CN113999448A - Halogen-free flame-retardant ethylene composition and application thereof in simulated plants - Google Patents
Halogen-free flame-retardant ethylene composition and application thereof in simulated plants Download PDFInfo
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- CN113999448A CN113999448A CN202111347574.2A CN202111347574A CN113999448A CN 113999448 A CN113999448 A CN 113999448A CN 202111347574 A CN202111347574 A CN 202111347574A CN 113999448 A CN113999448 A CN 113999448A
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- 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
- C08L23/06—Polyethene
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
- A41G1/00—Artificial flowers, fruit, leaves, or trees; Garlands
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- 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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- 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
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Abstract
The invention discloses a halogen-free flame-retardant ethylene composition and application thereof in simulated plants, wherein the composition comprises an intumescent halogen-free flame retardant and a softening agent, wherein the intumescent halogen-free flame retardant consists of a polyethylene carrier, a phosphorus flame retardant, a char forming agent, an anti-dripping agent and a dispersing agent. When the halogen-free flame-retardant ethylene composition is used for simulated plants, the obtained simulated plants can not release a large amount of toxic gas and black smoke in the combustion process, the combustion rate is low, and strong carcinogenic substances can not be generated.
Description
Technical Field
The invention relates to the technical field of simulated plants, in particular to a halogen-free flame-retardant ethylene composition and application thereof in simulated plants.
Background
In modern times, the simulated plant industry has been rapidly developed, and the simulated plants have become common articles in people's lives. The simulation plants mainly decorate the lives of people, create the atmosphere with the wind and light of a garden, and bring the feeling of returning to the nature to people. Particularly, in public environments, such as the leisure consumption fields of hotel decoration, playgrounds, bars and the like, the decoration of the simulation plants gives people a natural experience feeling.
The material of the simulation plant is a polyolefin material, the oxygen index of the polyolefin material is less than 22, the simulation plant belongs to a combustible substance, once a fire accident occurs, the simulation plant can aggravate the spread of fire, and therefore, a flame-retardant simulation plant needs to be developed to meet the requirement of indoor decoration.
The conventional flame retardant mainly comprises a brominated flame retardant, the brominated flame retardant has stable flame retardant performance and good compatibility with polymers, and plays an important role in the application market of organic flame retardants, but the brominated flame retardant is seriously dependent on brominated resources, so that the brominated resources are in short supply in recent years, and a large amount of black smoke is generated in the combustion process of a flame-retardant product during the application process of the brominated flame retardant, so that people can be influenced to escape in case of fire.
The halogen-free flame retardant intumescent flame retardant system generally comprises an acid source (dehydrating agent), a carbon source (charring agent) and a gas source (foaming agent), wherein when the material is heated, inorganic acid is released by the acid source, the inorganic acid and the carbon source generate esterification reaction, the carbon source dehydrates to form char, the gas source can generate non-combustible gas, the gas is filled into the carbon layer to expand and foam the carbon layer in a molten state, and when the reaction is nearly completed, the system is solidified to form a porous foam layer; the cracking of the acid source may also generate some free radicals, which act as gas phase quenching, promoting incomplete combustion of the cracked material, further reducing combustion intensity. The intumescent flame retardant is receiving more and more attention due to the advantages of high efficiency, low smoke, low toxicity, small addition amount, no molten drop and the like, and has larger development potential and space.
Disclosure of Invention
In view of the above, the present invention aims to provide a halogen-free flame retardant ethylene composition and its application in simulation plants. The obtained simulated plant does not release a large amount of toxic gas and black smoke in the dyeing process, has low combustion rate and does not generate strong carcinogenic substances.
In order to achieve the purpose, the invention adopts the following technical scheme:
the halogen-free flame retardant ethylene composition comprises the following components in percentage by mass: 20-35% of intumescent halogen-free flame retardant and 1-15% of softening agent.
In the technical scheme, the added softening agent can improve the toughness of the simulated plant, increase the impact strength of the material and improve the fracture problem caused by the action of external force in the transportation process.
Preferably, the halogen-free flame retardant ethylene composition further comprises the following components in percentage by mass: 45-60% of polyethylene, 2% of anti-ultraviolet agent and 8% of color master batch.
Preferably, the intumescent halogen-free flame retardant comprises the following components in percentage by mass: 18-49.4% of polyethylene carrier, 40-60% of phosphorus flame retardant, 10-20% of char forming agent, 0.3-1% of anti-dripping agent and 0.3-1% of dispersing agent.
Preferably, the softener comprises one or more of ethylene-octene copolymer (POE), ethylene-hexene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EAA) or ethylene-methyl methacrylate copolymer (EMA).
Preferably, the phosphorus-based flame retardant comprises ammonium polyphosphate (APP), Melamine Phosphate (MP), melamine polyphosphate (MPP), Melamine Cyanurate (MCA), bisphenol A bis (diphenyl) phosphate, triphenyl phosphate, caged bicyclic phosphate, phosphaphenanthrene compounds, diethylphosphinate, Melamine (ME), dicyandiamide cyanurate (DICY-CA), melamine polyphosphate, 4- (5, 5-dimethyl-2-oxo-1, 3, 2-dioxaphosphane-2-oxomethyl) -2,6, 7-trioxo-1-phosphido-bicyclo- [2,2,2] -octane-1-oxide (MOPO), melamine coated ammonium polyphosphate (MCAPP), tris (1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2,2,2] octane-4-methylene) phosphate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane (PEPA).
The preferable beneficial effects are that the phosphorus flame retardant plays a role of an acid source in an expansion system, all the substances can be heated and decomposed to generate acid, the function is that the phosphorus flame retardant and the carbon forming agent are subjected to esterification reaction, and in the esterification reaction process, the esterification product is dehydrated to form carbon, and the system starts to melt; the carbon layer is filled with gases such as water vapor and amine gas generated by esterification reaction and non-combustible gas generated by a gas source, so that the purpose of flame retardance is achieved.
Preferably, the char-forming agent comprises one or more of Pentaerythritol (PER), Dipentaerythritol (DPER), erythritol, starch, hydroxyl-containing organic resins, piperazine pyrophosphate (PAPP), and triazine derivatives.
The above preferable advantageous effects are that these substances are substances which are carbonized by being deprived of moisture by the dehydrating agent and function to provide the main base material for forming the foamy carbon layer.
Further preferably, the char-forming agent comprises one or more of Pentaerythritol (PER), piperazine pyrophosphate (PAPP) and triazine derivatives.
More preferably, the char-forming agent comprises piperazine pyrophosphate (PAPP) and triazine derivatives.
Furthermore, the triazine derivative is one of 1,3, 5-triazine, PT, CNCD-DA, CNCA-DA, PTCA, PETAT and EA, and has the beneficial effects that the triazine ring is a six-membered heterocyclic compound containing 3 nitrogen atoms, the ring structure has excellent chemical stability and thermal stability, and the triazine ring and the high-nitrogen structure have good carbon forming effect; the piperazine pyrophosphate has the advantages of high phosphorus content, good char forming performance and the like, and can inhibit the continuous combustion of materials in a gas phase and a condensed phase simultaneously.
Preferably, the anti-dripping agent is polytetrafluoroethylene dripping agent.
Preferably, the dispersant comprises one or a mixture of EBS and polyethylene wax.
The invention also aims to provide the application of the halogen-free flame retardant ethylene composition to simulated plants.
Preferably, the simulated plant consists of simulated plant leaves and a fixed plate, the simulated plant leaves are fixed on the fixed plate, wherein the simulated plant leaves and the fixed plate are obtained by injection molding of the halogen-free flame retardant ethylene composition.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects: according to the invention, the intumescent halogen-free flame retardant is added in the formula of the simulated plant leaves and the fixing plate, so that the flame retardant effect is achieved, the flame retardant problem of the simulated plants in the indoor use process is solved, and meanwhile, the mechanical properties of the simulated plants are basically kept not to be reduced; meanwhile, in the aspect of combustion, the simulated plant has low smoke quantity compared with a brominated flame retardant, and white smoke (black smoke and poor visibility in the combustion process of the brominated flame retardant system simulated plant) is generated in the combustion process, so that the simulated plant is high in visibility and more beneficial to escape.
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.
Example 1
Preparing a flame-retardant simulation plant: mixing polyethylene: 50 parts of ethylene-octene copolymer (POE): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: 25 parts of polyethylene carrier, 50 parts of ammonium polyphosphate (APP), 50 parts of triazine charring agent CNCD-DA15 parts, 5 parts of EBS dispersant and 5 parts of anti-dripping agent, mixing the powder in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, and granulating the mixed powder by using a double screw, wherein the temperature of the screw is set to 180 ℃.
The preparation method of the simulated plant comprises the following steps: the halogen-free flame retardant raw materials in the formula are granulated by a double screw for later use, and the uniformly mixed flame-retardant simulation plant mixture is subjected to injection molding by an injection molding machine to produce plant leaves and a fixing plate. The preparation method of the simulated plants in the following examples is the same.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 2
Preparing a flame-retardant simulation plant: mixing polyethylene: 50 parts of ethylene-octene copolymer (POE): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 15 parts of polyethylene carrier, 50 parts of ammonium polyphosphate (APP), 25 parts of Pentaerythritol (PER), 5 parts of Melamine (MEL), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, granulating the mixed powder by using a double screw, and setting the screw temperature to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 3
Preparing a flame-retardant simulation plant: mixing polyethylene: 50 parts of ethylene-octene copolymer (POE): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 45 parts of Melamine Phosphate (MP), 15 parts of pentaerythritol, 10 parts of melamine, 5 parts of EBS dispersant and 5 parts of anti-dripping agent powder in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, and granulating the mixed powder by using a double screw, wherein the temperature of the screw is set to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 4
Preparing a flame-retardant simulation plant: mixing polyethylene: 44.7 parts of ethylene-octene copolymer (POE): 10 parts of anti-ultraviolet agent, 0.3 part of color master batch: and (3) mixing 15 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant uniformly, and performing injection molding by using an injection molding machine, wherein the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: 20 parts of polyethylene carrier, 50 parts of 4- (5, 5-dimethyl-2-oxo-1, 3, 2-dioxaphosphane-2-oxomethyl) -2,6, 7-trioxo-1-phospha-bicyclo- [2,2,2] -octane-1-oxide (MOPO), 20 parts of triazine charring agent (CFA), 5 parts of EBS dispersant and 5 parts of anti-dripping agent are mixed in a high-speed mixer for 10min, the rotating speed of the mixer is 1500r/min, the mixed powder is granulated by a double screw, and the screw temperature is set to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 5
Preparing a flame-retardant simulation plant: mixing polyethylene: 47 parts of ethylene-octene copolymer (POE): 10 parts, 5 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 25 parts of melamine-coated ammonium polyphosphate (MCAP), 40 parts of ammonium polyphosphate (APP), 5 parts of triazine charring agent (CFA), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, granulating the mixed powder by using a double screw, and setting the temperature of the screw to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 6
Preparing a flame-retardant simulation plant: mixing polyethylene: 50 parts of ethylene-octene copolymer (POE): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 40 parts of ammonium polyphosphate (APP), 10 parts of triazine charring agent (CFA), 20 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, granulating the mixed powder by a double screw, and setting the screw temperature to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 7
Preparing a flame-retardant simulation plant: mixing polyethylene: 61 parts of ethylene-octene copolymer (POE): 5 parts of anti-ultraviolet agent, 2 parts of color master batch: 2 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 20 parts of melamine polyphosphate (MPP), 50 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, granulating the mixed powder by using a double screw, and setting the screw temperature to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 8
Preparing a flame-retardant simulation plant: mixing polyethylene: 50 parts of ethylene-vinyl acetate copolymer (EVA): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 20 parts of Melamine Cyanurate (MCA), 50 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, and granulating the mixed powder by using a double screw, wherein the temperature of the screw is set to 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 9
Preparing a flame-retardant simulation plant: mixing polyethylene: 45 parts of ethylene-vinyl acetate copolymer (EVA): 15 parts of anti-ultraviolet agent, 2 parts of color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 15 parts of polyethylene carrier, 25 parts of dicyandiamide cyanurate (DICY-CA), 50 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent powder in a high-speed mixer at the rotating speed of 1500r/min for 10min, and granulating the mixed powder by using a double screw, wherein the screw temperature is set to 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 10
Preparing a flame-retardant simulation plant: mixing polyethylene: 45 parts of ethylene-vinyl acetate copolymer (EVA): 10 parts, 2 parts of an anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 35 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 15 parts of polyethylene carrier, 25 parts of dicyandiamide cyanurate (DICY-CA), 50 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent powder in a high-speed mixer at the rotating speed of 1500r/min for 10min, and granulating the mixed powder by using a double screw, wherein the screw temperature is set to 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 11
Preparing a flame-retardant simulation plant: mixing polyethylene: 55 parts of ethylene-ethyl acrylate copolymer (EAA): 5 parts of ethylene-vinyl acetate copolymer (EVA): 5 parts of anti-ultraviolet agent, 2 parts of color master batch: 8 parts of the intumescent halogen-free flame retardant and 25 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 20 parts of Melamine Cyanurate (MCA), 50 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, and granulating the mixed powder by using a double screw, wherein the temperature of the screw is set to 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 12
Preparing a flame-retardant simulation plant: mixing polyethylene: 60 parts of ethylene-ethyl acrylate copolymer (EAA): 5 parts of anti-ultraviolet agent, 2 parts of color master batch: 8 parts of the intumescent halogen-free flame retardant and 25 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: 10 parts of polyethylene carrier, 20 parts of Melamine Cyanurate (MCA), 60 parts of piperazine pyrophosphate (PAPP), 5 parts of EBS dispersant and 5 parts of anti-dripping agent are mixed in a high-speed mixer for 10min, the rotating speed of the mixer is 1500r/min, the mixed powder is granulated by a double screw, and the temperature of the screw is set to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Example 13
Preparing a flame-retardant simulation plant: mixing polyethylene: 60 parts of ethylene-ethyl acrylate copolymer (EAA): 5 parts of anti-ultraviolet agent, 2 parts of color master batch: 8 parts of the intumescent halogen-free flame retardant and 25 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 49.4 parts of polyethylene carrier, 10 parts of Melamine Cyanurate (MCA), 40 parts of piperazine pyrophosphate (PAPP), 0.3 part of EBS dispersant and 0.3 part of anti-dripping agent in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, granulating the mixed powder by a double screw, and setting the temperature of the screw to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Comparative example 1
The simulation plant is mainly prepared from the following raw materials in parts by mass: polyethylene: 50 parts of a mixture; ethylene-octene copolymer (POE): 10 parts of (A); 2 parts of an anti-ultraviolet agent; color master batch: 8 parts of a mixture; and 30 parts of a flame retardant.
Preparation of the flame retardant: mixing 35 parts of polyethylene carrier, 45 parts of decabromodiphenylethane, 15 parts of antimony trioxide and 5 parts of EBS dispersing agent powder in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, granulating the mixed powder by using a double screw, and setting the temperature of the screw to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Comparative example 2
The simulation plant is mainly prepared from the following raw materials in parts by mass: polyethylene: 55 parts of (1); ethylene-octene copolymer (POE): 5 parts of a mixture; 2 parts of an anti-ultraviolet agent; color master batch: 8 parts of a mixture; and 30 parts of a flame retardant.
Preparation of the flame retardant: 30 parts of polyethylene carrier, 45 parts of decabromodiphenylethane, 15 parts of antimony trioxide, 5 parts of EBS dispersant and 5 parts of anhydrous zinc borate powder are mixed in a high-speed mixer for 10min, the rotating speed of the mixer is 1500r/min, and the mixed powder is granulated by a double screw, wherein the temperature of the screw is set to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Comparative examples 1-2 and examples 1-13 compare, examples 1-13 are halogen-free flame retardant intumescent agents, comparative examples are brominated intumescent systems, the results of the flame retardant test are shown in table 2, and the black smoke of comparative examples 1-2 is evident during burning, and there is no smoke during burning of examples 1-13, but there is little white smoke generated during extinguishing.
Comparative example 3
Preparing a flame-retardant simulation plant: mixing polyethylene: 60 parts, 2 parts of anti-ultraviolet agent and color master batch: 8 parts of the intumescent halogen-free flame retardant and 30 parts of the intumescent halogen-free flame retardant are mixed uniformly and are subjected to injection molding by an injection molding machine, and the temperature of the injection molding machine is set to be 200 ℃.
Preparing an intumescent halogen-free flame retardant: mixing 20 parts of polyethylene carrier, 45 parts of Melamine Phosphate (MP), 15 parts of pentaerythritol, 10 parts of melamine, 5 parts of EBS dispersant and 5 parts of anti-dripping agent powder in a high-speed mixer for 10min, wherein the rotating speed of the mixer is 1500r/min, and granulating the mixed powder by using a double screw, wherein the temperature of the screw is set to be 180 ℃.
Preparation of a test sample: the prepared material of the flame-retardant simulation plant is used for preparing a standard dumbbell-shaped sample strip with the thickness of 4mm, a standard sample strip with the thickness of 4mm and a sample strip with the thickness of 125 +/-5 mm multiplied by 13.0 +/-0.5 mm and the thickness of 3.2mm by an injection molding machine, and the test results are shown in table 2.
Compared with the example 8, the softening agent is added in the example 8, and the softening agent is not added in the comparative example 3, so that the product shows that the simulated plant made in the example 8 has good toughness, which is shown in that the injection molded sample of the formula in the example 8 has higher tensile strength and impact strength, and the specific test results are shown in the table 2.
And (3) testing mechanical properties:
tensile strength: the test was carried out at a tensile rate of 100mm/min using injection-molded standard dumbbell-shaped bars of 4mm thickness in accordance with standard ISO 527.
Impact strength: the test was carried out at a bending speed of 2mm/min according to ISO Standard 178 using injection-moulded standard bars of 4mm thickness.
And (3) evaluating the flame retardant property:
the test was carried out using the vertical burning ammonium standard UL-94.
Sample requirements: length and width: 125 ± 5mm by 13.0 ± 0.5mm, sample thickness 3.2 mm.
Specifically, the bunsen burner is placed at the lower end of a vertically placed sample strip, the ignition is carried out for 10s, then a fire source is removed, and the flaming combustion time of the sample is recorded: and if the sample is self-extinguished in the flame removal 30S, placing the bunsen burner at the lower end of the sample strip again for ignition 10S, recording the flame combustion time and the flameless combustion time of the sample after the flame source is removed, simultaneously observing whether molten drops are generated and whether the molten drops ignite absorbent cotton placed below the sample strip, and taking 5 sample strips as one group for each sample to be tested, and if the first group fails to pass the test, taking another group for testing. The flame retardancy ratings were classified into V-0, V-1 and V-2, and the respective ratings were evaluated according to the indices listed in Table 1, wherein the flame retardancy of V-0 was judged to be NC (not classifiable) and the worst flame retardancy was obtained if it was not within the index range listed in Table 1, and the evaluation results are shown in Table 2 below.
TABLE 1 UL94 determination index for combustion grade
TABLE 2
Compared with the common brominated flame retardant, the halogen-free intumescent flame retardant is an environment-friendly flame retardant, does not contain a large amount of toxic gas during combustion, has low smoke generation amount and low combustion rate, does not drip during combustion, and is an environment-friendly flame retardant.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The halogen-free flame retardant ethylene composition is characterized by comprising the following components in percentage by mass: 20-35% of intumescent halogen-free flame retardant and 1-15% of softening agent.
2. The halogen-free flame retardant ethylene composition according to claim 1, further comprising the following components in mass percent: 45-60% of polyethylene, 0.3-5% of anti-ultraviolet agent and 2-15% of color master batch.
3. The halogen-free flame retardant ethylene composition as claimed in claim 2, wherein the intumescent halogen-free flame retardant comprises the following components by mass percent: 18-49.4% of polyethylene carrier, 40-60% of phosphorus flame retardant, 10-20% of char forming agent, 0.3-1% of anti-dripping agent and 0.3-1% of dispersing agent.
4. The halogen-free flame retardant ethylene composition as claimed in claim 2, wherein the softening agent comprises one or more of ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and ethylene-methyl methacrylate copolymer.
5. The halogen-free flame retardant ethylene composition as claimed in claim 3, wherein the phosphorus-containing flame retardant comprises ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine cyanurate, bisphenol A bis (diphenyl) phosphate, triphenyl phosphate, caged bicyclic phosphate, phosphaphenanthrene compounds, diethylphosphinate, melamine, dicyandiamide cyanurate, melamine polyphosphate, 4- (5, 5-dimethyl-2-oxo-1, 3, 2-dioxaphosphorinane-2-oxomethyl) -2,6, 7-trioxo-1-phospha-bicyclo- [2,2,2] -octane-1-oxide, melamine coated ammonium polyphosphate, tris (1-oxo-1-phospha-2, one or more of 6, 7-trioxabicyclo [2,2,2] octane-4-methylene) phosphate and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane.
6. The halogen-free flame retardant ethylene composition as claimed in claim 3, wherein the char former comprises one or more of pentaerythritol, dipentaerythritol, erythritol, starch, organic resins containing hydroxyl groups, piperazine pyrophosphate and triazine derivatives.
7. The halogen-free flame retardant ethylene composition as claimed in claim 3, wherein the anti-dripping agent is a polytetrafluoroethylene based dripping agent.
8. The halogen-free flame-retardant ethylene composition as claimed in claim 3, wherein the dispersant comprises one or a mixture of EBS and polyethylene wax.
9. Use of the halogen-free flame retardant ethylene composition according to any of claims 1 to 8 in simulated plants.
10. The use of the halogen-free flame retardant ethylene composition according to claim 9 in artificial plants, wherein the artificial plants are composed of artificial plant leaves and a fixing plate, the artificial plant leaves are fixed on the fixing plate, wherein the artificial plant leaves and the fixing plate are obtained by injection molding of the halogen-free flame retardant ethylene composition according to any one of claims 1 to 8.
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