CN114605459A - Boron-containing char-forming flame retardant, preparation thereof and application thereof in durable flame-retardant polyester fabric - Google Patents
Boron-containing char-forming flame retardant, preparation thereof and application thereof in durable flame-retardant polyester fabric Download PDFInfo
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- CN114605459A CN114605459A CN202210500731.7A CN202210500731A CN114605459A CN 114605459 A CN114605459 A CN 114605459A CN 202210500731 A CN202210500731 A CN 202210500731A CN 114605459 A CN114605459 A CN 114605459A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 155
- 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 149
- 239000004744 fabric Substances 0.000 title claims abstract description 76
- 229920000728 polyester Polymers 0.000 title claims abstract description 73
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 58
- 125000003172 aldehyde group Chemical group 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 claims description 17
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- OBQRODBYVNIZJU-UHFFFAOYSA-N (4-acetylphenyl)boronic acid Chemical compound CC(=O)C1=CC=C(B(O)O)C=C1 OBQRODBYVNIZJU-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 13
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 150000004753 Schiff bases Chemical class 0.000 description 21
- 239000002262 Schiff base Substances 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 235000010338 boric acid Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229920004934 Dacron® Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BSZSTDBZIAGKCF-UHFFFAOYSA-N B(O)(O)O.N1CCNCC1 Chemical compound B(O)(O)O.N1CCNCC1 BSZSTDBZIAGKCF-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- UUOQPSKNKUVOBO-UHFFFAOYSA-N boric acid;1h-imidazole Chemical compound OB(O)O.C1=CNC=N1 UUOQPSKNKUVOBO-UHFFFAOYSA-N 0.000 description 2
- -1 boron modified flame-retardant Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
-
- 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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- 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
Landscapes
- 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)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a boron-containing char-forming flame retardant, a preparation method thereof and application thereof in durable flame-retardant polyester fabrics
(R is H or CH)3) (ii) a Adding the boron-containing char-forming flame retardant into a mixed system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, baking at a high temperature, and carrying out durable flame-retardant finishing on the polyester fabric. The preparation method is simple and convenient, and the raw materials are nontoxic and easy to obtain; the boron-containing group, the benzene ring and the Schiff in the prepared boron-containing char-forming flame retardantThe alkali C = N structure is organically combined to construct a synergistic flame-retardant system, the boron-containing complex carbon residue with high thermal stability can be formed in the thermal decomposition process, and the effect of protecting the polyester fabric is achieved, so that the flame-retardant effect of the polyester fabric is improved, the flame-retardant efficiency is high, and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of flame-retardant polyester fabrics, and relates to a boron-containing charring flame retardant, a preparation method thereof and application thereof in durable flame-retardant polyester fabrics.
Background
Dacron is firm and durable, has good elasticity, is not easy to deform, resists corrosion, is insulating, stiff and smooth, is easy to wash and dry, and has low price, so that the Dacron is widely applied to industrial textiles, clothing and decorative fabrics. But the polyester fabric has the defect of flammability, and the phenomenon of molten drops is serious in the combustion process, so that the application of the polyester fabric is greatly limited. Therefore, it is very necessary to perform durable flame retardant finishing on polyester fabrics.
Under the consideration of the requirements of environmental protection, safety and the like, boron flame retardants have attracted attention and attention as important varieties of halogen-free environment-friendly flame retardants. However, the boron-containing flame retardant alone has poor flame retardant efficiency, and needs to be used in combination with other flame retardants to improve the flame retardant efficiency. In order to further improve the flame retardant effect, a flame retardant synergist is often required to be added, the catalytic carbonization effect is enhanced, the flame retardant efficiency is improved, and the using amount of the flame retardant is reduced.
The invention patent CN113277995A discloses a preparation method of a flame-retardant synergist of piperazine borate and imidazole borate, wherein boric acid, piperazine and imidazole are used for preparing the flame-retardant synergist through an ionic bond reaction, and the flame-retardant synergist is compounded with melamine polyphosphate and diethyl aluminum hypophosphite to improve the flame-retardant property of a nylon 66 material, but the flame-retardant property of the nylon 66 material cannot be effectively improved by the single piperazine borate and imidazole borate flame-retardant synergist because the boron-containing synergistic flame retardant has poor flame-retardant efficiency and cannot play a catalytic carbonization effect.
Schiff bases are compounds containing C = N structures, and have high thermal stability and biocompatibility. The invention patent CN10307372A discloses a polyphosphonate intumescent flame retardant and a preparation method thereof, wherein the polyphosphonate intumescent flame retardant comprises a Schiff base structure, but the Schiff base structure does not contribute to the flame retardant effect. The invention patent CN106008933A discloses a phosphorus-containing Schiff base structure-containing flame retardant and a preparation method thereof, wherein the phosphorus-containing flame retardant and a triazine ring charring agent have higher charring performance, and the Schiff base structure of the flame retardant improves the biological performance of the flame retardant but does not help the flame retardant performance. The invention patent CN107778437A discloses a boron modified flame-retardant antibacterial polyurethane emulsion containing a Schiff base structure and a preparation method thereof, wherein a boron-containing flame retardant has a flame-retardant effect, but the flame-retardant effect of a flame-retardant polyurethane film is poor, and the flame-retardant polyurethane emulsion can not pass a vertical combustion test when being used for a textile coating, wherein the Schiff base structure only has an antibacterial effect, and the flame-retardant property is not improved.
Therefore, it is a technical problem how to develop an efficient flame retardant system by using a boron-containing flame retardant, and how to improve the thermal stability of carbon residue by adopting a Schiff base structure so as to improve the flame retardant performance instead of simply improving the biocompatibility of the flame retardant and use the flame retardant in preparing durable flame retardant polyester fabrics.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a boron-containing charring flame retardant, a preparation method thereof and application thereof in durable flame-retardant polyester fabrics.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a boron-containing char-forming flame retardant has the following chemical structure:
in the formula, R is H or CH3。
The invention also provides a preparation method of the boron-containing char-forming flame retardant, which comprises the following steps:
(1) dissolving aldehyde group-containing phenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting for a certain time at a certain temperature; the aldehyde group-containing phenylboronic acid is p-aldehyde phenylboronic acid or p-acetylphenylboronic acid;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), raising the temperature to a certain temperature, reacting for a certain time, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant.
As a preferred technical scheme:
according to the method, the molar ratio of the aldehyde group-containing phenylboronic acid to the p-aminobenzamide in the step (1) is 2-2.2: 1, wherein two amino groups in a molecule of the p-aminobenzamide and two aldehyde groups containing the aldehyde group-containing phenylboronic acid are subjected to Schiff base reaction, and the two moles of the aldehyde group-containing phenylboronic acid are grafted on two sides of a benzene ring of the p-aminobenzamide; the boric acid containing aldehyde group is slightly excessive, so that the p-aminobenzamide can be completely reacted to generate a target structure compound; the proportion of the ethanol to the aldehyde group-containing phenylboronic acid is 1-2 ml:1g, the addition of the ethanol promotes the aldehyde group-containing phenylboronic acid to be dissolved, the aldehyde group-containing phenylboronic acid can be well dissolved in the provided range, and the excessive aldehyde group-containing phenylboronic acid is wasted; the volume ratio of the ethanol to the distilled water is 1-1.5: 1.
According to the method, in the step (1), the reaction temperature is 60-70 ℃, the reaction time is 60-90 min, the aldehyde group-containing phenylboronic acid and the p-aminobenzamide have higher reaction rate within the provided reaction temperature and time, and the boiling point and volatilization condition of ethanol are considered.
According to the method, in the step (2), the molar ratio of the 1, 3-dichloropropanol to the aldehyde group-containing phenylboronic acid is 1-1.2: 1, and nucleophilic substitution reaction is carried out on two chlorine active groups of the 1, 3-dichloropropanol and two boric acids of the aldehyde group-containing phenylboronic acid to generate the six-membered ring borate structure.
According to the method, in the step (2), the reaction temperature is 60-70 ℃, and the reaction time is 50-70 min.
The method has the advantages that the pressure of the reduced pressure distillation in the step (2) is 30-40 kPa, and the temperature is 40-50 ℃.
The invention also provides the application of the boron-containing charring flame retardant in the durable flame-retardant polyester fabric, the boron-containing charring flame retardant is added into a mixed system of water and ethanol and uniformly mixed to obtain a finishing liquid, then the polyester fabric is immersed into the finishing liquid, the polyester fabric is immersed twice and rolled twice within 15min, and then the durable flame-retardant polyester fabric is prepared through pre-drying and baking treatment.
As a preferred technical scheme:
according to the application, the content of the boron-containing charring flame retardant in the finishing liquid is 150-200 g/L, the flame retardant content is high, the flame retardant effect is good, but the excessive content is wasted;
the dosage ratio of the ethanol to the boron-containing char-forming flame retardant is 2-3 mL:1g, the ethanol is used for dissolving the boron-containing char-forming flame retardant, the boron-containing char-forming flame retardant can be effectively dissolved by the dosage ratio provided by the invention, and the consumption is high, so that the waste is caused.
According to the application, after twice repeated padding, the padding rate of the polyester fabric is 80-100%, the padding rate is high, the content of the flame retardant on the fabric is high, and the flame retardant effect is improved, but the content is too high, the flame retardant on the fabric is saturated, the content of the flame retardant on the fabric cannot be further improved, and waste is caused;
the pre-drying temperature is 60-80 ℃, the pre-drying time is 3-4 min, the baking temperature is 120-130 ℃, the baking time is 3-5 min, the baking temperature is not lower than the vitrification temperature of terylene, the macromolecule chain segment of the terylene fiber can be effectively opened in the provided temperature range, the diffusion of the fire retardant into the fiber is promoted, and energy is wasted if the temperature is too high.
By the application, the damage length of the durable flame-retardant polyester fabric is not more than 11.2cm, no molten drops exist, the carbon residue at 700 ℃ is not less than 20% (the carbon residue of the unfinished polyester fabric is 10%), the damage length of the flame-retardant polyester fabric after 20 times of washing is not more than 14.2cm, and the durable flame-retardant polyester fabric has better char formation performance, flame retardance and washing resistance.
The principle of the invention is as follows:
boric acid is generated in the pyrolysis process of the boron-containing group in the boron-containing char-forming flame retardant, so that the boron-containing group has the catalytic char-forming capability; under the catalysis of boric acid, firstly decomposing polyol in a borate six-membered ring structure to form boron-containing carbon residue; under the catalysis of high temperature and boric acid, Schiff base structure decomposition is carried out, the decomposition of benzene ring connected with the Schiff base structure is promoted, the decomposition products of the Schiff base structure and the benzene ring form a nitrogen-containing heterocyclic structure, and boron-containing complex carbon residue is gradually formed to cover the surface of the polyester fabric; the Schiff base and the nitrogen-containing heterocyclic ring structure carbon residue formed by the benzene rings connected with the Schiff base have high thermal stability, the thermal stability of the boron-containing complex carbon residue is improved, the boron-containing complex carbon residue with high thermal stability can isolate the effects of heat and oxygen, the flame retardant property of the polyester fabric is improved, the benzene rings without flame retardant effect and the Schiff base C = N structure improve the flame retardant effect of boron-containing groups, so that the boron-containing groups, the benzene rings and the Schiff base C = N structure are organically combined to construct a synergistic flame retardant system, and the flame retardant efficiency is high;
the Schiff base C = N structure is generated by Schiff base reaction between aldehyde group in the aldehyde group-containing phenylboronic acid molecule and amino group in the p-aminobenzamide molecule; then, carrying out nucleophilic substitution reaction on active chlorine in 1, 3-dichloropropanol molecules and phenyl boronic acid containing aldehyde groups to generate six-membered cyclic borate; the carbon flame retardant molecule formed by the boron, benzene ring and Schiff base contains boron group, benzene ring and Schiff base C = N structure connected with the benzene ring, and has good flame retardant effect; the boron-containing char-forming flame retardant contains a six-membered ring borate and benzene ring structure, has good linearity, is similar to the structure of polyester macromolecular chain segment polyethylene terephthalate, and is combined with the polyester macromolecular chain segment by a similarity and intermiscibility principle; under the effect of high temperature, the dacron macromolecule chain segment is opened, and the fire retardant diffuses into the inside of the fiber macromolecule chain segment and is fixed inside the fiber after cooling, so that the fire-retardant dacron fabric has higher fire resistance and water washing resistance.
Has the beneficial effects that:
(1) according to the boron-containing char-forming flame retardant disclosed by the invention, a boron-containing group, a benzene ring and a Schiff base C = N structure are organically combined to construct a synergistic flame-retardant system, and boron-containing complex carbon residue with high thermal stability can be formed in a thermal decomposition process, so that a polyester fabric is protected, the flame-retardant effect of the polyester fabric is improved, and the flame-retardant efficiency is high;
(2) the boron-containing char-forming flame retardant has the advantages of simple and convenient synthesis method, nontoxic and easily-obtained raw materials, and better biocompatibility, and belongs to an environment-friendly halogen-free flame retardant;
(3) the boron-containing char-forming flame retardant molecule contains a six-membered ring borate and benzene ring structure, has good linearity, is combined with a polyester macromolecule chain segment through a similar intermiscibility principle, has good compatibility with polyester fabrics, and has a durable flame-retardant function and a wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a boron-containing char-forming flame retardant according to the present invention.
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 can be made by those skilled in the art after reading the contents of the present invention, and those equivalents also fall within the scope of the invention defined by the appended claims.
The test method adopted by the invention is as follows:
(1) testing the carbon residue: testing the residual carbon content of the flame-retardant polyester fabric and the unfinished polyester fabric by adopting a thermal analysis testing method under the condition of nitrogen;
(2) and (3) testing the flame retardance: the damage length of the fabric is measured according to the standard GB/T5455-2014 'measurement of smoldering and afterflame time of the damage length in the vertical direction of the textile combustion performance';
(3) water resistance test method: the washing method of the flame-retardant polyester fabric is referred to AATCC 61-2006 accelerated test of wash fastness for household and commercial use.
Example 1
A preparation method of a boron-containing char-forming flame retardant is shown in figure 1, and specifically comprises the following steps:
(1) dissolving p-aldehyde phenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting for 90min at 60 ℃;
wherein the molar ratio of the p-aldehyde phenylboronic acid to the p-aminobenzamide is 2: 1; the ratio of ethanol to p-aldehyde phenylboronic acid is 1ml:1 g; the volume ratio of the ethanol to the distilled water is 1: 1;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), heating to 60 ℃, reacting for 70min, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant;
wherein the molar ratio of the 1, 3-dichloropropanol to the aldehyde phenylboronic acid is 1: 1; the pressure of reduced pressure distillation is 30kPa, and the temperature is 50 ℃;
the chemical structural formula of the prepared boron-containing char-forming flame retardant is as follows:
example 2
The preparation method of the boron-containing char-forming flame retardant specifically comprises the following steps:
(1) dissolving p-acetylphenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting at 70 ℃ for 60 min;
wherein the molar ratio of the p-acetylphenylboronic acid to the p-aminobenzamide is 2.2: 1; the ratio of ethanol to p-acetylphenylboronic acid is 2ml:1 g; the volume ratio of the ethanol to the distilled water is 1.5: 1;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), heating to 70 ℃, reacting for 60min, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant;
wherein the molar ratio of the 1, 3-dichloropropanol to the p-acetylphenylboronic acid is 1.2: 1; the pressure of reduced pressure distillation is 40kPa, and the temperature is 40 ℃;
the chemical structural formula of the prepared boron-containing char-forming flame retardant is as follows:
example 3
The preparation method of the boron-containing char-forming flame retardant specifically comprises the following steps:
(1) dissolving p-aldehyde phenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting for 80min at 65 ℃;
wherein the molar ratio of the p-aldehyde phenylboronic acid to the p-aminobenzamide is 2.1: 1; the ratio of ethanol to p-aldehyde phenylboronic acid is 1.5ml:1 g; the volume ratio of the ethanol to the distilled water is 1.3: 1;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), heating to 65 ℃, reacting for 70min, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant;
wherein the molar ratio of the 1, 3-dichloropropanol to the p-aldehyde phenylboronic acid is 1.1: 1; the pressure of reduced pressure distillation is 35kPa, and the temperature is 45 ℃;
the chemical structural formula of the prepared boron-containing char-forming flame retardant is as follows:
example 4
The preparation method of the boron-containing char-forming flame retardant specifically comprises the following steps:
(1) dissolving p-acetylphenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting at 60 ℃ for 90 min;
wherein the molar ratio of the p-acetylphenylboronic acid to the p-aminobenzamide is 2.2: 1; the ratio of ethanol to p-acetylphenylboronic acid is 2ml:1 g; the volume ratio of the ethanol to the distilled water is 1.3: 1;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), heating to 70 ℃, reacting for 70min, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant;
wherein the molar ratio of the 1, 3-dichloropropanol to the p-acetylphenylboronic acid is 1.2: 1; the pressure of reduced pressure distillation is 40kPa, and the temperature is 50 ℃;
the chemical structural formula of the prepared boron-containing char-forming flame retardant is as follows:
example 5
A preparation method of durable flame-retardant polyester fabric specifically comprises the following steps:
adding the boron-containing char-forming flame retardant prepared in the example 1 into a mixed system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, soaking and rolling the polyester fabric twice within 15min, and then pre-drying and baking to prepare the durable flame-retardant polyester fabric;
wherein the content of the boron-containing char-forming flame retardant in the finishing liquid is 150 g/L; the proportion of the consumption of the ethanol and the boron-containing char-forming flame retardant is 3mL to 1 g; the rolling residual rate of the polyester fabric after twice repeated padding is 100 percent; the pre-drying temperature is 60 ℃, and the pre-drying time is 4 min; the baking temperature is 130 ℃, and the baking time is 3 min;
the damage length of the prepared durable flame-retardant polyester fabric is 11.2cm, no molten drops exist, the carbon residue at 700 ℃ is 20% (the carbon residue at 700 ℃ of the unfinished polyester fabric is 10%), the damage length of the flame-retardant polyester fabric after 20 times of washing is 14.2cm, and the durable flame-retardant polyester fabric has good char forming performance, flame retardant performance and washing resistance.
Example 6
A preparation method of durable flame-retardant polyester fabric specifically comprises the following steps:
adding the boron-containing char-forming flame retardant prepared in the embodiment 2 into a mixed system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, soaking and rolling the polyester fabric twice within 15min, and then pre-drying and baking to prepare the durable flame-retardant polyester fabric;
wherein the content of the boron-containing char-forming flame retardant in the finishing liquid is 160 g/L; the proportion of the using amount of the ethanol and the boron-containing char-forming flame retardant is 2.5mL to 1 g; the rolling allowance rate of the polyester fabric after twice repeated padding is 90 percent; the pre-drying temperature is 70 ℃, and the pre-drying time is 4 min; the baking temperature is 130 ℃, and the baking time is 4 min;
the damage length of the prepared durable flame-retardant polyester fabric is 10.8cm, no molten drop exists, the carbon residue at 700 ℃ is 23%, the damage length of the flame-retardant polyester fabric after 20 times of washing is 13.5cm, and the durable flame-retardant polyester fabric has better char forming performance, flame retardant performance and washing resistance.
Example 7
A preparation method of durable flame-retardant polyester fabric specifically comprises the following steps:
adding the boron-containing char-forming flame retardant prepared in the embodiment 3 into a mixed system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, soaking and rolling the polyester fabric twice within 15min, and then pre-drying and baking to prepare the durable flame-retardant polyester fabric;
wherein the content of the boron-containing char-forming flame retardant in the finishing liquid is 180 g/L; the proportion of the using amount of the ethanol and the boron-containing char-forming flame retardant is 2.5mL to 1 g; the rolling residual rate of the polyester fabric after twice repeated padding is 100 percent; the pre-drying temperature is 70 ℃, and the pre-drying time is 3 min; the baking temperature is 120 ℃, and the baking time is 5 min;
the damage length of the prepared durable flame-retardant polyester fabric is 10.3cm, no molten drop exists, the carbon residue at 700 ℃ is 25%, the damage length of the flame-retardant polyester fabric after 20 times of washing is 13.1cm, and the durable flame-retardant polyester fabric has better char forming performance, flame retardant performance and washing resistance.
Example 8
A preparation method of durable flame-retardant polyester fabric specifically comprises the following steps:
adding the boron-containing char-forming flame retardant prepared in the embodiment 4 into a mixing system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, soaking and rolling the polyester fabric twice within 15min, and then pre-drying and baking to prepare the durable flame-retardant polyester fabric;
wherein the content of the boron-containing char-forming flame retardant in the finishing liquid is 200 g/L; the proportion of the using amount of the ethanol and the boron-containing char-forming flame retardant is 2mL to 1 g; the rolling allowance rate of the polyester fabric after twice repeated padding is 80 percent; the pre-drying temperature is 80 ℃, and the pre-drying time is 4 min; the baking temperature is 120 ℃, and the baking time is 5 min;
the damage length of the prepared durable flame-retardant polyester fabric is 10.0cm, no molten drop exists, the carbon residue at 700 ℃ is 27%, the damage length of the flame-retardant polyester fabric after 20 times of washing is 13.0cm, and the durable flame-retardant polyester fabric has better char forming performance, flame retardant performance and washing resistance.
Claims (11)
1. The boron-containing char-forming flame retardant is characterized by having a chemical structure as shown in the following:
in the formula, R is H or CH3。
2. The method for preparing boron-containing char-forming flame retardant according to claim 1, comprising the steps of:
(1) dissolving aldehyde group-containing phenylboronic acid and p-aminobenzamide in ethanol/distilled water, and reacting for a certain time at a certain temperature; the aldehyde group-containing phenylboronic acid is p-aldehyde phenylboronic acid or p-acetylphenylboronic acid;
(2) adding a certain amount of 1, 3-dichloropropanol into the system reacted in the step (1), raising the temperature to a certain temperature, reacting for a certain time, and purifying by reduced pressure distillation to obtain the boron-containing char-forming flame retardant.
3. The method according to claim 2, wherein the molar ratio of the aldehyde-containing phenylboronic acid to the p-aminobenzamide in the step (1) is 2-2.2: 1; the proportion of the ethanol to the phenyl boronic acid containing aldehyde is 1-2 ml:1 g; the volume ratio of the ethanol to the distilled water is 1-1.5: 1.
4. The method according to claim 2, wherein the reaction temperature in the step (1) is 60 to 70 ℃ and the reaction time is 60 to 90 min.
5. The method according to claim 2, wherein the molar ratio of the 1, 3-dichloropropanol to the aldehyde-containing phenylboronic acid in step (2) is 1-1.2: 1.
6. The method according to claim 2, wherein the reaction temperature in the step (2) is 60 to 70 ℃ and the reaction time is 50 to 70 min.
7. The method according to claim 2, wherein the reduced pressure distillation in the step (2) is carried out at a pressure of 30 to 40kPa and a temperature of 40 to 50 ℃.
8. The use of the boron-containing char-forming flame retardant of claim 1 in durable flame retardant polyester fabrics, wherein: adding the boron-containing char-forming flame retardant into a mixed system of water and ethanol, uniformly mixing to obtain a finishing liquid, then soaking the polyester fabric into the finishing liquid, soaking and rolling the polyester fabric twice within 15min, and then pre-drying and baking to obtain the durable flame-retardant polyester fabric.
9. The application of the finishing liquid as claimed in claim 8, wherein the content of the boron-containing char-forming flame retardant in the finishing liquid is 150-200 g/L;
the proportion of the consumption of the ethanol and the boron-containing char-forming flame retardant is 2-3 mL to 1 g.
10. The application of claim 8, wherein the ginning allowance of the polyester fabric is 80-100%;
the pre-drying temperature is 60-80 ℃, the pre-drying time is 3-4 min, the baking temperature is 120-130 ℃, and the baking time is 3-5 min.
11. The use of claim 8, wherein the durable flame-retardant polyester fabric has a damaged length of not more than 11.2cm, no molten drop, a carbon residue amount of not less than 20% at 700 ℃, and a damaged length of not more than 14.2cm after 20 times of washing.
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| US6335423B1 (en) * | 1997-03-20 | 2002-01-01 | Pilkington Plc | Boroxine compositions |
| US20130116227A1 (en) * | 2010-07-13 | 2013-05-09 | Dainippon Sumitomo Pharma Co., Ltd. | Biaryl amide derivative or pharmaceutically acceptable salt thereof |
| CN104098455A (en) * | 2014-08-08 | 2014-10-15 | 江苏工程职业技术学院 | Method for preparing dihydroxyacetone through glycerol oxidation |
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2022
- 2022-05-10 CN CN202210500731.7A patent/CN114605459A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335423B1 (en) * | 1997-03-20 | 2002-01-01 | Pilkington Plc | Boroxine compositions |
| US20130116227A1 (en) * | 2010-07-13 | 2013-05-09 | Dainippon Sumitomo Pharma Co., Ltd. | Biaryl amide derivative or pharmaceutically acceptable salt thereof |
| CN104098455A (en) * | 2014-08-08 | 2014-10-15 | 江苏工程职业技术学院 | Method for preparing dihydroxyacetone through glycerol oxidation |
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| NICHELE, TATIANA Z. ET AL: "Pd-catalyzed Suzuki cross-coupling reactions of glycerol arylboronic esters", 《CATALYSIS COMMUNICATIONS》 * |
| PUZARI, AMLAN ET AL: "Palladium complexes with two unsymmetrical Schiff base ligands: highly active catalyst for activation of chloroarenes in Suzuki-Miyaura reaction", 《JOURNAL OF THE INDIAN CHEMICAL SOCIETY》 * |
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