CN115434142B - Preparation method of flame-retardant polyacrylonitrile fabric - Google Patents
Preparation method of flame-retardant polyacrylonitrile fabric Download PDFInfo
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- CN115434142B CN115434142B CN202211238299.5A CN202211238299A CN115434142B CN 115434142 B CN115434142 B CN 115434142B CN 202211238299 A CN202211238299 A CN 202211238299A CN 115434142 B CN115434142 B CN 115434142B
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- polyacrylonitrile fabric
- polyacrylonitrile
- flame retardant
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 178
- 239000004744 fabric Substances 0.000 title claims abstract description 170
- 239000003063 flame retardant Substances 0.000 title claims abstract description 124
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 53
- 238000010306 acid treatment Methods 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000002791 soaking Methods 0.000 claims abstract description 38
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 25
- 239000000467 phytic acid Substances 0.000 claims abstract description 25
- 229940068041 phytic acid Drugs 0.000 claims abstract description 25
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 25
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004246 zinc acetate Substances 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 4
- 150000002500 ions Chemical group 0.000 abstract description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 flame-retardant compound Chemical class 0.000 description 6
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920002972 Acrylic fiber Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application relates to a preparation method of flame-retardant polyacrylonitrile fabric, which comprises the steps of firstly carrying out acid treatment on the polyacrylonitrile fabric, wherein the acid treatment refers to soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature higher than the glass transition temperature of polyacrylonitrile for a certain time, then drying the polyacrylonitrile fabric to constant weight, sequentially and alternately soaking the polyacrylonitrile fabric subjected to the acid treatment in a polyethyleneimine solution and a phytic acid solution, taking out the polyacrylonitrile fabric after repeated operation for a plurality of times, and then soaking the polyacrylonitrile fabric in a zinc acetate solution for treatment to obtain the flame-retardant polyacrylonitrile fabric. According to the PAN fabric treated by the phytic acid, more active groups and negative ion groups are grafted on the surface, namely, -CN groups on the surface are subjected to acid hydrolysis to form carboxylic acid and phosphate groups, so that the surface of the fabric has electronegativity, the adhesion of the flame retardant is improved when the flame retardant is coated subsequently, the flame retardant washing fastness is improved, and finally the prepared flame retardant polyacrylonitrile fabric has good flame retardance and flame retardant washing fastness, excellent thermal stability and wide application prospect.
Description
Technical Field
The application belongs to the technical field of polyacrylonitrile fabrics, and relates to a preparation method of a flame-retardant polyacrylonitrile fabric.
Background
Although the polyacrylonitrile fiber has the advantages of softness, light weight, warmth retention and the like, the Limiting Oxygen Index (LOI) value of the polyacrylonitrile fiber is 17%, and the polyacrylonitrile fiber is extremely easy to burn when meeting fire. The industrialized nitril-chloridized fiber has good flame retardant property, but the fiber and the products thereof can emit a large amount of smoke and toxic hydrogen halide gas when being burnt, so that the popularization and the use of the nitril-chloridized fiber are greatly hindered.
The application patent CN 102936760A provides a method for synthesizing flame-retardant polyacrylonitrile fibers by grafting and blending, but the blending process may cause uneven dispersion of phosphorus-containing flame-retardant monomers, resulting in local defects of the overall flame-retardant and smoke-suppressing capabilities. CN 103451913A discloses a process for preparing ZnCl from polyacrylonitrile fibre with high content of 30-50 wt% 2 And (3) immersing the fiber in the mixed aqueous solution modifier of the acid, and then pre-oxidizing to obtain the polyacrylonitrile-based flame-retardant fiber. However, the tensile strength and the flame retardant property are still relatively poor, and the requirements in practical application cannot be met. Patent CN 106948172B discloses a method for obtaining flame-retardant fibers by immersing polyacrylonitrile fabric in a mixed solution of silane, phytic acid and urea for a period of time. However, this method has a problem that the flame retardant is poor in adhesion and is not washable. In patent CN 106988121A, the inventor firstly introduces glycidyl methacrylate on the surface of the fiber through an ultraviolet light grafting technology, and then accesses a phosphorus-containing group through amination and phosphorylation reaction, so that the method is complex in process and not suitable for large-scale popularization and application.
Therefore, how to form a multi-flame-retardant synergistic system and to be closely adhered to the surface of the polyacrylonitrile fabric so as to solve the problems of poor thermal stability, easy combustion and the like of the polyacrylonitrile fiber and the fabric, and has very important significance.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a preparation method of a flame-retardant polyacrylonitrile fabric.
In order to achieve the above purpose, the application adopts the following technical scheme:
the preparation method of the flame-retardant polyacrylonitrile fabric comprises the steps of sequentially and alternately soaking the Polyacrylonitrile (PAN) fabric subjected to acid treatment in a Polyethyleneimine (PEI) solution (with a bath ratio of 1:50) and a Phytic Acid (PA) solution (with a bath ratio of 1:50), repeating the operation for a plurality of times (each time when the Polyacrylonitrile (PAN) fabric is soaked in the polyethyleneimine solution and the phytic acid solution in sequence is regarded as one time), taking out, and then soaking in a zinc acetate solution (with a bath ratio of 1:50) for treatment to obtain the flame-retardant polyacrylonitrile fabric;
the acid treatment is to soak the polyacrylonitrile fabric in phytic acid solution with the temperature higher than the glass transition temperature of the polyacrylonitrile for a certain time, and then dry the fabric to constant weight (the drying temperature is 70-90 ℃, the drying time is required to be prolonged when the temperature is too low, and carbonization can be caused when the temperature is too high); the acid treatment temperature should be greater than the glass transition temperature of polyacrylonitrile, at which temperature the polyacrylonitrile chains are more mobile, facilitating the reaction between the acid and the inside of the fabric.
In the application, PA is used as acid treatment and phosphorus flame retardant, and mainly reacts with the surface groups of the fabric when being used as acid treatment, and is grafted with carboxylic acid groups, phosphoric acid groups and the like, so that the electronegativity of the surface of the fabric is beneficial to the assembly of PEI, the adhesive force of the flame retardant is increased, and the flame retardant washability is improved; as a flame retardant, a carbon layer is formed on the surface of the fabric during combustion, and heat conduction is blocked and oxygen is isolated. PEI is used as a flame-retardant compound agent and a nitrogen flame retardant, PEI has positive charges, can be subjected to electrostatic adsorption assembly with anions of PA, and has stronger adhesive force than that of directly coating the flame retardant; and PEI generates N when burned 2 And the like, and can dilute oxygen near the fabric and combustible gas generated by the combustion process of the fabric. The metal ions are used as the compound flame retardant, the metal ions can store a large amount of energy when in combustion, the generation of toxic gas is effectively prevented, the thermal stability of the fabric is integrally improved, and the PA, PEI and the metal ions have chelation, especially the PA, are extremely easy to chelate with the metal ions, and the metal ions can improve the thermal stability of the fabric, so that the flame retardant performance of the fabric can be increased from all directions by combining the metal ions.
The step of acid treatment of the fabric by the phytic acid is added to increase active groups such as-COOH and phosphoric acid on the surface of the fiber, thereby facilitating the assembly of the flame retardant. The PAN has the main CN group in the macromolecular chain, has stronger polarity and larger volume, lacks free hydrophilic groups, and has poor activity, so that the PAN fiber has poor hygroscopicity and poor flame retardant property. The glass transition temperature of the acrylic fiber is 80-100 ℃, and when the acrylic fiber is heated to 95 ℃, the activity of macromolecular chains in the acrylic fiber is strong, thereby being beneficial to the grafting of PAN.
If no grafting is carried out on the surface of PAN, the flame retardant is directly assembled layer by layer, no connection is formed between PA, PEI and PAN, and after the phytic acid is used for carrying out acid treatment on the fabric, active groups are grafted on the surface of the fiber, so that the adhesion of the flame retardant is facilitated, and the washability of the flame retardant and the addition amount of the flame retardant are increased.
As a preferable technical scheme:
according to the preparation method of the flame-retardant polyacrylonitrile fabric, the mass concentration of the polyethyleneimine solution is 1-15%, the mass concentration of the phytic acid solution is 5-15% (the concentration of the phytic acid solution used for acid treatment and flame-retardant finishing is in the range), and the mass concentration of the zinc acetate solution is 1-10%.
According to the preparation method of the flame-retardant polyacrylonitrile fabric, the phytic acid solution adopted by acid treatment is at the temperature of 92-98 ℃, the acid treatment temperature is lower than or higher than a set value, the number of grafted groups can be influenced, the temperature is optimal at 95 ℃, and at the moment, the maximum amount of carboxylic acid and phosphoric acid are grafted on the surface of the fabric.
According to the preparation method of the flame-retardant polyacrylonitrile fabric, the polyacrylonitrile fabric subjected to acid treatment is soaked in a polyethyleneimine solution or a phytic acid solution each time, washed by distilled water (bath ratio 1:100) and dried (drying temperature is 70-90 ℃).
According to the preparation method of the flame-retardant polyacrylonitrile fabric, the time of soaking the acid-treated polyacrylonitrile fabric in the polyethyleneimine solution or the phytic acid solution is 10-90 min each time, the time of washing with distilled water each time is not more than 5min, the drying temperature is 70-90 ℃, and the drying time is 30-90 min.
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following steps of: soaking in zinc acetate solution for 5-90 min, washing with distilled water (bath ratio 1:100), and drying (drying temperature is 70-90 ℃ and drying time is 15-90 min).
The preparation method of the flame-retardant polyacrylonitrile fabric comprises 10-30 times.
The preparation method of the flame-retardant polyacrylonitrile fabric has the advantages that the time is 0.5-1.5 h.
According to the preparation method of the flame-retardant polyacrylonitrile fabric, the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:15-20 during acid treatment, and the range of the mass ratio can ensure that the phytic acid aqueous solution just can infiltrate the fabric.
According to the preparation method of the flame-retardant polyacrylonitrile fabric, the LOI of the flame-retardant polyacrylonitrile fabric is 30-37%, and the LOI of the flame-retardant polyacrylonitrile fabric after 30 times of water washing is 25-29%;
the carbon residue rate of the flame-retardant polyacrylonitrile fabric at 900 ℃ under the air atmosphere is 20-40%;
the Heat Release Rate (HRR) of the flame-retardant polyacrylonitrile fabric is 128-228 kW/m 2 The Total Heat Release (THR) is 2.7-3.6 MJ/m 2 。
For LOI, the untreated PAN fabric is 17%, the PAN fabric coated with 10-30 layers of flame retardants is 20-25% after the untreated PAN fabric is subjected to acid treatment, and the modified PAN fabric coated with 10-30 layers of flame retardants is lifted to 30-37%;
for flame-retardant washability, the LOI of the PAN fabric which is not subjected to acid treatment for 10-30 layers of flame retardants is 21-23% after 30 times of water washing, and the LOI of the PAN fabric which is subjected to acid treatment for coating for 10-30 layers of flame retardants is 25-29% after 30 times of water washing;
for the carbon residue rate at 900 ℃ in the air atmosphere, the untreated PAN fabric is 3%, the PAN fabric directly coated with 10-30 layers of flame retardant is 5-10% after the non-acid treatment, and the modified PAN fabric coated with 10-30 layers of flame retardant is raised to 20-40%;
for a fabric Heat Release Rate (HRR), total Heat Release (THR), the HRR of untreated PAN fabric was 374kW/m 2 PAN fabric directly coated with 10-30 layers of flame retardant without acid treatment is 256-352 kW/m 2 The modified PAN fabric coated with 10-30 layers of flame retardant after acid treatment is reduced to 128-228 kW/m 2 The THR of the untreated PAN fabric was 7.5MJ/m 2 PAN fabric directly coated with 10-30 layers of flame retardant without acid treatment is 6.6-7.1 MJ/m 2 The modified PAN fabric coated with 10-30 layers of flame retardant after acid treatment is reduced to 2.7-3.6 MJ/m 2 。
The principle of the application is as follows:
the macromolecular chain of PAN mainly has-CN group, has stronger polarity and larger volume, lacks free hydrophilic group and is not easy to combine with flame retardant. The phytic acid has acidity, can be used as an acid treatment agent, has phosphate radical originally, has flame retardant property, and can be used as a flame retardant. According to the PAN fabric treated by the phytic acid, more active groups and negative ion groups are grafted on the surface, namely, -CN groups on the surface are subjected to acid hydrolysis to form carboxylic acid and carboxylic acid amine, and part of carboxylic acid and carboxylic acid amine are grafted with phosphate groups, so that the surface of the fabric has electronegativity, the adhesive force of the flame retardant is increased when the flame retardant is coated later, and the flame retardant washing resistance is improved. And the PAN fiber phytic acid hydrolysis product is mainly polyacrylic acid, other groups are fewer, and the hydrolysis time, the temperature and the like of PAN can be controlled, so that more carboxylic acid and phosphoric acid groups are grafted on the surface of PAN.
While most of the prior art treatments of PAN with acid are used for subsequent carbon fiber production, and also for dissolution recovery, or hydrolytic crosslinking to increase the strength of the fiber, no acid treatment is used for flame retardant modification.
The existing PAN is hydrolyzed by concentrated sulfuric acid, cyano groups in fibers are hydrolyzed into amide groups under the action of strong acid, then the amide groups are further hydrolyzed into carboxyl groups, along with the mass generation of the amide groups, the adjacent carboxyl groups and the amide groups undergo nucleophilic reaction to form an anhydride structure, and then the acid anhydride structure is rapidly hydrolyzed, but in the production process, the cost is high, and meanwhile, a large amount of alkali is needed for neutralization due to high industrial danger, and a large amount of waste water is generated to cause secondary pollution, so the PAN is rarely used in production.
The alkaline hydrolysis method is that in a water solution with a certain concentration, polyacrylonitrile is subjected to normal pressure hydrothermal treatment at 95-100 ℃ for several hours, and hydrophilic hydrolyzed polyacrylonitrile or acrylonitrile multi-component block copolymer is obtained. The alkaline hydrolysis of polyacrylonitrile is a partial hydrolysis, and the hydrolyzed end product mainly contains carboxyl, amido and unhydrolyzed cyano, and also contains a small amount of six-membered ring intermediates. The grafted groups of the product obtained by alkaline hydrolysis are disordered, and the cyano conversion rate is less than 100% due to the electrostatic repulsive effect of the ortho-groups. The carboxyl exists mainly in the form of sodium carboxylate under alkaline condition, and as sodium carboxylate is a strong electrolyte, hydrolysis products are easy to swell in water and even dissolve, so that hydrophilic groups are lost, and therefore, after PAN is subjected to alkaline hydrolysis, phosphoric acid flame retardant groups are grafted, and the flame retardant performance cannot be effectively improved; in addition, the fiber structure is destroyed in the reaction process, the order is reduced, the crystallinity is reduced, the fiber is easy to hydrolyze and rot, the strength is poor, and the mechanical property is reduced.
The beneficial effects are that:
(1) Compared with alkaline hydrolysis, acidic hydrolysis under certain conditions can effectively reduce the decline of the mechanical properties of the fibers, and more carboxylic acid can be grafted on the surface of the fabric by controlling the hydrolysis conditions;
(2) The phytic acid is a bio-based material, has higher flame-retardant phosphorus element content, has electronegativity, is strong acid, can be used as a flame retardant, is more environment-friendly than concentrated sulfuric acid used by conventional acidolysis, and can avoid secondary pollution;
(3) The polyethyleneimine is used as a nitrogen flame retardant, has cations, and can be chelated with metal ions when being self-assembled layer by layer with phytic acid, so that three compound flame retardant systems are successfully assembled together;
(4) Firstly, active groups are grafted on the surface of the fabric, then positive and negative ions and metal self-assembly are utilized, so that the problem of poor adhesive force of the post-treatment flame retardant is effectively increased, and the practicability of the fabric is improved;
(5) Compared with the conventional flame-retardant process, the application has the advantages of simple process and easy operation.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The water washing is carried out according to the GBT 3921-2008 standard.
The application adopts the following test method:
(1) LOI: LOI of the flame-retardant polyacrylonitrile fabric is tested by adopting a method of GB/T5454-1997 oxygen index method for testing the combustion performance of textiles;
(2) Carbon residue ratio: the carbon residue of the samples was tested at 900 ℃ using a thermogravimetric analyzer (TGA) under the following conditions: an air atmosphere, a flow rate of 40ml/min, and a heating rate of 20 ℃/min from 30 ℃ to 900 ℃;
(3) Heat Release Rate (HRR): testing the Heat Release Rate (HRR) of the flame-retardant polyacrylonitrile fabric by adopting a method of a cone calorimeter for measuring heat release rate of textiles imported and exported by SN/T5240-2020;
(4) Total Heat Release (THR): the Total Heat Release (THR) of the flame retardant polyacrylonitrile fabric was tested by the method of "cone calorimeter for determination of heat release rate of Inlet and outlet textiles" SN/T5240-2020.
Example 1
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature of 95 ℃ and the mass concentration of 10% for 1h, and then drying the polyacrylonitrile fabric at 80 ℃ to constant weight, thus finishing the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:20;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight is 1800) solution with the mass concentration of 10% (bath ratio is 1:50) and a phytic acid solution with the mass concentration of 10% (bath ratio is 1:50) for 30min each, washing with distilled water (bath ratio is 1:100) for 1min, drying at 80 ℃ for 30min, and repeating the steps of alternately soaking, washing and drying for 20 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 10% (the bath ratio is 1:50) for 30min, washing with distilled water (the bath ratio is 1:100) for 1min, and drying at 80 ℃ for 30min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 30%, the LOI of the flame-retardant polyacrylonitrile fabric after 30 times of washing is 25%, the carbon residue rate at 900 ℃ under the air atmosphere is 20%, and the heat release rate is 228kW/m 2 The total heat release was 3.6MJ/m 2 。
Comparative example 1
The preparation method of the flame retardant polyacrylonitrile fabric basically comprises the same steps as in example 1, except that the acid treatment in the step (1) is omitted;
the LOI of the prepared flame-retardant polyacrylonitrile fabric is 23%, the LOI after 30 times of water washing is 18%, the carbon residue rate at 900 ℃ under the air atmosphere is 13%, and the heat release rate is 277kW/m 2 The total heat release was 6.7MJ/m 2 。
Comparing comparative example 1 with example 1, it can be found that the LOI value of example 1, the LOI value after 30 times of washing, and the carbon residue ratio are significantly higher than those of comparative example 1, whereas the heat release rate and total heat release amount of example 1 are significantly lower than those of comparative example 1, because the PA-modified PAN fabric has active groups grafted on the surface, which is favorable for the attachment of flame retardant agent in layer-by-layer assembly.
Comparative example 2
The preparation method of the flame-retardant polyacrylonitrile fabric basically comprises the same steps as in example 1, wherein the steps (1) and (2) are as follows:
(1) Soaking the polyacrylonitrile fabric in NaOH solution with the temperature of 100 ℃ and the mass concentration of 3% for 1h, and then drying the polyacrylonitrile fabric at 80 ℃ to constant weight, thus finishing the alkali treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the NaOH solution is 1:20;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to alkali treatment in a phytic acid solution with the mass concentration of 10% (bath ratio of 1:50) and a polyethyleneimine (number average molecular weight of 1800) solution with the mass concentration of 10% (bath ratio of 1:50) for 30min each, washing with distilled water (bath ratio of 1:100) for 1min, drying at 80 ℃ for 30min, and repeating the steps of alternately soaking, washing and drying for 20 times;
the LOI of the prepared flame-retardant polyacrylonitrile fabric is 27%, the LOI after 30 times of water washing is 23%, the carbon residue rate at 900 ℃ under the air atmosphere is 13%, and the heat release rate is 253kW/m 2 The total heat release was 4.1MJ/m 2 。
Comparing comparative example 2 with example 1, it can be found that the LOI value of example 1, the LOI value after 30 times of water washing, and the carbon residue ratio are significantly higher than those of comparative example 2, whereas the heat release rate, the total heat release amount of example 1 are significantly lower than those of comparative example 2, because sodium carboxylate is easily swelled in water under alkaline conditions, and even dissolved, so that hydrophilic groups are lost, thereby affecting the subsequent flame retardant finishing.
Example 2
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature of 98 ℃ and the mass concentration of 5% for 0.5h, and then drying the polyacrylonitrile fabric to constant weight at 90 ℃ to finish the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:20;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight of 100000) solution with the mass concentration of 1 percent (bath ratio of 1:50) and a phytic acid solution with the mass concentration of 5 percent (bath ratio of 1:50) for 10 minutes, washing with distilled water (bath ratio of 1:100) for 2 minutes, drying at 90 ℃ for 60 minutes, and repeating the steps of alternately soaking, washing and drying for 10 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 1% (the bath ratio is 1:50) for 10min, washing with distilled water (the bath ratio is 1:100) for 2min, and drying at 90 ℃ for 60min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 37%, and the LOI of the flame-retardant polyacrylonitrile fabric after 30 times of water washing29%, a carbon residue at 900℃under an air atmosphere of 40% and a heat release rate of 128kW/m 2 The total heat release was 2.7MJ/m 2 。
Example 3
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature of 92 ℃ and the mass concentration of 15% for 1h, and then drying the polyacrylonitrile fabric to constant weight at 70 ℃ to finish the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:18;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight is 10000) solution with the mass concentration of 15% (bath ratio is 1:50) and a phytic acid solution with the mass concentration of 15% (bath ratio is 1:50) for 20min respectively, washing with distilled water (bath ratio is 1:100) for 3min, drying at 70 ℃ for 90min, and repeating the steps of alternately soaking, washing and drying for 30 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 5% (the bath ratio is 1:50) for 20min, washing with distilled water (the bath ratio is 1:100) for 3min, and drying at 70 ℃ for 90min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 35%, the LOI of the flame-retardant polyacrylonitrile fabric after 30 times of water washing is 28%, the carbon residue rate at 900 ℃ under the air atmosphere is 36%, and the heat release rate is 136kW/m 2 The total heat release was 2.9MJ/m 2 。
Example 4
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature of 94 ℃ and the mass concentration of 10% for 1.5h, and then drying the polyacrylonitrile fabric to constant weight at 80 ℃ to finish the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:15;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight is 10000) solution with the mass concentration of 5% (bath ratio is 1:50) and a phytic acid solution with the mass concentration of 10% (bath ratio is 1:50) for 60min respectively, washing with distilled water (bath ratio is 1:100) for 4min, drying at 80 ℃ for 30min, and repeating the steps of alternately soaking, washing and drying for 10 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 10% (the bath ratio is 1:50) for 60min, washing with distilled water (the bath ratio is 1:100) for 4min, and drying at 80 ℃ for 30min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 33%, the LOI of the flame-retardant polyacrylonitrile fabric after washing for 30 times is 27%, the carbon residue rate at 900 ℃ under the air atmosphere is 25%, and the heat release rate is 158kW/m 2 The total heat release amount was 3MJ/m 2 。
Example 5
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the temperature of 96 ℃ and the mass concentration of 10% for 1h, and then drying the polyacrylonitrile fabric at 80 ℃ to constant weight, thus finishing the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:20;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight is 10000) solution with the mass concentration of 10% (bath ratio is 1:50) and a phytic acid solution with the mass concentration of 10% (bath ratio is 1:50) for 90min respectively, washing with distilled water (bath ratio is 1:100) for 5min, drying at 80 ℃ for 30min, and repeating the steps of alternately soaking, washing and drying for 10 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 10% (the bath ratio is 1:50) for 90min, washing with distilled water (the bath ratio is 1:100) for 5min, and drying at 80 ℃ for 30min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 33%, and the flame-retardant polyacrylonitrile fabric is flame-retardant after 30 times of water washingThe LOI of the polyacrylonitrile fabric was 27%, the carbon residue at 900℃under an air atmosphere was 25%, and the heat release rate was 155kW/m 2 The total heat release was 2.9MJ/m 2 。
Example 6
The preparation method of the flame-retardant polyacrylonitrile fabric comprises the following specific steps:
(1) Soaking the polyacrylonitrile fabric in a phytic acid solution with the mass concentration of 10% at the temperature of 97 ℃ for 1h, and then drying the polyacrylonitrile fabric at the temperature of 80 ℃ to constant weight, thus finishing the acid treatment of the polyacrylonitrile fabric;
wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:20;
(2) Sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine (number average molecular weight is 10000) solution with the mass concentration of 10% (bath ratio is 1:50) and a phytic acid solution with the mass concentration of 10% (bath ratio is 1:50) for 30min respectively, washing with distilled water (bath ratio is 1:100) for 1min, drying at 80 ℃ for 30min, and repeating the steps of alternately soaking, washing and drying for 10 times;
(3) And (3) soaking the polyacrylonitrile fabric treated in the step (2) into a zinc acetate solution with the mass concentration of 10% (the bath ratio is 1:50) for 30min, washing with distilled water (the bath ratio is 1:100) for 1min, and drying at 80 ℃ for 30min to obtain the flame-retardant polyacrylonitrile fabric.
The LOI of the prepared flame-retardant polyacrylonitrile fabric is 34%, the LOI of the flame-retardant polyacrylonitrile fabric after 30 times of water washing is 27%, the carbon residue rate at 900 ℃ under the air atmosphere is 27%, and the heat release rate is 162kW/m 2 The total heat release was 2.8MJ/m 2 。
Claims (10)
1. A preparation method of flame-retardant polyacrylonitrile fabric is characterized by comprising the following steps: sequentially and alternately soaking the polyacrylonitrile fabric subjected to acid treatment in a polyethyleneimine solution and a phytic acid solution, repeating the operation for a plurality of times, taking out, and soaking in a zinc acetate solution for treatment to obtain the flame-retardant polyacrylonitrile fabric;
the acid treatment is to soak the polyacrylonitrile fabric in phytic acid solution with temperature higher than the glass transition temperature of polyacrylonitrile for a certain period of time and then dry the fabric to constant weight.
2. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the mass concentration of the polyethylenimine solution is 1-15%, the mass concentration of the phytic acid solution is 5-15%, and the mass concentration of the zinc acetate solution is 1-10%.
3. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the phytic acid solution used for the acid treatment has a temperature of 92-98 ℃.
4. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the acid-treated polyacrylonitrile fabric is washed with distilled water and dried after each immersion in a polyethyleneimine solution or phytic acid solution.
5. The method for preparing flame retardant polyacrylonitrile fabric according to claim 1, wherein the time of soaking the acid treated polyacrylonitrile fabric in the polyethylenimine solution or phytic acid solution is 10-90 min each time, the time of washing with distilled water each time is not more than 5min, the drying temperature is 70-90 ℃, and the drying time is 30-90 min.
6. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the step of immersing in a zinc acetate solution is: soaking in zinc acetate solution for 10-90 min, washing with distilled water and stoving.
7. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the number of times is 10 to 30.
8. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the certain time is 0.5-1.5 h.
9. The method for preparing a flame retardant polyacrylonitrile fabric according to claim 1, wherein the mass ratio of the polyacrylonitrile fabric to the phytic acid aqueous solution is 1:15-20.
10. The method for preparing the flame retardant polyacrylonitrile fabric according to claim 1, wherein the LOI of the flame retardant polyacrylonitrile fabric is 30-37%, and the LOI of the flame retardant polyacrylonitrile fabric after 30 times of water washing is 25-29%;
the carbon residue rate of the flame-retardant polyacrylonitrile fabric at 900 ℃ under the air atmosphere is 20-40%;
the heat release rate of the flame-retardant polyacrylonitrile fabric is 128-228 kW/m 2 The total heat release amount is 2.7-3.6 MJ/m 2 。
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| CN109942891B (en) * | 2019-03-12 | 2020-03-06 | 江南大学 | Phosphorus-nitrogen-zinc two-dimensional supermolecule coated molybdenum disulfide hybrid flame retardant and application thereof |
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| GB633441A (en) * | 1947-06-11 | 1949-12-19 | Andrew Mclean | Improvements in or relating to the flame-proofing of combustible materials |
| CN109183408A (en) * | 2018-08-15 | 2019-01-11 | 江南大学 | A kind of LBL self-assembly flame-proof cotton fabric and preparation method thereof |
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