CN110158177B - Polymerization method based on electrostatic spinning technology - Google Patents

Polymerization method based on electrostatic spinning technology Download PDF

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CN110158177B
CN110158177B CN201910446865.3A CN201910446865A CN110158177B CN 110158177 B CN110158177 B CN 110158177B CN 201910446865 A CN201910446865 A CN 201910446865A CN 110158177 B CN110158177 B CN 110158177B
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electrostatic spinning
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CN110158177A (en
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陈凤贵
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Yangtze Normal University
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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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/42—Nitriles
    • C08F120/44—Acrylonitrile
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile

Abstract

The invention discloses a polymerization method based on an electrostatic spinning technology, which comprises the steps of adding a monomer and a solvent into a container, introducing inert gas to empty the solution and oxygen in the container, adding an initiator into the container, uniformly stirring to obtain a mixed solution, introducing the mixed solution into electrostatic spinning equipment, and carrying out electrostatic spinning polymerization under the condition that the voltage is 20-35 kv to prepare a polymer with a nanofiber structure. The electrostatic spinning method is adopted for carrying out monomer polymerization reaction for the first time, and material molding is simultaneously realized in the polymerization process, so that the operation is simple and easy, the preparation method of the polymer is enriched, a new concept of applying a molding technology in the polymerization process is developed, and the idea of the traditional polymer preparation method is overturned. Also realizes that the nano-fiber material can be spun without directly depending on high molecular polymer. The invention also greatly improves the preparation efficiency of the nanofiber polymer material, effectively reduces energy consumption and cost and has good application prospect.

Description

Polymerization method based on electrostatic spinning technology
Technical Field
The invention relates to the technical field of nanofiber preparation, in particular to a polymerization method based on an electrostatic spinning technology.
Background
With the development of polymer chemistry, polymer polymers have been widely used in the fields of paints, flocculants, films, civil engineering and construction, paper making, dyeing, cosmetics, pharmaceuticals, inks, pigments, electronics, etc., due to their molecular structural characteristics, and specific physical and chemical properties. At present, the synthesis methods of the polymer mainly comprise aqueous solution polymerization, inverse emulsion polymerization, photo-initiated polymerization, microwave initiated polymerization and the like. At present, no relevant report of monomer polymerization by adopting an electrostatic spinning process exists.
The nanofiber material has a small fiber diameter, and has a plurality of excellent physical and chemical properties such as high porosity, high specific surface area, high surface energy and the like, so that the nanofiber material is widely applied to the fields of filter materials, waterproof moisture-permeable materials, battery separators, biological tissue engineering and the like. The electrostatic spinning technology is one of the main methods for preparing the nano-fiber at present, the process is simple and convenient to operate, and various high polymers such as PET, PA, PU, PVA, PAN, PVDF and the like can be processed into nano-fiber materials by the electrostatic spinning technology.
At present, a polymer is usually prepared firstly to prepare a target nanofiber structure material, and then a polymer solution is adopted for spinning, for example, the invention patent CN200710190220.5 discloses a high molecular polymer, the polymer and a preparation method of nanofiber thereof, wherein a monomer A, a monomer B and a monomer C are subjected to polymerization reaction in the presence of an initiation system, the reaction temperature is 40-120 ℃, and the reaction time is 4-24 hours; after the reaction is finished, the target copolymer is obtained through precipitation, filtration and drying, and the solvent-resistant nanofiber can be prepared through electrostatic spinning and crosslinking treatment of the polymer. The invention patent CN201811367948.5 discloses a preparation method of a fluorescent nanofiber membrane based on acrylic latex, which adopts an emulsion polymerization method to polymerize acrylic monomers and obtains the fluorescent nanofiber membrane through an electrostatic spinning process. However, the above methods usually use heating, light irradiation, etc. to provide the energy required for polymerization during the polymerization process, and the polymer needs further processing to form the target morphology. The polymerization and the molding are carried out step by step, which causes the defects of high cost, low efficiency and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polymerization forming method based on an electrostatic spinning technology, which provides a new choice for monomer polymerization, saves the steps of polymerization and post-treatment, greatly improves the efficiency and saves the cost.
In order to solve the technical problems, the invention adopts the following technical scheme: a polymerization method based on electrostatic spinning technology comprises the following steps:
1) adding a monomer and a solvent into a container, introducing inert gas to empty the solution and oxygen in the container, adding an initiator into the container, and uniformly stirring to obtain a mixed solution;
2) introducing the mixed solution prepared in the step 1) into electrostatic spinning equipment, and carrying out electrostatic spinning polymerization under the condition that the voltage is 20-35 kv to prepare the nanofiber structure polymer.
Based on a free radical polymerization mechanism, the monomers are instantaneously polymerized under the action of an initiator and a high-voltage power supply, and are spun into a polymer with a nanofiber structure, which is shown as the following formula.
Figure BDA0002073916340000021
Under the action of high voltage, on one hand, energy required for polymerization is provided for monomer polymerization; on the other hand, the polymer obtained by polymerization is instantaneously molded. The voltage is too low, the polymer product can not reach the molecular weight of the polymer, and the nanofiber can not be spun or is not uniform; the voltage is too high, the needle head is easy to block, and the nano fiber cannot be formed.
Preferably, the solvent is dimethylformamide, dimethyl sulfoxide, dimethylacetamide and H2One or more of O.
Preferably, the monomer is one or more of acrylonitrile, methyl methacrylate, methyl acrylate, acrylamide, acrylic acid and styrene.
Preferably, the initiator is azobisisobutyronitrile, azobisisoheptonitrile or benzoyl peroxide.
Preferably, the mass concentration of the monomer in the mixed solution is 8-20%. The electrostatic spinning concentration adopted by the invention is relatively higher than that of the common polymer electrostatic spinning, if the concentration is too low, the polymerization is too slow, the molecular weight is not removed, the polymerization efficiency is influenced, and the formed nano fiber cannot be obtained.
Preferably, the molar ratio of the monomer to the initiator is 50-1000: 1
Preferably, the inert atmosphere is nitrogen or argon.
Preferably, the flow velocity of the spinning solution in the electrostatic spinning is 0.3-1.5 mL/h. Since the outflow speed affects the polymerization time and the effect of electrostatic spinning, the voltage and the flow speed affect the polymerization effect, and the monomer polymerization and molding can be synchronously realized only by using the flow speed in the range and matching with the high voltage (20-35 kv), the mutual matching adjustment of the flow speed and the voltage is also one of the difficulties of the invention. This is also the main reason why conventional electrospinning parameters cannot achieve monomer polymerization, nor does one use electrospinning techniques to accomplish monomer polymerization.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the electrostatic spinning method to carry out polymerization reaction on the monomers for the first time, realizes material molding in the polymerization process, has simple and easy operation, enriches the preparation method of the polymer, develops the new concept of applying the molding technology in the polymerization process and subverts the idea of the traditional polymer preparation method. The nano-fiber material can be spun without directly depending on high molecular polymers, and has good application prospect.
2. The nanofiber structure polymer prepared by the method is based on the electrostatic spinning technology, effectively organically integrates the polymerization method with the forming method, saves the time and the post-treatment process required by the polymerization process compared with the traditional method, greatly improves the preparation efficiency of the nanofiber polymer material, and can also reduce the energy consumption and the cost. The diameter of the prepared nanofiber structure polymer is about 200nm, the fiber structure is relatively uniform, and the actual requirements are met.
Drawings
FIG. 1 is a scanning electron microscope image of the nanofiber structure polymer prepared in examples 1 to 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
1) Adding 20mL of distilled and purified Dimethylformamide (DMF) and purified acrylonitrile into a glass container to prepare a solution with the mass concentration of acrylonitrile being 20%, then introducing nitrogen into the container to expel oxygen for 30min, then adding azobisisobutyronitrile into the reaction container to ensure that the molar ratio of the azobisisobutyronitrile to the acrylonitrile is 1:50, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: electrostatic field voltage is 20kV, the outflow speed of the spinning solution is 0.5mL/h, and the polymer with the nanofiber structure is prepared.
Example 2
1) Adding 20mL of distilled and purified dimethyl sulfoxide (DMSO) and purified acrylonitrile into a glass container to prepare a solution with the mass concentration of acrylonitrile being 10%, then introducing nitrogen into the container to expel oxygen for 30min, then adding azobisisobutyronitrile into the reaction container to ensure that the molar ratio of the azobisisobutyronitrile to the acrylonitrile is 1:100, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: electrostatic field voltage is 25kV, the outflow speed of the spinning solution is 0.8mL/h, and the polymer with the nanofiber structure is prepared.
Example 3
1) Adding 20mL of distilled and purified dimethylacetamide (DMAc) and purified acrylonitrile into a glass container to prepare a solution with the mass concentration of 15%, introducing nitrogen into the container to discharge oxygen for 30min, adding Azodiisoheptonitrile (AIVN) into the reaction container to ensure that the molar ratio of even two iso-heptonitrile to acrylonitrile is 1:200, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: the electrostatic field voltage is 30kV, the outflow speed of the spinning solution is 1.0mL/h, and the polymer with the nanofiber structure is prepared.
Example 4
1) Adding 20mL of distilled and purified dimethylacetamide (DMAc) and purified acrylamide into a glass container to prepare a solution with the mass concentration of acrylamide being 15%, then introducing nitrogen into the container for discharging oxygen for 30min, then introducing nitrogen into the reaction container for discharging oxygen for 30min, then adding Azodiisoheptonitrile (AIVN) into the reaction container to ensure that the molar ratio of even two iso-heptonitrile to acrylonitrile is 1:500, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: electrostatic field voltage is 25kV, the outflow speed of the spinning solution is 0.5mL/h, and the polymer with the nanofiber structure is prepared.
Example 5
1) The purified acrylonitrile was mixed with methyl methacrylate (monomer molar ratio 3: 1) slowly adding the mixture into a reaction container filled with 20mL of distilled and purified dimethylacetamide (DMAc) to prepare a solution with the mass concentration of a monomer being 20%, introducing nitrogen into the reaction container to expel oxygen for 30min, adding Benzoyl Peroxide (BPO) into the reaction container to ensure that the molar ratio of the benzoyl peroxide to acrylonitrile is 1:200, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: the electrostatic field voltage is 35kV, the outflow speed of the spinning solution is 1.5mL/h, and the polymer with the nanofiber structure is prepared.
Example 6
1) The purified acrylonitrile was mixed with methyl methacrylate (monomer molar ratio 3: 1) slowly adding the mixture into a reaction container filled with 20mL of distilled and purified dimethylacetamide (DMAc) to prepare a solution with the mass concentration of 15%, introducing nitrogen into the reaction container to expel oxygen for 30min, adding Benzoyl Peroxide (BPO) into the reaction container to ensure that the molar ratio of the benzoyl peroxide to acrylonitrile is 1:200, and uniformly stirring to obtain a mixed solution;
2) sucking the mixed solution prepared in the step 1) into a needle tube, and carrying out electrostatic spinning polymerization, wherein the adjusting process parameters are as follows: electrostatic field voltage is 25kV, the outflow speed of the spinning solution is 0.8mL/h, and the polymer with the nanofiber structure is prepared.
The nanofiber structure polymer prepared in the examples 1 to 6 is observed for morphology by a scanning electron microscope, as shown in fig. 1.
As can be seen from fig. 1, the nanostructured fiber having a diameter of about 200nm was successfully obtained directly by electrospinning, and the nanostructured fiber was relatively uniform.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. A polymerization method based on electrostatic spinning technology is characterized by comprising the following steps:
1) adding a monomer and a solvent into a container, introducing inert gas to empty the solution and oxygen in the container, adding an initiator into the container, and uniformly stirring to obtain a mixed solution;
2) introducing the mixed solution prepared in the step 1) into electrostatic spinning equipment, and carrying out electrostatic spinning polymerization under the condition that the voltage is 20-35 kv, wherein the outflow speed of the spinning solution in the electrostatic spinning is 0.3-1.5 mL/h; preparing to obtain a polymer with a nanofiber structure;
the solvent is dimethylformamide, dimethyl sulfoxide, dimethylacetamide and H2One or more of O; the monomer is one or more of acrylonitrile, methyl methacrylate, methyl acrylate, acrylamide, acrylic acid and styrene; the initiator is azobisisobutyronitrile, azobisisoheptonitrile or benzoyl peroxide.
2. The polymerization method based on the electrospinning technique according to claim 1, wherein the mass concentration of the monomer in the mixed solution is 8 to 20%.
3. The polymerization method based on the electrospinning technique according to claim 1, wherein the molar ratio of the monomer to the initiator is 50 to 1000: 1.
4. The polymerization process according to claim 1, characterized in that the inert atmosphere is nitrogen or argon.
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Citations (2)

* Cited by examiner, † Cited by third party
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CN1847473A (en) * 2006-04-26 2006-10-18 北京化工大学 Electric spinning-in-situ photopolymerization apparatus and process for preparing nanometer fiber
CN108823676A (en) * 2018-05-25 2018-11-16 上海城市水资源开发利用国家工程中心有限公司 A method of super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1847473A (en) * 2006-04-26 2006-10-18 北京化工大学 Electric spinning-in-situ photopolymerization apparatus and process for preparing nanometer fiber
CN108823676A (en) * 2018-05-25 2018-11-16 上海城市水资源开发利用国家工程中心有限公司 A method of super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique

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