CN118241336A - Phosphorus-containing coated MCA flame-retardant nylon fiber material and preparation method thereof - Google Patents
Phosphorus-containing coated MCA flame-retardant nylon fiber material and preparation method thereof Download PDFInfo
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- CN118241336A CN118241336A CN202410368031.6A CN202410368031A CN118241336A CN 118241336 A CN118241336 A CN 118241336A CN 202410368031 A CN202410368031 A CN 202410368031A CN 118241336 A CN118241336 A CN 118241336A
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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 189
- 239000003063 flame retardant Substances 0.000 title claims abstract description 189
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 129
- 239000011574 phosphorus Substances 0.000 title claims abstract description 129
- 229920001778 nylon Polymers 0.000 title claims abstract description 119
- 239000002657 fibrous material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000004677 Nylon Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000004062 sedimentation Methods 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 229920006118 nylon 56 Polymers 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- -1 triethylene glycol bis (3-laurylthiopropionate) Chemical compound 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- PADKXWJUAXDOGB-UHFFFAOYSA-N n-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CCC(=O)NC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PADKXWJUAXDOGB-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 238000002074 melt spinning Methods 0.000 description 10
- 238000009987 spinning Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- DMHHYBUEZRZGDK-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound NC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DMHHYBUEZRZGDK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 239000005644 Dazomet Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a phosphorus-containing coated MCA flame-retardant nylon fiber material and a preparation method thereof, wherein melamine cyanurate is mixed with non-solvent liquid to prepare MCA suspension, then the MCA suspension is added into liquid phosphorus-containing flame retardant, after being treated based on a natural sedimentation method, the non-solvent liquid is removed to obtain uniformly dispersed phosphorus-containing coated MCA flame retardant, and the uniformly dispersed phosphorus-containing coated MCA flame retardant is used as a raw material component to be mixed with nylon resin and then prepared into the phosphorus-containing coated MCA flame-retardant nylon fiber material according to a conventional nylon fiber process. According to the method, through a simple sedimentation process, the phosphorus-containing coated MCA flame retardant with the phosphorus-nitrogen synergistic effect is synthesized; meanwhile, the excellent dispersing capability of the phosphorus-containing flame retardant is realized by utilizing the coating effect of the phosphorus-containing flame retardant. The preparation method has simple process and low cost, and has better market prospect.
Description
Technical Field
The invention belongs to the technical field of flame-retardant nylon fiber materials, relates to a phosphorus-containing coated MCA flame-retardant nylon fiber material and a preparation method thereof, and in particular relates to a preparation method of a phosphorus-containing coated MCA flame retardant based on a natural sedimentation method and a preparation method of a flame-retardant nylon fiber material by taking the phosphorus-containing coated MCA flame retardant as a raw material.
Background
Nylon fibers (nylon) are widely used in the fields of clothing, bedding, parachutes, various decorative fabrics, and the like, by virtue of their excellent mechanical properties, heat resistance, abrasion resistance, chemical resistance, and self-lubricity. However, unmodified nylon fibers have poor flame retardant properties, and vertical burning test can only pass the UL-94V-2 test, and severe dripping can be generated during burning to cause secondary burning, thereby seriously threatening the safety of people and property. Therefore, designing nylon fiber materials with excellent flame retardant properties is of great importance in widening the application market thereof.
At present, the flame retardant modification of the fiber material is mainly realized by three methods of copolymerization modification, blending modification and fiber post-treatment. The copolymerization modification is to add a flame retardant with reactivity with nylon in the polymerization process, so that the flame retardant participates in the polymerization reaction and is introduced into a nylon molecular chain structure; the blending modification is to mix the flame retardant and nylon resin in advance, extrude and granulate and melt-spin; the fiber post-treatment is to make the nylon fiber have flame retardant effect by surface grafting, coating and other methods. The research and development cost of the copolymerization flame retardant modification is higher, the durability of the fiber post-treatment method is slightly poor, and only the blending flame retardant modification process is simple and the performance is durable. Therefore, developing a mature blending modification process becomes an important direction for industrialization of flame-retardant nylon fibers.
In the prior art, the flame retardant modification of nylon fibers is generally independent of Melamine Cyanurate (MCA) flame retardant, and the flame retardant modified nylon fibers are widely applied to various nylon products by virtue of the characteristics of environmental protection, stability, high efficiency and the like. However, the difficulty of blending and modifying nylon fibers is the contradiction between the addition amount of the flame retardant, the dispersibility and the fiber strength. Too high an amount of flame retardant may result in a failure of continuous spinning, while too low an amount of flame retardant may make it difficult to ensure excellent flame retardant properties of the fiber. Therefore, how to improve the dispersibility of the flame retardant and the flame retardant efficiency is a key problem of blending modification of nylon fibers.
In summary, if a new technology for preparing the flame-retardant nylon fiber material is simpler, more efficient and easier to implement, theoretical and data support is provided for the industrial application of the novel flame-retardant nylon fiber and the fabric thereof.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a phosphorus-containing coated MCA flame-retardant nylon fiber material and a preparation method thereof, wherein the method synthesizes a phosphorus-containing coated MCA flame retardant with phosphorus-nitrogen synergistic effect through a simple sedimentation process; meanwhile, the excellent dispersing capability of the phosphorus-containing flame retardant is realized by utilizing the coating effect of the phosphorus-containing flame retardant. The preparation method has simple process and low cost, and has better market prospect.
In order to achieve the above object, the present invention is realized by adopting the technical scheme comprising the following technical measures.
The preparation method of the phosphorus-containing coated MCA flame-retardant nylon fiber material mainly comprises the following steps:
(1) Mixing melamine cyanurate with a non-solvent liquid to prepare an MCA suspension;
(2) Adding the MCA suspension obtained in the step (1) into a liquid phosphorus-containing flame retardant, and removing non-solvent liquid after treatment based on a natural sedimentation method to obtain a uniformly dispersed phosphorus-containing coated MCA flame retardant;
(3) Taking the phosphorus-containing coated MCA flame retardant obtained in the step (2) as a raw material component, blending with nylon resin, and preparing the phosphorus-containing coated MCA flame retardant nylon fiber material according to a conventional nylon fiber process; wherein, the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon resin is 1: (10-30).
In this context, the melamine cyanurate in the step (1) is a salt synthesized from melamine and cyanuric acid, and is a nitrogen-containing halogen-free environment-friendly flame retardant conventionally added to nylon materials, and can be obtained directly through the market or prepared by self according to the prior art.
In one of the technical schemes, the MCA suspension in the step (1) is prepared by hydrothermal reaction of melamine, cyanuric acid, deionized water and a catalyst, wherein the reaction temperature is 90-95 ℃ and the reaction time is 2-3 h. Further, the addition ratio of the melamine, the cyanuric acid, the deionized water and the catalyst is 20g:20g:200mL:1g; the catalyst is selected from any one of sodium hydroxide, sodium oxide, potassium oxide and potassium hydroxide.
In this context, the non-solvent liquid in step (1) is selected as a liquid solvent incapable of dissolving melamine cyanurate, so as to form a suspension system after being uniformly mixed, such as deionized water, absolute ethyl alcohol, dimethyl sulfoxide, and the like.
In one preferable technical scheme, in order to obtain the more uniformly dispersed phosphorus-containing coated MCA flame retardant in the step (2), the mass volume ratio of the melamine cyanurate to the non-solvent liquid in the step (1) is (5-10) g: (90-100) mL.
In this context, the liquid phosphorus flame retardant in step (2) is selected as a conventional phosphorus flame retardant suitable for nylon in the art, and can be in a liquid state at ordinary temperature or under certain conditions, and a person skilled in the art can select a suitable liquid phosphorus flame retardant according to the prior art literature or with reference to the nylon-related existing process.
To better illustrate the present invention and to provide a solution to reference, the liquid phosphorus-containing flame retardant is selected from any one of bisphenol a bis (diphenyl phosphate) (BDP), resorcinol bis diphenyl phosphate (RDP), and triphenyl phosphate (TPP).
The triphenyl phosphate (TPP) is usually solid at normal temperature, and is used in a state where it is heated to 40 to 50 ℃ and maintained at that temperature throughout the whole preparation process.
In one technical scheme, in order to improve the flame retardant property of the finally prepared phosphorus-containing coated MCA flame retardant nylon fiber material, the mass ratio of the liquid phosphorus-containing flame retardant to the melamine cyanurate in the phosphorus-containing coated MCA flame retardant in the step (2) is (1-2.2): (1-3).
In one more preferable technical scheme, in order to further improve the flame retardant property of the finally prepared phosphorus-containing coated MCA flame retardant nylon fiber material, the mass ratio of the liquid phosphorus-containing flame retardant to the melamine cyanurate in the phosphorus-containing coated MCA flame retardant in the step (2) is (1.8-2.2): 1.
In this context, the natural sedimentation process treatment described in step (2), in particular the standing, is carried out for at least 48 hours. After the natural sedimentation method treatment, melamine cyanurate enters into the liquid phosphorus-containing flame retardant, the liquid phosphorus-containing flame retardant is in a mutually-immiscible state with the non-solvent liquid, and then a conventional liquid separation treatment mode can be selected for the non-solvent liquid removal treatment.
In this context, the nylon resin in step (3) is a conventional nylon resin raw material selection for nylon fibers, and the skilled person can refer directly to the raw material selection for nylon fibers in the prior art and to the nylon resin selection in the prior art literature.
In one embodiment, the nylon resin in step (3) is selected from at least one of nylon 56, nylon 11, nylon 66, nylon 6 and nylon 12.
In this context, the specific process mode of the conventional nylon fiber process in the step (3) can be directly referred to the existing process or records in the prior art literature, especially the preparation process of the flame-retardant nylon fiber, and the phosphorus-containing coated MCA flame retardant can be directly used as a raw material component of the flame-retardant nylon fiber, namely, the flame retardant added in the flame-retardant nylon fiber in the prior art/process is replaced, and the flame-retardant nylon fiber is prepared according to the original process method and condition.
In order to better illustrate the invention and provide a technical scheme for reference, the phosphorus-containing coated MCA flame-retardant nylon fiber material is prepared by blending the phosphorus-containing coated MCA flame-retardant agent and nylon resin in the step (3) according to a conventional nylon fiber process, specifically, the phosphorus-containing coated MCA flame-retardant agent and the nylon resin are uniformly mixed, extruded and granulated by a double-screw extruder, and the obtained granules are subjected to melt spinning by an FDY type high-speed spinning machine to prepare the phosphorus-containing coated MCA flame-retardant nylon fiber material; wherein, the technological parameters of the melt spinning are as follows: the temperature interval is 250-260 ℃ in the first area and 250-260 ℃ in the second area; 250-260 ℃ in the third region and 255-265 ℃ in the fourth region; the aperture of the spinneret plate is 0.1-0.4 mm.
In one of the technical schemes, because the nylon resin is easy to get damp again in the storage and transportation processes, the nylon resin is preferably dried for 24 to 48 hours at the temperature of 80 to 100 ℃ before the nylon resin is blended in the step (3).
In one technical scheme, the raw material component in the step (3) further comprises an antioxidant, wherein the antioxidant comprises at least one of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionamide), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 2H, 3H) trione, triethylene glycol bis (3-laurylthiopropionate) and triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the addition amount of the antioxidant is 0.1-0.3 wt% of the total amount of the raw materials.
In one technical scheme, the raw material component in the step (3) further comprises a lubricant, wherein the lubricant comprises at least one of zinc stearate, stearic acid amide, fischer-Tropsch wax, ethylene bis stearic acid amide and polyethylene wax; the addition amount of the lubricant is 0.1-0.3 wt% of the total amount of the raw materials.
In this context, the mixing and drying are performed according to the conventional principles in chemical processes, and a person skilled in the art may perform specific operations according to common general knowledge.
The invention has the following beneficial effects:
1. In the preparation method of the phosphorus-containing coated MCA flame-retardant nylon fiber material, provided by the invention, in the phosphorus-containing coated MCA flame retardant prepared by a natural sedimentation method, the liquid phosphorus flame retardant and the rich nitrogen element of the MCA exert excellent synergistic flame retardant effect, and the preparation method has the advantages of low smoke, environmental protection, high efficiency and the like; in the embodiment, the peak value of the heat release rate of the flame-retardant nylon fiber is reduced from 922.56kW/m 2 which is not added to 286.39kW/m 2, and the flame-retardant effect is good.
2. According to the preparation method of the phosphorus-containing coated MCA flame-retardant nylon fiber material, disclosed by the invention, the phosphorus-containing coated MCA flame retardant prepared by a natural sedimentation method is not involved in the drying and crushing process of the flame retardant, and molecular aggregation caused by high surface energy is avoided, so that uniform dispersion of the phosphorus-containing coated MCA flame retardant is realized, and the flame retardance and mechanical properties of the nylon fiber are effectively improved.
Drawings
FIG. 1 is a cross-sectional electron micrograph of the product obtained by the preparation of comparative example 2 and example 1. In the figure, a is the product obtained by preparing comparative example 2, and b is the product obtained by preparing example 1, and it is obvious that the flame retardant particles in comparative example 2 are aggregated and have a larger size, and the flame retardant particles in example 1 have a smaller and uniform size.
Fig. 2 is a photograph of a phosphorus-containing coated MCA flame retardant nylon fiber material prepared in example 1. In the figure, a is a physical photo of the phosphorus-containing coated MCA flame-retardant nylon fiber material, b is a monofilament observation photo of the phosphorus-containing coated MCA flame-retardant nylon fiber material, and c is a spinning flow photo of the example 1; the phosphorus-containing coated MCA flame-retardant nylon fiber material prepared in example 1 has excellent spinnability, uniform monofilaments and an average diameter of 17.53um.
FIG. 3 is a photograph showing a comparative sample of the flame retardant nylon fiber material prepared in comparative example 3. In the figure, a is a flame-retardant nylon fiber material comparison sample physical photo, b is a monofilament observation photo of a flame-retardant nylon fiber material comparison sample, and c is a spinning flow photo of a comparison example 3; the flame-retardant nylon fiber material prepared in the comparative example 3 has no spinnability, cannot be wound, has uneven monofilaments and has poor mechanical strength.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention. While the following terms are believed to be well understood by those of ordinary skill in the art, the following definitions are set forth to aid in the description of the presently disclosed subject matter.
The preparation method of the phosphorus-containing coated MCA flame-retardant nylon fiber material mainly comprises the following steps:
(1) Mixing melamine cyanurate with a non-solvent liquid to prepare an MCA suspension;
(2) Adding the MCA suspension obtained in the step (1) into a liquid phosphorus-containing flame retardant, and removing non-solvent liquid after treatment based on a natural sedimentation method to obtain a uniformly dispersed phosphorus-containing coated MCA flame retardant;
(3) Taking the phosphorus-containing coated MCA flame retardant obtained in the step (2) as a raw material component, blending with nylon resin, and preparing the phosphorus-containing coated MCA flame retardant nylon fiber material according to a conventional nylon fiber process; wherein, the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon resin is 1: (10-30).
In this context, the melamine cyanurate in the step (1) is a salt synthesized from melamine and cyanuric acid, and is a nitrogen-containing halogen-free environment-friendly flame retardant conventionally added to nylon materials, and can be obtained directly through the market or prepared by self according to the prior art.
In one embodiment, the MCA suspension in step (1) is prepared by a hydrothermal reaction of melamine, cyanuric acid, deionized water and a catalyst at a temperature of 90 to 95 ℃ for a period of 2 to 3 hours. Further, the addition ratio of the melamine, the cyanuric acid, the deionized water and the catalyst is 20g:20g:200mL:1g; the catalyst is selected from any one of sodium hydroxide, sodium oxide, potassium oxide and potassium hydroxide.
In this context, the non-solvent liquid in the step (1) is selected from liquid solvents incapable of dissolving melamine cyanurate, so as to form a suspension system after being uniformly mixed, and in one embodiment, the non-solvent liquid is selected from any one of deionized water, absolute ethyl alcohol and dimethyl sulfoxide.
In one preferred embodiment, in order to obtain a more uniformly dispersed phosphorus-containing coated MCA flame retardant in step (2), the mass to volume ratio of melamine cyanurate to non-solvent liquid in step (1) is (5-10) g: (90-100) mL.
In this context, the liquid phosphorus flame retardant in step (2) is selected as a conventional phosphorus flame retardant suitable for nylon in the art, and can be in a liquid state at ordinary temperature or under certain conditions, and a person skilled in the art can select a suitable liquid phosphorus flame retardant according to the prior art literature or with reference to the nylon-related existing process.
To better illustrate the present invention and to provide a reference embodiment, the liquid phosphorus-containing flame retardant is selected to include any of bisphenol A bis (diphenyl phosphate) (BDP), resorcinol bis diphenyl phosphate (RDP), and triphenyl phosphate (TPP).
The triphenyl phosphate (TPP) is usually solid at normal temperature, and is used in a state where it is heated to 40 to 50 ℃ and maintained at that temperature throughout the whole preparation process.
In one embodiment, in order to improve the flame retardant property of the finally prepared phosphorus-containing coated MCA flame retardant nylon fiber material, the mass ratio of the liquid phosphorus-containing flame retardant to the melamine cyanurate in the phosphorus-containing coated MCA flame retardant in the step (2) is (1-2.2): (1-3).
In one more preferred embodiment, in order to further improve the flame retardant performance of the finally prepared phosphorus-containing coated MCA flame retardant nylon fiber material, the mass ratio of the liquid phosphorus-containing flame retardant to the melamine cyanurate in the phosphorus-containing coated MCA flame retardant in the step (2) is (1.8-2.2): 1.
In this context, the natural sedimentation process treatment described in step (2), in particular the standing, is carried out for at least 48 hours. After the natural sedimentation method treatment, melamine cyanurate enters into the liquid phosphorus-containing flame retardant, the liquid phosphorus-containing flame retardant is in a mutually-immiscible state with the non-solvent liquid, and then a conventional liquid separation treatment mode can be selected for the non-solvent liquid removal treatment.
In this context, the nylon resin in step (3) is a conventional nylon resin raw material selection for nylon fibers, and the skilled person can refer directly to the raw material selection for nylon fibers in the prior art and to the nylon resin selection in the prior art literature.
In one embodiment, the nylon resin in step (3) is selected from at least one of nylon 56, nylon 11, nylon 66, nylon 6, and nylon 12.
In this context, the specific process mode of the conventional nylon fiber process in the step (3) can be directly referred to the existing process or records in the prior art literature, especially the preparation process of the flame-retardant nylon fiber, and the phosphorus-containing coated MCA flame retardant can be directly used as a raw material component of the flame-retardant nylon fiber, namely, the flame retardant added in the flame-retardant nylon fiber in the prior art/process is replaced, and the flame-retardant nylon fiber is prepared according to the original process method and condition.
In order to better illustrate the invention and provide a reference embodiment, the phosphorus-containing coated MCA flame-retardant nylon fiber material is prepared according to the conventional nylon fiber process after being blended with the nylon resin in the step (3), specifically, the phosphorus-containing coated MCA flame retardant is uniformly mixed with the nylon resin, the mixture is extruded and granulated by a double-screw extruder, and the obtained granules are subjected to melt spinning by an FDY type high-speed spinning machine to prepare the phosphorus-containing coated MCA flame-retardant nylon fiber material; wherein, the technological parameters of the melt spinning are as follows: the temperature interval is 250-260 ℃ in the first area and 250-260 ℃ in the second area; 250-260 ℃ in the third region and 255-265 ℃ in the fourth region; the aperture of the spinneret plate is 0.1-0.4 mm.
In one embodiment, the nylon resin is preferably dried at 80-100 ℃ for 24-48 hours prior to blending the nylon resin in step (3) because the nylon resin is susceptible to moisture regain during storage and shipping.
In one embodiment, the feedstock component of step (3) further comprises an antioxidant selected from at least one of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1 h,2h,3 h) trione, triethylene glycol bis (3-laurylthiopropionate), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the addition amount of the antioxidant is 0.1-0.3 wt% of the total amount of the raw materials.
In one embodiment, the feedstock component of step (3) further comprises a lubricant selected from at least one of zinc stearate, stearic acid amide, fischer-tropsch wax, ethylene bisstearic acid amide, polyethylene wax; the addition amount of the lubricant is 0.1-0.3 wt% of the total amount of the raw materials.
In this context, the mixing and drying are performed according to the conventional principles in chemical processes, and a person skilled in the art may perform specific operations according to common general knowledge.
The present application will be explained in further detail with reference to examples. However, those skilled in the art will appreciate that these examples are provided for illustrative purposes only and are not intended to limit the present application.
Examples
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The application should not be construed as being limited to the particular embodiments described.
1. Raw materials
Zinc stearate (lubricant) Z104436 Shanghai aladine Biochemical technologies Co., ltd;
melamine A11295 Chemicals, inc.;
cyanuric acid CD108332 is available from dukoron chemical company, inc;
deionized water CD121010 is manufactured by dazomet chemical company, inc;
nylon 56E1273 national biotechnology development center limited;
Sodium hydroxide (catalyst) a12087 was available from metropolitan area of the family instrument;
bisphenol A bis (diphenyl phosphate) XK1018 Shanghai Ala Biochemical technologies Co., ltd;
Bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite (antioxidant) is available from Dou Shizhuo spectrum instruments Inc.
2. Preparation method
(1) Melamine, cyanuric acid, deionized water and catalyst sodium hydroxide are added according to the proportion of 20g:20g:200mL:1g of the components are mixed in a proportioning mode, and then the mixture is subjected to hydrothermal reaction for 2 hours at the temperature of 90 ℃ to prepare MCA suspension;
(2) Adding the MCA suspension obtained in the step (1) into a liquid phosphorus-containing flame retardant, standing for 48 hours based on a natural sedimentation method, and removing deionized water through liquid separation to obtain a uniformly dispersed phosphorus-containing coated MCA flame retardant;
(3) Blending the phosphorus-containing coated MCA flame retardant obtained in the step (2) with nylon 56, antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and lubricant zinc stearate, extruding and granulating by a double-screw extruder, and carrying out melt spinning on the obtained granules by using an FDY type high-speed spinning machine to obtain the phosphorus-containing coated MCA flame retardant nylon fiber material;
Wherein the addition amount of the antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is 0.2 weight percent of the total amount of the raw materials; the addition amount of the lubricant zinc stearate is 0.2 weight percent of the total amount of the raw materials;
wherein, the technological parameters of the melt spinning are as follows: the temperature interval is 250-260 ℃ in the first area and 250-260 ℃ in the second area; 250-260 ℃ in the third region and 255-265 ℃ in the fourth region; the spinneret aperture was 0.4mm.
3. Test method
Flame retardant and mechanical properties were tested according to ISO5660, GB/T14337-2008 standard.
Example 1
Example 1 a phosphorus-containing coated MCA flame-retardant nylon fiber material is prepared according to the preparation method 2;
Wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:20.
Example 2
Example 2a phosphorus-containing coated MCA flame retardant nylon fiber material was prepared according to the above "2. Preparation method";
Wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 1:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:20.
Example 3
Example 3a phosphorus-containing coated MCA flame retardant nylon fiber material was prepared according to the above "2. Preparation method";
Wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:25.
Example 4
Example 4a phosphorus-containing coated MCA flame retardant nylon fiber material is prepared according to the preparation method 2;
Wherein the liquid phosphorus-containing flame retardant is resorcinol bis-diphenyl phosphate (RDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:20.
Example 5
Example 5a phosphorus-containing coated MCA flame retardant nylon fiber material was prepared according to the above "2. Preparation method";
wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 1:2; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:20.
Example 6
Example 6 a phosphorus-containing coated MCA flame retardant nylon fiber material was prepared according to the above "2. Preparation method";
wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 1:3, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:20.
Example 7
Example 7a phosphorus-containing coated MCA flame retardant nylon fiber material was prepared according to the above "2. Preparation method";
wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:10.
Example 8
Example 1 a phosphorus-containing coated MCA flame-retardant nylon fiber material is prepared according to the preparation method 2;
Wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1:15.
Comparative example 1
Comparative example 1a flame retardant nylon fiber material comparative sample was prepared with reference to example 1, except that the natural sedimentation method in step (2) was allowed to stand for only 24 hours.
Comparative example 2
This comparative example 2 is based on example 3, but does not employ a liquid phosphorus flame retardant:
(1) Melamine, cyanuric acid, deionized water and catalyst sodium hydroxide are added according to the proportion of 20g:20g:200mL:1g of the components are mixed in a proportioning mode, and then the mixture is subjected to hydrothermal reaction for 2 hours at the temperature of 90 ℃ to prepare MCA suspension;
(2) Directly standing the MCA suspension obtained in the step (1) for 48 hours, and removing deionized water through suction filtration to obtain an MCA flame retardant;
(3) Blending the MCA flame retardant obtained in the step (2) with nylon 56, antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and lubricant zinc stearate, extruding and granulating by a double-screw extruder, and carrying out melt spinning on the obtained granules by using an FDY type high-speed spinning machine to obtain a flame-retardant nylon fiber material comparison sample;
Wherein the addition amount of the antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is 0.2 weight percent of the total amount of the raw materials; the addition amount of the lubricant zinc stearate is 0.2 weight percent of the total amount of the raw materials;
Wherein, the technological parameters of the melt spinning are as follows: the temperature interval is 250-260 ℃ in the first area and 250-260 ℃ in the second area; 250-260 ℃ in the third region and 255-265 ℃ in the fourth region; the aperture of the spinneret plate is 0.4mm;
Wherein, the mass ratio of the MCA flame retardant to the nylon 56 is 1:25.
Comparative example 3
This comparative example 3 is based on example 1, but without natural sedimentation, blending is performed directly:
(1) Melamine, cyanuric acid, deionized water and catalyst sodium hydroxide are added according to the proportion of 20g:20g:200mL:1g of the components are mixed in a proportioning mode, and then the mixture is subjected to hydrothermal reaction for 2 hours at the temperature of 90 ℃ to prepare MCA suspension;
(2) Directly standing the MCA suspension obtained in the step (1) for 48 hours, and removing deionized water through suction filtration to obtain an MCA flame retardant;
(3) Blending the MCA flame retardant obtained in the step (2) with a liquid phosphorus flame retardant, nylon 56, an antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and a lubricant zinc stearate, extruding and granulating by a double-screw extruder, and carrying out melt spinning on the obtained granules by using an FDY type high-speed spinning machine to obtain a flame retardant nylon fiber material comparison sample;
Wherein the addition amount of the antioxidant bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is 0.2 weight percent of the total amount of the raw materials; the addition amount of the lubricant zinc stearate is 0.2 weight percent of the total amount of the raw materials;
Wherein, the technological parameters of the melt spinning are as follows: the temperature interval is 250-260 ℃ in the first area and 250-260 ℃ in the second area; 250-260 ℃ in the third region and 255-265 ℃ in the fourth region; the aperture of the spinneret plate is 0.4mm;
Wherein the liquid phosphorus-containing flame retardant is bisphenol A bis (diphenyl phosphate) (BDP), and the mass ratio of the liquid phosphorus-containing flame retardant to melamine cyanurate is 2:1, a step of; the mass ratio of the total mass of the MCA flame retardant and the liquid phosphorus flame retardant to the nylon 56 is 1:20.
4. Test results
The products prepared in examples 1 to 2, examples 4 to 6 and comparative example 1 were used as samples, and were tested according to the above-mentioned "3. Test method", and the test results are shown in Table 1:
table 1 table of results of test of sample properties of examples 1 to 2, examples 4 to 6 and comparative example 1
As shown in Table 1, examples 1 and 4 illustrate that BDP is used as the liquid phosphorus flame retardant to more effectively improve the flame retardant property of nylon fibers; example 1 and comparative example 1 demonstrate that standing for 24 hours does not allow the MCA to settle completely, and has a greater impact on flame retardant properties; examples 1, 2 and examples 5, 6 illustrate that the mass ratio of liquid phosphorus flame retardant to melamine cyanurate is 2: the flame retardant effect is best in 1.
The products prepared in example 1, example 3, examples 7 to 8 and comparative example 2 were used as samples, and were tested according to the above-mentioned "3. Test method", and the test results are shown in Table 2:
table 2 table of sample performance test results for example 1, example 3, examples 7 to 8 and comparative example 2
| Example 1 | Example 3 | Example 7 | Example 8 | Comparative example 2 | |
| Breaking strength/cN/dtex | 3.5 | 3.7 | 1.3 | 1.4 | 1.3 |
| Fracture length rate/% | 45 | 46 | 15 | 13 | 12 |
| Heat release rate/kW/m 2 | 286.39 | 350.48 | 243.02 | 259.48 | 428.45 |
| Spinnability (spinnability) | Excellent (excellent) | Excellent (excellent) | Difference of difference | Difference of difference | Difference of difference |
As shown in table 2, examples 1 and 3 and examples 7 and 8 illustrate that the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon 56 is 1: the comprehensive performance is optimal at 20 hours; examples 1, 3 and comparative example 2 demonstrate that the natural sedimentation process effectively improves the overall performance of the MCA/nylon system, and figure 1 further demonstrates the above.
The products prepared in example 1 and comparative example 3 were used as samples, and were tested according to the "3. Test method" described above, and the test results are shown in table 3:
table 3 table of results of sample performance tests of example 1 and comparative example 3
As shown in Table 3, example 1 and comparative example 3 demonstrate that the overall performance of the product prepared in example 1 is all significantly higher than that of comparative example 3 without direct blending by natural sedimentation.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent and are within the scope of the present invention.
Claims (10)
1. The preparation method of the phosphorus-containing coated MCA flame-retardant nylon fiber material is characterized by mainly comprising the following steps of:
(1) Mixing melamine cyanurate with a non-solvent liquid to prepare an MCA suspension;
(2) Adding the MCA suspension obtained in the step (1) into a liquid phosphorus-containing flame retardant, and removing non-solvent liquid after treatment based on a natural sedimentation method to obtain a uniformly dispersed phosphorus-containing coated MCA flame retardant;
(3) Taking the phosphorus-containing coated MCA flame retardant obtained in the step (2) as a raw material component, blending with nylon resin, and preparing the phosphorus-containing coated MCA flame retardant nylon fiber material according to a conventional nylon fiber process; wherein, the mass ratio of the phosphorus-containing coated MCA flame retardant to the nylon resin is 1: (10-30).
2. The method of manufacture of claim 1, wherein: the non-solvent liquid in the step (1) is selected from any one of deionized water, absolute ethyl alcohol and dimethyl sulfoxide.
3. The method of manufacture of claim 1, wherein: the mass volume ratio of the melamine cyanurate to the non-solvent liquid in the step (1) is (5-10) g: (90-100) mL.
4. The method of manufacture of claim 1, wherein: the MCA suspension in the step (1) is prepared by carrying out hydrothermal reaction on melamine, cyanuric acid, deionized water and a catalyst, wherein the reaction temperature is 90-95 ℃ and the reaction time is 2-3 h; the catalyst is selected from any one of sodium hydroxide, sodium oxide, potassium oxide and potassium hydroxide.
5. The method of manufacture of claim 1, wherein: the liquid phosphorus-containing flame retardant in the step (2) is selected from any one of bisphenol A bis (diphenyl phosphate), resorcinol bis diphenyl phosphate and triphenyl phosphate.
6. The method of manufacture of claim 1, wherein: the mass ratio of the liquid phosphorus-containing flame retardant to the melamine cyanurate in the phosphorus-containing coated MCA flame retardant in the step (2) is (1-2.2): (1-3).
7. The method of manufacture of claim 1, wherein: the raw material component in the step (3) further comprises an antioxidant, wherein the antioxidant comprises at least one of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionamide), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1H, 2H, 3H) trione, triethylene glycol bis (3-laurylthiopropionate) and triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the addition amount of the antioxidant is 0.1-0.3 wt% of the total amount of the raw materials.
8. The method of manufacture of claim 1, wherein: the raw material component in the step (3) further comprises a lubricant, wherein the lubricant comprises at least one of zinc stearate, stearic acid amide, fischer-Tropsch wax, ethylene bis stearic acid amide and polyethylene wax; the addition amount of the lubricant is 0.1-0.3 wt% of the total amount of the raw materials.
9. The method of manufacture of claim 1, wherein: the nylon resin in step (3) is selected from at least one of nylon 56, nylon 11, nylon 66, nylon 6 and nylon 12.
10. The phosphorus-containing coated MCA flame retardant nylon fiber material prepared by the preparation method of the phosphorus-containing coated MCA flame retardant nylon fiber material according to any one of claims 1 to 9.
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