CN111269081B - Preparation method of hexafluoropropylene tripolymer - Google Patents
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Abstract
The invention relates to the field of fine chemical engineering, in particular to a preparation method of hexafluoropropylene trimer; according to the preparation method of the hexafluoropropylene tripolymer, the hexafluoropropylene tripolymer is prepared by adopting a gas phase catalytic synthesis method, and the preparation method has the advantages of no solvent and catalyst residue; the method adopts a method of adding hexafluoropropylene gas in multiple stages, which is beneficial to the full conversion of hexafluoropropylene dimer and avoids the generation of polymer caused by excessive hexafluoropropylene gas concentration; the copper bismuth doped complex catalytic material is creatively used as a catalyst for the reaction of hexafluoropropylene and hexafluoropropylene dimer, the catalyst can be used for catalyzing the reaction of hexafluoropropylene and hexafluoropropylene dimer with high selectivity to generate hexafluoropropylene trimer, and the content of polymer is reduced; the method has high yield, high purity of the prepared hexafluoropropylene tripolymer and very good industrial prospect.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a preparation method of hexafluoropropylene trimer.
Background
Hexafluoropropylene trimer is a very useful chemical raw material from which many fluorosurfactants can be derived. It can be used alone or together with other surfactants, thus playing a unique role in the fields of detergents, plastic coatings, textiles, leather, petroleum, electronics, pigments, etc.
201811459916.8 relates to a method for preparing perfluoroisobutyryl fluoride from hexafluoropropylene tripolymer. The preparation method comprises reacting oxygen and hexafluoropropylene dimer/hexafluoropropylene trimer as raw materials under the action of catalyst; wherein the molar ratio of oxygen to hexafluoropropylene dimer/hexafluoropropylene trimer is 1:10 to 10: 1; the contact reaction time is 0.1s to 200 s; the reaction pressure is 0-1 MPa; the reaction temperature is 150-600 ℃. The method for preparing the perfluoroisobutyryl fluoride from the hexafluoropropylene tripolymer provided by the invention has the advantages of mild reaction conditions, high product yield, no pollution and easiness in large-scale production.
201811458225.6 relates to a method for preparing perfluoropenta-carbon ketone by cracking hexafluoropropylene tripolymer. The method comprises the following steps: preparing perfluoropentacarbon from hexafluoropropylene tripolymer; the hexafluoropropylene tripolymer enters an oxidation furnace to carry out cracking reaction with oxygen under the action of a catalyst; rectifying the cracked product to obtain perfluoro-penta-carbon ketone. According to the invention, hexafluoropropylene dimer or hexafluoropropylene trimer is used as a raw material to generate perfluoro-penta-ketone, and then perfluoro-amyl ether is generated through an alkylation reagent reaction, so that the conversion efficiency is high, the conditions are mild, and the operation of the whole process is simple.
201811459912.X relates to a controllable polymerization method and device of hexafluoropropylene trimer, which is obtained by gas phase reaction of hexafluoropropylene under catalysis of load type ion fluoride; the reaction temperature is 260 ℃ to 320 ℃, and the contact time is 0.1s to 30 s; the loading capacity of the ionic fluoride is 10-20%; the carrier is activated carbon, aluminum oxide, silicon dioxide or magnesium oxide; the ionic fluoride is AgF, NaF, KF, RbF or CsF. The new route of the invention can be suitable for the existing enterprises producing fluorinated products, realizes long-term recycling, and has the characteristics of low cost and remarkable economic benefit.
The above patents and the prior art, hexafluoropropylene tripolymer, are mainly synthesized by a liquid phase method, the hexafluoropropylene oligomerization process by the liquid phase method is that a catalyst and an additive thereof are dissolved in an aprotic polar solvent, then hexafluoropropylene is introduced for oligomerization, and the product produced by the method necessarily contains a small amount of solvent and catalyst.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a hexafluoropropylene trimer.
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.6-1.2; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 4-8 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is hexafluoropropylene dimer steam, and the other feed inlets are hexafluoropropylene feed inlets; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 280-280 ℃, the temperature interval of the middle layer is 250-280 ℃, and the temperature interval of the high layer is 200-250 ℃; the reaction pressure in the gas phase reaction tower is 0.5-5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
according to the mass parts, 5-10 parts of copper chloride, 10-30 parts of dimethyl allyl silane and 3-8 parts of bismuth citrate are taken and added into 300 parts of 200-acetone N-methyl pyrrolidone, the mixture is stirred and mixed uniformly, then argon atmosphere is introduced, the temperature is controlled to be 60-77 ℃, 2.4-4.6 parts of ammonium persulfate is dissolved into 30-80 parts of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled for 1-5 hours; controlling the temperature to be 48-73 ℃ after the dropwise addition is finished, continuously reacting for 1-4h, then adding 0.5-2 parts of 2-vinyl-2-oxazoline, 0.3-3 parts of propenyl hexafluoroisopropyl ether and 0.1-1 part of chloroplatinic acid, controlling the temperature to be 50-67 ℃ and continuously reacting for 0.5-2h, then cooling to room temperature, adding 300-400 parts of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 40-70 ℃ for 5-8h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and the hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The dimethyl allyl silane generates a polymer, a Si-H bond is introduced into the polymer, the copper metal and bismuth citrate complex exist in the polymer, then the copper metal and 2-vinyl-2-oxazoline and propenyl hexafluoroisopropyl ether generate hydrosilylation reaction under the action of chloroplatinic acid, and simultaneously metal ions and oxazoline generate a metal complex to obtain the copper-bismuth doped complex catalytic material.
According to the preparation method of the hexafluoropropylene tripolymer, the hexafluoropropylene tripolymer is prepared by adopting a gas phase catalytic synthesis method, and the preparation method has the advantages of no solvent and catalyst residue; the method adopts a method of adding hexafluoropropylene gas in multiple stages, which is beneficial to the full conversion of hexafluoropropylene dimer and avoids the generation of polymer caused by excessive hexafluoropropylene gas concentration; the copper bismuth doped complex catalytic material is creatively used as a catalyst for the reaction of hexafluoropropylene and hexafluoropropylene dimer, the catalyst can be used for catalyzing the reaction of hexafluoropropylene and hexafluoropropylene dimer with high selectivity to generate hexafluoropropylene trimer, and the content of polymer is reduced; the method has high yield, high purity of the prepared hexafluoropropylene tripolymer and very good industrial prospect.
Drawings
FIG. 1 is a Fourier infrared spectrum of a hexafluoropropylene trimer prepared in example 2.
Detailed Description
The invention is further illustrated by the following specific examples:
in the specific embodiment of the invention, the content of hexafluoropropylene dimer is measured by adopting a gas phase analysis method, the temperature of a capillary column is 150 ℃, the temperature of a gasification chamber is 200 ℃, the temperature of a detector is 250 ℃, high-purity nitrogen is used as a carrier gas, and the detector is a hydrogen flame ionization detector.
Example 1
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.6; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 4 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is hexafluoropropylene dimer steam, and the other feed inlets are hexafluoropropylene feed inlets; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 280 ℃, the temperature interval of the middle layer is 250 ℃, and the temperature interval of the high layer is 200 ℃; the reaction pressure in the gas phase reaction tower is 0.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 5Kg of copper chloride, 10Kg of dimethyl allyl silane and 3Kg of bismuth citrate into 200Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 60 ℃, dissolving 2.4Kg of ammonium persulfate into 30Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling the dropwise adding for 1 h; and after the dropwise addition, controlling the temperature to be 48 ℃, continuously reacting for 1 hour, then adding 0.5Kg of 2-vinyl-2-oxazoline, 0.3Kg of propenyl hexafluoroisopropyl ether and 0.1Kg of chloroplatinic acid, controlling the temperature to be 50 ℃, continuously reacting for 0.5 hour, then cooling to room temperature, adding 300Kg of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 40 ℃ for 5 hours, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 93.7%.
Example 2
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas phase synthesis method, and utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 6Kg of copper chloride, 18Kg of dimethyl allyl silane and 5Kg of bismuth citrate into 252Kg of N-methylpyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 69 ℃, dissolving 3.3Kg of ammonium persulfate into 70Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling the dropwise adding for 2 hours; after the dropwise addition, controlling the temperature to be 55 ℃, continuously reacting for 2h, then adding 1Kg of 2-vinyl-2-oxazoline, 1Kg of propenyl hexafluoroisopropyl ether and 0.3Kg of chloroplatinic acid, controlling the temperature to be 58 ℃, continuously reacting for 1h, then cooling to room temperature, adding 320Kg of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 60 ℃ for 7h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 94.1%.
Example 3
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 1.2; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 8 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 310 ℃, the temperature interval of the middle layer is 280 ℃, and the temperature interval of the high layer is 250 ℃; the reaction pressure in the gas phase reaction tower is 5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 10Kg of copper chloride, 30Kg of dimethyl allyl silane and 8Kg of bismuth citrate into 300Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 77 ℃, dissolving 4.6Kg of ammonium persulfate into 80Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling the dropwise adding for 5 hours; controlling the temperature to be 73 ℃ after the dropwise addition, continuing to react for 4 hours, then adding 2Kg of 2-vinyl-2-oxazoline, 3Kg of propenyl hexafluoroisopropyl ether and 1Kg of chloroplatinic acid, controlling the temperature to be 67 ℃, continuing to react for 2 hours, then cooling to room temperature, adding 400Kg of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 70 ℃ for 8 hours, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 94.8%.
Comparative example 1
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of hexafluoropropylene trimer is characterized in that potassium fluoride is adopted in the reaction tower to catalyze the reaction.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 60.1%.
Comparative example 2
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 6Kg of copper chloride and 18Kg of dimethyl allyl silane into 252Kg of N-methyl pyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 69 ℃, dissolving 3.3Kg of ammonium persulfate into 70Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling the dropwise adding for 2 hours; after the dropwise addition, controlling the temperature to be 55 ℃, continuously reacting for 2h, then adding 1Kg of 2-vinyl-2-oxazoline, 1Kg of propenyl hexafluoroisopropyl ether and 0.3Kg of chloroplatinic acid, controlling the temperature to be 58 ℃, continuously reacting for 1h, then cooling to room temperature, adding 320Kg of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 60 ℃ for 7h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 81.8%.
Comparative example 3
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 6Kg of copper chloride, 18Kg of dimethyl allyl silane and 5Kg of bismuth citrate into 252Kg of N-methylpyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 69 ℃, dissolving 3.3Kg of ammonium persulfate into 70Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling the dropwise adding for 2 hours; and after the dropwise addition, controlling the temperature to be 55 ℃, continuously reacting for 2h, then adding 1Kg of propenyl hexafluoroisopropyl ether and 0.3Kg of chloroplatinic acid, controlling the temperature to be 58 ℃, continuously reacting for 1h, then cooling to room temperature, adding 320Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying the solid in vacuum at the temperature of 60 ℃ for 7h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 83.4%.
Comparative example 4
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper-bismuth doped complex catalytic material is prepared by the following method:
adding 6Kg of copper chloride, 18Kg of dimethyl allyl silane and 5Kg of bismuth citrate into 252Kg of N-methylpyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, then controlling the temperature to be 69 ℃, dissolving 3.3Kg of ammonium persulfate into 70Kg of isopropanol, and slowly dropwise adding into a reaction kettle for 2 hours; and after the dropwise addition, controlling the temperature to be 55 ℃, continuously reacting for 2h, then adding 1Kg of 2-vinyl-2-oxazoline and 0.3Kg of chloroplatinic acid, controlling the temperature to be 58 ℃, continuously reacting for 1h, then cooling to room temperature, adding 320Kg of acetone, extracting, evaporating the obtained solution to dryness to obtain a solid, drying the solid in vacuum at the temperature of 60 ℃ for 7h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 88.6%.
Comparative example 5
A hexafluoropropylene trimer is prepared according to the following method:
the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.9; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 6 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is used for feeding hexafluoropropylene dimer steam, and the other feed inlets are used for feeding hexafluoropropylene; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 300 ℃, the temperature interval of the middle layer is 270 ℃, and the temperature interval of the high layer is 230 ℃; the reaction pressure in the gas phase reaction tower is 2.5 MPa; the preparation method of the hexafluoropropylene tripolymer is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction.
The copper bismuth doped complex catalytic material is prepared by the following method:
adding 6Kg of copper chloride and 5Kg of bismuth citrate into 252Kg of N-methylpyrrolidone, stirring and mixing uniformly, introducing argon atmosphere, controlling the temperature to be 69 ℃, dissolving 3.3Kg of ammonium persulfate into 70Kg of isopropanol, slowly dropwise adding into a reaction kettle, and controlling dropwise adding for 2 hours; after the dropwise addition, controlling the temperature to be 55 ℃, continuously reacting for 2h, then adding 1Kg of 2-vinyl-2-oxazoline, 1Kg of propenyl hexafluoroisopropyl ether and 0.3Kg of chloroplatinic acid, controlling the temperature to be 58 ℃, continuously reacting for 1h, then cooling to room temperature, adding 320Kg of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 60 ℃ for 7h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
And the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
The rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
The hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
The present example did not undergo hydrosilylation.
The gas phase analysis result shows that the content of the hexafluoropropylene tripolymer prepared by the experiment is 76.7%.
Claims (4)
1. A preparation method of hexafluoropropylene trimer comprises the following steps: the preparation method adopts a gas-phase synthesis method, utilizes hexafluoropropylene dimer and hexafluoropropylene to synthesize hexafluoropropylene trimer in a gas-phase reaction tower, and is characterized in that the mass ratio of hexafluoropropylene dimer steam to hexafluoropropylene gas is 1: 0.6-1.2; the gas flow direction of the gas phase reaction tower flows from bottom to top, the tower body has 4-8 feed inlets, the tower bottom has 2 feed inlets, one feed inlet is hexafluoropropylene dimer steam, and the other feed inlets are hexafluoropropylene feed inlets; the temperature in the reaction tower is divided into three temperature intervals from bottom to top, wherein the temperature interval of the bottom layer is 280-280 ℃, the temperature interval of the middle layer is 250-280 ℃, and the temperature interval of the high layer is 200-250 ℃; the reaction pressure in the gas phase reaction tower is 0.5-5 MPa; the method is characterized in that a copper bismuth doped complex catalytic material is adopted in the reaction tower to catalyze the reaction;
the copper bismuth doped complex catalytic material is prepared by the following method: according to the mass parts, 5-10 parts of copper chloride, 10-30 parts of dimethyl allyl silane and 3-8 parts of bismuth citrate are taken and added into 300 parts of 200-acetone N-methyl pyrrolidone, the mixture is stirred and mixed uniformly, then argon atmosphere is introduced, the temperature is controlled to be 60-77 ℃, 2.4-4.6 parts of ammonium persulfate is dissolved into 30-80 parts of isopropanol, and the mixture is slowly dripped into a reaction kettle, and the dripping is controlled for 1-5 hours; controlling the temperature to be 48-73 ℃ after the dropwise addition is finished, continuously reacting for 1-4h, then adding 0.5-2 parts of 2-vinyl-2-oxazoline, 0.3-3 parts of propenyl hexafluoroisopropyl ether and 0.1-1 part of chloroplatinic acid, controlling the temperature to be 50-67 ℃ and continuously reacting for 0.5-2h, then cooling to room temperature, adding 300-400 parts of acetone, extracting, evaporating the obtained solution to dryness, drying the obtained solid in vacuum at 40-70 ℃ for 5-8h, and then crushing to obtain the copper-bismuth doped complex catalytic material.
2. The method according to claim 1, wherein the hexafluoropropylene trimer is produced by: and the hexafluoropropylene gas uniformly enters the reaction tower from each feed inlet of the hexafluoropropylene.
3. The method according to claim 1, wherein the hexafluoropropylene trimer is produced by: the rest hexafluoropropylene gas feed inlets are uniformly distributed on the tower body from bottom to top according to a spiral shape.
4. The method according to claim 1, wherein the hexafluoropropylene trimer is produced by: the hexafluoropropylene gas and hexafluoropropylene dimer gas enter the reaction zone after being uniformly mixed at the bottom inlet of the reaction tower.
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