CN116496439A - Method for synthesizing high molecular weight olefin functional polymer - Google Patents

Method for synthesizing high molecular weight olefin functional polymer Download PDF

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Publication number
CN116496439A
CN116496439A CN202310753388.1A CN202310753388A CN116496439A CN 116496439 A CN116496439 A CN 116496439A CN 202310753388 A CN202310753388 A CN 202310753388A CN 116496439 A CN116496439 A CN 116496439A
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solvent
olefin
pressure
combination
polymerization reaction
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王根林
丁克鸿
张留乔
徐林
王铖
冯青宇
史青
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Jiangsu Yangnong Chemical Group Co Ltd
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Jiangsu Yangnong Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The present invention provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising: introducing low-carbon olefin into the reactor, heating and boosting to a supercritical state, preparing a liquid solution from a functional monomer and an initiator, and adding the liquid solution into the reactor to perform polymerization reaction; and (3) carrying out gas-solid-liquid separation on the reacted system, discharging the low-carbon olefin, returning to use, mixing the rest materials with the first solvent, adding the mixture into the second solvent together to separate out solids, and carrying out solid-liquid separation to obtain the high-molecular-weight olefin functional polymer and the liquid-phase material. The invention is beneficial to the diffusion of the monomer to the active high molecular chain segment to realize the same-chain alternate copolymerization of the monomer and the functional monomer through the polymerization of the low carbon olefin in the supercritical state, has no solvent shielding effect on free radicals, has high monomer utilization rate and conversion efficiency, has high molecular chain segment activity capability and promotes the synthesis of high molecular weight olefin functional polymer; the method is simple to operate, saves energy consumption and is environment-friendly.

Description

Method for synthesizing high molecular weight olefin functional polymer
Technical Field
The invention belongs to the technical field of organic polymerization, and relates to a method for synthesizing a high molecular weight olefin functional polymer.
Background
The olefin functional polymer is used as a functional high polymer material, has wide application in the aspects of engineering plastic chain extension, high-performance composite material, nylon infiltration, ink dispersion, microencapsulation, filtration membrane film formation and the like, and is greatly concerned. The molecular chain of the olefin functional polymer has a large number of active groups, which can react with a plurality of functional groups, thereby preparing various products; in addition, the olefin functional polymer can be used for preparing microcapsules, and has good application prospects in the fields of pesticides, fragrances and medicines.
The synthetic raw materials of the olefin functional polymer mainly comprise olefin and functional monomers, and corresponding synthetic processes are needed according to different types of olefin or functional monomers in the synthetic raw materials of the olefin functional polymer. CN 101580564a discloses a method for synthesizing a high molecular weight alternating copolymer of styrene and maleic anhydride, which comprises: under the protection of nitrogen, adding monomer maleic anhydride and an initiator into a medium for full dissolution, adding monomer styrene into the system for dissolution, reacting at 50-90 ℃ for 0.5-72 h to obtain a dispersion system of high molecular weight styrene and maleic anhydride polymer microspheres, and performing centrifugal separation and vacuum drying to obtain a white solid of the high molecular weight styrene and maleic anhydride alternating copolymer. CN 102212166a discloses a new method for copolymerization of dicyclopentadiene and maleic anhydride, which is to add monomer and initiator into organic medium to dissolve under nitrogen protection, react for 2-12 h at 60-90 ℃ to obtain self-stabilizing dispersion system of monodisperse microsphere of alternating copolymer, and then centrifugally separate and dry to obtain white solid of alternating copolymer of dicyclopentadiene/maleic anhydride.
In the above patents, maleic anhydride is used as a functional monomer to polymerize with an olefin, but the olefin used is usually an olefin of at least C4, and is usually a liquid olefin such as a diene, a cycloolefin or an isoolefin, but the polymerization of a gaseous olefin of at most C4 is not involved. CN 113388123a discloses a preparation method of high-viscosity nylon, which comprises the following steps: the nylon salt prepolymer and the olefin-maleic anhydride copolymer are mixed and subjected to polycondensation reaction to prepare the high-viscosity nylon, and the process method for synthesizing the copolymer by using the olefin-maleic anhydride copolymer in the method is not clear although ethylene-maleic anhydride alternating copolymer and the like can be selected.
In the ethylene-maleic anhydride alternating copolymer, maleic anhydride forms a high molecular main chain through chemical bond and ethylene copolymerization, and has higher thermal stability, no migration of free maleic anhydride and no trouble of odor and VOC unlike the maleic anhydride grafts on the market. Based on the polymerization method commonly used at present, the traditional precipitation polymerization can realize the alternating copolymerization of monomers to obtain a solid functional polymer, but is limited by the concentration of the monomers, the molecular weight of the copolymer can not reach a high enough level, and the application is limited.
Supercritical fluid refers to a fluid whose temperature and pressure are above their critical states. Supercritical fluids are non-condensable gases that do not liquefy even if the pressure is increased because the liquid and gas boundaries disappear. The physical properties of supercritical fluid have both liquid and gas properties, are basically still a gas, but are different from common gases, are dense gases, have densities which are two orders of magnitude greater than that of common gases, are similar to liquids, have viscosities which are smaller than liquids, and have diffusion speeds which are about two orders of magnitude faster than liquids, so that the supercritical fluid has better flowability and transfer performance. The extremely low viscosity and zero surface tension of the supercritical fluid are beneficial to the diffusion of monomers to active high molecular chain ends, the activity capacity of molecular chain segments is improved, the solvent has no shielding effect on free radicals, and the negative reaction of transferring the free radicals to solvent chains can not occur. Therefore, the heating and pressurizing of the olefin to the supercritical state and the copolymerization of the olefin and the liquid-phase functional monomer can be used as an effective means for preparing the high-molecular-weight olefin functional polymer.
In summary, a proper synthesis process and polymerization mode are selected according to the characteristics of raw materials, supercritical olefin and liquid-phase functional monomer are utilized for copolymerization, and complex separation steps are not needed, so that an olefin functional polymer product with high molecular weight is obtained, and the industrial application prospect is wide.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for synthesizing a high molecular weight olefin functional polymer, which takes a low-carbon olefin fluid in a supercritical state as a reaction monomer to be copolymerized with the functional monomer, and adopts a polymerization process initiated by a free radical initiator. The co-chain alternating copolymerization of the olefin and the functional monomer is easy to realize under the polymerization process, the molecular chain segment activity, the monomer utilization rate and the conversion efficiency are greatly improved, the chain termination and the chain transfer are effectively inhibited, and the synthesis of the high molecular weight olefin functional polymer is realized; the post-reaction treatment process is simple, the reaction condition is mild, the separation and purification are easy, the energy consumption is saved, and the cost is reduced.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for synthesizing a high molecular weight olefin functional polymer, which comprises the following steps:
(1) Introducing low-carbon olefin into the reactor, heating and boosting to a supercritical state, preparing a homogeneous liquid solution of a functional monomer and an initiator, and adding the homogeneous liquid solution into the reactor to perform polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), returning the discharged low-carbon olefin to the step (1) for reuse, mixing the residual material with the first solvent after discharging, adding the mixture into the second solvent together to precipitate solids, and carrying out solid-liquid separation to obtain the high-molecular-weight olefin functional polymer and the liquid-phase material.
In the invention, for the synthesis of olefin functional polymers, the state of low-carbon olefin and the selection of functional monomers have important influence on the performance of the polymers, the supercritical low-carbon olefin and the liquid-phase functional monomers are adopted to react, the solvent has no shielding effect on free radicals, the monomer utilization rate and the conversion efficiency are high, the activity capacity of a molecular chain segment is high, the diffusion of the monomers to the active high-molecular chain segment is facilitated, the co-chain alternating copolymerization of olefin monomers and functional monomers is realized, and the high-molecular-weight olefin functional polymers are synthesized and obtained, and the post-treatment process is simple and easy to separate and purify; the method is simple to operate, mild in reaction conditions, low in cost and environment-friendly, and raw materials can be recycled, so that energy consumption is saved.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the reactor in the step (1) comprises a high-pressure reactor.
Preferably, before the light olefins are introduced in the step (1), the reactor is vacuumized and then is replaced by a shielding gas.
Preferably, the light olefins of step (1) comprise any one or a combination of at least two of ethylene, propylene, butene or butadiene, typical but non-limiting examples of which are: a combination of ethylene and propylene, a combination of propylene and butene, a combination of ethylene, propylene and butene, and the like.
Preferably, the supercritical state of the light olefins in step (1) is: the supercritical ethylene temperature is 9.19 ℃, such as 10 ℃, 30 ℃, 50 ℃, 80 ℃, 100 ℃, etc., the pressure is 5.04MPa, such as 6MPa, 10MPa, 15MPa, 20MPa, 30MPa, 40MPa, 50MPa, etc., the supercritical propylene temperature is 91.9 ℃, such as 92 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 150 ℃, etc., the pressure is 4.62MPa, such as 5MPa, 10MPa, 15MPa, 20MPa, 30MPa, 40MPa, 50MPa, etc., or the supercritical butene temperature is 146.4 ℃, such as 147 ℃, 148 ℃, 149 ℃, 150 ℃, etc., the pressure is 4.05MPa, such as 5MPa, 10MPa, 15MPa, 20MPa, 30MPa, 40MPa, 50MPa, etc., but not limited to the values recited, and other non-recited values within the respective value ranges are equally applicable.
As a preferred embodiment of the present invention, the functional monomer in step (1) includes any one or a combination of at least two of maleic anhydride, maleimide or maleic acid, and typical but non-limiting examples of such combinations are: a combination of maleic anhydride and maleimide, a combination of maleimide and maleic acid, a combination of maleic anhydride, maleimide and maleic acid, and the like.
Preferably, the initiator of step (1) comprises azo compounds and/or peroxide compounds.
Preferably, the azo-based compound includes any one or a combination of at least two of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobicyclohexylcarbonitrile, or dimethyl azobisisobutyrate, typical but non-limiting examples of such combinations are: a combination of azobisisobutyronitrile and azobisisovaleronitrile, a combination of azobisisobutyronitrile and azobisisoheptonitrile, a combination of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate, a combination of azobisisovaleronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate, and the like.
Preferably, the peroxide-based compound comprises benzoyl peroxide, dicumyl peroxide, diisobutyryl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, lauroyl peroxide, t-butyl peroxyneoheptanoate, t-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, di (hexadecyl) dicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxypivalate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis-butyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, t-butyl peroxy2-ethylhexanoate, bitetradecyl peroxydicarbonate, t-butyl peroxyneodecanoate, isopropyl peroxyneodecanoate, di-t-butyl peroxycyclohexylsulfonyl acetyl peroxide, 1, 3, 3-tetramethylbutyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate or pivaloate 1, 1, 3, 3-tetramethylbutyl peroxydicarbonate, or at least one or a combination of any two of the foregoing typical examples but not limiting the at least: a combination of benzoyl peroxide and lauroyl peroxide, a combination of benzoyl peroxide and dicumyl peroxide, a combination of dicumyl peroxide and diisopropyl peroxydicarbonate, a combination of benzoyl peroxide, lauroyl peroxide and dicumyl peroxide, and the like.
Preferably, the molar ratio of the initiator to the functional monomer in the step (1) is (0.001-0.01): 1, for example, 0.001:1, 0.002:1, 0.003:1, 0.005:1, 0.007:1 or 0.01:1, etc., but not limited to the recited values, other non-recited values within the range are equally applicable.
Preferably, the functional monomer and the initiator in the step (1) are pumped into the reactor at a constant speed after being prepared into a homogeneous liquid solution.
Preferably, the functional monomer and the initiator are preheated to a temperature above the melting temperature of the functional monomer, and the initiator is dissolved after the functional monomer is melted to form a homogeneous liquid solution.
Preferably, the feeding time of the homogeneous liquid solution in step (1) is 2-6 h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 6h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the feed temperature of the homogeneous liquid solution of step (1) is not lower than the melting temperature of the functional monomer.
In a preferred embodiment of the present invention, the polymerization reaction in the step (1) is carried out at a temperature of 55 to 150 ℃, for example, 55 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃ or the like, but the polymerization reaction is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
Preferably, the pressure of the polymerization reaction in the step (1) is 10 to 100MPa, for example, 10MPa, 15MPa, 20MPa, 30MPa, 50MPa, 60MPa, 80MPa or 100MPa, etc., but the polymerization reaction is not limited to the values listed, and other values not listed in the range are applicable.
Preferably, the polymerization reaction time in the step (1) is 10 to 24 hours, for example, 10 hours, 11 hours, 13 hours, 15 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, etc., but the polymerization reaction time is not limited to the recited values, and other non-recited values in the range of the recited values are equally applicable.
Preferably, in the polymerization reaction process in the step (1), the pressure is maintained by continuously introducing the low-carbon olefin.
In the preferred technical scheme of the invention, the low-carbon olefin is discharged in the gas-solid-liquid separation process in the step (2) and replaced by a protective gas, wherein the protective gas can be nitrogen or inert gas.
Preferably, the discharged low-carbon olefin is pressurized and returned to the step (1) for reuse.
Preferably, the mixing manner of the residual material and the first solvent in the step (2) is as follows: the remaining material is dissolved in the first solvent at a temperature of 35 to 80 ℃, for example 35 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, but the remaining material is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the first solvent of step (2) comprises any one or a combination of at least two of tetrahydrofuran, acetone, N-dimethylformamide, dimethyl sulfoxide, typical but non-limiting examples of such combinations being: a combination of acetone and tetrahydrofuran, a combination of acetone and dimethyl sulfoxide, a combination of N, N-dimethylformamide and dimethyl sulfoxide, and the like.
Preferably, the mass ratio of the first solvent to the remaining material in the step (2) is (1-100): 1, for example, 1:1, 5:1, 10:1, 20:1, 30:1, 50:1, 60:1, 80:1 or 100:1, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the second solvent of step (2) comprises any one or a combination of at least two of n-hexane, diethyl ether, n-heptane, n-pentane or n-butyl ether, and typical but non-limiting examples of such combinations are: a combination of n-hexane and diethyl ether, a combination of n-pentane and n-butyl ether, a combination of diethyl ether and n-butyl ether, a combination of n-hexane, n-heptane and n-pentane, and the like.
Preferably, after the residual material in step (2) is mixed with the first solvent, the mixture is added dropwise to the second solvent.
Preferably, the dropping speed is 0.5 to 20mL/min, for example, 0.5mL/min, 1mL/min, 3mL/min, 5mL/min, 8mL/min, 10mL/min, 12mL/min, 15mL/min, 18mL/min or 20mL/min, etc., but the dropping speed is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the stirring is performed during the dropping, and the stirring speed is 50 to 1000rpm, for example, 50rpm, 100rpm, 200rpm, 300rpm, 500rpm, 600rpm, 800rpm, 1000rpm, etc., but the stirring speed is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the volume ratio of the second solvent to the first solvent in the step (2) is 15:1 to 50:1, for example, 15:1, 20:1, 25:1, 30:1, 40:1, 45:1 or 50:1, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred embodiment of the present invention, the solid-liquid separation of step (2) comprises one or a combination of two of filtration, decantation or centrifugation, typical but non-limiting examples of which are: a combination of decantation and filtration, a combination of filtration and centrifugation, a combination of decantation, filtration and centrifugation, and the like, preferably filtration, and more preferably pressure filtration.
Preferably, the filtering comprises the steps of adopting a protective gas to carry out filter pressing, washing and drying the obtained filter cake, and crushing and collecting the filter cake.
Preferably, the drying is vacuum drying, and the pressure of the vacuum drying is-0.1 to-0.01 MPa, for example-0.1 MPa, -0.09MPa, -0.08MPa, -0.07MPa, -0.06MPa, -0.05MPa, -0.04MPa, -0.03MPa, -0.02MPa or-0.01 MPa, etc., but the vacuum drying is not limited to the recited values, and other non-recited values in the range of the values are equally applicable; the temperature is 30 to 120 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or 120 ℃, etc., but not limited to the values listed, and other values not listed in the range are applicable.
Preferably, the molecular weight of the olefin functional polymer in the step (2) is 100000 to 500000, for example 100000, 150000, 200000, 250000, 300000, 350000, 400000, 450000 or 500000, but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
In the present invention, the olefin functional polymer is a microspheroidal particle having a particle diameter of 10 to 50. Mu.m, for example, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm or 50 μm, etc., but the olefin functional polymer is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are similarly applicable.
As a preferable technical scheme of the invention, the liquid phase material in the step (2) is separated, and the obtained recovered solvent is returned to the step (2) for reuse.
Preferably, the liquid phase material separation process comprises any one or a combination of at least two of rectification, membrane separation, washing or extraction, typical but non-limiting examples of which are: a combination of rectification and membrane separation, a combination of rectification and extraction, a combination of rectification, membrane separation and washing, and the like.
Preferably, the rectified overhead fraction is separated to obtain a first solvent and a second solvent, and the first solvent and the second solvent are respectively returned to the step (2) for reuse.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Firstly, vacuumizing the high-pressure reaction kettle, introducing protective gas for replacement, then introducing low-carbon olefin into the high-pressure reaction kettle, heating and boosting to a supercritical state, wherein the low-carbon olefin comprises any one or a combination of at least two of ethylene, propylene, butylene and butadiene, then preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the functional monomer into the high-pressure reaction kettle, carrying out polymerization reaction, wherein the functional monomer comprises any one or a combination of at least two of maleic anhydride, maleimide and maleic acid, the initiator comprises azo compounds and/or peroxide compounds, the molar ratio of the initiator to the functional monomer is (0.001-0.01): 1, the feeding time of the homogeneous liquid solution is 2-6 h, the temperature of the polymerization reaction is 55-150 ℃, the pressure of the polymerization reaction is 10-100 MPa, the time of the polymerization reaction is 10-24 h, and the low-carbon olefin is continuously introduced in the polymerization reaction process to maintain the pressure;
(2) The system after the polymerization reaction in the step (1) is subjected to gas-solid-liquid separation, discharged low-carbon olefin is pressurized and returned to the step (1) for reuse, the residual material is added into a first solvent for dissolution, the dissolution temperature is 35-80 ℃, the first solvent comprises any one or a combination of at least two of tetrahydrofuran, acetone, N-dimethylformamide and dimethyl sulfoxide, and the mass ratio of the first solvent to the residual material is (1-100): 1, then, dripping the mixture into a second solvent to separate out solids, wherein the second solvent comprises any one or a combination of at least two of N-hexane, diethyl ether, N-heptane, N-pentane and N-butyl ether, the volume ratio of the second solvent to the first solvent is 15:1-50:1, the dripping speed is 0.5-20 mL/min, stirring is carried out in the dripping process, the stirring speed is 50-1000 rpm, then solid-liquid separation is carried out, filter pressing is carried out by adopting protective gas, the obtained filter cake is dried, the drying is vacuum drying, the vacuum drying pressure is-0.1-0.01 MPa, the temperature is 30-120 ℃, the high molecular weight olefin functional polymer and liquid phase material are obtained, and the molecular weight of the olefin functional polymer is 100000-500000;
(3) And (3) separating the liquid phase material obtained in the step (2), wherein the separation method comprises any one or a combination of at least two of rectification, membrane separation, washing and extraction, the rectified tower top fraction is separated to obtain a first solvent and a second solvent, and the first solvent and the second solvent are respectively returned to the step (2) for reuse.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method takes the low-carbon olefin fluid in a supercritical state as a reaction monomer to be copolymerized with other functional monomers, adopts a free radical initiator to initiate polymerization, is easy to realize the same-chain alternate copolymerization of olefin and the functional monomers, greatly improves the activity capacity of a molecular chain segment, the utilization rate and the conversion efficiency of the monomer, avoids the cage effect of a solvent on the free radical, realizes the synthesis of high-molecular-weight olefin functional polymers without the negative reaction of the transfer of the free radical to the solvent chain, and has the molecular weight of more than 150000;
(2) The method has simple post-treatment process, easy separation and purification and recyclable raw materials;
(3) The method disclosed by the invention is simple to operate, mild in reaction condition, low in cost and environment-friendly, and saves energy consumption.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The present invention provides in part a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Introducing low-carbon olefin into the reactor, heating and boosting to a supercritical state, preparing a homogeneous liquid solution of a functional monomer and an initiator, and adding the homogeneous liquid solution into the reactor to perform polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), returning the discharged low-carbon olefin to the step (1) for reuse, mixing the residual material with the first solvent after discharging, adding the mixture into the second solvent together to precipitate solids, and carrying out solid-liquid separation to obtain the high-molecular-weight olefin functional polymer and the liquid-phase material.
The following are exemplary but non-limiting examples of the invention:
example 1:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly vacuumizing a high-pressure reaction kettle, introducing nitrogen for replacement, introducing ethylene into the high-pressure reaction kettle, heating to raise the temperature to 70 ℃, raising the pressure to 20MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction for 3 hours, wherein the reaction time is 15 hours, the reaction temperature is 70 ℃, the reaction pressure is 20MPa, the functional monomer is maleic anhydride, the initiator is azobisisobutyronitrile, the molar ratio of the initiator to the functional monomer is 0.003:1, and continuously introducing ethylene to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding the rest material into acetone for dissolution at the temperature of 40 ℃, dripping the rest material into diethyl ether at the speed of 1.0mL/min to separate out solids, wherein the stirring speed in the dripping process is 100rpm, the mass ratio of the acetone to the rest material is 40:1, the volume ratio of the diethyl ether to the acetone is 25:1, then, carrying out pressure filtration by adopting nitrogen, and obtaining a filter cake which is dried in vacuum, wherein the pressure of the vacuum drying is-0.05 MPa, and the temperature is 30 ℃ to obtain a high-molecular-weight olefin functional polymer and a liquid-phase material;
(3) And (3) rectifying and separating the liquid phase material obtained in the step (2), and separating the distilled overhead fraction to obtain acetone and diethyl ether, wherein the acetone and the diethyl ether are respectively returned to the step (2) for reuse.
Example 2:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly, vacuumizing a high-pressure reaction kettle, introducing nitrogen for replacement, introducing ethylene into the high-pressure reaction kettle, heating to raise the temperature to 100 ℃, raising the pressure to 30MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction for 3.5 hours, wherein the reaction time is 18 hours, the reaction temperature is 100 ℃, the reaction pressure is 30MPa, the functional monomer is maleic anhydride, the initiator is benzoyl peroxide, the molar ratio of the initiator to the functional monomer is 0.001:1, and continuously introducing low-carbon olefin to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding N, N-dimethylformamide into the residual material, dissolving at 45 ℃, dropwise adding the residual material into N-hexane at a speed of 5.0mL/min to separate out solid, wherein the stirring speed in the dropwise adding process is 400rpm, the mass ratio of the N, N-dimethylformamide to the residual material is 50:1, the volume ratio of the N-hexane to the N, N-dimethylformamide is 20:1, then carrying out pressure filtration by adopting nitrogen, and carrying out vacuum drying on an obtained filter cake, wherein the vacuum drying pressure is-0.06 MPa, the temperature is 115 ℃, thus obtaining the high-molecular-weight olefin functional polymer and the liquid-phase material;
(3) And (3) rectifying and separating the liquid phase material obtained in the step (2), and separating the distilled overhead fraction to obtain N, N-dimethylformamide and N-hexane, wherein the N, N-dimethylformamide and N-hexane are returned to the step (2) respectively for reuse.
Example 3:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly, vacuumizing a high-pressure reaction kettle, introducing nitrogen for replacement, introducing ethylene into the high-pressure reaction kettle, heating to 120 ℃, raising the temperature to 12MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction for 2 hours, wherein the reaction time is 10 hours, the reaction temperature is 120 ℃, the reaction pressure is 12MPa, the functional monomer is maleic anhydride, the initiator is azodiisoheptonitrile, the molar ratio of the initiator to the functional monomer is 0.01:1, and continuously introducing low-carbon olefin to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding acetone and N, N-dimethylformamide mixed solvent with the volume ratio of 1:1 into the residual material, dissolving at the temperature of 60 ℃, dropwise adding the residual material into N-pentane at the rate of 7.5mL/min to separate out solid, stirring at the rate of 200rpm in the dropwise adding process, wherein the mass ratio of the mixed solvent to the residual material is 90:1, the volume ratio of the N-pentane to the mixed solvent is 30:1, then carrying out pressure filtration by adopting nitrogen, and carrying out vacuum drying on the obtained filter cake, wherein the vacuum drying pressure is-0.02 MPa, and the temperature is 120 ℃ to obtain the high-molecular-weight olefin functional polymer and the liquid-phase material;
(3) And (3) sequentially extracting and rectifying and separating the liquid phase material obtained in the step (2), and separating the rectified overhead fraction to obtain acetone, N-dimethylformamide and N-pentane, wherein the acetone, the N, N-dimethylformamide and the N-pentane are respectively returned to the step (2) for reuse.
Example 4:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly, vacuumizing a high-pressure reaction kettle, introducing argon for replacement, introducing propylene into the high-pressure reaction kettle, heating to raise the temperature to 100 ℃, raising the pressure to 15MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction for 4 hours, wherein the reaction time is 24 hours, the reaction temperature is 100 ℃, the reaction pressure is 15MPa, the functional monomer is maleimide, the initiator is dicumyl peroxide, the molar ratio of the initiator to the functional monomer is 0.007:1, and continuously introducing low-carbon olefin to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding acetone and dimethyl sulfoxide mixed solvent with the volume ratio of 1:1 into the residual material, dissolving at the temperature of 80 ℃, dropwise adding the mixed solvent into n-hexane at the speed of 10.0mL/min to separate out solid, stirring at the speed of 600rpm in the dropwise adding process, wherein the mass ratio of the mixed solvent to the residual material is 30:1, the volume ratio of the n-hexane to the mixed solvent is 50:1, then carrying out pressure filtration by adopting argon, and carrying out vacuum drying on an obtained filter cake, wherein the vacuum drying pressure is-0.08 MPa, and the temperature is 80 ℃ to obtain a high-molecular-weight olefin functional polymer and a liquid-phase material;
(3) And (3) rectifying and separating the liquid-phase material obtained in the step (2), and separating the distilled overhead fraction to obtain acetone, dimethyl sulfoxide and n-hexane, wherein the acetone, the dimethyl sulfoxide and the n-hexane are respectively returned to the step (2) for reuse.
Example 5:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly, vacuumizing a high-pressure reaction kettle, introducing argon for replacement, introducing 1-butene into the high-pressure reaction kettle, heating to raise the temperature to 150 ℃, raising the pressure to 40MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction, wherein the feeding time is 2.5h, the reaction time is 12h, the reaction temperature is 150 ℃, the reaction pressure is 40MPa, the functional monomer is maleic anhydride, the initiator is azo-diisoheptonitrile, the molar ratio of the initiator to the functional monomer is 0.005:1, and continuously introducing low-carbon olefin to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding N, N-dimethylformamide into the residual material, dissolving at 50 ℃, dripping the residual material into N-butyl ether at a speed of 15.0mL/min to separate out solid, wherein the stirring speed in the dripping process is 300rpm, the mass ratio of the N-dimethylformamide to the residual material is 5:1, the volume ratio of the N-butyl ether to the N, N-dimethylformamide is 15:1, then carrying out pressure filtration by adopting argon, and carrying out vacuum drying on an obtained filter cake, wherein the vacuum drying pressure is-0.1 MPa, and the temperature is 100 ℃ to obtain a high-molecular-weight olefin functional polymer and a liquid-phase material;
(3) And (3) sequentially carrying out membrane separation and rectification separation on the liquid-phase material obtained in the step (2), and separating the rectified tower top fraction to obtain N, N-dimethylformamide and N-butyl ether, wherein the N, N-dimethylformamide and the N-butyl ether are returned to the step (2) respectively for reuse.
Example 6:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly vacuumizing a high-pressure reaction kettle, introducing nitrogen for replacement, introducing ethylene and propylene in a molar ratio of 1:1 into the high-pressure reaction kettle, heating to raise the temperature to 30MPa, preparing a homogeneous liquid solution from a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction, wherein the feeding time is 6h, the reaction time is 20h, the reaction temperature is 100 ℃, the reaction pressure is 30MPa, the functional monomer is maleic anhydride, the initiator is lauroyl peroxide, the molar ratio of the initiator to the functional monomer is 0.004:1, and continuously introducing low-carbon olefin to maintain the pressure in the polymerization reaction process;
(2) Firstly, carrying out gas-solid-liquid separation on a system obtained after the polymerization reaction in the step (1), pressurizing discharged low-carbon olefin, returning to the step (1) for reuse, adding dimethyl sulfoxide into the residual material for dissolution at 35 ℃, dripping the residual material into diethyl ether at a speed of 20.0mL/min to separate out solids, wherein the stirring speed in the dripping process is 1000rpm, the mass ratio of the mixed solvent to the residual material is 60:1, the volume ratio of the diethyl ether to the dimethyl sulfoxide is 30:1, and then, carrying out pressure filtration by adopting nitrogen, thereby obtaining a filter cake, and carrying out vacuum drying, wherein the vacuum drying pressure is-0.09 MPa, and the temperature is 110 ℃ to obtain a high-molecular-weight olefin functional polymer and a liquid-phase material;
(3) And (3) rectifying and separating the liquid-phase material obtained in the step (2), and separating the distilled overhead fraction to obtain dimethyl sulfoxide and diethyl ether, wherein the dimethyl sulfoxide and the diethyl ether are respectively returned to the step (2) for reuse.
Example 7:
the present embodiment provides a method for synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Firstly vacuumizing a high-pressure reaction kettle, introducing nitrogen for replacement, introducing ethylene into the high-pressure reaction kettle, heating to raise the temperature to 55 ℃, raising the pressure to 80MPa, preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the solution into the high-pressure reaction kettle, performing polymerization reaction for 5 hours, wherein the reaction time is 16 hours, the reaction temperature is 55 ℃, the reaction pressure is 80MPa, the functional monomer is maleic anhydride, the initiator is azodiisoheptonitrile, the molar ratio of the initiator to the functional monomer is 0.008:1, and continuously introducing ethylene to maintain the pressure in the polymerization reaction process;
the operations of step (2) and step (3) are described in example 1.
According to the content detection of the raw material monomers and the olefin functional polymer before and after the reaction in the above examples, the conversion rate of the functional monomer, the yield of the olefin functional polymer and the anhydride value (including the acid value or the succinimide content) are calculated, the acid value in the anhydride values in examples 1-3 and 5-7 is tested by adopting the standard test method of ASTM D3644-98, and the succinimide content in example 4 is obtained by measuring the nitrogen element content conversion by an elemental analyzer; the polymer was tested for particle size and weight average molecular weight, and the results are shown in table 1.
TABLE 1 data on the results of the polymerization reactions in examples 1-7
As shown in Table 1, the conversion rate of the functional monomer can reach more than 85.0%, the yield of the polymer can reach more than 83.9%, and the anhydride value of the polymer is more than 63.3%; the molecular weight of the olefin functional polymer can reach more than 150000, the D50 is in the range of 10-25 mu m, and the particle size is in the range of 10-50 mu m.
It can be seen from the above examples that the method of the present invention uses the low-carbon olefin fluid in the supercritical state as the reactive monomer, and uses the polymerization process initiated by the free radical initiator to copolymerize with other functional monomers. The co-chain alternating copolymerization of the olefin and the functional monomer is easy to realize, the activity capacity of a molecular chain segment, the utilization rate of the monomer and the conversion efficiency are greatly improved, the chain termination and the chain transfer are effectively inhibited, the synthesis of the olefin functional polymer with high molecular weight is realized, and the molecular weight can reach more than 15 ten thousand; the method has simple post-treatment process, is easy to separate and purify, can recycle raw materials, and improves the conversion rate of the raw materials and the yield of products; the method is simple to operate, mild in reaction condition, low in cost and environment-friendly, and energy consumption is saved.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (10)

1. A method of synthesizing a high molecular weight olefin functional polymer, the method comprising the steps of:
(1) Introducing low-carbon olefin into the reactor, heating and boosting to a supercritical state, preparing a homogeneous liquid solution of a functional monomer and an initiator, and adding the homogeneous liquid solution into the reactor to perform polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), returning the discharged low-carbon olefin to the step (1) for reuse, mixing the residual material with the first solvent after discharging, adding the mixture into the second solvent together to precipitate solids, and carrying out solid-liquid separation to obtain the high-molecular-weight olefin functional polymer and the liquid-phase material.
2. The method of claim 1, wherein the reactor of step (1) comprises a high pressure autoclave;
before the low-carbon olefin is introduced, vacuumizing the reactor and then introducing a protecting gas for replacement;
the low-carbon olefin in the step (1) comprises any one or a combination of at least two of ethylene, propylene, butylene and butadiene;
the supercritical state of the low-carbon olefin in the step (1) is as follows: the temperature of the supercritical ethylene is more than or equal to 9.19 ℃, the pressure is more than or equal to 5.04MPa, the temperature of the supercritical propylene is more than or equal to 91.9 ℃, the pressure is more than or equal to 4.62MPa or the temperature of the supercritical butene is more than or equal to 146.4 ℃, and the pressure is more than or equal to 4.05MPa.
3. The method of claim 1, wherein the functional monomer of step (1) comprises any one or a combination of at least two of maleic anhydride, maleimide, or maleic acid;
the initiator in the step (1) comprises azo compounds and/or peroxide compounds;
the azo compound comprises any one or a combination of at least two of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile, azodicyclohexyl carbonitrile and dimethyl azodiisobutyrate;
the peroxide compound comprises any one or a combination of at least two of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate.
4. The method of claim 1, wherein the molar ratio of the initiator to the functional monomer in step (1) is (0.001-0.01): 1;
step (1), preparing a homogeneous liquid solution by using the functional monomer and the initiator, and then pumping the solution into a reactor at a constant speed;
the feeding time of the homogeneous liquid solution in the step (1) is 2-6 hours;
the feeding temperature of the homogeneous liquid solution in the step (1) is not lower than the melting temperature of the functional monomer.
5. The method of claim 1, wherein the polymerization reaction in step (1) is carried out at a temperature of 55-150 ℃;
the pressure of the polymerization reaction in the step (1) is 10-100 MPa;
the polymerization reaction time in the step (1) is 10-24 hours;
and (3) continuously introducing low-carbon olefin to maintain pressure in the polymerization reaction process in the step (1).
6. The method of claim 1, wherein the low-carbon olefin is discharged in the gas-solid-liquid separation process of the step (2), and is replaced by a shielding gas, and the discharged low-carbon olefin is returned to the step (1) for reuse after being pressurized;
the mixing mode of the residual materials and the first solvent in the step (2) is as follows: the rest materials are added into a first solvent for dissolution, and the dissolution temperature is 35-80 ℃;
the first solvent in the step (2) comprises any one or a combination of at least two of tetrahydrofuran, acetone, N-dimethylformamide and dimethyl sulfoxide;
and (2) the mass ratio of the first solvent to the rest materials is (1-100) 1.
7. The method of claim 1, wherein the second solvent of step (2) comprises any one or a combination of at least two of n-hexane, diethyl ether, n-heptane, n-pentane, or n-butyl ether;
after mixing the residual materials in the step (2) with the first solvent, dropwise adding the mixture into the second solvent, wherein the dropwise adding speed is 0.5-20 mL/min;
stirring is carried out in the dropping process, and the stirring speed is 50-1000 rpm;
the volume ratio of the second solvent to the first solvent in the step (2) is 15:1-50:1.
8. The method of claim 1, wherein the solid liquid separation of step (2) comprises one or a combination of two of filtration, decantation, or centrifugation;
the filtering comprises the steps of adopting protective gas to carry out filter pressing, washing, drying, crushing and collecting the obtained filter cake;
the drying is vacuum drying, the pressure of the vacuum drying is-0.1 to-0.01 MPa, and the temperature is 30-120 ℃;
and (2) the molecular weight of the olefin functional polymer in the step (2) is 100000-500000.
9. The method according to claim 1, wherein the liquid phase material of step (2) is separated, and the recovered solvent obtained is returned to step (2) for reuse;
the liquid phase material separation method comprises any one or a combination of at least two of rectification, membrane separation, washing or extraction;
and (3) separating the rectified overhead fraction to obtain a first solvent and a second solvent, and returning the first solvent and the second solvent to the step (2) respectively for reuse.
10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(1) Firstly, vacuumizing the high-pressure reaction kettle, introducing protective gas for replacement, then introducing low-carbon olefin into the high-pressure reaction kettle, heating and boosting to a supercritical state, wherein the low-carbon olefin comprises any one or a combination of at least two of ethylene, propylene, butylene and butadiene, then preparing a homogeneous liquid solution by using a functional monomer and an initiator, uniformly pumping the functional monomer into the high-pressure reaction kettle, carrying out polymerization reaction, wherein the functional monomer comprises any one or a combination of at least two of maleic anhydride, maleimide and maleic acid, the initiator comprises azo compounds and/or peroxide compounds, the molar ratio of the initiator to the functional monomer is (0.001-0.01): 1, the feeding time of the homogeneous liquid solution is 2-6 h, the temperature of the polymerization reaction is 55-150 ℃, the pressure of the polymerization reaction is 10-100 MPa, the time of the polymerization reaction is 10-24 h, and the low-carbon olefin is continuously introduced in the polymerization reaction process to maintain the pressure;
(2) The system after the polymerization reaction in the step (1) is subjected to gas-solid-liquid separation, discharged low-carbon olefin is pressurized and returned to the step (1) for reuse, the residual material is added into a first solvent for dissolution, the dissolution temperature is 35-80 ℃, the first solvent comprises any one or a combination of at least two of tetrahydrofuran, acetone, N-dimethylformamide and dimethyl sulfoxide, and the mass ratio of the first solvent to the residual material is (1-100): 1, then, dripping the mixture into a second solvent to separate out solids, wherein the second solvent comprises any one or a combination of at least two of N-hexane, diethyl ether, N-heptane, N-pentane and N-butyl ether, the volume ratio of the second solvent to the first solvent is 15:1-50:1, the dripping speed is 0.5-20 mL/min, stirring is carried out in the dripping process, the stirring speed is 50-1000 rpm, then solid-liquid separation is carried out, filter pressing is carried out by adopting protective gas, the obtained filter cake is dried, the drying is vacuum drying, the vacuum drying pressure is-0.1-0.01 MPa, the temperature is 30-120 ℃, the high molecular weight olefin functional polymer and liquid phase material are obtained, and the molecular weight of the olefin functional polymer is 100000-500000;
(3) And (3) separating the liquid phase material obtained in the step (2), wherein the separation method comprises any one or a combination of at least two of rectification, membrane separation, washing and extraction, the rectified tower top fraction is separated to obtain a first solvent and a second solvent, and the first solvent and the second solvent are respectively returned to the step (2) for reuse.
CN202310753388.1A 2023-06-26 2023-06-26 Method for synthesizing high molecular weight olefin functional polymer Pending CN116496439A (en)

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CN114426639A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Alpha-olefin-maleic anhydride copolymer and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN1223271A (en) * 1997-10-15 1999-07-21 纳幕尔杜邦公司 Copolymers of Maleic anhydrdide or acid and fluorinated olefins
CN101454360A (en) * 2006-05-23 2009-06-10 巴斯夫欧洲公司 Method for producing ethylene copolymers
WO2013132009A1 (en) * 2012-03-07 2013-09-12 Borealis Ag Process and plant for manufacturing polyethylene or ethylene based copolymers
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