A method for synthesizing olefin functional polymers from mixed gases

Abstract

This invention provides a method for synthesizing olefin functional polymers from a mixed gas. The method includes: introducing the mixed gas into a reactor and heating and pressurizing it to reach the reaction temperature and pressure; adding a raw material liquid prepared from functional monomers, initiators, and solvents into the reactor to initiate a polymerization reaction; subjecting the polymerized system to gas-solid-liquid separation, returning the discharged mixed gas for reuse, and separating the remaining material into solid and liquid phases to obtain the olefin functional polymer and the liquid phase material. This invention achieves alternating copolymerization of low-carbon gaseous olefins and functional monomers through a pressurized reaction, and avoids the separation of olefins by using mixed olefins, thus reducing energy consumption; by employing heterogeneous polymerization, it improves monomer concentration and raw material utilization, resulting in high reaction efficiency; the post-processing is simple and easy to separate and purify; the method is simple to operate, operates under mild conditions, and is environmentally friendly.

Description

Technical Field

[0001] This invention belongs to the field of organic polymerization technology and relates to a method for synthesizing olefin functional polymers from mixed gases. Background Technology

[0002] Olefin functional polymers, as functional polymer materials, have attracted great attention due to their wide range of applications in engineering plastic chain extension, high-performance composite materials, nylon wetting, ink dispersion, microencapsulation, and filtration membrane formation. The molecular chains of olefin functional polymers contain numerous active groups, which can react with various functional groups to prepare a variety of products. Furthermore, olefin functional polymers can be used in the preparation of microcapsules, showing promising applications in pesticides, fragrances, and pharmaceuticals.

[0003] The raw materials for synthesizing olefin functional polymers are mainly olefins and functional monomers. Depending on the type of olefin or functional monomer in the raw materials, different synthesis processes are required. CN 101235117A discloses a method for styrene / maleic anhydride copolymerization. This method involves dissolving maleic anhydride monomer, styrene, and an initiator (organic peroxide or azo compound) in a medium under nitrogen protection, and reacting at 60–90°C for 0.25–12 h to obtain a dispersion system of polymer microspheres. CN 102212166A discloses a novel method for the copolymerization of dicyclopentadiene and maleic anhydride. This method also involves dissolving the monomer and initiator in an organic medium under nitrogen protection, and reacting at 60–90°C for 2–12 h to obtain a self-stabilized dispersion system of alternating copolymer monodisperse microspheres. These microspheres are then centrifuged and dried to obtain a white solid of the dicyclopentadiene / maleic anhydride alternating copolymer.

[0004] The aforementioned patents all use maleic anhydride as a functional monomer to polymerize with olefins. However, the olefins used are usually C4 or higher olefins, and are typically liquid olefins such as dienes, cycloolefins, and isomeric olefins. The polymerization of gaseous olefins below C4 is not addressed. CN 113388123A discloses a method for preparing high-viscosity nylon, which includes: mixing nylon salt prepolymer and olefin-maleic anhydride copolymer, and carrying out a polycondensation reaction to prepare high-viscosity nylon. Although the olefin-maleic anhydride copolymer used in this method can be selected from ethylene-maleic anhydride alternating copolymers, the process for synthesizing this copolymer from low-carbon olefins is not specified.

[0005] Many production units in oil refineries generate waste gases containing unsaturated olefins and their hydrocarbon derivatives. Due to their high economic value, these gases are often comprehensively recycled and converted into other high-value products. However, the total amount of VOCs generated by small-scale and pilot-scale petrochemical plants is small and dispersed, lacking economic benefits, and comprehensive recycling is difficult. Furthermore, the treatment of these waste gases often fails to receive sufficient attention. In recent years, VOC control has received increasing attention, but targeted measures are still lacking, often relying on catalytic combustion technology for unsaturated hydrocarbons. In existing steam cracking ethylene simulation experimental units, the cracked gas emissions are large, and direct combustion with a flare not only poses safety hazards but also requires a large amount of heat for the combustion of the material flow. Generally, the cracked gas contains C1-C5 saturated alkanes and unsaturated hydrocarbons, which can be used as olefin feedstock for the synthesis of olefin functional polymers. In this case, the olefin-containing gas is a mixture of multiple components, and further separation and purification are necessary to prepare high-purity olefins. Currently, commonly used separation methods include cryogenic separation, absorption separation, membrane separation, and adsorption separation. However, these methods consume a lot of energy and involve complex processes, resulting in poor economic benefits. Therefore, how to react directly without separation and without affecting the reaction results is one of the key research areas.

[0006] In summary, for the synthesis of olefin functional polymers, especially the polymerization of low-carbon olefins below C4 with functional monomers, it is necessary to select appropriate synthesis processes based on the characteristics of the raw materials in order to improve production efficiency, simplify the separation process of raw materials and products, and reduce raw material and process costs. Summary of the Invention

[0007] To address the problems existing in the prior art, the present invention aims to provide a method for synthesizing olefin functional polymers from mixed gases. This method achieves alternating copolymerization of low-carbon gaseous olefins and functional monomers through a pressurized reaction. The use of mixed olefins avoids the separation of olefins, reducing energy consumption. The reaction employs heterogeneous polymerization, increasing monomer concentration and raw material utilization, resulting in the synthesis of solid olefin functional polymers with high reaction efficiency. The post-reaction processing is simple, easy to separate and purify, saves energy, and reduces costs.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] This invention provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0010] (1) After the mixed gas is introduced into the reactor, the temperature and pressure are increased. After reaching the reaction temperature and reaction pressure, the raw material liquid prepared by functional monomer, initiator and solvent is added into the reactor to carry out the polymerization reaction.

[0011] (2) The system after the polymerization reaction in step (1) is first subjected to gas-solid-liquid separation. The discharged mixed gas is returned to step (1) for reuse. The remaining material is discharged and then subjected to solid-liquid separation to obtain solid-phase olefin functional polymer and liquid-phase material.

[0012] In this invention, the selection of olefins and functional monomers significantly impacts the performance of olefin functional polymers. This invention chooses to react low-carbon gaseous olefins with liquid functional monomers. The difference in their phases makes the reaction more challenging when both the olefin and functional monomers are liquid. Furthermore, low-carbon gaseous olefins typically lack side chains, making the reaction more difficult compared to liquid olefins. This invention utilizes pressurized reaction and heterogeneous polymerization to increase monomer concentration and reaction rate, thereby improving feed conversion and product yield. It achieves alternating copolymerization of gaseous olefin monomers and functional monomers with the same chain. The use of mixed olefins avoids the need for olefin separation, reducing energy consumption. A relatively stable emulsion dispersion system is directly obtained after polymerization, with simple post-processing and easy separation and purification. The method is simple to operate, operates under mild reaction conditions, allows for the recycling of raw materials, saves energy, has low cost, and is environmentally friendly.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following technical solutions.

[0014] As a preferred technical solution of the present invention, the mixed gas in step (1) includes industrial waste gas, the source of which includes any one or at least two of combustion flue gas, process tail gas or waste gas in the device. Typical but non-limiting examples of such combinations include: a combination of combustion flue gas and process tail gas, a combination of process tail gas and waste gas in the device, a combination of combustion flue gas, process tail gas and waste gas in the device, etc.

[0015] Preferably, the composition of the mixed gas in step (1) includes low-carbon olefins.

[0016] Preferably, the composition of the mixed gas further includes any one or a combination of at least two of low-carbon alkanes, sulfur-containing compounds, nitrogen oxides, or particulate matter. Typical but non-limiting examples of such combinations include: combinations of low-carbon alkanes and sulfur-containing compounds, combinations of sulfur-containing compounds and nitrogen oxides, combinations of low-carbon alkanes, sulfur-containing compounds, and nitrogen oxides, and combinations of low-carbon alkanes, sulfur-containing compounds, nitrogen oxides, and particulate matter.

[0017] Preferably, the mixed gas in step (1) is pretreated before being used in the polymerization reaction.

[0018] Preferably, the pretreatment includes any one or a combination of at least two of desulfurization, denitrification, or dust removal. Typical but non-limiting examples of such combinations include: a combination of desulfurization and denitrification, a combination of denitrification and dust removal, and a combination of desulfurization, denitrification, and dust removal.

[0019] Preferably, the low-carbon olefin includes a combination of at least two of ethylene, propylene, butene, or butadiene. Typical but non-limiting examples of such combinations include combinations of ethylene and propylene, combinations of propylene and butene, combinations of ethylene, propylene, and butene, etc., wherein the butene includes isomers such as 1-butene, 2-butene, or isobutene.

[0020] Preferably, the low-carbon alkane includes any one or a combination of at least two of ethane, propane, or butane. Typical but non-limiting examples of such combinations include: combinations of ethane and propane, combinations of butane and propane, combinations of ethane, propane, and butane, etc.

[0021] As a preferred technical solution of the present invention, the reactor in step (1) includes any one of a batch reactor, a tubular reactor, a microchannel reactor, a fluidized bed reactor, or a boiling bed reactor.

[0022] Preferably, before the mixed gas is introduced in step (1), the reactor is first evacuated and then replaced with a protective gas, which can be nitrogen or an inert gas.

[0023] As a preferred technical solution 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. Typical but non-limiting examples of such combinations include: a combination of maleic anhydride and maleic acid, a combination of maleimide and maleic acid, a combination of maleic anhydride, maleimide and vinyl acetate, etc.

[0024] Preferably, the initiator in step (1) includes azo compounds and / or peroxide compounds.

[0025] Preferably, the azo compound includes any one or a combination of at least two of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, azobiscyclohexylformitrile, or dimethyl azobisisobutyrate. Typical but non-limiting examples of such combinations include: a combination of azobisisobutyronitrile and azobisisovalerate, a combination of azobisisobutyronitrile and azobisisoheptanenitrile, a combination of azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate, and a combination of azobisisovalerate, azobisisoheptanenitrile and dimethyl azobisisobutyrate, etc.

[0026] Preferably, the peroxide compounds include benzoyl peroxide, dicumyl peroxide, diisobutyryl peroxide, di(2,4-dichlorobenzoyl peroxide), dodecyl peroxide, tert-butyl peroxyheptanate, tert-butyl peroxyneodecanate, disec-butyl peroxydicarbonate, di(hexadecyl)dicarbonate peroxide, tert-pentyl peroxyneodecanate, tert-butyl peroxyneodecanate, di-(4-tert-butylcyclohexyl peroxydicarbonate), dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl peroxydicarbonate), and 2-ethylhexanoic acid peroxide. The combination of any one or at least two of the following: tert-butyl ester, ditetradecyl peroxide dicarbonate, tert-butyl peroxide acetate, cumyl peroxide neodecanoate, ditert-butyl peroxide, cyclohexylsulfonyl peroxide, 1,1,3,3-tetramethylbutyl peroxide neodecanoate, di-3-methoxybutyl peroxide dicarbonate, or 1,1,3,3-tetramethylbutyl peroxide pentavalerate. Typical but non-limiting examples of such combinations include: a combination of benzoyl peroxide and dodecyl peroxide, a combination of benzoyl peroxide and dicumyl peroxide, and a combination of dodecyl peroxide, dicumyl peroxide, and diisopropyl peroxide dicarbonate.

[0027] Preferably, the solvent in step (1) includes any one or a combination of at least two of organic alkanoates, alkanes, or aromatics. Typical but non-limiting examples of such combinations include: combinations of organic alkanoates and alkanes, combinations of alkanes and aromatics, and combinations of organic alkanoates, alkanes, and aromatics.

[0028] Preferably, the alkane compound includes 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 include: 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, etc.

[0029] Preferably, the aromatic compound includes any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene. Typical but non-limiting examples of such combinations include: combinations of benzene and ethylbenzene, combinations of benzene and toluene, combinations of ethylbenzene and xylene, combinations of benzene, ethylbenzene and xylene, etc.

[0030] Preferably, the general formula of the organic alkanoate compound is: Wherein, R1 is any one of H, C1-C20 alkane group or C6-C10 aromatic group, and R2 is any one of C1-C20 alkane group or C6-C10 aromatic group.

[0031] Preferably, the organic alkyl esters include any one or a combination of at least two of the following: ethyl formate, propyl formate, isobutyl formate, amyl 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. Typical but non-limiting examples of such combinations include combinations of ethyl acetate and butyl acetate, combinations of butyl acetate and isobutyl acetate, and combinations of butyl acetate and isoamyl acetate.

[0032] As a preferred technical solution of the present invention, the molar ratio of the initiator to the functional monomer in step (1) is (0.001~0.2):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 is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0033] Preferably, the mass ratio of the solvent to the functional monomer in step (1) is (2 to 50):1, for example, 2:1, 5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1 or 50:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] Preferably, the raw material liquid in step (1) is removed from impurities and preheated before being added to the reactor.

[0035] In this invention, the raw material liquid needs to be preheated before feeding to ensure that the monomers in the system are fully dissolved and do not precipitate; at the same time, the preheating temperature should not be too high, causing the initiator to decompose and be consumed prematurely. For the formation of the raw material liquid, the components need to be mixed. If there are undissolved impurities after mixing, they must be removed by filtration or other operations.

[0036] Preferably, the raw material liquid in step (1) is pressurized and pumped into the reactor by a delivery pump.

[0037] In this invention, since the mixed gas is first introduced into the reactor and pressurized, the raw material liquid also needs to be pressurized in advance before it can be introduced.

[0038] As a preferred technical solution of the present invention, the temperature of the polymerization reaction in step (1) is 50 to 150°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 140°C or 150°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0039] Preferably, the pressure of the polymerization reaction in step (1) is 0.1 to 10 MPa, such as 0.1 MPa, 0.5 MPa, 1 MPa, 3 MPa, 5 MPa, 6 MPa, 8 MPa or 10 MPa, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0040] Preferably, the residence time of the raw material liquid in step (1) is 0.01 to 10 h, such as 0.01 h, 0.1 h, 0.5 h, 1 h, 3 h, 5 h, 6 h, 8 h or 10 h, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0041] Preferably, during the polymerization reaction in step (1), a mixed gas is continuously introduced to maintain the pressure.

[0042] As a preferred technical solution of the present invention, the gas-solid-liquid separation process in step (2) discharges the mixed gas and replaces it with a protective gas, which can be nitrogen or an inert gas.

[0043] Preferably, the remaining material after the mixed gas is discharged in step (2) is discharged in a solid-liquid manner.

[0044] Preferably, the discharged mixed gas is pressurized and returned to step (1) for reuse until the remaining unreacted components remain.

[0045] As a preferred technical solution of the present invention, the solid-liquid separation method in step (2) includes any one or a combination of at least two of decantation, filtration, and centrifugation. Typical but non-limiting examples of such combinations include: a combination of decantation and filtration, a combination of filtration and centrifugation, a combination of decantation, filtration, and centrifugation, etc., with filtration being the preferred method.

[0046] Preferably, the filtration includes any one of gravity filtration, vacuum filtration, or pressure filtration.

[0047] Preferably, the filter used for filtration includes any one of an atmospheric pressure filter, a vacuum filter, or a pressurized filter.

[0048] Preferably, the remaining material is filtered by pressure using a protective gas, and the resulting filter cake is washed, dried, and then crushed.

[0049] Preferably, the washing is performed using the solvent in step (1), or an ether compound may be used, such as a C1-C10 saturated ether compound, preferably diethyl ether and / or propyl ether.

[0050] Preferably, the drying temperature is 30–120°C, such as 30°C, 40°C, 50°C, 60°C, 80°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The drying time is 1–72 hours, such as 1 hour, 6 hours, 12 hours, 18 hours, 24 hours, 30 hours, 36 hours, 42 hours, 48 ​​hours, 54 hours, etc. h, 60h, 66h or 72h, etc., but not limited to the listed values, other unlisted values ​​within this range are also applicable; the pressure is 0.1 to 101 kPa, such as 0.1 kPa, 1 kPa, 10 kPa, 20 Pa, 40 kPa, 60 kPa, 80 kPa or 101 kPa, etc., but not limited to the listed values, other unlisted values ​​within this range are also applicable, preferably 1 to 10 kPa.

[0051] Preferably, the olefin functional polymer in step (2) is a microsphere with a particle size of 10 to 50 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 50 μm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0052] As a preferred technical solution of the present invention, the liquid phase material in step (2) is separated, and the recovered solvent is returned to step (1) for reuse.

[0053] Preferably, the method for separating liquid phase materials includes any one or a combination of at least two of distillation, membrane separation, washing, or extraction. Typical but non-limiting examples of such combinations include: a combination of distillation and membrane separation, a combination of distillation and extraction, a combination of distillation, membrane separation, and washing, etc., with distillation being the preferred method.

[0054] Preferably, the recovered solvent is returned to step (1) and / or reused in step (1) for preparing the feed solution and / or filter washing cake.

[0055] As a preferred technical solution of the present invention, the method includes the following steps:

[0056] (1) After the mixed gas is introduced into the reactor, the temperature and pressure are increased. The composition of the mixed gas, in addition to low-carbon olefins, also includes any one or at least two of the following: low-carbon alkanes, sulfur-containing compounds, nitrogen oxides, or particulate matter. It is pretreated before being used in the polymerization reaction. The pretreatment includes any one or at least two of the following: desulfurization, denitrification, or dust removal. The low-carbon olefins include any one or at least two of the following: ethylene, propylene, 1-butene, isobutene, or butadiene. The low-carbon alkanes include any one or at least two of the following: ethane, propane, butane, or butadiene. The reactor includes any one of the following: a batch reactor, a tubular reactor, a microchannel reactor, a fluidized bed reactor, or a boiling bed reactor. After reaching the reaction temperature and pressure, the raw material liquid prepared from the functional monomers, initiator, and solvent is... The functional monomer is added to the reactor. It includes any one or a combination of at least two of maleic anhydride, maleimide, maleic acid, or vinyl acetate. The initiator includes azo compounds and / or peroxide compounds. The solvent includes any one or a combination of at least two of organic alkanoates, alkanes, or aromatics. The molar ratio of the initiator to the functional monomer is (0.001–0.2):1, and the mass ratio of the solvent to the functional monomer is (2–50):1. The feed liquid is pressurized by a transfer pump and pumped into the reactor at a uniform speed to carry out the polymerization reaction. The polymerization reaction temperature is 50–150°C, the pressure is 0.1–10 MPa, and the residence time is 0.01–10 h. During the polymerization reaction, a mixed gas is continuously introduced to maintain the pressure.

[0057] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is returned to step (1) for reuse after being pressurized. The remaining material is discharged in a solid-liquid manner and then separated by solid-liquid separation. The remaining material is filtered by pressure using a protective gas. The resulting filter cake is washed, dried and crushed to obtain solid-phase olefin functional polymer and liquid-phase material. The olefin functional polymer is microsphere particles with a particle size of 10-50 μm.

[0058] (3) Separate the liquid phase material obtained in step (2). The liquid phase material separation method includes any one or a combination of at least two of distillation, membrane separation, washing or extraction. The recovered solvent is returned to step (1) and / or step (2) for reuse in preparing raw material liquid and / or solid phase washing.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] (1) The method described in this invention achieves alternating copolymerization of the same chain of low-carbon gaseous olefins and functional monomers through pressurized reaction, synthesizing solid olefin functional polymers, and avoids the separation operation between olefins by using mixed olefins, thereby reducing energy consumption.

[0061] (2) The method described in this invention adopts heterogeneous polymerization, which improves monomer concentration and raw material utilization, and has high reaction efficiency. After polymerization, a relatively stable emulsion dispersion system can be obtained directly. The post-processing is simple, easy to separate and purify, and the raw materials can be recycled, thereby improving the conversion rate of raw materials and the yield of products.

[0062] (3) The method described in this invention is simple to operate, has mild reaction conditions, saves energy, has low cost, is green and environmentally friendly, and has high economic benefits. Detailed Implementation

[0063] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention is further described in detail below. However, the following embodiments are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0064] The present invention provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0065] (1) After the mixed gas is introduced into the reactor, the temperature and pressure are increased. After reaching the reaction temperature and reaction pressure, the raw material liquid prepared by functional monomer, initiator and solvent is added into the reactor to carry out the polymerization reaction.

[0066] (2) The system after the polymerization reaction in step (1) is first subjected to gas-solid-liquid separation. The discharged mixed gas is returned to step (1) for reuse. The remaining material is separated into solid and liquid phases to obtain solid-phase olefin functional polymer and liquid-phase material.

[0067] The following are typical but non-limiting embodiments of the present invention:

[0068] Example 1:

[0069] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0070] (1) After the mixed gas is introduced into the tubular reactor, the temperature and pressure are increased. The mixed gas contains ethylene and propylene in a molar ratio of 1:1. The mixed gas also includes ethane, propane and sulfur dioxide. It is first desulfurized before being introduced into the reactor. Before the mixed gas is introduced, nitrogen is introduced to replace it. After the reaction temperature and reaction pressure are reached, the raw material liquid prepared by functional monomer, initiator and solvent is 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 initiator to functional monomer is 0.03:1, and the mass ratio of solvent to functional monomer is 20:1. The polymerization reaction occurs at a temperature of 60°C, a pressure of 8 MPa and a residence time of 5 h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0071] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by nitrogen. The filter cake is washed, dried and crushed. The solvent used for washing is n-hexane to obtain solid-phase olefin functional polymer and liquid-phase material. The olefin functional polymer is microsphere particles.

[0072] (3) The liquid material obtained in step (2) is separated by distillation. The distillate from the top of the column after distillation is the solvent of each component recovered and returned to steps (1) and (2) for reuse in preparing raw material liquid and washing filter cake.

[0073] Example 2:

[0074] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0075] (1) After the mixed gas is introduced into the microchannel reactor, the temperature and pressure are increased. The mixed gas contains ethylene and propylene in a molar ratio of 1:2. The mixed gas also contains sulfur dioxide and nitrogen dioxide. It is first desulfurized and denitrified before being introduced into the reactor. Before the mixed gas is introduced, nitrogen is introduced to replace it. After the reaction temperature and reaction pressure are reached, the raw material liquid prepared by functional monomer, initiator and solvent is pumped into the reactor. The functional monomer is maleic anhydride, the initiator is benzoyl peroxide, and the solvent is butyl acetate. The molar ratio of initiator to functional monomer is 0.01:1, and the mass ratio of solvent to functional monomer is 4:1. A polymerization reaction occurs. The temperature of the polymerization reaction is 100°C, the pressure is 5 MPa, and the residence time is 0.01 h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0076] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by nitrogen. The filter cake is washed, dried and crushed. The solvent used for washing is butyl acetate. Solid-phase olefin functional polymer and liquid-phase material are obtained. The olefin functional polymer is microsphere particles.

[0077] (3) The liquid material obtained in step (2) is distilled and separated. The distillate from the top of the column is returned to steps (1) and (2) for reuse in preparing raw material liquid and washing filter cake.

[0078] Example 3:

[0079] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0080] (1) After the mixed gas is introduced into the reactor, the temperature and pressure are increased. The mixed gas contains ethylene and propylene in a molar ratio of 2:1. The mixed gas also includes propane. Before introducing the gas, nitrogen is introduced to purge the gas. After reaching the reaction temperature and reaction pressure, the raw material liquid prepared by the functional monomer, initiator and solvent is pumped into the reactor. The functional monomer is maleic anhydride, the initiator is azobisisobutyronitrile, the solvent is ethyl acetate, the molar ratio of the initiator to the functional monomer is 0.2:1, and the mass ratio of the solvent to the functional monomer is 50:1. A polymerization reaction occurs. The polymerization reaction temperature is 120°C, the pressure is 2 MPa, and the residence time is 3 h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0081] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by nitrogen. The filter cake is washed, dried and crushed. The solvent used for washing is ethyl acetate. Solid phase olefin functional polymer and liquid phase material are obtained. The olefin functional polymer is microsphere particles.

[0082] (3) The liquid material obtained in step (2) is distilled and separated. The distillate from the top of the column is returned to step (1) for reuse in preparing the raw material liquid.

[0083] Example 4:

[0084] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0085] (1) After the mixed gas is introduced into the tubular reactor, the temperature and pressure are increased. The low-carbon gas contains propylene and 1-butene in a molar ratio of 1:1. The mixed gas also includes propane, sulfur dioxide, nitrogen dioxide and dust. It is first treated by desulfurization, denitrification and dust removal before being introduced into the reactor. Before the mixed gas is introduced, argon gas is introduced to replace it. After reaching the reaction temperature and reaction pressure, the raw material liquid prepared by functional monomer, initiator and solvent is pumped into the tubular reactor. The functional monomer is maleimide. The initiator is azodicyclohexylformonitrile 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 initiator to functional monomer is 0.1:1. The mass ratio of solvent to functional monomer is 10:1. The polymerization reaction occurs. The temperature of the polymerization reaction is 150°C, the pressure is 0.2 MPa, and the residence time is 10 h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0086] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by argon gas. The filter cake is washed, dried and crushed. The solvent used for washing is cyclohexane to obtain solid-phase olefin functional polymer and liquid-phase material. The olefin functional polymer is microsphere particles.

[0087] (3) The liquid material obtained in step (2) is separated by distillation. The distillate from the top of the column after distillation is the solvent of each component recovered and returned to steps (1) and (2) for reuse in preparing raw material liquid and washing filter cake.

[0088] Example 5:

[0089] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0090] (1) After the mixed gas is introduced into the fluidized bed reactor, the temperature and pressure are increased. The low-carbon gas contains ethylene and isobutylene in a molar ratio of 2:1. The mixed gas also includes butane and particulate matter. It is first treated by dust removal before being introduced into the reactor. Before the mixed gas is introduced, argon gas is introduced to replace it. After reaching the reaction temperature and reaction pressure, the raw material liquid prepared by functional monomer, initiator and solvent is pumped into the fluidized bed reactor. The functional monomer is maleic acid, the initiator is dodecyl peroxide, the solvent is cyclohexane, the molar ratio of initiator to functional monomer is 0.005:1, and the mass ratio of solvent to functional monomer is 5:1. A polymerization reaction occurs. The temperature of the polymerization reaction is 80°C, the pressure is 10MPa, and the residence time is 1h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0091] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by argon gas. The filter cake is washed, dried and crushed. The solvent used for washing is cyclohexane to obtain solid-phase olefin functional polymer and liquid-phase material. The olefin functional polymer is microsphere particles.

[0092] (3) The liquid material obtained in step (2) is distilled and separated. The distillate from the top of the column is returned to steps (1) and (2) for reuse in preparing raw material liquid and washing filter cake.

[0093] Example 6:

[0094] This embodiment provides a method for synthesizing olefin functional polymers from a mixed gas, the method comprising the following steps:

[0095] (1) After the mixed gas is introduced into the reactor, the temperature and pressure are increased. The mixed gas contains ethylene, propylene and 1-butene in a molar ratio of 1:1:1. The mixed gas also includes propane and butane. Before the mixed gas is introduced, nitrogen is introduced to purge the mixture. After the reaction temperature and pressure are reached, the raw material liquid prepared by the functional monomer, initiator and solvent is pumped into the reactor. The functional monomer is vinyl acetate, the initiator is dimethyl azobisisobutyrate, 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, and the mass ratio of the solvent to the functional monomer is 15:1. A polymerization reaction occurs. The polymerization reaction temperature is 90°C, the pressure is 2 MPa, and the residence time is 6 h. The mixed gas is continuously introduced to maintain the pressure during the polymerization reaction.

[0096] (2) The material after the polymerization reaction in step (1) is first separated by gas-solid-liquid separation. The discharged mixed gas is pressurized and returned to step (1) for reuse. The remaining material is filtered by nitrogen. The filter cake is washed, dried and crushed. The solvent used for washing is diethyl ether to obtain solid-phase olefin functional polymer and liquid-phase material. The olefin functional polymer is microsphere particles.

[0097] (3) The liquid material obtained in step (2) is separated by distillation. The distillate from the top of the column after distillation is the solvent of each component recovered and returned to steps (1) and (2) for reuse in preparing raw material liquid and washing filter cake.

[0098] Based on the content detection of raw material monomers and olefin functional polymers before and after the reaction in the above embodiments, the conversion rate of functional monomers, the yield of olefin functional polymers and the acid anhydride value were calculated, and the particle size of the polymers was tested and calculated. The results are shown in Table 1.

[0099] Table 1. Results of polymerization reactions in Examples 1-6

[0100]

[0101] As shown in Table 1, in the above embodiments, using mixed gas as raw material and utilizing the low-carbon olefins therein, the olefin functional polymers are synthesized by the method described above. The conversion rate of functional monomers can reach more than 96%, and the polymer yield can also reach more than 93%. The acid anhydride value of the polymer is more than 64%, and the particle size range is about 10 to 50 μm.

[0102] As can be seen from the above embodiments, the method of the present invention achieves alternating copolymerization of low-carbon gaseous olefins and functional monomers through a pressurized reaction, synthesizing solid olefin functional polymers. The use of mixed olefins avoids the separation of olefins, reducing energy consumption. The method employs heterogeneous polymerization, increasing monomer concentration and raw material utilization, resulting in high reaction efficiency. After polymerization, a relatively stable emulsion dispersion system can be directly obtained. Post-processing is simple, easy to separate and purify, and the raw materials can be recycled, improving raw material conversion and product yield. The method is simple to operate, operates under mild reaction conditions, saves energy, has low cost, and is environmentally friendly.

[0103] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the method of the present invention, additions of auxiliary steps, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for synthesizing an olefin functional polymer from a mixed gas, characterized by, The method comprises the following steps: (1) After the mixed gas is introduced into the reactor, the temperature and pressure are raised, and after the reaction temperature and pressure are reached, the raw material liquid prepared by mixing the functional monomer, initiator and solvent is added into the reactor to generate a polymerization reaction; (2) The system after the polymerization reaction in step (1) is first subjected to gas-solid-liquid separation, the mixed gas discharged is returned to step (1) for reuse, and the remaining material is discharged and then subjected to solid-liquid separation to obtain a solid-phase olefin functional polymer and a liquid-phase material; In step (1), the composition of the mixed gas comprises low-carbon olefins; The composition of the mixed gas further comprises any one or a combination of at least two of low-carbon alkanes, sulfur-containing compounds, nitrogen oxides or particulate matters; The mixed gas in step (1) is first subjected to pretreatment and then used for the polymerization reaction; The pretreatment comprises any one or a combination of at least two of desulfurization, denitration or dust removal; The raw material liquid in step (1) is first subjected to impurity removal and preheating before being added into the reactor; The raw material liquid in step (1) is pumped into the reactor at a constant speed after being pressurized by a delivery pump; The temperature of the polymerization reaction in step (1) is 120-150℃; The pressure of the polymerization reaction in step (1) is 3-10 MPa; The residence time of the raw material liquid in step (1) is 0.01-3 h; During the polymerization reaction in step (1), the mixed gas is continuously introduced to maintain the pressure; The low-carbon olefins comprise at least two of ethylene, propylene, butylene or butadiene; The reactor in step (1) is a kettle-type reactor; The functional monomer in step (1) is maleic anhydride; The solvent in step (1) comprises any one or a combination of at least two of organic alkanoate compounds or aromatic hydrocarbon compounds.

2. The method of claim 1, wherein, The mixed gas in step (1) comprises industrial waste gas, and the source thereof comprises any one or a combination of at least two of combustion flue gas, process tail gas or waste gas in a device.

3. The method of claim 1, wherein, The low-carbon alkanes comprise any one or a combination of at least two of ethane, propane or butane.

4. The method of claim 1, wherein, Before the mixed gas in step (1) is introduced, the reactor is first evacuated and then introduced with a protective gas for replacement.

5. The method of claim 1, wherein, The initiator in step (1) comprises azo compounds and / or peroxide compounds.

6. The method of claim 5, wherein, The azo compounds comprise any one or a combination of at least two of azobisisobutyronitrile, azobisisopentyl nitrile, azobisisoheptyl nitrile, azobiscyclohexyl cyanide or dimethyl azobis isobutyrate.

7. The method of claim 5, wherein, The peroxide compounds comprise any one or a combination of at least two of dibenzoyl peroxide, dilauryl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate.

8. The method of claim 1, wherein, The structural general formula of the organic alkanoate compound is wherein 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.

9. The method of claim 1, wherein, The aromatic hydrocarbon compounds comprise any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene.

10. The method of claim 1, wherein, The molar ratio of the initiator to the functional monomer in step (1) is (0.001-0.2):

1.

11. The method of claim 1, wherein, The mass ratio of the solvent to the functional monomer in step (1) is (2-50):

1.

12. The method of claim 1, wherein, During the gas-solid-liquid separation in step (2), the mixed gas is discharged and replaced with a protective gas.

13. The method of claim 1, wherein, The remaining material after the mixed gas is discharged in step (2) is discharged in a solid-liquid manner.

14. The method of claim 1, wherein, The discharged mixed gas is returned to step (1) for reuse after being pressurized until no unreacted components remain.

15. The method of claim 1, wherein, The method of solid-liquid separation in step (2) comprises any one or a combination of at least two of decantation, filtration or centrifugation.

16. The method of claim 15, wherein, The method of solid-liquid separation in step (2) is pressure filtration.

17. The method of claim 1, wherein, The remaining material is subjected to pressure filtration under a protective atmosphere to obtain filter cake which is washed, dried and then crushed.

18. The method of claim 17, wherein, The washing is performed using the solvent in step (1).

19. The method of claim 17, wherein, The solvent used for the washing further comprises an ether compound, which comprises any one or a combination of at least two of C1-C10 saturated ether compounds.

20. The method of claim 19, wherein, The ether compound is diethyl ether and / or propyl ether.

21. The method of claim 1, wherein, The olefin functional polymer in step (2) is in the form of microspherical particles with a particle size of 10-50 μm.

22. The method of claim 1, wherein, The liquid phase material is separated to obtain recovered solvent which is returned to step (1) for reuse.

23. The method of claim 22, wherein, The method of separation of the liquid phase material comprises any one or a combination of at least two of distillation, membrane separation, washing or extraction.

24. The method of claim 23, wherein, The method of separation of the liquid phase material is distillation.

25. The method of claim 22, wherein, The recovered solvent is returned to step (1) and / or step (2) for reuse in preparing the raw material liquid and / or washing the filter cake.

26. The method of claim 1, wherein, The method comprises the following steps: (1) passing a mixed gas into a reactor, the mixed gas comprising, in addition to low-carbon olefins, any one or a combination of at least two of low-carbon alkanes, sulfur-containing compounds, nitrogen oxides or particulate matter, and performing pretreatment before use in a polymerization reaction, the pretreatment comprising any one or a combination of at least two of desulfurization, denitration or dust removal, the low-carbon olefins comprising at least two of ethylene, propylene, butene or butadiene, the low-carbon alkanes comprising any one or a combination of at least two of ethane, propane or butane, the reactor being a tank reactor, after the reactor reaches a reaction temperature and a reaction pressure, adding a raw material liquid prepared from a functional monomer, an initiator and a solvent into the reactor, the functional monomer being maleic anhydride, the initiator comprising an azo compound and / or a peroxide compound, the solvent comprising any one or a combination of at least two of organic alkanoate compounds or aromatic compounds, the molar ratio of the initiator to the functional monomer being (0.001-0.2):1, the mass ratio of the solvent to the functional monomer being (2-50):1, the raw material liquid being pumped into the reactor at a constant speed after being pressurized by a delivery pump, and a polymerization reaction occurring, the polymerization reaction being carried out at a temperature of 50-150°C, a pressure of 0.1-10 MPa and a residence time of 0.01-10 h, and the pressure being maintained by continuously passing the mixed gas during the polymerization reaction; (2) subjecting the material after the polymerization reaction in step (1) to gas-solid-liquid separation, returning the mixed gas discharged to step (1) after being pressurized for reuse, subjecting the remaining material to solid-liquid separation after being discharged in a solid-liquid manner, subjecting the remaining material to pressure filtration under a protective atmosphere to obtain filter cake, washing, drying and then crushing the filter cake to obtain solid-phase olefin functional polymer and liquid phase material, the olefin functional polymer being in the form of microspherical particles with a particle size of 10-50 μm; (3) separating the liquid phase material obtained in step (2) by any one or a combination of at least two of distillation, membrane separation, washing or extraction, and the recovered solvent is returned to step (1) and / or step (2) for use again in preparing the raw material liquid and / or washing the filter cake.

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