CN114634531B - Preparation method and application of phosphorus-containing flame-retardant hydrophobing agent - Google Patents
Preparation method and application of phosphorus-containing flame-retardant hydrophobing agent Download PDFInfo
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- CN114634531B CN114634531B CN202210534805.9A CN202210534805A CN114634531B CN 114634531 B CN114634531 B CN 114634531B CN 202210534805 A CN202210534805 A CN 202210534805A CN 114634531 B CN114634531 B CN 114634531B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 137
- 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 133
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 75
- 239000011574 phosphorus Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004890 Hydrophobing Agent Substances 0.000 title description 3
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 135
- 229920000728 polyester Polymers 0.000 claims abstract description 92
- 239000000835 fiber Substances 0.000 claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000000047 product Substances 0.000 claims abstract description 45
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 32
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 31
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005642 Oleic acid Substances 0.000 claims abstract description 31
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000013067 intermediate product Substances 0.000 claims abstract description 31
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 31
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000004744 fabric Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005096 rolling process Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004017 vitrification Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007730 finishing process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 229910014572 C—O—P Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AKAAHMXNWDUFTD-UHFFFAOYSA-N 5-(trifluoromethyl)-2-benzofuran-1,3-dione Chemical compound FC(F)(F)C1=CC=C2C(=O)OC(=O)C2=C1 AKAAHMXNWDUFTD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000009941 weaving 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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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a preparation method and application of a phosphorus-containing flame-retardant hydrophobic agent, wherein the preparation method comprises the following steps: firstly, oleic acid and bromine are reacted and then hydrolyzed to obtain an intermediate product I, then the intermediate product I and phosphorus trichloride are reacted to form an intermediate product II, and finally the intermediate product II is hydrolyzed to obtain the phosphorus-containing flame-retardant hydrophobic agent, wherein the molar ratio of the oleic acid to the bromine is 1: 1-1.1, and the molar ratio of the phosphorus trichloride to the oleic acid is more than or equal to 1.7/2; the application is as follows: after a phosphorus-containing flame-retardant hydrophobic agent is dissolved in a solvent to obtain flame-retardant hydrophobic finishing liquid, modifying a polyester fiber product by a rolling-drying-baking method to obtain a flame-retardant hydrophobic polyester fiber product, wherein the baking temperature is not lower than the glass transition temperature of the polyester fiber product and not higher than the softening temperature of the polyester fiber product. The phosphorus-containing flame-retardant hydrophobic agent synthesized by the method has high flame-retardant efficiency and hydrophobic efficiency, is environment-friendly, and the prepared polyester fiber product has excellent flame-retardant performance, hydrophobic performance and washing resistance.
Description
Technical Field
The invention belongs to the technical field of functional modification of textiles, relates to a preparation method and application of a phosphorus-containing flame-retardant hydrophobic agent, and particularly relates to a preparation method of the phosphorus-containing flame-retardant hydrophobic agent and a method for flame-retardant hydrophobic modification of a polyester fiber product by using the phosphorus-containing flame-retardant hydrophobic agent.
Background
The polyester fiber is the first large variety of synthetic fiber and has wide application range. Outdoor products such as tents, backpacks, etc. have high requirements on the flame retardant property and the hydrophobic property of polyester fabrics. The polyester material is easy to burn and generates molten drops, which is not beneficial to the wide application of the polyester fabric. With the increasing demand for environmental protection, sustainable development and environmental protection, halogen-based flame retardants are challenging and will be gradually replaced by halogen-free flame retardants. The phosphorus flame retardant is one of the flame retardants with better application at present, has wide sources, and has the advantages of good thermal stability, low toxicity and the like. However, the phosphorus flame retardant has poor water washing resistance on textiles and is limited to a certain extent. In addition, the polyester fabric can not meet the waterproof requirement of the product, the polyester fabric is finished by adopting a fluorine-containing waterproof agent in the conventional hydrophobic finishing, but part of the fluorine-containing waterproof agent is gradually eliminated by the market due to the environmental protection problem.
Chinese patent CN111560661A discloses an antifouling flame-retardant polyester fiber and a preparation method thereof, trimethyl phosphate is used as a stabilizer, 5-trifluoromethyl phthalic anhydride is used as a third monomer, esterification and condensation reactions are carried out on phthalic anhydride and ethylene glycol to prepare copolyester, and the copolyester is obtained through melt spinning. But the copolymerization method can generate great influence on the physical property of the polyester fiber, so that the spinning is not easy to form, the production process requirement is harsh, and the hydrophobic property of the method is mainly generated by fluorine-containing monomers which are harmful to the environment.
The post-finishing method has the advantages of simple flow, easy implementation, high efficiency and the like, and can make up for the defects of the copolymerization method to a certain extent, however, a two-step method of flame-retardant finishing and hydrophobic finishing is often adopted when the post-finishing method is adopted to prepare the flame-retardant hydrophobic polyester fiber product in the prior art, and the process flow is complicated, so that the research of a finishing agent with both flame-retardant performance and hydrophobic performance is urgently needed, and the flame-retardant hydrophobic fabric is simply and conveniently prepared through the post-finishing technology. The phosphorus-containing polyglycerol fatty acid ester flame retardant plasticizers disclosed in the literature (preparation and application of phosphorus-containing polyglycerol fatty acid ester flame retardant plasticizers [ J ]. forest chemical and industry, 2016, 36(1): 77-84.), however, the bonding force of these compounds to polyester fiber products is limited, and the flame retardant hydrophobically modified polyester fiber products which are washable by the post-finishing method are difficult to prepare.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a phosphorus-containing flame-retardant hydrophobic agent. According to the invention, oleic acid, bromine and phosphorus trichloride are used as raw materials to synthesize a phosphorus-containing flame-retardant hydrophobic agent, the phosphorus-containing structure and oleic acid are linked through 2-3C-O-P structures (wherein C represents carbon, and P represents phosphorus), the structure is stable and is not easy to hydrolyze, meanwhile, the phosphorus-containing flame-retardant hydrophobic agent is applied to flame-retardant hydrophobic modification of a polyester fiber product, in the high-temperature baking process, a polyester macromolecular chain segment is opened, and a hydrophobic chain segment of the phosphorus-containing flame-retardant hydrophobic agent diffuses into the polyester chain segment and is combined with polyester fibers through a similar intermiscibility principle.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a phosphorus-containing flame-retardant hydrophobic agent comprises the steps of firstly reacting oleic acid with bromine, then carrying out hydrolysis treatment to obtain an intermediate product I, then reacting the intermediate product I with phosphorus trichloride to form an intermediate product II, and finally carrying out hydrolysis treatment on the intermediate product II to obtain the phosphorus-containing flame-retardant hydrophobic agent, wherein the molar ratio of oleic acid to bromine is 1: 1-1.1, bromine is slightly excessive, unsaturated double bonds in oleate can be ensured to be completely reacted, the hydrolysis reaction enables the added bromine to be replaced by hydroxyl groups, and the molar ratio of phosphorus trichloride to oleic acid is more than or equal to 1.7/2.
In the reaction process, unsaturated double bonds of oleic acid and bromine are subjected to addition reaction, a hydroxyl structure is formed after hydrolysis, nucleophilic substitution reaction is carried out on the hydroxyl structure and active chlorine of phosphorus trichloride to generate 2-3C-O-P structures, carboxyl groups at the end of oleic acid and phosphorus trichloride are subjected to acyl chloride reaction, acyl chloride groups are hydrolyzed to generate carboxyl groups during hydrolysis treatment, and redundant phosphorus trichloride is hydrolyzed to generate phosphoric acid, so that the hydrolysis treatment on an intermediate product II is required because the acyl chloride structure and the active chlorine structure are unstable, and the intermediate product II is easy to react with water molecules in the storage, baking and finishing processes, and the carboxyl groups and the P-OH structures are stable and cannot react in the storage, baking and finishing processes;
the molar ratio of the oleic acid to the phosphorus trichloride is adjustable, and when the molar ratio of the phosphorus trichloride to the oleic acid is more than or equal to 1.3, the structural formula of the intermediate product II is as follows:
the target product, namely the phosphorus-containing flame-retardant hydrophobic agent has 2C-O-P structures, and the structural formula is as follows:
when the molar ratio of phosphorus trichloride to oleic acid is 1.7/2, the phosphorus-containing flame-retardant hydrophobing agent has 3C-O-P structures, and the structural formula of a target product, namely the phosphorus-containing flame-retardant hydrophobing agent is as follows:
when the molar ratio of phosphorus trichloride to oleic acid is 1.7/2-1.3, the reaction product is a mixture of a phosphorus-containing flame-retardant hydrophobic agent with 2C-O-P structures and a phosphorus-containing flame-retardant hydrophobic agent with 3C-O-P structures;
compared with 2C-O-P structures, the C-O-P structure with 3C-O-P structures has higher stability and better water washing resistance effect, because the conditions for breaking 3C-O-P structures are more rigorous than those for breaking 2C-O-P structures.
As a preferable technical scheme:
the preparation method of the phosphorus-containing flame-retardant hydrophobic agent comprises the following specific steps:
(a) placing oleic acid into a container (a three-neck flask and the like), dropwise adding bromine, raising the temperature to 60-70 ℃ after dropwise adding, reacting for 40-50 min, adding distilled water (the addition of the distilled water is beneficial to replacing the bromine added in the double bond addition of oleic acid molecules into hydroxyl), continuing reacting for 30-40 min, and filtering and separating the product to obtain an intermediate product I;
(b) and (2) dropwise adding phosphorus trichloride into the intermediate product I, raising the temperature to 50-60 ℃ after dropwise adding is finished (the reaction temperature is set so as to ensure that the reaction rate is high, the reaction efficiency of the phosphorus trichloride and the volatilization condition of the phosphorus trichloride need to be comprehensively considered), adding distilled water after reacting for 2-4 h, continuing reacting for 0.5-1 h, separating the supernatant to obtain the phosphorus-containing flame-retardant hydrophobic agent, and separating the supernatant to realize the separation of the phosphorus-containing flame-retardant hydrophobic agent, the phosphorus trichloride and oleic acid because the phosphorus-containing flame-retardant hydrophobic agent is insoluble in water.
The invention also provides application of the phosphorus-containing flame-retardant hydrophobic agent prepared by the preparation method of the phosphorus-containing flame-retardant hydrophobic agent, the phosphorus-containing flame-retardant hydrophobic agent is dissolved in a solvent to obtain a flame-retardant hydrophobic finishing liquid, and the polyester fiber product is modified by a rolling-baking method to obtain the flame-retardant hydrophobic polyester fiber product, wherein the baking temperature is not lower than the glass transition temperature of the polyester fiber product and not higher than the softening temperature of the polyester fiber product.
As a preferred technical scheme:
in the above application, the solvent is ethanol or a mixed solution of ethanol and water; oleic acid is insoluble in water, can be dissolved in alcohol and ether, and can be dissolved in benzene and chloroform; dissolving phosphoric acid in water, alcohol, glycerol, ethers and essential oil, wherein the water solution is weakly acidic; the phosphorus-containing flame-retardant hydrophobic agent has poor water solubility, can be dissolved in ethanol, an ethanol/water mixed system and an ether solvent, and adopts ethanol or an ethanol/water mixed system with good volatility in consideration of application performance, so that the solvent can be volatilized in the drying process.
By the application, the concentration of the flame-retardant hydrophobic finishing liquid is 150-300 g/L, the concentration is too low, the flame-retardant hydrophobic effect is poor, the concentration is too high, and the flame-retardant effect is good but is wasted.
The process flow of the rolling-drying-baking method is as follows: padding → pre-baking → baking, wherein the padding can be one-padding-one-padding, or two-padding-two-padding, preferably two-padding-two-padding, and the specific process flow of the padding-baking method comprises the following steps: impregnation → rolling → pre-baking → baking; in the rolling-drying-baking method, the rolling retention rate of rolling is 100-120%, the pre-drying temperature is 60-80 ℃, the pre-drying time is 3-5 min, the baking temperature is 160-180 ℃, and the baking time is 2-5 min; the higher rolling residual rate can ensure that the phosphorus-containing flame-retardant hydrophobic agent on the polyester fiber product has higher content and better flame-retardant hydrophobic effect; 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, the macromolecular chain segment of the polyester fiber can not be opened, and the hydrophobic chain segment of the phosphorus-containing flame-retardant hydrophobic agent can not be embedded into the fiber; the temperature is high, the time is long, the macromolecular chain segment of the polyester fiber is opened, and the hydrophobic chain segment of the phosphorus-containing flame-retardant hydrophobic agent can be embedded into the fiber and generates stable combination through the similar intermiscibility principle; the macromolecular chain segment of the polyester fiber can be effectively opened within the temperature and time range provided by the invention, so that the hydrophobic chain segment of the phosphorus-containing flame-retardant hydrophobic agent is well embedded into the fiber.
As mentioned above, the polyester fiber product is a raw polyester fiber fabric or a regenerated polyester fiber fabric.
According to the application, phosphorus is introduced into oleic acid through 2-3C-O-P structures, and the phosphorus-containing flame-retardant hydrophobic agent is blocked in the polyester fiber, so that flame-retardant and hydrophobic effects are achieved; according to the invention, the hydrophobic long-chain block of the phosphorus-containing flame-retardant hydrophobic agent is controlled to enter the polyester fiber in the finishing process, so that the phosphorus-containing flame-retardant hydrophobic agent and the polyester fiber are stably combined, and the water washing resistance of the flame-retardant hydrophobic polyester fiber product is obviously improved; the contact angle of the flame-retardant hydrophobic polyester fiber product with water is higher than 110 o And the LOI is more than 26.5 percent, the damage length in a vertical burning test after 0 time of water washing is not more than 12.8cm, and the damage length in the vertical burning test after 20 times of water washing is not more than 14.8 cm.
The invention mechanism is as follows:
the oleic acid molecule contains unsaturated double bond and bromine, and can generate nucleophilic substitution reaction with phosphorus trichloride after being hydrolyzed in distilled water,synthesizing a phosphorus-containing flame-retardant hydrophobic agent with 2-3C-O-P structures, wherein the phosphorus-containing flame-retardant hydrophobic agent has a plurality of hydrophobic chain segments (for example
Two hydrophobic chain segments are provided, one is arranged at the left and the right of the phosphorus-containing group), one hydrophobic chain segment can be embedded into the polyester fiber under the high-temperature baking condition through the similar intermiscibility principle to realize the combination of the phosphorus-containing flame-retardant hydrophobic agent and the polyester fiber product, and because the molecular chain segment of the phosphorus-containing flame-retardant hydrophobic agent is longer and is difficult to be completely embedded into the fiber, the other hydrophobic chain segment is exposed on the outer surface of the fiber to play a role in hydrophobic property.
The phosphorus-containing flame-retardant hydrophobic agent contains a hydrophobic chain segment and a plurality of C-O-P structures, and has good hydrolytic stability in the water washing process, thereby endowing the polyester fiber product with durable flame-retardant hydrophobic performance.
The hydrophobic chain segment of the phosphorus-containing flame-retardant hydrophobic agent and the polyester form a bracket effect, the polyester is melted and dripped during combustion, and the long carbon chain of the flame retardant is carbonized into a support body during combustion, so that molten fibers can be gathered and prevented from being melted and dripped, and the effect of inhibiting the melting and dripping is achieved; the phosphorus-containing group of the phosphorus-containing flame-retardant hydrophobic agent can form a protective layer on the surface of the fiber in the thermal decomposition process to isolate heat and oxygen, thereby improving the flame retardant property of the polyester fiber product.
Has the advantages that:
(1) the oleic acid and phosphorus trichloride raw materials used in the invention have sufficient sources and low toxicity, and the prepared phosphorus-containing flame-retardant hydrophobic agent belongs to an environment-friendly functional finishing agent;
(2) the phosphorus-containing flame-retardant hydrophobic agent prepared by the invention has a good flame-retardant anti-dripping effect, the hydrophobic chain segment in the molecule endows the polyester fiber product with a good hydrophobic effect, and the hydrophobic chain segment can be embedded with the polyester fiber, so that the prepared flame-retardant hydrophobic polyester fiber product has good water washing resistance;
(3) the invention has simple process flow, and the prepared polyester fiber product has better flame retardant property, hydrophobic property and higher water washing resistance, and has wide application prospect.
Drawings
FIG. 1 is a contact angle test chart of the flame retardant hydrophobic polyester fiber article of example 3;
FIG. 2 is a vertical burning pattern before and after washing 20 times of the flame retardant hydrophobic polyester fiber product of example 3 with water.
Detailed Description
The present invention will be further described with reference to the following 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 can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
(1) Preparing a phosphorus-containing flame-retardant hydrophobic agent: adding 28.2g of oleic acid (0.1 mol) into a three-neck flask, stirring, slowly dropwise adding 16.0g of bromine (0.1 mol), reacting at 60 ℃ for 50min, adding 20mL of distilled water, continuing to react for 40min, and separating the supernatant to obtain an intermediate product I; then slowly dropwise adding 17.9g of phosphorus trichloride (0.13 mol) into a three-neck flask in which the intermediate product I is positioned, heating to 60 ℃ after dropwise adding is finished within 1h (the dropwise adding time is controlled to be about 1h as much as possible, the time cannot be too short, and the reaction cannot be sufficiently short), reacting for 2h to obtain an intermediate product II, keeping the temperature unchanged, adding 31.7mL of distilled water, continuously reacting for 0.7h, and separating the supernatant to obtain the phosphorus-containing flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the phosphorus-containing flame-retardant hydrophobic agent is dissolved in ethanol to prepare 200g/L flame-retardant hydrophobic finishing liquid, and the flame-retardant hydrophobic finishing liquid is used for treating the virgin polyester fabric (120 g/m) 2 Crossed fabric) is subjected to two-dipping and two-rolling treatment, the dipping time is 5min each time, the rolling residual rate of each rolling is 110%, then the primary polyester fabric is dried for 3min at 80 ℃, then is dried for 5min at 160 ℃, and is dried after being washed to obtain the flame-retardant hydrophobic polyester fiber product.
Comparative example 1
Dissolving oleic acid in ethanol to prepare finishing liquid with the concentration of 200g/L, and weaving the primary polyester by adopting the finishing liquidSubstance (120 g/m) 2 And (2) interweaving the fabric, performing two-dipping and two-rolling treatment in the same way as in the embodiment 1), wherein the dipping time is 5min, and the rolling residual rate of each rolling is 110%, then drying the original polyester fabric at 80 ℃ for 3min, then baking at 160 ℃ for 5min, and finally drying after water washing to obtain the modified polyester fiber product.
Comparative example 2
Reacting 17.9g of phosphorus trichloride (0.13 mol) with 31.7mL of distilled water at 60 ℃ for 0.7h, then mixing with ethanol to prepare finishing liquid with the concentration of 200g/L, and adopting the finishing liquid to carry out treatment on a raw polyester fabric (120 g/m) 2 And (3) carrying out two-dipping and two-rolling treatment on the mixed fabric in the same way as in the example 1), wherein the dipping time is 5min each time, the rolling residual rate of each rolling is 110%, then drying the primary polyester fabric at 80 ℃ for 3min, then drying at 160 ℃ for 5min, and drying after water washing to obtain the modified polyester fiber product.
Example 2
(1) Preparing a phosphorus-containing flame-retardant hydrophobic agent: adding 28.2g of oleic acid (0.1 mol) into a three-neck flask, stirring, slowly dropwise adding 17.6g of bromine (0.11 mol), reacting at 70 ℃ for 40min, adding 20mL of distilled water, continuing to react for 30min, and separating the supernatant to obtain an intermediate product I; then slowly dripping 17.9g of phosphorus trichloride (0.13 mol) into a three-neck flask in which the intermediate product I is positioned, heating to 60 ℃ after finishing dripping within 1h (the dripping time is controlled to be about 1h as far as possible, the time cannot be too short, and the reaction cannot be sufficiently short), reacting for 2h to obtain an intermediate product II, keeping the temperature unchanged, adding 31.7mL of distilled water, continuously reacting for 0.5h, and separating the supernatant to obtain a phosphorus-containing flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the phosphorus-containing flame-retardant hydrophobic agent is dissolved in ethanol to prepare 150g/L flame-retardant hydrophobic finishing liquid, and the flame-retardant hydrophobic finishing liquid is used for treating the virgin polyester fabric (120 g/m) 2 Crossed fabric) is subjected to two-dipping and two-rolling treatment, the dipping time is 5min each time, the rolling residual rate of each rolling is 120%, then the primary polyester fabric is dried for 4min at 80 ℃, then is dried for 4min at 170 ℃, and is dried after being washed to obtain the flame-retardant hydrophobic polyester fiber product.
Example 3
(1) Preparing a phosphorus-containing flame-retardant hydrophobic agent: adding 56.4g of oleic acid (0.2 mol) into a three-neck flask, stirring, slowly dropwise adding 32.0g of bromine (0.2 mol), reacting at 65 ℃ for 45min, adding 20mL of distilled water, continuing to react for 40min, and separating the supernatant to obtain an intermediate product I; then slowly dripping 23.3g of phosphorus trichloride (0.17 mol) into a three-neck flask in which the intermediate product I is positioned, heating to 57 ℃ after finishing dripping within 1h (the dripping time is controlled to be about 1h as far as possible, the time cannot be too short, and the reaction cannot be sufficiently short), reacting for 3h to obtain an intermediate product II, keeping the temperature unchanged, adding 63.4mL of distilled water, continuing to react for 1h, and separating the supernatant to obtain the phosphorus-containing flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the phosphorus-containing flame-retardant hydrophobic agent is dissolved in ethanol to prepare 300g/L flame-retardant hydrophobic finishing liquid, and the flame-retardant hydrophobic finishing liquid is adopted to treat regenerated polyester fabric (120 g/m) 2 Crossed fabric) is subjected to two-dipping and two-rolling treatment, the dipping time is 7min each time, the rolling residual rate of each rolling is 100%, then the regenerated polyester fabric is dried for 5min at the temperature of 60 ℃, then is dried for 2min at the temperature of 180 ℃, and is dried after being washed to obtain the flame-retardant hydrophobic polyester fiber product.
Example 4
(1) Preparing a phosphorus-containing flame-retardant hydrophobic agent: adding 56.4g of oleic acid (0.2 mol) into a three-neck flask, stirring, slowly dropwise adding 33.6g of bromine (0.21 mol), reacting at 67 ℃ for 43min, adding 20mL of distilled water, continuing to react for 40min, and separating the supernatant to obtain an intermediate product I; then slowly dripping 23.3g of phosphorus trichloride (0.17 mol) into a three-neck flask in which the intermediate product I is positioned, heating to 60 ℃ after finishing dripping within 1h (the dripping time is controlled to be about 1h as far as possible, the time cannot be too short, and the reaction cannot be sufficiently short), reacting for 3h to obtain an intermediate product II, keeping the temperature unchanged, adding 63.4mL of distilled water, continuously reacting for 0.8h, and separating the supernatant to obtain the phosphorus-containing flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the phosphorus-containing flame-retardant hydrophobic agent is dissolved in ethanol to prepare 250g/L flame-retardant hydrophobic finishing liquid, and the flame-retardant hydrophobic finishing liquid is used for treating regenerated polyester fabrics (120 g/m) 2 Interwoven fabric) And (3) carrying out two-dipping and two-rolling treatment, wherein the dipping time is 7min each time, the rolling residual rate of each rolling is 100%, then drying the regenerated polyester fabric at 60 ℃ for 5min, then baking at 180 ℃ for 2min, washing with water, and drying to obtain the flame-retardant hydrophobic polyester fiber product.
The flame retardant hydrophobic polyester fiber fabrics prepared in examples 1-4 and the modified polyester fiber fabrics prepared in comparative examples 1-2 were tested for flame retardant property, hydrophobic property and water washing resistance.
The Limiting Oxygen Index (LOI) of the fabric is determined according to GB/T5454-1997 textile Combustion Performance test oxygen index method.
The damage length of the fabric is measured according to the standard GB/T5455-2014 'determination of smoldering and afterflame time of damage length in the vertical direction of the burning performance of the textile'.
The combustion performance of the fabric is evaluated according to the GB/T17591 and 2006 flame-retardant fabric standard.
The contact angle of the fabric is measured according to DB 44/T1872-2016 contact angle method for measuring the wettability of textile surfaces.
The washing method of the flame-retardant hydrophobic polyester fiber fabric is referred to AATCC 61-2006 accelerated test of washing fastness for household and business.
The flame retardant properties of the flame retardant hydrophobic polyester fiber fabric were finally measured as follows:
TABLE 1
As can be seen from the table, the unfinished polyester fiber fabric is completely burnt in the vertical burning process, the damaged length is 30cm, and serious molten drops are generated, which indicates that the flame retardant property is poor; the contact angle of the unfinished polyester fiber fabric was 0 o Indicating that it has poor hydrophobic properties. The LOI of the polyester fiber fabric finished by the phosphorus-containing flame-retardant hydrophobic agent is increased from 20.1 percent to more than 26.5 percent, the damage length is obviously reduced, no molten drop is generated, and the contact angle is higher than 110 o (the invention is exemplified by the flame retardant hydrophobic polyester fiber article of example 3As shown in fig. 1), indicating that the flame retardant hydrophobic polyester fiber fabric has excellent flame retardant property and hydrophobic property.
As shown in Table 1, the polyester fiber fabric finished by the phosphorus-containing flame-retardant hydrophobic agent can still be self-extinguished in a vertical combustion test after being washed for 20 times, the damage length is less than 15.0cm, no molten drop is generated, and the effect that B is achieved 1 Requirement for flame retardancy (the present invention exemplarily shows a vertical burning picture before and after washing the flame retardant hydrophobic polyester fiber article of example 3 with water for 20 times, as shown in fig. 2). As shown in comparative example 1 and comparative example 2, the polyester fiber fabric independently finished by oleic acid and phosphorus trichloride can respectively obtain better flame retardant property and hydrophobic property, but the finished fabric loses flame retardant effect after being washed by water and has poor water washing resistance. The results show that the polyester fiber fabric finished by the phosphorus-containing flame-retardant hydrophobic agent has good flame retardant property, hydrophobic property and water 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 (8)
1. The preparation method of the phosphorus-containing flame-retardant hydrophobic agent is characterized by comprising the steps of firstly reacting oleic acid with bromine, then carrying out hydrolysis treatment to obtain an intermediate product I, then reacting the intermediate product I with phosphorus trichloride to form an intermediate product II, and finally carrying out hydrolysis treatment on the intermediate product II to obtain the phosphorus-containing flame-retardant hydrophobic agent, wherein the molar ratio of oleic acid to bromine is 1: 1-1.1, and the molar ratio of phosphorus trichloride to oleic acid is more than or equal to 1.7/2.
2. The preparation method of the phosphorus-containing flame-retardant hydrophobic agent according to claim 1, characterized by comprising the following steps:
(a) placing oleic acid into a container, dropwise adding bromine, raising the temperature to 60-70 ℃ after dropwise adding, reacting for 40-50 min, adding distilled water, continuing to react for 30-40 min, and filtering and separating a product to obtain an intermediate product I;
(b) and (3) dropwise adding phosphorus trichloride into the intermediate product I, raising the temperature to 50-60 ℃ after dropwise adding, reacting for 2-4 h, adding distilled water, continuing to react for 0.5-1 h, and separating supernatant to obtain the phosphorus-containing flame-retardant hydrophobic agent.
3. The application of the phosphorus-containing flame-retardant hydrophobic agent prepared by the preparation method of the phosphorus-containing flame-retardant hydrophobic agent as claimed in any one of claims 1 to 2 is characterized in that the phosphorus-containing flame-retardant hydrophobic agent is dissolved in a solvent to obtain a flame-retardant hydrophobic finishing liquid, and then the polyester fiber product is modified by a rolling-baking method to obtain the flame-retardant hydrophobic polyester fiber product, wherein the baking temperature is not lower than the vitrification temperature of the polyester fiber product and not higher than the softening temperature of the polyester fiber product.
4. The use according to claim 3, wherein the solvent is ethanol or a mixture of ethanol and water.
5. The use according to claim 3, wherein the concentration of the flame-retardant hydrophobic finishing liquor is 150 to 300 g/L.
6. The use according to claim 3, wherein the rolling-drying-baking method comprises a rolling residual rate of 100-120%, a pre-drying temperature of 60-80 ℃, a pre-drying time of 3-5 min, a baking temperature of 160-180 ℃ and a baking time of 2-5 min.
7. Use according to claim 3, characterized in that the polyester fabric is a raw polyester fabric or a regenerated polyester fabric.
8. Use according to claim 3, characterized in that the fire-retardant hydrophobic polyester fiber article has a contact angle with water higher than 110 o And the LOI is more than 26.5 percent, the damage length in the vertical burning test after 0 time of water washing is not more than 12.8cm, and the damage length in the vertical burning test after 20 times of water washing is not more than 14.8 cm.
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