CN114015230A - Fireproof flame-retardant nylon material and preparation method thereof - Google Patents
Fireproof flame-retardant nylon material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- 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 75
- 239000004677 Nylon Substances 0.000 title claims abstract description 44
- 229920001778 nylon Polymers 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 30
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000012745 toughening agent Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 150000007974 melamines Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000001205 polyphosphate Substances 0.000 claims abstract description 15
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 238000001746 injection moulding Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 21
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003094 microcapsule Substances 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical group CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention aims to provide a fireproof flame-retardant nylon material and a preparation method thereof, wherein the material comprises the following components in parts by weight: nylon 6660-80 parts, toughening agent 5-10 parts, glass fiber 15-20 parts, antioxidant 1-3 parts, lubricant 1-2 parts, and flame retardant 10-15 parts; the flame retardant comprises modified melamine polyphosphate and aluminum hypophosphite; the preparation method comprises the following steps: s41, weighing all the raw materials in parts by weight, respectively placing the nylon 66 and the toughening agent in drying equipment for drying S42, mixing the nylon 66 and the toughening agent dried in the step S41, and then adding the glass fiber, the antioxidant and the lubricant for melting and mixing at the temperature of 300-320 ℃; s43, after melting and mixing, the temperature is increased to 230 ℃ below 200 ℃, a flame retardant is added for stirring, after the completion of extrusion, water cooling, grain cutting and drying, and the fireproof flame-retardant nylon material is obtained after injection molding.
Description
Technical Field
The invention relates to a nylon material, in particular to a fireproof flame-retardant nylon material and a preparation method thereof.
Background
Polyamide is commonly known as Nylon (Nylon), and is called Polyamide (PA for short) in English, and is a general name of thermoplastic resin containing repeated amide groups- (NHCO) -on a molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The aliphatic PA has many varieties, large yield and wide application, and the name is determined by the specific carbon atom number of the synthetic monomer. Invented by the american famous chemist caroth and his research group.
The nylon material has wide application, the wear resistance is higher than other fibers, 10 times higher than that of cotton and 20 times higher than that of wool, and the wear resistance of the blended fabric can be greatly improved by slightly adding some polyamide fibers; aiming at fire prevention and flame retardance, the flame-retardant PA comprises a halogen-containing flame-retardant system and a halogen-free flame-retardant system, the existing halogen-free flame-retardant system adopts red phosphorus and melamine salts, the red phosphorus limits the storage scene of nylon and the color of the nylon, the melamine salts have poor thermal stability, the resistance of the nylon is reduced in a humid environment, and potential safety hazards exist.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a fireproof flame-retardant nylon material which is stable in state and excellent in fireproof flame-retardant effect:
in order to achieve the purpose, the invention provides the following technical scheme:
the fireproof flame-retardant nylon material comprises the following components in parts by weight:
nylon 6660-80 parts, toughening agent 5-10 parts, glass fiber 15-20 parts, antioxidant 1-3 parts, lubricant 1-2 parts, and flame retardant 10-15 parts; the flame retardant comprises modified melamine polyphosphate and aluminum hypophosphite.
Preferably, the material comprises the following components in parts by weight: nylon 6675 parts, toughening agent 8 parts, antioxidant 2 parts, lubricant 1 part, and flame retardant 12 parts.
Preferably, the preparation method of the nylon 66 comprises the following steps:
s1, mixing pentaerythritol and phosphorus oxychloride according to a molar ratio of 1:5, stirring for 60-80min at 60 ℃ under the protection of nitrogen, then heating to 105 ℃, refluxing for 9-10h, distilling under reduced pressure, and drying to constant weight after removing phosphorus oxychloride to obtain white powder;
s2, mixing the white powder obtained in the step S1 with p-aminobenzoic acid in dichloromethane for reaction until no hydrogen chloride is generated, performing vacuum filtration to obtain a DTDBA crude product, washing the DTDBA crude product, and drying to obtain DTDBA;
s3, mixing the DTDBA obtained in the step S2 with water, controlling the temperature at 60 ℃, dissolving ethylenediamine in the water, dripping the ethylenediamine in a mixed solution of the DTDBA and the water, and after complete reaction, performing rotary evaporation drying on a product to obtain a solid product;
s4, mixing the solid product obtained in the step S3 with PA66 salt and water, adjusting the pH value to be neutral, adding sodium hypochlorite, heating in a nitrogen environment at the pressure of 1.7MPa and the temperature of 300 ℃, and reacting for 1 h; and then continuously reducing the pressure for 1h to a normal pressure state, maintaining the temperature at 300 ℃, and reacting for 1h to obtain the nylon 66.
Preferably, the toughening agent is an ABS toughening agent.
Preferably, the antioxidant is a hindered phenol antioxidant.
Preferably, the lubricant is one of polyamide wax and ethylene bis stearamide.
Preferably, the preparation method of the modified melamine polyphosphate comprises the following steps:
s11, dissolving melamine in glacial acetic acid, stirring at 120 ℃, and stirring until the melamine is completely dissolved to obtain a solution A;
s12, dissolving polyphosphoric acid in glacial acetic acid, stirring at 120 ℃, and stirring until polyphosphoric acid is completely dissolved to obtain a solution B;
s13, dropwise adding the solution B obtained in the step S12 to the solution A obtained in the step S11 at the temperature of 120 ℃, and carrying out post-treatment after complete reaction to obtain the modified melamine polyphosphate.
Preferably, the preparation method of the flame retardant comprises the following steps:
s21, modifying melamine phosphate and sodium dodecyl sulfate, adding an N ' N-dimethylformamide solvent, wherein the solid-to-liquid ratio of the modified melamine phosphate to the N ' N-dimethylformamide is 100:3g/L, the volume ratio of the sodium dodecyl sulfate to the N ' N-dimethylformamide is 1:50, raising the temperature to 40 ℃, mechanically stirring and ultrasonically treating for 0.5h to obtain a dispersion liquid of the modified melamine phosphate;
s22, adding hexachlorocyclotriphosphazene, KH550 and triethylamine into the modified melamine phosphate dispersion liquid obtained in the step 1, wherein the molar ratio of hexachlorocyclotriphosphazene to KH550 is 1:6, the molar ratio of KH550 to triethylamine is 1:1, reacting at the temperature of 40 ℃ for 8h, cooling to room temperature, carrying out vacuum filtration, and carrying out vacuum drying at the temperature of 90 ℃ for 24h to obtain the modified melamine phosphate microcapsule flame retardant;
s31, dissolving urea in formaldehyde at a solid-to-liquid ratio of 1:2g/mL, adjusting the pH value to 8-9 by sodium bicarbonate, and heating to 70 ℃ to react for 1.5h to obtain a urea-formaldehyde prepolymer;
s32, placing aluminum hypophosphite and alkylphenol polyoxyethylene ether in a beaker, wherein the mass ratio of the aluminum hypophosphite to the alkylphenol polyoxyethylene ether is 25:1, adding ethanol, and stirring and dispersing for 30min to obtain an aluminum hypophosphite dispersion liquid, wherein the solid-to-liquid ratio of the aluminum hypophosphite to the ethanol is 2:10 g/mL;
and S33, mixing the aluminum hypophosphite dispersion liquid with the urea formaldehyde prepolymer, adding m-benzenediol, methanol and ammonium chloride, reacting, and performing post-treatment to obtain the aluminum hypophosphite microcapsule flame retardant.
A method for preparing a fireproof flame-retardant nylon material comprises the following steps,
s41, weighing all the raw materials in parts by weight, and respectively placing the nylon 66 and the toughening agent in drying equipment for drying
S42, mixing the nylon 66 dried in the step S41 with a toughening agent, and then adding glass fiber, an antioxidant and a lubricant for melt mixing at the temperature of 300-320 ℃;
s43, melting and mixing, heating to the temperature of 200 ℃ and 230 ℃, adding a flame retardant, stirring, extruding, cooling by water, granulating, drying, and performing injection molding to obtain the fireproof flame-retardant nylon material
DTDBA in this application is 4, 4' - ((3, 9-diepoxy-2, 4,8, 10-tetraoxy-3, 9-diphosphino spiro [5,5] undecane-3-9-diacyl) bis (azophenyl)) dibenzoic acid.
KH550 is gamma-aminopropyltriethoxysilane, a silane coupling agent.
Has the advantages that:
the invention provides nylon 66 with good flame retardant property, wherein modified melamine polyphosphate and aluminum hypophosphite are used as flame retardants, and the cooperation of the modified melamine polyphosphate and the aluminum hypophosphite ensures the strength of the nylon 66 and provides a good flame retardant effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The fireproof flame-retardant nylon material comprises: nylon 6660 parts, toughening agent 5 parts, glass fiber 15 parts, antioxidant 1 part, lubricant 1 part and flame retardant 10 parts;
nylon 66 is commercially available, the toughening agent is commercially available ABS toughening agent, the antioxidant is 2, 6-di-tert-butyl-4-cresol, the lubricant is polyamide wax, and the flame retardant is modified melamine polyphosphate and aluminum hypophosphite; the weight ratio of the modified melamine polyphosphate to the aluminum hypophosphite is 5: 1.
The preparation method of the modified melamine polyphosphate comprises the following steps:
s11, dissolving melamine in glacial acetic acid, stirring at 120 ℃, and stirring until the melamine is completely dissolved to obtain a solution A;
s12, dissolving polyphosphoric acid in glacial acetic acid, stirring at 120 ℃, and stirring until polyphosphoric acid is completely dissolved to obtain a solution B;
s13, dropwise adding the solution B obtained in the step S12 to the solution A obtained in the step S11 at the temperature of 120 ℃, and carrying out post-treatment after complete reaction to obtain the modified melamine polyphosphate.
The preparation method of the fireproof flame-retardant nylon material comprises the following steps:
s41, respectively placing the nylon 66 and the ABS toughening agent in drying equipment for drying;
s42, mixing the nylon 66 dried in the step S41 and an ABS toughening agent, and then adding glass fiber, 2, 6-di-tert-butyl-4-cresol and polyamide wax for melt mixing at the temperature of 300 ℃;
and S43, after melting and mixing, adding the modified melamine polyphosphate and the aluminum hypophosphite at the temperature of 200 ℃, stirring, extruding, cooling with water, granulating, drying, and performing injection molding to obtain the fireproof flame-retardant nylon material.
In the application, the modified melamine polyphosphate and the aluminum hypophosphite are matched together to be used as a flame retardant, so that the flame retardant property of the flame retardant is greatly improved.
Example 2
The difference between the example 2 and the example 1 is only nylon 66, and the preparation method of the nylon 66 in the example 2 is as follows:
s1, mixing pentaerythritol and phosphorus oxychloride according to a molar ratio of 1:5, stirring for 60-80min at 60 ℃ under the protection of nitrogen, then heating to 105 ℃, refluxing for 9-10h, distilling under reduced pressure, and drying to constant weight after removing phosphorus oxychloride to obtain white powder;
s2, mixing the white powder obtained in the step S1 with p-aminobenzoic acid in dichloromethane for reaction until no hydrogen chloride is generated, performing vacuum filtration to obtain a DTDBA crude product, washing the DTDBA crude product, and drying to obtain DTDBA;
s3, mixing the DTDBA obtained in the step S2 with water, controlling the temperature at 60 ℃, dissolving ethylenediamine in the water, dripping the ethylenediamine in a mixed solution of the DTDBA and the water, and after complete reaction, performing rotary evaporation drying on a product to obtain a solid product;
s4, mixing the solid product obtained in the step S3 with PA66 salt and water, adjusting the pH value to be neutral, adding sodium hypochlorite, heating in a nitrogen environment at the pressure of 1.7MPa and the temperature of 300 ℃, and reacting for 1 h; and then continuously reducing the pressure for 1h to a normal pressure state, maintaining the temperature at 300 ℃, and reacting for 1h to obtain the nylon 66.
In the embodiment, the nylon 66 is prepared by directly using the reactive flame retardant DTDBA as a raw material, so that the flame retardant effect is improved, and the addition amount of the DTDBA salt is generally 3-4 wt%.
Example 3
The difference between the embodiment 3 and the embodiment 1 is only that the flame retardant is prepared by the method comprising the steps of S21, modified melamine phosphate and sodium dodecyl sulfate, adding N ' N-dimethylformamide solvent, wherein the solid-to-liquid ratio of the modified melamine phosphate to the N ' N-dimethylformamide is 100:3g/L, the volume ratio of the sodium dodecyl sulfate to the N ' N-dimethylformamide is 1:50, raising the temperature to 40 ℃, mechanically stirring and ultrasonically processing for 0.5h to obtain a dispersion liquid of the modified melamine phosphate;
s22, adding hexachlorocyclotriphosphazene, KH550 and triethylamine into the modified melamine phosphate dispersion liquid obtained in the step 1, wherein the molar ratio of hexachlorocyclotriphosphazene to KH550 is 1:6, the molar ratio of KH550 to triethylamine is 1:1, reacting at the temperature of 40 ℃ for 8h, cooling to room temperature, carrying out vacuum filtration, and carrying out vacuum drying at the temperature of 90 ℃ for 24h to obtain the modified melamine phosphate microcapsule flame retardant;
s31, dissolving urea in formaldehyde at a solid-to-liquid ratio of 1:2g/mL, adjusting the pH value to 8-9 by sodium bicarbonate, and heating to 70 ℃ to react for 1.5h to obtain a urea-formaldehyde prepolymer;
s32, placing aluminum hypophosphite and alkylphenol polyoxyethylene ether in a beaker, wherein the mass ratio of the aluminum hypophosphite to the alkylphenol polyoxyethylene ether is 25:1, adding ethanol, and stirring and dispersing for 30min to obtain an aluminum hypophosphite dispersion liquid, wherein the solid-to-liquid ratio of the aluminum hypophosphite to the ethanol is 2:10 g/mL;
and S33, mixing the aluminum hypophosphite dispersion liquid with the urea formaldehyde prepolymer, adding m-benzenediol, methanol and ammonium chloride, reacting, and performing post-treatment to obtain the aluminum hypophosphite microcapsule flame retardant.
In the embodiment, the modified melamine phosphate and the aluminum hypophosphite are prepared into the microcapsule flame retardant, so that the application scene of the nylon 66 is greatly improved, and the influence of the environment such as humidity on the flame retardant is basically eliminated.
Example 4
Example 4 differed from example 2 only in the flame retardant, which was prepared in accordance with example 3.
Example 5
The fireproof flame-retardant nylon material comprises: nylon 6680 parts, toughening agent 10 parts, glass fiber 20 parts, antioxidant 3 parts, lubricant 3 parts, and flame retardant 15 parts; other preparation methods and preparation conditions were the same as in example 4.
Example 6
The fireproof flame-retardant nylon material comprises: nylon 6675 parts, toughening agent 8 parts, antioxidant 2 parts, lubricant 1 part, and flame retardant 12 parts; other preparation methods and preparation conditions were the same as in example 4.
Comparative example 1
Comparative example 1 differs from example 1 only in that no modified melamine phosphate was added and the other preparation methods and preparation conditions were in accordance with example 1.
Comparative example 2
Comparative example 2 is different from example 1 only in that aluminum hypophosphite was not added, and other preparation methods and preparation conditions were identical to those of example 1.
The fireproof flame-retardant nylon materials obtained in the comparative examples 1-2 of the grades 1-6 of the examples are detected, and the detection results are shown in the following table 1.
TABLE 1
In Table 1, the tensile test strength standard is ISO-527, the bending strength test standard is 1SO-178, the notched Izod impact strength test standard is ISO-180, and the flame retardant rating after passing through a humid environment is that nylon is placed for 3 hours in an environment with the humidity of 90%.
As shown in table 1, as compared with comparative examples 1 and 2, in the flame retardant effect, the modified melamine phosphate can be better flame retardant when being combined with aluminum hypophosphite; as can be seen from the comparison of the rest of examples 1 and 2, the flame retardant effect after passing through a humid environment can be improved by doping the flame retardant when the nylon 66 is prepared; compared with the embodiment 1, the embodiment 3 has the advantages that the flame retardant is prepared into the microcapsule and mixed into the nylon 66, so that the mechanical strength of the nylon can be improved, and the flame retardant effect after the nylon passes through a humid environment can be greatly improved; compared with the example 3, the example 4 shows that the flame retardant is mixed in the nylon 66 preparation process and the flame retardant is prepared into the microcapsule and mixed in the nylon 66 for use, so that the excellent flame retardant effect can be achieved, and the mechanical strength of the nylon can be ensured; it can be seen from comparison of examples 5-6 with example 4 that the modified melamine phosphate has good mechanical strength and flame retardant effect within the range of the formulation set in the present application, and it can be seen from example 1 that the resistance is reduced within an acceptable range after the modified melamine phosphate is used in a humid environment, and the use risk is not generated as the melamine phosphate, while it can be seen from examples 2-5 that the resistance is not changed basically, and the use safety is further ensured.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not constitute an admission of the corresponding technical solution.
Claims (9)
1. The fireproof flame-retardant nylon material is characterized by comprising the following components in parts by weight:
nylon 6660-80 parts, toughening agent 5-10 parts, glass fiber 15-20 parts, antioxidant 1-3 parts, lubricant 1-2 parts, and flame retardant 10-15 parts; the flame retardant comprises modified melamine polyphosphate and aluminum hypophosphite.
2. The fireproof flame-retardant nylon material of claim 1, wherein the material comprises, in parts by weight: nylon 6675 parts, toughening agent 8 parts, antioxidant 2 parts, lubricant 1 part, and flame retardant 12 parts.
3. The fireproof flame-retardant nylon material of claim 1, wherein the preparation method of the nylon 66 comprises the following steps:
s1, mixing pentaerythritol and phosphorus oxychloride according to a molar ratio of 1:5, stirring for 60-80min at 60 ℃ under the protection of nitrogen, then heating to 105 ℃, refluxing for 9-10h, distilling under reduced pressure, and drying to constant weight after removing phosphorus oxychloride to obtain white powder;
s2, mixing the white powder obtained in the step S1 with p-aminobenzoic acid in dichloromethane for reaction until no hydrogen chloride is generated, performing vacuum filtration to obtain a DTDBA crude product, washing the DTDBA crude product, and drying to obtain DTDBA;
s3, mixing the DTDBA obtained in the step S2 with water, controlling the temperature at 60 ℃, dissolving ethylenediamine in the water, dripping the ethylenediamine in a mixed solution of the DTDBA and the water, and after complete reaction, performing rotary evaporation drying on a product to obtain a solid product;
s4, mixing the solid product obtained in the step S3 with PA66 salt and water, adjusting the pH value to be neutral, adding sodium hypochlorite, heating in a nitrogen environment at the pressure of 1.7MPa and the temperature of 300 ℃, and reacting for 1 h; and then continuously reducing the pressure for 1h to a normal pressure state, maintaining the temperature at 300 ℃, and reacting for 1h to obtain the nylon 66.
4. The fireproof flame-retardant nylon material of claim 1, wherein the toughening agent is an ABS toughening agent.
5. The fireproof flame-retardant nylon material of claim 1, wherein the antioxidant is a hindered phenol antioxidant.
6. The fireproof flame-retardant nylon material of claim 1, wherein the lubricant is one of ═ ethylene bis stearamide.
7. The fireproof flame-retardant nylon material of claim 1, wherein the preparation method of the modified melamine polyphosphate comprises the following steps:
s11, dissolving melamine in glacial acetic acid, stirring at 120 ℃, and stirring until the melamine is completely dissolved to obtain a solution A;
s12, dissolving polyphosphoric acid in glacial acetic acid, stirring at 120 ℃, and stirring until polyphosphoric acid is completely dissolved to obtain a solution B;
s13, dropwise adding the solution B obtained in the step S12 to the solution A obtained in the step S11 at the temperature of 120 ℃, and carrying out post-treatment after complete reaction to obtain the modified melamine polyphosphate.
8. The fireproof flame-retardant nylon material of claim 1, wherein the preparation method of the flame retardant comprises the following steps:
s21, modified melamine phosphate and a sodium dodecyl sulfate dispersing agent, and adding an N ' N-dimethylformamide solvent, wherein the solid-to-liquid ratio of the modified melamine phosphate to the N ' N-dimethylformamide is 100:3g/L, the volume ratio of the dispersing agent to the N ' N-dimethylformamide solvent is 1:50, raising the temperature to 40 ℃, mechanically stirring and ultrasonically treating for 0.5h to obtain a dispersion liquid of the modified melamine phosphate;
s22, adding hexachlorocyclotriphosphazene, KH550 and triethylamine into the modified melamine phosphate dispersion liquid obtained in the step 1, wherein the molar ratio of hexachlorocyclotriphosphazene to KH550 is 1:6, the molar ratio of KH550 to triethylamine is 1:1, reacting at the temperature of 40 ℃ for 8h, cooling to room temperature, carrying out vacuum filtration, and carrying out vacuum drying at the temperature of 90 ℃ for 24h to obtain the modified melamine phosphate microcapsule flame retardant;
s31, dissolving urea in formaldehyde at a solid-to-liquid ratio of 1:2g/mL, adjusting the pH value to 8-9 by sodium bicarbonate, and heating to 70 ℃ to react for 1.5h to obtain a urea-formaldehyde prepolymer;
s32, placing aluminum hypophosphite and alkylphenol polyoxyethylene ether in a beaker, wherein the mass ratio of the aluminum hypophosphite to the alkylphenol polyoxyethylene ether is 25:1, adding ethanol, and stirring and dispersing for 30min to obtain an aluminum hypophosphite dispersion liquid, wherein the solid-to-liquid ratio of the aluminum hypophosphite to the ethanol is 2:10 g/mL;
and S33, mixing the aluminum hypophosphite dispersion liquid with the urea formaldehyde prepolymer, adding m-benzenediol, methanol and ammonium chloride, reacting, and performing post-treatment to obtain the aluminum hypophosphite microcapsule flame retardant.
9. A method for preparing the flameproof and flame-retardant nylon material of any of claims 1 to 8, comprising the steps of,
s41, weighing all the raw materials in parts by weight, and respectively placing the nylon 66 and the toughening agent in drying equipment for drying
S42, mixing the nylon 66 dried in the step S41 with a toughening agent, and then adding glass fiber, an antioxidant and a lubricant for melt mixing at the temperature of 300-320 ℃;
s43, after melting and mixing, the temperature is increased to 200 ℃ and 230 ℃, a flame retardant is added for stirring, and after the completion of extrusion, water cooling, grain cutting and drying, the fireproof flame-retardant nylon material is obtained after injection molding.
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Application publication date: 20220208 |