor, and 1.6g of elemental iodine and 0.4g of magnesium chloride were added to dissolve the materials. 32g (less than 360 μm) of magnesium powder was then added. To the reaction mixture was added 0.5g of tetrabutyl titanate for reaction. After stirring, heating until the reflux temperature of the reaction system is reached, and carrying out the reaction until the reaction is finished, namely, no more hydrogen is discharged. Then washing, separating and drying.
The preparation of the solid catalyst component comprises the steps of adding 10g of alkoxy magnesium particles, 50mL of toluene, 3mL of polymethyl hydrosiloxane (m approximately 35), 2.8mL of di-n-butyl phthalate (DNBP) and 1.2mL of diethyl phthalate into a 100mL reaction kettle fully replaced by high-purity nitrogen, heating to 80 ℃ for 2 hours to prepare suspension X1, simultaneously, adding 10mL of toluene and 90mL of titanium tetrachloride into a 300mL reaction kettle fully replaced by high-purity nitrogen, heating to 80 ℃, then adding the suspension X1, slowly heating to 115 ℃, adding 1.0mL of 3, 5-heptanediol dibenzoate in the heating process, keeping the temperature for 2 hours, and then press-filtering the liquid clean. Adding 30mL of titanium tetrachloride and 120mL of toluene, heating to 110 ℃, keeping the temperature for 1 hour, filtering and cleaning the liquid, adding 120mL of titanium tetrachloride and 120mL of toluene, heating to 110 ℃, stirring for 1 hour, treating for 2 times, filtering the liquid, washing the obtained solid with 150mL of hexane for 4 times at 60 ℃, filtering the liquid, and drying to obtain solid powder, namely the solid catalyst component 1.
Preparation example 2
Preparation of magnesium alkoxide pellets in a reactor with a stirrer, a reflux condenser, a thermometer and a burette were installed. After sufficient displacement with nitrogen, 500mL of ethanol having a water content of less than 200ppm and 10mL of isooctanol having a water content of less than 200ppm were added to the reactor, and 1.6g of elemental iodine and 0.4g of magnesium chloride were added to dissolve the materials. 32g (less than 360 μm) of magnesium powder was then added. 5.0g of tetraethyl titanate was added to the reaction mixture to carry out the reaction. After stirring, heating until the reflux temperature of the reaction system is reached, and carrying out the reaction until the reaction is finished, namely, no more hydrogen is discharged. Then washing, separating and drying.
Preparation of solid catalyst component the solid catalyst component 2 was obtained by using the magnesium alkoxide pellets prepared in this preparation example, and the remainder was the same as in preparation example 1.
Preparation example 3
The procedure was as in preparation example 1, except that 2.8mL of diisobutyl phthalate was used in place of 2.8mL of di-n-butyl phthalate, all of which were the same, to obtain solid catalyst component 3.
Preparation example 4
The procedure was as in preparation example 1, except that 3.0mL of tetramethyl cyclotetrasiloxane was used instead of 3mL of polymethylhydrosiloxane (n.apprxeq.35), the remainder being the same, to obtain solid catalyst component 4.
Example 1
Referring to fig. 1, the preparation device comprises a polymerization reactor 1, a mixer 2, a conveying booster pump 3, a devolatilization device 4, a granulating device 6 and a 1-butene recovery device 7 which are sequentially arranged, wherein the polymerization reactor 1 is provided with two (only one is shown in fig. 1) connected in series, the polymerization reactor is a liquid-phase stirred tank reactor, the devolatilization device is provided with two connected in series, a heat exchanger 5 is arranged in front of each devolatilization device, the devolatilization device 4 is a flash tank, the polymer melt outlet of the last devolatilization device 4 is connected with the granulating device 6 along the material flow direction, the 1-butene outlet is connected with the 1-butene recovery device 7, the granule outlet of the granulating device 6 is connected with a feed bin 8, and the 1-butene outlet of the 1-butene recovery device 7 is connected with the polymerization reactor 1.
The preparation process of this example comprises that the catalyst system comprises a solid catalyst component 1, triethylaluminum and dicyclopentyl dimethoxy silane, the components of the catalyst system are continuously introduced into a polymerization reactor after precontacting for 8min at 6 ℃, the flow rate of Triethylaluminum (TEA) is 6.33g/hr, the flow rate of dicyclopentyl dimethoxy silane (DCPMS) is 0.25g/hr, the flow rate of the solid catalyst component 1 is 0.6g/hr, and the molar ratio of TEA to DCPMS is 50:1.
The polymerization was carried out in two stirred tank reactors connected in series with liquid phase, 1-butene was continuously fed into the reactors in an amount of 5.9kg/hr and hydrogen in an amount of 50ppm (H 2/1-butene molar ratio), the polymerization temperature was 70℃and the polymerization pressure was 2.0MPa, and the residence time in the two reactors was 120min and 60min, respectively.
After polymerization, mixing the polymer solution with an antioxidant and a deactivation agent in a mixer 2, wherein the antioxidant is 1010 and 168 (mass ratio 1:1), the dosage of the antioxidant is 0.5 percent of the weight of the polymer, the deactivation agent is propylene glycol, the dosage of the deactivation agent is 0.5 percent of the weight of the polymer, and the obtained mixture is pressurized to 4.1MPa and heated to 148 ℃ to obtain a mixture containing supercritical 1-butene;
The mixture containing the supercritical 1-butene is subjected to devolatilization treatment in a first devolatilization device, the operating pressure is 2.6MPa and the temperature is 130 ℃, then the temperature is raised to 190 ℃, the mixture enters a second devolatilization device for devolatilization treatment, the operating pressure is 0.5MPa and the temperature is 170 ℃, polymer melt and 1-butene are obtained, 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 repeated use.
Example 2
The difference from example 1 is that liquid antioxidant 1135 is selected instead of antioxidants 1010 and 168, the remainder being the same.
Example 3
The difference from example 1 was that the hydrogen concentration was 50ppm in the reactor, and the rest was the same.
Example 4
The difference from example 1 was that the hydrogen concentration was 400ppm in the reactor, and the rest was the same.
Example 5
The difference from example 1 was that the feed monomers were 1-butene and ethylene, and that C2/(C2+C4) was 0.6mol%, the remainder being the same.
Example 6
The difference from example 1 was that the feed monomers were 1-butene and ethylene, C2/(C2+C4) was 6.2mol%, and the remainder were the same.
Example 7
The difference from example 1 is that the polymer is pressurized to 4.5MPa and warmed to 160℃before devolatilization, the remainder being the same.
Example 8
The difference from example 1 is that the polymerization reaction was carried out using n-hexane as a solvent to form a solution system of n-hexane, and the rest was the same.
Example 9
The difference from example 1 is that in the catalyst system, solid catalyst component 2 is used instead of solid catalyst component 1, the remainder being identical.
Example 10
The difference from example 1 is that in the catalyst system, solid catalyst component 3 was used instead of solid catalyst component 1, the remainder being identical.
Example 11
The difference from example 1 is that in the catalyst system, a solid catalyst component 4 is used instead of the solid catalyst component 1, the remainder being identical.
Comparative example 1
The difference from example 1 is that no antioxidant and no deactivator are added to the mixer after the polymerization is completed, the remainder being the same.
Comparative example 2
The difference from example 1 is that the mixture is warmed to 135 ℃ before entering the devolatilization apparatus, the remainder being the same.
Comparative example 3
The difference from example 1 is that the catalyst is a commercial DQ type catalyst, and the rest are the same.
The polymer powders prepared in each example and comparative example were subjected to characterization analysis, and the results are shown in Table 1.
TABLE 1
As is clear from Table 1, the catalyst system of the present invention has a high polymerization yield, and the MFR of the polymer can be adjusted, and the molecular weight distribution is narrow (3.5 to 5.0). The method has the advantages that an antioxidant and a deactivator are not added into the mixer, the polymer is degraded in the subsequent high-temperature devolatilization process, the mass flow rate of the polymer melt is increased, the temperature rise before devolatilization is reduced, the property of the obtained polymer is not changed greatly, but the pipeline is easy to be blocked in the running process of the device, and compared with the commercial DQ type catalyst, the method has higher yield, higher isotactic index and narrower molecular weight distribution of the polymer.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (34)
1. The preparation process of the polybutene-1 resin is characterized by comprising the following steps:
1) Under the action of a Ziegler-Natta catalyst system, carrying out polymerization reaction on 1-butene and optional C 2-C10 alpha-olefin monomers 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 the supercritical 1-butene to obtain a polymer melt;
the Ziegler-Natta catalyst system comprises a solid catalyst component, an organic aluminum compound and an external electron donor, wherein the solid catalyst component comprises reaction products of alkoxy magnesium particles, an internal electron donor and a titanium-containing halide, and the internal electron donor comprises a carboxylate compound, a polyol ester compound and an organosilicon compound containing Si-H functional groups.
2. The process for preparing polybutene-1 resin according to claim 1, wherein the alkoxy magnesium particles contain the reaction product of magnesium powder, mixed alcohol, halogenating agent and crosslinking agent, wherein the halogenating agent is halogen simple substance and/or inorganic halide, and the crosslinking agent is titanate compound;
the mole ratio of halogen atoms in the halogenating agent to magnesium powder is (0.0002-0.2): 1.
3. The process for producing polybutene-1 resin according to claim 2, wherein the magnesium powder is spherical magnesium powder particles having an average particle diameter of 360 μm or less and the oxide film thickness of the magnesium powder is 0.5 μm or less.
4. The process for producing polybutene-1 based resins according to claim 2, wherein the mixed alcohol is a mixture of alcohols of C 1-C10.
5. The process for preparing polybutene-1 based resins according to claim 4, wherein the mixed alcohol is a mixture of ethanol and isooctanol, wherein ethanol is 80-99% by weight and isooctanol is 1-20% by weight.
6. The process for preparing polybutene-1 resin according to claim 2, wherein the halogenating agent is at least one selected from elemental iodine, elemental bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide and alkoxymagnesium halide.
7. The process for producing polybutene-1 based resins according to claim 6, wherein the halogenating agent is at least one selected from elemental iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halides.
8. The process for producing polybutene-1 based resins according to claim 7, wherein the halogenating agent is a mixture of elemental iodine and magnesium chloride.
9. The process for preparing polybutene-1 based resins according to claim 2, wherein the titanate compound has the structure shown in formula I:
(R 1'O)aTi(OR2')b(OR3')cXd formula I
In the formula I, R 1'、R2 'and R 3' are the same or different and are each selected from H or alkyl, X is selected from alkoxy, carboxyl, chloro, sulfonic, phosphoric or sulfuric, a, b, c and d are independently integers from 0 to 4, and a+b+c+d=4.
10. The process for preparing polybutene-1 based resins according to claim 9, wherein R 1'、R2 'and R 3' are selected from alkyl groups of C 1-C10.
11. The process for preparing polybutene-1 based resin according to claim 10, wherein the titanate-based compound is 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 isomers thereof.
12. The process for preparing polybutene-1 based resins according to claim 11, wherein the titanate compound is at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.
13. The process for producing polybutene-1 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 atom in the halogenating agent to the magnesium powder is (0.0025-0.05) 1.
14. The process for preparing polybutene-1 based resins according to claim 13, wherein the weight ratio of titanate compound to magnesium powder is (0.02-2) 1 and the molar ratio of mixed alcohol to magnesium powder is (2.5-18) 1.
15. The process for preparing polybutene-1 resin according to claim 1, wherein the carboxylic acid ester compound is selected from benzoic acid monoester compounds or phthalic acid ester compounds having the structure shown in formula II,
In formula II, R 1 and R 2 are independently selected from substituted or unsubstituted C 1-C8 alkyl, C 3-C10 cycloalkyl or C 6-C20 aryl, R 3-R6 is independently selected from hydrogen, halogen, C 1-C4 alkyl or C 1-C4 alkoxy;
The polyol ester compound is selected from the diol ester compounds with the structure shown in a formula III,
In formula III, R 1' and R 2' are identical or different and are each selected from the group consisting of substituted or unsubstituted C 1-C20 linear alkyl, C 3-C20 branched alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, C 7-C20 arylalkyl, C 2-C10 alkylene, C 10-C20 condensed ring aryl, R 3'-R8' are the same or different and are each selected from hydrogen, halogen, substituted or unsubstituted C 1-C20 straight-chain alkyl, C 3-C20 branched-chain alkyl, C 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, C 7-C20 arylalkyl, C 2-C10 alkylene, A fused ring aryl of C 10-C20, or at least one of R 3'-R6' is cyclic with at least one of R 7'-R8';
The organosilicon compound containing Si-H functional groups is selected from organosilicon compounds with structures shown in a formula IV and/or a formula V,
In the formula IV, R 1-R7 are the same or different and are each selected from the group consisting of C 1-C12 straight-chain alkyl, C 3-C12 branched-chain alkyl, C 3-C10 cycloalkyl, C 7-C20 alkylaryl, substituted or unsubstituted aryl hydrocarbon of C 6-C20, and the polymerization degree m is an integer from 2 to 100;
In the formula V, R 8 is selected from linear alkyl of C 1-C12, branched alkyl of C 3-C12, cycloalkyl of C 3-C10, alkylaryl of C 7-C20, substituted or unsubstituted aryl of C 6-C20, and the polymerization degree n is an integer of 3-20;
The molar ratio of the carboxylate compound to magnesium in the alkoxy magnesium particles is (0.01-5) 1, the molar ratio of the polyol ester compound to 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 magnesium in the alkoxy magnesium particles is (0.01-5) 1.
16. The process for preparing polybutene-1 based resins according to claim 15, wherein at least three of R 3-R6 are hydrogen.
17. The process for preparing polybutene-1 based resin according to claim 16, wherein the carboxylic acid ester compound is selected from at least one of 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, dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, ding Wuzhi, ding Ji, pentyl hexyl phthalate and isomers thereof.
18. The process for producing polybutene-1 based resins according to claim 15, wherein the diol ester compound is at least one of 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 dipentyl ester, 2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 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 producing polybutene-1 based resins 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 polybutene-1 based resins 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, polymethylhydrosiloxane, polyethylhydrosiloxane, polyphenylhydrosiloxane, polycyclohexylhydrosiloxane, tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and pentamethylcyclopentasiloxane.
21. The process for producing polybutene-1 based resins according to claim 15, wherein the molar ratio of the carboxylic acid ester compound to magnesium in the alkoxymagnesium particles is (0.02-2): 1, the molar ratio of the polyhydric alcohol ester compound to magnesium in the alkoxymagnesium particles is (0.02-2): 1, and the molar ratio of the Si-H functional group-containing organosilicon compound to magnesium in the alkoxymagnesium particles is (0.02-2): 1.
22. The process for producing polybutene-1 based resins according to claim 1, wherein the titanium-containing halide has a structure represented by the formula VI,
TiX 1 e(OR7)4-e VI
In formula VI, X 1 is halogen, R 7 is C 1-C20 hydrocarbyl, and e is an integer from 0 to 4.
23. The process for preparing polybutene-1 based resins according to claim 22, wherein X 1 is chlorine and R 7 is C 1-C5 alkyl.
24. The process for producing polybutene-1 based resin according to claim 1, wherein the organoaluminum compound is selected from the group consisting of an alkylaluminum compound represented by the formula VII and/or an aluminum compound of aluminoxane;
AlR 9' hX'(3-h) A VII
In the formula VII, R 9' is selected from alkyl of C 1-C20, aralkyl of C 7-C20 and aryl of C 6-C20, X' is halogen, and h is an integer of 0-3;
the molar ratio of aluminum in the organic aluminum compound to titanium in the solid catalyst component is (10-500): 1;
the external electron donor is at least one selected from alkoxy silane, amino silane, organic amine compound and ether compound.
25. The process for preparing polybutene-1 based resins according to claim 24, wherein the organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, diethylaluminum chloride, monoethylaluminum dichloride, dimethylaluminum monochloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, tris (2-methyl-3-phenyl-butyl) aluminum, tris (2-phenyl-butyl) aluminum, methylaluminoxane, tetra (isobutyl) aluminoxane, tetra (2, 4-trimethyl-pentyl) aluminoxane, tetra (2, 3-dimethylbutyl) aluminoxane and tetra (2, 3-trimethylbutyl) aluminoxane.
26. The process for producing polybutene-1 based resins according to claim 24, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is (25-100): 1.
27. The process for preparing polybutene-1 based resins according to claim 1, wherein 1-butene and optionally C 2-C10 α -olefin monomers are polymerized in liquid 1-butene;
the polymerization temperature is 30-100 deg.c and the polymerization pressure is 1.0-5.0MPa.
28. The process for producing polybutene-1 resins according to claim 27, wherein the polymerization temperature is 40-90℃and the polymerization pressure is 2.0-4.0MPa.
29. The process for preparing polybutene-1 based resins according to claim 1, wherein the antioxidant is at least one selected from the group consisting of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants and sulfide antioxidants, and the amount of the antioxidant is 0.1 to 1.0% by weight of the polymer;
The deactivation agent is water, oxygen, carbon dioxide, carbon monoxide or alcohols, wherein the alcohols are selected from methanol, ethanol, propanol, ethylene glycol, propylene glycol or glycerol, and the dosage of the deactivation agent is 0.1-1.0% of the weight of the polymer;
the pressurizing pressure is above 4.0231MPa of critical pressure of 1-butene, and the temperature is 146.69-250 ℃.
30. The process for preparing polybutene-1 based resins according to claim 29, wherein the antioxidants are hindered phenol antioxidants and phosphite antioxidants.
31. The process for producing polybutene-1 based resins according to claim 1, wherein the devolatilization treatment is carried out at a temperature of 100 to 250℃and a pressure of 0 to 4.0MPaG;
and the devolatilization treatment also obtains 1-butene, the polymer melt is granulated, and the 1-butene is reused after condensation and purification.
32. The process for producing polybutene-1 based resins according to claim 31, wherein the pressure is 0 to 3.0MpaG.
33. The process for preparing polybutene-1 resin according to any one of claims 1 to 32, wherein the process adopts a preparation device of polybutene-1 resin, the preparation device comprises a polymerization reactor, a mixer, a conveying booster pump and devolatilization devices which are sequentially arranged, one or more polymerization reactors are arranged in series, at least two devolatilization devices are arranged in series, and a heat exchanger is arranged in front of each devolatilization device.
34. The process for producing polybutene-1 resin according to claim 33, further comprising a granulating device and a 1-butene recovering device, wherein the polymer melt outlet of the last devolatilizing device is connected to the granulating device, the 1-butene outlet is connected to the 1-butene recovering device, the pellet outlet of the granulating device is connected to the silo, and the 1-butene outlet of the 1-butene recovering device is connected to the polymerization reactor in the flow direction of the material.
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