CN115160648B - Flame retardant, preparation method thereof and flame-retardant resin - Google Patents

Flame retardant, preparation method thereof and flame-retardant resin Download PDF

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CN115160648B
CN115160648B CN202210801138.6A CN202210801138A CN115160648B CN 115160648 B CN115160648 B CN 115160648B CN 202210801138 A CN202210801138 A CN 202210801138A CN 115160648 B CN115160648 B CN 115160648B
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flame retardant
flame
doped zinc
resin
fatty acid
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CN115160648A (en
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章彬
蒋学鑫
王韶晖
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Anhui Estone Material Technology Co ltd
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Anhui Estone Material Technology Co ltd
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    • 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
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a flame retardant, a preparation method thereof and flame-retardant resin, and relates to the technical field of flame-retardant materials, wherein the flame retardant comprises doped zinc metaborate and an anionic surfactant coated on the surface of the doped zinc metaborate; wherein the chemical formula of the doped zinc metaborate is as follows: zn (zinc) 1‑x M x B 2 O 4 X is more than or equal to 0.05 and less than or equal to 0.45; m is selected from at least one of group VIB, group VIIB and group VIII metals. According to the invention, the surface modification is carried out on the doped zinc metaborate, so that the lipophilicity of the doped zinc metaborate can be increased, the compatibility of the doped zinc metaborate with the polymeric resin is improved, and the mechanical property of the prepared flame-retardant resin is obviously improved.

Description

Flame retardant, preparation method thereof and flame-retardant resin
Technical field:
the invention relates to the technical field of flame-retardant materials, in particular to a flame retardant, a preparation method thereof and flame-retardant resin.
The background technology is as follows:
zinc borate is an environment-friendly non-halogen flame retardant, has the characteristics of no toxicity, low water solubility, high thermal stability and the like, and is widely applied to the fields of plastics, rubber, paint and the like. The zinc borate can be decomposed into zinc oxide and boron oxide through heat absorption at a certain temperature to form an adhesive-state inorganic flame-retardant ceramic coating, so that the adhesive-state inorganic flame-retardant ceramic coating is attached to the surface of a substrate to prevent combustible gas from escaping, and meanwhile, the heat released by the combustion of the substrate can be partially offset in the heat absorption process, so that the flame-retardant effect is further improved. However, with ZnB 2 O 4 The flame-retardant resin used as the flame retardant has low density of the surface carbon layer formed after combustion and uneven distribution of the carbon layer, so that the application range of the flame-retardant resin is limited. In addition, znB 2 O 4 Poor compatibility in resin, easy agglomeration, and deterioration of mechanical properties of the resin, so that ZnB 2 O 4 Is greatly limited in its application.
Chinese patent CN 103937031a discloses a modified zinc borate and a preparation method thereof, in which polydimethylsiloxane and a silane coupling agent are used as a modifier, and boric acid, zinc oxide and the modifier are reacted in water to obtain the modified zinc borate. Although the method improves various mechanical properties of the material, the method has complicated steps, complex chemical reaction process and difficult control, and is not beneficial to industrialized popularization and production.
The invention comprises the following steps:
the invention aims to solve the technical problems of unsatisfactory flame retardant effect and poor compatibility with polymeric resin in the prior art, and provides a flame retardant, a preparation method thereof and flame retardant resin.
The inventor of the invention discovers that the zinc metaborate doped can improve the density of the surface carbon layer after resin combustion and the uniformity of carbon layer distribution; however, the surface of the doped zinc metaborate is polar, hydrophilic and oleophobic, so that the doped zinc metaborate is difficult to uniformly disperse in the polymeric resin when being blended with a resin base material, and the poor compatibility with the polymeric resin can lead to the fact that the mechanical property of the polymeric resin can not be effectively improved, thus the further application of the doped zinc metaborate is limited. By selecting a proper surface modifier to carry out surface modification on the doped zinc metaborate, the lipophilicity of the doped zinc metaborate can be increased, the compatibility of the doped zinc metaborate with the polymer resin is improved, and the mechanical property of the prepared flame-retardant resin is further improved.
In order to achieve the above object, one of the objects of the present invention is to provide a flame retardant comprising doped zinc metaborate and an anionic surfactant coated on the surface of the doped zinc metaborate; wherein the chemical formula of the doped zinc metaborate is as follows: zn (zinc) 1-x M x B 2 O 4 X is more than or equal to 0.05 and less than or equal to 0.45; m is selected from at least one of group VIB, group VIIB and group VIII metals.
It is a second object of the present invention to provide a method for preparing a flame retardant, the method comprising:
carrying out high-temperature solid phase reaction on a mixture obtained by mixing a zinc source, a boron source and a doping source to obtain doped zinc metaborate; then stirring the doped zinc metaborate and an anionic surfactant in the presence of a solvent; and carrying out suction filtration and drying on the mixture obtained by mixing to obtain the flame retardant.
Wherein the doping source is selected from at least one of a group VIB metal source, a group VIIB metal source and a group VIII metal source.
The third object of the present invention is to provide a flame retardant composite comprising a primary flame retardant and a synergistic flame retardant; the main flame retardant is the flame retardant or the flame retardant prepared according to the method.
The fourth object of the present invention is to provide a flame-retardant resin comprising 100 parts by weight of a polymeric resin, 5 to 80 parts by weight of the aforementioned flame-retardant composite and 0 to 70 parts by weight of an auxiliary agent, based on 100 parts by weight of the polymeric resin.
The beneficial effects of the invention are as follows:
1) According to the invention, the zinc metaborate is doped, and then the doped zinc metaborate is subjected to surface modification, so that the lipophilicity of the zinc metaborate can be increased, the compatibility of the zinc metaborate with the polymeric resin is improved, and the mechanical property and flame retardant property of the flame retardant resin are obviously improved;
2) The preparation method provided by the invention is simple and can be used for industrial production.
Description of the drawings:
FIG. 1 is an XRD pattern of the products obtained in preparation examples 1 to 3 and preparation example 10;
FIG. 2 is an XRD pattern of the product of preparation 9;
FIG. 3 is SEM images of the product of preparation example 1 at various magnification;
FIG. 4 is an SEM image of the product of preparation 11 at various magnification levels;
FIG. 5 is an SEM image of the product of preparation example 16;
FIG. 6 is an SEM image of the product of preparation example 17 at various magnification levels;
FIG. 7 is an SEM image of the product of preparation 18 at various magnification levels;
FIG. 8 is an SEM image of the product of preparation 19 at various magnification levels.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
As described above, the present invention provides a flame retardant comprising doped zinc metaborate and an anionic surfactant coated on the surface of the doped zinc metaborate; wherein the chemical formula of the doped zinc metaborate is as follows: zn (zinc) 1-x M x B 2 O 4 X is more than or equal to 0.05 and less than or equal to 0.45; m is selected from at least one of group VIB, group VIIB and group VIII metals.
The flame retardant provided by the invention has good compatibility with the polymeric resin, and can improve the flame retardant property and mechanical property of the flame retardant resin. Preferably, the anionic surfactant is selected from at least one of phosphate, fatty acid, sulfonate and sulfate, preferably phosphate.
In the present invention, preferably, the phosphate salt is at least one selected from the group consisting of a hexaalkyl phosphate salt, a dodecyl phosphate salt, a hexadecyl phosphate salt and an octadecyl phosphate salt; further preferred is a hexaalkyl phosphate, which may be at least one of sodium phytate, magnesium phytate, aluminum phytate and zinc phytate, for example.
In the present invention, preferably, the fatty acid salt is selected from C 2 -C 18 For example, at least one of stearate, laurate, palmitate, oleate and acetate; further preferably C 16 -C 18 At least one of the fatty acid salts of (a) and (b). Further, the fatty acid salt is at least one selected from the group consisting of potassium fatty acid, sodium fatty acid, calcium fatty acid, magnesium fatty acid, aluminum fatty acid, zinc fatty acid and ammonium fatty acid, and further preferably at least one selected from the group consisting of sodium fatty acid, magnesium fatty acid, zinc fatty acid and aluminum fatty acid.
In the invention, the sulfonate is at least one selected from fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, sodium alkylbenzenesulfonate, sulfosuccinate and alkyl sulfonate; the sulfate salt is at least one selected from sodium laurylsulfate and sodium laurylsulfate.
In the invention, the method for measuring the oil absorption value comprises the following steps: 1g of powder to be measured is weighed, dioctyl phthalate (DOP) is dropwise added, and the mixture is slowly ground until the mixture is ground by an ink regulating knife to ensure that the mixture is not scattered, and the mass of the DOP is recorded; the oil absorption value is calculated as follows:
oil absorption value=m 3 /m 2 ×100％
Wherein m is 3 For DOP mass, m 2 The quality of the powder to be measured.
The oil absorption value can represent the polarity of the powder to be measured, and the smaller the oil absorption value is, the smaller the polarity of the surface of the powder to be measured is.
In the invention, the oil absorption value of the flame retardant is 0.3-0.8; preferably 0.3 to 0.78.
In the invention, the proportion of the doped zinc metaborate and the anionic surfactant should be controlled within a reasonable range, and too high proportion of the doped zinc metaborate can lead to the fact that the surface of the doped zinc metaborate cannot be effectively coated by the anionic surfactant, i.e. the lipophilicity of the doped zinc metaborate cannot be effectively improved; preferably, the weight ratio of the doped zinc metaborate to the anionic surfactant is (0.5-10): 1.
In the present invention, with respect to ZnB 2 O 4 (ZnO·B 2 O 3 ) Doped zinc metaborate (Zn) 1-x M x B 2 O 4 ) The flame-retardant effect of the flame-retardant resin can be obviously improved on the premise of not reducing the mechanical property of the flame-retardant resin, so that the flame-retardant resin has high oxygen index and forms a compact and uniform carbon layer after combustion. Preferably, M is at least one selected from Cr, mn, fe, co, ni, W and Mo; further preferably at least one of Mn, fe, co, ni and Mo.
In the invention, the doping amount of the metal M should be controlled within a reasonable range, and under the preferable condition, x is more than or equal to 0.1 and less than or equal to 0.25.
The present invention also provides a method of preparing a flame retardant, the method comprising:
carrying out high-temperature solid phase reaction on a mixture obtained by mixing a zinc source, a boron source and a doping source to obtain doped zinc metaborate; then stirring the doped zinc metaborate and an anionic surfactant in the presence of a solvent; and carrying out suction filtration and drying on the mixture obtained by mixing to obtain the flame retardant.
Wherein the doping source is selected from at least one of a group VIB metal source, a group VIIB metal source and a group VIII metal source.
In the present invention, the stirring conditions include: the temperature is 25-80 ℃ and the time is 1-8h. The anionic surfactant can be coated on the surface of the doped zinc metaborate by stirring, so that the polarity of the doped zinc metaborate is reduced, the compatibility of the doped zinc metaborate and the polymeric resin is improved, and the mechanical property of the prepared flame-retardant resin is improved.
In the present invention, the weight ratio of the doped zinc metaborate to the anionic surfactant is (0.5-10): 1, preferably (1-5): 1, and for example, may be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any value in the range formed by any two of the above ratios.
Preferably, the anionic surfactant is selected from at least one of phosphate, fatty acid, sulfonate and sulfate, preferably phosphate.
In the present invention, preferably, the phosphate salt is at least one selected from the group consisting of a hexaalkyl phosphate salt, a dodecyl phosphate salt, a hexadecyl phosphate salt and an octadecyl phosphate salt; further preferred is a hexaalkyl phosphate, which may be at least one of sodium phytate, magnesium phytate, aluminum phytate and zinc phytate, for example.
In the present invention, preferably, the fatty acid salt is selected from C 2 -C 18 At least one of the fatty acid salts of (a); for example, at least one of stearate, laurate, palmitate, oleate and acetate; further preferably C 16 -C 18 At least one of the fatty acid salts of (a) and (b). Further, the fatty acid salt is at least one selected from the group consisting of potassium fatty acid, sodium fatty acid, calcium fatty acid, magnesium fatty acid, aluminum fatty acid, zinc fatty acid and ammonium fatty acid, and further preferably at least one selected from the group consisting of sodium fatty acid, magnesium fatty acid, zinc fatty acid and aluminum fatty acid.
In the invention, the sulfonate is at least one selected from fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, sodium alkylbenzenesulfonate, sulfosuccinate and alkyl sulfonate; the sulfate salt is at least one selected from sodium laurylsulfate and sodium laurylsulfate.
In the invention, the zinc source is selected from at least one of zinc oxide and zinc salt; the zinc salts include, but are not limited to, zinc sulfate, zinc nitrate, and zinc chloride; the boron source is selected from at least one of boron oxide, borate and boric acid; the borates include, but are not limited to, sodium tetraborate.
In the invention, the VIB metal source is selected from VIB metal oxide and/or VIB metal salt; the group VIB metal oxides include, but are not limited to, chromia, molybdenum oxide, and tungsten oxide; the group VIB metal salts include, but are not limited to, at least one of chromium salts, molybdenum salts, molybdates, tungstates, and tungsten salts.
In the present invention, the group VIIB metal source is selected from group VIIB metal oxides and/or group VIIB metal salts; the group VIIB metal oxides include, but are not limited to, manganese oxide, manganomanganic oxide; the group VIIB metal salts include, but are not limited to, at least one of manganese chloride, manganese sulfate, and manganese nitrate.
In the present invention, preferably, the group VIII metal source is selected from the group consisting of a group VIII metal oxide and/or a group VIII metal salt; the group VIII metal oxides include, but are not limited to, iron oxide, cobalt oxide, and nickel oxide; the group VIB metal salts include, but are not limited to, at least one of iron salts, cobalt salts, and nickel salts.
In some preferred embodiments of the present invention, the zinc source is calculated as zinc element, the boron source is calculated as boron element, the doping source is calculated as metal element, and the molar ratio of the zinc source, the doping source and the boron source is (0.55-0.95): (0.05-0.45): 2, preferably (0.7-0.9): (0.1-0.3): 2.
Preferably, the conditions of the high temperature solid phase reaction include: the reaction temperature is 900-1050 ℃; the reaction time is 12-24h.
The invention also provides a flame retardant prepared by the method.
The invention also provides a flame retardant composite, which comprises a main flame retardant and a synergistic flame retardant; wherein the main flame retardant is the flame retardant or the flame retardant prepared by the method.
The synergistic flame retardant is at least one selected from halogen flame retardants, phosphorus flame retardants, inorganic flame retardants, organic silicon flame retardants and nitrogen flame retardants.
The halogen flame retardant includes, but is not limited to, at least one of chlorinated polyethylene, bis (hexachlorocyclopentadiene) cyclooctane, chlorinated paraffin, tetrabromobisphenol A, decabromodiphenylethane, tris (bromophenyl) triazine, brominated epoxy, decabromodiphenylether, hexabromocyclododecane, tetrabromophthalic anhydride, hexabromobenzene, octabromodiphenylether, brominated polystyrene, brominated polycarbonate oligomer, brominated phenoxy resin.
The phosphorus flame retardant includes, but is not limited to, polyphosphates, ammonium phosphate, monophosphates, bisphosphates, and polyphosphates, and may be, for example, at least one of ammonium polyphosphate, monoammonium phosphate, triammonium pyrophosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dimethylphenyl phosphate, tributyl phosphate, xylyl diphenyl phosphate, resorcinol bis- (diphenyl phosphate), bisphenol bis- (diphenyl phosphate), diphenyl pentaerythritol diphosphate, and the like.
The inorganic flame retardant includes, but is not limited to, at least one of a hydroxide flame retardant and a metal oxide; the hydroxide flame retardant includes, but is not limited to, aluminum hydroxide and magnesium hydroxide; the metal oxides include, but are not limited to, aluminum oxide, magnesium oxide, and antimony oxide.
The silicone flame retardant includes, but is not limited to, at least one of silicone oil, hydrogen-containing silicone oil, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methoxytriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane, polydimethylsiloxane, polymethylvinylsiloxane, polymethylphenylsiloxane, polymethyltrifluoropropyl siloxane, silicone resin, and the like.
The nitrogen-based flame retardant includes, but is not limited to, at least one of melamine, melamine phosphate, melamine cyanurate, derivatives thereof, and the like.
The synergistic flame retardant is preferably a halogen-free flame retardant, and further preferably aluminum hydroxide and/or magnesium hydroxide.
In order to further optimize the flame retardant effect of the flame retardant composite, it is further preferred that the weight ratio of the main flame retardant to the synergistic flame retardant of the present invention is (2-10): 1, preferably (3-5): 1.
The invention also provides a flame-retardant resin, which comprises 100 parts by weight of the polymeric resin, 5-80 parts by weight of the flame-retardant compound and 0-70 parts by weight of an auxiliary agent based on 100 parts by weight of the polymeric resin.
In the present invention, the flame retardant compound is preferably used in an amount of 10 to 50 parts by weight, more preferably 25 to 45 parts by weight, based on 100 parts by weight of the polymeric resin.
In some preferred embodiments of the present invention, in order to further optimize the flame retardant effect and mechanical properties of the flame retardant resin, the flame retardant resin comprises 100 parts by weight of a polymeric resin, 25 to 45 parts by weight of a flame retardant compound, and 20 to 60 parts by weight of an auxiliary agent.
In the present invention, the kind of the polymer resin may be known to those skilled in the art, and includes, but is not limited to, at least one of polypropylene resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polyphenylene ether resin, polyamide resin, polycarbonate, epoxy resin, polyurethane, acrylic resin, polyacrylonitrile resin, polyvinyl alcohol resin, bismaleimide resin, polyimide resin, cyanate ester resin, and silicone rubber, natural rubber, ethylene propylene rubber, polyisoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene rubber, butyl rubber, fluororubber, fluorosilicone rubber, or copolymers thereof. Such copolymers include, but are not limited to, propylene/ethylene copolymer resins, ethylene/vinyl acetate copolymer resins, acrylonitrile/butadiene/styrene copolymer resins.
In the present invention, the kind of the auxiliary agent may be adjusted according to actual needs, and the kind of the auxiliary agent may be known to those skilled in the art, including but not limited to at least one of fluxing agents, compatibilizing agents, and lubricants.
In the present invention, the fluxing agent is an alkaline fluxing agent, an acidic fluxing agent, or a neutral fluxing agent, including but not limited to calcium oxide, magnesium oxide, sodium oxide, potassium oxide; the acidic fluxing agents include, but are not limited to, low melting glass frits; the neutral fluxing agents include, but are not limited to, fluorite and alumina.
In the present invention, the compatibilizing agent includes, but is not limited to, at least one of a cyclic anhydride type compatibilizing agent, an acrylic type compatibilizing agent, an epoxy type compatibilizing agent, an oxazoline type compatibilizing agent, and an imide type compatibilizing agent. The cyclic anhydride-type compatibilizers include, but are not limited to, maleic anhydride grafts. The maleic anhydride grafts include, but are not limited to, at least one of MAH-g-PE, MAH-g-POE, MAH-g-EVA, and MAH-g-EPDM.
In the present invention, the lubricant includes, but is not limited to, at least one of fatty acid, fatty acid salt, fatty acid amide, metal soap, PE wax, organosilicon compound, and naphthenic oil.
The invention is illustrated in detail by means of the following preparations and examples:
the testing method comprises the following steps:
1) Limiting Oxygen Index (LOI) was determined according to the method specified in ISO 4589-2.
2) Carbon residue amount test method: will have a mass of m 0 Placing the sample in a thermogravimetric analyzer, wherein the oxygen flow rate is 20mL/min, the heating rate is 10 ℃/min, the temperature range is 30-800 ℃ under the air atmosphere, and the mass is m 1 Residual sample of (c) residual carbon content=m 1 /m 0 ×100％。
3) Tensile strength was measured according to the method specified in GB/T1040.2-2006.
4) Elongation at break was measured according to the method specified in GB/T1040-2006.
5) The method for measuring the oil absorption value comprises the following steps: 1g of powder to be measured is weighed, dioctyl phthalate (DOP) is dropwise added, and the mixture is slowly ground until the mixture is ground by an ink regulating knife to ensure that the mixture is not scattered, and the mass of the DOP is recorded;
oil absorption value=m 3 /m 2 ×100％
Wherein m is 3 For DOP mass, m 2 The quality of the powder to be measured.
Silicone rubber is commercially available with a density of 1.45g/cm 3 Hardness (shore a) was 59;
naphthenic oils are commercially available and have a flash point of 190-226℃and a density of 850-902g/m 3 The aniline point is 66-82 ℃ and the viscosity index is 28;
a compatibilizer (MAH-g-PE) having a melt index of 1.5 to 2.5g/10min and a Maleic Anhydride (MAH) content of 0.5 to 0.8wt% based on the matrix resin PE.
1. Preparation of doped zinc metaborate
Preparation example 1
Mixing zinc oxide, nickel oxide and boron oxide at room temperature, grinding, sieving with 300 mesh sieve, tabletting, placing into a muffle furnace, heating to 950 deg.C at 1deg.C/min, maintaining for 24 hr, naturally cooling, grinding thoroughly, and sieving to obtain zinc metaborate doped Zn 0.85 Ni 0.15 B 2 O 4 -1。
FIG. 3 is SEM images of the product of preparation example 1 at various magnification; as can be seen from FIG. 3, zn 0.85 Ni 0.15 B 2 O 4 The surface of-1 is smooth.
Preparation examples 2 to 9
The procedure of preparation 1 was followed, except that: the types, amounts and reaction conditions of the raw materials for preparing the doped zinc metaborate are shown in table 1.
TABLE 1
Preparation example 10
The procedure of preparation 1 was followed, except that: the zinc metaborate is directly prepared without doping the zinc metaborate, and the method is specifically as follows:
zinc oxide and oxidation at room temperatureMixing boron according to a molar ratio of 1:1, grinding and sieving with a 300-mesh sieve, tabletting, putting into a muffle furnace, heating to 950 ℃ at a speed of 1 ℃/min, preserving heat for 24 hours, naturally cooling, grinding fully, and sieving to obtain zinc metaborate ZnB 2 O 4 。
FIG. 1 shows XRD patterns of the products of preparation examples 1-3 and preparation example 10, and it can be seen from FIG. 1 that the XRD patterns of zinc metaborate with different nickel doping concentrations are all similar to those of ZnB 2 O 4 The patterns are consistent, which shows that the product prepared by the invention is doped zinc metaborate, and nickel atoms in the doped zinc metaborate replace part of zinc atoms.
Fig. 2 is an XRD pattern of the product of preparation 9, as can be seen from fig. 2: when Sb is used as doping element, a hetero peak appears in XRD spectrum, indicating that the product is Sb 2 O 3 And ZnB 2 O 4 Is not successfully doped with ZnB 2 O 4 That is, elements other than those of groups VIB, VIIB and VIII cannot be doped with ZnB 2 O 4 Is a kind of medium.
2. The following preparation examples are given as Zn 0.85 Ni 0.15 B 2 O 4 Description of the preparation of flame retardants by way of example
PREPARATION EXAMPLE 11
1) Drying sodium phytate at 100 ℃ for 4 hours for standby;
2) 80g of Zn 0.85 Ni 0.15 B 2 O 4 Uniformly stirring 1 and 5L of deionized water to obtain slurry, and pouring the slurry into a three-neck flask; pouring 20g of dried sodium phytate into a three-neck flask, and mechanically stirring at 40 ℃ for reaction for 2h (the rotating speed is controlled at 300 r/min); then carrying out suction filtration on the product, washing a filter cake obtained by suction filtration by deionized water, transferring to a glass dish, and drying for 2 hours at 100 ℃ to obtain the flame retardant Zn 0.85 Ni 0.15 B 2 O 4 -1-SP 1 The properties are shown in Table 2.
Preparation examples 12 to 15
According to the method of preparation example 1, except that Zn 0.85 Ni 0.15 B 2 O 4 The weight ratio of-1 to sodium phytate is shown in Table 2.
TABLE 2
As can be seen from Table 2, zn which was not surface-modified 0.85 Ni 0.15 B 2 O 4 -1 has an oil absorption value of 0.91, indicating a high polarity value; when Zn is 0.85 Ni 0.15 B 2 O 4 When the weight ratio of the-1 to the sodium phytate is 4:1, the obtained flame retardant Zn 0.85 Ni 0.15 B 2 O 4 -1-SP 1 The lowest oil absorption value, i.e. the lowest polarity.
PREPARATION EXAMPLES 16 to 19
Zn according to the method of preparation example 1 0.85 Ni 0.15 B 2 O 4 -1 to sodium fatty acid in a weight ratio of 4:1; the differences are: the species used with sodium fatty acid are shown in table 3.
TABLE 3 Table 3
Product(s) Fatty acid sodium salt Oil absorption value (%)
PREPARATION EXAMPLE 11 Zn 0.85 Ni 0.15 B 2 O 4 -1-SP 1 Sodium phytate 43
PREPARATION EXAMPLE 16 Zn 0.85 Ni 0.15 B 2 O 4 -1-SS Sodium stearate 56
Preparation example 17 Zn 0.85 Ni 0.15 B 2 O 4 -1-SAT Acetic acid sodium salt 71
PREPARATION EXAMPLE 18 Zn 0.85 Ni 0.15 B 2 O 4 -1-SL Lauric acid sodium salt 78
Preparation example 19 Zn 0.85 Ni 0.15 B 2 O 4 -1-SO Oleic acid sodium salt 63
FIG. 4 is an SEM image of the product of preparation example 11 at various magnifications, FIG. 5 is an SEM image of the product of preparation example 16, FIG. 6 is an SEM image of the product of preparation example 17 at various magnifications, FIG. 7 is an SEM image of the product of preparation example 18 at various magnifications, and FIG. 8 is an SEM image of the product of preparation example 19 at various magnifications.
As can be seen from FIGS. 4A and 4B, sodium phytate is present in Zn 0.85 Ni 0.15 B 2 O 4 -1 a uniform coating is formed on the surface of the substrate; FIG. 4D is a graph showing the distribution of EDS elements of the marked portion of FIG. 4C, and it can be seen from FIG. 4D that sodium elements are uniformly distributed in Zn 0.85 Ni 0.15 B 2 O 4 -1 surface, also demonstrating uniform distribution of sodium phytate over Zn 0.85 Ni 0.15 B 2 O 4 -1.
As can be seen by comparing fig. 4 with fig. 5-8: sodium phytate, sodium stearate, sodium acetate, sodium laurate and sodium oleate can form a coating layer on the surface doped with zinc metaborate; relative to Zn 0.85 Ni 0.15 B 2 O 4 -1-SP 1 When sodium fatty acid (sodium stearate, sodium acetate, sodium laurate and sodium oleate) is used for coating the doped zinc metaborate, the sodium fatty acid is agglomerated on the surface of the doped zinc metaborate, and the uniformity of a coating layer formed on the surface of the doped zinc metaborate is relatively poor, so that the modified flame retardant (Zn) is obtained 0.85 Ni 0.15 B 2 O 4 -1-SS、Zn 0.85 Ni 0.15 B 2 O 4 -1-SAT、Zn 0.85 Ni 0.15 B 2 O 4 -1-SL、Zn 0.85 Ni 0.15 B 2 O 4 -1-SO) is also higher than Zn 0.85 Ni 0.15 B 2 O 4 -1-SP 1 。
3. Preparation of flame-retardant resin
Examples 1 to 7 and comparative examples 1 to 2
1000 parts of a blend resin (750 parts of EVA, 180 parts of LLDPE and 70 parts of silicone rubber) were pre-banburying in a torque rheometer at a rotation speed of 50r/min and a temperature of 150 ℃ for 3min, then 80 parts of a compatibilizer (MAH-g-PE), 120 parts of naphthenic oil, 80 parts of magnesium oxide, 350 parts of a main flame retardant and 100 parts of magnesium hydroxide were added to carry out banburying for 15min, cooling to room temperature, and after repeating banburying for 5 times, a substrate obtained by banburying was pressed into a shape in a flat vulcanizing machine, and the types of the main flame retardants and the properties of the flame retardant resin are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 3, the doped zinc metaborate is capable of reducing the flame retardant resin without decreasing the flame retardant resin as compared with comparative example 2 (pure zinc metaborate)On the premise of mechanical property, the oxygen index of the flame-retardant resin is obviously improved; the flame retardant resin in example 1 (15 mol% nickel content) had an LOI of up to 33.7% and a carbon residue of up to 42.7%, indicating Zn 0.85 Ni 0.15 B 2 O 4 The flame retardant effect of-1 is best.
Examples 8 to 10 and comparative example 3
The procedure of example 1 was followed except that the types and amounts of the flame retardant and the synergistic flame retardant were as shown in Table 5, and the flame retardant properties and mechanical properties of the obtained flame retardant resin were as shown in Table 5.
Comparative example 4
The procedure of example 1 was followed, except that: znO, B is adopted 2 O 3 And NiO in place of Zn 0.85 Ni 0.15 B 2 O 4 -1; the composition of the flame retardant is as follows: 161 parts of ZnO, 26 parts of NiO and 163 parts of B 2 O 3 And 100 parts of Mg (OH) 2 Wherein ZnO, niO and B 2 O 3 The molar ratio of (2) to (3) was 0.85:0.15:1, and the flame retardant properties and mechanical properties of the obtained flame retardant resin are shown in Table 5.
TABLE 5
Examples 11 to 19
1000 parts of a blend resin (750 parts of EVA, 180 parts of LLDPE and 70 parts of silicone rubber) were pre-banburying in a torque rheometer at a rotation speed of 50r/min and a temperature of 150 ℃ for 3min, then 80 parts of a compatibilizer (MAH-g-PE), 120 parts of naphthenic oil, 80 parts of magnesium oxide, 350 parts of a main flame retardant and 100 parts of magnesium hydroxide were added to carry out banburying for 15min, cooling to room temperature, and after repeating banburying for 5 times, a substrate obtained by banburying was pressed into a shape in a flat vulcanizing machine, and the types of the main flame retardants and the properties of the flame retardant resin are shown in Table 6.
Comparative example 5
1000 parts of blend resin (750 parts of EVA, 180 parts of LLDPE and 70 parts of silicone rubber) were pre-banburying in a torque rheometer at a rotation speed of 50r/min and a temperature of 150 ℃ for 3min, then 80 parts of compatilizer (MAH-g-PE), 120 parts of naphthenic oil, 80 parts of magnesium hydroxide, 350 parts of doped main flame retardant (280 parts of doped zinc metaborate powder and 70 parts of sodium phytate powder) and 100 parts of magnesium hydroxide were added to carry out banburying for 15min, cooling to room temperature, and then banburying was repeated for 5 times, and then the substrate obtained by banburying was pressed into a shape in a flat vulcanizing machine, and the types of the main flame retardants and the properties of the flame retardant resin are shown in Table 6.
TABLE 6
As can be seen from Table 6, the elongation at break and the tensile strength of the flame-retardant resins prepared in examples 11 to 19 are significantly higher than those of the flame-retardant resin prepared in example 1, i.e., the zinc metaborate doped with the anionic surfactant is coated, so that the elongation at break and the tensile strength of the flame-retardant resin can be significantly improved; and filling Zn 0.85 Ni 0.15 B 2 O 4 Compared with the flame retardant resin of-1 (example 1), the Zn-filled resin composition of the present invention 0.85 Ni 0.15 B 2 O 4 -1-SP 1 The elongation at break of the flame retardant resin (example 11) was increased by 27.5%, and the tensile strength was increased by 45.8%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the present invention, a number of simple variants of the technical solution of the present invention are possible, including the combination of the various technical features in any other suitable way, for example, the coating of the doped zinc metaborate prepared in preparation examples 2-8 with an anionic surfactant; or coating the doped zinc metaborate by using sulfonate and sulfate; such simple variations and combinations are also considered to be within the scope of the present disclosure.

Claims (20)

1. A flame retardant, characterized in that: comprises doped zinc metaborate and an anionic surfactant coated on the surface of the doped zinc metaborate; wherein the chemical formula of the doped zinc metaborate is as follows: zn (zinc) 1-x M x B 2 O 4 X is more than or equal to 0.05 and less than or equal to 0.25; m is selected from at least one of Cr, mn, fe, co, ni, W and Mo.
2. The flame retardant of claim 1, wherein: the oil absorption value of the flame retardant is 0.3-0.8.
3. The flame retardant of claim 2, wherein: the oil absorption value of the flame retardant is 0.3-0.78.
4. The flame retardant of claim 1, wherein: the weight ratio of the doped zinc metaborate to the anionic surfactant is (0.5-10): 1.
5. The flame retardant of claim 1, wherein: x is more than or equal to 0.1 and less than or equal to 0.25.
6. The flame retardant of claim 1, wherein: the anionic surfactant is selected from at least one of phosphate, fatty acid, sulfonate and sulfate.
7. The flame retardant of claim 6, wherein: the phosphate salt is at least one selected from the group consisting of hexaalkyl phosphate salt, dodecyl phosphate salt, hexadecyl phosphate salt and octadecyl phosphate salt.
8. The flame retardant of claim 6, wherein: the fatty acid salt is selected from C 2 -C 18 At least one of the fatty acid salts of (a) and (b).
9. The flame retardant of claim 7, wherein: the phosphate is hexaalkyl phosphate.
10. The flame retardant of claim 8, wherein: the fatty acid salt is C 16 -C 18 At least one of the fatty acid salts of (a) and (b).
11. A method of preparing a flame retardant, the method comprising:
carrying out high-temperature solid phase reaction on a mixture obtained by mixing a zinc source, a boron source and a doping source to obtain doped zinc metaborate; then stirring the doped zinc metaborate and an anionic surfactant in the presence of a solvent; filtering and drying the mixture obtained by stirring to obtain the flame retardant;
wherein the chemical formula of the doped zinc metaborate is as follows: zn (zinc) 1-x M x B 2 O 4 X is more than or equal to 0.05 and less than or equal to 0.25; m is at least one selected from Cr, mn, fe, co, ni, W and Mo;
the zinc source is calculated by zinc element, the boron source is calculated by boron element, the doping source is calculated by metal element, and the mole ratio of the zinc source, the doping source and the boron source is (0.75-0.95): (0.05-0.25): 2.
12. The method according to claim 11, wherein: the weight ratio of the doped zinc metaborate to the anionic surfactant is (0.5-10): 1.
13. The method according to claim 11, wherein: the conditions of the high temperature solid phase reaction include: the temperature is 900-1050 ℃ and the time is 12-48 h.
14. The method according to claim 11, wherein: the stirring conditions include: the temperature is 25-80 ℃ and the time is 1-8h.
15. A flame retardant composite comprising a primary flame retardant and a synergistic flame retardant, characterized in that: the primary flame retardant is a flame retardant according to any one of claims 1 to 10 or a flame retardant prepared according to any one of claims 11 to 14.
16. The flame retardant composite of claim 15, wherein: the synergistic flame retardant is at least one selected from halogen flame retardants, phosphorus flame retardants, inorganic flame retardants, organic silicon flame retardants and nitrogen flame retardants.
17. The flame retardant composite of claim 15, wherein: the weight ratio of the main flame retardant to the synergistic flame retardant is (2-10): 1.
18. The flame retardant composite of claim 17, wherein: the weight ratio of the main flame retardant to the synergistic flame retardant is (3-5): 1.
19. A flame retardant resin, characterized in that: the flame retardant resin comprises 100 parts by weight of the polymeric resin, 5 to 80 parts by weight of the flame retardant composite according to any one of claims 15 to 18, and 0 to 70 parts by weight of the auxiliary agent, based on 100 parts by weight of the polymeric resin.
20. The flame retardant resin of claim 19, wherein: the auxiliary agent is at least one selected from fluxing agent, compatilizer and lubricant.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103937031A (en) * 2014-05-14 2014-07-23 山东川君化工股份有限公司 Modified zinc borate and preparation method thereof
CN107740179A (en) * 2017-09-28 2018-02-27 中国科学院理化技术研究所 Purposes of the Firebrake ZB crystal in laser crystal
CN111363267A (en) * 2020-03-16 2020-07-03 哈尔滨理工大学 Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030166757A1 (en) * 2001-06-22 2003-09-04 Hajime Nishihara Particulate coated flame-retardant for polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103937031A (en) * 2014-05-14 2014-07-23 山东川君化工股份有限公司 Modified zinc borate and preparation method thereof
CN107740179A (en) * 2017-09-28 2018-02-27 中国科学院理化技术研究所 Purposes of the Firebrake ZB crystal in laser crystal
CN111363267A (en) * 2020-03-16 2020-07-03 哈尔滨理工大学 Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material

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