CN117051602A - Flame-retardant coating adhesive for nylon fabric and preparation method thereof - Google Patents
Flame-retardant coating adhesive for nylon fabric and preparation method thereof Download PDFInfo
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- CN117051602A CN117051602A CN202311275931.8A CN202311275931A CN117051602A CN 117051602 A CN117051602 A CN 117051602A CN 202311275931 A CN202311275931 A CN 202311275931A CN 117051602 A CN117051602 A CN 117051602A
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- coating adhesive
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 50
- 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 46
- 229920001778 nylon Polymers 0.000 title claims abstract description 34
- 239000004677 Nylon Substances 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 239000004744 fabric Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 9
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims abstract description 8
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 64
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 230000001105 regulatory effect Effects 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 5
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229920006052 Chinlon® Polymers 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract description 2
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 abstract 2
- 239000004970 Chain extender Substances 0.000 abstract 1
- 239000002981 blocking agent Substances 0.000 abstract 1
- 238000004945 emulsification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0034—Polyamide fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses flame-retardant coating adhesive for nylon fabric and a preparation method thereof. 2-aminobenzothiazole, phosphorus oxychloride and ethylene glycol are used as raw materials to synthesize phosphorus-nitrogen-sulfur-containing polyester diol, isophorone diisocyanate, polyether or polyester diol and phosphorus-nitrogen-sulfur-containing polyester diol are reacted, 2-dimethylolpropionic acid is used as a hydrophilic chain extender, methyl ethyl ketoxime is used as a blocking agent, blocking type flame-retardant aqueous polyurethane emulsion is obtained through high-speed shearing and emulsification, and a proper amount of thickener is added to obtain the flame-retardant coating adhesive for nylon fabrics. The flame-retardant coating adhesive contains three flame-retardant elements of phosphorus, nitrogen and sulfur, so that the nylon fabric is endowed with good flame-retardant performance; the Schiff base imine structure containing C=N can prevent the generation of molten drops; contains blocked isocyanate groups, and is crosslinked with active groups on the fiber after being heated and deblocked; the molecular chains of polyurethane and chinlon both contain amide groups, have similar and compatible structures, and have durable flame-retardant performance.
Description
Technical Field
The invention relates to the technical field of textile printing and dyeing auxiliary synthesis, in particular to flame-retardant coating adhesive for nylon fabric and a preparation method thereof.
Background
Flame retardants are a class of additives that can prevent a polymeric material from igniting or suppressing flame propagation. Nylon has been widely used in civil and military fields due to its excellent properties, however, it has high flammability and serious dripping problems during combustion, which brings hidden danger to life safety of people. The flame retardant used for nylon fabrics in the market at present is few, because the flame retardant effect of common flame retardants such as phosphorus-based flame retardants, phosphorus-nitrogen synergistic flame retardants and the like on nylon is not obvious, and in addition, the flame retardant finishing method of nylon fabrics is usually a padding baking method, but the flame retardant is difficult to penetrate into the fiber and can only be attached to the surface of the fabric in a small adsorption amount, so that the washed fastness of the finished fabric is poor in flame retardant effect. Therefore, flame retardation research of nylon fabrics has become an important subject.
Disclosure of Invention
Aiming at the defects of the prior art of nylon flame retardance, the invention provides a flame retardant coating adhesive capable of endowing nylon fabrics with better durability and flame retardance and a preparation method thereof.
The technical scheme for achieving the aim of the invention is to provide a preparation method of flame-retardant coating adhesive for nylon fabric, which comprises the following steps:
(1) 15 parts of 2-aminobenzothiazole, 30-35 parts of triethylamine and 40-60 parts of tetrahydrofuran are added into a reaction vessel with a stirrer and a condensing reflux device according to parts by weight; starting a condensing reflux device and a stirrer, regulating the temperature to 0-5 ℃, gradually dropwise adding 15-20 parts of phosphorus oxychloride, finishing dropwise adding within 40-70 min, carrying out heat preservation reaction for 2-3 hours at the temperature of 0-5 ℃, heating to 30-40 ℃, and carrying out heat preservation reaction for 3-4 hours; then adjusting the temperature to 0-5 ℃, adding 6-8 parts of ethylene glycol to react for 1-2 hours, heating to 60-70 ℃, preserving heat to react for 8-12 hours, and cooling to room temperature; filtering the reaction solution to remove insoluble substances, regulating the temperature of the filtrate to 30-40 ℃, regulating the pressure to-0.08 to-0.1 Mpa, and carrying out reduced pressure distillation to remove and recycle tetrahydrofuran to obtain an intermediate I;
(2) Adding 10-30 parts of the intermediate I prepared in the step (1), 10-20 parts of acetone and 20 parts of polyester diol or polyether diol into a reaction container with a stirrer, a condensation reflux device and a dropping funnel, starting the condensation reflux device and the stirrer, gradually heating to 70-80 ℃, adding 0.05-0.1 part of dibutyltin dilaurate, gradually dropwise adding 15-18 parts of isophorone diisocyanate, finishing dropwise adding within 30-60 min, and reacting at the temperature of 70-80 ℃ under the condition of keeping the temperature for 2-3 h; 1 to 3 parts of 2, 2-dimethylolpropionic acid is completely dissolved in 2 to 5 parts of N, N-dimethylformamide, then added into a reaction vessel, the temperature is regulated to 80 to 90 ℃, after the reaction is carried out at the temperature of 1.5 to 2 h, 1 to 6 parts of methyl ethyl ketoxime is added into the reaction vessel, and the reaction at the temperature of 1 to 1.5 h is continued; cooling the reaction liquid to 40-50 ℃, adding 1-3 parts of triethylamine into a reaction container, and keeping the temperature at 40-50 ℃ for reaction of 0.5-1 h; regulating the pressure to be-0.08 to-0.1 Mpa, distilling under reduced pressure to remove and recycle acetone, adding 125-180 parts of deionized water, and stirring at a high speed of 1500-3000 rpm for 0.5-1 h to obtain aqueous polyurethane emulsion;
(3) Slowly adding 3-6 parts of thickener into the aqueous polyurethane emulsion prepared in the step (2), and stirring at a rotating speed of 1000-1500 rpm to obtain the aqueous polyurethane flame-retardant coating adhesive.
The polyether glycol in the step (2) comprises one of polyethylene glycol-1000 and polypropylene glycol-1000; the polyester diol comprises polycaprolactone diol-1000.
The technical scheme of the invention also comprises the flame-retardant coating adhesive for the nylon fabric, which is prepared by the preparation method.
The preparation of the waterborne polyurethane flame-retardant coating adhesive for chinlon in the technical scheme of the invention is mainly based on the following principle: the phosphorus atom on phosphorus oxychloride being SP 3 The hybridization, p=o bond provides the lone pair electron on the oxygen phosphorus orbit to the P-Cl bond related shoulder bond, thus forming P bond, its chlorine atom is easily replaced by nucleophile, but with the replacement of chlorine atom, the reactivity of the remaining P-Cl bond will decrease, so the product of partially replacing chlorine atom can be obtained by controlling the reaction condition. The invention firstly uses phosphorus oxychloride to react with 2-aminobenzothiazole to obtain benzothiazole-2-phosphoramide dichloro intermediate, and then the intermediate is polycondensed with excessive glycolObtaining a polymer with hydroxyl ends by reaction, and then reacting the polymer with the hydroxyl ends as soft segments with isophorone diisocyanate to synthesize an isocyanate group-terminated polyurethane prepolymer; further utilizing the hydroxyl group of the 2, 2-dimethylolpropionic acid to react with isocyanate groups in the polyurethane prepolymer for chain extension; and then blocking isocyanate at the tail end of the molecule by using methyl ethyl ketoxime, emulsifying to obtain flame-retardant waterborne polyurethane emulsion, and finally adding a proper amount of thickener to prepare the waterborne polyurethane flame-retardant coating adhesive under high-speed stirring. According to the invention, three flame retardant elements including phosphorus, nitrogen and sulfur are introduced into the polyurethane main chain, so that further pyrolysis of nylon can be effectively restrained, and the flame retardant property of the fabric is improved; the flame-retardant adhesive contains a Schiff base imine structure with C=N, chemical crosslinking is easy to occur at high temperature, and a six-membered ring structure is formed, so that the formation of a carbon layer can be promoted, and the generation of molten drops can be prevented by improving the melt viscosity in the combustion process of nylon fabric; in addition, the coating adhesive contains blocked isocyanate groups, can be chemically crosslinked with active groups on fibers after being heated and unsealed, and simultaneously, as the molecular chains of polyurethane and nylon all contain amide groups, the structure is similar and compatible, and after being heated at high temperature, a eutectic structure can be formed, so that the nylon fabric can be endowed with better durable flame retardant property by utilizing the chemical crosslinking and the eutectic effect.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the three flame-retardant elements of phosphorus, nitrogen and sulfur are introduced into the main chain of the molecule of the synthesized waterborne polyurethane flame-retardant coating glue, and the synergistic flame-retardant effect of the three elements can be utilized to effectively inhibit the pyrolysis of nylon, so that the fabric is endowed with better flame-retardant performance; the flame-retardant adhesive contains a Schiff base imine structure with C=N, chemical crosslinking is easy to occur at high temperature, and a six-membered ring structure is formed, so that the formation of a carbon layer can be promoted, the melt viscosity in the combustion process of nylon fabric can be improved, and the generation of molten drops is prevented.
2. The invention adopts methyl ethyl ketoxime to end-cap the water-based polyurethane, and the blocked isocyanate group can be deblocked during high-temperature baking, and can perform chemical crosslinking with active groups in nylon fiber molecules, thereby improving the film forming performance and the fixing capability of the polyurethane on the fiber; in addition, as the molecular chains of the polyurethane and the nylon all contain amide groups, the polyurethane and the nylon have similar and compatible structures, and a eutectic effect can be generated between the polyurethane and the nylon after the polyurethane and the nylon are baked at high temperature, and the nylon fabric can have better durable flame retardant property due to the double effects of crosslinking and eutectic.
Drawings
Fig. 1 is an infrared spectrogram of a waterborne polyurethane flame-retardant coating adhesive provided by the embodiment of the invention.
Description of the embodiments
The technical scheme of the invention is further described below with reference to the accompanying drawings and the specific embodiments.
Example 1
The embodiment provides a waterborne polyurethane flame-retardant coating adhesive, which is prepared by the following steps:
(1) 15.00 g of 2-aminobenzothiazole, 33.06 g triethylamine, 55.00: 55.00 g tetrahydrofuran were added to a reaction vessel equipped with a stirrer and a condensate reflux apparatus; starting a condensing reflux device and a stirrer, regulating the temperature to 3 ℃, gradually adding 19.93 g phosphorus oxychloride, dropwise adding within 60 min to complete, keeping the temperature at the temperature for reaction for 3 hours, heating to 35 ℃, keeping the temperature for reaction for 3.5 hours, regulating the temperature to 5 ℃, adding 7.15 g glycol for reaction for 2 hours, heating to 65 ℃, keeping the temperature for reaction for 10 hours, filtering the reaction solution to remove insoluble matters, regulating the temperature of the filtrate to 35 ℃, keeping the pressure to-0.085 Mpa, decompressing, distilling to remove and recycling tetrahydrofuran to obtain the intermediate I.
(2) Adding 30 g intermediate I, 20 g acetone and 20 g polyethylene glycol-1000 into a reaction vessel with a stirrer, a condensation reflux device and a dropping funnel; starting a condensing reflux device and a stirrer, gradually heating to 80 ℃, adding 0.1 g dibutyl tin dilaurate, gradually dropwise adding 15.56 g isophorone diisocyanate, and finishing dropwise adding within 60 min, and carrying out heat preservation reaction at the temperature of 2 h; 2.62 g of 2, 2-dimethylolpropionic acid is completely dissolved in 3 g of N, N-dimethylformamide, and then is added into a reaction vessel, the temperature is regulated to 80 ℃, after the reaction is carried out at the temperature of 2 h, 1.12 g methyl ethyl ketoxime is added into the reaction vessel for continuous thermal insulation reaction 1 h; after the reaction solution was cooled to 40 ℃, 2.17. 2.17 g triethylamine was added to the reaction vessel, the reaction was carried out at 50 ℃ for 0.5 hours under heat preservation, the pressure was adjusted to-0.09 Mpa, acetone was removed and recovered by distillation under reduced pressure, and after 166.5. 166.5 g deionized water was added, the mixture was stirred at a high speed at a rotational speed of 1500 rpm for 1 hour to obtain an aqueous polyurethane emulsion.
(3) Slowly adding the 4 g thickener into the aqueous polyurethane emulsion prepared in the step (2), and stirring at a rotating speed of 1500 rpm to obtain the aqueous polyurethane flame-retardant coating adhesive.
Referring to fig. 1, an infrared spectrogram of the aqueous polyurethane flame-retardant coating adhesive provided in the embodiment; 3329.8 cm in the drawing -1 The N-H telescopic vibration absorption peak is 2949.0 cm -1 And 2860.8 cm -1 respectively-CH 3 and-CH 2 Peak of telescopic vibration absorption 1710.3 cm -1 At c=o, the peak of telescopic vibration absorption, 1537.4 cm -1 The in-plane bending absorption peak of N-H is 1641.1 cm -1 At c=n, the characteristic peak of stretching vibration, furthermore 2270.0 cm -1 The characteristic peak of stretching vibration of the poly-NCO disappears, and the peak indicates the formation of an amide bond (NHCOO-) in polyurethane; 1233.4 cm -1 At p=o characteristic absorption peak, 1040.6 cm -1 And 960.0 cm -1 At the characteristic absorption peak of P-O-C, while 3449.5 cm -1 The corresponding-OH broad characteristic absorption peak disappeared, indicating that the product had been successfully synthesized.
Example 2
The preparation steps of the aqueous polyurethane flame-retardant coating adhesive provided by the embodiment are as follows:
(1) 22.50 g of 2-aminobenzothiazole, 45.00 g triethylamine, 60.00 g tetrahydrofuran were charged into a reaction vessel equipped with a stirrer and a condensate reflux apparatus; starting a condensing reflux device and a stirrer, regulating the temperature to 4 ℃, gradually adding 22.50 g phosphorus oxychloride, dropwise adding within 65 min to complete, carrying out heat preservation reaction for 2.5 hours at the temperature, raising the temperature to 30 ℃, carrying out heat preservation reaction for 4 hours at the temperature, regulating the temperature to 3 ℃, adding 9.00 g glycol to react for 1 hour, raising the temperature to 60 ℃, carrying out heat preservation reaction for 12 hours at the temperature, filtering the reaction solution to remove insoluble matters, regulating the temperature of the filtrate to 30 ℃, carrying out pressure to-0.09 Mpa, carrying out reduced pressure distillation to remove and recycling tetrahydrofuran, and obtaining the intermediate I.
(2) 15.00 g intermediate I, 15.00 g acetone and 30 g polyethylene glycol-1000 were added to a reaction vessel with a stirrer, a condensate reflux unit, and a dropping funnel; starting a condensing reflux device and a stirrer, gradually heating to 70 ℃, adding 0.075 g dibutyl tin dilaurate, gradually dropwise adding 22.50 g isophorone diisocyanate, finishing dropwise adding within 45 min, and carrying out heat preservation reaction at the temperature of 2.5 h; after 1.50 g of 2, 2-dimethylolpropionic acid is completely dissolved in 3 g of N, N-dimethylformamide, the mixture is added into a reaction vessel, the temperature is adjusted to 85 ℃, after the mixture is subjected to heat preservation reaction at the temperature of 2 h, 1.50 g methyl ethyl ketoxime is added into the reaction vessel for continuous heat preservation reaction of 1 h; after the reaction solution was cooled to 45 ℃, 3.00 g g triethylamine was added to the reaction vessel, the reaction was carried out at a temperature of 50 ℃ for 0.5 hour, the pressure was adjusted to-0.08 Mpa, acetone was removed and recovered by distillation under reduced pressure, 186.50 g g of deionized water was added, and the mixture was stirred at a high speed at 2000 rpm for 0.5 hour to obtain an aqueous polyurethane emulsion.
(3) Slowly adding 4.50 g thickener into the aqueous polyurethane emulsion prepared in the step (2), and stirring at a rotating speed of 1500 rpm to obtain the aqueous polyurethane flame-retardant coating adhesive.
Example 3
The preparation steps of the aqueous polyurethane flame-retardant coating adhesive provided by the embodiment are as follows
(1) 30.00 g of 2-aminobenzothiazole, 70.00 g triethylamine, 120.00 g tetrahydrofuran were charged into a reaction vessel equipped with a stirrer and a condensate reflux apparatus; starting a condensing reflux device and a stirrer, regulating the temperature to 5 ℃, gradually adding 40.00 g phosphorus oxychloride, dropwise adding within 70 min, reacting for 3 hours at the temperature, heating to 40 ℃, reacting for 4 hours at the temperature, regulating the temperature to 5 ℃, adding 16.00 g glycol, reacting for 2 hours, heating to 70 ℃, reacting for 12 hours at the temperature, filtering the reaction solution to remove insoluble matters, regulating the temperature of the filtrate to 40 ℃, the pressure to-0.1 Mpa, distilling under reduced pressure to remove and recovering tetrahydrofuran, thus obtaining the intermediate I.
(2) Adding the intermediate I of 60 g, acetone of 40 g and polyethylene glycol-1000 of 40 g into a reaction vessel with a stirrer, a condensation reflux device and a dropping funnel; starting a condensing reflux device and a stirrer, gradually heating to 80 ℃, adding 0.2 g dibutyl tin dilaurate, gradually dropwise adding 36.00 g isophorone diisocyanate, and finishing dropwise adding within 60 min, and carrying out heat preservation reaction at the temperature for 3 h; after 6 g of 2, 2-dimethylolpropionic acid is completely dissolved in 10 g of N, N-dimethylformamide, the mixture is added into a reaction vessel, the temperature is regulated to 90 ℃, after the mixture is subjected to heat preservation reaction at the temperature of 2 h, 12.00 g methyl ethyl ketoxime is added into the reaction vessel for continuous heat preservation reaction of 1.5 h; after the reaction solution was cooled to 50 ℃, 6.00 g g triethylamine was added to the reaction vessel, the reaction was carried out at a temperature of 50 ℃ under a constant temperature of 1.1 h, the pressure was adjusted to-0.1 Mpa, acetone was removed and recovered by distillation under reduced pressure, 360.00 g g deionized water was added, and the mixture was stirred at a high speed of 0.5 g h at a rotational speed of 3000 rpm to obtain an aqueous polyurethane emulsion.
(3) Slowly adding the 12 g thickener into the aqueous polyurethane emulsion prepared in the step (2), and stirring at a rotation speed of 2000 rpm to obtain the aqueous polyurethane flame-retardant coating adhesive.
The aqueous polyurethane flame-retardant coating glue obtained in the examples 1, 2 and 3 is respectively taken to finish nylon fabrics,
the specific finishing method comprises the following steps: coating the coating adhesive on nylon fabric (30 cm ×40 cm) by adopting an N047 type knife coater, wherein the coating thickness is 1 mm, the knife speed is 40 m/min, the temperature is 25 ℃, the coating adhesive is coated on one side of the fabric twice, the baking is 110 s at 140 ℃, and the coating addition amount of the nylon fabric is 30 g/m 2 。
Referring to GB/T5454-1997 oxygen index method for textile combustion performance test, an oxygen index instrument is adopted to carry out an oxygen index LOI test on nylon fabric; referring to GB/T5455-2014 vertical method for testing the burning performance of textiles, a vertical burning tester is used for testing the continuous burning time, smoldering time and damage length of the fabrics before and after finishing; wash fastness according to AATCC 61-2007: the method 1A in the acceleration determines the wash fastness of the fabric. Application performance test results of the flame retardant coating adhesive obtained in each example the test results are shown in table 1.
TABLE 1
Claims (3)
1. The preparation method of the flame-retardant coating adhesive for the nylon fabric is characterized by comprising the following steps of:
(1) 15 parts of 2-aminobenzothiazole, 30-35 parts of triethylamine and 40-60 parts of tetrahydrofuran are added into a reaction vessel with a stirrer and a condensing reflux device according to parts by weight; starting a condensing reflux device and a stirrer, regulating the temperature to 0-5 ℃, gradually dropwise adding 15-20 parts of phosphorus oxychloride, finishing dropwise adding within 40-70 min, carrying out heat preservation reaction for 2-3 hours at the temperature of 0-5 ℃, heating to 30-40 ℃, and carrying out heat preservation reaction for 3-4 hours; then adjusting the temperature to 0-5 ℃, adding 6-8 parts of ethylene glycol to react for 1-2 hours, heating to 60-70 ℃, preserving heat to react for 8-12 hours, and cooling to room temperature; filtering the reaction solution to remove insoluble substances, regulating the temperature of the filtrate to 30-40 ℃, regulating the pressure to-0.08 to-0.1 Mpa, and carrying out reduced pressure distillation to remove and recycle tetrahydrofuran to obtain an intermediate I;
(2) Adding 10-30 parts of the intermediate I prepared in the step (1), 10-20 parts of acetone and 20 parts of polyester diol or polyether diol into a reaction container with a stirrer, a condensation reflux device and a dropping funnel, starting the condensation reflux device and the stirrer, gradually heating to 70-80 ℃, adding 0.05-0.1 part of dibutyltin dilaurate, gradually dropwise adding 15-18 parts of isophorone diisocyanate, finishing dropwise adding within 30-60 min, and reacting at the temperature of 70-80 ℃ under the condition of keeping the temperature for 2-3 h; 1 to 3 parts of 2, 2-dimethylolpropionic acid is completely dissolved in 2 to 5 parts of N, N-dimethylformamide, then added into a reaction vessel, the temperature is regulated to 80 to 90 ℃, after the reaction is carried out at the temperature of 1.5 to 2 h, 1 to 6 parts of methyl ethyl ketoxime is added into the reaction vessel, and the reaction at the temperature of 1 to 1.5 h is continued; cooling the reaction liquid to 40-50 ℃, adding 1-3 parts of triethylamine into a reaction container, and keeping the temperature at 40-50 ℃ for reaction of 0.5-1 h; regulating the pressure to be-0.08 to-0.1 Mpa, distilling under reduced pressure to remove and recycle acetone, adding 125-180 parts of deionized water, and stirring at a high speed of 1500-3000 rpm for 0.5-1 h to obtain aqueous polyurethane emulsion;
(3) Slowly adding 3-6 parts of thickener into the aqueous polyurethane emulsion prepared in the step (2), and stirring at a rotating speed of 1000-1500 rpm to obtain the aqueous polyurethane flame-retardant coating adhesive.
2. The method for preparing the flame-retardant coating adhesive for nylon fabrics according to claim 1, which is characterized in that: the polyether glycol in the step (2) comprises one of polyethylene glycol-1000 and polypropylene glycol-1000; the polyester diol comprises polycaprolactone diol-1000.
3. A flame retardant coating adhesive for nylon fabrics obtained by the preparation method of claim 1.
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