CN103204989A - Method for preparing nylon 6 for fibers from hindered amine prepolymerization unit - Google Patents
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Abstract
The invention relates to a method for preparing nylon 6 for fibers from a hindered amine prepolymerization unit. The nylon 6 for fibers is formed by polymerizing caprolactam and the hindered amine prepolymerization unit in the mass ratio of 1000:(0.5-10). The hindered amine prepolymerization unit is generated by pre-condensing a piperidine derivative with a steric-hinerance effect and 6-aminocaproic acid in the presence of a catalyst, wherein the molar ratio of the piperidine derivative with the steric-hinerance effect to 6-aminocaproic acid to the catalyst is equal to 2:1:(0.1-0.3); the reaction temperature is 125-270 DEG C; and the reaction time lasts for 0.5-20 hours. By the method, the problems of nylon fiber yellowing and unstable quality can be effectively solved, and the obtained anti-yellowing nylon 6 for fibers is uniform in molecular weight distribution, good in viscosity stability, free of oxidization and ageing, and suitable for processing high-quality nylon fibers.
Description
Technical field
The present invention relates to a kind of preparation method of fiber usefulness nylon 6, relate in particular to a kind of method that is prepared fiber usefulness nylon 6 by hindered amine pre-polymerization unit.
Background technology
Along with the continuous expansion in China tynex market, the promotion that increased rapidly by the superfine denier fiber demand, to the production capacity of polymeric amide and synthetic quality, especially polyamide molecular weight distributes and has higher requirement.
Yellow be tynex produce with use in an important techniques problem existing, tracing it to its cause mainly contains following influence factor: light, heat cause that polymeric amide is aging, oxidation, cause chain rupture to be decomposed, thereby cause yellowing; Airborne oxynitrides causes the amino oxidation of polymeric amide, generates yellow substance, causes yellowing; Cause yellowing under the meta-alkalescence condition.
In order to solve the problems of the technologies described above, mainly take following measure at present in practice: for fear of alkaline condition, adopt citric acid as anti-yellow treatment agent; Generate nitro-compound in order to prevent airborne oxynitrides from causing the amino oxidation of polymeric amide, be combined by the positively charged ion of phenol xanthochromia agent on polymeric amide, seal its cation group, prevent the yellow substance precipitation that generates; Add hindered amine as the method for photostabilizer in order to suppress the photooxidation droping reaction, to adopt, suppress the photooxidation droping reaction by the number of ways such as energy of catching free radical, hydroperoxide decomposition and transmission excited state molecule.
Chinese invention patent ZL200510122192.4 discloses nylon 6/ poly methylene imine molecular composite material and preparation method thereof.This inventive features is to adopt para-amino benzoic acid phenyl ester or Toluene-2,4-diisocyanate for this matrix material, the 4-vulcabond carries out end-blocking to poly methylene imine and is prepared into the macromole activator, cause the ε-Ji Neixianan anionic ring-opening polymerization then, obtaining triblock copolymer is nylon 6/ poly methylene imine molecular composite material.This molecular composite material is because the employing of block copolymerization technology, improved the consistency of poly methylene imine and nylon-6 matrix body, improved the dispersion effect of poly methylene imine in nylon 6, material mechanical performance is greatly improved, and shock strength is 26.21kJ/m2 when tensile strength 85MPa.
Chinese invention patent application 201110114496.1 discloses a kind of ultra-fine sea-island fibre nylon 6 slice and manufacture method thereof.This invention is polymerized by hexanolactam and auxiliary agent, and the ratio of hexanolactam and auxiliary agent is 100:7-10, and described auxiliary agent is to be made in the 3-6:40-60:3-6:10-40 ratio by binary acids end-capping reagent, water, amine end-capping reagent, isophthaloyl piperylhydrazine.
Chinese invention patent ZL200410011153.2 discloses a kind of high impact strength nylon alloy and preparation method thereof.This invents described nylon alloy composition has nylon resin 60-85 weight part, Polyurethane Thermoplastic Elastomer 15-40 weight part, polymeric plasticizer 0.5-5 weight part.The preparation method is after each component is mixed in proportion, and adds in the duplex forcing machine; Control screw zones temperature is 150-250 ℃, and the control screw speed is in the 10-100rpm scope; Said polymeric plasticizer is the multipolymer that the polyamide 1010 reaction of hydroxy-end capped polyethylene glycol adipate and carboxy blocking makes.
Chinese invention patent ZL03115279.1 discloses the preparation method of super toughness, high visocity nylon 6 resin.This method may further comprise the steps: (1) carries out vacuum hydro-extraction to hexanolactam and catalyzer, obtain water content less than the caprolactam monomer of 300ppm, (2) add promotor, mix the back caprolactam monomer is carried out the open loop pre-polymerization, obtain prepolymer, (3) prepolymer is carried out mass polymerization, add the end-blocking auxiliary agent in the back fully in polymerization, described mass polymerization is with the successive reaction extrusion molding prepolymer to be carried out continuous bulk polymerization.
Chinese invention patent ZL200810020776.4 discloses a kind of preparation method of original position PI modified nylon composite material, step is: the first step: the preparation polyimide preformed polymer, 1-1.6:1 dianhydride/the diamine monomer that will have an ehter bond group is dissolved in the polar solvent in molar ratio, and stirring reaction at room temperature, then add the solvent refluxing cyclisation, remove the moisture in the system, add isocyanic ester, reaction obtains isocyanate-terminated PI macromole, add hexanolactam blocked isocyanate group, add methanol extraction and go out PI, washing and drying is standby afterwards, the amount that accounts for caprolactam monomer weight percent 5%-15% by PI adds in the hexanolactam melt maintenance system viscosity 0.02-1Pas; Second step: by the 50%-85% volume fraction carbon fiber is laid in the mould, preheating with NaOH, primary antioxidant, auxiliary antioxidant in proportion, mixes back injection mould home position polymerization reaction down at 90 ℃-120 ℃ and makes the FRP sheet material with the performed polymer of the first step manufacturing.
The nylon composite materials that Chinese invention patent application 201210091705.X discloses a kind of high temperature resistant nylon and had good fracture toughness property.This high temperature resistant nylon is to be prepared by 100 parts of aromatic dicarboxylic acids, 100-102 part aliphatie diamine, 2-4 part end-capping reagent and 1-2 part phosphorus-containing catalyst; Aromatic dicarboxylic acid wherein is made up of the terephthalic acid of 80-95% and the naphthalic acid of 5-20%; The nylon composite materials of this invention is to be prepared by 70-85 part high temperature resistant nylon, 15-25 part ethylene-octene copolymer and 0.5-13 part auxiliary agent.This invention is passed through elastomeric formulation content in the proportion optimization of phthalic acid and naphthalic acid in the nylon building-up process and the modified nylon process preferred, prepare a kind of big modified nylon materials of initial impact energy of rupture, can keep long-term operational characteristics and the life-span of material effectively.
Chinese invention patent application 201010564494.8 discloses a kind of high temperature resistant semi-aromatic nylon and preparation method thereof, with 75-95 part nylon salt, 0.2-0.8 part end-capping reagent, 0.1-0.6 part catalyzer, 0.5-1 part oxidation inhibitor, 0.1-0.5 part lubricant, 30-50 part deionized water joins and stirs in the polymermaking autoclave, the high temperature resistant nylon prepolymer that in the high pressure stirred autoclave, synthesizes, this prepolymer is successively melt extruded by twin screw extruder for twice, improved devolatilization efficient, shortened the tackify time, can make the smooth discharging of high-viscosity polymer in the reactor simultaneously; Successively adopt different extrusion temperatures, prevented the high temperature degradation of prepolymer.
Chinese invention patent application 201080035261.7 discloses a kind of improved nylon and method, this disclosure of an invention relates to polymkeric substance such as nylon 66, it has low yellow degree and outstanding retention of whiteness, and the increase that is used on the molecular weight wherein is unfavorable melt extrusion and injection-molded application.This polymkeric substance is the phosphorus compound inclusion that adopts by weight 150 to 300ppm amount, for example, and the preparation of sodium hypophosphite inclusion." end-blocking " additive that adds when polymerization is initial is as the existence of the additive that is selected from acetic acid, propionic acid, phenylformic acid or succsinic acid, and having alleviated unfavorable molecular weight effectively increases.
Hindered amine as light stabilizer (HALS) is the class additive of polymeric material very efficiently, is research kind maximum, with fastest developing speed in all kinds of photostabilizers.20th century, the mid-1970s was total to company's development by Japan three, and its light stabilising effect is 2～4 times of ordinary light stablizer, and hindered amine light stabilizer is nontoxic, raw material is easy to get, and is synthetic easy, has good consistency with many resins.
Chinese invention patent ZL201010600090.X discloses a kind of electric wire and cable jacket special-purpose nylon matrix material, the quality percentage composition of its contained component and each component is as follows: nylon 8 6%-96%, primary antioxidant 0.1%-2.0%, auxiliary antioxidant 0.1%-2.0%, lubricant releasing agent 0.1-2.0%, photostabilizer 0.1-2.0%, lubricant 0.1-2.0%, nucleator 0.1-2.0%, tackifier 0.3-2.0%, described primary antioxidant is selected phenolic antioxidant for use, and described auxiliary antioxidant is selected thio-2 acid dibasic acid esters or phosphorous acid ester for use, and described lubricant releasing agent is selected from calcium stearate, described photostabilizer is selected from hindered amine light stabilizer, described lubricant is selected the two ammonium stearate of ethylene for use, silicone powder or its composition, described nucleator is selected nanomete talc powder for use, and described tackifier are selected the nylon 6 that contains reactive group for use.Prescription is simple, and used each component is cheap and easy to get, and cost is lower, with termite-proof, the anti-mouse, wear-resisting, corrosion-resistant of the electric wire and cable jacket of this nylon composite materials preparation.
Chinese invention patent ZL92114759.7 discloses a kind of method for making that is used as the multipolymer that contains the hindered amine side group of photostabilizer, have 2 on the side chain of this photostabilizer, 2,6, the preparation method of the multipolymer of 6-tetramethyl-piperidyl (hindered amine) is by the 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine and α-vinyl monomer make by free radical precipitation process for copolymerization.Owing to replaced the aromatics organic solvent with aliphatics straight chain or naphthenic hydrocarbon in the copolymerization, not only eliminate the pollution of aromatic hydrocarbons, and simplified technology, improved yield.
Hindered amine uses in the method that the goods prescription is taked to mix interpolation usually as a kind of auxiliary agent at present.Although hindered amine has various advantages as photostabilizer in polymkeric substance, but because its consumption is few, it is inhomogeneous to certainly lead to mixing in melt-mixing, still be in free blend state with polymkeric substance, so, must cause disperseing inhomogeneous, and assemble the defective that produces owing to producing this additive, and then reduce polymer properties and limit its light stabilization.
Polymeric amide xanthochromia at above-mentioned existence, and to the pursuit of high-quality tynex, the invention discloses a kind of method that is prepared fiber usefulness nylon 6 by hindered amine pre-polymerization unit, so that it is good to obtain light fastness, product molecular weight distribution is even, good quality, the fiber that is conducive to process superfine denier fiber is with nylon 6.
Summary of the invention
The objective of the invention is in a kind of method that is prepared fiber usefulness nylon 6 by hindered amine pre-polymerization unit of exploitation, solve the nylon fiber yellow and the quality instability problem that exist in the prior art, obtain even molecular weight distribution simultaneously, viscosity stability is good, can prevent polymeric amide oxidation, aging, be suitable for processing the anti-yellow fiber nylon 6 of high-quality tynex.
The present invention adopts following technical scheme:
A kind ofly prepare fiber with the method for nylon 6 by hindered amine pre-polymerization unit, it is characterized in that:
(1) piperidine derivative and the 6-aminocaprolc acid with space steric effect is the ratio of 2:1 with the mol ratio, add in the reactor and mix, and the adding mol ratio is (0.1～0.3) catalyzer, under 125 ℃～270 ℃ temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour～20 hours, make hindered amine pre-polymerization unit.
(2) with hexanolactam and hindered amine pre-polymerization unit with mass ratio l000:(0.5～10) mixed, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 250 ℃～270 ℃ of prepolymerization temperature, under the condition that main polymerization temperature is 230 ℃～250 ℃, through polymerization in 2 hours～17 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
The piperidine derivative of described space steric effect is 4-amino-2,2,6,6-tetramethyl piperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines, 2,2,6,6-tetramethyl--4-piperidines is pure and mild 1,2,2,6, the mixture of one or more in 6-pentamethyl--4-piperidines alcohol.
Described catalyzer is one or more the mixture in acetic acid, propionic acid, hydrochloric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, the Zeo-karb.
The present invention compared with prior art has significant technical progress and tangible positively effect:
1, hindered amine is the organic amine compound that a class has steric restriction.Hindered amine has the good restraining effect to the photooxidation droping reaction of superpolymer and organic compound.Hindered amine is different with the mode of action of UV stabilizer, but suppresses the photooxidation droping reaction by the number of ways such as energy of catching free radical, hydroperoxide decomposition and transmission excited state molecule.The molecular weight of hindered amine initial production is little, and its thermotolerance and anti-extractibility are all poor.
With itself and 6-aminocaprolc acid condensation, can be by the amino 4-amino-2,2 of band, 6,6-tetramethyl piperidine or 4-amino-1,2,2,6, carboxyl condensation in 6-pentamethyl-piperidines and the 6-aminocaprolc acid molecule generates amido linkage, has sealed this carboxyl, the amino that obtains dissociating is conducive to follow-up polymerization process and grows to single direction; In like manner, 2,2,6,6-tetramethyl--4-piperidines alcohol or 1, carboxyl condensation in 2,2,6,6-pentamethyl--4-piperidines alcohol and the 6-aminocaprolc acid molecule, generate ester bond, sealed this carboxyl, the amino that obtains dissociating also is conducive to follow-up polymerization process and grows to single direction.Therefore, the hindered amine pre-polymerization unit of making can improve the molecular weight of hindered amine, and then improves its performance.On the other hand, hindered amine pre-polymerization unit is added in the hexanolactam reaction system, can be used as the center of chain reaction, in the series reaction process, be conducive to improve the homogeneity of the molecular weight distribution of polymeric amide.
2, owing on the termination of each bar nylon 6 molecular chain, all connect the hindered amine end group, therefore, can limit the problem of the issuable two-way extension of condensation polymerization process, can recently design product degree of polymerization according to feeding intake.
3, the nylon 6 that synthesizes according to the present invention owing to all connected the end group of hindered amine on the termination of each molecular chain, therefore, can improve its distributing homogeneity, can improve the stable ununiformity of light that produces under admixture.
In sum, the present invention can effectively solve nylon fiber yellow and quality instability problem by adopting above production technique, obtain even molecular weight distribution, viscosity stability is good, can prevent nylon oxidation, aging, is suitable for processing the anti-yellow fiber nylon 6 of high-quality nylon fiber.
Specific embodiments
The present invention is further described below in conjunction with embodiment:
Embodiment 1
(1) with 2 parts of 4-amino-2,2,6, the 6-tetramethyl piperidine adds in the reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.3 part of acetic acid, under 125 ℃ of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 20 hours, make hindered amine pre-polymerization unit.
(2) with hexanolactam and the hindered amine pre-polymerization unit mixed with mass ratio l000:3, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 250 ℃ of prepolymerization temperature, under the condition that main polymerization temperature is 230 ℃, through polymerization in 5 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
Embodiment 2
(1) with 2 parts of 4-amino-2,2,6, the 6-tetramethyl piperidine adds in the reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.1 part of sulfuric acid, under 150 ℃ of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 1 hour, make hindered amine pre-polymerization unit.
(2) with hexanolactam and the hindered amine pre-polymerization unit mixed with mass ratio l000:10, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 250 ℃ of prepolymerization temperature, under the condition that main polymerization temperature is 250 ℃, through polymerization in 2 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
Embodiment 3
(1) just 2 part 2,2,6,6-tetramethyl--4-piperidines alcohol adds in the reactor with 1 part of 6-aminocaprolc acid and mixes, and add 0.1 part of Phenylsulfonic acid, under 270 ℃ of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour, make hindered amine pre-polymerization unit.
(2) with hexanolactam and the hindered amine pre-polymerization unit mixed with mass ratio l000:0.5, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 270 ℃ of prepolymerization temperature, under 230 ℃ of conditions of main polymerization temperature, through polymerization in 14 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
Embodiment 4
(1) with 2 part 1,2,2,6,6-pentamethyl--4-piperidines alcohol adds in the reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.3 part of Zeo-karb, under 125 ℃ of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 15 hours, make hindered amine pre-polymerization unit.
(2) with hexanolactam and the hindered amine pre-polymerization unit mixed with mass ratio l000:1, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 270 ℃ of prepolymerization temperature, under 230 ℃ of conditions of main polymerization temperature, through polymerization in 17 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
Claims (5)
1. one kind prepares fiber with the method for nylon 6 by hindered amine pre-polymerization unit, it is characterized in that: described to prepare fiber by hindered amine pre-polymerization unit be to be polymerized by hexanolactam and hindered amine pre-polymerization unit with nylon 6, and the mass ratio of hexanolactam and hindered amine pre-polymerization unit is l000:(0.5～10).
2. according to claim 1ly prepare fiber with the method for nylon 6 by hindered amine pre-polymerization unit, it is characterized in that, described hindered amine pre-polymerization unit is existed down in catalyzer by the piperidine derivative with space steric effect and 6-aminocaprolc acid, generates through precondensation.The piperidine derivative of described space steric effect: 6-aminocaprolc acid: the mol ratio of catalyzer is 2:1:(0.1～0.3); Temperature of reaction is 125 ℃～270 ℃; Reaction times is 0.5 hour～20 hours.
3. the preparation method of hindered amine pre-polymerization according to claim 2 unit is characterized in that the piperidine derivative of described space steric effect is 4-amino-2,2,6,6-tetramethyl piperidine, 4-amino-1,2,2,6,6-pentamethyl-piperidines, 2,2,6,6-tetramethyl--4-piperidines pure and mild 1,2,2, the mixture of one or more in 6,6-pentamethyl--4-piperidines alcohol.
4. the preparation method of hindered amine pre-polymerization according to claim 2 unit, it is characterized in that described catalyzer is one or more the mixture in acetic acid, propionic acid, hydrochloric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, the Zeo-karb.
5. according to claim 1ly prepare fiber with the method for nylon 6 by hindered amine pre-polymerization unit, it is characterized in that, pass through following steps successively:
(1) piperidine derivative and the 6-aminocaprolc acid with space steric effect is the ratio of 2:1 with the mol ratio, add in the reactor and mix, and the adding mol ratio is (0.1～0.3) catalyzer, under 125 ℃～270 ℃ temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour～20 hours, make hindered amine pre-polymerization unit;
(2) with hexanolactam and hindered amine pre-polymerization unit with mass ratio l000:(0.5～10) mixed, carried by the volume pump metering, after the static mixer mixing, add pressurization prepolymerization-normal pressure master polymerization successive polymerization reactor and carry out polyreaction: 250 ℃～270 ℃ of prepolymerization temperature, under the condition that main polymerization temperature is 230 ℃～250 ℃, through polymerization in 2 hours～17 hours, obtain described fiber Nylon 6 by the preparation of hindered amine pre-polymerization unit, polymer melt is extruded tape continuously through melt metering pump then, through pelletizing, continuous extraction behind the nitrogen successive drying, obtains anti-yellow fiber nylon 6 slice.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN113056500A (en) * | 2018-11-20 | 2021-06-29 | 伍德依文达菲瑟有限责任公司 | Process for preparing polyamide 6 |
| CN114349957A (en) * | 2020-10-13 | 2022-04-15 | 华峰集团有限公司 | Preparation method of weather-aging-resistant polyamide resin |
| CN115125727A (en) * | 2022-07-25 | 2022-09-30 | 南通大学 | Yellowing-resistant fabric and preparation method thereof |
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| JP2001261819A (en) * | 2000-03-14 | 2001-09-26 | Unitika Ltd | Nylon 6 or copolymer thereof, and process for preparation thereof |
| CN1537139A (en) * | 2001-06-14 | 2004-10-13 | Light-stabilized polymers cmprising light-stabilizing moieties, articles therefrom and method of making the same |
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| US5618909A (en) * | 1995-07-27 | 1997-04-08 | Alliedsignal Inc. | Light stabilized polyamide substrate and process for making |
| JP2001261819A (en) * | 2000-03-14 | 2001-09-26 | Unitika Ltd | Nylon 6 or copolymer thereof, and process for preparation thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113056500A (en) * | 2018-11-20 | 2021-06-29 | 伍德依文达菲瑟有限责任公司 | Process for preparing polyamide 6 |
| CN113056500B (en) * | 2018-11-20 | 2023-12-08 | 伍德依文达菲瑟有限责任公司 | Process for the preparation of polyamide 6 |
| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN114349957A (en) * | 2020-10-13 | 2022-04-15 | 华峰集团有限公司 | Preparation method of weather-aging-resistant polyamide resin |
| CN114349957B (en) * | 2020-10-13 | 2023-10-03 | 华峰集团有限公司 | Preparation method of weather-resistant polyamide resin |
| CN115125727A (en) * | 2022-07-25 | 2022-09-30 | 南通大学 | Yellowing-resistant fabric and preparation method thereof |
| CN115125727B (en) * | 2022-07-25 | 2024-05-28 | 南通大学 | Yellowing-resistant fabric and preparation method thereof |
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