CN114634532A - Preparation method and application of flame-retardant hydrophobic agent - Google Patents
Preparation method and application of flame-retardant hydrophobic agent Download PDFInfo
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- CN114634532A CN114634532A CN202210534811.4A CN202210534811A CN114634532A CN 114634532 A CN114634532 A CN 114634532A CN 202210534811 A CN202210534811 A CN 202210534811A CN 114634532 A CN114634532 A CN 114634532A
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- retardant
- intermediate product
- retardant hydrophobic
- hydrophobic agent
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- 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 130
- 239000003063 flame retardant Substances 0.000 title claims abstract description 129
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 116
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 82
- 239000013067 intermediate product Substances 0.000 claims abstract description 67
- 239000000835 fiber Substances 0.000 claims abstract description 60
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 45
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 37
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 28
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 27
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005642 Oleic acid Substances 0.000 claims abstract description 27
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 230000006378 damage Effects 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000007598 dipping method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 150000001263 acyl chlorides Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920004933 Terylene® Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a preparation method and application of a flame-retardant hydrophobic agent, wherein the preparation method comprises the following steps: firstly, oleic acid reacts with bromine, then hydrolysis treatment is carried out to obtain an intermediate product I, then the intermediate product I reacts with phosphorus oxychloride to generate an intermediate product II, finally the intermediate product II reacts with phenol or benzyl alcohol to form an intermediate product III, and then the intermediate product III is hydrolyzed to prepare the flame-retardant hydrophobic agent, wherein the molar ratio of the oleic acid to the bromine is 1: 1-1.1, the molar ratio of the oleic acid to the phosphorus oxychloride is 1: 1.3-1.5, and the molar ratio of the oleic acid to the phenol or the benzyl alcohol is 1: 1-1.2; the application comprises the following steps: after the flame-retardant hydrophobic agent is dissolved in a solvent to obtain flame-retardant hydrophobic finishing liquid, the polyester fiber product is modified by a rolling-drying-baking method to obtain the flame-retardant hydrophobic polyester fiber product. The flame-retardant hydrophobic agent disclosed by the invention has a higher flame-retardant function and a hydrophobic function, is a halogen-free fluorine-free environment-friendly multifunctional finishing agent, and has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of functional modification of textiles, relates to a preparation method and application of a flame-retardant hydrophobic agent, and particularly relates to a preparation method of a flame-retardant hydrophobic agent and a method for preparing a flame-retardant hydrophobic modified polyester fiber product by using the same.
Background
The polyester fiber is cracked at high temperature by a free radical synchronous crosslinking mechanism. The thermal decomposition generates a lot of heat, low molecular smoke and combustible substances. In order to improve the flame retardant property of polyester fiber products, various types of flame retardants have been developed in recent years, and most of them are halogen-containing flame retardants. However, the halogen flame retardant can release toxic gases such as hydrogen halide and the like in the combustion process and bring harm to physical and mental health and ecological environment of people along with dense smoke. The existing commercialized cyclic phosphate ester flame retardant can improve the flame retardant property of polyester fiber products, but has the defect of large smoke quantity, the release of smoke in fire can obstruct the sight of escapers, so that panic is caused, toxic gas in the smoke can cause shock of human bodies, and escape opportunities are missed. Therefore, the development of a novel halogen-free and smoke-suppressing flame-retardant technology for polyester fiber products is urgently needed.
On the other hand, polyester fiber products with single flame retardant function have been difficult to meet the complex requirements of different fields, and how to endow flame retardant polyester fiber fabrics with multiple functions, such as hydrophobicity and the like, has also gained more and more attention and research. Research on the preparation of the polyester fiber fabric with flame retardant and hydrophobic functions can effectively prevent stains and water solution from damaging the flame retardant function of the fabric, prolong the service life of the flame retardant fabric and further promote the practical application of polyester fiber products in various fields such as protective clothing, furniture decoration, outdoor packaging and the like. And the textile products are often subjected to washing treatment, so the washing resistance requirement of the functional textiles is strict. The development of the flame-retardant hydrophobic polyester fiber product with washing resistance is extremely important.
The prior art discloses compounds with both flame retardant property and hydrophobic property, such as phosphorus-containing polyglycerol fatty acid ester flame retardant plasticizers disclosed in documents (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 the compounds and polyester fiber products is limited, and the flame retardant hydrophobic modified polyester fiber products which are washable are difficult to prepare by a post-finishing method.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a flame-retardant hydrophobic agent.
The invention aims to solve the problems in the prior art from the following three aspects by designing a compound simultaneously containing phosphorus flame-retardant elements, a hydrophobic chain segment and a benzene ring ester end group:
(1) the hydrophobic chain segment in the flame-retardant hydrophobic agent can be combined with the terylene under the high-temperature baking condition by the similar intermiscibility principle;
(2) the structure of the benzene ring ester end group in the flame-retardant hydrophobic agent is similar to that of a macromolecular chain segment of terylene, and the flame-retardant hydrophobic agent can easily enter the interior of terylene fiber and can generate better combination;
(3) the hydrophobic chain segment in the flame-retardant hydrophobizing agent can be matched with the benzene ring ester end group structure, a larger hammer structure different from a linear chain is formed, the structure can be clamped and embedded inside polyester fibers after entering the polyester fibers, so that the whole structure is more difficult to separate from the polyester fibers, namely, the benzene ring ester end group hammer structure can play a role of a clamping point, although the hydrophobic linear long chain can be combined with the polyester fibers, the hydrophobic chain segment can still slide relative to the polyester fibers, the hydrophobic chain segment is difficult to slide after the benzene ring ester end group hammer structure is introduced, and the hydrophobic chain segment can be combined with the polyester fibers more tightly.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a 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 oxychloride to generate an intermediate product II, finally reacting the intermediate product II with phenol or benzyl alcohol to form an intermediate product III, and then carrying out hydrolysis treatment on the intermediate product III to obtain the flame-retardant hydrophobic agent, wherein:
the molar ratio of oleic acid to bromine is 1: 1-1.1, bromine is slightly excessive, the unsaturated double bond in oleate can be ensured to be reacted completely, and the added bromine is replaced by hydroxyl through hydrolysis reaction;
the molar ratio of oleic acid to phosphorus oxychloride is 1: 1.3-1.5, and the phosphorus oxychloride is slightly excessive, so that hydroxyl and carboxyl in the intermediate product I molecule are ensured to completely participate in the reaction;
the molar ratio of the oleic acid to the phenol or benzyl alcohol is 1: 1-1.2, and the phenol or benzyl alcohol is slightly excessive, so that the end acyl chloride in the oleic acid molecule is ensured to completely participate in the reaction;
in the reaction process of oleic acid and bromine, unsaturated double bond of oleic acid and bromine generate addition reaction, then hydroxyl is connected on two sides of the double bond through hydrolysis, phosphorus oxychloride and hydroxyl in oleic acid generate nucleophilic substitution reaction, and the carboxyl end group of the oleic acid and phosphorus oxychloride have acyl chloride reaction, then phenol or benzyl alcohol is adopted to react with the acyl chloride end group to generate a benzene ring ester end group (the adding speed and the using amount of the phenol or the benzyl alcohol are controlled, so that the phenol or the benzyl alcohol preferentially reacts with the acyl chloride end group, and a hammer structure of the benzene ring ester end group is introduced), during hydrolysis treatment, the reason why the excessive phosphorus oxychloride is hydrolyzed to generate phosphoric acid and the intermediate product III is hydrolyzed is that the active P-Cl structure is unstable, the compound is easy to react with water molecules in the storage and baking finishing processes, and the P-OH structure is stable and does not react in the storage and baking finishing processes;
the structural formula of the flame-retardant hydrophobic agent is as follows:
(I) phenol-based flame-retardant hydrophobing agents;
(II) a benzyl alcohol-based flame-retardant hydrophobic agent.
As a preferred technical scheme:
the preparation method of the 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, continuing to react for 30-40 min, and separating supernatant to obtain an intermediate product I;
(b) dropwise adding phosphorus oxychloride into the intermediate product I, reacting for 2-4 h at 50-60 ℃ after dropwise adding to obtain an intermediate product II, wherein the reactive chlorine in the phosphorus oxychloride molecule and the hydroxyl in the intermediate product I undergo nucleophilic substitution reaction and react with oleic acid terminal carboxyl to produce acyl chloride, and the reaction temperature is set so as to ensure that the reaction rate is high, and the reaction efficiency of the phosphorus oxychloride and the volatilization condition of the phosphorus oxychloride need to be comprehensively considered;
(c) and keeping the temperature unchanged, dropwise adding phenol or benzyl alcohol into the intermediate product II, reacting for 1-2 hours after dropwise adding, adding distilled water, continuing reacting for 0.5-1 hour, and separating supernatant to obtain the flame-retardant hydrophobic agent.
The invention also provides application of the flame-retardant hydrophobic agent prepared by the preparation method of the flame-retardant hydrophobic agent, the 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 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 mixture of ethanol and water.
According to the application, the concentration of the flame-retardant hydrophobic finishing liquid is 100-250 g/L, and the concentration of the flame-retardant hydrophobic finishing liquid can be properly reduced due to the high efficiency of the phosphorus-containing flame retardant.
According to the application, the rolling residual rate of rolling in the rolling-drying-baking method 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.
As mentioned above, the polyester fiber product is a raw polyester fiber fabric or a regenerated polyester fiber fabric.
The flame-retardant hydrophobic polyester fiber product has a contact angle with water higher than 114oAnd the LOI is more than 26.7 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 30 times of water washing is not more than 14.8 cm.
Has the advantages that:
(1) according to the preparation method of the flame-retardant hydrophobic agent, the prepared flame-retardant hydrophobic agent has a high flame-retardant function and a high hydrophobic function, is a halogen-free fluorine-free environment-friendly multifunctional finishing agent, and has a wide application prospect;
(2) the method 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 vertical burning pattern of the flame retardant hydrophobic polyester fiber article of example 2 after being washed with water 30 times;
fig. 2 is a contact angle test chart of an unfinished polyester fabric and the flame retardant hydrophobic polyester fiber article of example 5.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 16.0g of bromine (0.1mol) is slowly dripped, after the dripping is finished, the reaction is carried out for 50min at 60 ℃, adding 10mL of distilled water, continuing the reaction for 40min, separating the supernatant to obtain an intermediate product I, slowly dropwise adding 19.9g of phosphorus oxychloride (0.13 mol) into the intermediate product I, after the dropwise addition is finished within 1h (the dropwise addition time is controlled to be about 1h as far as possible, the dropwise addition time cannot be too short, the time is too short, the reaction is insufficient), the temperature is adjusted to 50 ℃, the reaction is carried out for 4h to obtain an intermediate product II, then keeping the temperature unchanged, slowly dropwise adding 9.4g of phenol (0.1mol) into the intermediate product II, reacting for 1h after dropwise adding to obtain an intermediate product III, keeping the temperature unchanged, adding 15.8mL of distilled water into the intermediate product III, continuing reacting for 0.5h, and separating supernatant to obtain the flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: dissolving the flame-retardant hydrophobic agent in ethanol to obtain a flame-retardant hydrophobic finishing liquid with the concentration of 200g/L, and then adopting the flame-retardant hydrophobic finishing liquid to treat the virgin polyester fabric (120 g/m)2Crossed fabric) is subjected to two-dipping and two-rolling treatment, the dipping time is 13min each time, the rolling residual rate of each rolling is 120%, then the primary polyester fabric is dried for 3min at 80 ℃, then is dried for 3min at 180 ℃, and is dried after being washed by water to obtain the flame-retardant hydrophobic polyester fiber product.
Comparative example 1
(1) Firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 16.0g of bromine (0.1mol) is slowly dripped, after the dripping is finished, the mixture reacts for 50min at 60 ℃, 10mL of distilled water is added, the reaction is continued for 40min, the supernatant is separated to obtain an intermediate product I, then 19.9g of phosphorus oxychloride (0.13 mol) is slowly dripped into the intermediate product I, after the dripping is finished 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), the temperature is adjusted to 50 ℃, the reaction is continued for 4h to obtain an intermediate product II, finally, the temperature is kept unchanged, after 15.8mL of distilled water is added into the intermediate product II, the reaction is continued for 0.5h, and the supernatant is separated to obtain a flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the preparation method is basically the same as that of example 1, except that the flame-retardant hydrophobic finishing liquid is prepared by dissolving the flame-retardant hydrophobic agent of comparative example 1 in ethanol, and the concentration of the flame-retardant hydrophobic finishing liquid is 200 g/L.
Example 2
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 17.6 g of bromine (0.11mol) is slowly dripped, after the dripping is finished, the reaction is carried out for 40min at 70 ℃, adding 10mL of distilled water, continuing to react for 40min, separating the supernatant to obtain an intermediate product I, slowly dropwise adding 23.0g of phosphorus oxychloride (0.15 mol) into the intermediate product I, after the dropwise adding is finished within 1h (the dropwise adding time is controlled to be about 1h as far as possible, the dropwise adding time cannot be too short, the time is too short, the reaction is insufficient), the temperature is adjusted to 60 ℃, the reaction is carried out for 2h to obtain an intermediate product II, then keeping the temperature unchanged, slowly dropwise adding 11.3g of phenol (0.12mol) into the intermediate product II, reacting for 2h after dropwise adding to obtain an intermediate product III, finally keeping the temperature unchanged, adding 15.8mL of distilled water into the intermediate product III, continuing reacting for 1h, and separating supernatant to obtain the flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: dissolving the flame-retardant hydrophobic agent in ethanol to obtain 100g/L flame-retardant hydrophobic finishing liquid, and then adopting the flame-retardant hydrophobic finishing liquid to treat the virgin polyester fabric (120 g/m)2Crossed fabric) is subjected to two-dipping and two-rolling treatment, the dipping time is 8min each time, the rolling residual rate of each rolling is 110%, then the primary polyester fabric is dried for 4min at 65 ℃, then is dried for 4min at 170 ℃, and is dried after being washed by water to obtain the flame-retardant hydrophobic polyester fiber product.
Example 3
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 16.0g of bromine (0.1mol) is slowly dripped, after the dripping is finished, the reaction is carried out for 55min at 65 ℃, adding 10mL of distilled water, continuing the reaction for 30min, separating the supernatant to obtain an intermediate product I, slowly dropwise adding 18.4g of phosphorus oxychloride (0.12mol) into the intermediate product I, after the dropwise adding is finished within 1h (the dropwise adding time is controlled to be about 1h as far as possible, the dropwise adding time cannot be too short, the time is too short, the reaction is insufficient), the temperature is adjusted to 55 ℃, the reaction is carried out for 3h to obtain an intermediate product II, then keeping the temperature unchanged, slowly dropwise adding 10.3g of phenol (0.11mol) into the intermediate product II, reacting for 1h after dropwise adding to obtain an intermediate product III, keeping the temperature unchanged, adding 15.8mL of distilled water into the intermediate product III, continuing reacting for 0.5h, and separating supernatant to obtain the flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: dissolving the flame-retardant hydrophobic agent in ethanol to obtain 130g/L flame-retardant hydrophobic finishing liquid, and then adopting the flame-retardant hydrophobic finishing liquid to treat the primary polyester fabric (120 g/m)2Mixed fabric) is subjected to two-dipping and two-rolling treatment, the time of each dipping is 10min, the rolling residual rate of each rolling is 105%, then the raw polyester fabric is dried for 4min at 75 ℃, then is dried for 5min at 160 ℃, and is dried after being washed to obtain the flame-retardant hydrophobic polyester fiber product.
Example 4
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 16.0g of bromine (0.1mol) is slowly dripped, after the dripping is finished, the reaction is carried out for 50min at 60 ℃, adding 10mL of distilled water, continuing the reaction for 40min, separating the supernatant to obtain an intermediate product I, slowly dropwise adding 19.9g of phosphorus oxychloride (0.13 mol) into the intermediate product I, after the dropwise addition is finished within 1h (the dropwise addition time is controlled to be about 1h as far as possible, the dropwise addition time cannot be too short, the time is too short, the reaction is insufficient), the temperature is adjusted to 50 ℃, the reaction is carried out for 4h to obtain an intermediate product II, keeping the temperature unchanged, slowly dropwise adding 10.8g of benzyl alcohol (0.1mol) into the intermediate product II, reacting for 1h after dropwise adding to obtain an intermediate product III, keeping the temperature unchanged, adding 15.8mL of distilled water into the intermediate product III, continuing reacting for 0.5h, and separating supernatant to obtain the flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: dissolving the flame-retardant hydrophobic agent in a mixed solution of ethanol and water with a mass ratio of 1:1 to obtain a flame-retardant hydrophobic finishing liquid with a concentration of 160g/L, and then adopting the flame-retardant hydrophobic finishing liquid to treat the regenerated polyester fiber fabric (120 g/m)2Crossed fabric) is subjected to two-dipping and two-rolling treatment, the time of each dipping is 12min, the rolling residual rate of each rolling is 100%, then the regenerated polyester fiber fabric is dried for 3.5min at 70 ℃, and then the regenerated polyester fiber fabric is subjected to secondary dipping and two-rolling treatmentBaking at 165 ℃ for 4.5min, washing with water and drying to obtain the flame-retardant hydrophobic polyester fiber product.
Comparative example 2
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 16.0g of bromine (0.1mol) is slowly dripped, after the dripping is finished, the mixture reacts for 50min at 60 ℃, 10mL of distilled water is added, the reaction is continued for 40min, the supernatant is separated to obtain an intermediate product I, then 19.9g of phosphorus oxychloride (0.13 mol) is slowly dripped into the intermediate product I, after the dripping is finished within 1h (the dripping time is controlled to be about 1h as much as possible, the time cannot be too short, and the reaction cannot be sufficient), the temperature is adjusted to 50 ℃, the reaction is carried out for 4h to obtain an intermediate product II, finally, the temperature is kept unchanged, after 15.8mL of distilled water is added into the intermediate product II, the reaction is continued for 0.5h, and the supernatant is separated to obtain a flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: the preparation method is basically the same as that of example 4, except that the flame-retardant hydrophobic finishing liquid is prepared by dissolving the flame-retardant hydrophobic agent of comparative example 2 in ethanol, and the concentration of the flame-retardant hydrophobic finishing liquid is 160 g/L.
Example 5
(1) Preparation of the flame-retardant hydrophobic agent: firstly, 28.2g of oleic acid (0.1mol) is put into a three-neck flask, 17.6 g of bromine (0.11mol) is slowly dripped, after the dripping is finished, the reaction is carried out for 40min at 70 ℃, adding 10mL of distilled water, continuing to react for 40min, separating the supernatant to obtain an intermediate product I, slowly dropwise adding 23.0g of phosphorus oxychloride (0.15 mol) into the intermediate product I, after the dropwise addition is finished within 1h (the dropwise addition time is controlled to be about 1h as much as possible, the dropwise addition time cannot be too short, the time is too short, and the reaction is insufficient), the temperature is adjusted to 60 ℃, the reaction is carried out for 2h to obtain an intermediate product II, keeping the temperature unchanged, slowly dripping 13.0g of benzyl alcohol (0.12mol) into the intermediate product II, reacting for 2 hours after dripping is finished to obtain an intermediate product III, keeping the temperature unchanged, adding 15.8mL of distilled water into the intermediate product III, continuing reacting for 1 hour, and separating supernate to obtain the flame-retardant hydrophobic agent;
(2) preparation of flame-retardant hydrophobic polyester fiber product: dissolving the flame-retardant hydrophobic agent in a mixture of ethanol and water with the mass ratio of 1:1After the flame-retardant hydrophobic finishing liquid with the concentration of 250g/L is obtained in the combined liquid, the flame-retardant hydrophobic finishing liquid is adopted to treat the regenerated polyester fiber fabric (120 g/m)2Crossed fabric) is subjected to two-dipping and two-rolling treatment, the time of each dipping is 14min, the rolling residual rate of each rolling is 117%, then the regenerated polyester fiber fabric is dried for 5min at 60 ℃, then is baked for 3.5min at 173 ℃, and is dried after being washed to obtain the flame-retardant hydrophobic polyester fiber product.
The flame retardant hydrophobic polyester fiber fabrics prepared in examples 1-5 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 GB/T5455-2014 Standard "determination of smoldering and afterflame time of damage length in the vertical direction of the burning performance of the fabric".
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 refers to AATCC 61-2006 accelerated test of washing fastness for household and commercial use.
The flame retardant properties of the flame retardant hydrophobic polyester fiber fabric were finally measured as follows:
as shown in the table, the damage length of the unfinished polyester fabric is 30cm, the melt drop is serious, and the LOI is only 20.0 percent, which indicates that the flame retardant property of the polyester fabric is poor; and the contact angle of the unfinished polyester fabric is 0oThe hydrophobic property is poor. The contact angle of the finished polyester fabric (i.e., the flame retardant hydrophobic polyester fiber product prepared in examples 1-5) was raised to 114 oThe above has better hydrophobic property. LOI of the finished polyester fabric increased to 26.7% above, the damage length is reduced to below 12.8cm, which shows that the flame retardant property is better. After being washed by water for 30 times, the flame-retardant polyester fabric can still be self-extinguished, the damage length is less than 14.8cm, and the flame-retardant polyester fabric meets the requirement of flame retardance B1Grade standard, show that the finished polyester fabric has excellent washing resistance. In addition, the finished polyester fabric in the comparative example also has better flame retardant property and hydrophobic property.
Compared with the example 1, the polyester fabric finished in the comparative example 1 loses the flame retardant effect after being washed for 30 times, which shows that the flame retardant durability is poorer than that of the example 1, because the hydrophobic long chain of the finishing agent of the comparative example 1 slides in the washing process, the flame retardant effect is reduced, and the finishing agent with a hammer structure in the example 1 has better washing resistance effect.
Compared with example 4, the polyester fabric finished in comparative example 2 loses the flame retardant effect after being washed for 30 times, which shows that the flame retardant durability is poorer than that of example 4, because the hydrophobic long chain of the finishing agent of comparative example 2 slips in the washing process, the flame retardant effect is reduced, and the finishing agent with a hammer structure in example 4 has better washing resistance.
As shown in fig. 2, which is a contact angle test chart of the unfinished polyester fabric and the flame retardant hydrophobic polyester fiber product of example 1, it can be seen that the finished polyester fabric has a good hydrophobic property.
Claims (8)
1. A preparation method of a flame-retardant hydrophobic agent is characterized by 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 oxychloride to generate an intermediate product II, finally reacting the intermediate product II with phenol or benzyl alcohol to form an intermediate product III, and then carrying out hydrolysis treatment on the intermediate product III to obtain the flame-retardant hydrophobic agent, wherein the molar ratio of the oleic acid to the bromine is 1: 1-1.1, the molar ratio of the oleic acid to the phosphorus oxychloride is 1: 1.3-1.5, and the molar ratio of the oleic acid to the phenol or benzyl alcohol is 1: 1-1.2.
2. The preparation method of the 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 separating supernatant to obtain an intermediate product I;
(b) dropwise adding phosphorus oxychloride into the intermediate product I, and reacting at 50-60 ℃ for 2-4 h after dropwise adding to obtain an intermediate product II;
(c) and keeping the temperature unchanged, dropwise adding phenol or benzyl alcohol into the intermediate product II, reacting for 1-2 h after dropwise adding, adding distilled water, continuing to react for 0.5-1 h, and separating supernatant to obtain the flame-retardant hydrophobic agent.
3. The application of the flame-retardant hydrophobic agent prepared by the preparation method of the flame-retardant hydrophobic agent according to any one of claims 1 to 2 is characterized in that the 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 glass transition 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 100 to 250 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 virgin polyester fabric or a recycled 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 114oAnd the LOI is more than 26.7 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 30 times of water washing is not more than 14.8 cm.
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| CN116065386A (en) * | 2023-01-16 | 2023-05-05 | 苏州大学 | Flame-retardant smoke-suppressing anti-dripping regenerated polyester fabric and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010070467A (en) * | 2008-09-16 | 2010-04-02 | Miyoshi Oil & Fat Co Ltd | Cyclic phosphorylated compound |
| US8822712B1 (en) * | 2010-09-01 | 2014-09-02 | The United States Of America, As Represented By The Secretary Of Agriculture | Process to prepare a phosphorous containing vegetable oil based lubricant additive |
| CN106146562A (en) * | 2015-03-26 | 2016-11-23 | 方建华 | A kind of production method of phosphorous nitride methyl oleate green lubrication additive |
| CN108003195A (en) * | 2016-10-31 | 2018-05-08 | 中国人民解放军后勤工程学院 | Phosphorous nitride is modified the preparation method of methyl oleate lubricating oil biodegradation promotor |
-
2022
- 2022-05-17 CN CN202210534811.4A patent/CN114634532A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010070467A (en) * | 2008-09-16 | 2010-04-02 | Miyoshi Oil & Fat Co Ltd | Cyclic phosphorylated compound |
| US8822712B1 (en) * | 2010-09-01 | 2014-09-02 | The United States Of America, As Represented By The Secretary Of Agriculture | Process to prepare a phosphorous containing vegetable oil based lubricant additive |
| CN106146562A (en) * | 2015-03-26 | 2016-11-23 | 方建华 | A kind of production method of phosphorous nitride methyl oleate green lubrication additive |
| CN108003195A (en) * | 2016-10-31 | 2018-05-08 | 中国人民解放军后勤工程学院 | Phosphorous nitride is modified the preparation method of methyl oleate lubricating oil biodegradation promotor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116065386A (en) * | 2023-01-16 | 2023-05-05 | 苏州大学 | Flame-retardant smoke-suppressing anti-dripping regenerated polyester fabric and preparation method thereof |
| CN116065386B (en) * | 2023-01-16 | 2023-12-15 | 苏州大学 | Flame-retardant smoke-suppressing anti-dripping regenerated polyester fabric and preparation method thereof |
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