CN112813529B - Bio-based degradable polymer nanofiber and non-woven fabric - Google Patents
Bio-based degradable polymer nanofiber and non-woven fabric Download PDFInfo
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
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Abstract
The invention provides a bio-based degradable polymer nanofiber, which belongs to the field of bio-based degradable fibers, wherein refined lactic acid is added with a catalyst and a modifier to carry out polymerization reaction to obtain modified polylactic acid, the modified polylactic acid, an electret master batch, a high-molecular electret and an auxiliary agent are uniformly mixed to prepare a mixture, the mixture is fed into a screw extruder to be melted and extruded into a melt, the melt is blown into polylactic acid fibers through spinneret holes, and the modifier is a graft modified carbon nano tube; the invention takes the carbon nano tube which is sequentially modified by the amino cellulose and grafted by the polylactic acid as the modifier, effectively accelerates the crystallization rate of the polylactic acid, and improves the melt processing performance and the heat resistance of the polylactic acid.
Description
Technical Field
The invention relates to the field of bio-based degradable fibers, in particular to a bio-based degradable polymer nanofiber and a non-woven fabric.
Background
At present, domestic products mainly use polypropylene (PP) non-woven fabrics, and the products are single in structure and lack competitiveness. The development of a new generation of bio-based degradable non-woven fabric not only completely meets the requirements of protective articles on safety and usability, but also endows the products with new green environmental protection characteristics, and accords with the latest development trend of the field. Polylactic acid is a polymer obtained by polymerizing lactic acid serving as a main raw material, and the raw material is sufficient in source and can be regenerated. The production process of polylactic acid is pollution-free, and the product can be biodegraded, so that the polylactic acid can be recycled in nature, and is an ideal green high polymer material.
The diversification of the sources of the bio-based degradable polylactic acid (PLA) resin and the enlargement of the polymerization scale lead the cost to be close to the level of the general petroleum-based resin (PP, PET and the like), and the price cannot be influenced by the oil price in the future; the PLA spinning process is similar to PP and PET, and the PLA fiber and the non-woven fabric can be produced by using the existing PP and PET spinning lines, so that the equipment investment and the processing cost are greatly saved; after being used and abandoned, the PLA non-woven fabric can be completely biodegraded within months under the composting condition, not only does not cause burden to the environment, but also participates in natural circulation.
However, polylactic acid is a semi-crystalline polymer, has low crystallization rate, high hardness, poor processing thermal stability, narrow processing temperature window, and the like, and is limited to be applied to the field of non-woven fabrics, so that modification of polylactic acid is a hot point of research. The development of polylactic acid functional non-woven fabrics can promote the development of the non-woven fabric industry and related industries, promote the independent innovation capability of the related industries, and have good market prospect.
Disclosure of Invention
Aiming at the problems of low crystallization rate, poor toughness and the like of polylactic acid, the invention provides a bio-based degradable polymer nanofiber and a non-woven fabric.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a bio-based degradable polymer nanofiber comprises the following steps:
s1, performing rotary evaporation refining on the industrial lactic acid to obtain refined lactic acid, adding a catalyst and a modifier to perform polymerization reaction, and obtaining modified polylactic acid after the reaction is finished;
s2, preparing the modified polylactic acid into fibers by a melt-blowing method: uniformly mixing the modified polylactic acid, the electret master batch, the polymer electret and the auxiliary agent to prepare a mixture, feeding the mixture into a screw extruder to be melted and extruded into a melt, and blowing the melt into polylactic acid fibers through a spinneret orifice;
the modifier is a graft-modified carbon nanotube, and the preparation method of the graft-modified carbon nanotube comprises the following steps:
a1, adding a nitric acid solution into the carbon nano tube, refluxing for 12h under the condition of 80 ℃ water bath, wherein the mass fraction of the nitric acid solution is 50 percent, the mass ratio of the nitric acid solution to the carbon nano tube is 8:1, and sequentially adding concentrated HNO after the refluxing treatment3With concentrated H2SO4Mixed acid of (3), NaOH solution, H2O2Treating the solution, washing the solution to be neutral by using distilled water, and drying the solution to obtain a first modified carbon nano tube;
2, weighing 10g of dry short stapled cotton fiber, adding the dry short stapled cotton fiber into 200ml of dimethylformamide solution, stirring and heating to 100 ℃, keeping the temperature and stirring for reaction for 2 hours, removing a heat source, adding 20g of anhydrous lithium chloride, continuously stirring to cool, adding 30ml of triethylamine solution, stirring uniformly, dropwise adding 20ml of p-chloro toluene sulfone-containing dimethylamide solution under the condition of ice water bath, continuously stirring for reaction for 24 hours after dropwise adding, standing for precipitation, filtering out the precipitate, washing with deionized water and absolute ethyl alcohol respectively, dissolving in 80ml of dimethyl sulfoxide after drying, adding 15ml of ethylenediamine solution, stirring at 100 ℃ for reaction for 4 hours, cooling to room temperature, adding acetone to separate out the precipitate, washing the precipitate with acetone and absolute ethyl alcohol respectively, drying to obtain amino modified cellulose, preparing into 3g/L of solution with 1% by mass of acetic acid solution, obtaining amino modified cellulose solution; wherein the mass fraction of the p-chloro toluene sulfone in the dimethylamide solution of the p-chloro toluene sulfone is 10%;
a3, dispersing the first modified carbon nano tube prepared in the step a1 in the amino modified cellulose solution prepared in the step a2, stirring and reacting for 1-2 hours, filtering out precipitates, and washing with an acetic acid solution with the mass fraction of 1% and deionized water in sequence to obtain a second modified carbon nano tube; wherein the mass mixing ratio of the first modified carbon nanotube to the amino modified cellulose solution is 1: (15-30);
4, weighing 1g of the second modified carbon nano tube, dispersing in 20ml of a dimethyl amide solution, replacing the reaction atmosphere with nitrogen, adding 0.077g of a catalyst and 2.9g of lactic acid, sealing the reaction system, heating to 80 ℃ under the protection of nitrogen, keeping the temperature, stirring, reacting for 24 hours, cooling to room temperature, filtering out precipitates, washing with dimethyl amide, absolute ethyl alcohol and deionized water in sequence, and drying to obtain the grafted and modified carbon nano tube.
Preferably, the mixing ratio of the purified lactic acid, the catalyst and the modifier in step S1 is 100: (1-1.8): (5-12); in the step S2, the mass mixing ratio of the modified polylactic acid, the electret masterbatch, the polymer electret and the auxiliary agent is 100: (4-10): (0.4-1.2): (0.1-5).
Preferably, the catalyst is p-dimethylaminopyridine.
Preferably, the temperature of the melt is 180 ℃, the size of the spinneret orifice is 0.5mm, and the speed of the spinneret orifice is 600 m/min.
Preferably, the polymer electret is one or more of polycarbonate, polymethyl methacrylate and polyvinylidene fluoride.
Preferably, the auxiliary agent comprises one or more of an antioxidant, a compatibilizer and a nucleating agent; the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the compatilizer is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted propylene-based elastomer, methyl methacrylate grafted polypropylene, methyl methacrylate grafted propylene-based elastomer, glycidyl methacrylate grafted polypropylene or glycidyl methacrylate grafted propylene-based elastomer; the nucleating agent is stearate, and the stearate is one or more of lithium stearate, sodium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate and aluminum distearate.
The invention also aims to provide a non-woven fabric prepared from the nano-fibers, which is prepared by stretching the bio-based degradable polymer nano-fibers through air flow to form reticular fibers with uniformly laid filaments and bonding the reticular fibers through a hot roller.
Preferably, the reticular fibers also comprise P-N type thermoelectric oxide nano fibers.
More preferably, the P-N type thermoelectric oxide nanofiber is Ca3Co4O9And (3) nano fibers.
Preferably, the Ca3Co4O9The preparation method of the nanofiber comprises the following steps:
respectively weighing calcium acetate monohydrate and cobalt acetate tetrahydrate according to a stoichiometric ratio by taking calcium acetate as a calcium source and cobalt acetate as a cobalt source, dissolving the calcium acetate monohydrate by using methanol to prepare a solution with the concentration of 0.25g/ml to obtain a solution A, dissolving the cobalt acetate tetrahydrate by using a propionic acid solution to prepare a solution with the concentration of 0.2g/ml to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, and adjusting the mixed solution of the methanol and the propionic acid to a mixed solutionAdding polyvinylpyrrolidone with final concentration of 0.04g/l into the solution with acetate concentration of 0.2mol/l, stirring thoroughly to dissolve, performing ultrasonic dispersion to obtain spinning solution, and preparing Ca by electrostatic spinning process3Co4O9And (3) nano fibers.
The invention has the beneficial effects that:
aiming at the problems of low crystallization rate and poor processing performance of polylactic acid, the modified carbon nano tube modified by amino cellulose and polylactic acid graft is used as a modifier of the polylactic acid, so that the crystallization rate of the polylactic acid is effectively increased, the flexibility and the heat resistance of the polylactic acid are further improved while the crystallization rate and the crystallinity are improved, the melt processing performance and the heat resistance of the polylactic acid are improved, and the production and performance application range of the polylactic acid are widened.
Detailed Description
The invention is further described with reference to the following examples.
Embodiments of the present invention relate to the preparation of bio-based degradable polymer nanofibers and non-woven fabrics,
the method comprises the following steps:
s1, performing rotary evaporation refining on the industrial lactic acid to obtain refined lactic acid, adding a catalyst and a modifier to perform polymerization reaction, and obtaining modified polylactic acid after the reaction is finished;
s2, preparing the modified polylactic acid into fibers by a melt-blowing method: uniformly mixing the modified polylactic acid, the electret master batch, the polymer electret and the auxiliary agent to prepare a mixture, feeding the mixture into a screw extruder to be melted and extruded into a melt, and blowing the melt into polylactic acid fibers through a spinneret orifice;
the modifier is a graft-modified carbon nanotube, and the preparation method of the graft-modified carbon nanotube comprises the following steps:
a1, adding the carbon nano tube into nitric acid solution, refluxing for 12h under the condition of 80 ℃ water bath,the mass fraction of the nitric acid solution is 50 percent, the mass ratio of the nitric acid solution to the carbon nano tube is 8:1, and concentrated HNO is sequentially added after the reflux treatment is finished3With concentrated H2SO4Mixed acid of (3), NaOH solution, H2O2Treating the solution, washing the solution to be neutral by using distilled water, and drying the solution to obtain a first modified carbon nano tube;
2, weighing 10g of dry short stapled cotton fiber, adding the dry short stapled cotton fiber into 200ml of dimethylformamide solution, stirring and heating to 100 ℃, keeping the temperature and stirring for reaction for 2 hours, removing a heat source, adding 20g of anhydrous lithium chloride, continuously stirring to cool, adding 30ml of triethylamine solution, stirring uniformly, dropwise adding 20ml of p-chloro toluene sulfone-containing dimethylamide solution under the condition of ice water bath, continuously stirring for reaction for 24 hours after dropwise adding, standing for precipitation, filtering out the precipitate, washing with deionized water and absolute ethyl alcohol respectively, dissolving in 80ml of dimethyl sulfoxide after drying, adding 15ml of ethylenediamine solution, stirring at 100 ℃ for reaction for 4 hours, cooling to room temperature, adding acetone to separate out the precipitate, washing the precipitate with acetone and absolute ethyl alcohol respectively, drying to obtain amino modified cellulose, preparing into 3g/L of solution with 1% by mass of acetic acid solution, obtaining amino modified cellulose solution; wherein the mass fraction of the p-chloro toluene sulfone in the dimethylamide solution of the p-chloro toluene sulfone is 10%;
a3, dispersing the first modified carbon nano tube prepared in the step a1 in the amino modified cellulose solution prepared in the step a2, stirring and reacting for 1-2 hours, filtering out precipitates, and washing with an acetic acid solution with the mass fraction of 1% and deionized water in sequence to obtain a second modified carbon nano tube; wherein the mass mixing ratio of the first modified carbon nanotube to the amino modified cellulose solution is 1: (15-30);
4, weighing 1g of the second modified carbon nano tube, dispersing in 20ml of a dimethyl amide solution, replacing the reaction atmosphere with nitrogen, adding 0.077g of a catalyst and 2.9g of lactic acid, sealing the reaction system, heating to 80 ℃ under the protection of nitrogen, keeping the temperature, stirring, reacting for 24 hours, cooling to room temperature, filtering out precipitates, washing with dimethyl amide, absolute ethyl alcohol and deionized water in sequence, and drying to obtain the grafted and modified carbon nano tube.
Aiming at the problems of low crystallization rate and poor processing performance of polylactic acid, the modified carbon nano tube is used as a modifier of the polylactic acid, so that the crystallization rate of the polylactic acid is effectively accelerated, and the melt processing performance and the heat resistance of the polylactic acid are improved; the carbon nano tube has heterogeneous nucleation effect on the polylactic acid and accelerates the crystallization rate of the polylactic acid, but the reinforcing effect of the carbon nano tube is also not beneficial to improving the flexibility of the polylactic acid, the invention takes the carbon nano tube as a substrate and adopts the amino cellulose modified grafting and the polylactic acid grafting, the method improves the crystallinity, further improves the flexibility and heat resistance, widens the production and performance application range, and particularly introduces hydroxyl and carboxyl functional group active sites on the surface of the carbon nano tube by surface activation treatment of the carbon nano tube, then grafts toughened cellulose and polylactic acid molecular chains for increasing compatibility through the active sites, reduces the polarity of the modified carbon nano tube, is easy to be compatible with polylactic acid, improves the crystallization speed and the crystallinity, and the polylactic acid is easy to crystallize, so that the polylactic acid fiber and the non-woven fabric have high toughness, excellent impact resistance and good processing thermal stability.
Preferably, the mixing ratio of the purified lactic acid, the catalyst and the modifier in step S1 is 100: (1-1.8): (5-12); in the step S2, the mass mixing ratio of the modified polylactic acid, the electret masterbatch, the polymer electret and the auxiliary agent is 100: (4-10): (0.4-1.2): (0.1-5).
Preferably, the catalyst is p-dimethylaminopyridine.
Preferably, the temperature of the melt is 180 ℃, the size of the spinneret orifice is 0.5mm, and the speed of the spinneret orifice is 600 m/min.
Preferably, the polymer electret is one or more of polycarbonate, polymethyl methacrylate and polyvinylidene fluoride.
Preferably, the auxiliary agent comprises one or more of an antioxidant, a compatibilizer and a nucleating agent; the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the compatilizer is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted propylene-based elastomer, methyl methacrylate grafted polypropylene, methyl methacrylate grafted propylene-based elastomer, glycidyl methacrylate grafted polypropylene or glycidyl methacrylate grafted propylene-based elastomer; the nucleating agent is stearate, and the stearate is one or more of lithium stearate, sodium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate and aluminum distearate.
The embodiment of the invention also relates to a non-woven fabric prepared from the nano-fiber, which is prepared by stretching the bio-based degradable polymer nano-fiber through air flow to form a reticular fiber with uniformly laid filaments and then bonding the reticular fiber through a hot roller.
Preferably, the reticular fibers also comprise P-N type thermoelectric oxide nano fibers.
More preferably, the P-N type thermoelectric oxide nanofiber is Ca3Co4O9And (3) nano fibers.
Preferably, the Ca3Co4O9The preparation method of the nanofiber comprises the following steps:
respectively weighing calcium acetate monohydrate and cobalt acetate tetrahydrate according to a stoichiometric ratio by taking calcium acetate as a calcium source and cobalt acetate as a cobalt source, dissolving the calcium acetate monohydrate by using methanol to prepare a solution with the concentration of 0.25g/ml to obtain a solution A, dissolving the cobalt acetate tetrahydrate by using a propionic acid solution to prepare a solution with the concentration of 0.2g/ml to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, adjusting the mixed solution of the methanol and the propionic acid to the acetate concentration of 0.2mol/l in the mixed solution, adding polyvinylpyrrolidone with the final concentration of 0.04g/l, fully stirring to dissolve, performing ultrasonic dispersion to obtain a spinning solution, and preparing the Ca by using an electrostatic spinning process3Co4O9And (3) nano fibers.
The addition of the electret master batch can improve the electret effect of polylactic acid, improve the electrostatic adsorption effect of polylactic acid fiber and polylactic acid fiber fabric, and obviously improve the surface charge density, the filtering performance and the performanceThe antibacterial property, in order to avoid the influence of adding excessive filler on the processability of the polylactic acid, excessive electret master batch is not suitable to be added; the carbon nano tube has the photothermal effect with the characteristics of nano metal, and in order to further improve the electrostatic adsorption effect of the polylactic acid fiber, the Ca with the thermoelectric effect is blended and doped in the modified polylactic acid non-woven fabric fiber in a blending way in combination with the good photothermal effect of the carbon nano tube3Co4O9The nanofiber improves the electrode effect among fibers, further improves the adsorption and filtration performance of the polylactic acid fiber, and particularly utilizes the heat effect and Ca of the carbon nanotube3Co4O9The thermoelectric effect of the nano-fiber converts light energy into electric energy, so that the surface charge density is improved, and meanwhile, the problem of easy charge dissipation in direct electret treatment can be solved due to the photoinitiation effect.
Example 1
A bio-based degradable polymer nanofiber, which is prepared by the following steps:
s1, carrying out rotary evaporation refining on industrial lactic acid to obtain refined lactic acid, adding a catalyst and a modifier to carry out polymerization reaction, and obtaining modified polylactic acid after the reaction is finished, wherein the mass mixing ratio of the refined lactic acid to the catalyst to the modifier is 100: 1.2: 8;
s2, preparing the modified polylactic acid into fibers by a melt-blowing method: uniformly mixing the modified polylactic acid, the electret master batch, the polymer electret and the auxiliary agent to obtain a mixture, feeding the mixture into a screw extruder to be melted and extruded into a melt, and blowing the melt into polylactic acid fibers through a spinneret orifice, wherein the mass mixing ratio of the modified polylactic acid, the electret master batch, the polymer electret and the antioxidant is 100: 6: 0.6: 0.2; the temperature of the melt is 180 ℃, the size of the spinneret orifice is 0.5mm, and the speed of the spinneret orifice is 600 m/min;
the catalyst is p-dimethylaminopyridine; the polymer electret is polyvinylidene fluoride; the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester or diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ];
the modifier is a graft-modified carbon nanotube, and the preparation method of the graft-modified carbon nanotube comprises the following steps:
a1, adding a nitric acid solution into the carbon nano tube, refluxing for 12h under the condition of 80 ℃ water bath, wherein the mass fraction of the nitric acid solution is 50 percent, the mass ratio of the nitric acid solution to the carbon nano tube is 8:1, performing suction filtration after the reflux treatment is finished, washing with distilled water to remove residual nitric acid, mixing concentrated HNO according to the ratio of 1:33With concentrated H2SO4Preparing mixed acid, mixing carbon nano tube and mixed acid according to the proportion of 1:5, performing ultrasonic treatment for 4H, performing suction filtration, washing with distilled water to remove residual mixed acid, adding 4 times of 40% NaOH solution by mass into the obtained carbon nano tube, performing ultrasonic treatment for 2H, performing suction filtration, washing with distilled water, adding 3 times of 20% H by mass2O2Treating the solution for 2h, centrifuging, washing the precipitate with distilled water to neutrality, and drying to obtain a first modified carbon nanotube;
2, weighing 10g of dry short stapled cotton fiber, adding the dry short stapled cotton fiber into 200ml of dimethylformamide solution, stirring and heating to 100 ℃, keeping the temperature and stirring for reaction for 2 hours, removing a heat source, adding 20g of anhydrous lithium chloride, continuously stirring to cool, adding 30ml of triethylamine solution, stirring uniformly, dropwise adding 20ml of p-chloro toluene sulfone-containing dimethylamide solution under the condition of ice water bath, continuously stirring for reaction for 24 hours after dropwise adding, standing for precipitation, filtering out the precipitate, washing with deionized water and absolute ethyl alcohol respectively, dissolving in 80ml of dimethyl sulfoxide after drying, adding 15ml of ethylenediamine solution, stirring at 100 ℃ for reaction for 4 hours, cooling to room temperature, adding acetone to separate out the precipitate, washing the precipitate with acetone and absolute ethyl alcohol respectively, drying to obtain amino modified cellulose, preparing into 3g/L of solution with 1% by mass of acetic acid solution, obtaining amino modified cellulose solution; wherein the mass fraction of the p-chloro toluene sulfone in the dimethylamide solution of the p-chloro toluene sulfone is 10%;
a3, dispersing the first modified carbon nano tube prepared in the step a1 in the amino modified cellulose solution prepared in the step a2, stirring and reacting for 1-2 hours, filtering out precipitates, and washing with an acetic acid solution with the mass fraction of 1% and deionized water in sequence to obtain a second modified carbon nano tube; wherein the mass mixing ratio of the first modified carbon nanotube to the amino modified cellulose solution is 1: (15-30);
4, weighing 1g of the second modified carbon nano tube, dispersing in 20ml of a dimethyl amide solution, replacing the reaction atmosphere with nitrogen, adding 0.077g of a catalyst and 2.9g of lactic acid, sealing the reaction system, heating to 80 ℃ under the protection of nitrogen, keeping the temperature, stirring, reacting for 24 hours, cooling to room temperature, filtering out precipitates, washing with dimethyl amide, absolute ethyl alcohol and deionized water in sequence, and drying to obtain the grafted and modified carbon nano tube.
Comparative example 1
A bio-based degradable polymer nanofiber prepared as in example 1 but without the addition of a modifier.
Comparative example 2
A bio-based degradable polymer nanofiber prepared as in example 1 but with unmodified carbon nanotubes as the modifier.
Example 2
A non-woven fabric containing the nano-fibers in the embodiment 1 is prepared by stretching the bio-based degradable polymer nano-fibers through air flow to form reticular fibers with uniformly laid filaments, and bonding the reticular fibers through hot rollers;
the air flow drawing conditions are as follows: cooling air 20 deg.C, humidity 40%, stretching airflow speed 0.5m/s, hot roller bonding temperature 140 deg.C.
Comparative example 3
A non-woven fabric comprising the nano-fiber of comparative example 1, wherein the bio-based degradable polymer nano-fiber is stretched by air flow to form a reticular fiber with uniformly laid filaments, and the reticular fiber is bonded by hot rollers;
the air flow drawing conditions are as follows: cooling air 20 deg.C, humidity 40%, stretching airflow speed 0.5m/s, hot roller bonding temperature 140 deg.C.
Comparative example 4
A non-woven fabric comprising the nanofibers of comparative example 2, wherein the nanofibers of the bio-based degradable polymer are stretched by air flow to form a reticular fiber with uniformly laid filaments, and the reticular fiber is bonded by hot rollers;
the air flow drawing conditions are as follows: cooling air 20 deg.C, humidity 40%, stretching airflow speed 0.5m/s, hot roller bonding temperature 140 deg.C.
Example 3
A non-woven fabric containing the nano-fibers in the embodiment 1 is prepared by stretching the bio-based degradable polymer nano-fibers through air flow to form reticular fibers with uniformly laid filaments, and bonding the reticular fibers through hot rollers;
the air flow drawing conditions are as follows: cooling air at 20 ℃, humidity at 40%, stretching airflow at a speed of 0.5m/s and hot roller bonding temperature at 140 ℃;
the reticular fibers also comprise P-N type thermoelectric oxide nano fibers; the P-N type thermoelectric oxide nano-fiber is Ca3Co4O9A nanofiber; the Ca3Co4O9The preparation method of the nanofiber comprises the following steps:
respectively weighing calcium acetate monohydrate and cobalt acetate tetrahydrate according to a stoichiometric ratio by taking calcium acetate as a calcium source and cobalt acetate as a cobalt source, dissolving the calcium acetate monohydrate by using methanol to prepare a solution with the concentration of 0.25g/ml to obtain a solution A, dissolving the cobalt acetate tetrahydrate by using a propionic acid solution to prepare a solution with the concentration of 0.2g/ml to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, adjusting the mixed solution of the methanol and the propionic acid to the acetate concentration of 0.2mol/l in the mixed solution, adding polyvinylpyrrolidone with the final concentration of 0.04g/l, fully stirring to dissolve, performing ultrasonic dispersion to obtain a spinning solution, and preparing the Ca by using an electrostatic spinning process3Co4O9And (3) nano fibers.
Performance testing
The tensile strength and the elongation at break of the non-woven fabric are measured according to GB/T1040-2006, and the heat distortion temperature is measured according to GB/T1634-2004;
the determination of the classification efficiency is tested on a test bed conforming to GB/14295-;
the test results are given in the following table:
| parameter(s) | Example 1 | Comparative example 1 | Comparative example 2 |
| Fiber diameter (μm) | 3-7 | 3-7 | 3-7 |
| Degree of crystallinity (%) | 58 | 29 | 46 |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. A bio-based degradable non-woven fabric is characterized in that bio-based degradable polymer nano fibers are stretched through airflow to form reticular fibers with uniformly laid filaments, and the reticular fibers are bonded through hot rollers and also contain P-N type thermoelectric oxide nano fibers;
the preparation method of the bio-based degradable polymer nanofiber comprises the following steps:
s1, performing rotary evaporation refining on the industrial lactic acid to obtain refined lactic acid, adding a catalyst and a modifier to perform polymerization reaction, and obtaining modified polylactic acid after the reaction is finished;
s2, uniformly mixing the modified polylactic acid, the electret master batch, the polymer electret and the auxiliary agent to obtain a mixture, feeding the mixture into a screw extruder to be melted and extruded into a melt, and blowing the melt into polylactic acid fibers through spinneret holes;
the modifier is a graft-modified carbon nanotube, and the preparation method of the graft-modified carbon nanotube comprises the following steps:
a1, adding a nitric acid solution into the carbon nano tube, refluxing for 12h under the condition of 80 ℃ water bath, wherein the mass fraction of the nitric acid solution is 50 percent, the mass ratio of the nitric acid solution to the carbon nano tube is 8:1, and sequentially adding concentrated HNO after the refluxing treatment3With concentrated H2SO4Mixed acid of (3), NaOH solution, H2O2Treating the solution, washing the solution to be neutral by using distilled water, and drying the solution to obtain a first modified carbon nano tube;
2, weighing 10g of dry short stapled cotton fiber, adding the dry short stapled cotton fiber into 200ml of dimethylformamide solution, stirring and heating to 100 ℃, keeping the temperature and stirring for reaction for 2 hours, removing a heat source, adding 20g of anhydrous lithium chloride, continuously stirring to cool, adding 30ml of triethylamine solution, stirring uniformly, dropwise adding 20ml of p-chloro toluene sulfone-containing dimethylamide solution under the condition of ice water bath, continuously stirring for reaction for 24 hours after dropwise adding, standing for precipitation, filtering out the precipitate, washing with deionized water and absolute ethyl alcohol respectively, dissolving in 80ml of dimethyl sulfoxide after drying, adding 15ml of ethylenediamine solution, stirring at 100 ℃ for reaction for 4 hours, cooling to room temperature, adding acetone to separate out the precipitate, washing the precipitate with acetone and absolute ethyl alcohol respectively, drying to obtain amino modified cellulose, preparing into 3g/L of solution with 1% by mass of acetic acid solution, obtaining amino modified cellulose solution; wherein the mass fraction of the p-chloro toluene sulfone in the dimethylamide solution of the p-chloro toluene sulfone is 10%;
a3, dispersing the first modified carbon nano tube prepared in the step a1 in the amino modified cellulose solution prepared in the step a2, stirring and reacting for 1-2 hours, filtering out precipitates, and washing with an acetic acid solution with the mass fraction of 1% and deionized water in sequence to obtain a second modified carbon nano tube; wherein the mass mixing ratio of the first modified carbon nanotube to the amino modified cellulose solution is 1: (15-30);
4, weighing 1g of the second modified carbon nano tube, dispersing in 20ml of a dimethyl amide solution, replacing the reaction atmosphere with nitrogen, adding 0.077g of a catalyst and 2.9g of lactic acid, sealing the reaction system, heating to 80 ℃ under the protection of nitrogen, keeping the temperature, stirring, reacting for 24 hours, cooling to room temperature, filtering out precipitates, washing with dimethyl amide, absolute ethyl alcohol and deionized water in sequence, and drying to obtain the grafted and modified carbon nano tube.
2. The biodegradable nonwoven fabric according to claim 1, wherein the mixing ratio of the refined lactic acid, the catalyst and the modifier in step S1 is 100: (1-1.8): (5-12); in the step S2, the mass mixing ratio of the modified polylactic acid, the electret masterbatch, the polymer electret and the auxiliary agent is 100: (4-10): (0.4-1.2): (0.1-5).
3. The biodegradable nonwoven fabric according to claim 1, wherein said catalyst is p-dimethylaminopyridine.
4. The biodegradable nonwoven fabric of claim 1, wherein said melt has a temperature of 180 ℃, said spinneret holes have a size of 0.5mm, and said spinneret holes have a speed of 600 m/min.
5. The biodegradable nonwoven fabric according to claim 1, wherein the polymer electret is one or more of polycarbonate, polymethyl methacrylate, and polyvinylidene fluoride.
6. The biodegradable non-woven fabric according to claim 1, wherein the auxiliary agent comprises one or more of an antioxidant, a compatibilizer, and a nucleating agent; the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the compatilizer is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted propylene-based elastomer, methyl methacrylate grafted polypropylene, methyl methacrylate grafted propylene-based elastomer, glycidyl methacrylate grafted polypropylene and glycidyl methacrylate grafted propylene-based elastomer; the nucleating agent is stearate, and the stearate is one or more of lithium stearate, sodium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate and aluminum distearate.
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