CN111423463B - Preparation method and application of reactive boron-containing flame retardant - Google Patents
Preparation method and application of reactive boron-containing flame retardant Download PDFInfo
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- CN111423463B CN111423463B CN202010453329.9A CN202010453329A CN111423463B CN 111423463 B CN111423463 B CN 111423463B CN 202010453329 A CN202010453329 A CN 202010453329A CN 111423463 B CN111423463 B CN 111423463B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 136
- 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 132
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 239000004327 boric acid Substances 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- -1 borate carboxylate Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 27
- 238000005096 rolling process Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- QFSNCROGCLRZHC-UHFFFAOYSA-N 2,3-dihydroxypropoxyboronic acid Chemical compound OCC(O)COB(O)O QFSNCROGCLRZHC-UHFFFAOYSA-N 0.000 claims 5
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 18
- 150000005846 sugar alcohols Polymers 0.000 abstract description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 239000004753 textile Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 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 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 108010022355 Fibroins Proteins 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
-
- 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
- D06M2101/10—Animal fibres
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method and application of a reactive boron-containing flame retardant, wherein the preparation method of the reactive boron-containing flame retardant comprises the following steps: firstly, carrying out esterification reaction on boric acid and polyhydric alcohol to obtain hydroxyl-containing polyhydric alcohol borate, and then carrying out esterification reaction on the polyhydric alcohol borate and polycarboxylic acid to obtain carboxyl-containing polyhydric alcohol borate carboxylate, namely the reactive boron-containing flame retardant; the application of the reactive boron-containing flame retardant is as follows: preparing a reactive boron-containing flame retardant into a solution, adjusting the pH value of the solution to be acidic, and finishing the silk fiber product by using the solution as a flame-retardant finishing liquid through a dipping-baking method, wherein the baking temperature is not lower than the temperature at which carboxyl in the reactive boron-containing flame retardant and amino and hydroxyl in silk fiber undergo covalent crosslinking reaction. The flame retardant synthesized by the invention has high flame retardant efficiency and is harmless to the environment, belongs to an environment-friendly flame retardant, and can be used for replacing halogen flame retardants. The silk fiber product prepared by the flame retardant has excellent flame retardant property and washing resistance.
Description
Technical Field
The invention belongs to the technical field of functional finishing of textiles, and relates to a preparation method and application of a reactive boron-containing flame retardant, in particular to a preparation method of a reactive boron-containing flame retardant and a method for flame-retardant finishing of silk fiber products by using the same.
Background
Textile products have been widely used in various fields of life, but also bring fire hazards to people. The indoor ornaments include bedding, carpet, curtain, wall cloth, etc., and a large number of textiles used on airplanes, trains and ships are inflammable articles. The burning of textiles can cause serious damage to the safety of human life and property. Harmful gases such as carbon monoxide, hydrogen cyanide, nitric oxide, ammonia and aldehydes generated by the combustion of textiles can also suffocate and even poison victims. In order to protect the safety of life and property of people, researchers develop a series of flame retardants to improve the flame retardant property of textiles. The traditional textile flame retardant is mainly halogen-containing flame retardant and phosphorus-containing flame retardant. The halogen flame retardant has good flame retardant effect, but is polluted in the using process to cause harm to human bodies, and is limited or even forbidden to be used along with the continuous improvement of environmental protection laws and regulations. The phosphorus flame retardant has good flame retardant effect, good flame retardant performance and durability of finished textiles, but has the problems of easy discoloration of fabrics, formaldehyde generation and the like. The boron flame retardant has the characteristics of good flame retardant performance, low toxicity, smoke suppression and the like, and accords with the development trend of non-halogenation and ecologization of the flame retardant. Boron resources in China are rich, most of the boron resources exist in the form of oxygen-containing compounds such as boric acid and the like, and the boron source has a good application prospect.
Boron flame retardants such as boric acid and borax are two ancient flame retardants, and were primarily used for flame-retardant finishing of cellulose fibers and protein fibers in the early days, and because of poor fastness to washing, their application to fabrics was limited to a certain extent and can only be used for non-durable flame-retardant finishing of fabrics (Zhao Xue, Zhu Ping, Zhang Jian Wao. flame-retardant research and development dynamics of boron flame retardants [ J ] dyeing and finishing technology, 2006,28(4): 9-12; Zhang Qianhua. flame-retardant finishing of modified borosilicate sol to real silk fabrics and its performance research [ D ]. Suzhou university, 2016).
Silk is an important protein fiber, has the excellent characteristics of good luster, comfortable wearing, ecological health care and the like, and is known as 'fiber queen'. At present, silk products are mostly used for making clothes, bedding, ornaments and the like, and most of developed national legislation stipulates that products such as evening dresses, interior decoration materials and the like must have a certain flame retardant function.
The boron flame retardant has wide application prospect in silk fiber products, but boric acid is easy to dissolve in water and is combined with silk fibers in a lack of covalent bonds, so that the flame-retardant silk fabric is not resistant to washing, and the actual application value of the flame-retardant silk fiber products is greatly reduced.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a reactive boron-containing flame retardant. The invention takes boric acid, polyalcohol and polycarboxylic acid as raw materials to prepare the reactive boron-containing flame retardant, and applies the reactive boron-containing flame retardant to the flame retardant modification of silk fiber products, and the reactive boron-containing flame retardant is combined with the silk fibers through firm covalent bonds. The flame-retardant silk fiber product prepared by the method has excellent flame-retardant effect and good washing resistance, and has important practical application value.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a reactive boron-containing flame retardant comprises the steps of carrying out esterification reaction on boric acid and polyhydric alcohol to obtain hydroxyl-containing polyhydric alcohol borate, and carrying out esterification reaction on the polyhydric alcohol borate and polycarboxylic acid to obtain carboxyl-containing polyhydric alcohol borate carboxylate to obtain the reactive boron-containing flame retardant.
According to the invention, carboxyl capable of being bonded with silk fiber is introduced into boric acid, so that the water washing resistance of the finally prepared flame-retardant silk fiber product is improved.
As a preferred technical scheme:
according to the preparation method of the reactive boron-containing flame retardant, under the high-temperature condition, boric acid radicals of boric acid and hydroxyl groups of polyhydric alcohol are subjected to esterification reaction, the molar ratio of the boric acid to the polyhydric alcohol is 1: 1-3, the esterification reaction temperature of the boric acid and the polyhydric alcohol is 130-150 ℃, the time is 1-3 hours, the esterification reaction temperature needs to reach a certain value to ensure that the esterification reaction is smoothly carried out, the esterification reaction temperature is not too high, otherwise, the polyhydric alcohol is boiled and volatilized, and the esterification reaction is not facilitated.
In the above method for preparing a reactive boron-containing flame retardant, the polyol is ethylene glycol, glycerol, pentaerythritol or mannitol.
According to the preparation method of the reactive boron-containing flame retardant, under a high temperature condition, residual hydroxyl groups in the polyol borate can be subjected to esterification reaction with carboxyl groups of the polycarboxylic acid, the molar ratio of the polyol borate to the polycarboxylic acid is 1-2.5: 1 (in the invention, compared with the polycarboxylic acid according to the theoretical yield of the polyol borate, the molar ratio of boric acid, the polyol and the polycarboxylic acid is about 1:2:1, the boric acid is reacted with the polyol, the polyol is slightly excessive, about two residual hydroxyl groups are contained in each borate molecule, then the excessive polyol borate is adopted to react with the polycarboxylic acid, each boric acid is ensured to correspond to 1 polycarboxylic acid molecule, the residual carboxyl groups in the polycarboxylic acid are also reacted with wool fibers), and the esterification reaction temperature of the polyol borate and the polycarboxylic acid is 130-150 ℃ and the esterification reaction time is 1-2 h.
In the above method for preparing the reactive boron-containing flame retardant, the polycarboxylic acid is citric acid or butanetetracarboxylic acid.
The invention also provides application of the reactive boron-containing flame retardant prepared by the preparation method of the reactive boron-containing flame retardant, the reactive boron-containing flame retardant is prepared into a solution, the pH value of the solution is adjusted to be acidic, and then the solution is used as a flame-retardant finishing liquid to finish silk fiber products by a dipping-baking method, wherein the baking temperature is not lower than the temperature at which carboxyl in the reactive boron-containing flame retardant and amino and hydroxyl in the silk fibers are subjected to covalent crosslinking reaction, and the silk fiber products are acid-resistant and alkali-resistant, so that the pH value of the finishing liquid is adjusted to be acidic during finishing.
According to the invention, the reactive boron-containing flame retardant is controlled to react with the silk fiber in the finishing process, so that the boron-containing flame retardant is not easy to remove by washing, and the washing resistance of the flame-retardant silk fiber product is obviously improved.
As a preferred technical scheme:
the use of a reactive boron-containing flame retardant as described above, comprising the steps of:
(1) dissolving a reactive boron-containing flame retardant in water to obtain a solution with the concentration of 50-300 g/L, wherein the concentration is too low, the flame retardant effect is poor, the concentration is too high, the flame retardant effect is good, but the waste is caused;
(2) regulating the pH value of the solution to 3-5 by using triethanolamine or a sodium hydroxide solution to obtain a flame-retardant finishing liquid, wherein the pH value of the finishing liquid is not too low, otherwise, the strong influence of the acid of the finishing liquid on the fabric is too large;
(3) the silk fiber product is soaked in the flame-retardant finishing liquid, redundant water is removed by rolling, the rolling residual rate is 90-110%, the higher rolling residual rate can ensure that the flame retardant content on the silk fiber product is higher, and the flame-retardant effect is better;
(4) and (3) performing pre-baking and baking treatment on the silk fiber product in sequence to obtain the flame-retardant silk fiber product.
The application of the reactive boron-containing flame retardant is that the silk fiber product is an electric spinning, double-crepe or crepe satin silk fiber fabric.
The application of the reactive boron-containing flame retardant comprises the steps of pre-drying at 60-90 ℃ for 3-8 min, baking at 140-160 ℃ for 2-5 min; the pre-drying temperature and time are selected as long as the drying effect can be achieved; the baking temperature and time are selected according to the following steps: the temperature is low, the time is short, and the degree of covalent crosslinking reaction between carboxyl in the reactive boron-containing flame retardant and amino and hydroxyl in the silk fiber is low; the temperature is high, the time is long, and the effect of covalent crosslinking reaction between carboxyl in the reactive boron-containing flame retardant and amino and hydroxyl in the silk fiber is good; the carboxyl in the reactive boron-containing flame retardant can well react with the amino and the hydroxyl in the silk fiber within the temperature and time range provided by the invention.
The invention mechanism is as follows:
boric acid molecules contain three borate radicals, and can perform esterification crosslinking reaction with hydroxyl of polyhydric alcohol such as glycerol to generate polyhydric alcohol borate, hydroxyl in the polyhydric alcohol borate can perform esterification crosslinking reaction with carboxyl of polycarboxylic acid at high temperature to synthesize a reactive boron-containing flame retardant, and carboxyl in the reactive boron-containing flame retardant and amino and hydroxyl in silk fibers generate covalent crosslinking reaction under high-temperature baking conditions, so that the silk fiber product is endowed with durable flame retardant performance, and the reactive boron-containing flame retardant can form a protective layer on the fiber surface in the thermal decomposition process to isolate heat and oxygen, so that the flame retardant performance of the silk product is improved.
Has the advantages that:
(1) the boric acid, the polyol and the polycarboxylic acid used in the invention have sufficient raw material sources and low toxicity, and the prepared reactive boron-containing flame retardant belongs to an environment-friendly flame retardant;
(2) the reactive boron-containing flame retardant prepared by the invention has high flame retardant efficiency and high reactivity of carboxyl in molecules, and can generate covalent crosslinking with silk fibers under a high temperature condition.
Drawings
FIG. 1 shows the carbon length of the flame-retardant silk crepe in example 1 and comparative example 1 of the present invention after washing with water for different times.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Preparation of reactive boron-containing flame retardant: uniformly mixing 24.8g of boric acid (0.4mol), 36.8g of glycerol (0.4mol) and 10.6g of sodium hypophosphite (0.1mol) in a 250mL triangular flask, reacting for 2 hours at 145 ℃ to obtain light yellow viscous liquid, adding 46.8g (0.2mol) of butane tetracarboxylic acid into the system, reacting for 1 hour at 130 ℃ to obtain a reactive boron-containing flame retardant, and purifying the flame retardant by adopting toluene;
(2) preparing a flame-retardant finishing liquid with the concentration of 300g/L by using the reactive boron-containing flame retardant, adjusting the pH value to 4 by using sodium hydroxide, soaking silk double-crepe in the finishing liquid for 10min, then soaking and rolling twice, wherein the rolling residue rate is 110%, then drying the silk double-crepe at 70 ℃ for 5min, then baking at 150 ℃ for 3min, and drying after washing.
Comparative example 1
Mixing 24.8g of boric acid (0.4mol), 36.8g of glycerol (0.4mol), 10.6g of sodium hypophosphite (0.1mol) and 46.8g of butane tetracarboxylic acid (0.2mol) in a beaker, preparing a flame-retardant finishing liquid with the concentration of 300g/L, adjusting the pH value to 4 by using triethanolamine, soaking and rolling a double-crepe silk in the finishing liquid for 10min, then soaking and rolling the double-crepe silk for two times, wherein the rolling residual rate is 110%, then drying the double-crepe silk at 70 ℃ for 5min, then drying the double-crepe silk at 150 ℃ for 3min, washing the double-crepe silk with water and then drying the double-crepe silk.
Example 2
(1) Preparation of reactive boron-containing flame retardant: the same as example 1;
(2) preparing a flame-retardant silk fabric: preparing a flame-retardant finishing liquid with the concentration of 150g/L by using the reactive boron-containing flame retardant, adjusting the pH value to 5 by using triethanolamine, soaking silk double-crepe in the finishing liquid for 10min, then soaking and rolling twice, wherein the rolling residual rate is 90%, then drying the silk double-crepe at 80 ℃ for 3min, then drying at 160 ℃ for 3min, washing with water and drying.
Example 3
(1) Preparation of reactive boron-containing flame retardant: uniformly mixing 24.8g of boric acid (0.4mol), 36.8g of glycerol (0.4mol) and 10.6g of sodium hypophosphite (0.1mol) in a 250mL triangular flask, reacting for 2 hours at 140 ℃ to obtain light yellow viscous liquid, adding 38.4g (0.2mol) of citric acid into the system, reacting for 2 hours at 150 ℃ to obtain a reactive boron-containing flame retardant, and purifying the flame retardant by adopting toluene;
(2) preparing a flame-retardant silk fabric: preparing a flame-retardant finishing liquid with the concentration of 100g/L by using the reactive boron-containing flame retardant, adjusting the pH value to 4 by using triethanolamine, soaking silk electric power spinning in the finishing liquid for 10min, then soaking and rolling twice, wherein the rolling residual rate is 90%, then drying the silk electric power spinning at 60 ℃ for 8min, then drying at 150 ℃ for 4min, and drying after washing.
Example 4
(1) Preparation of reactive boron-containing flame retardant: the same as in example 3;
(2) preparing a flame-retardant silk fabric: preparing a flame-retardant finishing liquid with the concentration of 200g/L by using the reactive boron-containing flame retardant, adjusting the pH value to 3 by using sodium hydroxide, soaking the fibroin crepe satin in the finishing liquid for 10min, then soaking and rolling twice, wherein the rolling residual rate is 100%, then drying the fibroin crepe satin at 80 ℃ for 4min, then baking at 145 ℃ for 5min, and drying after washing.
The flame retardant performance and the water washing resistance of the flame retardant silk fabrics prepared in examples 1-4 and comparative example 1 were tested.
The Limiting Oxygen Index (LOI) of the fabric is determined according to GB/T5454-1997 textile Combustion Performance test oxygen index method.
The carbon length of the fabric is measured according to the standard GB/T5455-2014 'determination of smoldering and afterflame time of the damage length of the textile in the vertical direction of the burning performance'.
The combustion performance of the fabric is evaluated according to the GB/T17591 and 2006 flame-retardant fabric standard.
The washing method of the flame-retardant silk fabric refers to AATCC 61-2006 accelerated test of washing fastness for household and commercial use.
The flame retardant properties of the flame retardant silk fabric were finally measured as follows:
as can be seen from the table, the unfinished silk fabric is completely burned in the vertical burning process, the carbon length is 30cm, which shows that the flame retardant property is poor, the LOI of the silk fabric finished by the reactive boron-containing flame retardant is increased from 23.6% of the unfinished silk fabric to more than 28.2%, the carbon length is obviously reduced, which shows that the flame retardant property of the flame retardant silk fabric is excellent.
As shown in Table 1 and figure 1, the reactive boron-containing flame retardant-finished silk fabric still can be self-extinguished in a vertical combustion test after being washed for 25 times by family water, and the carbon length is lower than 15.0cm and reaches B1Requirements for grade flame retardant properties. As shown in comparative example 1, the flame-retardant silk fabric of the simply-mixed flame-retardant system of boric acid and the like can have better flame-retardant performance, but the finished fabric loses the flame-retardant effect after being washed by water and has poor water washing resistance.
The results show that the silk fabric finished by the reactive boron-containing flame retardant has good flame retardant performance and washing resistance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a reactive boron-containing flame retardant is characterized by comprising the following steps: firstly, carrying out esterification reaction on boric acid and glycerol to obtain glycerol borate containing hydroxyl, and then carrying out esterification reaction on the glycerol borate and polycarboxylic acid to obtain glycerol borate carboxylate containing carboxyl, so as to obtain the reactive boron-containing flame retardant, wherein the esterification reaction temperature of the boric acid and the glycerol is 130-150 ℃, and the esterification reaction temperature of the glycerol borate and the polycarboxylic acid is 130-150 ℃; the polycarboxylic acid is citric acid or butanetetracarboxylic acid.
2. The method of claim 1, wherein the molar ratio of boric acid to glycerol is 1: 1-3, and the esterification reaction time of boric acid and glycerol is 1-3 h.
3. The preparation method of the reactive boron-containing flame retardant according to claim 1, wherein the molar ratio of the glycerol borate to the polycarboxylic acid is 1-2.5: 1, and the esterification reaction time of the glycerol borate and the polycarboxylic acid is 1-2 h.
4. The application of the reactive boron-containing flame retardant prepared by the preparation method of the reactive boron-containing flame retardant according to any one of claims 1 to 3 is characterized by comprising the following steps:
(1) dissolving a reactive boron-containing flame retardant in water to obtain a solution with the concentration of 50-300 g/L;
(2) regulating the pH value of the solution to 3-5 by using triethanolamine or a sodium hydroxide solution to obtain a flame-retardant finishing liquid;
(3) dipping the silk fiber product into the flame-retardant finishing liquid, and removing excessive water by rolling, wherein the rolling allowance is 90-110%;
(4) and (3) performing pre-baking and baking treatment on the silk fiber product in sequence to obtain the flame-retardant silk fiber product, wherein the baking temperature is not lower than the temperature at which the carboxyl in the reactive boron-containing flame retardant and the amino and hydroxyl in the silk fiber undergo covalent crosslinking reaction.
5. Use of a reactive boron-containing flame retardant according to claim 4, characterized in that the silk fiber product is an electro-spun, double-creped or crepe satin silk fiber fabric.
6. The use of the reactive boron-containing flame retardant according to claim 4, wherein the pre-baking temperature is 60-90 ℃, the pre-baking time is 3-8 min, the baking temperature is 140-160 ℃, and the baking time is 2-5 min.
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