CN107663716B - Electrostatic spinning process of brominated butyl rubber - Google Patents
Electrostatic spinning process of brominated butyl rubber Download PDFInfo
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- CN107663716B CN107663716B CN201610608891.8A CN201610608891A CN107663716B CN 107663716 B CN107663716 B CN 107663716B CN 201610608891 A CN201610608891 A CN 201610608891A CN 107663716 B CN107663716 B CN 107663716B
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- butyl rubber
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- 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
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- 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
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- 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
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses an electrostatic spinning process of brominated butyl rubber, which comprises the following steps: step 1, adding brominated butyl rubber into an organic solvent, and stirring to obtain a brominated butyl rubber solution; step 2, adding a surfactant into the brominated butyl rubber solution obtained in the step 1, and stirring to obtain a spinning solution; step 3, carrying out electrostatic spinning to obtain a fiber film primary product; and 4, extracting the fiber film primary product, and then carrying out post-treatment to obtain the brominated butyl rubber fiber film. Wherein, in the process: firstly, the spinnability of the brominated butyl rubber is improved by adding the surfactant; secondly, before electrostatic spinning, a release agent and/or liquid paraffin and/or zinc stearate are sprayed on the receiving screen, so that the obtained fiber film has self-supporting property; thirdly, after electrostatic spinning, extraction and post-treatment are carried out, so that the appearance of the obtained fiber film is controllable. In addition, the method is simple in process and easy to implement.
Description
Technical Field
The invention relates to the field of electrostatic spinning, in particular to an electrostatic spinning process, and particularly relates to an electrostatic spinning process of brominated butyl rubber.
Background
Electrostatic spinning is a processing technology in which a polymer is subjected to stretching by applying a high-voltage power supply in a solution or molten state, is sprayed to form superfine fibers, and is received by a yarn receiving device to prepare the electrostatic spinning. The method is simple to operate, efficient, low in cost and wide in application, can be used for preparing films of nano-scale fibers or micron-scale fibers, and can be used for large-scale industrial production.
Brominated butyl rubber (BIIR) is widely used in protective products such as gas masks, gloves and the like because of its low permeability, biological non-toxicity and good comprehensive properties. However, solid brominated butyl rubber lacks breathability, causes thermal stress on the user's skin, and is not well suited for use in everyday life. The breathable brominated butyl rubber fiber film is prepared through electrostatic spinning, the porosity and the surface area of the breathable brominated butyl rubber fiber film can be artificially designed and regulated, the defects of solid brominated butyl rubber are overcome, and meanwhile the breathable brominated butyl rubber fiber film has better elasticity and elongation.
However, brominated butyl rubber has a high viscosity and a high rebound resilience, and therefore is difficult to spin, and it is difficult to perform electrospinning of brominated butyl rubber by the conventional process. At present, the research on the brominated butyl rubber electrostatic spinning process at home and abroad is few, no complete system is formed, and no good effect is obtained.
Disclosure of Invention
In order to solve the above problems, the present inventors have made intensive studies to design an electrospinning process of brominated butyl rubber, in which both raw materials and post-treatment are improved, the problem of difficulty in spinning of brominated butyl rubber is solved, and an electrospinning process of brominated butyl rubber is obtained, thereby completing the present invention.
The invention provides an electrostatic spinning process of brominated butyl rubber, which is embodied in the following aspects:
(1) an electrospinning process of brominated butyl rubber, wherein the process comprises the steps of:
step 1, adding brominated butyl rubber into a solvent, and stirring to obtain a brominated butyl rubber solution;
step 2, adding a surfactant into the brominated butyl rubber solution obtained in the step 1, and stirring to obtain a spinning solution;
step 3, performing electrostatic spinning by using the spinning solution obtained in the step 2 to obtain a fiber film primary product;
step 4, extracting the fiber film primary product, and then carrying out post-treatment to obtain a brominated butyl rubber fiber film;
(2) the process according to the above (1), wherein, in the step 1,
the Mooney viscosity of the brominated butyl rubber is 20-50 MU, preferably 30-40 MU, and more preferably 35 MU; and/or
Based on the total weight of the brominated butyl rubber and the solvent, the content of the brominated butyl rubber is 1-25%, preferably 5-20%, and more preferably 10-20%; and/or
The solvent is selected from organic solvents, preferably one or more selected from N-hexane, tetrahydrofuran, chloroform, carbon tetrachloride, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide, and more preferably one or more selected from N-hexane, tetrahydrofuran and chloroform;
(3) the process according to the above (1) or (2), wherein,
in step 2, the surfactant is selected from one or more of an anionic surfactant, a cationic surfactant and a zwitterionic surfactant, preferably from one or more of dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, cetyl pyridinium chloride and cetyl pyridinium bromide, and more preferably from dodecyl trimethyl ammonium bromide and/or sodium dodecyl benzene sulfonate; and/or
In the step 1 and the step 2, the content of the surfactant is 0.1-7%, preferably 0.5-5%, and more preferably 1-4% based on the weight of the brominated butyl rubber;
(4) the process according to one of the above (1) to (3), wherein in step 2, an anti-sticking auxiliary agent and/or a functional auxiliary agent may be further added, wherein the functional auxiliary agent preferably comprises one or more of an accelerator, a vulcanizing agent, a sterilization auxiliary agent, a cosmetic auxiliary agent, a magnetic auxiliary agent, a conductive auxiliary agent and a fluorescence auxiliary agent; the anti-sticking auxiliary agent and the functional auxiliary agent can be added separately or together;
(5) the process according to one of the above (1) to (4), wherein,
the anti-sticking auxiliary agent is selected from one or more of paraffin, zinc stearate, stearic acid soap, organic silicon anti-sticking agents, polyethylene wax, talcum powder, diatomite and calcium carbonate, preferably selected from one or more of paraffin, zinc stearate and polyethylene wax, and more preferably selected from zinc stearate; and/or
The promoter is selected from one or more of a promoter TT, a promoter M, a promoter D, a promoter H, a promoter ZDMC, a promoter ZBX, a promoter NA-22 and a promoter CZ, preferably selected from one or more of a promoter TT, a promoter M and a promoter D, and more preferably selected from a promoter TT; and/or
The vulcanizing agent is selected from one or more of sulfur, sulfur donor, peroxide, metal oxide, polyamine, p-quinone dioxime and bismaleimide, preferably selected from one or more of sulfur, tetramethyl thiuram disulfide, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, magnesium oxide, aluminum oxide, lead oxide, zinc oxide, hexamethylene diamine, triethylene tetramine, dicyclohexyl diamine, p-quinone dioxime and bismaleimide, and more preferably selected from sulfur and/or zinc oxide; and/or
The sterilization auxiliary agent is selected from one or more of nano silver, nano copper, nano zinc, triclosan and fluoxafloxacin; and/or
The beauty auxiliary agent comprises a beauty skin care product, an age pigment medicament, an acne medicament and the like; and/or
The magnetic auxiliary agent is selected from one or more of nano ferrite, alnico and rare earth permanent magnet materials (such as neodymium iron boron), and is preferably a nano ferromagnet; and/or
The conductive auxiliary agent is selected from one or more of carbon black, graphene, nano silver, nano copper and carbon nano tubes; and/or
The fluorescence auxiliary agent is a carbon quantum dot;
(6) the process according to one of the above (1) to (5), wherein,
when the anti-sticking auxiliary agent is added alone, the content of the anti-sticking auxiliary agent is 0.1-20%, preferably 0.5-10%, more preferably 5-10%, based on the weight of the brominated butyl rubber; and/or
When the functional additive is added separately, the content of the functional additive is 0.5-30%, preferably 1-20%, more preferably 5-10%, based on the weight of the brominated butyl rubber; and/or
When an anti-sticking auxiliary agent and a functional auxiliary agent are added together, the total content of the anti-sticking auxiliary agent and the functional auxiliary agent is 1-30%, preferably 2-25%, more preferably 5-15%, based on the weight of the brominated butyl rubber;
(7) the process according to one of the above (1) to (6), wherein,
before step 3, spraying one or more of a release agent, liquid paraffin and zinc stearate on the receiving screen, preferably spraying the release agent; and/or
In step 3: the negative voltage of the spinning voltage is-1 to 2.5 kV; the positive voltage of the spinning voltage is 5-20 kV, preferably 8-18 kV; the distance between the spinning nozzle and the receiving screen is 5-40 cm, preferably 10-30 cm, and more preferably 20 cm;
(8) the process according to one of the above (1) to (7), wherein, in step 4,
extracting with one or more of methanol, ethanol and dichloromethane, preferably with methanol and/or ethanol, more preferably with ethanol; and/or
The extraction time is 1-15 h, preferably 1-10 h, and more preferably 5-10 h; and/or
The post-treatment is low-temperature treatment or high-temperature treatment, preferably low-temperature treatment; wherein the low temperature is below 10 ℃, and the high temperature is above 40 ℃; and/or
Optionally, the post-treatment also includes ultraviolet irradiation or radiation, such as alpha rays, beta rays, gamma rays, and the like;
(9) the process according to one of the above (1) to (8), wherein,
the low-temperature treatment is freeze-drying and air-cooling drying, preferably freeze-drying; and/or
The high-temperature treatment is heating, vacuum drying or drying by a blast oven; and/or
The time of the low-temperature treatment is 1-50 h, preferably 1-30 h, and more preferably 5-20 h; and/or
The time of the high-temperature treatment is 1-20 min, preferably 1-15 min, and more preferably 1-10 min.
In a second aspect, the invention provides a brominated butyl rubber fiber film, preferably obtained by electrospinning according to the process of the first aspect.
Drawings
FIG. 1 shows a scanning electron micrograph of a fibrous film made from example 4;
FIG. 2 shows a scanning electron micrograph of a film prepared from comparative example 1;
fig. 3 shows a scanning electron micrograph of the fiber film obtained in comparative example 3.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
According to a first aspect of the present invention there is provided a process for electrospinning of brominated butyl rubber, wherein the process comprises the steps of:
step 1, adding brominated butyl rubber into a solvent, and stirring to obtain a brominated butyl rubber solution.
According to a preferred embodiment of the present invention, in the step 1, the Mooney viscosity of the brominated butyl rubber is 20 to 50 MU.
In a further preferred embodiment, in step 1, the Mooney viscosity of the brominated butyl rubber is from 30 to 40 MU.
In a still further preferred embodiment, in step 1, the mooney viscosity of the brominated butyl rubber is 35 MU.
The brominated butyl rubber does not need to be degraded or plasticated to break molecular chains before electrostatic spinning, and can be directly matched with a solvent to obtain a solution for electrostatic spinning. In the present invention, the unit of the Mooney viscosity is MU, but M may be used.
According to a preferred embodiment of the present invention, in step 1, the total bromine content of the brominated butyl rubber is 5 to 40%.
In a further preferred embodiment, in step 1, the total bromine content of the brominated butyl rubber is 15 to 30%.
In a still further preferred embodiment, in step 1, the total bromine content of the brominated butyl rubber is (19 ± 0.2)%.
According to a preferred embodiment of the present invention, in step 1, the brominated butyl rubber is present in an amount of 1 to 25% by weight, based on the total weight of the brominated butyl rubber and the solvent.
In a further preferred embodiment, in step 1, the brominated butyl rubber is contained in an amount of 5 to 20% by weight, based on the total weight of the brominated butyl rubber and the solvent.
In a further preferred embodiment, in step 1, the brominated butyl rubber is present in an amount of 10 to 20% by weight, based on the total weight of the brominated butyl rubber and the solvent.
The brominated butyl rubber is used in an amount as described above, and when the brominated butyl rubber is contained in the solution in an amount (mass fraction) of 1 to 25%, the spinning is continuously and stably performed during electrospinning, and when the brominated butyl rubber is contained in an amount (mass fraction) of less than 1%, the concentration is too low, the electrospinning continuity is poor, and when the brominated butyl rubber is contained in an amount (mass fraction) of more than 25%, the concentration is too high, the viscosity is too high, and the spinning is not easy, and therefore, the brominated butyl rubber content (mass fraction) needs to be strictly controlled for the electrospinning of brominated butyl rubber.
According to a preferred embodiment of the present invention, in step 1, the solvent is selected from organic solvents.
In a further preferred embodiment, in step 1, the solvent is selected from one or more of N-hexane, tetrahydrofuran, chloroform, carbon tetrachloride, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
In a still further preferred embodiment, in step 1, the solvent is selected from one or more of n-hexane, tetrahydrofuran and chloroform.
The choice of the solvent is not critical, as long as it can dissolve the brominated butyl rubber and can be used for electrostatic spinning, and the boiling point of the solvent is not too low, and is not lower than 40 ℃.
And 2, adding a surfactant into the brominated butyl rubber solution obtained in the step 1, and stirring to obtain a spinning solution.
In a preferred embodiment of the present invention, in step 2, the surfactant is selected from one or more of an anionic surfactant, a cationic surfactant and a zwitterionic surfactant.
In a further preferred embodiment, in step 2, the surfactant is selected from one or more of dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, cetylpyridinium chloride and cetylpyridinium bromide.
In a still further preferred embodiment, in step 2, the surfactant is selected from dodecyltrimethylammonium bromide and/or sodium dodecylbenzenesulfonate.
The surface active agent is added to improve the electrostatic spinning performance of the brominated butyl rubber, the brominated butyl rubber has a small dielectric constant and is not easy to be polarized and charged, and after the surface active agent is added, the brominated butyl rubber can generate charges under voltage, so that electrostatic spinning can be performed. After the surfactant is added, continuous fibers are ejected from a nozzle during electrostatic spinning of the brominated butyl rubber system, and the fibers fall on a receiving screen to finally form a fiber film; if the surfactant is not added, the droplets are ejected from the nozzle instead of continuous fibers, and the droplets can fall on the receiving screen from the nozzle under a stronger electric field, but the finally formed thin film on the receiving screen is not a fiber film, the appearance is obviously different from that of the fiber film, and meanwhile, the mechanical property is far inferior to that of the fiber film formed after the surfactant is added.
According to a preferred embodiment of the present invention, in step 1 and step 2, the surfactant is contained in an amount of 0.1 to 7% based on the weight of the brominated butyl rubber.
In a further preferred embodiment, in step 1 and step 2, the surfactant is present in an amount of 0.5 to 5% based on the weight of the brominated butyl rubber.
In a still further preferred embodiment, in step 1 and step 2, the surfactant is present in an amount of 1 to 4% based on the weight of the bromobutyl rubber.
The amount of the surfactant is not too small, and if the amount is less than 0.1%, the electrostatic spinning performance of the brominated butyl rubber is slightly improved, even the electrostatic spinning performance cannot be improved, and meanwhile, the amount is not too large, as long as the best improvement effect can be achieved, but more surfactant is added, the better the additive is, and the amount is too large, so that unnecessary waste is caused, and the appearance of the final fiber film can be influenced.
In the present invention, brominated butyl rubber does not require degradation or mastication at the early stage, but the amount of surfactant is small, and the process is directed to electrospinning of brominated butyl rubber. In the prior art, relevant technicians have studied electrostatic spinning on butyl rubber, but before the butyl rubber is used, the butyl rubber needs to be degraded for 30 times to obtain butyl rubber with short molecular chains and then electrostatic spinning is carried out, and the concentration of the used butyl rubber is too small, but the concentration of cetyl trimethyl ammonium bromide is too large, which is different from the view point of the invention; the main reason for this analysis is that the two subjects are different, and the subject of the present invention is brominated butyl rubber rather than butyl rubber, which is more polar than butyl rubber.
According to a preferred embodiment of the present invention, in step 2, an anti-sticking aid and/or a functional aid may also be added, i.e., both the anti-sticking aid and the functional aid may be added separately or together.
In a further preferred embodiment, the functional additives include accelerators, vulcanizing agents, sterilization additives, cosmetic additives, magnetic additives, conductive additives and fluorescent additives.
According to a preferred embodiment of the present invention, the anti-sticking auxiliary agent is selected from one or more of paraffin wax, zinc stearate, soap stearate, silicone type anti-sticking agent, polyethylene wax, talc, diatomaceous earth and calcium carbonate.
In a further preferred embodiment, the anti-sticking aid is selected from one or more of paraffin wax, zinc stearate, soap of stearic acid and polyethylene wax.
In a still further preferred embodiment, the release aid is zinc stearate.
The brominated butyl rubber solution has high viscosity, so the brominated butyl rubber solution has high viscosity and is easy to stick together, thereby not only being unfavorable for spinning, but also the fiber obtained after spinning is easy to agglomerate, the appearance is not easy to control, and the brominated butyl rubber solution can not be self-supported. Thus, in the present invention, an anti-sticking agent is added, wherein the purpose of the anti-sticking aid is to reduce the viscosity of the brominated butyl rubber solution: one can improve the spinnability of the brominated butyl rubber; secondly, the brominated butyl rubber can be prevented from being bonded with fibers during electrostatic spinning; and thirdly, the stripping property of the brominated butyl rubber fiber film is improved, so that the brominated butyl rubber fiber film is easy to strip off the receiving screen without tearing, and self-supporting is realized.
The self-supporting film is a film which is easy to peel off from the receiving screen without tearing after electrostatic spinning is finished.
According to a preferred embodiment of the present invention, when the anti-blocking aid is added alone, the anti-blocking aid is contained in an amount of 0.1 to 20% based on the weight of the brominated butyl rubber.
In a further preferred embodiment, when the anti-blocking aid is added alone, the anti-blocking aid is present in an amount of 0.5 to 10% based on the weight of the brominated butyl rubber.
In a further preferred embodiment, when the anti-blocking aid is added alone, the anti-blocking aid is present in an amount of 5 to 10% based on the weight of the brominated butyl rubber.
When the dosage of the anti-sticking auxiliary agent is less than 0.1%, the dosage is too low, and the anti-sticking effect is slight; when the dosage of the anti-sticking auxiliary agent is more than 20 percent, the dosage is too high, so that the elasticity of the brominated butyl rubber is greatly reduced, the vibration reduction performance of the obtained fiber film is reduced, and even the electrostatic spinning performance of the brominated butyl rubber is possibly influenced seriously, and the spinnability of the brominated butyl rubber is reduced.
According to a preferred embodiment of the invention, the promoter comprises one or more of promoter TT, promoter M, promoter D, promoter H, promoter ZDMC, promoter ZBX, promoter NA-22 and promoter CZ.
In a further preferred embodiment, the accelerator is selected from one or more of accelerator TT, accelerator M and accelerator D.
In a still further preferred embodiment, the accelerator is selected from accelerator TT.
Wherein the accelerant TT is tetramethyl thiuram disulfide; the accelerant M is 2-mercaptol benzothiazole; the accelerator D is also called N, N' -diphenylguanidine, and the molecular formula is C13H13N3(ii) a The accelerant H is hexamethylenetetramine; the accelerator ZDMC is zinc dimethyldithiocarbamate; the molecular formula of the accelerant ZBX is C10H18O2S4Zn; the accelerant NA-22 is ethylene thiourea, and the molecular formula is C3H6N2S; the accelerant CZ is N-cyclohexyl-2-benzothiazole sulfonamide.
Wherein the accelerator is used for accelerating the vulcanization of the brominated butyl rubber.
According to a preferred embodiment of the present invention, the vulcanizing agent is selected from one or more of sulfur, sulfur donors, peroxides, metal oxides, polyamines, p-quinonedioxime and bismaleimide.
In a further preferred embodiment, the vulcanizing agent is selected from one or more of sulfur, tetramethylthiuram disulfide, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, magnesium oxide, aluminum oxide, lead oxide, zinc oxide, hexamethylenediamine, triethylenetetramine, dicyclohexylenediamine, p-quinonedioxime, and bismaleimide.
In a still further preferred embodiment, the vulcanizing agent is selected from sulphur and/or zinc oxide.
The vulcanizing agent functions to vulcanize the brominated butyl rubber.
According to a preferred embodiment of the present invention, the sterilization assistant is selected from one or more of nano silver, nano copper, nano zinc and fluoxafloxacin.
In a further preferred embodiment, the bactericidal additive is nano silver.
The nano silver, the nano copper, the nano zinc and the oxyfluorfen have the functions of sterilization, bacteriostasis and antibiosis, and the film obtained by electrostatic spinning after the sterilization auxiliary agent is added into the raw materials can be used for band-aid, dressing and the like.
According to a preferred embodiment of the present invention, the cosmetic auxiliary may be a cosmetic skin care product, an age spot agent, an acne agent, or the like.
The fiber film obtained by electrostatic spinning after adding the beauty auxiliary agent into the brominated butyl rubber system can be used for facial masks.
According to a preferred embodiment of the present invention, the magnetic auxiliary is selected from one or more of nano ferrite, alnico and rare earth permanent magnetic materials.
In a further preferred embodiment, the magnetic adjuvant is a nano ferrite.
The magnetic auxiliary has magnetism, and a film obtained by electrostatic spinning after the magnetic auxiliary is added into the raw materials can be used for filtering sewage.
According to a preferred embodiment of the present invention, the conductive auxiliary agent is selected from one or more of carbon black, graphene, carbon nanotubes, nano silver and nano copper.
The conductive auxiliary agent can endow the brominated butyl rubber with conductive antibacterial property, when the conductive auxiliary agent is added into the raw materials, a film obtained through electrostatic spinning has conductive property, and when the film is used for a band-aid, a dressing and the like, the conductive auxiliary agent and the like can enable the band-aid, the dressing and the like to conduct weak current on the surface of skin, and wound healing can be accelerated.
According to a preferred embodiment of the present invention, the fluorescence assistant is a carbon quantum dot.
Wherein, the fluorescent auxiliary agent is added in the raw materials to endow the film obtained by electrostatic spinning with certain fluorescent property.
According to a preferred embodiment of the present invention, when the functional aid is added alone, the content of the functional aid is 0.5 to 30% based on the weight of the brominated butyl rubber.
In a further preferred embodiment, when the functional aid is added alone, the content of the functional aid is 1 to 20% based on the weight of the brominated butyl rubber.
In a further preferred embodiment, when the functional aid is added alone, the content of the functional aid is 5 to 10% based on the weight of the brominated butyl rubber.
Wherein, the addition amount of the functional additive cannot be too small, and too small can not play a corresponding functional role, and too much can influence the performance of the brominated butyl rubber.
In a preferred embodiment of the invention, when the anti-blocking auxiliary and the functional auxiliary are added together, the total content of the anti-blocking auxiliary and the functional auxiliary is 1 to 30%, based on the weight of the brominated butyl rubber.
In a further preferred embodiment, when the antiblocking aid is added together with the functional aid, the total content of antiblocking aid and functional aid is from 2 to 25%, based on the weight of brominated butyl rubber.
In a further preferred embodiment, when the anti-blocking aid is added together with the functional aid, the total content of the anti-blocking aid and the functional aid is 5 to 15%, based on the weight of the brominated butyl rubber.
The anti-sticking auxiliary agent and the functional auxiliary agent are added into the brominated butyl rubber system as additives, and if the addition amount of the anti-sticking auxiliary agent and the functional auxiliary agent is too large, the viscosity of the brominated butyl rubber system can be greatly reduced, the spinning is influenced, and even the performances of the brominated butyl rubber as rubber, such as damping performance, low permeability, ageing resistance and the like, are influenced.
And 3, performing electrostatic spinning by using the spinning solution obtained in the step 2 to obtain a fiber film primary product.
According to a preferred embodiment of the present invention, one or more of a release agent, liquid paraffin and zinc stearate is sprayed on the receiving screen before step 3.
In a further preferred embodiment, before step 3, a release agent is sprayed on the receiving screen.
Wherein the spraying of a release agent, liquid paraffin or zinc stearate on the receiving screen further promotes the peeling of the fibrous film from the receiving screen, rather than sticking to the receiving screen and not being self-supporting. Therefore, spraying a release agent, liquid paraffin, or zinc stearate on the receiving screen is advantageous for improving the self-supporting property of the resulting fiber film. Wherein, the zinc stearate exists in a solution state, and the concentration thereof is not limited.
In a preferred embodiment of the present invention, in step 3, the negative voltage of the spinning voltage is-1 to 2.5kV and the positive voltage of the spinning voltage is 5 to 20kV when electrostatic spinning is performed.
In a further preferred embodiment, in step 3, the negative voltage of the spinning voltage is-1 to-2.5 kV and the positive voltage of the spinning voltage is 8 to 18kV when the electrostatic spinning is performed.
According to a preferred embodiment of the invention, when electrostatic spinning is carried out, the distance between the spinning nozzle and the receiving screen is 5-40 cm.
In a further preferred embodiment, when carrying out electrostatic spinning, the distance between the spinning nozzle and the receiving screen is 10-30 cm.
In a further preferred embodiment, the spinning nozzle is spaced 20cm from the receiving screen when electrospinning is carried out.
And 4, extracting the fiber film primary product, and then carrying out post-treatment to obtain the brominated butyl rubber fiber film.
According to a preferred embodiment of the present invention, in step 4, one or more of methanol, ethanol and dichloromethane are used for extraction.
In a further preferred embodiment, in step 4, extraction is carried out with methanol and/or ethanol.
In a still further preferred embodiment, in step 4, extraction is performed with ethanol.
Wherein the purpose of extraction is to remove the high boiling point solvent from the fiber film precursor, so that the fiber film precursor can be self-supporting rather than sticky-like. Solvent for extraction: one is miscible with the solvent in step 1, and the second has a lower boiling point and can be easily removed after a post-treatment.
According to a preferred embodiment of the present invention, in step 4, the extraction time is 1-15 h.
In a further preferred embodiment, in the step 4, the extraction time is 1-10 h.
In a further preferred embodiment, in the step 4, the extraction time is 5-10 h.
In the invention, the extraction can be directly soaking the fiber film primary product in the extracting agent.
According to a preferred embodiment of the invention, in step 4, the post-treatment is a low-temperature treatment or a high-temperature treatment.
In a further preferred embodiment, in step 4, the post-treatment is a low-temperature treatment.
Wherein the low temperature is below 10 ℃, and the high temperature is above 40 ℃. The purpose of the work-up is to remove the extractant when the extraction is carried out.
According to a preferred embodiment of the present invention, the low-temperature treatment is freeze-drying and air-cooling.
In a further preferred embodiment, the low temperature treatment is lyophilization.
Wherein, the freeze-drying is carried out at a low temperature under vacuum, and the extractant is removed by utilizing the vacuum; the air-cooler is used for blowing the sample by cold air, so that the volatilization of the extracting agent is accelerated, and the aim of removing the extracting agent is fulfilled.
According to a preferred embodiment of the present invention, the time for the low temperature treatment is 1 to 50 hours.
In a further preferred embodiment, the time for the low-temperature treatment is 1 to 30 hours.
In a further preferred embodiment, the time for the low-temperature treatment is 5 to 20 hours.
The low-temperature treatment is carried out at a low temperature, so that the performance of the product is not affected, and the post-treatment time can be properly prolonged to even reach 40h in order to ensure the post-treatment efficiency.
According to a preferred embodiment of the invention, the high temperature treatment is heating, vacuum drying or forced air oven drying.
In a further preferred embodiment, the time of the high temperature treatment is 1 to 20min, preferably 1 to 15min, and more preferably 1 to 10 min.
Among them, the time for the high temperature treatment is not too long, because the too long time may affect the properties of the bromobutyl rubber itself.
In the invention, the effect of low-temperature treatment is obviously better than that of high-temperature treatment in the post-treatment, because the fiber film with controllable appearance can be obtained in the low-temperature treatment, the rebound resilience of the brominated butyl rubber is reduced, and the finally obtained fiber film has good appearance. For this reason, the inventors have not clarified, but a large number of experimental results show that the low-temperature treatment, especially the freeze-drying, can significantly improve the morphology of the fiber film.
According to a preferred embodiment of the invention, in step 4, optionally, the post-treatment further comprises ultraviolet irradiation or radiation.
In a further preferred embodiment, the radiation comprises alpha radiation, beta radiation, gamma radiation, and the like.
Wherein the ultraviolet irradiation or the radiation is performed for the purpose of promoting the vulcanization crosslinking of the brominated butyl rubber.
In a second aspect, the invention provides a brominated butyl rubber fiber film.
According to a preferred embodiment of the present invention, the brominated butyl rubber fiber film is obtained by electrospinning according to the electrospinning process described in the first aspect.
The brominated butyl rubber fiber film is smooth in appearance and controllable in appearance.
According to a preferred embodiment of the present invention, the brominated butyl rubber fiber film is a porous structure, thereby imparting water absorption and filtration functions to the film.
In the present invention, the functional assistant refers to an assistant capable of imparting certain functions to the final product, including electrical conductivity, magnetism, fluorescence, bactericidal properties, and the like.
The invention has the following beneficial effects:
(1) the process provided by the invention is simple and easy to realize;
(2) the spinnability of the brominated butyl rubber can be realized by utilizing the process provided by the invention;
(3) the brominated butyl rubber fiber film with controllable morphology can be obtained by utilizing the process provided by the invention;
(4) the brominated butyl rubber fiber film obtained by electrostatic spinning by the process is of a porous structure and has water absorption and filtration functions.
Examples
The invention is further described below by means of specific examples. However, these examples are only illustrative and do not limit the scope of the present invention. In the examples: the brominated butyl rubber is purchased from Zhejiang Xinhui New materials GmbH; the release agent is available from Qiyuan fine chemical engineering, Inc.
EXAMPLE 1 preparation of brominated butyl rubber fiber film
Weighing 4.45g of brominated butyl rubber into a round-bottom flask, adding 50mL of tetrahydrofuran, and stirring to obtain a brominated butyl rubber solution;
then adding 4.45mg of dodecyl trimethyl ammonium bromide, and stirring for 3 hours at the temperature of 50 ℃ in water bath and at the speed of 400r/min to obtain spinning solution;
spraying liquid paraffin on a receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 20kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into methanol for extraction for 15h, and then freeze-drying for 40h to obtain the brominated butyl rubber fiber film.
EXAMPLE 2 preparation of brominated butyl rubber fiber film
Weighing 5.2g of brominated butyl rubber in a round-bottom flask, adding 50mL of normal hexane, and stirring to obtain a brominated butyl rubber solution;
respectively adding 0.026g of octadecyl trimethyl ammonium bromide, 0.026g of paraffin, 0.1g of accelerant TT and 0.1g of sulfur, and stirring for 3h at the temperature of 50 ℃ in water bath and at the speed of 400r/min to obtain spinning solution;
spraying a release agent on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 18kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into methanol for extraction for 10h, and then freeze-drying for 30h to obtain the brominated butyl rubber fiber film.
EXAMPLE 3 preparation of brominated butyl rubber fiber film
Weighing 11g of brominated butyl rubber in a round-bottom flask, adding 50mL of dimethyl sulfoxide, and stirring to obtain a brominated butyl rubber solution;
respectively adding 0.11g of chlorohexadecyl pyridine, 0.11g of stearic acid soap and 0.55g of nano silver, and stirring for 3 hours at the temperature of 50 ℃ in water bath and at the speed of 400r/min to obtain spinning solution;
spraying a release agent on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 15kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into ethanol for extraction for 5h, and then freeze-drying for 20h to obtain the brominated butyl rubber fiber film.
EXAMPLE 4 preparation of brominated butyl rubber fiber film
Weighing 6.2g of brominated butyl rubber in a round-bottom flask, adding 50mL of tetrahydrofuran, and stirring to obtain a brominated butyl rubber solution;
then respectively adding 0.2g of sodium dodecyl benzene sulfonate and 0.31g of polyethylene wax, and stirring for 3 hours at the temperature of 50 ℃ in a water bath and at the speed of 400r/min to obtain spinning solution;
spraying a release agent on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 15kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into ethanol for extraction for 10h, and then freeze-drying for 5h to obtain the brominated butyl rubber fiber film.
EXAMPLE 5 preparation of brominated butyl rubber fiber film
Weighing 6.2g of brominated butyl rubber in a round-bottom flask, adding 50mL of tetrahydrofuran, and stirring to obtain a brominated butyl rubber solution;
respectively adding 0.67g of sodium dodecyl benzene sulfonate and 0.5g of zinc stearate, and stirring for 3 hours at the temperature of 50 ℃ in a water bath and at the speed of 400r/min to obtain spinning solution;
spraying a release agent on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 12kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into ethanol for extraction for 10h, and then blowing by using an air cooler for 40h to obtain the brominated butyl rubber fiber film.
EXAMPLE 6 preparation of brominated butyl rubber fiber film
Weighing 13.34g of brominated butyl rubber in a round-bottom flask, adding 50mL of tetrahydrofuran, and stirring to obtain a brominated butyl rubber solution;
respectively adding 0.5g of cetylpyridinium bromide, 1.334g of talcum powder, 0.67g of carbon quantum dots and 1.33g of nano ferrite, and stirring for 3 hours at the temperature of 50 ℃ in a water bath and at the speed of 400r/min to obtain spinning solution;
spraying a release agent on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 8kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into methanol for extraction for 15h, and then heating at 80 ℃ for 1min to obtain the brominated butyl rubber fiber film.
EXAMPLE 7 preparation of brominated butyl rubber fiber film
Weighing 8.65g of brominated butyl rubber in a round-bottom flask, adding 50mL of tetrahydrofuran, and stirring to obtain a brominated butyl rubber solution;
then respectively adding 1g of dodecyl trimethyl ammonium bromide, 1.1g of paraffin and 1.1g of carbon nano tube, and stirring for 3 hours at the temperature of 50 ℃ in water bath and at the speed of 400r/min to obtain spinning solution;
spraying zinc stearate on the receiving screen, and carrying out electrostatic spinning to obtain a fiber film primary product; wherein the spinning conditions are as follows: adjusting the distance between a spinning nozzle and a receiving screen to be 20cm, adjusting the voltage to be 18kV until liquid drops form a cone shape, then spraying out from a nozzle, and obtaining a fiber film primary product on the receiving screen;
and (3) immersing the fiber film primary product into methanol for extraction for 15h, and then drying in a forced air oven at 50 ℃ for 15min to obtain the brominated butyl rubber fiber film.
Comparative example
Comparative example 1 preparation of brominated butyl rubber fiber film
The preparation process of example 4 was repeated except that no surfactant was added, and as a result, it was found that, in electrospinning, not continuous fibers but discontinuous droplets were ejected from a nozzle, and the discontinuous droplets reached a receiving screen under a high electric field to form a film, which was formed only after the solvent in the solution was volatilized under the high electric field, but not a fiber thin film. That is, brominated butyl rubber has no spinnability and does not form fibers without the addition of a surfactant.
Comparative example 2 preparation of brominated butyl rubber fiber film
The preparation process of example 4 is repeated except that polyethylene wax is not added in step 2 and no release agent is sprayed on the receiving screen in step 3, and as a result, it is found that electrostatic spinning is achieved, but after electrostatic spinning is completed, the electrostatic spinning is not easily peeled off from the receiving screen and can be peeled off under the action of external force, so that the film is easily torn under the action of external force and a complete film cannot be obtained, and meanwhile, the mechanical property of the film is affected due to tearing of the film during peeling, and meanwhile, internal stress may exist in the material and also affects the performance of the material, and a self-supporting fiber film cannot be obtained.
Comparative example 3 preparation of brominated butyl rubber fiber film
The procedure of example 4 was repeated except that extraction was not carried out.
Examples of the experiments
Experimental example 1 scanning Electron microscope test
Scanning electron microscope tests are respectively carried out on the brominated butyl rubber fiber films obtained in the experimental example 4, the comparative example 1 and the comparative example 3, and the scanning electron microscope spectrograms of the brominated butyl rubber fiber films are respectively shown in figures 1-3, wherein:
comparing fig. 1 and 2, the shape of the fibers can be clearly seen in fig. 1, and the fibers are three-dimensional; the shape of the fibers is not visible in fig. 2, but rather the state of the beads, and a planar state rather than a three-dimensional state is presented; therefore, the addition of the surfactant is proved to improve the spinnability of the brominated butyl rubber, so that the brominated butyl rubber forms spinning fibers under the action of an electric field and finally forms a fiber film;
comparing fig. 1 and fig. 3, the shape of the fiber can be clearly seen in fig. 1, and the fiber has strong stereoscopic impression; although fibers are visible in fig. 3, the fibers have adhered together and no voids are visible throughout the fibrous membrane; thus, extraction was demonstrated to improve the morphology of the fiber film.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (5)
1. An electrospinning process of brominated butyl rubber, the process comprising the steps of:
step 1, adding brominated butyl rubber into a solvent, and stirring to obtain a brominated butyl rubber solution;
the Mooney viscosity of the brominated butyl rubber is 35 MU;
based on the total weight of the brominated butyl rubber and the solvent, the content of the brominated butyl rubber is 10-20%;
the solvent is selected from one or more of n-hexane, tetrahydrofuran and chloroform;
step 2, adding a surfactant into the brominated butyl rubber solution obtained in the step 1, and stirring to obtain a spinning solution;
the surfactant is dodecyl trimethyl ammonium bromide and/or dodecyl benzene sulfonic acid sodium;
in the step 1 and the step 2, the content of the surfactant is 1-4% based on the weight of the brominated butyl rubber;
in the step 2, an anti-sticking auxiliary agent and/or a functional auxiliary agent are/is also added, wherein the functional auxiliary agent is one or more selected from an accelerant, a vulcanizing agent, a sterilization auxiliary agent, a cosmetic auxiliary agent, a magnetic auxiliary agent, a conductive auxiliary agent and a fluorescent auxiliary agent;
the anti-sticking auxiliary agent is selected from one or more of paraffin, zinc stearate, stearic acid soap, organic silicon anti-sticking agents, polyethylene wax, diatomite, calcium carbonate and talcum powder;
the promoter is selected from one or more of a promoter TT, a promoter M, a promoter D, a promoter H, a promoter ZDMC, a promoter ZBX, a promoter NA-22 and a promoter CZ;
the vulcanizing agent is selected from one or more of sulfur, sulfur donor, peroxide, metal oxide, polyamine, p-quinone dioxime and bismaleimide;
the sterilization auxiliary agent is selected from one or more of nano silver, nano copper, nano zinc, triclosan and fluoxafloxacin;
the magnetic auxiliary agent is selected from one or more of nano ferrite, alnico and rare earth permanent magnet materials;
the conductive auxiliary agent is selected from one or more of carbon black, graphene, carbon nano tubes, nano copper and nano silver;
the fluorescence auxiliary agent is a carbon quantum dot;
when an anti-sticking aid is added alone, the content of the anti-sticking aid is 0.1-20% based on the weight of the brominated butyl rubber;
when the functional additive is added separately, the content of the functional additive is 0.5-30% based on the weight of the brominated butyl rubber;
when an anti-sticking auxiliary agent and a functional auxiliary agent are added together, the total content of the anti-sticking auxiliary agent and the functional auxiliary agent is 1-30% based on the weight of the brominated butyl rubber;
step 3, performing electrostatic spinning by using the spinning solution obtained in the step 2 to obtain a fiber film primary product;
before step 3, spraying a release agent on the receiving screen; the aluminum foil is provided with demoulding paper or non-woven fabric;
in step 3: the negative voltage of the spinning voltage is-1 to-2.5 kV; the positive voltage of the spinning voltage is 8-18 kV; the distance between the spinneret orifice and the receiving screen is 10-30 cm;
step 4, extracting the fiber film primary product, and then carrying out post-treatment to obtain a brominated butyl rubber fiber film;
extracting with methanol and/or ethanol;
the extraction time is 1-10 h;
the post-treatment is low-temperature treatment; wherein the low-temperature treatment comprises freeze-drying and drying by an air cooler;
the low-temperature treatment time is 1-50 h;
the post-treatment may also include ultraviolet irradiation or radiation.
2. The process according to claim 1,
when an anti-sticking aid is added alone, the content of the anti-sticking aid is 0.5-10% based on the weight of the brominated butyl rubber; and/or
When the functional additive is added separately, the content of the functional additive is 1-20% based on the weight of the brominated butyl rubber; and/or
When an anti-sticking aid and a functional aid are added together, the total content of the anti-sticking aid and the functional aid is 2-25% based on the weight of the brominated butyl rubber.
3. The process according to claim 2,
when an anti-sticking aid is added alone, the content of the anti-sticking aid is 5-10% based on the weight of the brominated butyl rubber; and/or
When the functional additive is added separately, the content of the functional additive is 5-10% based on the weight of the brominated butyl rubber; and/or
When an anti-sticking aid and a functional aid are added together, the total content of the anti-sticking aid and the functional aid is 5-15% based on the weight of the brominated butyl rubber.
4. The process according to claim 1,
the low-temperature treatment is freeze-drying; and/or
The time of the low-temperature treatment is 1-30 h.
5. The process according to claim 4,
the time of the low-temperature treatment is 5-20 h.
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