CN113024708A - Method for preparing fluorine-propylene polymer nano material by micro-channel continuous flow - Google Patents
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
Abstract
The invention discloses a method for preparing a fluorine-propylene polymer nano material by micro-channel continuous flow. The method comprises the following specific steps: taking an acrylic acid monomer as an oil phase, taking an alkyl vinyl sulfonate aqueous solution as a water phase, and emulsifying the oil phase and the water phase in a micro mixer to prepare a pre-emulsion; and pumping the pre-emulsion, the fluorine-containing monomer and the initiator aqueous solution into a micro-channel continuous flow reactor for reaction, and discharging the reaction product in a cold water bath after the reaction is finished to obtain the fluorine-propylene polymer nano material. The invention adopts the micro-channel continuous flow reactor to realize controllable multiphase micro-scale flow, strengthens the processes of mass transfer, heat transfer and mixing in the reaction process, and easily realizes the regulation and control of preparation conditions by regulating the operation parameters such as flow, retention time and the like, greatly shortens the reaction time and improves the polymerization efficiency.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a method for preparing a fluorine-propylene polymer nano material by a microchannel continuous flow.
Background
Emulsion polymerization is one of the important methods for producing high molecular materials, and plays an important role in the fields of synthetic resins, synthetic rubbers, adhesives, coatings, fabric treating agents, paper sizing agents, functional polymer microspheres and the like.
At present, polymers are generally prepared in a tank reactor, the operation time is generally several hours, the size of the reactor is in the order of meters, and the defects of low mass and heat transfer efficiency, difficult regulation and control of residence time and temperature and the like exist. Because the free radical polymerization has an automatic acceleration phenomenon, the defects of the stirred tank reactor are easy to cause the problems of slow heat transfer, low mixing efficiency, long reaction time, easy scaling, sudden polymerization and the like in the emulsion polymerization process, and all can influence the performance of the polymer.
The microchannel continuous flow reactor can conveniently control reaction parameters such as reaction temperature, reactant proportion, reaction time and the like through a temperature control system and flow regulation, and a polymerization product with narrow molecular weight distribution can be obtained by utilizing the heat transfer performance of the microreactor. In addition, the system of the micro-channel continuous flow reactor is relatively closed, so that the micro-channel continuous flow reactor is not easy to be invaded by impurities such as water, air and the like, and part of complicated impurity removal protection measures can be omitted.
Disclosure of Invention
The invention provides a method for preparing a fluorine-propylene polymer nano material by micro-channel continuous flow aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a method for preparing a fluorine-propylene polymer nano material by micro-channel continuous flow specifically comprises the following steps:
(1) preparing a pre-emulsion: mixing acrylic acid monomer and fluorine-containing monomer in any proportion to obtain an oil phase; dissolving an emulsifier in deionized water according to the mass ratio of 0.01-0.5:1 to obtain an emulsifier aqueous solution as a water phase; pumping the oil phase and the water phase into a micro mixer according to the flow rate ratio of 0.1-1:1 for emulsification to obtain pre-emulsion;
(2) preparing an initiator aqueous solution: mixing a water-soluble initiator and deionized water according to a mass ratio of 1:50-100, and stirring to obtain an initiator aqueous solution;
(3) preparing a fluorine-propylene polymer nano material: and (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor according to the flow rate ratio of 10-20:1 for reaction, and discharging the reaction product at room temperature in a cold water bath to obtain the fluorine-propylene polymer nano material, wherein the fluorine-propylene polymer nano material is dispersed in water in the form of nano particles.
Further, the acrylic monomer may be acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, or isooctyl acrylate.
Further, the fluorine-containing monomer can be tetrafluoroethylene or fluorine-containing acrylate monomer.
Further, the micro mixer used in the step 1 has a mixing structure of a T-shaped mixer, the inner diameter is 0.5-1mm, the mixing time is 1-2min, and the temperature is room temperature.
Further, in the step 1, the emulsifier may be sodium lauryl sulfate, alkyl sulfonate or alkyl benzene sulfonate.
Further, in the step 2, the water-soluble initiator may be azobisisobutyronitrile, benzoyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide, a hydrogen peroxide derivative or VA-016.
Further, the inner diameter of the micro-channel continuous flow reactor in the step 3 is 1-2mm, the reaction residence time is 30-180min, and the reaction temperature is 50-90 ℃.
Compared with the traditional process for preparing the fluoropropylene polymer nano material by using the kettle type reactor, the method for preparing the fluoropropylene polymer nano material by using the continuous flow of the microchannel has the advantages that the continuous flow of the microchannel can flow in a controllable multiphase micro scale at present, the mixing, mass transfer and heat transfer processes in the polymerization reaction process are enhanced, the reaction time is greatly shortened, and the polymerization efficiency is improved; in addition, because the continuous flow of the micro-channel has excellent heat transfer capacity, the heat released by the reaction is dissipated in time, the accurate control of the temperature is realized, and the problem of sudden aggregation caused by overhigh temperature in the traditional method is solved; moreover, the continuous flow of the micro-channel adopts a continuous feeding mode, thereby greatly improving the operation efficiency. Generally, the method has the advantages of high reaction speed, simple operation, flexible production, safety, controllability, high integration, continuity and the like.
Drawings
FIG. 1 is a morphology chart of a fluoropropylene polymer nano-material prepared by the embodiment of the invention.
Detailed Description
The invention discloses a method for preparing a fluorine-propylene polymer nano material by micro-channel continuous flow, which comprises the following steps:
(1) preparing a pre-emulsion: mixing acrylic acid monomer and fluorine-containing monomer in any proportion to obtain an oil phase; dissolving an emulsifier in deionized water according to the mass ratio of 0.01-0.5:1 to obtain an emulsifier aqueous solution as a water phase; pumping the oil phase and the water phase into a micro mixer according to the flow rate ratio of 0.1-1:1 for emulsification to obtain a pre-emulsion.
The acrylic monomer may be acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate or isooctyl acrylate.
The fluorine-containing monomer can be tetrafluoroethylene or fluorine-containing acrylate monomer.
The mixing structure of the micro mixer is a T-shaped mixer, the inner diameter is 0.5-1mm, the mixing time is 1-2min, and the temperature is room temperature.
The emulsifier may be sodium lauryl sulfate, alkyl sulfonate or alkyl benzene sulfonate.
(2) Preparing an initiator aqueous solution: mixing a water-soluble initiator and deionized water according to a mass ratio of 1:50-100, and stirring to obtain an initiator aqueous solution;
the water-soluble initiator can be azodiisobutyronitrile, benzoyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide derivatives or VA-016.
(3) Preparing a fluorine-propylene polymer nano material: and (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor according to the flow rate ratio of 10-20:1 for reaction, and discharging the reaction product at room temperature in a cold water bath to obtain the fluorine-propylene polymer nano material, wherein the fluorine-propylene polymer nano material is dispersed in water in the form of nano particles.
The inner diameter of the micro-channel continuous flow reactor is 1-2mm, the reaction residence time is 30-180min, and the reaction temperature is 50-90 ℃.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Step 1 preparation of Pre-emulsion
Taking an acrylic acid monomer and a tetrafluoroethylene monomer as oil phases, fully dissolving sodium dodecyl sulfate in deionized water according to the mass ratio of 0.01:1, taking a sodium dodecyl sulfate aqueous solution as a water phase, adding the oil phases and the water phases into a micro mixer according to the flow rate ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 0.5mm, the mixing time is 2min, the reaction temperature is room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
And initiator ammonium persulfate: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 10:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1mm, the reaction temperature is 90 ℃, and the reaction residence time is 30 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material. The monomer conversion was found to be 94.5% and the particle size was 80.12 nm.
FIG. 1 is a morphology diagram of a fluoropropylene polymer nano-material obtained by a transmission electron microscope, and it can be seen from the diagram that the synthesized soap-free emulsion has regular latex particles and uniform distribution.
Example 2
Step 1 preparation of Pre-emulsion
Taking a methyl acrylate monomer and a fluorine-containing acrylate monomer as oil phases, fully dissolving alkyl sulfonate in deionized water according to the mass ratio of 0.01:1, taking an alkyl sulfonate aqueous solution as a water phase, adding the oil phases and the water phases into a micro mixer according to the flow ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 0.5mm, the mixing time is 2min, the reaction temperature is room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
With initiator azobisisobutyronitrile: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 10:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1mm, the reaction temperature is 90 ℃, and the reaction residence time is 30 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 3
Step 1 preparation of Pre-emulsion
Taking a hexyl acrylate monomer and a fluorine-containing acrylate monomer as oil phases, fully dissolving alkyl sulfonate in deionized water according to the mass ratio of 0.01:1, taking an alkyl benzene sulfonate aqueous solution as a water phase, adding the oil phases and the water phases into a micro mixer at the flow rate ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 0.5mm, the mixing time is 2min, and the reaction temperature is room temperature, thus preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
With the initiator hydrogen peroxide: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 10:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1mm, the reaction temperature is 90 ℃, and the reaction residence time is 150 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 4
Step 1 preparation of Pre-emulsion
Taking an ethyl acrylate monomer and a fluorine-containing acrylate monomer as oil phases, fully dissolving alkyl sulfonate in deionized water according to the mass ratio of 0.05:1, taking an alkyl sulfonate aqueous solution as a water phase, adding the oil phases and the water phases into a micro mixer according to the flow ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 0.5mm, the mixing time is 2min, the reaction temperature is room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
With the initiator benzoyl peroxide: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 100.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 20:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1.5mm, the reaction temperature is 90 ℃, and the reaction residence time is 100 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 5
Step 1 preparation of Pre-emulsion
Butyl acrylate monomer and fluorine-containing acrylate monomer are used as oil phase, alkyl sulfonate is fully dissolved in deionized water according to the mass ratio of 0.01:1, alkyl sulfonate water solution is used as water phase, the oil phase and the water phase are simultaneously fed into a micro mixer according to the flow ratio of 0.1:1, a T-shaped micro mixer is selected, the inner diameter is 0.75mm, the mixing time is 2min, the reaction temperature is room temperature, and under the conditions, the pre-emulsion is prepared.
Step 2, preparing an initiator aqueous solution
With initiator hydrogen peroxide derivative: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 15:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1.5mm, the reaction temperature is 90 ℃, and the reaction residence time is 150 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 6
Step 1 preparation of Pre-emulsion
Taking an isobutyl acrylate monomer and a fluorine-containing acrylate monomer as oil phases, fully dissolving sodium dodecyl sulfate in deionized water according to the mass ratio of 0.1:1, taking a sodium dodecyl sulfate aqueous solution as a water phase, adding the oil phases and the water phases into a micro mixer at the flow rate ratio of 1:1, selecting a T-shaped micro mixer, controlling the inner diameter to be 0.75mm, mixing the mixture for 2min, controlling the reaction temperature to be room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
With the initiator potassium persulfate: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 15:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1.5mm, the reaction temperature is 60 ℃, and the reaction residence time is 180 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 7
Step 1 preparation of Pre-emulsion
Taking isooctyl acrylate monomer and fluorine-containing acrylate monomer as oil phase, fully dissolving alkyl sulfonate in deionized water according to the mass ratio of 0.5:1, taking alkyl sulfonate aqueous solution as water phase, adding the oil phase and the water phase into a micro mixer according to the flow ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 0.75mm, the mixing time is 1.5min, the reaction temperature is room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
With initiator hydrogen peroxide derivative: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 15:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 1.5mm, the reaction temperature is 50 ℃, and the reaction residence time is 70 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
Example 8
Step 1 preparation of Pre-emulsion
Taking a hexyl acrylate monomer and a fluorine-containing acrylate monomer as oil phases, fully dissolving sodium dodecyl sulfate in deionized water according to the mass ratio of 0.5:1, taking a sodium dodecyl sulfate aqueous solution as a water phase, feeding the oil phases and the water phase into a micro mixer at the flow rate ratio of 1:1, selecting a T-shaped micro mixer, wherein the inner diameter is 1mm, the mixing time is 1min, the reaction temperature is room temperature, and preparing the pre-emulsion under the conditions.
Step 2, preparing an initiator aqueous solution
And an initiator VA-016: deionized water is prepared into an initiator aqueous solution according to the mass ratio of 1: 50.
Step 3 of preparing the fluorine-propylene polymer nano material
And (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor for reaction through a polytetrafluoroethylene tube at a flow rate ratio of 10:1 by using a constant flow pump. Wherein, the inner diameter of the micro-channel continuous flow reactor channel is 2mm, the reaction temperature is 90 ℃, and the reaction residence time is 30 min. And after the reaction is finished, discharging in a cold water bath to obtain the fluorine-propylene polymer nano material.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (7)
1. A method for preparing a fluorine-propylene polymer nano material by micro-channel continuous flow is characterized by comprising the following steps:
(1) preparing a pre-emulsion: mixing acrylic acid monomer and fluorine-containing monomer in any proportion to obtain an oil phase; dissolving an emulsifier in deionized water according to the mass ratio of 0.01-0.5:1 to obtain an emulsifier aqueous solution as a water phase; pumping the oil phase and the water phase into a micro mixer according to the flow rate ratio of 0.1-1:1 for emulsification to obtain pre-emulsion;
(2) preparing an initiator aqueous solution: mixing a water-soluble initiator and deionized water according to a mass ratio of 1:50-100, and stirring to obtain an initiator aqueous solution;
(3) preparing a fluorine-propylene polymer nano material: and (3) introducing the pre-emulsion prepared in the step (1) and the initiator aqueous solution prepared in the step (2) into a micro-channel continuous flow reactor according to the flow rate ratio of 10-20:1 for reaction, and discharging the reaction product at room temperature in a cold water bath to obtain the fluorine-propylene polymer nano material, wherein the fluorine-propylene polymer nano material is dispersed in water in the form of nano particles.
2. The microchannel continuous flow process of preparing fluoropropylene polymer nanomaterial of claim 1, wherein the acrylic monomer is acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, or isooctyl acrylate.
3. The microchannel continuous flow process for preparing fluoropropylene polymer nanomaterial according to claim 1, wherein the fluorine-containing monomer is tetrafluoroethylene or a fluorine-containing acrylate monomer.
4. The microchannel continuous flow method for preparing fluoropropylene polymer nanomaterial according to claim 1, wherein the micromixer used in step 1 has a T-shaped mixer with an inner diameter of 0.5-1mm, a mixing time of 1-2min and a room temperature.
5. The microchannel continuous flow process for preparing fluoropropylene polymer nanomaterial according to claim 1, wherein in step 1, the emulsifier is selected from sodium dodecyl sulfate, alkyl sulfonate and alkyl benzene sulfonate.
6. The microchannel continuous flow process for preparing fluoropropylene polymer nanomaterial according to claim 1, wherein in step 2, the water-soluble initiator is azobisisobutyronitrile, benzoyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide derivatives or VA-016.
7. The microchannel continuous flow process for preparing fluoropropylene polymer nanomaterial according to claim 1, wherein the microchannel continuous flow reactor in the step 3 has an inner diameter of 1-2mm, a reaction residence time of 30-180min and a reaction temperature of 50-90 ℃.
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