CN114031522B - Halogen-free and phosphorus-free intumescent flame retardant as well as preparation method and application thereof - Google Patents
Halogen-free and phosphorus-free intumescent flame retardant as well as preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 185
- 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 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 39
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 27
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 27
- 210000002268 wool Anatomy 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 phenolic aromatic aldehyde Chemical class 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002262 Schiff base Substances 0.000 claims abstract description 19
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 20
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 18
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 9
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 9
- 235000012141 vanillin Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 50
- 238000002791 soaking Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000004753 textile Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical group NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009145 protein modification Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- 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
- 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
- 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
- D06M2101/12—Keratin fibres or silk
-
- 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)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application relates to a halogen-free and phosphorus-free intumescent flame retardant, and a preparation method and application thereof, wherein the preparation method comprises the following steps: the halogen-free and phosphorus-free intumescent flame retardant is prepared by adopting phenolic aromatic aldehyde and urea or dicyandiamide to carry out Schiff base reaction, wherein the phenolic aromatic aldehyde is a compound containing a benzene ring and simultaneously carrying phenolic hydroxyl and aldehyde groups on the benzene ring; the application is as follows: preparing a halogen-free and phosphorus-free intumescent flame retardant into a flame-retardant finishing liquid, finishing the protein fiber product by an impregnation-drying method, and controlling the impregnation temperature to enable molecules of the halogen-free and phosphorus-free intumescent flame retardant to diffuse into the fiber to obtain the flame-retardant protein fiber product. The phenolic aromatic aldehyde, urea and dicyandiamide in the application are nontoxic products, and the prepared flame retardant is a halogen-free and phosphorus-free environment-friendly intumescent flame retardant system. The raw materials are easy to obtain, the preparation process is simple, and the prepared flame-retardant silk and wool fiber products have better flame retardant property and important practical application value.
Description
Technical Field
The application belongs to the technical field of functional finishing of textiles, and relates to a halogen-free and phosphorus-free intumescent flame retardant, a preparation method and application thereof.
Background
The textile is closely related to the daily life of people, and the protein fiber has better natural comfort and is widely favored by consumers, so the protein fiber has wide application in the fields of home decoration, bedding, public transportation decoration and the like. Fire is reported to be one of the main causes of human property loss and death, and protein fiber products burn rapidly once ignited and release a great amount of toxic gases such as carbon monoxide, hydrogen cyanide, nitrogen oxide, ammonia and aldehydes, which seriously threatens the life and property safety of people, so the flame retardant modification of protein fiber fabrics is of great concern. With the progress and development of society, the flame retardant field is continuously expanded, the demand for flame retardants is increasing, the establishment of various environmental protection regulations is promoted by people for environmental protection, and the requirements on flame retardant performance of textiles are stricter.
The flame retardant is a functional chemical auxiliary agent which can effectively improve the flame resistance of flammable polymers. By 2019, the annual demand for global flame retardants has exceeded 120 ten thousand tons. The conventional flame retardants can be classified into halogen-based and halogen-free flame retardants. With the increasing importance of people on environment and safety, the halogen-free flame retardant is developed into a hot spot for flame retardant research of high-molecular polymers because of high efficiency, low price and no secondary hazard caused by toxic and harmful gases and substances generated during combustion. The organic phosphorus flame retardant has excellent and efficient flame retardant performance, has been developed greatly in development and application, and has been rapidly increased in throughput and sales in recent years, and the application in textiles is becoming widespread. However, research on the toxicity of the organic phosphorus flame retardant and the pollution condition of the organic phosphorus flame retardant in the environment shows that the organic phosphorus flame retardant has a great threat to the human ecosystem and human health. Therefore, there is a need to develop a halogen-free and phosphorus-free intumescent flame retardant.
The flame retardant mainly achieves the flame retardant effect through the simultaneous action of a gas-phase flame retardant mechanism, a solid-phase flame retardant mechanism or a plurality of flame retardant mechanisms. The flame retardant mainly comprises halogen flame retardant, phosphorus flame retardant, sulfur flame retardant, boron flame retardant and the like, and a compound synergistic flame retardant system such as intumescent flame retardant, wherein the intumescent flame retardant has the advantages of halogen-free environment protection and synergistic efficiency. However, the existing intumescent flame retardants mostly use phosphorus flame retardants as main components, and the halogen-free and phosphorus-free intumescent flame retardants have low flame retardant efficiency and are difficult to use as intumescent flame retardants. Document 1 (silane coupling agent modified tea saponin intumescent flame retardant and paint application [ J ]. Hunan university journal (Nature science edition), 2014,41 (2): 119-124) adopts silane coupling agent (KH-550) to modify tea saponin composite intumescent flame retardant (formula is pentaerythritol, ammonium polyphosphate and tea saponin), and is applied to flame retardant paint, and the formula of the intumescent flame retardant still contains ammonium polyphosphate flame retardant. Therefore, developing an efficient halogen-free and phosphorus-free intumescent flame retardant and using the same to improve the flame retardant property of protein fiber products would be of great significance.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a halogen-free and phosphorus-free intumescent flame retardant as well as a preparation method and application thereof.
In order to achieve the above purpose, the application adopts the following technical scheme:
the halogen-free and phosphorus-free intumescent flame retardant is prepared by adopting phenolic aromatic aldehyde and urea or dicyandiamide to perform Schiff base reaction, wherein the phenolic aromatic aldehyde is a compound containing benzene rings and simultaneously carrying phenolic hydroxyl groups and aldehyde groups on the benzene rings.
The phenolic aromatic aldehyde contains aldehyde groups and hydroxyl groups, is an important chemical intermediate, and is widely applied to synthesis of medicines, fragrances and catalysts; aldehyde groups can be subjected to aldol condensation with active amino groups, namely Schiff base reaction; the application adopts phenolic aromatic aldehyde and urea or dicyandiamide to synthesize the flame retardant through Schiff base reaction; the phenolic aromatic aldehyde, urea and dicyandiamide have no flame retardant property; the phenolic hydroxyl group, the Schiff base C=N structure, the amino group and the benzene ring in the synthesized flame retardant molecule act together to play a role in intumescent flame retardance.
The phenolic aromatic aldehyde such as parahydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldehyde or vanillin and urea or dicyandiamide are nontoxic products, and the prepared flame retardant is a halogen-free and phosphorus-free environment-friendly intumescent flame retardant system.
Compared with halogen flame retardants and phosphorus flame retardants, the flame retardant prepared by the method has the advantages of easily obtained and nontoxic raw materials, belongs to an ecological environment-friendly flame retardant system, does not pollute the use process, and does not harm human bodies.
Although the prior art for preparing the flame retardant by utilizing the Schiff base reaction exists, the Schiff base system in the prior art must be used together with phosphorus element, sulfur element or other main stream flame retardant elements to have flame retardant effect, the Schiff base reaction is only a carrier, but not a key of flame retardance, and the prior art cannot prepare the intumescent flame retardant which does not contain main stream flame retardant elements such as phosphorus and the like by adopting the Schiff base reaction.
As a preferable technical scheme:
the preparation method of the halogen-free and phosphorus-free intumescent flame retardant comprises the following specific steps: firstly, dissolving phenolic aromatic aldehyde and urea or dicyandiamide in a mixed system of water and ethanol to obtain a solution, then heating the solution to a certain temperature, preserving heat for a period of time, and finally removing water and ethanol to obtain the pale yellow halogen-free and phosphorus-free intumescent flame retardant.
The preparation method of the halogen-free and phosphorus-free intumescent flame retardant comprises the step of preparing the phenolic aromatic aldehyde from more than one of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldehyde and vanillin.
According to the preparation method of the halogen-free and phosphorus-free intumescent flame retardant, the mass content of phenolic aromatic aldehyde in the solution is 5-15%, the molar ratio of urea or dicyandiamide to the phenolic aromatic aldehyde is 1-2:2, and the volume ratio of water to ethanol is 90:10-80:20; the content of phenolic aromatic aldehyde and urea or dicyandiamide in the solution is too low, and the finally obtained flame retardant effect is poor; too high, waste is caused, and cost is increased; the molar ratio of the phenolic aromatic aldehyde to urea or dicyandiamide is too small, so that the urea or dicyandiamide is easy to waste; too large, which easily results in incomplete reaction; the addition of proper ethanol in water is helpful for the dissolution of phenolic aromatic aldehyde, and the reaction of aldehyde group and amino group in the system is fully ensured.
The preparation method of the halogen-free and phosphorus-free intumescent flame retardant has the advantages that the certain temperature is 70-95 ℃ and the period of time is 40-110 min; the temperature is increased on the premise of ensuring that the solution does not boil, which is favorable for the dissolution of phenolic aromatic aldehyde and the Schiff base reaction, so the Schiff base reaction temperature is set to be 70-95 ℃; the Schiff base reaction time is determined according to the Schiff base reaction, and is too short, incomplete, too long, less in increase of the reaction degree and energy-saving.
The application also provides an application of the halogen-free and phosphorus-free intumescent flame retardant prepared by the preparation method of any one of the halogen-free and phosphorus-free intumescent flame retardant, which is characterized in that after the halogen-free and phosphorus-free intumescent flame retardant is prepared into flame retardant finishing liquid, protein fiber products are finished by an impregnation-drying method (impregnation, drying and drying), the impregnation temperature is controlled to enable halogen-free and phosphorus-free intumescent flame retardant molecules to diffuse into the fibers (under the action of the temperature, fiber gaps are opened to facilitate the diffusion of the flame retardant molecules into the fibers, and the flame retardant is mainly combined with protein fibers through hydrogen bonds, van der Waals forces and the like), so that the flame retardant protein fiber products are obtained.
As a preferable technical scheme:
the application is that the dipping temperature is 70-95 ℃, the dipping time is 20-60 min, the dipping bath ratio is 1:30-50, the drying temperature is 60-100 ℃, and the drying time is 2-5 min; the impregnation temperature is increased, so that the halogen-free and phosphorus-free intumescent flame retardant is dissolved, the flame retardant is easy to diffuse into the fiber, and the solution can be boiled at a higher temperature; the dipping time is too short, the adsorption is less, the time is too long, and the energy is wasted; the dipping bath ratio is too small to submerge the fabric, and is too high to waste; the drying temperature is low or the drying time is short, the drying effect cannot be achieved, and the physical properties such as strength of the fabric and the like are greatly influenced by the fact that the temperature is too high and the drying time is too long.
In the application, the solvent in the flame-retardant finishing liquid is water and ethanol with the volume ratio of 90:10-80:20, and the mass content of the halogen-free and phosphorus-free intumescent flame retardant is 8-18%; the flame-retardant finishing liquid is obtained by dissolving a halogen-free and phosphorus-free intumescent flame retardant in a mixed system of water and ethanol, and water and ethanol can not be removed when the halogen-free and phosphorus-free intumescent flame retardant is prepared, and the finally obtained product is the flame-retardant finishing liquid; the phenolic hydroxyl structure in the halogen-free and phosphorus-free intumescent flame retardant makes the flame retardant have poor water solubility, and the flame retardant is dissolved by adopting a mixed system of water and ethanol, so that the flame retardant is convenient to apply to protein fibers; the ethanol content in the mixed system should be proper, the ethanol content is too little, and the halogen-free and phosphorus-free intumescent flame retardant has poor solubility; too high an ethanol content results in a reduced boiling point of the solvent system, which is detrimental to the diffusion of the flame retardant into the fiber interior and increases costs.
For the applications described above, the protein fiber product is a silk or wool fiber or fabric.
In the application, the carbon length of the flame-retardant protein fiber product is less than 13cm,accords with B in GB/T17591-2006 fire-retardant fabric 1 The requirement of the grade flame retardant property.
The mechanism of the application is as follows:
under a certain temperature, phenolic aromatic aldehyde such as p-hydroxybenzaldehyde, vanillin and the like and urea or dicyandiamide undergo Schiff base addition reaction to obtain the halogen-free and phosphorus-free intumescent flame retardant. The halogen-free and phosphorus-free intumescent flame retardant enters the protein fiber under the action of temperature, combines with the protein fiber through hydrogen bond and Van der Waals force, and is adsorbed on the protein fiber. The Schiff base C=N structure, amino, phenolic hydroxyl, benzene ring and the like in the halogen-free phosphorus-free intumescent flame retardant jointly act to form the intumescent flame retardant, the Schiff base C=N structure, the amino, the phenolic hydroxyl, the benzene ring and the like in molecules can participate in the char formation reaction of protein fibers in the combustion process, the thermal decomposition path of the protein fibers is changed, the protein fibers are effectively promoted to be expanded into char, protein fibers below a carbon layer are protected, the flame retardant performance of the protein fibers is improved, wherein the phenolic hydroxyl can be used as an acid source, the benzene ring and the C=N structure can be used as a carbon source, the amino can be used as an air source, in the heating process, the phenolic hydroxyl and the C=N structure are subjected to esterification reaction, the amino is used as a catalyst of the esterification reaction, the reaction is accelerated, a reaction product is melted in the heating process, and the air source decomposition product enables the melted product to be expanded and foamed, at the moment, the carbon source is further decomposed to form a complete intumescent system, and finally is solidified into an intumescent carbon layer, so that a good flame retardant isolation effect is achieved. The halogen-free and phosphorus-free intumescent flame retardant plays a role in flame retardance through a cluster aggregation principle (the molecular weight of a compound is large, and when the compound is arranged according to a certain rule, the compound has a special structure, so that the compound has a phenomenon of higher flame retardance than similar small molecules). The phenolic aromatic aldehyde, urea and dicyandiamide alone cannot effectively promote the protein fiber to form charcoal, so that the flame retardant effect cannot be achieved.
Generally, flame retardant elements such as halogen, phosphorus, silicon, sulfur and the like are main stream flame retardant elements, while nitrogen belongs to synergistic flame retardant elements, and the independent flame retardant effect is poor.
The beneficial effects are that:
(1) In the application, phenolic aromatic aldehyde such as parahydroxyben-zaldehyde, m-hydroxyben-zaldehyde, salicylaldehyde or vanillin and urea or dicyandiamide are nontoxic products, and the prepared flame retardant is a halogen-free and phosphorus-free environment-friendly flame retardant system;
(2) The phenolic hydroxyl structure, the schiff base C=N structure, the amino, the benzene ring and other groups in the halogen-free and phosphorus-free flame retardant prepared by the application can promote and participate in the char formation reaction of protein fibers in the combustion process, thereby playing a role in intumescent flame retardance and having excellent flame retardance of flame-retardant protein fiber products;
(3) The application has the advantages of simple process, short flow, environmental protection, sustainability, low economic cost, wide application prospect and important practical application value.
Drawings
FIG. 1 is a photograph of flame retardant silk fabrics and flame retardant wool fabrics of examples 1-4 of the present application after vertical burning, wherein a corresponds to example 1, b corresponds to example 2, c corresponds to example 3, and d corresponds to example 4;
fig. 2 is a scanning electron microscope image of carbon residue after vertical burning of the flame retardant silk fabric (a) of example 2 and the flame retardant wool fabric (b) of example 4.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
The preparation method of the flame-retardant silk fabric comprises the following specific steps:
(1) Preparation of halogen-free and phosphorus-free intumescent flame retardant: dissolving 0.1mol of p-hydroxybenzaldehyde and 0.1mol of urea in a mixed system of 85mL of water and 15mL of ethanol to obtain a solution, heating the solution to 80 ℃, preserving heat for 90min, and removing water and ethanol to obtain the halogen-free and phosphorus-free intumescent flame retardant;
(2) Preparation of flame-retardant silk fabric: firstly, completely dissolving halogen-free and phosphorus-free intumescent flame retardant into a mixed system of 85mL of water and 15mL of ethanol to obtain flame-retardant finishing liquid, then soaking real silk fabric in the flame-retardant finishing liquid, heating to 80 ℃ with the soaking bath ratio of 1:40, preserving heat for 60min, squeezing out excessive moisture, and drying at 70 ℃ for 4min to obtain the flame-retardant real silk fabric.
Comparative example 1
The preparation method of the modified silk fabric comprises the following specific processes: dissolving 0.1mol of p-hydroxybenzaldehyde in a mixed system of 85mL of water and 15mL of ethanol to obtain a finishing liquid, soaking the real silk fabric in the finishing liquid, heating to 80 ℃ for 60min with a soaking bath ratio of 1:40, squeezing out excessive water, and drying at 70 ℃ for 4min to obtain the modified real silk fabric.
Comparative example 2
The preparation method of the modified silk fabric comprises the following specific processes: dissolving 0.1mol of urea in a mixed system of 85mL of water and 15mL of ethanol to obtain a finishing liquid, soaking the real silk fabric in the finishing liquid at a soaking bath ratio of 1:40, heating to 80 ℃, preserving heat for 60min, squeezing out excessive water, and drying at 70 ℃ for 4min to obtain the modified real silk fabric.
Example 2
A preparation method of flame-retardant real silk electric textile fabric comprises the following specific steps:
(1) Preparation of halogen-free and phosphorus-free intumescent flame retardant: dissolving 0.15mol of m-hydroxybenzaldehyde and 0.125mol of dicyandiamide in a mixed system of 80mL of water and 20mL of ethanol to obtain a solution, heating the solution to 85 ℃, preserving heat for 70min, and removing water and ethanol to obtain the halogen-free and phosphorus-free intumescent flame retardant;
(2) Preparation of flame-retardant silk electric textile fabrics: the preparation method comprises the steps of firstly, dissolving halogen-free and phosphorus-free intumescent flame retardant into a mixed system of 80mL of water and 20mL of ethanol to obtain flame-retardant finishing liquid, then immersing real silk electric textile in the flame-retardant finishing liquid, heating to 75 ℃ with the dipping bath ratio of 1:30, preserving heat for 50min, squeezing out excessive moisture, and drying at 80 ℃ for 3min to obtain the flame-retardant real silk electric textile.
Example 3
A preparation method of flame-retardant wool fabric comprises the following specific steps:
(1) Preparation of halogen-free and phosphorus-free intumescent flame retardant: dissolving 0.75mol of salicylaldehyde and 0.6mol of dicyandiamide in a mixed system of 90mL of water and 10mL of ethanol to obtain a solution, heating the solution to 90 ℃, preserving heat for 80min, and removing water and ethanol to obtain the halogen-free and phosphorus-free intumescent flame retardant;
(2) Preparing flame-retardant wool textile fabrics: firstly, completely dissolving halogen-free and phosphorus-free intumescent flame retardant in a mixed system of 90mL of water and 10mL of ethanol to obtain flame-retardant finishing liquid, then soaking wool fabric in the flame-retardant finishing liquid, heating to 90 ℃ with the soaking bath ratio of 1:50, preserving heat for 40min, squeezing out excessive moisture, and drying at 90 ℃ for 2min to obtain the flame-retardant wool fabric.
Comparative example 3
The preparation method of the modified wool fabric comprises the following specific processes: dissolving 0.75mol of salicylaldehyde in a mixed system of 90mL of water and 10mL of ethanol to obtain finishing liquid, soaking wool fabric in the finishing liquid at a soaking bath ratio of 1:50, heating to 90 ℃, preserving heat for 40min, squeezing out excessive water, and drying at 90 ℃ for 2min to obtain the modified wool fabric.
Comparative example 4
The preparation method of the modified wool fabric comprises the following specific processes: dissolving 0.6mol of dicyandiamide in a mixed system of 90mL of water and 10mL of ethanol to obtain finishing liquid, soaking wool fabric in the finishing liquid at a soaking bath ratio of 1:50, heating to 90 ℃, preserving heat for 40min, squeezing out excessive water, and drying at 90 ℃ for 2min to obtain the modified wool fabric.
Example 4
A preparation method of flame-retardant wool fabric comprises the following specific steps:
(1) Preparation of halogen-free and phosphorus-free intumescent flame retardant: dissolving 0.115mol of vanillin and 0.1mol of urea in a mixed system of 85mL of water and 15mL of ethanol to obtain a solution, heating the solution to 95 ℃, preserving heat for 70min, and removing water and ethanol to obtain the halogen-free and phosphorus-free intumescent flame retardant;
(2) Preparing flame-retardant wool textile fabrics: firstly, completely dissolving halogen-free and phosphorus-free intumescent flame retardant into a mixed system of 90mL of water and 10mL of ethanol to obtain flame-retardant finishing liquid, then soaking wool fabric in the flame-retardant finishing liquid, heating to 95 ℃ with the soaking bath ratio of 1:45, preserving heat for 60min, squeezing out excessive moisture, and drying at 100 ℃ for 2min to obtain the flame-retardant wool fabric.
The fabrics prepared in examples 1 to 4 and comparative examples 1 to 4 were tested for flame retardant properties.
The carbon length is measured according to GB/T5455-2014 standard of determination of smoldering and continuous burning time of damage length of vertical direction of burning property of textile. The combustion performance is evaluated according to the GB/T17591-2006 flame retardant fabric standard.
The char length and flame retardant rating of the fabrics produced in examples 1-4 and comparative examples 1-4 are shown in the following table:
as can be seen from the table, the unfinished silk fabric and the unfinished wool fabric are completely burnt in the vertical burning process, and the carbon length is 30cm, which shows that the flame retardant property is poor. The pure silk fabrics finished by the parahydroxybenzaldehyde, the pure silk fabrics finished by the urea, the pure silk fabrics finished by the metahydroxybenzaldehyde, the wool fabrics finished by the salicylaldehyde, the wool fabrics finished by the dicyandiamide and the wool fabrics finished by the vanillin are completely burnt in a vertical burning test, and the carbon length is 30cm, which shows that the pure burning-free function of the parahydroxybenzaldehyde, the metahydroxybenzaldehyde, the salicylaldehyde, the vanillin, the urea and the dicyandiamide is realized when the parahydroxybenzaldehyde, the metahydroxybenzaldehyde, the salicylaldehyde, the vanillin, the urea and the dicyandiamide are singly used or only physically mixed. The carbon length of the silk and wool fabrics after being finished by the halogen-free phosphorus-free intumescent flame retardant is lower than 15cm, thus reaching B in GB/T17591-2006 flame retardant fabrics 1 The requirement of the grade flame retardant property shows that the halogen-free and phosphorus-free intumescent flame retardant has better flame retardant property, and the main reason is that phenolic hydroxyl, schiff base C=N structure, amino, benzene ring and the like in the halogen-free and phosphorus-free intumescent flame retardant are mutually matched to form an intumescent flame retardant system, so that the flame retardant effect is achieved. FIG. 1 shows photographs of flame retardant silk and wool fabrics of examples 1 to 4 of the present application after vertical burning, wherein a corresponds to example 1, b corresponds to example 2, c corresponds to example3, d corresponds to example 4, fig. 2 shows a scanning electron microscope image of carbon residue after vertical burning of the flame retardant real silk (a) of example 2 and the flame retardant wool fabric (b) of example 4, and fig. 1 and 2 further demonstrate that the halogen-free and phosphorus-free intumescent flame retardant of the application has a better intumescent flame retardant effect.
The above embodiments illustrate that silk and wool fiber products modified with halogen-free and phosphorus-free intumescent flame retardants have better flame retardant properties. The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present application, and these improvements and modifications should also be regarded as the protection scope of the present application.
Claims (8)
1. A preparation method of halogen-free and phosphorus-free intumescent flame retardant is characterized in that: the halogen-free and phosphorus-free intumescent flame retardant is prepared by adopting phenolic aromatic aldehyde and urea or dicyandiamide to carry out Schiff base reaction, wherein the phenolic aromatic aldehyde is one of parahydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldehyde or vanillin.
2. The preparation method of the halogen-free and phosphorus-free intumescent flame retardant as claimed in claim 1, which is characterized by comprising the following specific processes: firstly, dissolving phenolic aromatic aldehyde and urea or dicyandiamide in a mixed system of water and ethanol to obtain a solution, then heating the solution to 70-95 ℃, preserving heat for 40-110 min, and finally removing water and ethanol to obtain the halogen-free and phosphorus-free intumescent flame retardant.
3. The preparation method of the halogen-free and phosphorus-free intumescent flame retardant according to claim 2, wherein the mass content of phenolic aromatic aldehyde in the solution is 5-15%, the molar ratio of urea or dicyandiamide to phenolic aromatic aldehyde is 1-2:2, and the volume ratio of water to ethanol is 90:10-80:20.
4. The use of a halogen-free and phosphorus-free intumescent flame retardant prepared by the preparation method of any one of claims 1-3, characterized in that: preparing a halogen-free and phosphorus-free intumescent flame retardant into a flame-retardant finishing liquid, finishing the protein fiber product by an impregnation-drying method, and controlling the impregnation temperature to enable molecules of the halogen-free and phosphorus-free intumescent flame retardant to diffuse into the fiber to obtain the flame-retardant protein fiber product.
5. The use according to claim 4, wherein the impregnation temperature is 70-95 ℃, the impregnation time is 20-60 min, the impregnation bath ratio is 1:30-50, the drying temperature is 60-100 ℃, and the drying time is 2-5 min.
6. The application of claim 4, wherein the solvent in the flame-retardant finishing liquid is water and ethanol with a volume ratio of 90:10-80:20, and the mass content of the halogen-free and phosphorus-free intumescent flame retardant is 8-18%.
7. The method according to claim 4, wherein the protein fiber product is silk or wool fiber.
8. The method according to claim 4, wherein the flame retardant protein fiber product has a carbon length of less than 13cm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162394A (en) * | 1990-09-18 | 1992-11-10 | 501 Chemco Inc. | Fire-retardant chemical compositions |
| US5430081A (en) * | 1993-11-16 | 1995-07-04 | Sumitomo Chemical Company, Ltd. | Fire retardant additive and fire retardant thermoplastic resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162394A (en) * | 1990-09-18 | 1992-11-10 | 501 Chemco Inc. | Fire-retardant chemical compositions |
| US5430081A (en) * | 1993-11-16 | 1995-07-04 | Sumitomo Chemical Company, Ltd. | Fire retardant additive and fire retardant thermoplastic resin composition |
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