CN119684544B - A method for synthesizing olefin copolymers based on microchannel reaction - Google Patents
A method for synthesizing olefin copolymers based on microchannel reaction Download PDFInfo
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Abstract
本发明公开了一种基于微通道反应合成烯烃共聚物的方法，属于烯烃聚合领域，该方法在微通道反应器中进行，包含：将负载型微球引发剂与溶剂A和溶剂B在微通道反应器中进行混合，混合温度为20~40℃，然后将四氟乙烯单体和其它共聚单体一起通入到微通道反应器进行聚合反应，聚合反应温度为60~180℃，压力为0.1~5MPa。其中，所述负载型微球引发剂为负载有过硫酸盐引发剂的聚苯乙烯/钠基蒙脱土微球或聚苯乙烯/沸石微球；所述溶剂A选自有机溶剂；所述溶剂B选自含氟离子液体。本发明解决了现有方法反应控制困难、产物分子量低、产物分布不均的问题，具有反应时间短、合成效率高、产物分子量高且分布窄的特点。The invention discloses a method for synthesizing olefin copolymers based on microchannel reaction, which belongs to the field of olefin polymerization. The method is carried out in a microchannel reactor, comprising: mixing a loaded microsphere initiator with solvent A and solvent B in a microchannel reactor, the mixing temperature is 20-40°C, and then introducing tetrafluoroethylene monomer and other comonomers into the microchannel reactor for polymerization reaction, the polymerization reaction temperature is 60-180°C, and the pressure is 0.1-5MPa. Wherein, the loaded microsphere initiator is polystyrene/sodium montmorillonite microspheres or polystyrene/zeolite microspheres loaded with persulfate initiator; the solvent A is selected from organic solvents; and the solvent B is selected from fluorine-containing ionic liquids. The invention solves the problems of difficult reaction control, low product molecular weight, and uneven product distribution in the existing method, and has the characteristics of short reaction time, high synthesis efficiency, high product molecular weight and narrow distribution.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a method for synthesizing an olefin copolymer based on a microchannel reaction.
Background
Polyolefin has been widely used in the fields of packaging, film, pipe, electronics, electricity, automobiles, etc. because of its excellent chemical stability and corrosion resistance, non-toxicity, low cost, etc. Wherein, polytetrafluoroethylene is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer, and the material has the characteristics of acid resistance, alkali resistance and resistance to various organic solvents, and is almost insoluble in all solvents. Tetrafluoroethylene monomer in polytetrafluoroethylene has wide application in fields of chemical industry, machinery, electronics, electrical appliances, military industry, aerospace, environmental protection and the like due to outstanding physical and chemical properties.
However, in practical applications, although the structure of polyolefin has a certain similarity, phase separation structure often occurs between different polyolefins or when polyolefin is mixed with other polymers, resulting in deterioration of mechanical properties of the polymers, while block copolymers combining the structure with polyolefin having different properties have good mechanical properties and processability. For example, polytetrafluoroethylene (PTFE) has special "insoluble and infusible" characteristics, which make it difficult to process, and tetrafluoroethylene and other monomers are copolymerized to prepare various polytetrafluoroethylene-based copolymers, such as FEP (tetrafluoroethylene-trifluoropropene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), etc., which can improve the processability of polytetrafluoroethylene, while maintaining the excellent physicochemical properties of polytetrafluoroethylene.
Currently, the polymerization methods of tetrafluoroethylene copolymer mainly include emulsion polymerization, high temperature suspension copolymerization, supercritical polymerization, radiation polymerization, etc. The method comprises the following steps:
(1) Emulsion polymerization processes are generally easy to operate using aqueous media to produce FEP. In this heterogeneous process, perfluoro surfactants such as perfluoro octanoic acid are used and gently stirred to obtain small ellipsoidal particles. The perfluoro surfactant has excellent aqueous solution dispersion stability and can reduce chain transfer reaction on surfactant molecules, so that the perfluoro surfactant is widely applied to the preparation of the poly (perfluoroethylene-propylene), and the method has the advantages of high polymerization speed, high molecular weight, complex polymer separation and precipitation process, more auxiliary agent varieties, large consumption and more residual impurities in the product;
(2) The high-temperature suspension copolymerization is carried out in an anchor-type stainless steel autoclave, the polymerization medium is deoxidized deionized water, the initiator is persulfate, such as potassium persulfate, and the like, and the method can increase the stability of the end group of a polymer product, but after the polymerization is finished, the dispersant is difficult to remove from the polymer product, so that the performance of the polymer product is influenced;
(3) The supercritical polymerization is to dissolve two reaction monomers in supercritical carbon dioxide, and add peroxide as polymerization initiator to initiate polymerization, and the peroxide initiator is also organic perfluoro peroxide. The method has high stability, high impact strength, good toughness and long fatigue life, but has higher requirements on the properties of the surfactant, is easy to dissolve in ScCO 2 and can inhibit polymer precipitation;
(4) The radiation polymerization is also thermal polymerization, namely, copolymerization is carried out under the conditions of the temperature of 70-350 ℃ and the pressure of 200atm or more and the existence of a polymerization accelerator, the radiation energy in the radiation polymerization is high, the monomer which is difficult to polymerize can be polymerized, the obtained polymer has higher purity, but the radiation effect is not selective, and the reaction is complex.
In the four tetrafluoroethylene polymerization methods, the problems of difficult reaction control, complex polymerization products, low molecular weight of the products, uneven product distribution and the like exist, and tetrafluoroethylene has the characteristics of severe reaction and the like in the polymerization process, and a large amount of heat is released to cause difficult control of reaction temperature so as to influence the yield and structural performance of the polymerization products.
It should be noted that the information disclosed in the above background section is only for enhancing understanding of the background of the present disclosure and thus may include information that does not constitute prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a method for synthesizing an olefin copolymer based on a microchannel reaction, which solves the problems of difficult reaction control, low molecular weight of a product and uneven product distribution in the existing method and has the characteristics of short reaction time, high synthesis efficiency, high molecular weight of the product and narrow distribution.
In order to achieve the aim, the invention provides a method for synthesizing an olefin copolymer based on a microchannel reaction, which is carried out in a microchannel reactor and comprises the steps of mixing a supported microsphere initiator with a solvent A and a solvent B in the microchannel reactor at a mixing temperature of 20-40 ℃, and then introducing tetrafluoroethylene monomer and other comonomers into the microchannel reactor together for polymerization, wherein the molar ratio of the tetrafluoroethylene monomer to the other comonomers is (0.1-1): (0.05-1), the polymerization temperature is 60-180 ℃, and the pressure is 0.1-5 MPa.
The supported microsphere initiator is polystyrene/sodium montmorillonite microsphere or polystyrene/zeolite microsphere loaded with persulfate initiator, the solvent A is selected from organic solvents, and the solvent B is selected from fluorine-containing ionic liquid.
The key technology of the invention is that the supported microsphere initiator, the solvent A and the solvent B are mixed and heated in a microchannel reactor, tetrafluoroethylene monomer and olefin comonomer are taken as raw materials, and the olefin copolymer is synthesized under the combined action of the supported microsphere initiator, the solvent A and the solvent B. The invention adopts two solvents of fluorine-containing ionic liquid and organic solution to carry out mixed reaction on different olefins and initiators, and can effectively accelerate the reaction rate. The supported microsphere initiator is adopted, wherein the initiator is persulfate, so that the polymerization rate can be accelerated, the polymerization period can be shortened, and the supported microsphere initiator provided by the invention has the characteristics of better dispersibility, high polymerization efficiency, difficulty in blocking a pipeline and the like because the initiator is supported on porous microspheres. And moreover, the micro-channel reactor is adopted to carry out polymerization reaction, so that the reaction can be effectively radiated, the polymerization temperature and pressure are controlled to synthesize a target product, the polymerization efficiency and the polymerization quality of the copolymer can be effectively improved through the micro-channel reactor, and the problems of high purity, better performance, high molecular weight, narrow distribution product, low molecular weight, uneven distribution and the like of the polymerization product are better solved.
The method can synthesize multipolymer in a microreactor, and the multipolymer can be alternatively copolymerized, randomly copolymerized or segmented copolymerized, so that the synthesized multipolymer has wider application range.
Preferably, the polymerization reaction temperature is 60-150 ℃.
Preferably, the pressure is 2.2-3.7 MPa.
Preferably, the persulfate is selected from any one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the supported microsphere initiator is prepared by the following method:
(1) Preparation of polystyrene/sodium montmorillonite microsphere or polystyrene/zeolite microsphere
Uniformly stirring sodium montmorillonite or zeolite and water, centrifuging, taking supernatant, adding a pore-forming agent, heating, adding a dispersing agent when the reaction temperature is 30 ℃, adding styrene and organic peroxide when the reaction temperature is 70 ℃ and rapidly heating to 80 ℃, and carrying out vacuum filtration, washing and drying after the reaction is finished to obtain the polystyrene/sodium montmorillonite microsphere or polystyrene/zeolite microsphere;
(2) Initiator loading
Dispersing the polystyrene/sodium montmorillonite microspheres or the polystyrene/zeolite microspheres in water, stirring at a constant temperature of 20-40 ℃, standing, adding an inorganic salt initiator, fully stirring, and drying in a vacuum oven at a low temperature to obtain powder which is called a supported initiator.
Preferably, the pore-forming agent is selected from any one or more than two of polyethylene glycol, polyurethane and urea, or/and the dispersing agent is selected from polyvinyl alcohol.
The fluorine-containing ionic liquid is formed by combining cations and anions, wherein the cations comprise any one of alkyl quaternary ammonium ions, pyridinium positive ions, imidazolium positive ions and alkyl triazole ions, the carbon number of an alkyl group in the alkyl triazole ions is 1-3, and the anions comprise any one of BF 4 —、PF6 —, trifluoromethyl sulfonamide ions and trifluoromethyl sulfonic acid ions.
Preferably, the organic solvent is selected from any one or more of benzene, toluene, phenol, cyclohexane, dichlorobenzene and acetonitrile.
Preferably, the molar ratio of the supported microsphere initiator to the solvent A or the solvent B is (1-5): 2-4, or/and the molar ratio of the solvent A or the solvent B is (1): 1, or/and the molar ratio of the supported microsphere initiator to the tetrafluoroethylene monomer or other comonomers is (1-3): 2-5.
Preferably, the volume ratio of the tetrafluoroethylene monomer to the other comonomer is 1:1.
Preferably, the mixing time of the supported microsphere initiator, the solvent A and the solvent B is 0.1-2 h, or/and the polymerization reaction is carried out, the introducing amount of the tetrafluoroethylene monomer and other comonomers is 20-200 mL, the introducing flow rate of the monomers is 5-30 mL/min, the introducing time interval of the polymerized monomers is 10-240 s, and the reaction time is 5-120 min.
The invention realizes the synthesis of different types of copolymers by controlling the flow and the dosage of tetrafluoroethylene monomer and other olefin comonomer which are introduced into the microchannel reactor (for example, by adopting a metering pump) and controlling the time interval of entering the microchannel reactor.
Preferably, the other comonomer has the chemical formula CF 2＝CFR1 or CH 2＝CHR2, wherein R 1 and R 2 are independently selected from H, fluoro or non-fluoro alkyl, fluoro or non-fluoro vinyl, the fluoro or non-fluoro alkyl, fluoro or non-fluoro vinyl having a carbon chain length of C 1~C6, and the fluoro or non-fluoro alkyl, fluoro or non-fluoro vinyl containing or not containing an oxygen atom between carbon atoms.
In particular, the fluorine-containing or non-fluorine-containing alkyl group, fluorine-containing or non-fluorine-containing vinyl group may have a substituent or not.
The invention realizes the copolymerization of tetrafluoroethylene monomer and other olefin by adopting different polymer monomers,
Preferably, the micro-channel reactor is made of nickel or alloy thereof, or/and has an inner diameter of 2-4 mm and a length of 500-5000 mm, or/and has 3-5 raw material supplementing points for supplementing solvent, initiator and polymer monomer.
The method for synthesizing the olefin copolymer based on the microchannel reaction solves the problems of difficult reaction control, low molecular weight of products and uneven product distribution in the prior method, and has the following advantages:
(1) The invention takes the load microsphere initiator to participate in the polymerization reaction, can effectively improve the polymerization efficiency, and simultaneously avoids causing the blockage of the reactor;
(2) The invention adopts two solvents of fluorine-containing ionic liquid and organic solution to carry out mixed reaction on different olefins and initiators, thereby effectively accelerating the reaction rate;
(3) The invention adopts the micro-channel reactor to carry out polymerization reaction, can effectively dissipate heat of the reaction, controls the polymerization temperature to synthesize a target product, can effectively improve the polymerization efficiency and the polymerization quality of the copolymer through the micro-channel reactor, and better solves the problems of low molecular weight, uneven distribution and the like of the polymerization product;
(4) The invention can synthesize multipolymer in the micro-reactor by controlling the flow and the dosage of the polymerized monomer and controlling the time interval of the polymerized monomer entering the micro-channel reactor, and the multipolymer can be alternatively copolymerized, randomly copolymerized or segmented copolymerized, and the synthesized multipolymer has wider application range.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific conditions were not specified in the examples, and the examples were conducted under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, all features defined in numerical ranges or percentage ranges, such as values, amounts, and concentrations, are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
The features mentioned in the present invention can be combined in any desired manner, and all possible combinations are to be regarded as being within the scope of the description provided that these combinations of features are not contradictory. The various features disclosed in the specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the disclosed features are merely general examples of equivalent or similar features.
The invention provides a method for synthesizing an olefin copolymer based on a microchannel reaction, which is carried out in a microchannel reactor and comprises the steps of mixing a supported microsphere initiator with a solvent A and a solvent B in the microchannel reactor at a mixing temperature of 20-40 ℃, and then introducing tetrafluoroethylene monomer and other comonomers into the microchannel reactor together for polymerization reaction, wherein the molar ratio of the tetrafluoroethylene monomer to the other comonomers is (0.1-1) (0.05-1), the polymerization reaction temperature is 60-180 ℃, and the pressure is 0.1-5 MPa. The supported microsphere initiator is polystyrene/sodium montmorillonite microsphere or polystyrene/zeolite microsphere loaded with persulfate initiator, the solvent A is selected from organic solvent, and the solvent B is selected from fluorine-containing ionic liquid.
The microchannel reactor is a heat exchanger with equivalent channel diameter of 10-1000 μm, tens of fine flow channels are arranged in a flat tube of the heat exchanger, two ends of the flat tube are connected with a round header, and heat generated in the reaction process can be effectively and timely conducted out through the heat exchanger, so that a certain reaction temperature is maintained. In addition, the micro-channel reactor technology can effectively enhance the mass transfer effect of a material system, miniaturize and miniaturize a large-scale reaction process, easily realize the rapid adjustment of the concentration, pressure and temperature of the material system, and finally realize the flexible adjustment of the properties of the product.
The invention can effectively realize the copolymerization of tetrafluoroethylene monomer and other olefins by the micro-channel reactor, and can produce high molecular weight and narrow distribution products with higher purity and better performance by controlling parameters such as temperature, pressure and the like.
The method for synthesizing an olefin copolymer based on a microchannel reaction according to the present invention will be described in detail with reference to experimental examples, examples and comparative examples.
Experimental example 1
1. Preparation of supported microsphere initiator
The preparation method of the potassium persulfate-loaded polystyrene/sodium montmorillonite microsphere comprises the following steps:
(1) Weighing 100g of sodium montmorillonite, adding 100mL of deionized water, stirring uniformly, centrifuging by a high-speed centrifuge, adding 5g of polyethylene glycol (pore-forming agent) into a three-neck flask, adding 0.5g of polyvinyl alcohol (dispersing agent) when the reaction temperature is 30 ℃, weighing 10g of styrene and 0.5g of benzoyl peroxide (initiator) when the temperature is raised to 70 ℃, adding the mixture into the three-neck flask, quickly raising the temperature to 80 ℃, carrying out vacuum suction filtration after reacting for 2 hours, washing the obtained sample with deionized water for a plurality of times, and carrying out vacuum drying at 80 ℃ to obtain white polystyrene/sodium montmorillonite microspheres;
(2) Dispersing the polystyrene/sodium montmorillonite microspheres in 100mL of deionized water, stirring at a constant temperature of 20-40 ℃, standing for 24 hours, then adding 50g of potassium persulfate, fully stirring, and drying at a low temperature of 60 ℃ in a vacuum oven to obtain powder, namely the potassium persulfate-loaded polystyrene/sodium montmorillonite microspheres, namely the loaded microsphere initiator.
The preparation method of the polystyrene/sodium montmorillonite microsphere loaded with ammonium persulfate and the polystyrene/zeolite microsphere loaded with potassium persulfate refers to the preparation method of the polystyrene/sodium montmorillonite microsphere loaded with potassium persulfate.
2. Structural characterization
The analysis of a portion of the microsphere sample was performed using a specific surface area and pore size analyzer (BSD-660S), and the data are shown in Table 1 below, and it was found from the pore volume and specific surface area data before and after loading of the microspheres that the polystyrene/sodium montmorillonite microsphere/zeolite microsphere had a relatively developed pore structure and specific surface area, and that the specific surface area and porosity were slightly reduced after loading with persulfate.
TABLE 1 pore volume and specific surface area data for Supported microsphere initiators
Example 1
A method for synthesizing an olefin copolymer based on a microchannel reaction, the inner diameter of a microchannel reactor being 3mm and the length of the microchannel reactor being 3000mm, the method comprising:
Firstly, mixing and heating 0.05mol of polystyrene/sodium montmorillonite microspheres (initiator) loaded with potassium persulfate, 0.1mol of benzene (solvent A) and 0.2mol of pyridinium positive ions and BF 4 — liquid (solvent B) in a micro-channel reactor, wherein the mixing temperature is 30 ℃, the mixing time is 1h, then sequentially introducing 0.15mol of tetrafluoroethylene and 0.05mol of ethylene into the micro-channel reactor for polymerization reaction to obtain a block copolymer, wherein the tetrafluoroethylene monomer introduction flow is 30mL/min, the ethylene monomer introduction flow is 5mL/min, the introduction time interval between polymerization monomers is 240s, the polymerization reaction temperature is 100 ℃, the reaction residence time is 10min, and the pressure is 2.2MPa.
After the completion of the reaction, the reaction mixture was degassed and desolventized, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), whereby the molecular weight M n=11.2×104 of the produced olefin copolymer was found to have a molecular weight distribution pdi=1.34.
Example 2
A method for synthesizing an olefin copolymer based on a microchannel reaction using the same microchannel reactor as in example 1, the method comprising:
Firstly, mixing and heating 0.3mol of polystyrene/sodium montmorillonite microsphere (initiator) loaded with ammonium persulfate, 0.5mol of toluene (solvent A) and 0.5mol of pyridinium positive ions and BF 4 — liquid (solvent B) in a micro-channel reactor, wherein the mixing temperature is 30 ℃, the mixing time is 0.5h, then sequentially introducing 1mol of tetrafluoroethylene and 1mol of ethylene into the micro-channel reactor for polymerization reaction to obtain an alternating copolymer, wherein the tetrafluoroethylene monomer introduction flow is 15mL/min, the ethylene introduction flow is 5mL/min, the introduction time interval between the polymerized monomers is 20s, the polymerization reaction temperature is 120 ℃, the reaction residence time is 60min, and the pressure is 2.9MPa.
After the completion of the reaction, the reaction mixture was degassed and desolventized, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), whereby the molecular weight M n=13.2×104 of the produced olefin copolymer was found to have a molecular weight distribution pdi=1.56.
Example 3
A method for synthesizing an olefin copolymer based on a microchannel reaction using the same microchannel reactor as in example 1, the method comprising:
Firstly, mixing and heating 0.3mol of polystyrene/zeolite microsphere (initiator) loaded with potassium persulfate, 0.5mol of toluene (solvent A) and 0.5mol of alkyl quaternary ammonium ion and trifluoromethyl sulfonamide ionic liquid (solvent B) in a micro-channel reactor, wherein the mixing temperature is 30 ℃, the mixing time is 0.5h, then sequentially introducing 1mol of tetrafluoroethylene and 0.5mol of ethylene into the micro-channel reactor for polymerization reaction to obtain a random copolymer, wherein the monomer introduction flow rates are 5mL/min, the introduction time interval between the polymerized monomers is 10s, the polymerization reaction temperature is 150 ℃, the reaction residence time is 60min, and the pressure is 3.7MPa.
After the completion of the reaction, the reaction mixture was degassed and desolventized, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), whereby the molecular weight mn=9.7x10 4 and the molecular weight distribution pdi=1.26 of the produced olefin copolymer were obtained.
Example 4
A method for synthesizing an olefin copolymer based on a microchannel reaction using the same microchannel reactor as in example 1, the method comprising:
Firstly, mixing and heating 0.3mol of polystyrene/zeolite microsphere (initiator) loaded with potassium persulfate, 0.1mol of benzene (solvent A) and 0.5mol of alkyl quaternary ammonium ion and trifluoromethyl sulfonamide ionic liquid (solvent B) in a micro-channel reactor, wherein the mixing temperature is 30 ℃, the mixing time is 0.5h, then sequentially introducing 1mol of tetrafluoroethylene and 0.1mol of hexafluoropropylene into the micro-channel reactor for polymerization reaction to obtain a random copolymer, wherein the monomer introduction flow rates are 5mL/min, the introduction time interval between the polymerized monomers is 10s, the polymerization reaction temperature is 60 ℃, the reaction residence time is 30min, and the pressure is 2.1MPa.
After the completion of the reaction, the reaction mixture was degassed and desolventized, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), whereby the molecular weight mn=9.3×10 4 and the molecular weight distribution pdi=1.23 of the produced olefin copolymer were obtained.
Comparative example 1
A process for the synthesis of an olefin copolymer, which reaction is substantially the same as in example 1, except that:
The reaction was carried out using a 1L autoclave.
The reaction mixture was degassed and desolventized after the completion of the reaction, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), as a result, the molecular weight M n=9.3×103 of the prepared olefin copolymer was found to have a molecular weight distribution pdi=3.02, and the molecular weight of the product was higher and the product distribution was more concentrated in the method for synthesizing an olefin copolymer using a microchannel reactor in example 1 of the present invention, as compared with example 1.
Comparative example 2
A method for synthesizing an olefin copolymer based on a microchannel reaction using a microchannel reactor substantially the same as that of example 1, except that:
The solvent is benzene only, and the fluorine-containing ionic liquid is not added as the solvent.
The reaction mixture was degassed and desolventized after the completion of the reaction, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), as a result, the molecular weight M n=11.2×103 of the prepared olefin copolymer, the molecular weight distribution pdi=2.14, and compared with example 1, the present invention example 1 uses benzene together with the fluorine-containing ionic liquid as a solvent, and the obtained product has a higher molecular weight and a more concentrated product distribution.
Comparative example 3
A method for synthesizing an olefin copolymer based on a microchannel reaction using a microchannel reactor substantially the same as that of example 1, except that:
the polymerization temperature was 210 ℃.
After the reaction, the reaction mixture was degassed and desolventized, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), and as a result, the molecular weight M n=14.1×103 of the prepared olefin copolymer, the molecular weight distribution pdi=2.63, and it was found that the high temperature polymerization resulted in the destruction of the molecular structure, resulting in a lower quality polymer.
Comparative example 4
A method for synthesizing an olefin copolymer based on a microchannel reaction using a microchannel reactor substantially the same as that of example 1, except that:
The initiator used in this comparative example was potassium persulfate, and no microspheres were used for loading.
After the reaction, the reaction solution was degassed and desolvated, and then the polymerization product was analyzed by high temperature gel chromatography (PL-GPC 220), and as a result, the molecular weight M n=10.4×103 of the prepared olefin copolymer, the molecular weight distribution pdi=2.56, was higher and the product distribution was more concentrated, compared with example 1, in which the polystyrene/sodium montmorillonite microsphere loaded with potassium persulfate was used as the initiator in example 1.
From the experimental data of the above examples and comparative examples, the copolymers prepared by polymerizing tetrafluoroethylene and other comonomer in two solvents and at a suitable polymerization temperature using a microchannel reaction in the examples of the present invention have a higher molecular weight and a narrower molecular weight distribution than the comparative examples.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (7)
1. A process for synthesizing an olefin copolymer based on a microchannel reaction, the process being carried out in a microchannel reactor and comprising:
mixing a supported microsphere initiator with a solvent A and a solvent B in a microchannel reactor at a mixing temperature of 20-40 ℃, and then introducing tetrafluoroethylene monomer and other comonomers into the microchannel reactor together for polymerization reaction, wherein the molar ratio of the tetrafluoroethylene monomer to the other comonomers is (0.1-1): (0.05-1), the polymerization reaction temperature is 60-180 ℃ and the pressure is 2.2-3.7 MPa;
The supported microsphere initiator is a polystyrene/sodium montmorillonite microsphere or a polystyrene/zeolite microsphere loaded with a persulfate initiator, wherein the persulfate is selected from any one or more than two of potassium persulfate, sodium persulfate and ammonium persulfate;
the preparation method of the polystyrene/sodium montmorillonite microsphere loaded with potassium persulfate comprises the following steps:
(1) Weighing 100g of sodium montmorillonite, adding 100mL of deionized water, stirring uniformly, centrifuging by using a high-speed centrifuge, adding 5g of polyethylene glycol into a three-neck flask, adding 0.5g of polyvinyl alcohol when the reaction temperature is 30 ℃, weighing 10g of styrene and 0.5g of benzoyl peroxide when the temperature is raised to 70 ℃, adding the mixture into the three-neck flask, quickly heating to 80 ℃, carrying out vacuum suction filtration after reacting for 2 hours, washing the obtained sample with deionized water for a plurality of times, and carrying out vacuum drying at 80 ℃ to obtain white polystyrene/sodium montmorillonite microspheres;
(2) Dispersing the polystyrene/sodium montmorillonite microspheres in 100mL of deionized water, stirring at a constant temperature of 20-40 ℃, standing for 24 hours, then adding 50g of potassium persulfate, fully stirring, and drying at a low temperature of 60 ℃ in a vacuum oven to obtain powder, wherein the powder is the polystyrene/sodium montmorillonite microspheres loaded with potassium persulfate, namely a loaded microsphere initiator;
the preparation method of the polystyrene/sodium montmorillonite microsphere loaded with ammonium persulfate and the polystyrene/zeolite microsphere loaded with potassium persulfate refers to the preparation method of the polystyrene/sodium montmorillonite microsphere loaded with potassium persulfate;
The solvent A is selected from organic solvents;
the solvent B is selected from fluorine-containing ionic liquid.
2. The method for synthesizing an olefin copolymer based on a microchannel reaction according to claim 1, wherein the fluorine-containing ionic liquid is composed of a combination of cations and anions;
The cation comprises any one of alkyl quaternary ammonium ion, pyridinium positive ion, imidazolium positive ion and alkyl triazole ion, wherein the carbon number of an alkyl in the alkyl triazole ion is 1-3;
The anion comprises any one of BF 4 —、PF6 —, trifluoromethyl sulfonamide ion and trifluoromethyl sulfonic acid ion.
3. The method for synthesizing an olefin copolymer based on a microchannel reaction according to claim 1, wherein the organic solvent is selected from any one or two or more of benzene, toluene, phenol, cyclohexane, dichlorobenzene and acetonitrile.
4. The method for synthesizing an olefin copolymer based on a microchannel reaction according to claim 1, wherein the molar ratio of the supported microsphere initiator to the solvent A or the solvent B is (1-5): 2-4;
Or/and the mol ratio of the solvent A or the solvent B is 1:1;
Or/and the molar ratio of the supported microsphere initiator to the tetrafluoroethylene monomer is (1-3) (2-5).
5. The method for synthesizing an olefin copolymer based on a microchannel reaction according to claim 1, wherein the mixing time of the supported microsphere initiator with the solvent a and the solvent B is 0.1 to 2 hours;
or/and the polymerization reaction, wherein the introducing amount of the tetrafluoroethylene monomer and other comonomers is 20-200 mL, the introducing amount of the monomers is 5-30 mL/min, the introducing time interval of the polymerized monomers is 10-240 s, and the reaction time is 5-120 min.
6. The method for synthesizing an olefin copolymer based on a microchannel reaction according to claim 1, wherein the other comonomer has a chemical structural formula of CF 2＝CFR1 or CH 2＝CHR2;
Wherein R 1 and R 2 are independently selected from H, a fluorine-containing or non-fluorine-containing alkyl group, a fluorine-containing or non-fluorine-containing vinyl group, the fluorine-containing or non-fluorine-containing alkyl group, the fluorine-containing or non-fluorine-containing vinyl group having a carbon chain length of C 1~C6;
The fluorine-containing or non-fluorine-containing alkyl group, fluorine-containing or non-fluorine-containing vinyl group, contains or does not contain an oxygen atom between carbon atoms.
7. The method for synthesizing an olefin copolymer based on a microchannel reaction according to any one of claims 1 to 6, wherein the material of the microchannel reactor is nickel or an alloy thereof;
Or/and the inner diameter of the micro-channel reactor is 2-4 mm, and the length of the micro-channel reactor is 500-5000 mm;
Or/and, the micro-channel reactor contains 3-5 raw material supplementing points for supplementing the solvent, the initiator and the polymer monomer.
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