CN116640251A

CN116640251A - Method for synthesizing olefin functional polymer by mixed gas

Info

Publication number: CN116640251A
Application number: CN202310617193.4A
Authority: CN
Inventors: 王根林; 丁克鸿; 张留乔; 王铖; 王真贝; 聂庆超
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 from mixed gas, which comprises the following steps: introducing the mixed gas 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 system after the polymerization reaction, returning the discharged mixed gas for reuse, and carrying out solid-liquid separation on the rest materials to obtain the olefin functional polymer and the liquid-phase material. The invention realizes the same-chain alternating copolymerization of the low-carbon gaseous olefin and the functional monomer through the pressurized reaction of the low-carbon gaseous olefin and the functional monomer, and avoids the separation operation between the olefins through the use of mixed olefin, thereby reducing the energy consumption; by adopting a heterogeneous polymerization mode, the monomer concentration and the raw material utilization rate are improved, and the reaction efficiency is high; the post-treatment process is simple and easy to separate and purify; the method is simple to operate, mild in condition and environment-friendly.

Description

Method for synthesizing olefin functional polymer by mixed gas

Technical Field

The invention belongs to the technical field of organic polymerization, and relates to a method for synthesizing an olefin functional polymer by mixed gas.

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 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 deg.c to obtain self-stable 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.

Many production facilities in refineries produce off-gas containing unsaturated olefins and hydrocarbon derivatives thereof, which are often recycled and converted to other high value products due to their high economic value. The petrochemical industry pilot scale test and pilot scale test device, the total amount of the produced VOC is small and dispersed, the economic benefit is lacked, the comprehensive recycling is difficult, and meanwhile, the exhaust treatment of the waste gas often cannot draw enough attention. In recent years, the treatment of VOC is more and more important, but no targeted measure is available, and the catalytic combustion technology of unsaturated hydrocarbon is often adopted. In the existing steam cracking ethylene simulation experiment device, the discharge amount of cracking gas is large, and the direct burning point torch is adopted for processing, so that potential safety hazards exist, and a large amount of heat is required to be provided for material flow burning. Generally, the components in the pyrolysis gas contain saturated alkane and unsaturated hydrocarbon of C1-C5, and can be used as olefin raw materials for synthesizing olefin functional polymers, and the olefin-containing gas is a mixture of a plurality of components, and if the olefin with higher purity is prepared, the olefin needs to be separated and purified. The separation methods commonly used at present mainly comprise a cryogenic method, an absorption method, a membrane separation method, an adsorption method and the like, but the separation energy consumption is higher, the process is complex, and the economic benefit is poor, so that how to directly react without affecting the reaction result under the condition of no separation is one of the important points of the current research.

In summary, for the synthesis of olefin functional polymers, especially the polymerization of lower olefins with carbon numbers below C4 and functional monomers, a suitable synthesis process is also required to be selected according to the characteristics of the raw materials, 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 by mixed gas, which realizes the co-chain alternating copolymerization of low-carbon gaseous olefin and functional monomer through the pressurized reaction of the low-carbon gaseous olefin and the functional monomer, and avoids the separation operation between the olefins through the use of the mixed olefin, thereby reducing the energy consumption; the reaction adopts a heterogeneous polymerization mode, so that the monomer concentration and the raw material utilization rate are improved, and the solid olefin functional polymer is synthesized, so that 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 from mixed gas, which comprises the following steps:

(1) Introducing the mixed gas 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), returning the discharged mixed gas to the step (1) for reuse, discharging the residual materials, and carrying out solid-liquid separation to obtain the solid-phase olefin functional polymer and the liquid-phase materials.

In the invention, for the synthesis of olefin functional polymers, the selection of olefin and functional monomers has an important influence on the performance of the polymers, the invention selects low-carbon gaseous olefin to react with liquid functional monomers, the difference of the phases of the low-carbon gaseous olefin and the liquid functional monomers ensures that the difficulty is relatively higher when the low-carbon gaseous olefin and the functional monomers are liquid, the low-carbon gaseous olefin generally does not contain side chains, and the reaction difficulty is higher compared with that of the liquid olefin; after polymerization is completed, a relatively stable emulsion dispersion system can be directly obtained, the post-treatment process is simple, and separation and purification are easy; 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 mixed gas in step (1) comprises an industrial waste gas, the source of which comprises any one or a combination of at least two of combustion flue gas, process tail gas or waste gas in equipment, and typical but non-limiting examples of such combinations are: a combination of combustion flue gas and process tail gas, a combination of process tail gas and waste gas in equipment, a combination of combustion flue gas, process tail gas and waste gas in equipment, and the like.

Preferably, the composition of the mixed gas of step (1) comprises a low carbon olefin.

Preferably, the composition of the mixed gas further includes any one or a combination of at least two of lower alkanes, sulfur compounds, nitrogen oxides, or particulates, typical but non-limiting examples of which are: a combination of a low-carbon alkane and a sulfur-containing compound, a combination of a sulfur-containing compound and a nitrogen oxide, a combination of a low-carbon alkane, a sulfur-containing compound, a nitrogen oxide and a particulate matter, and the like.

Preferably, the mixed gas in step (1) is pretreated and then used for polymerization.

Preferably, the pretreatment includes any one or a combination of at least two of desulfurization, denitrification, or dedusting, typical but non-limiting examples of which are: a combination of desulfurization and denitrification, a combination of denitrification and dust removal, a combination of desulfurization, denitrification and dust removal, and the like.

Preferably, the lower olefins include 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, wherein the butene comprises 1-butene, 2-butene, or an isomer of isobutene, and the like.

Preferably, the lower alkane comprises any one or a combination of at least two of ethane, propane or butane, typical but non-limiting examples of which are: a combination of ethane and propane, a combination of butane and propane, a combination of ethane, propane and butane, and the like.

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 in the step (1) is introduced, the reactor is vacuumized and then is replaced by introducing a protective gas, wherein 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: combinations of maleic anhydride and maleic acid, combinations of maleimide and maleic acid, combinations of maleic anhydride, maleimide 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-heptane and n-octane, 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 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. For the formation of the raw material liquid, the components are required to be mixed, and if undissolved impurities exist after the components are mixed, the undissolved impurities are required to be removed by adopting operations such as filtration.

Preferably, the raw material liquid in the step (1) is pumped into the reactor by a conveying 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 mixed gas is discharged in the gas-solid-liquid separation process in the step (2), and is replaced by a shielding gas, wherein the shielding gas can be nitrogen or inert gas.

Preferably, the residual materials after the mixed gas is discharged in the step (2) are discharged in a solid-liquid mode.

Preferably, the discharged mixed gas returns to the step (1) for reuse after being pressurized until the non-reactive components remain.

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 and centrifugation, and the combination is typically, but not limited to, the following: a combination of decantation and filtration, a combination of filtration and centrifugation, etc., preferably filtration.

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 120 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, or 120 ℃, etc., but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable; the time is 1 to 72 hours, for example, 1 hour, 6 hours, 12 hours, 18 hours, 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours or 72 hours, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable; 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 distillation and extraction, a combination of distillation, membrane separation and washing, and the like, preferably distillation.

Preferably, the recovered solvent is returned to step (1) and/or step (1) is reused for formulating the feed solution and/or filter cake.

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

(1) The mixed gas is introduced into a reactor and then heated and boosted, the composition of the mixed gas comprises any one or a combination of at least two of low-carbon alkane, sulfur-containing compound, nitrogen oxide or particulate matters, the pretreatment is carried out firstly and then the mixed gas is used for polymerization reaction, the pretreatment comprises any one or a combination of at least two of desulfurization, denitration or dust removal, the low-carbon alkane comprises at least two of ethylene, propylene, 1-butene, isobutene or butadiene, the low-carbon alkane comprises any one or a combination of at least two of ethane, propane, butane or butadiene, the reactor comprises a kettle type reactor, a tubular reactor, a micro-channel reactor, a fluidized bed reactor or an ebullated bed reactor, after the reaction temperature and the reaction pressure are reached, the raw material liquid prepared by a functional monomer, an initiator and a solvent is added into the reactor, the functional monomer comprises any one or a combination of at least two of maleic anhydride, maleimide, maleic acid or vinyl acetate, the functional monomer comprises an azo compound and/or a peroxide compound, the polymerization initiator is mixed with the polymerization solvent, the polymerization ratio of the functional monomer and the monomer is 0.01-0.0.01 to 50 m.0.0-0 mol percent of the polymerization initiator and the monomer is carried out by a pump (the ratio of the polymerization reaction liquid is 0.0.01 to 0.0 m to 0 m.0), continuously introducing mixed gas in the polymerization reaction process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials subjected to the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning the mixed gas to the step (1) for reuse, discharging the residual materials in a solid-liquid mode, carrying out solid-liquid separation, carrying out filter pressing on the residual materials by adopting a protective gas, washing and drying the obtained filter cake, and crushing 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) And (3) separating the liquid phase material obtained in the step (2), wherein the liquid phase material 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) for preparing raw material liquid and/or solid phase washing.

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

(1) The method realizes the same-chain alternating copolymerization of the low-carbon gaseous olefin and the functional monomer through the pressurized reaction of the low-carbon gaseous olefin and the functional monomer, synthesizes the solid olefin functional polymer, avoids the separation operation between the olefins through the use of mixed olefin, and reduces the energy consumption;

(2) The method adopts a heterogeneous polymerization mode, so that the monomer concentration and the raw material utilization rate are improved, and the reaction efficiency is high; 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 process for synthesizing an olefin functional polymer from a mixed gas, the process comprising the steps of:

(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), returning the discharged mixed gas to the step (1) for reuse, and carrying out solid-liquid separation on the rest materials to obtain the solid-phase 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 an olefin functional polymer from a mixed gas, the method comprising the steps of:

(1) Introducing mixed gas into a tubular reactor, heating and boosting, wherein the mixed gas contains ethylene and propylene in a molar ratio of 1:1, the mixed gas also comprises ethane, propane and sulfur dioxide, after desulfurization treatment, the mixed gas is introduced into the reactor, nitrogen is introduced into the reactor before the mixed gas is introduced, after the mixed gas reaches reaction temperature and reaction pressure, 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 azobisisobutyronitrile, 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 is carried out, the temperature of the polymerization reaction is 60 ℃, the pressure is 8MPa, the retention time is 5h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning to the step (1) for reuse, carrying out filter pressing 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) After the mixed gas is introduced into the microchannel reactor, the temperature and the pressure are raised, wherein the mixed gas comprises the following components in a molar ratio of 1:2, sulfur dioxide and nitrogen dioxide are added into the mixed gas, after desulfurization and denitration treatment, nitrogen is added into the mixed gas to replace the mixed gas before the mixed gas is added, 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 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 is carried out, the temperature of the polymerization reaction is 100 ℃, the pressure is 5MPa, the residence time is 0.01h, and the mixed gas is continuously added in the polymerization reaction process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning to the step (1) for reuse, carrying out filter pressing 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 mixed gas into a reaction kettle, heating and boosting, wherein the mixed gas contains ethylene and propylene in a molar ratio of 2:1, the mixed gas further comprises propane, nitrogen is introduced into the reaction kettle for replacement before introducing, 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 reaction kettle, the functional monomer is maleic anhydride, the initiator is azodiisoheptanenitrile, 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 is carried out, the temperature of the polymerization reaction is 120 ℃, the pressure is 2MPa, the residence time is 3h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning to the step (1) for reuse, carrying out filter pressing 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 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) for reuse to prepare raw material liquid.

Example 4:

(1) Introducing mixed gas into a tubular reactor, heating and boosting, wherein the low-carbon gas contains propylene and 1-butene in a molar ratio of 1:1, the mixed gas also comprises propane, sulfur dioxide, nitrogen dioxide and dust, desulfurization, denitration and dust removal are carried out firstly, then the mixed gas is introduced into the reactor, argon is introduced into the reactor for replacement before the mixed gas is introduced into the reactor, 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 tubular reactor, the functional monomers are maleimide, the initiator is azodicyclohexyl carbonitrile and dicumyl peroxide in a molar ratio of 1:1, the solvent is benzene and xylene in a 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 temperature of the polymerization reaction is 150 ℃, the pressure is 0.2MPa, the retention time is 10h, and the mixed gas is continuously introduced in the polymerization process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning to the step (1) for reuse, 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 mixed gas into a fluidized bed reactor, heating and boosting, wherein the low-carbon gas contains ethylene and isobutene in a molar ratio of 2:1, the mixed gas also comprises butane and particulate matters, the mixed gas is subjected to dust removal treatment and then introduced into the reactor, argon is introduced into the reactor before the mixed gas is introduced, 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 fluidized bed reactor, the functional monomer is maleic acid, the initiator is lauroyl peroxide, 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 5:1, the polymerization reaction temperature is 80 ℃, the pressure is 10MPa, the residence time is 1h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

Example 6:

(1) Introducing mixed gas into a reaction kettle, heating and boosting, wherein the mixed gas contains ethylene, propylene and 1-butene in a molar ratio of 1:1, the mixed gas also comprises propane and butane, nitrogen is introduced into the mixed gas for replacement before the mixed gas is introduced into the reaction kettle 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 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 5:1, the molar 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 residence time is 6h, and the mixed gas is continuously introduced in the polymerization reaction process to maintain the pressure;

(2) Carrying out gas-solid-liquid separation on the materials obtained after the polymerization reaction in the step (1), pressurizing the discharged mixed gas, returning to the step (1) for reuse, carrying out filter pressing 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 washing solvent, wherein the olefin functional polymer is microspherical particles;

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 particle size of the polymer was tested and calculated, and the results are shown in table 1.

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

As is clear from Table 1, in the above examples, the conversion of the functional olefin monomer was 96% or more, the yield of the polymer was 93% or more, the acid anhydride value of the polymer was 64% or more, and the particle diameter was about 10 to 50. Mu.m, using the mixed gas as a raw material and using the low-carbon olefin therein to synthesize the functional olefin polymer by the above method.

It can be seen from the above embodiments that the method of the present invention realizes the co-chain alternating copolymerization of the low carbon gaseous olefin and the functional monomer through the pressurized reaction of the two, synthesizes the solid olefin functional polymer, and avoids the separation operation between the olefins and reduces the energy consumption through the use of the mixed olefin; the method adopts a heterogeneous polymerization mode, so that the monomer concentration and the raw material utilization rate are improved, and the reaction efficiency is high; 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 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

1. A process for synthesizing an olefin functional polymer from a mixed gas, the process comprising the steps of:

2. The method of claim 1, wherein the mixed gas of step (1) comprises an industrial waste gas, the source of which comprises any one or a combination of at least two of combustion flue gas, process tail gas, or waste gas within a plant;

preferably, the composition of the mixed gas of step (1) comprises a low carbon olefin;

preferably, the composition of the mixed gas further comprises any one or a combination of at least two of low-carbon alkane, sulfur-containing compound, nitrogen oxide or particulate matter;

preferably, the mixed gas in the step (1) is pretreated and then used for polymerization reaction;

preferably, the pretreatment comprises any one or a combination of at least two of desulfurization, denitrification or dedusting;

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

preferably, the lower alkane comprises any one or a combination of at least two of ethane, propane or butane.

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 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-heptane, n-pentane, n-octane and 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;

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.

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 mixed gas is discharged during the gas-solid-liquid separation in step (2) and replaced with a shielding gas;

preferably, the residual materials after the mixed gas is discharged in the step (2) are discharged in a solid-liquid mode;

8. The process according to any one of claims 1 to 7, wherein the solid liquid separation process of step (2) comprises any one or a combination of at least two of decantation, filtration or centrifugation, preferably filter pressing;

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 at least two of distillation, membrane separation, washing or extraction, preferably distillation;

preferably, the recovered solvent is returned to step (1) and/or step (2) for reuse for formulating the feed solution and/or washing the filter cake.

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

(1) Introducing mixed gas into a reactor, heating and boosting the mixed gas, wherein the mixed gas comprises any one or a combination of at least two of low-carbon alkane, sulfur-containing compound, nitrogen oxide or particulate matters, the mixed gas comprises any one or a combination of at least two of sulfur removal, denitration or dust removal, the low-carbon alkane comprises at least two of ethylene, propylene, butylene or butadiene, the low-carbon alkane comprises any one or a combination of at least two of ethane, propane or butane, the reactor comprises any one of a kettle-type reactor, a tubular-type reactor, a micro-channel reactor or 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 or vinyl acetate, the initiator comprises an azo compound and/or a peroxide compound, the solvent comprises an organic alkane compound, the polymerization initiator and the polymerization solvent is fed into the reactor at a constant rate of 0.1-0.01-0.1 mol/0 mol ratio of the polymerization initiator to the polymerization monomer or the monomer is maintained at a constant rate of 0.0.01-0.0:0:0;

(3) And (3) separating the liquid phase material obtained in the step (2), wherein the liquid phase material 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) for preparing raw material liquid and/or washing filter cakes.