CN111893750A - Preparation method of flame-retardant cotton fabric - Google Patents
Preparation method of flame-retardant cotton fabric Download PDFInfo
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- CN111893750A CN111893750A CN202010800638.9A CN202010800638A CN111893750A CN 111893750 A CN111893750 A CN 111893750A CN 202010800638 A CN202010800638 A CN 202010800638A CN 111893750 A CN111893750 A CN 111893750A
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- 239000004744 fabric Substances 0.000 title claims abstract description 128
- 229920000742 Cotton Polymers 0.000 title claims abstract description 107
- 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 66
- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 239000000571 coke Substances 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 229920000137 polyphosphoric acid Polymers 0.000 abstract description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 2
- 239000008103 glucose Substances 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WQZGKKKJIJFFOK-ZZWDRFIYSA-N L-glucose Chemical compound OC[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-ZZWDRFIYSA-N 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229960002761 levoglucose Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
-
- 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
- D06M13/322—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 nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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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
- 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
- D06M13/322—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 nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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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
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method of a flame-retardant cotton fabric, which comprises the following steps of pretreating a pure cotton fabric: mixing a silane coupling agent and a sodium hypophosphite solution to prepare a pretreatment solution, adjusting the pH value to 4-5 by using acetic acid, adding a pure cotton fabric, heating, taking out and baking; flame-retardant finishing of pure cotton fabric: preparing a water-alcohol mixed solution containing ammonium dihydrogen phosphate, EDC and NHS, immersing the pretreated cotton fabric, treating at 4 ℃, taking out, washing and drying. The invention utilizes phosphoric acid and polyphosphoric acid decomposed by the finishing agent after being heated to react with hydroxyl on the No. 6 carbon atom for dehydration, and then further carry out elimination reaction to form C ═ C double bond, thereby promoting the formation of the heat-insulating oxygen-insulating coke layer and fundamentally preventing the generation of the levorotatory glucose.
Description
Technical Field
The invention belongs to the technical field of flame retardance of cotton fabrics, and particularly relates to a preparation method of a flame-retardant cotton fabric.
Background
The cotton fabric is high in quality and low in price, is popular with people, and is widely applied to daily wear, building material application and the like. However, the cotton fabric is greatly limited in the application process because the main component of the cotton fabric is combustible cellulose, and the application range of the cotton fabric is limited. The combustion of cotton fabric is that the cotton fabric is heated to produce thermal cracking and oxidative cracking in the air to form levorotatory glucose monomer and produce combustible gas, and the heat released during the combustion process further decomposes the cellulose to form a cyclic process until the fabric is completely burnt.
Firstly, utilizing a silane coupling agent KH550 to pretreat a pure cotton fabric by a heating and dipping method; and then, performing flame retardant finishing on the pretreated cotton fabric by using ammonium dihydrogen phosphate as a main raw material through EDC/NHS catalytic reaction. The flame retardant mechanism is mainly characterized in that phosphoric acid and polyphosphoric acid decomposed by heating of a finishing agent are reacted with hydroxyl on a No. 6 carbon atom for dehydration in advance, and then elimination reaction is further carried out to form C-C double bonds, so that the formation of a heat-insulating oxygen-insulating coke layer is promoted, and the generation of levoglucose is fundamentally prevented. In addition, a large amount of phosphorus-oxygen free radicals are generated in the heating reaction process, and can capture active free radicals formed by decomposition of the pure cotton fabric, so that the chain reaction is effectively prevented from being carried out.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a preparation method of the flame-retardant cotton fabric.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing flame-retardant cotton fabric, wherein: pretreatment of pure cotton fabric: mixing a silane coupling agent and a sodium hypophosphite solution to prepare a pretreatment solution, adjusting the pH value to 4-5 by using acetic acid, adding a pure cotton fabric, heating, taking out and baking;
flame-retardant finishing of pure cotton fabric: preparing a water-alcohol mixed solution containing ammonium dihydrogen phosphate, EDC and NHS, immersing the pretreated cotton fabric, treating at 4 ℃, taking out, washing and drying.
As an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: mixing a silane coupling agent and a sodium hypophosphite solution to prepare a pretreatment solution, adjusting the pH value to 4-5 by using acetic acid, mixing a 9 wt% silane coupling agent KH550 aqueous solution and a 3 wt% sodium hypophosphite aqueous solution, and adjusting the pH value to 4.5 by using acetic acid.
As an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: adding pure cotton fabric, wherein the bath ratio is 1: 50.
as an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: the heating is carried out for 1h at 80 ℃.
As an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: taking out and baking for 5min at 170 ℃.
As an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: preparing a water-alcohol mixed solution containing ammonium dihydrogen phosphate, EDC and NHS, wherein the concentration of the ammonium dihydrogen phosphate is 25-30 wt%; the EDC is 5 wt% in concentration; the NHS concentration was 2.5 wt%.
As an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: the water-alcohol mixed solution is characterized in that the volume ratio of alcohol to water is 7: 3.
as an optimal scheme of the preparation method of the flame-retardant cotton fabric, the method comprises the following steps: the immersed pretreated cotton fabric is immersed in MES serving as a buffering agent according to a bath ratio of 1:50, and the pH value of the immersed cotton fabric is adjusted to 4.5.
The invention has the beneficial effects that: .
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the mechanism of condensation of silane coupling agents with themselves and their covalent bonding to cellulose.
FIG. 2 is the catalytic bonding mechanism for EDC/NHS.
FIG. 3 is an infrared spectrum of cotton fabric before and after flame retardant finishing.
FIG. 4 is an electron microscope image of the surface of cotton fiber before and after flame retardant finishing (a) raw cotton fabric (b) finished cotton fabric (c) raw cotton fabric burned and (d) finished cotton fabric burned.
FIG. 5 is an energy spectrum analysis chart of cotton fabric before and after flame retardant finishing after combustion (a) after finishing (b) before finishing.
FIG. 6 is a stress-strain curve of three cotton fabrics (1 for raw cotton fabric, 2 for pretreated cotton fabric, 3 for flame retardant finished fabric).
FIG. 7 is a TG analysis and DTG analysis chart before and after the flame retardant finishing of cotton fabrics.
FIG. 8 shows the results of a vertical burn test; (a) raw cotton fabric, (b) cotton fabric after flame retardant finishing, and (c) cotton fabric after 20 times of washing after flame retardant finishing.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Pretreatment of pure cotton fabric: preparing a pretreatment solution: silane coupling agent KH550(9 wt%, g/mL), sodium hypophosphite (3 wt%, g/mL), adjusting pH to 4.5 with acetic acid, mixing pure cotton fabric according to a bath ratio of 1:50 is immersed in the pretreatment solution, heated and stirred for 1h at 80 ℃, taken out and baked for 5min at 170 ℃ by a heat setting machine. FIG. 1 shows the mechanism of condensation of silane coupling agents with themselves and their covalent bonding to cellulose. The silicon ethoxy of KH550 is hydrolyzed into silicon hydroxyl in water, on one hand, the silicon hydroxyl can generate etherification reaction with hydroxyl on the number 6 carbon atom of the cotton fabric through the catalytic action to form Si-O-C combination; on the other hand, the silicon hydroxyl formed by the hydrolysis of KH550 can be condensed to form a macromolecular structure, and can form strong hydrogen bonding action and van der Waals force with cellulose. The combination of the two aspects can be firmly fixed on the cotton fiber.
Flame-retardant finishing of pure cotton fabric: preparing a water-alcohol mixed solution (alcohol: water 7: 3) containing 25 wt% of ammonium dihydrogen phosphate, 5 wt% of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and 2.5 wt% of NHS (N-hydroxysuccinimide), adjusting the pH to 4.5 by using MES as a buffering agent, immersing the pretreated cotton fabric in the mixed solution according to a bath ratio of 1:50, treating the cotton fabric at 4 ℃ for 24 hours, taking out the cotton fabric, washing the cotton fabric twice by cold water, and drying the cotton fabric to obtain a treated sample. FIG. 2 is the catalytic bonding mechanism for EDC/NHS.
And (3) performance characterization:
fourier infrared spectroscopy (IR): the change in chemical structure of the fabric before and after flame-retardant finishing was examined using a NEXUS-670 Fourier transform Infrared Spectroscopy (FTIR) instrument from NICOLET, USA.
Scanning Electron Microscopy (SEM) + energy spectral analysis (EDX): the change in the fiber microstructure of the fabric before and after flame-retardant finishing was examined, and the surface morphology of the sample was observed using a NovaNnanoSEM450 field scanning electron microscope (EESEM) by EFI corporation of usa, and surface element analysis was performed.
Limiting Oxygen Index (LOI): the limited oxygen index LOI was measured using an HC-2 type oxygen index measuring instrument (Jiangning district analytical instruments, China, Nanjing city) to evaluate the flame retardant properties of the finished fabric.
Thermogravimetric analysis: the thermal stability of the samples was measured using a NETZSCH thermogravimetric analyzer (navy corporation, germany), with a temperature rise rate of 10 ℃/min, air atmosphere.
Vertical burning test: the fabric was subjected to a combustion test using a VF-1 vertical combustion tester (Moistes combustion technology (China) Co., Ltd.), and the after-flame time and smoldering time were recorded.
And (3) mechanical property analysis: tensile break properties of the fabrics were measured using a CMT4304 miniaturised controlled electronic Universal tester (MTS Corp., USA).
The experimental results are as follows:
infrared analysis (IR): FIG. 3 shows the content of KH550 in 9% and NH in raw cotton fabric and flame-retardant finished cotton fabric4H2PO425% in amount, and, if not specified below, finished cotton fabrics are all products under these conditions). Wave number is 3300--1The broad peak is derived from the stretching vibration of O-H and N-H, is caused by hydroxyl of cotton fabric, amido of the cotton fabric modified by silane coupling agent and combined moisture, and is obviously O-H single peak before modification, and N-H double peak is increased after modification. 2940 and 2850cm-1The peaks at the left and right are the stretching vibration of saturated C-H, and 1100cm-1、1130cm-1And 1000cm-1Typical C-O and C-O-C absorption peaks are shown. The modified cotton fabric has a plurality of new characteristic absorption peaks at 1730cm-1A stretching vibration peak of C ═ O appears in the vicinity, and this is caused by residual NHS; at 1285cm-1And 720cm-1Characteristic absorption peaks of Si-O appear on the left and right; at 1235cm-1Characteristic absorption peaks of P ═ O appear on the left and right sides; 1570cm-1The C-N stretching vibration appears at the left and the right, and 1270cm-1The weak peaks on the left and right should belong to the C-N stretching vibration of secondary amines. The above data demonstrate the successful grafting of the flame retardant finish to cotton fibersAnd (4) dimension.
Scanning Electron Microscopy (SEM) + energy spectral analysis (EDX): as can be seen from fig. 4(a), the surface of the cotton fabric as it is relatively smooth, the roughness of the fiber surface after flame retardant finishing (fig. 4(b)) becomes large, and there is obvious adhesion of substances, indicating that the flame retardant finishing agent was successfully introduced. It can be seen from the electron microscope picture of fig. 4(c) that the damage of the fiber is serious after the raw cotton fabric is burnt, and the surface of the fiber (fig. 4(d)) after finishing has an obvious carbon layer, which has a better protection effect on the cotton fiber. FIG. 5 is a spectral analysis of burnt cotton fabric, from which it can be seen that the unfinished cotton fabric was only C, O after burning, while the finished cotton fabric had C, N, O, P, Si elements, of which the N content is low mainly because most of the N elements form N after burning2And NH3And volatilizes. This further confirms that the flame retardant finish bonds well with cotton fabrics.
And (3) mechanical property analysis: from FIG. 6, it can be analyzed that the tensile break strength of the fabric without the flame retardant treatment is 16.32 MPa; the tensile strength of the fabric pretreated by the silane coupling agent is 13.69 MPa; the tensile break strength of the flame retardant finish treated fabric was 11.73 MPa. The breaking strength of the fabric subjected to flame retardant finishing is reduced compared with that of the fabric not subjected to flame retardant finishing. Mainly because the flame retardant action is carried out under the weak acidic condition which can affect the 1, 4-glycosidic bond of the cellulose macromolecule chain to cause the reduction of the strength. In addition, chemical crosslinking during finishing may cause stress concentration at weak points on the fibers, resulting in a decrease in strength. It can also be seen from the figure that although the breaking strength of the fabric is somewhat reduced, the elongation at break does not vary much.
Thermogravimetric analysis: fig. 7 shows the weight loss of the original cloth and the fabric treated by the flame retardant in the range of 0-600 ℃ measured under the oxygen condition. Several characteristics can be found by analysis: the initial decomposition temperature of the flame-retardant finished cotton fabric is 303.52 ℃, while the initial decomposition temperature of the original cloth is 316.25 ℃, which shows that the flame retardant is decomposed before the fabric, and effective substances are released for flame retardance. By comparing the two thermogravimetric curves, the final residue rate of the flame-retardant treated fabric is 12.44%, the residue rate of the original fabric is 0.63%, and the residue rate of the flame-retardant treated fabric is far higher than that of the original fabric, which indicates that the flame-retardant finishing agent effectively promotes the formation of a carbon layer. As can be seen from the DTG curve, the first exothermic peak of the flame-retardant finished cotton fabric is slightly advanced, mainly due to the advanced decomposition of the finishing agent, and the second exothermic peak lags behind the original fabric, which shows that the flame retardant can delay the thermal degradation of the fabric. As can be seen from the DTG curve, the exotherm peak for the flame retardant treated fabric is much lower than for the original fabric, especially the second exotherm peak due to oxidative degradation. The flame retardant can reduce the degradation degree of macromolecular chains, and the TG curve can also show that the quality reduction gradient of the raw cotton fabric is higher than that of the cotton fabric after flame-retardant finishing.
And (3) analyzing the combustion performance: TABLE 1 variation of KH550 dosage and NH4H2PO4The influence of the concentration on the oxygen limiting index LOI, the oxygen limiting index of the cotton fabric is only 17.8, and the cotton fabric can reach 31.9 after finishing. It can be seen from the data in the table that as the amount of KH550 is increased, LOI begins to increase because the number of active sites on the cotton fabric that react with EDC/NHS to attach phosphorus groups increases, but too much KH550 may cause self-condensation addition polymerization, reducing its ability to react with the cotton macromolecular chains, and rather, causing a decrease in flame retardant effectiveness. With NH4H2PO4The increase in concentration, LOI generally tends to increase and then the increase tends to be gradual, since the number of active sites is limited and excess NH is present4H2PO4And do not bond effectively with cotton fibers. Selecting optimum conditions (KH550 dosage of 9% and NH)4H2PO425%) on cotton fabric, the LOI decreases somewhat, after 20 washes to 27.5 and after 50 washes to 25.1, after a subsequent washing treatment. Although the reduction was significant, it was still higher than the raw cotton fabric, indicating durable flame retardant performance.
TABLE 1 LOI under different conditions
The vertical burning test shows that the raw cotton fabric is easy to ignite when meeting fire, burns quickly until the fly ash is almost burnt out, and has the afterflame time of 17.4 seconds and the smoldering time of 42.6 seconds. The finished fabric is difficult to ignite, and is extinguished immediately after a fire source is removed, so that the phenomena of continuous combustion and smoldering are not obvious. After 20 times of washing, the flame retardant effect is good, the flame retardant agent is still difficult to ignite, and the flame retardant agent is extinguished immediately after a fire source is removed, so that the phenomena of continuous combustion and smoldering are not obvious. After burning, a remarkable carbon layer appears on the fabric, and fly ash is not burnt like the original cotton fabric. The flame retardant effect of the cotton fabric after 20 times of washing is reduced from the carbon length after combustion. FIG. 8 shows the results of a vertical burn test; fig. 8(a) raw cotton fabric, (b) flame retardant finished cotton fabric, (c) flame retardant finished cotton fabric after 20 washes.
In summary, the invention firstly utilizes silane coupling agent KH550 to pretreat the pure cotton fabric by a heating and dipping method; and then, performing flame retardant finishing on the pretreated cotton fabric by using ammonium dihydrogen phosphate as a main raw material through EDC/NHS catalytic reaction. The flame retardant mechanism is mainly characterized in that phosphoric acid and polyphosphoric acid decomposed by heating of a finishing agent are reacted with hydroxyl on a No. 6 carbon atom for dehydration in advance, and then elimination reaction is further carried out to form C-C double bonds, so that the formation of a heat-insulating oxygen-insulating coke layer is promoted, and the generation of levoglucose is fundamentally prevented. In addition, a large amount of phosphorus-oxygen free radicals are generated in the heating reaction process, and can capture active free radicals formed by decomposition of the pure cotton fabric, so that the chain reaction is effectively prevented from being carried out.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of flame-retardant cotton fabric is characterized by comprising the following steps: pretreatment of pure cotton fabric: mixing a silane coupling agent and a sodium hypophosphite solution to prepare a pretreatment solution, adjusting the pH value to 4-5 by using acetic acid, adding a pure cotton fabric, heating, taking out and baking;
flame-retardant finishing of pure cotton fabric: preparing a water-alcohol mixed solution containing ammonium dihydrogen phosphate, EDC and NHS, immersing the pretreated cotton fabric, treating at 4 ℃, taking out, washing and drying.
2. A method for preparing a flame retardant cotton fabric according to claim 1, characterized in that: mixing a silane coupling agent and a sodium hypophosphite solution to prepare a pretreatment solution, adjusting the pH value to 4-5 by using acetic acid, mixing a 9 wt% silane coupling agent KH550 aqueous solution and a 3 wt% sodium hypophosphite aqueous solution, and adjusting the pH value to 4.5 by using acetic acid.
3. A method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: adding pure cotton fabric, wherein the bath ratio is 1: 50.
4. a method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: the heating is carried out for 1h at 80 ℃.
5. A method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: taking out and baking for 5min at 170 ℃.
6. A method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: preparing a water-alcohol mixed solution containing ammonium dihydrogen phosphate, EDC and NHS, wherein the concentration of the ammonium dihydrogen phosphate is 25-30 wt%; the EDC is 5 wt% in concentration; the NHS concentration was 2.5 wt%.
7. A method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: the water-alcohol mixed solution is characterized in that the volume ratio of alcohol to water is 7: 3.
8. a method for preparing a flame retardant cotton fabric according to claim 1 or 2, characterized in that: the immersed pretreated cotton fabric is immersed in MES serving as a buffering agent according to a bath ratio of 1:50, and the pH value of the immersed cotton fabric is adjusted to 4.5.
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