CN116496139A - High-selectivity preparation method of perfluorononene - Google Patents

High-selectivity preparation method of perfluorononene Download PDF

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CN116496139A
CN116496139A CN202310463375.0A CN202310463375A CN116496139A CN 116496139 A CN116496139 A CN 116496139A CN 202310463375 A CN202310463375 A CN 202310463375A CN 116496139 A CN116496139 A CN 116496139A
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perfluorononene
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styrene
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陈兆武
谢琳
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Shenzhen Jiashunyi Industrial Co ltd
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Shenzhen Jiashunyi Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a high-selectivity preparation method of perfluorononene, which catalyzes hexafluoropropylene to generate perfluorononene under the combined action of an aza-organosilicon supported catalyst and a phase transfer promoter, and solves the problems of low efficiency, high loss, high cost and toxicity of a large amount of crown ether, low trimer selectivity and high dimer content selectivity of the catalyst in the traditional method. The perfluorinated nonene can be applied to the industry fields of cleaning, dilution and the like.

Description

High-selectivity preparation method of perfluorononene
Technical Field
The invention belongs to the technical field of fluorine-containing compound preparation, and particularly relates to a high-selectivity preparation method of perfluorononene.
Background
Perfluorononene is a chemical raw material, and is also called hexafluoropropylene trimer and trimer; perfluorononene is generally a mixture of three isomers, and has an important role in the fine product industry because it is generally used directly without separation in terms of purification cost and convenient use performance in the fields of washing, dilution, and the like because of its close boiling point.
Perfluorononene is generally synthesized by a gas phase method and a liquid phase method; the gas phase method can continuously react hexafluoropropylene in the tubular reactor through the catalyst layer, has the advantages of high automation degree, convenient post-treatment and high equipment investment; the liquid phase method is characterized in that a catalyst is mixed in an aprotic solvent, hexafluoropropylene is introduced into the liquid phase for reaction, and the hexafluoropropylene can be intermittently or continuously, and has the advantages of convenient separation, high single conversion rate and yield and better selectivity, complex post-treatment, washing and the like accompanied by the loss of the catalyst, and generally expensive and toxic crown ether which has good solubility with each solvent and is more easy to lose are required to be added. And the liquid phase method is more beneficial to industrialized production by combining all factors in the production process to comprehensively consider.
For example, patent CN 114057539A discloses a preparation method of hexafluoropropylene oligomer, adding a main catalyst alkali metal salt and an auxiliary catalyst cucurbituril into a polar aprotic solvent, introducing hexafluoropropylene gas at a temperature of 0-130 ℃ and a pressure of 0-1MPa, and reacting for 0.5-5h. The use of the composite catalyst is helpful for regulating and improving the selectivity of hexafluoropropylene trimer. But the selectivity and yield of the trimer remain undesirable.
A method for preparing hexafluoropropylene trimer by liquid phase method is also disclosed in patent CN 113912473A. Adding metal fluoride, a synergist and hexafluoropropylene dimer into a high-pressure reaction kettle, introducing inert gas, starting stirring, slowly introducing hexafluoropropylene, and reacting for 1-4h at 30-100 ℃; and cooling to room temperature after the reaction is finished, discharging materials in the reaction kettle from the bottom of the reaction kettle, and obtaining a lower-layer reaction product hexafluoropropylene trimer through liquid separation operation because the product and the catalyst solvent system are not mutually soluble. The trimer with higher conversion rate can be obtained by taking the dimer as a raw material, but the preparation process of the dimer is similar to that of the trimer, which is equivalent to doubling the production cost, and the synergist is crushed by grinding, so that the specific surface area is greatly different due to irregular particles, the reaction stability is reduced, and the efficiency is reduced.
Therefore, in the production method of perfluorononene in the prior art, agglomeration and dispersion are poor due to the fact that the traditional catalyst is easy to absorb moisture, and efficiency is affected; the addition of a large amount of crown ether substances increases the cost investment, and is toxic, the loss of the catalyst and the auxiliary agent is large, the cost is high, the selectivity of the total trimer, namely perfluorononene, is low, the content of the dimer, namely perfluorohexene, is high, and the yield is low.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a high-selectivity preparation method of perfluorononene, which can solve the problems of low efficiency, large loss, high cost for using a large amount of crown ether, toxicity, low trimer selectivity and high dimer content caused by easy agglomeration of a catalyst.
The technical scheme adopted by the invention is as follows:
high-selectivity preparation method of perfluorononene
The method comprises the following steps: the weight portions are as follows:
s01, adding 1-5 parts of aza-organosilicon supported catalyst, 0.5-2.0 parts of phase transfer promoter and 80-150 parts of solvent into a stainless steel closed reaction kettle, replacing the mixture by vacuum nitrogen until the oxygen content is less than or equal to 20ppm, and then charging nitrogen to the micro-positive pressure of 0.05MPa;
s02, slowly introducing 150-250 parts of hexafluoropropylene, simultaneously starting a stirring device of a reaction kettle to continuously stir, and keeping the temperature at 40-90 ℃; continuously stirring and reacting for 2-5 h; obtaining a suspension;
s03, cooling and discharging: cooling to room temperature, standing, layering liquid in the reaction kettle, separating liquid, and taking the lower liquid to obtain the perfluorinated nonene after refining.
Further, the step S01 further includes the following operations: preparation of an aza-organosilicon supported catalyst:
s011, the weight portions are as follows: taking 20-50 parts of DMF, adding 10-20 parts of nano fumed silica, 0.2-1.0 parts of hexamethyldisilazane, 0.53-0.8 parts of vinyl alkoxy silane and 0.01 part of water;
s012, heating to 30-50 ℃ and stirring for 30-90 min;
s013, performing reduced pressure distillation to obtain aza-modified nano silicon dioxide;
s014, adding 50-80 parts of tetrahydrofuran, 2-8 parts of alkali metal fluoride salt, 5-20 parts of aza-modified nano silicon dioxide, 0.5-1 part of styrene, 0.1-0.3 part of fluorinated styrene, 0.01-0.05 part of vinylguanamine and 0.01-0.05 part of potassium acrylate into a closed autoclave;
s015, stirring and heating to 45-65 ℃ after removing water and deoxidizing;
s016, adding 0.05-0.3 part of initiator;
s017, keeping the temperature at 45-65 ℃ and stirring for 3-6 h;
s018, cooling to room temperature, and discharging;
and S019, performing spray drying to obtain the aza-organosilicon supported catalyst.
Further, the particle size of the nano fumed silica added in the step S011 is 20-50 nm.
Further, the vinyl alkoxysilane added in the step S011 is vinyl ethoxysilane.
Further, the fluorinated styrene added in the step S014 is one or more mixtures of 4-fluoro styrene, 3-fluoro styrene, pentafluoro styrene, 2-trifluoromethyl styrene, 3-trifluoromethyl styrene, 4-trifluoromethyl styrene.
Further, the alkali metal fluoride salt added in the step S014 is one or a mixture of more of sodium fluoride, potassium fluoride and cesium fluoride.
Further, the initiator added in the step S016 is an initiator solution composed of 30% concentration of azobisisobutyronitrile dissolved in tetrahydrofuran.
Still further, the process for preparing the azaorganosilicon supported catalyst further comprises the following:
taking 20, 40 or 50 parts of N, N-dimethylformamide;
10 parts of fumed silica having a particle size of 20nm, or 20 parts of fumed silica having a particle size of 35nm, or 15 parts of fumed silica having a particle size of 50nm is added;
1.0 part, 0.2 part or 0.6 part of hexamethyldisilazane is added;
adding 0.8 part, 0.53 part or 0.65 part of vinyl ethoxy silane;
stirring at 40deg.C for 60min, or at 30deg.C for 90min, or at 50deg.C for 30min;
still further, the process for preparing the azaorganosilicon supported catalyst further comprises the following:
80 parts, 50 parts or 60 parts of tetrahydrofuran are added into a closed autoclave;
adding 2 parts of alkali potassium fluoride, 8 parts of cesium fluoride or 5 parts of potassium fluoride;
adding 5 parts, 20 parts or 10 parts of aza-modified nano silicon dioxide;
10 parts, 0.5 part or 0.7 part of styrene is added;
adding 0.1 part of 4-fluoro styrene, 0.3 part of pentafluorostyrene or 0.2 part of 4-trifluoromethyl styrene;
adding 0.01 part, 0.05 part or 0.03 part of vinylguanamine;
adding 0.05 part, 0.01 part or 0.03 part of potassium acrylate;
stirring and heating to 60 ℃ after removing water and deoxidizing;
then 0.3 part of initiator prepared by dissolving azodiisobutyronitrile with the concentration of 30 percent in tetrahydrofuran is added;
keeping the temperature for reaction for 3 hours;
cooling to room temperature and discharging;
finally, spray drying to obtain the aza-organosilicon supported catalyst.
Finally, the solvent added in the step S01 is acetonitrile, DMF, ethylene glycol diethyl ether, propylene glycol monomethyl ether or diethylene glycol dibutyl ether.
The beneficial effects of the invention are as follows:
a high-selectivity preparation method of perfluorononene, under the combined action of an aza-organosilicon supported catalyst and a phase transfer promoter, catalyzes hexafluoropropylene to generate perfluorononene, solves the problems of low efficiency, high loss, high cost and toxicity of a large amount of crown ether used, low trimer selectivity and high dimer content selectivity of the traditional method due to easy agglomeration of the catalyst. The perfluorinated nonene can be applied to the industry fields of cleaning, dilution and the like.
1. The catalyst has good dispersibility, good synergy with the phase inversion promoter, high activity, convenient post-treatment, less catalyst residue after layering, and high-purity perfluorononene can be obtained by conventional refining;
2. the reaction condition is mild, the comprehensive cost is low, the toxicity of crown ether is solved, the method is suitable for industrial scale-up production, and the perfluorinated nonene can be applied to the industrial fields of cleaning, dilution and the like;
3. the trimer selectivity exceeds 98.5%, the hexafluoropropylene conversion rate exceeds 99.5%, and the efficiency is high.
Drawings
FIG. 1 is a structural formula of a phase transfer promoter in a high selectivity preparation method of perfluorononene according to an embodiment I of the present invention;
FIG. 2 is a synthetic process expression for preparing an inversion promoter in the high selectivity preparation method of perfluorononene according to the first embodiment of the present invention;
FIG. 3 is an infrared spectrum of a perfluorononene product when subjected to analytical testing in the high selectivity preparation process of perfluorononene of example one of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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 without the inventive effort, are intended to be within the scope of the present invention.
The invention provides a high-selectivity preparation method of perfluorononene, which adopts the following overall planning scheme:
1) Adding 1-5 parts of aza-organosilicon supported catalyst, 0.5-2.0 parts of phase transfer promoter and 80-150 parts of solvent into a stainless steel closed reaction kettle, performing nitrogen-vacuum displacement until the oxygen content is less than or equal to 20ppm, and then charging nitrogen to the micro positive pressure of 0.05MPa;
2) Slowly introducing 150-250 parts of hexafluoropropylene, simultaneously starting stirring and keeping the temperature of 40-90 ℃ for reacting for 2-5 h; and keeping the temperature at 40-90 ℃; continuously stirring and reacting for 2-5 h; obtaining a product mixture in a liquid phase turbidity state, stopping stirring, and rapidly layering, wherein the lower liquid is a product, and the upper liquid is a solvent mixture containing a catalyst;
3) Cooling and discharging, cooling to room temperature, standing, separating liquid after the liquid in the reaction kettle is layered, and taking the lower liquid to obtain the perfluorinated nonene liquid after refining.
The preparation method of the aza-organosilicon supported catalyst comprises the following steps of: adding 10-20 parts of nano fumed silica, 0.2-1.0 part of hexamethyldisilazane, 0.53-0.8 part of vinyl alkoxy silane and 0.01 part of water into 20-50 parts of DMF (namely N, N-dimethylformamide and dimethylformamide, which are the same below), heating to 30-50 ℃ and stirring for 30-90 min, and then performing reduced pressure distillation to obtain aza-modified nano silica; adding 50-80 parts of tetrahydrofuran, 2-8 parts of alkali metal fluoride salt, 5-20 parts of aza-modified nano silicon dioxide, 0.5-1 part of styrene, 0.1-0.3 part of fluorinated styrene, 0.01-0.05 part of vinylguanamine and 0.01-0.05 part of potassium acrylate into a closed autoclave, stirring and heating to 45-65 ℃ after removing water and oxygen, adding 0.05-0.3 part of azobisisobutyronitrile (30% concentration dissolved in tetrahydrofuran), keeping the temperature at 45-65 ℃, stirring and reacting for 3-6 hours, cooling to room temperature, discharging, and then spray drying to obtain the aza-organosilicon supported catalyst;
the particle size of the nano fumed silica is 20-50 nm, the vinyl alkoxy silane is vinyl ethoxy silane, the fluorinated styrene can be one or more of 4-fluoro styrene, 3-fluoro styrene, pentafluorostyrene, 2-trifluoromethyl styrene, 3-trifluoromethyl styrene and 4-trifluoromethyl styrene, and the alkali metal fluoride salt is at least one of sodium fluoride, potassium fluoride and cesium fluoride;
wherein the solvent is one of acetonitrile, DMF, ethylene glycol diethyl ether, propylene glycol monomethyl ether and diethylene glycol dibutyl ether;
wherein the structural formula of the phase transfer promoter can be represented as shown in FIG. 1.
The high-selectivity preparation method of the perfluorononene is to catalyze and add under the synergistic effect of an aza-organosilicon supported catalyst and a phase transfer promoter to generate the perfluorononene, hexafluoropropylene monomers enter aprotic polar solvents in a liquid phase, water and oxygen are not contained in a kettle, the generation of byproducts can be effectively controlled, the forward effect is provided for the generation of hexafluoropropylene oligomers, and the oxygen content of the system in the preparation process is less than or equal to 20ppm and nitrogen is filled to 0.05MPa of micro positive pressure to prevent air from entering.
The reaction temperature in the high-selectivity preparation method of the perfluorononene is 40-90 ℃. The reaction temperature has a larger influence on the synthesis of the perfluorononene, the reaction speed is slower when the temperature is too low, the phenomenon of higher dimer content is more likely to occur, and the reaction efficiency is influenced; too high a temperature results in severe reaction, increased by-product content and easier production of multimers, such as tetramers, pentamers, etc. The reaction time of the invention is 2 to 5 hours, and the reaction time has an important influence on the content of the perfluorononene, and the effect is similar to the influence of the reaction temperature, so that the reaction time is 2 to 5 hours, preferably 2 to 3 hours. The preparation method comprises the following steps of: 1) Adding 1-5 parts of aza-organosilicon supported catalyst, 0.5-2.0 parts of phase transfer promoter and 80-150 parts of solvent into a stainless steel closed reaction kettle, performing nitrogen-vacuum displacement until the oxygen content is less than or equal to 20ppm, and charging nitrogen to the micro-positive pressure of 0.05MPa; 2) Slowly introducing 150-250 parts of hexafluoropropylene, simultaneously starting stirring and keeping the temperature of 40-90 ℃ for reacting for 2-5 h; 3) Cooling, discharging, standing, separating liquid, taking the lower layer, and refining to obtain the perfluorononene.
The aza-organosilicon supported catalyst of the invention is a porous shell-core polymer modified organosilicon compound. The method has good system compatibility and catalytic selectivity, ensures the rapid and stable reaction speed, has the effect of uniformly dissociating F-ions, can rapidly isomerise and convert hexafluoropropylene dimer therein into trimer, namely perfluorononene, simultaneously improves the conversion rate of hexafluoropropylene monomers, and improves the efficiency.
The aza-organosilicon supported catalyst of the invention grafts active aza-silane and unsaturated silane with gas phase silicon dioxide containing polyhydroxy to form fluffy structure of the outer end of the core, and then forms hollow porous shell by polymerization of vinyl group, wherein complex alkali metal fluoride is wrapped, and the shape is fixed by spray drying. To ensure adequate modification sites and overall specific surface area, the fumed silica has a particle size of 20 to 50nm, preferably 30 to 50 nm; the addition of the hexamethylenedisilazane is too small, so that residual hydroxyl is too much to cause poor compatibility, and the excessive addition occupies the intervention quantity of vinyl alkoxy silane to influence the pore distribution and the framework stability of the subsequent shell layer; the fluorinated styrene may be one or more of 4-fluoro styrene, 3-fluoro styrene, pentafluoro styrene, 2-trifluoromethyl styrene, 3-trifluoromethyl styrene, 4-trifluoromethyl styrene.
The preparation method of the aza-organosilicon supported catalyst comprises the following steps of: adding 10-20 parts of nano fumed silica, 0.2-1.0 part of hexamethyldisilazane, 0.53-0.8 part of vinyl alkoxy silane and 0.01 part of water into 20-50 parts of N, N-dimethylformamide, heating to 30-50 ℃, stirring for 30-90 min, and then performing reduced pressure distillation to obtain aza-modified nano silica; 50-80 parts of tetrahydrofuran, 2-8 parts of alkali metal fluoride salt, 5-20 parts of aza-modified nano silicon dioxide, 0.5-1.0 part of styrene, 0.1-0.3 part of fluorinated styrene, 0.01-0.05 part of vinylguanamine and 0.01-0.05 part of potassium acrylate are added into a closed autoclave, stirring and heating to 45-65 ℃ after dewatering and deoxidizing, 0.05-0.3 part of azo diisobutyronitrile (30% concentration is dissolved in tetrahydrofuran) is added, the temperature is kept for reaction for 3-6 hours, then the reaction is carried out, and the reaction product is discharged after cooling to room temperature, and then the aza-organosilicon supported catalyst is obtained through spray drying.
The final forming mode of the aza-organosilicon supported catalyst is spray drying, has the advantages of regular formation and uniform granularity, is beneficial to the maximum specific surface area in the catalytic reaction process, ensures the reaction to be quicker and smoother, and avoids side reactions, such as hexafluoropropylene polymers, caused by too fast reaction at certain part due to uneven point activity. Fumed silica is an organosilicon compound having hydroxyl groups in multiple forms, and the residual hydroxyl shells when dispersed in a liquid phase system after the shell-core structure is formed effectively lock trace moisture in the system inside, thereby reducing the generation of side reactions in the liquid phase. The addition of hexamethylenedisilazane can effectively reduce the number of hydroxyl groups on the surface of nano silicon dioxide, increase the compatibility and dispersibility with the organic solvent of the invention, reduce agglomeration, and promote the complexation with the phase inversion promoter in the catalytic system of the invention, so as to quickly carry metal ions and promote the dissociation of F-ions. The potassium acrylate compound can effectively increase the distribution of gaps and the control of porosity in the shell structure, and the fluorinated styrene can increase the adsorption and attack probability of hexafluoropropylene monomer and hexafluoropropylene dimer, so that the reaction is ensured. The vinyl guanamine can be cooperated with the phase inversion accelerant while improving the stable structure of the shell, so that the selectivity of the trimer, namely the perfluorinated nonene, is effectively improved.
The structural formula of the phase transfer promoter disclosed by the invention shows that the phase transfer promoter is a crown ether structural compound with sulfur-nitrogen modification, solves the problems of large addition amount and toxicity of crown ether when only crown ether is used, simultaneously maintains the phase transfer characteristic of crown ether and the function of carrying alkali metal ions, can cooperate with a catalyst in the presence of ammonium sulfate to improve the high selectivity of catalytic reaction, reduces the occurrence of side reaction, can effectively promote the collision opportunity of dimer anions and hexafluoropropylene in a system, and improves the trimer content. The preparation of the phase inversion promoter is that the 2-hydroxymethyl 18-crown-6 reacts with the allyl halide to react with the mercaptoethylamine after substitution reaction, and the synthesis process is shown in figure 2.
In principle, as the solvent of the present invention, a solvent which does not affect the compatibility of the catalyst and the monomer of the present invention and does not give adverse effects on the reaction may be used, and the solvent used in the present invention is one of polar solvents acetonitrile, DMF, ethylene glycol diethyl ether, propylene glycol monomethyl ether, diethylene glycol dibutyl ether, but is not limited to these solvents.
The invention is characterized in that:
1. the trimer selectivity exceeds 98.5%, the hexafluoropropylene conversion rate exceeds 99.5%, and the efficiency is high;
2. the catalyst has good dispersibility, good synergy with the phase inversion promoter, high activity, convenient post-treatment, less catalyst residue after layering, and high-purity perfluorononene can be obtained by conventional refining;
3. the reaction condition is mild, the comprehensive cost is low, the toxicity of crown ether is solved, and the method is suitable for industrial scale-up production.
The specific operation content is as follows:
first) analytical testing
(1) Product analysis: fourier transform infrared spectra (FT-IR) were measured using a Nicolet 6700 fourier transform infrared spectrum analyzer (germanium crystal ATR total reflection) from Thermo corporation of united states.
(2) Purity analysis: the gas chromatography measurement was carried out using high purity nitrogen as carrier gas at a capillary column temperature of 150 c, a vaporization chamber temperature of 200 c, and a detector temperature of 250 c, which ionizes the detector with a hydrogen flame.
FIG. 3 is an infrared spectrum of the product perfluorononene product of the present invention.
Preparation of a di) aza-organosilicon supported catalyst:
c01: adding 10 parts of fumed silica with the particle size of 20nm, 1.0 part of hexamethyldisilazane, 0.8 part of vinyl ethoxysilane and 0.01 part of water into 20 parts of N, N-dimethylformamide, heating to 40 ℃, stirring for 60min, and then performing reduced pressure distillation to obtain aza-modified nano-silica; 80 parts of tetrahydrofuran, 2 parts of alkali potassium fluoride, 5 parts of aza-modified nano silicon dioxide, 1.0 part of styrene, 0.1 part of 4-fluoro styrene, 0.01 part of vinylguanamine and 0.05 part of potassium acrylate are added into a closed autoclave, stirring and heating to 60 ℃ after removing water and deoxidizing, 0.3 part of azodiisobutyronitrile (30% concentration dissolved in tetrahydrofuran) is added, after the reaction is carried out for 3 hours, the temperature is reduced to room temperature, the materials are discharged, and then the aza-organosilicon supported catalyst is obtained through spray drying.
C02: adding 20 parts of fumed silica with the particle size of 35nm, 0.2 part of hexamethyldisilazane, 0.53 part of vinyl ethoxysilane and 0.01 part of water into 50 parts of N, N-dimethylformamide, heating to 30 ℃, stirring for 90min, and then performing reduced pressure distillation to obtain aza-modified nano silica; 50 parts of tetrahydrofuran, 8 parts of cesium fluoride, 20 parts of aza-modified nano silicon dioxide, 0.5 part of styrene, 0.3 part of pentafluorostyrene, 0.05 part of vinylguanamine and 0.01 part of potassium acrylate are added into a closed autoclave, stirring and heating to 65 ℃ after removing water and deoxidizing, 0.05 part of azobisisobutyronitrile (30% concentration dissolved in tetrahydrofuran) is added, the temperature is kept for reaction for 6 hours, the mixture is cooled to room temperature and discharged, and then the aza-organosilicon supported catalyst is obtained through spray drying.
C03: 15 parts of fumed silica with the particle size of 50nm, 0.6 part of hexamethyldisilazane, 0.65 part of vinyl ethoxysilane and 0.01 part of water are added into 40 parts of N, N-dimethylformamide, and after heating to 50 ℃, stirring is carried out for 30min, reduced pressure distillation is carried out, thus obtaining aza-modified nano-silica; 60 parts of tetrahydrofuran, 5 parts of potassium fluoride, 10 parts of aza-modified nano silicon dioxide, 0.7 part of styrene, 0.2 part of 4-trifluoromethyl styrene, 0.03 part of vinylguanamine and 0.03 part of potassium acrylate are added into a closed autoclave, stirring and heating to 45 ℃ after removing water and deoxidizing, 0.1 part of azobisisobutyronitrile (30% concentration is dissolved in tetrahydrofuran) is added, the reaction is carried out for 4 hours, the reaction is carried out after cooling to room temperature, and then the aza-organosilicon supported catalyst is obtained through spray drying.
Three) comparative examples:
comparative catalyst DC04: no hexamethyldisilazane was added, and the other steps were the same as for CO 1.
Comparative catalyst DC05: the fluorinated styrene is not added, and the other steps are the same as those of the preparation method of C01.
Fourth, examples one to eight in the implementation process; the specific formulation contents of examples one to eight are shown in Table 1:
embodiment one: 4 parts of the catalyst prepared in the operation step C01; 1.2 parts of phase transfer promoter; the proportioning solvent is 120 parts of acetonitrile; the proportion of hexafluoropropylene is 220 parts; the reaction temperature is 75 ℃; the reaction time with continuous stirring was 4h.
Embodiment two: 3 parts of catalyst prepared in the operation step C01; 1.0 part of phase transfer promoter; the proportioning solvent is 80 parts of diethylene glycol dibutyl ether; the proportion of hexafluoropropylene is 180 parts; the reaction temperature is 75 ℃; the reaction time with continuous stirring was 3h.
Embodiment III: proportioning 5 parts of the catalyst prepared in the C02 operation step; 2.0 parts of phase transfer promoter; the proportioning solvent is 150 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 90 ℃; the reaction time with continuous stirring was 5h.
Embodiment four: 2 parts of catalyst prepared in the operation step of C03; 1.0 part of phase transfer promoter; the proportioning solvent is 1000 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 250 parts; the reaction temperature is 60 ℃; the reaction time was 2h with continuous stirring.
Fifth embodiment: 3 parts of the catalyst prepared in the C02 operation step are proportioned; 1.5 parts of phase transfer promoter; the proportioning solvent is 100 parts of ethylene glycol diethyl ether; the proportion of hexafluoropropylene is 150 parts; the reaction temperature is 40 ℃; the reaction time with continuous stirring was 3h.
Example six: 3 parts of the catalyst prepared in the C02 operation step are proportioned; 2.0 parts of phase transfer promoter; the proportioning solvent is 90 parts of propylene glycol monomethyl ether; the proportion of hexafluoropropylene is 180 parts; the reaction temperature is 50 ℃; the reaction time with continuous stirring was 3h.
Embodiment seven: 4 parts of the catalyst prepared in the operation step C01; 1.0 part of phase transfer promoter; the proportioning solvent is 120 parts of acetonitrile; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 60 ℃; the reaction time was 2h with continuous stirring.
Example eight: proportioning 5 parts of catalyst prepared in the operation step of C03; proportioning 0.5 part of phase transfer promoter; the proportioning solvent is 120 parts of acetonitrile; the proportion of hexafluoropropylene is 250 parts; the reaction temperature is 75 ℃; the reaction time with continuous stirring was 4h.
Fifth) comparative examples 1 to 4 as comparative verification; the specific formulation contents of comparative examples 1 to 4 are shown in Table 1:
comparative example 1: 5 parts of cesium fluoride; 2.0 parts of a phase transfer promoter; the proportioning solvent is 150 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 90 ℃; the reaction time with continuous stirring was 5h.
Comparative example 2: proportioning 5 parts of the catalyst prepared in the C02 operation step; no phase transfer promoter is added; the proportioning solvent is 150 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 90 ℃; the reaction time with continuous stirring was 5h.
Comparative example 3: 5 parts of a comparative catalyst DC04;2.0 parts of a phase transfer promoter; the proportioning solvent is 150 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 90 ℃; the reaction time with continuous stirring was 5h.
Comparative example 4: 5 parts of a comparative catalyst DC05;2.0 parts of a phase transfer promoter; the proportioning solvent is 150 parts of N, N-dimethylformamide; the proportion of hexafluoropropylene is 200 parts; the reaction temperature is 90 ℃; the reaction time with continuous stirring was 5h.
The specific formulation contents of examples one to eight and comparative examples 1 to 4 are shown in Table 1.
Table 1:
sixth) comparative verification results of examples one to eight and comparative examples 1 to 4 are shown in table 2.
Table 2:
as can be seen from Table 2, the perfluorinated nonene (trimer) obtained by the synergistic catalytic reaction of the aza-organosilicon supported catalyst and the phase inversion promoter has high selectivity, rapid and stable reaction, less catalyst residues and convenient subsequent refining. In comparative example 1, only alkali metal fluoride is used as the catalyst, the reaction site is released too rapidly and byproducts are more generated, such as tetramer, pentamer and the like, and the content of dimer is higher, which is caused by uneven dispersion of the independent catalyst, agglomeration and dispersion coexistence; comparative example 2 only uses the inventive azaorganosilicon supported catalyst without using the inventive phase inversion promoter, and neither the monomer conversion nor the perfluorononene (trimer) selectivity is high, so that it can be seen that the inventive azaorganosilicon supported catalyst has an ideal synergistic effect with the phase inversion promoter; comparative example 3 does not add hexamethyldisilazane when preparing the catalyst of the present invention, lacks occupancy of hydroxyl groups on the silica surface, and also adversely affects selectivity and synergy with the phase inversion promoter; comparative example 4 does not use fluorinated styrene, resulting in a reduced and uneven probability of collision of dimer with monomer in the reaction, resulting in a similar adverse effect as comparative example 3. This also demonstrates that not only does the catalyst of the present invention have a synergistic effect with the inversion promoter, but the components of the catalyst also have good synergistic effects. All components are present at the same time to have a significant effect in the reaction.
The invention is not limited to the above-described alternative embodiments, and any person who may derive other various forms of products in the light of the present invention, however, any changes in shape or structure thereof, all falling within the technical solutions defined in the scope of the claims of the present invention, fall within the scope of protection of the present invention.

Claims (10)

1. A high-selectivity preparation method of perfluorononene is characterized by comprising the following steps: the method comprises the following steps: the weight portions are as follows:
s01, adding 1-5 parts of aza-organosilicon supported catalyst, 0.5-2.0 parts of phase transfer promoter and 80-150 parts of solvent into a stainless steel closed reaction kettle, replacing the mixture by vacuum nitrogen until the oxygen content is less than or equal to 20ppm, and then charging nitrogen to the micro-positive pressure of 0.05MPa;
s02, slowly introducing 150-250 parts of hexafluoropropylene, simultaneously starting a stirring device of a reaction kettle to continuously stir, and keeping the temperature at 40-90 ℃; continuously stirring and reacting for 2-5 h; obtaining a suspension;
s03, cooling and discharging: cooling to room temperature, standing, layering liquid in the reaction kettle, separating liquid, and taking the lower liquid to obtain the perfluorinated nonene after refining.
2. The process for the high selectivity production of perfluorononene according to claim 1, characterized in that: the step S01 further includes the following operations: preparation of an aza-organosilicon supported catalyst:
s011, the weight portions are as follows: taking 20-50 parts of DMF, adding 10-20 parts of nano fumed silica, 0.2-1.0 parts of hexamethyldisilazane, 0.53-0.8 parts of vinyl alkoxy silane and 0.01 part of water;
s012, heating to 30-50 ℃ and stirring for 30-90 min;
s013, performing reduced pressure distillation to obtain aza-modified nano silicon dioxide;
s014, adding 50-80 parts of tetrahydrofuran, 2-8 parts of alkali metal fluoride salt, 5-20 parts of aza-modified nano silicon dioxide, 0.5-1 part of styrene, 0.1-0.3 part of fluorinated styrene, 0.01-0.05 part of vinylguanamine and 0.01-0.05 part of potassium acrylate into a closed autoclave;
s015, stirring and heating to 45-65 ℃ after removing water and deoxidizing;
s016, adding 0.05-0.3 part of initiator;
s017, keeping the temperature at 45-65 ℃ and stirring for 3-6 h;
s018, cooling to room temperature, and discharging;
and S019, performing spray drying to obtain the aza-organosilicon supported catalyst.
3. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the particle size of the nano fumed silica added in the step S011 is 20-50 nm.
4. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the vinyl alkoxysilane added in the step S011 is vinyl ethoxysilane.
5. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the fluorinated styrene added in the step S014 is one or more of 4-fluoro styrene, 3-fluoro styrene, pentafluoro styrene, 2-trifluoromethyl styrene, 3-trifluoromethyl styrene and 4-trifluoromethyl styrene.
6. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the alkali metal fluoride salt added in the step S014 is one or a mixture of more of sodium fluoride, potassium fluoride and cesium fluoride.
7. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the initiator added in the step S016 is an initiator solution formed by dissolving 30% concentration of azobisisobutyronitrile in tetrahydrofuran.
8. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the process for preparing the aza-organosilicon supported catalyst further comprises the following:
taking 20, 40 or 50 parts of N, N-dimethylformamide;
10 parts of fumed silica having a particle size of 20nm, or 20 parts of fumed silica having a particle size of 35nm, or 15 parts of fumed silica having a particle size of 50nm is added;
1.0 part, 0.2 part or 0.6 part of hexamethyldisilazane is added;
adding 0.8 part, 0.53 part or 0.65 part of vinyl ethoxy silane;
stirring at 40deg.C for 60min, or at 30deg.C for 90min, or at 50deg.C for 30min;
and (3) distilling under reduced pressure to obtain aza-modified nano silicon dioxide.
9. The process for the high selectivity production of perfluorononene according to claim 2, characterized in that: the process for preparing the aza-organosilicon supported catalyst further comprises the following:
80 parts, 50 parts or 60 parts of tetrahydrofuran are added into a closed autoclave;
adding 2 parts of alkali potassium fluoride, 8 parts of cesium fluoride or 5 parts of potassium fluoride;
adding 5 parts, 20 parts or 10 parts of aza-modified nano silicon dioxide;
10 parts, 0.5 part or 0.7 part of styrene is added;
adding 0.1 part of 4-fluoro styrene, 0.3 part of pentafluorostyrene or 0.2 part of 4-trifluoromethyl styrene;
adding 0.01 part, 0.05 part or 0.03 part of vinylguanamine;
adding 0.05 part, 0.01 part or 0.03 part of potassium acrylate;
stirring and heating to 60 ℃ after removing water and deoxidizing;
then 0.3 part of initiator prepared by dissolving azodiisobutyronitrile with the concentration of 30 percent in tetrahydrofuran is added;
keeping the temperature for reaction for 3 hours;
cooling to room temperature and discharging;
finally, spray drying to obtain the aza-organosilicon supported catalyst.
10. The process for highly selective production of perfluorononene according to claim 5, wherein: the solvent added in the step S01 is acetonitrile, DMF, ethylene glycol diethyl ether, propylene glycol monomethyl ether or diethylene glycol dibutyl ether.
CN202310463375.0A 2023-04-20 2023-04-20 High-selectivity preparation method of perfluorononene Pending CN116496139A (en)

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