CN116640249A

CN116640249A - Method for synthesizing olefin functional polymer and co-producing alkane

Info

Publication number: CN116640249A
Application number: CN202310617192.XA
Authority: CN
Inventors: 王根林; 丁克鸿; 王铖; 徐林; 张留乔; 聂庆超; 崔天宇
Original assignee: Jiangsu Yangnong Chemical Group Co Ltd
Current assignee: Jiangsu Yangnong Chemical Group Co Ltd
Priority date: 2023-05-29
Filing date: 2023-05-29
Publication date: 2023-08-25

Abstract

The invention provides a method for synthesizing an olefin functional polymer and co-producing alkane, which comprises the following steps: introducing a mixed gas containing low-carbon olefin into a reactor, raising the temperature and the pressure, and adding a raw material solution prepared from a functional monomer, an initiator and a solvent into the reactor to perform polymerization reaction after the reaction temperature and the reaction pressure are reached; and (3) carrying out gas-solid-liquid separation on the reacted system, recovering the low-carbon olefin, and carrying out solid-liquid separation on the rest materials to obtain the solid-phase olefin functional polymer and the liquid-phase material. The invention takes the mixed gas containing the low-carbon olefin as the raw material, realizes the same-chain alternating copolymerization of the low-carbon olefin and the functional monomer through the pressurizing reaction of the low-carbon olefin and the functional monomer, consumes the olefin to purify the alkane while synthesizing the olefin functional polymer, and avoids the separation energy consumption of the low-carbon olefin and the functional monomer; the invention has simple post-treatment process, easy separation and recycling of raw materials; the method is simple to operate, mild in reaction condition and environment-friendly.

Description

Method for synthesizing olefin functional polymer and co-producing alkane

Technical Field

The invention belongs to the technical field of organic polymerization, and relates to a method for synthesizing an olefin functional polymer and co-producing alkane.

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 101235117a discloses a method for styrene/maleic anhydride copolymerization, which comprises dissolving maleic anhydride monomer, styrene, initiator organic peroxide or azo compound in medium under nitrogen protection, reacting with 60-90 deg.c for 0.25-12 h to obtain dispersion system of polymer microsphere. CN 101781387a discloses a method for maleic anhydride/conjugated diene copolymerization, which comprises: under the protection of nitrogen, adding monomer maleic anhydride and an initiator into a medium for full dissolution, then adding monomer conjugated diene into the system for dissolution, reacting for 0.5-73 h at 50-90 ℃ to obtain a disperse system of maleic anhydride and conjugated diene copolymer microspheres, and then carrying out centrifugal separation and vacuum drying to obtain white solid of the maleic anhydride and conjugated diene copolymer.

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, or a derivative thereof, 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 petrochemical processes, petroleum fractionation products are commonly used as a feedstock to break hydrocarbons having long chain molecules into various short chain gaseous hydrocarbons and small amounts of liquid hydrocarbons at higher temperatures than cracking to provide organic chemical feedstocks. This process is known in the industry as petroleum cracking and is a petroleum process which aims to obtain short-chain unsaturated hydrocarbons as the main object.

The pyrolysis gas contains various components, wherein various gas-phase olefins and alkanes are adopted, and various high-purity monomers are required to be obtained as chemical raw materials, so that the petroleum pyrolysis gas is required to be separated and purified; in addition to the process of purifying and separating the cracked gas, there is a case where the alkane and the alkene are mixed in the process of interconverting the alkene and the alkane. For example, in the production of ethane from ethylene, ethylene is not completely converted; in the process of preparing olefin from alkane, the problem of difficult separation is also existed; when olefins are used as reactants to prepare polymers, it is not always the case that high purity olefins are used. The separation and purification of alkane and alkene gases, including a cryogenic method, an absorption method, an adsorption method and the like, but the separation cost and the process energy consumption are high, so that how to directly react without influencing the reaction result under the condition of no separation is one of the important points of the current research, and no method for synchronously carrying out the reaction and the purification exists at present.

In summary, for the synthesis of olefin functional polymers, especially the polymerization of lower olefins with carbon numbers below C4 and functional monomers, it is necessary to select a suitable process to synthesize the polymers according to the composition of the raw materials, and at the same time, to purify the remaining components, so as to improve the production efficiency, simplify the separation process of the raw materials and the products, and reduce the cost of the raw materials and the process.

Disclosure of Invention

Aiming at the problems existing in the prior art, the invention aims to provide a method for synthesizing an olefin functional polymer and co-producing alkane, which takes mixed gas containing low-carbon olefin as a raw material, realizes the co-chain alternating copolymerization of the low-carbon gaseous olefin and a functional monomer through the pressurizing reaction of the low-carbon gaseous olefin and the functional monomer, consumes the alkene in the mixed gas to purify the alkane while synthesizing the solid olefin functional polymer, and avoids the extra separation energy consumption of the alkane and the alkene gas; the reaction adopts a heterogeneous polymerization mode, so that the monomer concentration and the raw material utilization rate are improved, and the reaction efficiency is high; the post-reaction treatment process is simple, easy to separate and purify, energy-saving and cost-reducing.

To achieve the purpose, the invention adopts the following technical scheme:

the invention provides a method for synthesizing an olefin functional polymer and co-producing alkane, which comprises the following steps:

(1) Introducing a mixed gas containing low-carbon olefin into a reactor, raising the temperature and the pressure, and adding a raw material solution prepared from a functional monomer, an initiator and a solvent into the reactor to perform polymerization reaction after the reaction temperature and the reaction pressure are reached;

(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), collecting discharged gas for standby, discharging the rest materials, and carrying out solid-liquid separation to obtain the solid-phase olefin functional polymer and the liquid-phase material.

In the invention, for the synthesis of olefin functional polymer, the selection of olefin and functional monomer has important influence on the performance of the polymer, the invention selects low-carbon gaseous olefin to react with liquid functional monomer, the difference of the two phases leads the difficulty to be relatively higher when the low-carbon gaseous olefin and the functional monomer are both in liquid state, and the low-carbon gaseous olefin generally does not contain side chains, compared with the liquid olefin, the reaction difficulty is higher, the invention improves the concentration of the monomer and the reaction rate in a pressurizing reaction and heterogeneous polymerization mode, improves the conversion rate of raw materials and the yield of products, realizes the same-chain alternating copolymerization of the gaseous olefin monomer and the functional monomer, can directly obtain a relatively stable milky dispersion system after the polymerization is finished, has simple post-treatment process and is easy to separate and purify;

for the selection of the low-carbon olefin, the mixed gas containing the low-carbon olefin is used as a raw material, and the residual alkane component is purified through the reaction consumption of the low-carbon olefin, so that the alkane and the olefin are not required to be additionally separated, the high energy consumption of the separation of the alkane and the olefin gas is avoided, and the high-purity alkane is obtained; the method is simple to operate, mild in reaction conditions, low in cost, environment-friendly and high in economic benefit, 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 technical scheme of the invention, the mixed gas in the step (1) is industrial gas, and sources thereof comprise a petroleum cracking process and/or an alkane and alkene conversion process.

Preferably, the mixed gas containing the low-carbon olefin in the step (1) further comprises gaseous alkane.

Preferably, the lower olefins include 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 gaseous alkane comprises any one or a combination of at least two of ethane, propane, isobutane or n-butane, typical but non-limiting examples of such combinations are: a combination of ethane and propane, a combination of propane and n-butane, a combination of ethane, propane and n-butane, and the like.

The volume fraction of the light olefins in the light olefin-containing mixed gas is preferably 50 to 99.5%, for example, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% or 99.5%, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.

As a preferable technical scheme of the invention, the reactor in the step (1) comprises any one of a kettle reactor, a tubular reactor, a micro-channel reactor, a fluidized bed reactor or a boiling bed reactor.

Preferably, before the mixed gas containing the low-carbon olefin in the step (1) is introduced, the reactor is vacuumized and then is replaced by a protective gas, and the protective gas can be nitrogen or inert gas.

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, maleic acid or vinyl acetate, and typical but non-limiting examples of the combination are: a combination of maleic anhydride and maleimide, a combination of maleimide and maleic acid, a combination of maleic anhydride and vinyl acetate, a combination of maleic anhydride, maleimide and maleic acid, a combination of maleic anhydride, maleic acid and vinyl acetate, 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 at least one of dibenzoyl peroxide, dicumyl peroxide, diisobutyryl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, lauroyl peroxide, t-butyl neoheptanoate peroxide, t-butyl neodecanoate peroxide, di-sec-butyl dicarbonate peroxide, di (hexadecyl) dicarbonate, t-amyl neodecanoate peroxide, t-butyl pivalate peroxide, bis- (4-t-butylcyclohexyl) peroxide, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, dibutyl peroxydicarbonate, bis (2-ethylhexyl) peroxide, t-butyl 2-ethylhexanoate peroxide, ditetradecyl peroxydicarbonate, t-butyl acetate, cumyl peroxyneodecanoate, di-t-butyl peroxide, cyclohexylsulfonyl acetyl peroxide, 1, 3-tetramethylbutyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate, or 1, 3-tetramethylbutyl peroxypivalate, or at least a combination of any of the foregoing exemplary embodiments but not limited thereto: a combination of dibenzoyl peroxide and lauroyl peroxide, a combination of dibenzoyl peroxide and dicumyl peroxide, a combination of lauroyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate, and the like.

Preferably, the solvent of step (1) comprises any one or a combination of at least two of organic alkanoates, alkanes or aromatics, typical but non-limiting examples of which are: a combination of an organic alkanoate compound and an alkane compound, a combination of an alkane compound and an aromatic hydrocarbon compound, a combination of an organic alkanoate compound, an alkane compound and an aromatic hydrocarbon compound, and the like.

Preferably, the alkanes include any one or a combination of at least two of n-hexane, cyclohexane, n-pentane, n-heptane, n-octane, or n-decane, typical but non-limiting examples of such combinations being: a combination of n-hexane and cyclohexane, a combination of cyclohexane and n-heptane, a combination of n-hexane, cyclohexane and n-heptane, and the like.

Preferably, the aromatic compounds include any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene, typical but non-limiting examples of which are: benzene and ethylbenzene, benzene and toluene, ethylbenzene and xylene, benzene, ethylbenzene and xylene, and the like.

Preferably, the organic alkanoate compound has a general formula ofWherein R1 is any one of H, C1-C20 alkyl or C6-C10 aryl, and R2 is any one of C1-C20 alkyl or C6-C10 aryl.

Preferably, the organic alkanoate compound includes any one or a combination of at least two of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, or isoamyl phenylacetate, as typical but non-limiting examples: a combination of ethyl acetate and butyl acetate, a combination of butyl acetate and isobutyl acetate, a combination of butyl acetate and isoamyl acetate, and the like.

In a preferred embodiment of the present invention, the molar ratio of the initiator to the functional monomer in step (1) is (0.001 to 0.2): 1, for example, 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.15:1 or 0.2:1, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.

Preferably, the mass ratio of the solvent to the functional monomer in the step (1) is (2-50): 1, such as 2:1, 5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1 or 50:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the raw material liquid in the step (1) is subjected to impurity removal and preheating before being added into a reactor.

In the invention, the raw material liquid needs to be preheated before feeding so as to ensure that monomers in the system are fully dissolved and are not separated out; meanwhile, the preheating temperature is not easy to be too high, so that the initiator is decomposed and consumed prematurely. If undissolved impurities exist after mixing, the undissolved impurities are removed by adopting operations such as filtration and the like.

Preferably, the raw material liquid in the step (1) is pumped into the reactor at a constant speed after being pressurized by a delivery pump.

In the present invention, since the mixed gas is introduced into the reactor and pressurized, the raw material liquid is also pressurized in advance.

In a preferred embodiment of the present invention, the polymerization reaction in the step (1) is carried out at a temperature of 50 to 150 ℃, for example, 50 ℃, 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 0.1 to 10MPa, for example, 0.1MPa, 0.5MPa, 1MPa, 3MPa, 5MPa, 6MPa, 8MPa or 10MPa, etc., but the polymerization reaction is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.

Preferably, the residence time of the raw material liquid in step (1) is 0.01 to 10 hours, for example, 0.01 hours, 0.1 hours, 0.5 hours, 1 hour, 3 hours, 5 hours, 6 hours, 8 hours or 10 hours, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.

Preferably, in the polymerization reaction process of the step (1), the mixed gas is continuously introduced to maintain the pressure.

In the preferred technical scheme of the invention, the gas 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 main composition of the vented gases comprises gaseous alkanes and unreacted lower olefins.

In the invention, as the mixed gas is the mixed gas of the alkene and the alkane, the alkene is consumed through polymerization reaction, and the rest alkane is equivalent to being purified and can be collected for standby; if the olefin content in the discharged gas is still high, the method can return to the step (1) for reuse until the olefin content is reduced below the usable standard.

Preferably, the residual material in the step (2) is discharged in a solid-liquid mode.

As a preferred embodiment of the present invention, the solid-liquid separation method of step (2) comprises any one or a combination of at least two of decantation, filtration or centrifugation, and typical but non-limiting examples of such combinations are: a combination of decantation and filtration, a combination of filtration and centrifugation, a combination of decantation, filtration and centrifugation, and the like.

Preferably, the filtration comprises any one of gravity filtration, vacuum filtration or pressure filtration.

Preferably, the filter used for the filtration includes any one of an atmospheric filter, a vacuum filter, and a pressurized filter.

Preferably, the residual materials are subjected to filter pressing by adopting a protective gas, and the obtained filter cake is washed, dried and crushed.

Preferably, the washing is carried out using the solvent of step (1), but also using ether compounds, such as C1-C10 saturated ether compounds, preferably diethyl ether and/or propyl ether.

Preferably, the drying temperature is 30 to 150 ℃, for example, 30 ℃, 50 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably 80 to 120 ℃; the time is 1 to 72 hours, for example, 1 hour, 5 hours, 10 hours, 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours or 72 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable, preferably 24 to 72 hours; the pressure is 0.1 to 101kPa, for example, 0.1kPa, 1kPa, 10kPa, 20Pa, 40kPa, 60kPa, 80kPa, 101kPa, or the like, but is not limited to the values listed, and other values not listed in the range are similarly applicable, and preferably 1 to 10kPa.

Preferably, the olefin functional polymer in the step (2) is a microspheroidal particle having a particle size of 10 to 50. Mu.m, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 50 μm, etc., but not limited to the values recited, and other values not recited in the range of values are equally 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 (1) for reuse.

Preferably, the liquid phase material separation process comprises any one or a combination of at least two of distillation, membrane separation, washing or extraction, typical but non-limiting examples of which are: a combination of distillation and membrane separation, a combination of washing and extraction, a combination of distillation, membrane separation and washing, and the like, preferably distillation, and more preferably rectification.

Preferably, the solvent recovered by separation is returned to step (1) and/or step (2) for reuse, raw material liquid is prepared and/or filter cake is washed.

As a preferred technical solution of the present invention, the method comprises the steps of:

(1) Introducing a mixed gas containing low-carbon olefin into a reactor, heating and boosting, wherein the mixed gas containing low-carbon olefin also comprises gaseous alkane, the low-carbon olefin comprises any one or a combination of at least two of ethylene, propylene, butylene or butadiene, the gaseous alkane comprises any one or a combination of at least two of ethane, propane, isobutane or n-butane, the volume fraction of the low-carbon olefin is 50-99.5%, the reactor comprises any one of a kettle type reactor, a tubular reactor, a microchannel reactor, a fluidized bed reactor or a ebullated bed reactor, after the reaction temperature and the reaction pressure are reached, a raw material liquid prepared from functional monomers, an initiator and a solvent is added into the reactor, the functional monomers comprise any one or a combination of at least two of maleic anhydride, maleimide, maleic acid or vinyl acetate, the initiator comprises any one or a combination of at least two of organic alkanoic acid, alkane compounds or aromatic hydrocarbon compounds, the molar ratio of the functional monomers to the polymerization initiator is 0.001, the polymerization initiator is maintained at the polymerization temperature of between 0.001 ℃ and 0.01-50 MPa, and the polymerization time is kept at the polymerization reaction temperature of between 1 and 0.01-50 mass percent (the polymerization reaction time is kept in the pump-1);

(2) The material after the polymerization reaction in the step (1) is subjected to gas-solid-liquid separation to discharge gas, the main components of the discharged gas comprise gaseous alkane and unreacted low-carbon olefin, the residual material is subjected to solid-liquid separation, the residual material is subjected to filter pressing by adopting a protective gas, and the obtained filter cake is washed, dried and crushed to obtain a solid-phase olefin functional polymer and a liquid-phase material, wherein the olefin functional polymer is microspherical particles with the particle size of 10-50 mu m;

(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 distillation, membrane separation, washing or extraction, and the obtained recovered solvent is returned to the step (1) and/or used in the step (2) again for preparing raw material liquid and/or washing filter cakes.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the method, the mixed gas containing the low-carbon olefin is used as a raw material, the low-carbon gaseous olefin and the functional monomer are subjected to a pressurizing reaction to realize the same-chain alternating copolymerization of the low-carbon gaseous olefin and the functional monomer, and the olefin in the mixed gas is consumed to purify the alkane while the solid olefin functional polymer is synthesized, so that the extra separation energy consumption of the alkane and the olefin gas is avoided, and the purity of the obtained alkane can reach more than 95%;

(2) The method adopts a heterogeneous polymerization mode, improves the monomer concentration and the raw material utilization rate, synthesizes the solid olefin functional polymer, and has high reaction efficiency; after the polymerization is finished, a relatively stable emulsion dispersion system can be directly obtained, the post-treatment process is simple, the separation and purification are easy, the raw materials can be recycled, and the conversion rate of the raw materials and the product yield are improved;

(3) The method disclosed by the invention is simple to operate, mild in reaction condition, low in cost, environment-friendly and high in economic benefit, 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 an olefin functional polymer and co-producing an alkane, the method comprising the steps of:

The following are exemplary but non-limiting examples of the invention:

example 1:

the embodiment provides a method for synthesizing an olefin functional polymer and combining alkane, which comprises the following steps:

(1) Introducing a mixed gas containing low-carbon olefin into a tubular reactor, heating and boosting, wherein the mixed gas comprises low-carbon olefin and gaseous alkane, the low-carbon olefin is ethylene, the volume fraction of the mixed gas is 90%, the gaseous alkane is ethane, nitrogen is introduced into the tubular reactor for replacement before the mixed gas is introduced, after the reaction temperature and the reaction pressure are reached, raw materials prepared from a functional monomer, an initiator and a solvent are pumped into the tubular reactor, the functional monomer is maleic anhydride, the initiator is azodiisobutyronitrile, the solvent is ethyl acetate and butyl acetate in a volume ratio of 1:1, the molar ratio of the initiator to the functional monomer is 0.03:1, the mass ratio of the solvent to the functional monomer is 20:1, the polymerization reaction temperature is 55 ℃, the pressure is 8MPa, the retention time is 7h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Collecting the materials subjected to the polymerization reaction in the step (1) to a middle tank for cooling and depressurization, collecting discharged gas, carrying out pressure filtration on the rest materials by adopting nitrogen, washing and drying the obtained filter cake, crushing, and obtaining solid-phase olefin functional polymer and liquid-phase materials by using normal hexane as a solvent for washing, wherein the olefin functional polymer is microspherical particles;

(3) And (3) rectifying and separating the liquid phase material obtained in the step (2), wherein the distilled overhead fraction is recovered component solvents, and the recovered component solvents are returned to the step (1) and the step (2) for reuse respectively and are used for preparing raw material liquid and washing filter cakes.

Example 2:

(1) Introducing mixed gas containing low-carbon olefin into a microchannel reactor, heating and boosting, wherein the mixed gas comprises the low-carbon olefin and gaseous alkane, the low-carbon olefin is ethylene, the volume fraction of the mixed gas is 80%, the gaseous alkane is ethane, nitrogen is introduced into the mixed gas for replacement before the mixed gas is introduced into the microchannel reactor to reach the reaction temperature and the reaction pressure, raw materials prepared from a functional monomer, an initiator and a solvent are pumped into the microchannel reactor, the functional monomer is maleic anhydride, the initiator is dibenzoyl peroxide, the solvent is butyl acetate, the molar ratio of the initiator to the functional monomer is 0.01:1, the mass ratio of the solvent to the functional monomer is 4:1, the polymerization reaction temperature is 100 ℃, the pressure is 6MPa, the residence time is 0.1h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Collecting the materials obtained after the polymerization reaction in the step (1) to a middle tank for cooling and depressurizing, collecting discharged gas, carrying out pressure filtration on the rest materials by adopting nitrogen, washing and drying the obtained filter cake, crushing, and obtaining solid-phase olefin functional polymer and liquid-phase materials by using butyl acetate as a washing solvent, wherein the olefin functional polymer is microspherical particles;

(3) And (3) distilling and separating the liquid phase material obtained in the step (2), and returning the distilled overhead fraction to the step (1) and the step (2) for reuse, so as to prepare raw material liquid and wash filter cakes.

Example 3:

(1) Introducing a mixed gas containing low-carbon olefin into a kettle reactor, heating and boosting, wherein the mixed gas comprises the low-carbon olefin and gaseous alkane, the low-carbon olefin is propylene, the volume fraction of the mixed gas is 95%, the gaseous alkane is propane, nitrogen is introduced into the kettle reactor for replacement before the mixed gas is introduced, after the reaction temperature and the reaction pressure are reached, raw materials prepared from a functional monomer, an initiator and a solvent are pumped into the kettle reactor, the functional monomer is maleic anhydride, the initiator is azo-diisoheptonitrile, the solvent is ethyl acetate, the molar ratio of the initiator to the functional monomer is 0.2:1, the mass ratio of the solvent to the functional monomer is 50:1, the polymerization reaction temperature is 120 ℃, the pressure is 3MPa, the residence time is 3h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Collecting the materials obtained after the polymerization reaction in the step (1) to a middle tank for cooling and depressurizing, collecting discharged gas, carrying out pressure filtration on the rest materials by adopting nitrogen, washing and drying the obtained filter cake, crushing, and obtaining solid-phase olefin functional polymer and liquid-phase materials by using ethyl acetate as a solvent for washing, wherein the olefin functional polymer is microspherical particles;

(3) And (3) distilling and separating the liquid phase material obtained in the step (2), wherein the distilled overhead fraction is a recovered solvent, and the recovered solvent is returned to the step (1) for reuse to prepare raw material liquid.

Example 4:

(1) Introducing mixed gas containing low-carbon olefin into a fluidized bed reactor, heating and boosting, wherein the mixed gas comprises low-carbon olefin and gaseous alkane, the low-carbon olefin is propylene, the volume fraction of the mixed gas is 85%, the gaseous alkane is propane, argon is introduced for replacement before the mixed gas is introduced, after the reaction temperature and the reaction pressure are reached, raw materials prepared from functional monomers, an initiator and a solvent are pumped into the fluidized bed reactor, the functional monomers are maleimide, the initiator is dicumyl peroxide, the solvent is benzene and xylene with the volume ratio of 1:1, the molar ratio of the initiator to the functional monomers is 0.1:1, the mass ratio of the solvent to the functional monomers is 10:1, the polymerization reaction temperature is 150 ℃, the pressure is 0.3MPa, the residence time is 10h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Collecting the materials subjected to the polymerization reaction in the step (1) to a middle tank for cooling and depressurization, collecting discharged gas, carrying out pressure filtration on the rest materials by adopting argon, washing and drying the obtained filter cake, crushing, and obtaining solid-phase olefin functional polymer and liquid-phase materials by using cyclohexane as a solvent for washing, wherein the olefin functional polymer is microspherical particles;

Example 5:

(1) Introducing a mixed gas containing low-carbon olefin into a kettle reactor, heating and boosting, wherein the mixed gas comprises low-carbon olefin and gaseous alkane, the low-carbon olefin is ethylene and propylene, the volume ratio of the low-carbon olefin to the mixed gas is 45% and 50%, the gaseous alkane is propane, argon is introduced for replacement before introducing the mixed gas, after the mixed gas reaches the reaction temperature and the reaction pressure, raw materials prepared from a functional monomer, an initiator and a solvent are pumped into the kettle reactor, the functional monomer is maleic acid, the initiator is azodiisovaleronitrile and lauroyl peroxide in a molar ratio of 1:1, the solvent is cyclohexane, the molar ratio of the initiator to the functional monomer is 0.005:1, the mass ratio of the solvent to the functional monomer is 30:1, the polymerization reaction is carried out, the temperature of the polymerization reaction is 80 ℃, the pressure is 10MPa, the retention time is 1h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(3) And (3) distilling and separating the liquid phase material obtained in the step (2), wherein the distilled overhead fraction is a recovered solvent, and the recovered solvent is returned to the step (1) and the step (2) for reuse and is used for preparing raw material liquid and washing filter cakes.

Example 6:

(1) Introducing mixed gas containing low-carbon olefin into a microchannel reactor, heating and boosting, wherein the mixed gas comprises low-carbon olefin and gaseous alkane, the low-carbon olefin is ethylene and propylene, the volume fraction of the mixed gas is 40% and 40%, the gaseous alkane is ethane, nitrogen is introduced to replace the mixed gas before introducing the mixed gas, after the mixed gas reaches the reaction temperature and the reaction pressure, raw materials prepared from a functional monomer, an initiator and a solvent are pumped into a reaction kettle, the functional monomer is vinyl acetate, the initiator is dimethyl azodiisobutyrate, the solvent is butyl acetate and ethyl acetate in a volume ratio of 1:1, the mole ratio of the initiator to the functional monomer is 0.15:1, the mass ratio of the solvent to the functional monomer is 15:1, the polymerization reaction temperature is 90 ℃, the pressure is 2MPa, the retention time is 4h, and the mixed gas is continuously introduced in the polymerization process to maintain the pressure;

(2) Collecting the materials subjected to the polymerization reaction in the step (1) to a middle tank for cooling and depressurization, collecting discharged gas, carrying out pressure filtration on the rest materials by adopting nitrogen, washing and drying the obtained filter cake, crushing, and obtaining solid-phase olefin functional polymer and liquid-phase materials by using diethyl ether as a solvent for washing, wherein the olefin functional polymer is microspherical particles;

(3) And (3) rectifying and separating the liquid phase material obtained in the step (2), recovering the solvent from the rectified tower top fraction serving as each component, and respectively returning to the step (1) and the step (2) for reuse, so as to prepare raw material liquid and wash filter cakes.

The conversion of the functional monomer, the yield of the olefin functional polymer and the acid anhydride value were calculated from the content measurements of the raw material monomer and the olefin functional polymer before and after the reaction in the above examples, and the purity of the gas collected after the reaction was measured, and the results are shown in table 1.

TABLE 1 data on the results of the polymerization reactions in examples 1-6

As can be seen from Table 1, in the above examples, the conversion rate of the functional monomer can reach more than 96% and the yield of the polymer can reach more than 93%, and the anhydride value of the polymer is more than 69.0% by using the mixed gas containing the low-carbon olefin as the raw material and adopting the method to synthesize the olefin functional polymer; the content of olefin in the residual gas after the reaction consumption is reduced to below 5%, and the alkane purity is above 95%.

According to the embodiment, the mixed gas containing the low-carbon olefin is taken as a raw material, the same-chain alternating copolymerization of the low-carbon gaseous olefin and the functional monomer is realized through the pressurizing reaction of the low-carbon gaseous olefin and the functional monomer, and the olefin in the mixed gas is consumed to purify the alkane while the solid olefin functional polymer is synthesized, so that the additional separation energy consumption of the alkane and the olefin gas is avoided; the method adopts a heterogeneous polymerization mode, improves the monomer concentration and the raw material utilization rate, synthesizes the solid olefin functional polymer, and has high reaction efficiency; after the polymerization is finished, a relatively stable emulsion dispersion system can be directly obtained, the post-treatment process is simple, the separation and purification are easy, the raw materials can be recycled, and the conversion rate of the raw materials and the product yield are improved; the method is simple to operate, mild in reaction condition, low in cost, environment-friendly and high in economic benefit, and saves energy consumption.

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

1. A method of synthesizing an olefin functional polymer and co-producing an alkane, the method comprising the steps of:

2. The method of claim 1, wherein the mixed gas of step (1) is an industrial gas, the source of which comprises a petroleum cracking process and/or an alkane to alkene conversion process;

preferably, the mixed gas containing the low-carbon olefin in the step (1) further comprises gaseous alkane;

preferably, the low-carbon olefin comprises any one or a combination of at least two of ethylene, propylene, butylene or butadiene;

preferably, the gaseous alkane comprises any one or a combination of at least two of ethane, propane, n-butane or isobutane;

preferably, the volume fraction of the low-carbon olefin in the mixed gas containing the low-carbon olefin is 50-99.5%.

3. The method of claim 1 or 2, wherein the reactor of step (1) comprises any one of a tank reactor, a tubular reactor, a microchannel reactor, a fluidized bed reactor, or an ebullated bed reactor;

preferably, before the mixed gas containing the low-carbon olefin in the step (1) is introduced, the reactor is vacuumized and then is replaced by the shielding gas.

4. A method according to any one of claims 1 to 3, wherein the functional monomer of step (1) comprises any one or a combination of at least two of maleic anhydride, maleimide, maleic acid or vinyl acetate;

preferably, the initiator of step (1) comprises azo compounds and/or peroxide compounds;

preferably, the azo compound comprises any one or a combination of at least two of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile, azodicyclohexyl carbonitrile or dimethyl azodiisobutyrate;

preferably, the peroxide compound comprises any one or a combination of at least two of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate;

preferably, the solvent in the step (1) comprises any one or a combination of at least two of organic alkanoate compounds, alkane compounds or aromatic hydrocarbon compounds;

preferably, the structural general formula of the organic alkyl acid ester compound isWherein R1 is any one of H, C1-C20 alkyl or C6-C10 aryl, and R2 is any one of C1-C20 alkyl or C6-C10 aryl;

preferably, the alkane compound comprises any one or a combination of at least two of n-hexane, cyclohexane, n-pentane, n-heptane, n-octane or n-decane;

preferably, the aromatic hydrocarbon compound comprises any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene.

5. The process according to any one of claims 1 to 4, wherein the molar ratio of initiator to functional monomer in step (1) is from (0.001 to 0.2) 1;

preferably, the mass ratio of the solvent to the functional monomer in the step (1) is (2-50): 1;

preferably, the raw material liquid in the step (1) is subjected to impurity removal and preheating before being added into a reactor;

6. The process of any one of claims 1-5, wherein the temperature of the polymerization reaction of step (1) is 50 to 150 ℃;

preferably, the pressure of the polymerization reaction in the step (1) is 0.1-10 MPa;

preferably, the retention time of the raw material liquid in the step (1) is 0.01-10 h;

7. The method according to any one of claims 1 to 6, wherein the gas is discharged during the gas-solid-liquid separation in step (2);

preferably, the main composition of the vented gases comprises gaseous alkanes and unreacted lower olefins;

8. The method of any one of claims 1-7, wherein the method of solid liquid separation of step (2) comprises any one or a combination of at least two of decantation, filtration, or centrifugation;

preferably, the filtration comprises any one of gravity filtration, vacuum filtration or pressure filtration;

preferably, the filter used for filtering comprises any one of an atmospheric filter, a vacuum filter or a pressurized filter;

preferably, the residual materials are subjected to filter pressing by adopting a protective gas, and the obtained filter cake is crushed after washing and drying;

preferably, the washing is performed with the solvent of step (1);

preferably, the solvent used for washing also comprises an ether compound, wherein the ether compound comprises any one or a combination of at least two of C1-C10 saturated ether compounds, preferably diethyl ether and/or propyl ether;

preferably, the olefin functional polymer in the step (2) is microspherical particles with the particle size of 10-50 μm.

9. The method according to any one of claims 1 to 8, wherein the liquid phase material of step (2) is separated and the recovered solvent obtained is returned to step (1) for reuse;

preferably, the liquid phase material separation method comprises any one or a combination of at least two of distillation, membrane separation, washing or extraction;

preferably, the recovered solvent is returned to step (1) and/or step (2) for reuse, raw material liquid is prepared and/or filter cake is washed.

10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of:

(1) Introducing a mixed gas containing low-carbon olefin into a reactor, heating and boosting, wherein the mixed gas containing low-carbon olefin also comprises gaseous alkane, the low-carbon olefin comprises any one or a combination of at least two of ethylene, propylene, butylene and butadiene, the gaseous alkane comprises any one or a combination of at least two of ethane, propane, isobutane and n-butane, the volume fraction of the low-carbon olefin is 50-99.5%, the reactor comprises any one of a kettle-type reactor, a tubular reactor, a micro-channel reactor and a tower-type reactor, after the reaction temperature and the reaction pressure are reached, a raw material liquid prepared from functional monomers, an initiator and a solvent is added into the reactor, the functional monomers comprise any one or a combination of at least two of maleic anhydride, maleimide, maleic acid and vinyl acetate, the initiator comprises any one or a combination of at least two of azo compounds and/or peroxide compounds, the solvent comprises any one or a combination of organic alkanoate compounds, the alkane initiator or the aromatic hydrocarbon compound, the molar ratio of the functional monomers to the raw material liquid is maintained at the polymerization temperature of 0.001-0.0 MPa (the polymerization reaction time is kept at the polymerization temperature of between 1 and 50.0.001 ℃ in the polymerization pump-0.1:0-50:0);

(2) The material after the polymerization reaction in the step (1) is subjected to gas-solid-liquid separation, gas is discharged in the gas-solid-liquid separation process, the main components of the discharged gas comprise gaseous alkane and unreacted low-carbon olefin, the residual material is subjected to solid-liquid separation, the residual material is subjected to filter pressing by adopting protective gas, the obtained filter cake is washed and dried and then crushed, and a solid-phase olefin functional polymer and a liquid-phase material are obtained, wherein the olefin functional polymer is microspherical particles, and the particle size is 10-50 mu m;

(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 distillation, membrane separation, washing or extraction, and the obtained recovered solvent is returned to the step (1) and/or used again in the step (2) to prepare raw material liquid and/or wash a filter cake.