CN113214542B - Composite antimony trioxide flame retardant and preparation method thereof - Google Patents
Composite antimony trioxide flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN113214542B CN113214542B CN202110538064.7A CN202110538064A CN113214542B CN 113214542 B CN113214542 B CN 113214542B CN 202110538064 A CN202110538064 A CN 202110538064A CN 113214542 B CN113214542 B CN 113214542B
- Authority
- CN
- China
- Prior art keywords
- antimony trioxide
- flame retardant
- parts
- stirring
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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)
Abstract
The invention discloses a composite antimony trioxide flame retardant, and relates to the technical field of flame retardants. The invention discloses a composite antimony trioxide flame retardant which is prepared from the following raw materials in parts by weight: 40-60 parts of surface modified antimony trioxide, 10-30 parts of silane modified halloysite nanotubes, 20-30 parts of amine phosphate, 2-3 parts of coupling agent and 3-5 parts of organic copper salt heat stabilizer; the phosphate amine salt is polymerized from pentaerythritol, phosphorus pentoxide and isobutyramide, wherein the mass ratio of the pentaerythritol to the phosphorus pentoxide to the isobutyramide is (1.5-2.5) 1: (1.8-3.6). The components of the composite antimony trioxide flame retardant provided by the invention have good compatibility, and have excellent interface bonding force with plastic materials, and the composite antimony trioxide flame retardant is uniformly dispersed, so that plastic products applied by the composite antimony trioxide flame retardant have excellent flame retardance and smoke suppression, and the mechanical properties of the plastic products are improved.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a composite antimony trioxide flame retardant and a preparation method thereof.
Background
Antimony trioxide (Sb)2O3) The white crystal powder is yellow when heated, is white or gray after being cooled, has the relative density of 5.22-5.67, is mainly applied to white pigments, paints and plastics, and can play a role in pigment and flame retardance.
Sb2O3As an efficient flame-retardant synergist, the flame-retardant synergist has been widely applied to high polymer materials such as plastics, rubber products and the like. When the Sb is applied to a polymer product, on the one hand, Sb is Sb because the surface polarities of the Sb and the polymer product are different2O3The powder is hydrophilic and oleophobic, the surface of the polymer matrix is oleophilic and hydrophobic, the difference between the two is large, which results in poor compatibility, the interaction between the interfaces is small, Sb2O3The direct addition of (2) can affect the processability and mechanical properties of the material; on the other hand, Sb2O3The powder particles have large surface tension, are easy to agglomerate, are not beneficial to dispersion in a polymer matrix, and have poor dispersibility and compatibility in plastics. If Sb2O3The mechanical property, optical property, flame retardant property and the like of the composite material can be influenced by uneven dispersion in the material. To improve Sb2O3The compatibility and the dispersibility of the powder in the organic polymer material can carry out surface organic modification on the powder, and the Sb after the surface modification2O3The powder reduces the surface tension, enhances the interaction of interfaces, is more uniformly dispersed in a high polymer matrix, improves the mechanical property of the product, and can also reduce Sb2O3The addition amount of the powder saves precious antimony resources, reduces production cost and improves the flame-retardant synergistic effect of riding products.
Sb2O3Generally, the halogen-containing flame retardant is used as a flame retardant to produce a good effect by synergistic action with other halogen-based flame retardants, but when the halogen-containing flame retardant is used, a great deal of smoke and toxic corrosive harmful gases are generated during combustion, and eighty percent of death accidents in fire are caused by suffocation of the smoke and the harmful gases. The invention of China patent CN201210143074.1 discloses a low-smoke antimony trioxide compound flame retardant and a preparation method thereof, the flame retardant is prepared by compounding antimony trioxide, hydrotalcite, zinc borate, montmorillonite and a coupling agent, and has good flame retardant and smoke suppression performances, but most of the components are hydrophilic and oleophobic and have poor compatibility with a polymer matrix, so that the mechanical properties of the polymer are general or reduced, and the use effect of a polymer product is influenced.
Disclosure of Invention
The invention aims to provide a composite antimony trioxide flame retardant and a preparation method thereof, wherein the flame retardant has good compatibility among components, excellent interface bonding force with plastic materials and uniform dispersion, so that plastic products applied by the flame retardant have excellent flame retardance and smoke suppression, and the mechanical properties of the plastic products are improved.
In order to realize the purpose of the invention, the invention provides a composite antimony trioxide flame retardant which is prepared from the following raw materials in parts by weight: 40-60 parts of surface modified antimony trioxide, 10-30 parts of silane modified halloysite nanotubes, 20-30 parts of amine phosphate, 2-3 parts of coupling agent and 3-5 parts of organic copper salt heat stabilizer.
The phosphate amine salt is polymerized from pentaerythritol, phosphorus pentoxide and isobutyramide, wherein the mass ratio of the pentaerythritol to the phosphorus pentoxide to the isobutyramide is (1.5-2.5) 1: (1.8-3.6).
Further, the preparation method of the surface modified antimony trioxide comprises the following steps: adding 25% antimony trioxide slurry into lauryl alcohol ether phosphate, stirring for 1-2h at 70-80 ℃, filtering, drying and grinding to obtain surface modified antimony trioxide, wherein the mass ratio of the antimony trioxide slurry to the lauryl alcohol ether phosphate is 1: (0.1-0.25).
Further, the preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding the alkalified halloysite nanotube into polyethylene glycol, uniformly stirring, adding vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Further, the mass ratio of the alkalized halloysite nanotube to the polyethylene glycol is 1: (1.5-2.4), wherein the mass ratio of the alkalized halloysite nanotube to vinyl trimethoxy silane is 1: (0.05-0.1).
Further, the preparation method of the phosphate amine salt comprises the following steps: adding pentaerythritol into a proper amount of ethanol, uniformly mixing, then adding phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
Further, the coupling agent is one of a titanate coupling agent or an aluminate coupling agent.
The preparation method of the composite antimony trioxide flame retardant comprises the following specific steps: adding surface modified antimony trioxide into a proper amount of ethanol, uniformly mixing, adding ammonium phosphate, heating to 50-60 ℃, stirring for 30min, adding a coupling agent and an organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding a silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The composite antimony trioxide flame retardant prepared by the invention can be applied to plastic and rubber products, such as polyethylene, polypropylene, EVA, PS, styrene butadiene rubber, nitrile butadiene rubber, PVC and other plastic and rubber materials.
The invention achieves the following beneficial effects:
1. the antimony trioxide of the invention adopts lauryl alcohol ether phosphate for surface modification, the surface modification does not change the crystal structure of the antimony trioxide, but the surface of the antimony trioxide and the lauryl alcohol ether phosphate generate chemical combination, so that the surface modified antimony trioxide has lipophilicity, the antimony trioxide is uniformly dispersed when the flame retardant of the invention is prepared, and can generate chemical combination with the surfaces of other components of the flame retardant, thereby improving the flame retardant effect of the flame retardant, improving the compatibility with plastic resin, and further improving the mechanical property and the flame retardance of plastic products; the surface of the antimony trioxide is modified, so that the use amount of the antimony trioxide is relatively reduced, and the cost is reduced.
2. The halloysite nanotube is of a hollow tubular structure, has mesopores and macropores, and has excellent adsorption performance, the halloysite nanotube is modified by vinyl trimethoxy silane, so that the surface of the halloysite nanotube is combined with Si-O-Si bonds, most of aluminum hydroxyl groups of the halloysite nanotube are positioned in the inner cavity of the halloysite nanotube, and the outside of the halloysite nanotube is mainly siloxane and a small amount of silicon hydroxyl groups and aluminum hydroxyl groups exposed at the edge of the halloysite nanotube, so that the compatibility between the halloysite nanotube and other components of a flame retardant is improved, and the heat resistance, the weather resistance and the smoke suppression of the flame retardant are also improved, thereby the flame retardance and the weather resistance of the halloysite nanotube are improved when the halloysite nanotube is applied to plastic products; the silane-modified halloysite nanotubes have a high aspect ratio, which in combination with the polymer, allows external pressure to be transferred from the polymer to the nanotubes, thereby enhancing the mechanical strength and toughness of the plastic article.
3. The phosphate amine salt is a novel intumescent flame retardant polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, has excellent flame retardant properties such as oxygen isolation, heat insulation and smoke suppression, has excellent oil solubility, can have good compatibility with antimony trioxide and silane modified halloysite nanotubes after surface modification, and has excellent flame retardant synergy with other components in the flame retardant, thereby improving the mechanical strength and toughness of plastic products, improving the flame retardance of the plastic products and having good smoke suppression effect.
4. The organic copper salt heat stabilizer improves the processing and using temperature of the composite antimony trioxide flame retardant, simultaneously improves the processing and using temperature of a plastic product, avoids yellowing and brittleness and reduction of mechanical properties caused by thermal oxidative degradation in the processing process, and also improves the flame retardant temperature of the plastic product; in addition, the organic copper salt heat stabilizer contains a small amount of copper element, and can be compounded with antimony trioxide for use, so that the further smoke suppression effect is achieved, the carbon residue rate of the plastic product during combustion is increased, and the smoke generation amount is further reduced.
5. The surface-modified antimony trioxide, the silane-modified halloysite nanotubes and the amine phosphate are adopted to prepare the composite antimony trioxide flame retardant under the action of the coupling agent and the heat stabilizer, so that the compatibility among the components is increased, the self-owned flame retardant and smoke suppression effects of the components are maintained, the components are mutually synergistic, the flame retardant has better flame retardant performance, the antimony trioxide can achieve good flame retardant and smoke suppression effects under the condition that halogen is not added, the raw materials are environment-friendly, harmful gas is not generated in the combustion process, the flame retardant is an environment-friendly composite flame retardant, and the environment-friendly concept is met.
6. The invention has less usage amount in plastic products, only 1-7wt%, can achieve excellent flame-retardant and smoke-suppression effects, reduces the usage amount of antimony trioxide, reduces the cost and saves resources.
7. The composite antimony trioxide flame retardant improves the hydrophilicity of each component, has excellent lipophilicity, has excellent compatibility with plastic or rubber raw materials and additives, has excellent interface bonding force with plastic materials, can be uniformly dispersed in the plastic materials, obviously improves the flame retardance and smoke suppression effect of plastic products, and improves the mechanical property and toughness of the plastic products.
Detailed Description
The technical solutions in the embodiments of the present invention are 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 organic copper salt heat stabilizer used in the invention is an organic copper salt heat stabilizer which is produced by NOFA and has a model number of Finner-336.
The composite antimony trioxide flame retardant and the preparation method thereof according to the present invention will be described with reference to the following specific examples.
Example 1
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 40 parts of surface modified antimony trioxide into 60 parts of ethanol, uniformly mixing, then adding 30 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, then adding 2 parts of titanate coupling agent and 5 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 30 parts of silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The phosphate amine salt is polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, and the preparation method comprises the following steps: adding 150g of pentaerythritol into 100g of ethanol, uniformly mixing, then adding 100g of phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding 180g of isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
The preparation method of the surface modified antimony trioxide comprises the following steps: adding 1kg of antimony trioxide slurry with the mass concentration of 25% into 100g of lauryl alcohol ether phosphate, stirring for 2 hours at 70 ℃, then filtering, drying and grinding to obtain the surface modified antimony trioxide.
The preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding 1kg of the alkalified halloysite nanotube into 1.5kg of polyethylene glycol, uniformly stirring, adding 100g of vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Example 2
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 60 parts of surface modified antimony trioxide into 120 parts of ethanol, uniformly mixing, adding 30 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 3 parts of aluminate coupling agent and 3 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 10 parts of silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The phosphate amine salt is polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, and the preparation method comprises the following steps: adding 250g of pentaerythritol into 180g of ethanol, uniformly mixing, then adding 100g of phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding 360g of isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
The preparation method of the surface modified antimony trioxide comprises the following steps: adding 1kg of antimony trioxide slurry with the mass concentration of 25% into 250g of lauryl alcohol ether phosphate, stirring for 1h at 80 ℃, then filtering, drying and grinding to obtain the surface modified antimony trioxide.
The preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; then adding 1kg of alkalified halloysite nanotube into 2.4kg of polyethylene glycol, uniformly stirring, adding 50g of vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Example 3
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 50 parts of surface modified antimony trioxide into 80 parts of ethanol, uniformly mixing, adding 30 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 2.4 parts of aluminate coupling agent and 3.5 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 20 parts of silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The phosphate amine salt is polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, and the preparation method comprises the following steps: adding 220g of pentaerythritol into 190g of ethanol, uniformly mixing, then adding 100g of phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding 280g of isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
The preparation method of the surface modified antimony trioxide comprises the following steps: adding 1kg of antimony trioxide slurry with the mass concentration of 25% into 170g of lauryl alcohol ether phosphate, stirring for 2 hours at 80 ℃, and then filtering, drying and grinding to obtain the surface modified antimony trioxide.
The preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding 1kg of the alkalified halloysite nanotube into 1.6kg of polyethylene glycol, uniformly stirring, adding 80g of vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Example 4
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 60 parts of surface modified antimony trioxide into 90 parts of ethanol, uniformly mixing, adding 20 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 2.2 parts of aluminate coupling agent and 4.3 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 20 parts of silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The phosphate amine salt is polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, and the preparation method comprises the following steps: adding 200g of pentaerythritol into 150g of ethanol, uniformly mixing, then adding 100g of phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding 240g of isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
The preparation method of the surface modified antimony trioxide comprises the following steps: adding 1kg of antimony trioxide slurry with the mass concentration of 25% into 200g of lauryl alcohol ether phosphate, stirring for 2 hours at 80 ℃, then filtering, drying and grinding to obtain the surface modified antimony trioxide.
The preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding 1kg of the alkalified halloysite nanotube into 2.1kg of polyethylene glycol, uniformly stirring, adding 75g of vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Example 5
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 57 parts of surface modified antimony trioxide into 65 parts of ethanol, uniformly mixing, adding 25 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 2.5 parts of titanate coupling agent and 4 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 18 parts of silane modified halloysite nanotubes, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The phosphate amine salt is polymerized by pentaerythritol, phosphorus pentoxide and isobutyramide, and the preparation method comprises the following steps: adding 235g of pentaerythritol into 200g of ethanol, uniformly mixing, then adding 100g of phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding 320g of isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
The preparation method of the surface modified antimony trioxide comprises the following steps: adding 1kg of antimony trioxide slurry with the mass concentration of 25% into 225g of lauryl alcohol ether phosphate, stirring for 2h at 80 ℃, then filtering, drying and grinding to obtain the surface modified antimony trioxide.
The preparation method of the silane modified halloysite nanotube comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding 1kg of the alkalified halloysite nanotube into 1.9kg of polyethylene glycol, uniformly stirring, adding 82g of vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
Comparative example 1
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 57 parts of antimony trioxide into 65 parts of ethanol, uniformly mixing, adding 25 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 2.5 parts of titanate coupling agent and 4 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 18 parts of silane modified halloysite nanotubes, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The preparation method and components of the amine phosphate salt and silane-modified halloysite nanotubes in comparative example 1 are the same as those in example 5, and reference is made to example 5.
Comparative example 2
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 57 parts of surface modified antimony trioxide into 65 parts of ethanol, uniformly mixing, heating to 50-60 ℃, stirring for 30min, then adding 2.5 parts of titanate coupling agent and 4 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 18 parts of silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The preparation method and components of the surface-modified antimony trioxide and silane-modified halloysite nanotubes in comparative example 2 are the same as those in example 5, and reference is made to example 5.
Comparative example 3
The preparation method of the composite antimony trioxide flame retardant comprises the following steps: adding 57 parts of surface-modified antimony trioxide into 65 parts of ethanol, uniformly mixing, adding 25 parts of amine phosphate, heating to 50-60 ℃, stirring for 30min, adding 2.5 parts of titanate coupling agent and 4 parts of organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding 18 parts of halloysite nanotubes, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
The preparation method and the components of the surface-modified antimony trioxide and the amine phosphate salt in the comparative example 3 are the same as those in the example 5, and the specific reference is made to the example 5.
Application example 1
The composite antimony trioxide flame retardant prepared in the above examples 4 and 5 and comparative examples 1 to 3 was applied to polypropylene, and the performance, formulation composition and performance test results of the materials were tested according to the national standards as follows.
TABLE 1 PP recipe composition and Performance test results
Application example 2
The composite antimony trioxide flame retardant prepared in the above examples 4 and 5 and comparative examples 1 to 3 was applied to polyvinyl chloride, and the properties, formulation compositions and performance test results of the materials were tested according to the national standards as follows.
Application example 3
The composite antimony trioxide flame retardant prepared in the above examples 4 and 5 and comparative examples 1 to 3 was applied to ethylene propylene rubber, and the performance, formulation composition and performance test results of the materials were tested according to the national standards as follows.
From the performance monitoring results of the application examples, the composite antimony trioxide flame retardant has excellent flame-retardant and smoke-suppression performance when added into PP, PVC and ethylene propylene rubber, and improves the mechanical property and toughness of plastic products to a certain extent. The addition of the amine phosphate salt obviously improves the flame-retardant and smoke-suppressing performance of the flame retardant and improves the mechanical property and toughness of the plastic product; after the antimony trioxide and the halloysite nanotubes are subjected to surface modification, the bonding force among the components is improved, the flame retardant and smoke suppression performance of the flame retardant is improved, and the mechanical property and the toughness of a plastic product are improved.
It should be noted that the composite antimony trioxide flame retardant prepared by the invention can be applied to plastics and rubber materials such as polyethylene, EVA, PS, styrene butadiene rubber, nitrile butadiene rubber and the like besides PP, PVC and ethylene propylene rubber, and is not limited to the above-mentioned plastics and rubber materials.
All possible combinations of the technical features of the embodiments described above may not be described for the sake of brevity, but should be considered as being within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. The composite antimony trioxide flame retardant is characterized by comprising the following raw materials in parts by weight: 40-60 parts of surface modified antimony trioxide, 10-30 parts of silane modified halloysite nanotubes, 20-30 parts of amine phosphate, 2-3 parts of coupling agent and 3-5 parts of organic copper salt heat stabilizer;
the phosphate amine salt is polymerized from pentaerythritol, phosphorus pentoxide and isobutyramide, wherein the mass ratio of the pentaerythritol to the phosphorus pentoxide to the isobutyramide is (1.5-2.5) 1: (1.8-3.6).
2. The composite antimony trioxide flame retardant of claim 1, wherein the surface-modified antimony trioxide is prepared by the following method: adding 25% antimony trioxide slurry into lauryl alcohol ether phosphate, stirring for 1-2h at 70-80 ℃, filtering, drying and grinding to obtain surface modified antimony trioxide, wherein the mass ratio of the antimony trioxide slurry to the lauryl alcohol ether phosphate is 1: (0.1-0.25).
3. The composite antimony trioxide flame retardant of claim 1, wherein the preparation method of the silane-modified halloysite nanotubes comprises the following steps: adding the halloysite nanotube into a 30wt% NaOH solution, ultrasonically stirring for 30min, stirring for 30-60min at 40-50 ℃, filtering, washing with deionized water, drying, and grinding into powder to obtain an alkalized halloysite nanotube; and then adding the alkalified halloysite nanotube into polyethylene glycol, uniformly stirring, adding vinyltrimethoxysilane, and stirring and reacting at 80-100 ℃ for 2-3h to obtain the silane modified halloysite nanotube.
4. The composite antimony trioxide flame retardant according to claim 3, wherein the mass ratio of the alkalized halloysite nanotube to the polyethylene glycol is 1: (1.5-2.4), wherein the mass ratio of the alkalized halloysite nanotube to vinyl trimethoxy silane is 1: (0.05-0.1).
5. The composite antimony trioxide flame retardant of claim 1, wherein the preparation method of the phosphate amine salt comprises the following steps: adding pentaerythritol into a proper amount of ethanol, uniformly mixing, then adding phosphorus pentoxide, stirring for 30min at 50 ℃, distilling under reduced pressure at normal temperature to remove ethanol, then adding isobutyramide at normal temperature, heating to 70 ℃, and reacting for 1-2h to obtain the phosphate amine salt.
6. The composite antimony trioxide flame retardant according to claim 1, characterized in that the coupling agent is one of titanate coupling agent or aluminate coupling agent.
7. The preparation method of the composite antimony trioxide flame retardant according to any one of claims 1 to 6, characterized by comprising the following specific steps: adding surface modified antimony trioxide into a proper amount of ethanol, uniformly mixing, adding ammonium phosphate, heating to 50-60 ℃, stirring for 30min, adding a coupling agent and an organic copper salt heat stabilizer, heating to 90-100 ℃, stirring for 1h, cooling to 60 ℃, adding a silane modified halloysite nanotube, stirring for 30min, cooling to normal temperature, and grinding to obtain the composite antimony trioxide flame retardant.
8. The use of the antimony trioxide compounded flame retardant prepared by the preparation method according to claim 7 as a flame retardant component in plastic products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110538064.7A CN113214542B (en) | 2021-05-18 | 2021-05-18 | Composite antimony trioxide flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110538064.7A CN113214542B (en) | 2021-05-18 | 2021-05-18 | Composite antimony trioxide flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113214542A CN113214542A (en) | 2021-08-06 |
| CN113214542B true CN113214542B (en) | 2022-05-20 |
Family
ID=77093030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110538064.7A Active CN113214542B (en) | 2021-05-18 | 2021-05-18 | Composite antimony trioxide flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113214542B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120676A (en) * | 2023-01-03 | 2023-05-16 | 连云港传奇阻燃科技有限公司 | Flame-retardant modified material for polystyrene insulation board and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
| CN104667474A (en) * | 2015-03-31 | 2015-06-03 | 朴美兰 | Environment-friendly efficient anti-explosion anti-flaming multifunctional water-based fire extinguishing agent |
| CN105754327A (en) * | 2016-03-04 | 2016-07-13 | 广西华锑科技有限公司 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
| CN110452528A (en) * | 2019-07-15 | 2019-11-15 | 山东省科学院能源研究所 | Microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method |
| CN112538146A (en) * | 2020-12-03 | 2021-03-23 | 广东金柏新材料科技股份有限公司 | Flame-retardant thermoplastic polyurethane material and preparation method thereof |
-
2021
- 2021-05-18 CN CN202110538064.7A patent/CN113214542B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
| CN104667474A (en) * | 2015-03-31 | 2015-06-03 | 朴美兰 | Environment-friendly efficient anti-explosion anti-flaming multifunctional water-based fire extinguishing agent |
| CN105754327A (en) * | 2016-03-04 | 2016-07-13 | 广西华锑科技有限公司 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
| CN110452528A (en) * | 2019-07-15 | 2019-11-15 | 山东省科学院能源研究所 | Microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method |
| CN112538146A (en) * | 2020-12-03 | 2021-03-23 | 广东金柏新材料科技股份有限公司 | Flame-retardant thermoplastic polyurethane material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113214542A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106957454B (en) | A kind of nano material coated fire retardant and preparation method thereof | |
| CN108410066B (en) | SiO (silicon dioxide)2Preparation method of nano particle modified expandable graphite and flame-retardant polypropylene | |
| KR102180931B1 (en) | Graphene oxide filler with aminated flame retardant, and polypropylene nanocomposite using the same | |
| CN113214542B (en) | Composite antimony trioxide flame retardant and preparation method thereof | |
| CN112250985B (en) | Halogen-free flame-retardant ABS composition and preparation method and application thereof | |
| CN101235175B (en) | Preparation method of anti-flaming polypropylene composite material | |
| CN105367915A (en) | Anti-aging high-flame-retardant ethylene propylene diene monomer rubber pipe | |
| CN110903513A (en) | Silicon dioxide core-shell antibacterial flame retardant and preparation method thereof | |
| CN111073174B (en) | Odorless antistatic PVC composite material and preparation method thereof | |
| CN108623844A (en) | DOPO-LDH composite fire retardants and preparation method thereof and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and its application | |
| CN111363318B (en) | Flame-retardant smoke-suppressing PTT polyester composite material and preparation method therefor | |
| CN112898231A (en) | Preparation method and application of metal ion modified polyphosphoric acid piperazine | |
| CN112094502A (en) | High-temperature-resistant mixed silicone rubber and preparation method thereof | |
| CN107011581A (en) | A kind of anti-static halogen-free flame-retardant polypropylene plastics and preparation method thereof | |
| CN108250573B (en) | Thermo-oxidative aging resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN107987316A (en) | A kind of anti-flaming smoke-inhibiting agent, its preparation method and PVC flame-retardant smoke inhibitions material prepared therefrom | |
| CN104629158A (en) | Modified mining cable sheathing material | |
| CN110483941B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof | |
| CN113789042B (en) | Flame-retardant environment-friendly PC-ABS composite plastic master batch and preparation method thereof | |
| CN113234324A (en) | Flame-retardant ceramizable organic silicon material and preparation method thereof | |
| CN112063181A (en) | Mixing silicone rubber and preparation method thereof | |
| CN107652520B (en) | Flame-retardant polyethylene product and preparation method thereof | |
| CN114213712B (en) | Flame retardant, preparation method and application thereof | |
| CN117777615B (en) | High-temperature-resistant flame-retardant PVC material and preparation method thereof | |
| CN116875021B (en) | PC/ABS alloy material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A composite antimony trioxide flame retardant and its preparation method Effective date of registration: 20230320 Granted publication date: 20220520 Pledgee: Xinhua branch of the China Co truction Bank Corp. Pledgor: HUNAN LOUDI HUAXING ANTIMONY INDUSTRY Co.,Ltd. Registration number: Y2023980035276 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |