CN113667053A - Methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material and preparation method thereof - Google Patents
Methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material and preparation method thereof Download PDFInfo
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- CN113667053A CN113667053A CN202111023042.3A CN202111023042A CN113667053A CN 113667053 A CN113667053 A CN 113667053A CN 202111023042 A CN202111023042 A CN 202111023042A CN 113667053 A CN113667053 A CN 113667053A
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 title claims abstract description 82
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title claims abstract description 37
- 239000011148 porous material Substances 0.000 title claims abstract description 32
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 18
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- -1 polyoxyethylene Polymers 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 3
- 238000007599 discharging Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 95
- 229910052742 iron Inorganic materials 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 84
- 239000000047 product Substances 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 35
- 239000004810 polytetrafluoroethylene Substances 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 21
- 239000010949 copper Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000004831 Hot glue Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000012703 microemulsion polymerization Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/58—Polymerisation initiated by direct application of electric current
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material, which comprises the following steps: (1) assembling a reaction device, and discharging oxygen from the reaction device; (2) adding sodium persulfate, sodium dodecyl sulfate, alkylphenol polyoxyethylene and water into a reaction device, and then mixing and stirring to prepare a mixed solution a; (3) adding MMA and BMA into the mixed solution a, and then mixing and stirring to prepare mixed solution b; (4) connecting a power supply to enable the mixed solution b to carry out electrochemical polymerization to obtain a primary product; (5) standing the primary product to prepare a standing product; (6) taking out the standing product, performing demulsification treatment, performing suction filtration and drying to obtain the product. Compared with the prior art, the invention has the following advantages: (1) the initiation temperature is low, and the heat energy is easy to evacuate; (2) the preparation is convenient, and the time control is accurate; (3) the controllability of the polymerization degree of the product can be enhanced.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material and a preparation method thereof.
Background
Emulsion polymerization generally employs an emulsifier to disperse monomers in water to form micelles, and polymerization is initiated by an initiator entering the micelles from the water. Emulsions are classified into forward emulsions (oil-in-water), bicontinuous emulsions, and inverse emulsions (water-in-oil) according to the ratio of the water phase. The appearance of the bicontinuous emulsion is similar to that of a sponge, and the two phases mutually permeate and are communicated with each other. The microemulsion polymerization is a single-chain molecular polymerization reaction or a low-chain-number molecular polymerization reaction of a transparent or semitransparent stable system with low viscosity and anisotropy and containing substances such as water, oil, surfactant and the like in a proper proportion. The microemulsion polymerization particles are small, the distribution is narrow, the stability is good, the interfacial tension is low, and the solubilization capacity is large. The electrochemical polymerization can control the molecular weight of the polymer through the current magnitude, the reaction temperature is low, the polymerization start and end can be controlled through switching the current, and the time precision is high. When the specific reaction system of the electrochemical polymerization is matched with a specific device, the material can be more conveniently added, and the molecular weight of the product is finely regulated and controlled for the second time.
In the process of initiating polymerization reaction by initiator, energy is usually provided by means of temperature rise, and the traditional method is a difficult process for controlling the reaction rate of polymer whether searching for high temperature resistant initiator or optimizing mechanical equipment to better dissipate heat energy. It is both labor intensive and difficult to ensure product quality. The conventional emulsion polymerization usually adopts persulfate as an initiator, the initiation temperature is generally above 50 ℃, and the temperature control is difficult. The polymerization temperature of methyl methacrylate, butyl methacrylate and other substances is usually 60 ℃ or above, and sudden polymerization is easily generated at 90 ℃, and the viscosity of the system is increased, and gel effect and even danger are generated due to overhigh temperature.
Chinese patent application document 'a methyl methacrylate polymer and a preparation method and application thereof (application number: 202011216723.7)' discloses a methyl methacrylate polymer and a preparation method and application thereof, wherein a polymerization temperature of 40-60 ℃ is adopted when polymethyl methacrylate is prepared in a first step experiment, and a methyl methacrylate polymer prepolymer containing a side group is obtained. Methyl methacrylate, glycidyl methacrylate or glycidyl acrylate and an initiator azobisisobutyronitrile are polymerized at the temperature of 40-60 ℃ and reacted for 0.5-1 h to obtain the methyl methacrylate prepolymer containing epoxy side groups. This is a traditional way of polymerization, after which it is necessary to improve the polymer properties by continuing the experiment with the introduction of other substances. This patent is incorporated herein by reference only to illustrate that the conventional MMA polymerization is relatively high in temperature and complicated in procedure, and not to improve the polymerization system or the specific experimental method for optimizing this patent.
Disclosure of Invention
Based on this, it is necessary to make the emulsion polymerization temperature of methyl methacrylate and butyl methacrylate higherHigh molecular weight, difficult control, doping or multi-step phenol copolymerization with other substances and the like, provides an electrochemical preparation method for a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate at normal temperature, and Fe introduced by the method2+Only existing in the water phase can not enter the latex bundle to influence the reaction and the polymer product, and the whole experiment only changes the current and the initial feeding amount, but can bring different molecular weights, thereby generating good technical effect.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
(1) assembling a reaction device, and discharging oxygen from the reaction device;
(2) adding sodium persulfate, sodium dodecyl sulfate, alkylphenol polyoxyethylene and water into a reaction device, and then mixing and stirring to prepare a mixed solution a;
(3) adding MMA and BMA into the mixed solution a prepared in the step (2), and then mixing and stirring to prepare mixed solution b;
(4) connecting a power supply to carry out electrochemical polymerization on the mixed solution b prepared in the step (3) to prepare a primary product;
(5) standing the primary product prepared in the step (4) to prepare a standing product;
(6) and (4) taking out the standing product prepared in the step (5), performing demulsification treatment, performing suction filtration, and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Further, the reaction device in the step (1) mainly comprises an iron sheet, a multi-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode.
Further, the neck flask comprises a three-neck flask or a four-neck flask.
Further, the adding amount of the sodium persulfate in the step (2) is 1.885-7.54 g.
Further, the mass ratio of the sodium dodecyl sulfate to the alkylphenol ethoxylates in the step (2) is 2: 1.
Further, the mass ratio of MMA to BMA described in the step (3) is 1: 1.
Further, the temperature for electrochemical polymerization in the step (4) is 25 ℃, and the polymerization time is 8-16 h.
Further, the time for standing the primary product in the step (5) is 1 h.
Further, the product in the step (6) is subjected to demulsification treatment by using methanol.
Compared with the prior art, the invention has the following advantages:
(1) the initiation temperature is low, and heat energy is easy to evacuate: the invention adopts an electrochemical method to initiate sodium persulfate to generate sulfate radicals, and compared with the conventional sodium persulfate, the energy for generating the radicals comes from more electric energy rather than heat energy, so that the required initiation temperature can be reduced, and meanwhile, the lower actual temperature can also better ensure the transfer and evacuation of the heat energy generated in the reaction process, and the generation of problems such as local overheating is reduced.
(2) The preparation is convenient, and the time control is accurate: the preparation method is simple, only a three-neck flask or a four-neck flask is needed, reactants and the used iron sheet electrodes are all located in the flask, the reaction start and stop can be controlled only by switching a power supply, the reaction rate is regulated and controlled by changing the current, and compared with the traditional method of heating and cooling by needing time, the method is more accurate in time control.
(3) In a certain current range, larger current brings larger product molecular weight, and polymers with different molecular weights can be obtained by regulating and controlling the current. Compared with the traditional emulsion polymerization of methyl methacrylate and butyl methacrylate, which is difficult to control the molecular weight distribution and molecular weight of the polymer, the method enhances the controllability of the polymerization degree of the product.
Drawings
The accompanying drawings, which form a part of the specification, are included to provide a further understanding of the application, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application.
FIG. 1 is a schematic view of a part of a reaction apparatus required for electrochemical emulsion polymerization of the present invention.
In the figure, 1, 2 and 3 are closed three-neck flask mouths, wherein: 1. 3 an iron sheet electrode can be accessed; 2, connecting double branch ports into double ports for introducing inert gas and adding liquid samples; 4 and 5 are working and counter electrodes of the iron sheet (or vice versa); 6 is raw material and product.
FIG. 2 is a schematic diagram of a key process of polymerization.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
It is suggested that mechanical paddles are used in the following examples.
Example 1
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is connected with one of the three-neck flasks when the flask is a three-neck flask, and is used as a gas path branch of inert protective gas in the reaction process, wherein the inert gas is nitrogen;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 3.77g of sodium persulfate and 5.34g of sodium dodecyl sulfate and dodecylphenol polyoxyethylene ether in total mass into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecylphenol polyoxyethylene ether is 2:1, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.1A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 2
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is used as a gas path branch of inert protective gas in the reaction process, wherein when the flask is a three-neck flask, a glass three-way pipe is arranged and connected with one of the three-neck flask;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 3.77g of sodium persulfate and 5.34g of sodium dodecyl sulfate and dodecylphenol polyoxyethylene ether in total mass into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecylphenol polyoxyethylene ether is 2:1, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.12A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 3
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
when the flask is a three-neck flask, two ports of the gas path branch are used as gas path branches of inert protective gas in the reaction process;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 3.77g of sodium persulfate and 5.34g of sodium dodecyl sulfate and dodecylphenol polyoxyethylene ether in total mass into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecylphenol polyoxyethylene ether is 2:1, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.14A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 4
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask also comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is used as a gas path branch of inert protective gas in the reaction process, wherein when the flask is a three-neck flask, a glass three-way pipe is arranged and connected with one of the three-neck flask;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 3.77g of sodium persulfate and 5.34g of sodium dodecyl sulfate and dodecylphenol polyoxyethylene ether in total mass into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecylphenol polyoxyethylene ether is 2:1, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.16A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 5
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is used as a gas path branch of inert protective gas in the reaction process, wherein when the flask is a three-neck flask, a glass three-way pipe is arranged and connected with one of the three-neck flask;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 1.885g of sodium persulfate, 2.67g of total mass of sodium dodecyl sulfate and dodecyl phenol polyoxyethylene ether into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecyl phenol polyoxyethylene ether is 2:1, adding 80mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: to the mixed solution a obtained in step S2, 80g of purified MMA 40g and 40g of BMA were added, and the mixture was mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.12A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing the nitrogen into the system) and reacts for 8 hours to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 6
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is used as a gas path branch of inert protective gas in the reaction process, wherein when the flask is a three-neck flask, a glass three-way pipe is arranged and connected with one of the three-neck flask;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 5.66g of sodium persulfate, 5.34g of sodium dodecyl sulfate and dodecyl phenol polyoxyethylene ether in the total mass ratio of 2:1 into a reaction device, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.12A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
Example 7
A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material comprises the following steps:
s1: assembling a reaction device (see figure 1), and introducing nitrogen to carry out oxygen discharge on the reaction device;
the reaction device comprises an iron sheet, a three-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode;
the iron sheet is cleaned by 1mol/L hydrochloric acid, an oxide layer is removed, the iron sheet is smooth and free of impurities and smaller than the diameter of a burning bottle opening, and two different burning bottle openings are led out through red copper wires respectively and are used as a working electrode and a counter electrode respectively;
the red copper wire is always positioned above the reaction liquid level, a small part of the red copper wire is exposed outside the PTFE stick, and the PTFE is polytetrafluoroethylene;
the PTFE stick is hollow and comprises a red copper wire, two ends of the red copper wire are coated by hot melt adhesive, and the red copper wire is wrapped in the red copper wire, extends out of the bottle openings of the working electrode and the counter electrode and is connected with a power supply and a switch;
the three-neck flask comprises stirring fan blades;
the stirring fan blades are connected with a PTFE rod containing a red copper wire, the fan blades are close to the liquid center, and the rotating speed is proper during working;
the external control device comprises a switch, a red copper wire and a plain red copper clamp, and the other end of the external control device is connected with the electrochemical workstation through the red copper wire;
the gas path branch is used as a gas path branch of inert protective gas in the reaction process, wherein when the flask is a three-neck flask, a glass three-way pipe is arranged and connected with one of the three-neck flask;
the temperature control device is a thermometer with a use range of 50 ℃ and a water bath device;
the thermometer extends into the opening where the working electrode wire is located and has a certain distance with the iron sheet;
the reference electrode extends into the counter electrode from the counter electrode bottle mouth and is at a distance from the counter electrode iron sheet.
S2: adding 7.54g of sodium persulfate, 5.34g of sodium dodecyl sulfate and dodecyl phenol polyoxyethylene ether in total mass into a reaction device, wherein the mass ratio of the sodium dodecyl sulfate to the dodecyl phenol polyoxyethylene ether is 2:1, adding 160mL of deoxygenated deionized water, and mixing and stirring at 25 ℃ for 30min to obtain a mixed solution a.
S3: 160g of purified 80g of MMA and 80g of BMA were added to the mixed solution a obtained in step S2, and they were mixed and stirred at 25 ℃ for 30 minutes to obtain a mixed solution b.
S4: and (5) connecting the iron sheet with the surface oxide removed, which is prepared in the step (S1), with an external control device through a flat-mouth red copper clamp, respectively extending into two far bottle mouths of the three-necked flask, and opening the electrochemical workstation.
S5: and (2) connecting a power supply, adjusting the current to 0.12A, wherein the current is constant current, except that the gas path branch can introduce and lead out gas, other inlets form a gas-tight state, so that the mixed liquid b prepared in the step S3 is subjected to electrochemical polymerization, and in the polymerization process (shown in figure 2), nitrogen is continuously introduced above the system (without introducing into the system) and reacts for 16h to obtain a primary product.
S6: stopping introducing nitrogen, cutting off the power supply, and standing the primary product for 1h to obtain a standing product.
S7: and (4) taking out the standing product prepared in the step (S6), adding methanol for demulsification treatment, performing suction filtration and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
The mass-average relative molecular weights of the products of examples 1, 2, 3 and 4 were determined
Number average relative molecular weight
And dispersion coefficient HI collated record as shown in table 1.
TABLE 1
As can be seen from Table 1: under the condition that other quantities are not changed, the larger the current is, the relative molecular weight of the product is correspondingly increased within the range of 0.10-0.16A. The experiment system is matched with the device to control the molecular weight of the product by changing the current amount without changing the temperature, the temperature rise and fall operation is not required to be performed within a time period, and the molecular weight of the product at 25 ℃ is regulated and controlled only by connecting an electrochemical workstation capable of accurately regulating and controlling the current. The experiment is operated in a constant current mode in the whole process, and the current can be changed within a set time by setting a program in the future to obtain materials with different shapes and functions.
The mass-average relative molecular weight M omega and the number-average relative molecular weight M of the products of examples 2 and 5 were measurednAnd dispersion coefficient HI collated record as shown in table 2. Wherein: a total ratio of 1 indicates the original charge ratio, i.e. a series of charge settings other than the current setting, 80gMMA and 80gBMA, as shown in example 1; an overall ratio of 0.5 refers to a series of feed settings other than the current setting, such as 40gMMA and 40gBMA feeds (other raw material amounts and reaction times are correspondingly reduced to 1/2). In examples 2 and 5, 0.12A was used as the current.
TABLE 2
As is clear from Table 2, when the total amount of charge and the reaction time were reduced to 1/2,
the error is 7 percent,
the error is 8%. In the range of the proper bearing capacity of the flask and the device, the feeding amount is changed in a multiple and integral manner, and the molecular weight of the product is not changed greatly. The device is matched with the experimental system, the product does not change greatly under the feeding ratio, and certain experimental stability is achieved.
The mass-average relative molecular weight M omega and number-average relative molecular weight M of the products of examples 2, 6 and 7 were comparednAnd dispersion coefficient HI collated record as shown in table 3. In examples 2, 6 and 7, the current used was 0.12A.
TABLE 3
As can be seen from Table 3: besides the regulation of the molecular weight of the product by using the current, the experimental device and the reaction system shown in the invention can also regulate the molecular weight of the product by changing the dosage of the initiator. In the future, the amount of the initiator can be changed to be used as a secondary regulation factor to more accurately regulate and control the molecular weight of the product.
The above description should not be taken as limiting the invention to the specific embodiments, but rather, as will be readily apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined in the claims appended hereto.
Claims (10)
1. A preparation method of a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material is characterized by comprising the following steps:
(1) assembling a reaction device, and discharging oxygen from the reaction device;
(2) adding sodium persulfate, sodium dodecyl sulfate, alkylphenol polyoxyethylene and water into a reaction device, and then mixing and stirring to prepare a mixed solution a;
(3) adding MMA and BMA into the mixed solution a prepared in the step (2), and then mixing and stirring to prepare mixed solution b;
(4) connecting a power supply to carry out electrochemical polymerization on the mixed solution b prepared in the step (3) to prepare a primary product;
(5) standing the primary product prepared in the step (4) to prepare a standing product;
(6) and (4) taking out the standing product prepared in the step (5), performing demulsification treatment, performing suction filtration, and drying to obtain the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material.
2. The method for preparing a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein the reaction device in step (1) mainly comprises an iron sheet, a multi-neck flask, a gas path branch, an external control device, a temperature control device and a reference electrode.
3. The method for preparing a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein said neck flask comprises a three-neck flask or a four-neck flask.
4. The method for preparing a methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material as claimed in claim 1, characterized in that the addition amount of sodium persulfate in the step (2) is 1.885-7.54 g.
5. The method for preparing a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein the mass ratio of the sodium dodecyl sulfate to the alkylphenol ethoxylates in the step (2) is 2: 1.
6. The method for preparing a bicontinuous emulsion copolymerized porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein the mass ratio of MMA to BMA in step (3) is 1: 1.
7. The preparation method of the methyl methacrylate and butyl methacrylate bicontinuous emulsion copolymerization porous material as claimed in claim 1, characterized in that the temperature for carrying out electrochemical polymerization in the step (4) is 25 ℃, and the polymerization time is 8-16 h.
8. The method for preparing a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein the time for the preliminary product standing treatment in the step (5) is 1 h.
9. The method for preparing a bicontinuous emulsion copolymerization porous material of methyl methacrylate and butyl methacrylate as claimed in claim 1, wherein the demulsification treatment is carried out on the product obtained in step (6) by using methanol.
10. A co-continuous emulsion porous material of methyl methacrylate and butyl methacrylate prepared by the method of any one of claims 1 to 9.
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