CN114539713A - Synergistic flame retardant, flame-retardant ABS composite material and preparation method thereof - Google Patents
Synergistic flame retardant, flame-retardant ABS composite material and preparation method thereof Download PDFInfo
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- CN114539713A CN114539713A CN202210414858.7A CN202210414858A CN114539713A CN 114539713 A CN114539713 A CN 114539713A CN 202210414858 A CN202210414858 A CN 202210414858A CN 114539713 A CN114539713 A CN 114539713A
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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 107
- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 21
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 17
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- -1 (2, 4-di-tert-butyl) phenyl Chemical group 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 55
- 239000000203 mixture Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920000137 polyphosphoric acid Polymers 0.000 description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- CTMFECUQKLSOGJ-UHFFFAOYSA-N 4-bromotriazine Chemical compound BrC1=CC=NN=N1 CTMFECUQKLSOGJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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 provides a synergistic flame retardant, a flame-retardant ABS composite material and a preparation method thereof, belonging to the technical field of high polymer materials. The synergistic flame retardant is prepared by the following steps: 1) mixing dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid, and reacting to obtain a solution A; 2) drying the solution A to obtain a solid B; 3) and calcining the solid B to obtain the synergistic flame retardant. The synergistic flame retardant provided by the invention is matched with the flame retardant MPP, and the flame retardant effect can be effectively improved when the synergistic flame retardant is added into an ABS material.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a synergistic flame retardant, a flame-retardant ABS composite material and a preparation method thereof.
Background
ABS plastic is terpolymer of acrylonitrile (A) -butadiene (B) -styrene (S), and is a widely used polymer plastic. The ABS plastic integrates the performances of three components, and the characteristics of the three components enable the ABS plastic to become thermoplastic plastic with good comprehensive performances of 'hardness, toughness, high rigidity, good strength, glossiness, heat resistance and excellent dimensional stability'. The ABS plastic has the advantages of excellent dimensional stability and the like, so that the ABS plastic is widely applied to the fields of household appliances, electronic appliances, automobiles and the like. However, in some specific application fields, the requirement on the flame retardant property of the material is high, and the common ABS material cannot meet the requirement, so that the application of the ABS material in some specific fields is limited.
In the prior art, flame retardant is usually added to improve the flame retardant property of ABS, for example, in patent CN110256833A, bisphenol A bis, bromotriazine, modified montmorillonite and hydrotalcite are used as flame retardant, and are matched with anti-dripping agent to be added to ABS material to improve the flame retardant property, but the patent has large dosage of flame retardant and relatively complex components. And the flame retardant MPP and the synergistic flame retardant zinc borate are adopted to improve the flame retardant property of the ABS, but the flame retardant property is poor.
Disclosure of Invention
The invention provides a synergistic flame retardant, a flame-retardant ABS composite material and a preparation method thereof. The synergistic flame retardant provided by the invention is matched with the flame retardant MPP, can improve the flame retardant effect, and is added into the ABS composite material, so that the ABS composite material has high-efficiency flame retardant performance.
In order to achieve the purpose, the invention provides a synergistic flame retardant which is prepared by the following steps:
1) mixing dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid, and reacting to obtain a solution A;
2) drying the solution A to obtain a solid B;
3) and calcining the solid B to obtain the synergistic flame retardant.
Preferably, in the step 1), the reaction is carried out under ultrasonic conditions; the reaction conditions are as follows: temperature: 50-70 ℃, time: 10-16 h; ultrasonic power: 200 to 600 w.
Preferably, in the step 2), the drying temperature is 50-70 ℃ and the drying time is 6-8 h.
Preferably, in the step 3), the calcination temperature is 740-800 ℃ and the time is 10-16 h.
Preferably, the mass ratio of the dodecyl trimethyl ammonium bromide, the phosphoric acid, the water, the bismuth nitrate and the phosphomolybdic acid in the step 1) is (2-4): (24-30): (120-160): (30-36): (20-24).
The invention provides a flame-retardant ABS composite material, which comprises the following components in parts by weight:
80-100 parts of ABS, 16-18 parts of flame retardant MPP, 4-8 parts of synergistic flame retardant and 0.1-0.5 part of antioxidant; the synergistic flame retardant is the synergistic flame retardant of any one of the above schemes.
Preferably, the antioxidant is one or more of tris (2, 4-di-tert-butyl) phenyl phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
The invention also provides a preparation method of the flame-retardant ABS composite material, which comprises the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
Compared with the prior art, the invention has the advantages and positive effects that:
the flame-retardant synergist provided by the invention comprises bismuth oxide negativePhosphomolybdic acid in the phosphomolybdic acid-carrying flame-retardant synergist is decomposed to generate oxyacid and phosphate, a liquid film and a carbon layer protection matrix are formed on the surface of the ABS composite material, and the liquid film and the carbon layer protection matrix interact with each other to form a higher-quality carbon layer which covers the surface of the material to protect the matrix and improve the flame-retardant property of the ABS composite material. Bi in flame retardant synergist2O3Reacting with the MPP-decomposed polyphosphoric acid to inhibit the decomposition of polyphosphoric acid into P by bismuth-forming phosphate2O5More phosphorus participates in esterification and char formation, and the flame retardant property of the ABS composite material is further improved. The flame-retardant synergist provided by the invention is used in cooperation with MPP, so that the flame-retardant property of ABS can be effectively improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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.
The invention provides a synergistic flame retardant which is prepared by the following steps:
1) mixing dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid, and reacting to obtain a solution A;
2) drying the solution A to obtain a solid B;
3) and calcining the solid B to obtain the synergistic flame retardant.
The method comprises the steps of mixing dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid, and reacting to obtain a solution A. In the present invention, the mass ratio of the dodecyltrimethylammonium bromide, the phosphoric acid, the water, the bismuth nitrate and the phosphomolybdic acid is preferably (2-4): (24-30): (120-160): (30-36):
(20-24). It is understood that the skilled person can select suitable reaction ratios within the above preferred ratio ranges, such as 2:24:120:30:20, 4:30:160:36:24 or 3:24:150:36:21, etc. The reaction is preferably carried out under ultrasonic conditions. The power of the ultrasonic wave is preferably 200-600 w. The temperature of the reaction is preferably 50-70 ℃; the reaction time is preferably 10-16 h.
After the solution A is obtained, the solution A is dried to obtain a solid B. In the present invention, it is preferable that the solution a is filtered and washed before being dried. In the present invention, the washing solvent is preferably water. In the invention, the drying temperature is preferably 50-70 ℃, and the drying time is preferably 6-8 h.
After the solid B is obtained, the invention calcines the solid B to obtain the synergistic flame retardant. In the present invention, the temperature of the calcination is preferably 740-800 ℃ and the time is preferably 10-16 h.
According to the invention, dodecyl trimethyl ammonium bromide is used as a template, molybdenum phosphate is loaded on bismuth oxide through reaction, and bismuth oxide loaded phosphomolybdic acid is obtained, namely the flame retardant synergist.
The invention also provides a flame-retardant ABS composite material, which comprises the following components in parts by weight:
80-100 parts of ABS, 16-18 parts of flame retardant MPP, 4-8 parts of synergistic flame retardant and 0.1-0.5 part of antioxidant; the synergistic flame retardant is the synergistic flame retardant of any one of the above schemes.
The flame-retardant ABS composite material provided by the invention comprises ABS. Comprises 80 to 100 portions by weight. It is understood that the ABS content may be 80, 81, 90, 95, 100 parts or any value within the above range. The source of the ABS is not particularly limited in the invention, and the ABS can be obtained by adopting conventional commercial products in the field.
The flame-retardant ABS composite material provided by the invention comprises a flame retardant MPP. Comprises 16 to 18 portions by weight. It is understood that the flame retardant may be present in an amount of 16, 17, 18 parts or any value within the above range. The source of the MPP is not particularly limited in the invention, and the conventional commercial products in the field can be adopted.
The flame-retardant ABS composite material provided by the invention comprises a synergistic flame retardant. Comprises 4 to 8 portions by weight. It is understood that the amount of the synergistic flame retardant may be 4, 5, 7, 8 parts or any value within the above range. The synergistic flame retardant disclosed by the invention is the synergistic flame retardant disclosed by the scheme.
The flame-retardant ABS composite material provided by the invention comprises an antioxidant. Comprises 0.1 to 0.5 portion by weight. It is understood that the antioxidant may be present in an amount of 0.1, 0.2, 0.3, 0.4, 0.5 parts or any amount within the above range. In the present invention, the antioxidant is preferably one or more of tris (2, 4-di-tert-butyl) phenyl phosphite (abbreviated as Irganox168), tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (abbreviated as Irganox1010) and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (abbreviated as Irganox 1330).
In the invention, the mechanism of the flame retardant ABS composite material for performing flame retardance is as follows: phosphomolybdic acid in the flame-retardant synergist is decomposed to generate oxyacid and phosphate, a liquid film and a carbon layer protection matrix are formed on the surface of the ABS composite material, and the liquid film and the carbon layer protection matrix interact with each other to form a higher-quality carbon layer which covers the surface of the material to protect the matrix and improve the flame-retardant property of the ABS composite material. Bi in flame retardant synergist2O3Reacting with the MPP-decomposed polyphosphoric acid to inhibit the decomposition of polyphosphoric acid into P by bismuth-forming phosphate2O5More phosphorus participates in esterification and char formation, and the flame retardant property of the ABS composite material is further improved.
The invention also provides a preparation method of the flame-retardant ABS composite material, which comprises the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are as follows:
ABS (model 757K), zhenjianqimei; MPP, Shenzhen Jinlonghua technology Limited; dodecyl trimethyl ammonium bromide, chemical ltd, jonan hui chuanchuan; weifang Huabo chemical Co., Ltd; bismuth nitrate, Shandong Polychemist Co., Ltd; phosphomolybdic acid, available from Shanghai Peng chemical Co., Ltd; deionized water, beijing baiolai bock technologies ltd; antioxidants (type Irganox168, Irganox1010, Irganox1330), Pasteur, Germany.
Example 1
(1) Weighing 80 parts of ABS, 16 parts of MPP, 4 parts of synergistic flame retardant M1 and 0.1 part of antioxidant Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P1.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 180 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 200 ℃, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 200 r/min.
The synergistic flame retardant M1 is prepared by the following steps:
(1) weighing 20g of template agent dodecyl trimethyl ammonium bromide, 240g of phosphoric acid, 1.2kg of deionized water, 300g of bismuth nitrate and 200g of phosphomolybdic acid, adding into a reaction vessel, and carrying out ultrasonic reaction at 50 ℃ for 10 hours (with the power of 600w) to form a solution A;
(2) and filtering, washing and drying the solution A at 50 ℃ for 8h to obtain a solid B.
(3) And (3) calcining the solid B in a muffle furnace at 740 ℃ for 10h to obtain the synergistic flame retardant M1.
Example 2
(1) Weighing 100 parts of ABS, 18 parts of MPP, 8 parts of synergistic flame retardant M2, 0.1 part of Irganox1010, 0.2 part of Irganox168 and 0.2 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (2) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 210 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃, the temperature of a machine head is 230 ℃, and the rotating speed of a screw is 280 r/min.
The synergistic flame retardant M2 is prepared by the following steps:
(1) weighing 40g of template agent dodecyl trimethyl ammonium bromide, 300g of phosphoric acid, 1.6kg of deionized water, 360g of bismuth nitrate and 240g of phosphomolybdic acid, adding into a reaction vessel, and carrying out ultrasonic reaction at 70 ℃ for 16h (with the power of 200w) to form a solution A;
(2) and filtering, washing and drying the solution A at 60 ℃ for 7h to obtain a solid B.
(3) And (3) calcining the solid B in a muffle furnace at 800 ℃ for 16h to obtain the synergistic flame retardant M2.
Example 3
(1) Weighing 90 parts of ABS, 17 parts of MPP, 6 parts of synergistic flame retardant M3, 0.1 part of Irganox168 and 0.2 part of Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P3.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 215 ℃, the temperature of the third zone is 215 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of a machine head is 220 ℃, and the rotating speed of a screw is 240 r/min.
The synergistic flame retardant M3 is prepared by the following steps:
(1) weighing 30g of template agent dodecyl trimethyl ammonium bromide, 270g of phosphoric acid, 1.4kg of deionized water, 330g of bismuth nitrate and 220g of phosphomolybdic acid, adding into a reaction vessel, and carrying out ultrasonic reaction at 60 ℃ for 13h (with the power of 500w) to form a solution A;
(2) and filtering, washing and drying the solution A at 70 ℃ for 6h to obtain a solid B.
(3) And (3) calcining the solid B in a muffle furnace at 770 ℃ for 13h to obtain bismuth oxide loaded phosphomolybdic acid, namely the synergistic flame retardant M3.
Example 4
(1) Weighing 85 parts of ABS, 17 parts of MPP, 8 parts of synergistic flame retardant M4 and 0.1 part of Irganox1010, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P4.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 205 ℃, the temperature of the second zone is 218 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃, the temperature of the sixth zone is 225 ℃, the temperature of a machine head is 225 ℃ and the rotating speed of a screw is 230 r/min.
The synergistic flame retardant M4 is prepared by the following steps:
(1) weighing 25g of template dodecyl trimethyl ammonium bromide, 295g of phosphoric acid, 1.45kg of deionized water, 345g of bismuth nitrate and 225g of phosphomolybdic acid, adding into a reaction vessel, and carrying out ultrasonic reaction at 65 ℃ for 15 hours (with the power of 500w) to form a solution A;
(2) and filtering, washing and drying the solution A at 65 ℃ for 7h to obtain a solid B.
(3) And (3) calcining the solid B in a muffle furnace at 780 ℃ for 14h to obtain the synergistic flame retardant M4.
Example 5
(1) Weighing 85 parts of ABS, 16 parts of MPP, 7 parts of synergistic flame retardant M5 and 0.1 part of Irganox1330, mixing and uniformly stirring to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the ABS composite material P5.
The double-screw extruder comprises six temperature zones which are sequentially arranged, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 225 ℃, the temperature of the fourth zone is 225 ℃, the temperature of the fifth zone is 225 ℃ and the temperature of the sixth zone is 225 ℃; the head temperature of the double-screw extruder is 225 ℃, and the screw rotating speed is 225 r/min.
The synergistic flame retardant M5 is prepared by the following steps:
(1) weighing 26g of template dodecyl trimethyl ammonium bromide, 290g of phosphoric acid, 1.55kg of deionized water, 320g of bismuth nitrate and 230g of phosphomolybdic acid, adding into a reaction vessel, and carrying out ultrasonic reaction at 55 ℃ for 15h (with the power of 500w) to form a solution A;
(2) and filtering, washing and drying the solution A at 65 ℃ for 7h to obtain a solid B.
(3) And (3) calcining the solid B in a muffle furnace at 765 ℃ for 14h to obtain the synergistic flame retardant M5.
Comparative example 1
The difference from example 5 is that no synergistic flame retardant is added, and the other operations are exactly the same as example 5. The specific formula is as follows:
85 parts of ABS, 16 parts of MPP and 0.1 part of Irganox 1330.
Comparative example 2
The difference from the example 5 is that zinc borate is adopted as a synergistic flame retardant, and the specific formula is as follows:
85 parts of ABS, 16 parts of MPP, 7 parts of zinc borate and 0.1 part of Irganox 1330.
Comparative example 3
The difference from example 5 is that the flame retardant used in example 5 in patent CN110256833A is specifically formulated as follows:
85 parts of ABS, 16 parts of flame retardant, 0.5 part of anti-dripping agent PTEE and 0.1 part of Irganox 1330.
Performance test
The flame retardant performance of the ABS composite materials prepared in the examples and comparative examples was tested, and the specific test standard was UL94, and the specific results are shown in table 1.
TABLE 1ABS composite Properties
As can be seen from Table 1, the flame-retardant synergist prepared by the invention has good flame-retardant effect when added into an ABS material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The synergistic flame retardant is characterized by being prepared by the following steps:
1) mixing dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid, and reacting to obtain a solution A;
2) drying the solution A to obtain a solid B;
3) and calcining the solid B to obtain the synergistic flame retardant.
2. The synergistic flame retardant of claim 1, wherein in step 1), the reaction is carried out under ultrasonic conditions; the reaction conditions are as follows: temperature: 50-70 ℃, time: 10-16 h; ultrasonic power: 200 to 600 w.
3. The synergistic flame retardant of claim 1, wherein in the step 2), the drying temperature is 50-70 ℃ and the drying time is 6-8 h.
4. The synergistic flame retardant of claim 1, wherein in the step 3), the calcination temperature is 740-800 ℃ and the calcination time is 10-16 h.
5. The synergistic flame retardant of claim 1, wherein the mass ratio of dodecyl trimethyl ammonium bromide, phosphoric acid, water, bismuth nitrate and phosphomolybdic acid in the step 1) is (2-4): (24-30): (120-160): (30-36): (20-24).
6. The flame-retardant ABS composite material is characterized by comprising the following components in parts by weight:
80-100 parts of ABS, 16-18 parts of flame retardant MPP, 4-8 parts of synergistic flame retardant and 0.1-0.5 part of antioxidant; the synergistic flame retardant is defined in any one of claims 1-5.
7. The flame retardant ABS composite material of claim 6 wherein the antioxidant is one or more of tris (2, 4-di-tert-butyl) phenyl phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
8. The preparation method of the flame-retardant ABS composite material as claimed in any of claims 6 to 7, characterized by comprising the following steps:
mixing the materials, and extruding and granulating the obtained mixed material to obtain the flame-retardant ABS composite material;
the extrusion granulation is carried out in a double-screw extruder, and the double-screw extruder adopts six temperature zones which are sequentially arranged when carrying out the extrusion granulation, and the six temperature zones sequentially respectively comprise: the temperature of the first zone is 180-210 ℃, the temperature of the second zone is 200-230 ℃, the temperature of the third zone is 200-230 ℃, the temperature of the fourth zone is 200-230 ℃, the temperature of the fifth zone is 200-230 ℃, and the temperature of the sixth zone is 200-230 ℃; the head temperature of the double-screw extruder is 200-230 ℃, and the screw rotating speed is 200-280 r/min.
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Application publication date: 20220527 Assignee: Haike Technology Innovation Service (Jiangsu) Co.,Ltd. Assignor: Shandong Haike Innovation Research Institute Co.,Ltd. Contract record no.: X2023980046100 Denomination of invention: A synergistic flame retardant and flame retardant ABS composite material and its preparation method Granted publication date: 20230811 License type: Common License Record date: 20231110 |