CN114808470B - Anti-blocking and antioxidant mat and preparation method thereof - Google Patents
Anti-blocking and antioxidant mat and preparation method thereof Download PDFInfo
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- CN114808470B CN114808470B CN202210132166.3A CN202210132166A CN114808470B CN 114808470 B CN114808470 B CN 114808470B CN 202210132166 A CN202210132166 A CN 202210132166A CN 114808470 B CN114808470 B CN 114808470B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
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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
- D01F6/88—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
- D01F6/90—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 polyamides
- D01F6/905—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 polyamides of aromatic polyamides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0034—Polyamide fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
Abstract
The invention discloses an anti-blocking and anti-oxidation mat and a preparation method thereof, wherein the mat comprises a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 20-40 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 6-8 parts of aziridine crosslinking agent, 1-3 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 10-15 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning. The mat has good performance stability, sufficient anti-blocking and oxidation resistance and long service life.
Description
Technical Field
The invention relates to the technical field of mats, in particular to an anti-blocking and antioxidant mat and a preparation method thereof.
Background
In recent years, with the development of economy and the improvement of the living standard of people, the demand for improving the living quality is increasing, and the mat is used as a daily article capable of improving sitting and lying feeling and avoiding uncomfortable body for a long time, and is attracting attention. Currently, the mat products in the market are various, and the summer sleeping mat is a common mat which is often used for being laid for cooling in summer and has the functions of ventilation, cooling, no sweat adhesion and the like. The summer sleeping mat can be divided into a straw mat, a thin bamboo mat, a rattan mat, a bamboo mat and the like according to different selected materials. However, with the development of society and economy, people pay attention to not only the cooling effect, but also the comfort and safety of the summer sleeping mat.
The conventional summer sleeping mat is woven by the bamboo mat or the straw mat, and the sweat permeated by the skin of a human body is high in hot summer when the summer sleeping mat is used, and the mat is poor in anti-adhesion and oxidation resistance due to the material problem of the mat, so that the use effect of people on the comfort and safety of the mat is seriously affected, and the service life of the mat is reduced.
In order to solve the above problems, chinese patent application CN110512432a discloses a method for preparing an anti-blocking and anti-oxidation mat, S1: the method comprises the steps of uniformly stirring and mixing metallocene low-density polyethylene, polyvinylidene fluoride, tert-butyl peroxypropionate, maleic anhydride, polyethylene oxide, silicon carbide fibers, nano silicon fluoride powder, polyethylene glycol and composite cage-type silsesquioxane, and granulating by twin-screw extrusion, and drawing to obtain wefts; s2: stirring and uniformly mixing butyl-2, 3-dienenitrile, tartaric acid, methyl acrylate, hexadecyl trimethyl ammonium chloride, polyethylene oxide, trimethoxy silane propyl modified polyethylenimine and composite cage type silsesquioxane to obtain mixed emulsion; s3: and weaving the warp and the weft to obtain a fabric layer, coating the mixed emulsion on the surface of the fabric layer, and drying to obtain the mat. The mat prepared by the invention has excellent anti-blocking and anti-oxidation properties. However, the mat has a large number of raw materials, poor compatibility among the raw materials, easy phase separation in the long-term use process, further improved performance stability and comprehensive performance, and further improved anti-blocking and oxidation resistance.
Therefore, the development of the anti-blocking and anti-oxidation mat with good performance stability and sufficient anti-blocking and anti-oxidation performances and long service life and the preparation method thereof meet the market demand, have wide market value and application prospect, and have very important significance for promoting the development of the mat field.
Disclosure of Invention
The invention mainly aims to provide an anti-blocking and anti-oxidation mat with good performance stability and sufficient anti-blocking and anti-oxidation performances and long service life and a preparation method thereof.
In order to achieve the above purpose, the invention provides an anti-blocking and anti-oxidation mat, which is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 20-40 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 6-8 parts of aziridine crosslinking agent, 1-3 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 10-15 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
Preferably, the preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours under the atmosphere of inert gas at 65-75 ℃, precipitating the mixture in water, washing the precipitated polymer with water for 3-6 times, and finally drying the mixture to constant weight at 85-95 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
Preferably, the mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, the itaconic acid, the N- (3-dimethylaminopropyl) methacrylamide, the vinylferrocene, the initiator and the high boiling point solvent is 1 (0.3-0.6): 3-5): 0.03-0.05): 0.04-0.07): 20-30.
Preferably, the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the solvent is any one of cyclohexanone, propylene glycol methyl ether and n-butanol.
Preferably, the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
Preferably, the preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 3-5 hours at the normal pressure of 130-145 ℃, heating to 190-200 ℃, reacting for 4-6 hours, vacuumizing to 500Pa, heating to 230-240 ℃, continuing to perform polycondensation reaction for 8-10 hours, cooling to room temperature, regulating to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying to constant weight in a vacuum drying box at 85-95 ℃ to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
Preferably, the molar ratio of the 2, 3-quinoline dicarboxylic acid, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the dimethyl sulfoxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1 (6-10): (0.8-1.2): 0.5.
Another object of the present invention is to provide a method for preparing an anti-blocking and anti-oxidation mat, which is characterized by comprising the following steps:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
Preferably, the spinning temperature of the melt spinning in the step S1 is 230-250 ℃, the spinning speed is 2200-3200m/min, the stretching temperature is 60-80 ℃, and the total stretching multiplying power is 3-5.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The preparation method of the anti-blocking and anti-oxidation mat disclosed by the invention has the advantages of simple process, convenience in operation, high preparation efficiency and high finished product qualification rate, can realize organic unification of economic benefit and social benefit, and is suitable for continuous large-scale production.
(2) The anti-blocking and anti-oxidation mat disclosed by the invention has the advantages that through the reasonable selection of the functional layer components and the proportion thereof, the anti-blocking and anti-oxidation performance of the manufactured mat product is sufficient under the mutual cooperation and combined action; the functional layer film-forming polymer is 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer; the adhesive contains benzotriazole group, hydroxyl phenyl group, ester group, carboxyl group, ferrocene, amide group and dimethylamino group, which are synergistic, and can improve the performance stability and the bonding strength with a substrate; carboxyl in the molecular structure can provide a crosslinking reaction site, and carboxyl on the 2,3,5, 6-tetrafluoroterephthalic acid can chemically react with an aziridine crosslinking agent to form an interpenetrating network structure, so that the antioxidation and anti-blocking performance can be enhanced, and the performance stability is improved; the introduced tetrafluorophenyl group as a hydrophobic structure can further improve the anti-blocking property.
(3) The invention discloses an anti-blocking and anti-oxidation mat, which is formed by weaving functional fibers serving as wefts and coconut fibers serving as warps; the advantages of the two fibers are combined, the comprehensive performance of the mat is improved, and the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning; quinoline, amide, phenyl and triazinyl are simultaneously introduced into the molecular chain of the formed polycondensate, and the synergistic effect can improve the ageing resistance and the compatibility with the functional layer, thereby effectively prolonging the service life of the polycondensate.
(4) The anti-blocking and anti-oxidation mat disclosed by the invention is good in performance stability, sufficient in anti-blocking and anti-oxidation performance and long in service life by reasonably selecting the raw materials and the formula of the functional layer and the mat body.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 20 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 6 parts of aziridine crosslinking agent, 1 part of 2,3,5, 6-tetrafluoroterephthalic acid and 10 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 3 hours under the atmosphere of inert gas at 65 ℃, precipitating the mixture in water, washing the precipitated polymer with water for 3 times, and finally drying the mixture to constant weight at 85 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, an initiator and a high boiling point solvent is 1:0.3:3:0.03:0.04:20; the initiator is azodiisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The solvent is cyclohexanone; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
The preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 3 hours at the normal pressure of 130 ℃, heating to 190 ℃, reacting for 4 hours, vacuumizing to 500Pa, heating to 230 ℃, continuing to perform polycondensation reaction for 8 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3 times, and finally drying to constant weight at the temperature of 85 ℃ in a vacuum drying oven to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
The molar ratio of the 2, 3-quinoline dicarboxylic acid, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the dimethyl sulfoxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1:6:0.8:0.5.
The preparation method of the anti-blocking and anti-oxidation mat is characterized by comprising the following steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
The spinning temperature of the melt spinning in the step S1 is 230 ℃, the spinning speed is 2200m/min, the stretching temperature is 60 ℃, and the total stretching multiplying power is 3.
Example 2
An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 25 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 6.5 parts of aziridine crosslinking agent, 1.5 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 12 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 3.5 hours under the atmosphere of inert gas at 67 ℃, precipitating out the mixture in water, washing the precipitated polymer with water for 4 times, and finally drying the mixture to constant weight at 87 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, an initiator and a high boiling point solvent is 1:0.4:3.5:0.035:0.05:23; the initiator is azodiisobutyronitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The solvent is propylene glycol methyl ether; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
The preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 3.5 hours at the normal pressure of 135 ℃, then heating to 193 ℃, reacting for 4.5 hours, vacuumizing to 500Pa, heating to 233 ℃, continuing to perform polycondensation reaction for 8.5 hours, cooling to room temperature, regulating to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and finally drying to constant weight at 87 ℃ in a vacuum drying oven to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
The molar ratio of the 2, 3-quinoline dicarboxylic acid, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the dimethyl sulfoxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1:7:0.9:0.5.
The preparation method of the anti-blocking and anti-oxidation mat is characterized by comprising the following steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
The spinning temperature of the melt spinning in the step S1 is 235 ℃, the spinning speed is 2400m/min, the stretching temperature is 65 ℃, and the total stretching multiplying power is 3.5.
Example 3
An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 30 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 7 parts of aziridine crosslinking agent, 2 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 13 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 4 hours under the atmosphere of inert gas at 70 ℃, precipitating the mixture in water, washing the precipitated polymer with water for 5 times, and finally drying the mixture to constant weight at 90 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, an initiator and a high boiling point solvent is 1:0.45:4:0.04:0.055:25; the initiator is azodiisobutyronitrile; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is neon.
The solvent is n-butanol; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
The preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 4 hours at the normal pressure of 139 ℃, then heating to 195 ℃ for 5 hours, vacuumizing to 500Pa, heating to 235 ℃, continuing to perform polycondensation reaction for 9 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying to constant weight at 90 ℃ in a vacuum drying oven to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
The molar ratio of the 2, 3-quinoline dicarboxylic acid to the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the dimethyl sulfoxide to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:8:1:0.5.
The preparation method of the anti-blocking and anti-oxidation mat is characterized by comprising the following steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
The spinning temperature of the melt spinning in the step S1 is 240 ℃, the spinning speed is 2800m/min, the stretching temperature is 70 ℃, and the total stretching multiplying power is 4.
Example 4
An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 35 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 7.5 parts of aziridine crosslinking agent, 2.5 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 14 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours under the atmosphere of 73 ℃ and inert gas, precipitating out the mixture in water, washing the precipitated polymer with water for 6 times, and finally drying the mixture to constant weight at 93 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, an initiator and a high boiling point solvent is 1:0.55:4.5:0.045:0.065:28; the initiator is azodiisobutyronitrile; the high boiling point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:2:2; the inert gas is argon.
The solvent is cyclohexanone; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
The preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 4.5 hours at the normal pressure of 143 ℃, then heating to 198 ℃, reacting for 5.5 hours, vacuumizing to 500Pa, heating to 238 ℃, continuing to perform polycondensation reaction for 9.5 hours, cooling to room temperature, regulating to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying to constant weight at 93 ℃ in a vacuum drying oven to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
The molar ratio of the 2, 3-quinoline dicarboxylic acid, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the dimethyl sulfoxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1:9.5:1.1:0.5.
The preparation method of the anti-blocking and anti-oxidation mat is characterized by comprising the following steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
The spinning temperature of the melt spinning in the step S1 is 245 ℃, the spinning speed is 3100m/min, the stretching temperature is 75 ℃, and the total stretching multiplying power is 4.5.
Example 5
An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 40 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 8 parts of aziridine crosslinking agent, 3 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 15 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
The preparation method of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the following steps: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 5 hours under the atmosphere of inert gas at 75 ℃, precipitating the mixture in water, washing the precipitated polymer with water for 6 times, and finally drying the mixture to constant weight in a vacuum drying oven at 95 ℃ to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
The mass ratio of the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, an initiator and a high boiling point solvent is 1:0.6:5:0.05:0.07:30; the initiator is azodiisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The solvent is propylene glycol methyl ether; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
The preparation method of the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 5 hours at the normal pressure of 145 ℃, heating to 200 ℃, reacting for 6 hours, vacuumizing to 500Pa, heating to 240 ℃, continuing to perform polycondensation reaction for 10 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying to constant weight at the temperature of 95 ℃ in a vacuum drying oven to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
The molar ratio of the 2, 3-quinoline dicarboxylic acid, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the dimethyl sulfoxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1:10:1.2:0.5.
The preparation method of the anti-blocking and anti-oxidation mat is characterized by comprising the following steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
The spinning temperature of the melt spinning in the step S1 is 250 ℃, the spinning speed is 3200m/min, the stretching temperature is 80 ℃, and the total stretching multiplying power is 5.
Comparative example
An anti-blocking and anti-oxidation mat which is the same as example 1 of chinese patent application CN110512432 a.
The anti-blocking and anti-oxidation mats according to the examples and comparative examples of the present invention were respectively subjected to the related performance test, and the test results are shown in table 1; the water content and contact angle test method is described in Chinese patent application CN 110512432A; oxidation resistance is achieved by placing the mats of each example in Fenton's reagent (containingWith 4 ppm Fe 2+ 3% hydrogen peroxide solution) for 8 hours, the smaller the dry weight reduction rate value, the higher the oxidation resistance.
TABLE 1
As can be seen from Table 1, the anti-blocking and anti-oxidation mats prepared according to the examples of the present invention have higher anti-blocking and anti-oxidation properties than the comparative examples, which are the result of the synergistic effect of the components.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. An anti-adhesion and anti-oxidation mat is characterized by comprising a mat body and a functional layer coated on the surface of the mat body; the functional layer is prepared from the following raw materials in parts by weight: 20-40 parts of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer, 6-8 parts of aziridine crosslinking agent, 1-3 parts of 2,3,5, 6-tetrafluoroterephthalic acid and 10-15 parts of solvent; the mat body is woven by taking functional fibers as wefts and coconut fiber as warps; the functional fiber is prepared from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning.
2. The anti-blocking and anti-oxidant mat of claim 1, wherein the method for preparing the 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer comprises the steps of: adding 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours under the atmosphere of inert gas at 65-75 ℃, precipitating the mixture in water, washing the precipitated polymer with water for 3-6 times, and finally drying the mixture to constant weight at 85-95 ℃ in a vacuum drying oven to obtain the 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate/itaconic acid/N- (3-dimethylaminopropyl) methacrylamide/vinylferrocene copolymer.
3. The mat of claim 2, wherein the mass ratio of 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, itaconic acid, N- (3-dimethylaminopropyl) methacrylamide, vinylferrocene, initiator, high boiling point solvent is 1 (0.3-0.6): 3-5): 0.03-0.05): 0.04-0.07: 20-30.
4. The antiblocking antioxidant mat of claim 2, wherein the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
5. The anti-blocking and anti-oxidation mat according to claim 1, wherein the solvent is any one of cyclohexanone, propylene glycol methyl ether, n-butanol; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100.
6. The anti-blocking and anti-oxidation mat according to claim 1, wherein the preparation method of the 2, 3-quinolinedicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate comprises the following steps: dissolving 2, 3-quinoline dicarboxylic acid and 2, 4-diamino-6-phenyl-1, 3, 5-triazine in dimethyl sulfoxide, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, replacing air in a kettle with nitrogen, reacting for 3-5 hours at the normal pressure of 130-145 ℃, heating to 190-200 ℃, reacting for 4-6 hours, vacuumizing to 500Pa, heating to 230-240 ℃, continuing to perform polycondensation reaction for 8-10 hours, cooling to room temperature, regulating to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying to constant weight in a vacuum drying box at 85-95 ℃ to obtain the 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate.
7. The mat of claim 6, wherein the molar ratio of 2, 3-quinolinedicarboxylic acid, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, dimethylsulfoxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine is 1:1 (6-10): 0.8-1.2): 0.5.
8. A method of making an anti-blocking and anti-oxidant mat according to any one of claims 1 to 7, comprising the steps of:
s1, preparing functional fibers from 2, 3-quinoline dicarboxylic acid/2, 4-diamino-6-phenyl-1, 3, 5-triazine polycondensate through melt spinning, and weaving on a weaving machine by taking the functional fibers as weft yarns and coconut fibers as warp yarns to obtain a mat main body;
and S2, uniformly mixing the raw materials of the functional layer in parts by weight, coating the mixture on the surface of the mat main body, and drying to obtain the anti-adhesion and anti-oxidation mat.
9. The method for producing an anti-blocking and anti-oxidation mat according to claim 8, wherein the melt spinning in step S1 has a spinning temperature of 230 to 250 ℃, a spinning speed of 2200 to 3200m/min, a stretching temperature of 60 to 80 ℃ and a total stretching ratio of 3 to 5.
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| CN111607889A (en) * | 2020-05-29 | 2020-09-01 | 江兰春 | Antibacterial and mildew-proof fabric |
| CN111945286A (en) * | 2020-07-22 | 2020-11-17 | 邓生平 | Preparation method of antistatic breathable moisture-absorbing fabric |
| CN112812482A (en) * | 2020-12-30 | 2021-05-18 | 纪道红 | Anti-aging plastic material and preparation method thereof |
| CN112904510A (en) * | 2021-02-04 | 2021-06-04 | 高建东 | Fireproof flame-retardant plastic optical cable and preparation method thereof |
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| CN101781385A (en) * | 2009-01-16 | 2010-07-21 | 中国中化集团公司 | Benzotriazole water soluble polymer ultraviolet absorber and preparation method and application thereof |
| CN102268751A (en) * | 2011-05-28 | 2011-12-07 | 东华大学 | Ultraviolet-aging-resistant polyphenylene sulfide fibers and preparation method thereof |
| CN110512432A (en) * | 2019-07-15 | 2019-11-29 | 宁波东方席业有限公司 | A kind of oxidation resistant straw mats of resist blocking and that and preparation method thereof |
| CN111607889A (en) * | 2020-05-29 | 2020-09-01 | 江兰春 | Antibacterial and mildew-proof fabric |
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