CN111004441A - Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof - Google Patents
Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof Download PDFInfo
- Publication number
- CN111004441A CN111004441A CN201911325163.6A CN201911325163A CN111004441A CN 111004441 A CN111004441 A CN 111004441A CN 201911325163 A CN201911325163 A CN 201911325163A CN 111004441 A CN111004441 A CN 111004441A
- Authority
- CN
- China
- Prior art keywords
- halogen
- free flame
- glow
- cti
- polypropylene material
- 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.)
- Pending
Links
Classifications
-
- 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
- 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
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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 halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance, which comprises the following components in parts by weight: 40-80 parts of polypropylene resin, 15-30 parts of halogen-free flame retardant, 5-20 parts of glass fiber, 1-5 parts of compatilizer, 0.5-5 parts of antioxidant, 0.5-5 parts of auxiliary agent and 0.2-2 parts of lubricant. The Glow Wire Ignition Temperature (GWIT) and the Glow Wire Flammability Index (GWFI) of the halogen-free flame-retardant high-glow-wire high-CTI unattended electric appliance polypropylene material are high, the mechanical property is excellent, the preparation process is simple, halogen-free and environment-friendly, the halogen-free and environment-friendly material standards of customers are met, and the cost is low; the components of the invention are mature materials, are convenient for large-scale popularization and use, and can meet the application requirements of a plurality of fields such as automobiles, electronics, household appliances and the like.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, relates to a modified flame-retardant polypropylene material and a preparation method thereof, and more particularly relates to a halogen-free flame-retardant high glow wire high CTI unattended electric appliance polypropylene material and a preparation method thereof.
Background
Modern electronic and electrical equipment has more than 40% of parts by weight composed of flammable plastic insulating materials, and the electronic and electrical equipment can cause fire due to ignition of the materials caused by overheating, electric leakage, short circuit, spark, aging and the like, thereby causing great threat to the life and property safety of people. Therefore, regulations are successively issued in various countries of the world to make strict regulations on the flame retardant property, heat resistance, electrical property and the like of plastic insulating materials used in electronic and electrical equipment. The polypropylene (PP) is one of the preferred plastic varieties in the household appliance industry due to the characteristics of low density, good chemical resistance, low price, excellent comprehensive performance and the like, and the dosage of the PP accounts for about 30 percent.
With the continuous emergence of new personalized and intelligent household electrical appliances, higher requirements are also put forward on the safety application of PP in the household electrical appliances. Electronic and electric products generally have two requirements for flame retardance, heat resistance and electric performance of plastic insulating materials, namely high glow wire and high CTI. According to the IEC60695 glow wire flame retardant test evaluation standards implemented by the european union International Electrotechnical Commission (IEC) requirements industry, the IEC organization, in IEC60335 safety standards for household and similar appliances, sets forth that the flame retardant properties of plastic parts used in long-term unattended appliances must meet the requirements of no ignition or a burning time of less than 5s within 30s of a UL 94V-0 and 750 ℃ glow wire contact material, i.e., a Glow Wire Ignition Temperature (GWIT) of greater than 750 ℃. The GWIT temperature of 850 ℃ and the Glow Wire Flammability Index (GWFI) of 950 ℃ are also required for specific parts such as connectors, contact switches, motors, and breaker housings. Wherein the flame-retardant modified PP material is required by the unattended electric appliance to meet the relevant regulations of the modified PP material for the unattended electric appliance for a long time, which are proposed by the International Electrotechnical Commission (IEC).
Halogen-containing flame-retardant materials can generate a large amount of smoke and toxic corrosive hydrogen halide gas in the flame-retardant process, thereby causing secondary harm. China also reports national standards of the grade of the combustion performance of building materials and products, the standards have common characteristics with RoHs and WEEE instructions issued by European Union 2003, namely, the heat release rate, the fire development rate, the smoke generation performance, the corrosiveness and the toxicity of combustion products and the like are emphasized on the evaluation of the flame retardant performance of materials, and in order to pass the new standards, the traditional halogen flame retardant materials have no effect, and people are shifted to the use of char-forming flame retardant plastics (particularly intumescent flame retardant plastics) and thermosetting flame retardant plastics. Therefore, the development of a halogen-free flame-retardant high glow wire high CTI polypropylene material for unattended electric appliances is important for the upgrading and updating of the electric appliances to gradually become specialized, high-performance, safe and environment-friendly.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant high glow wire high CTI (comparative tracking index) polypropylene material for an unattended electric appliance and a preparation method thereof.
Based on the above purpose, the invention adopts the technical scheme that:
a halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following components in parts by weight:
preferably, the halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended electric appliance comprises the following components in parts by weight:
preferably, the halogen-free flame retardant is one or more of poly ammonium polyphosphate, expanded graphite, melamine phosphate, zinc borate, ammonium polyphosphate (APP), triglycidyl isocyanurate (TGIC), tricresyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tributyl phosphate, trioctyl phosphate, cresyl diphenyl phosphate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, and dimethyl methyl phosphate (DMMP) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
Preferably, the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, tetraethyl N, N-p-phenylenediamine (2-hydroxy) dibenzyl phosphate, dimethyl methyl phosphate and DOPO in a proportion of 0-5: 2-6: 2-6: 4-10: 4-10: 0-8 percent of the total weight.
More preferably, the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, tetraethyl N, N-p-phenylenediamine (2-hydroxy) dibenzyl phosphate, dimethyl methyl phosphate and DOPO in a weight ratio of 0-4: 3-5: 3-5: 6-10: 6-10: 1-6.
The expanded graphite is a novel halogen-free flame retardant, the initial expansion temperature of the expandable graphite is about 220 ℃, the expandable graphite is expanded at the temperature of 220 ℃ and is expanded at 280 ℃ slightly, and the volume of the expandable graphite can reach more than 100 times of the original volume, even 280 times. The expandable graphite mainly plays the following roles in the flame-retardant process: (1) forming a tough carbon layer on the surface of the high polymer to separate the combustible from the heat source; (2) a large amount of heat is absorbed in the expansion process, so that the temperature of the system is reduced; (3) acid radical ions in the interlayer are released in the expansion process, dehydration and carbonization are promoted, and free radicals generated by combustion can be combined to break chain reaction. The expandable graphite is compounded with phosphorus compound and metal oxide to produce coordination effect, and the aim of flame retarding can be achieved by adding a small amount of the expandable graphite.
Ammonium polyphosphate is an inorganic flame retardant with good performance, is cheaper than an organic flame retardant, has low toxicity and good thermal stability, and can be used for flame retardance of plastics independently or in combination with other flame retardants. At high temperatures, APP rapidly decomposes into ammonia and polyphosphoric acid, the ammonia diluting the oxygen concentration in the gas phase, thereby acting as a flame retardant. Polyphosphoric acid is a strong dehydrating agent, can dehydrate and carbonize polymers to form a carbon layer, isolates the polymers from contacting with oxygen, and plays a role in preventing combustion in a solid phase.
Triglycidyl isocyanurate is a crystalline heterocyclic epoxy compound, three epoxy groups are very active, can be subjected to high-density crosslinking with hydroxyl in polyester resin, and is very stable in heterocyclic ring, and excellent in heat resistance, weather resistance, light resistance, corrosion resistance, chemical resistance and mechanical properties.
The phosphate flame retardant has enhanced chemical stability and water and solvent resistance due to the existence of P-C bonds, and is a flame retardant with great development prospect. In addition, the phosphorus-nitrogen flame retardant has small smoke amount due to the synergistic action of P-N, basically does not generate toxic gas, not only has good flame retardant effect, but also can greatly reduce the dosage of the flame retardant. Thus, N, N-p-phenylenediamine (2-hydroxy) dibenzyl-tetraethyl phosphate is an organic flame retardant with great development prospect.
Dimethyl methyl phosphate (DMMP) is an internal addition type flame retardant, and has the most remarkable characteristics of high phosphorus content up to 25 percent and high flame retardant efficiency. The same effect can be achieved by only half or less of the amount of the conventional flame retardant, and the influence on the physicochemical properties of the synthetic material itself is reduced to a low level due to the small amount of the flame retardant. DMMP is an additive flame retardant widely used in polyurethane foam plastics, unsaturated polyester resin, epoxy resin and furan resin materials, and the product has self-extinguishing property, low temperature resistance, plasticity, ultraviolet stability and antistatic property which are superior to those of products added with other flame retardants. Use experiments show that the flame retardant grades with different requirements can be achieved by adding 6-15% of DMMP. The DMMP is applied to unsaturated polyester resin, has good compatibility and excellent flame retardance, and can be prepared into flame-retardant glass fiber reinforced plastic and flame-retardant transparent glass fiber reinforced plastic products.
DOPO is mainly applied to the fields of flame retardance, special functional polymers, epoxy resin, luminescent materials, modified materials and the like, particularly has wide application in the field of electronic and electric appliance materials, particularly in the field of electronic and electric appliance materials, and has the unique advantage of no need of flame retardance modification by using the DOPO modified polymer.
Preferably, the polypropylene resin has a density of 0.90 to 0.91g/cm3The melting point is 168-172 ℃.
Preferably, the glass fiber is hydrolysis resistant glass fiber.
More preferably, the length of the hydrolysis resistant glass fiber is 3-6 mm.
Preferably, the compatilizer is one or more of polypropylene-maleic acid glycoside copolymer, styrene-maleic anhydride copolymer, polyethylene octene copolymer elastomer-maleic anhydride copolymer, ethylene propylene diene monomer rubber-maleic anhydride copolymer and polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer.
Preferably, the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant and thioether antioxidant.
More preferably, the antioxidant is one or more of tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, pentaerythritol tetrapentaerythritol ester and dilauryl thiodipropionate.
Preferably, the auxiliary agent is one or more of an antibacterial agent, an anti-UV agent, a nucleating agent and an anti-dripping agent.
More preferably, the antimicrobial agent is a nano antimicrobial agent. Further preferably, the antibacterial agent is one or more of nano zinc oxide, nano copper oxide and nano lithium carbonate.
Preferably, the anti-UV agent is one or more of histamine, chlorobenzotriazole, 2-hydroxy-4-octoxybenzophenone, hydroxybenzophenone, hydroxyphenyl benzotriazole and hydroxyphenyl triazine.
Preferably, the nucleating agent is one or more of talcum powder, aluminum oxide, montmorillonite, kaolin, calcium carbonate, sodium phenylphosphinate, zinc phenylphosphinate and copper acetate
Preferably, the anti-dripping agent is a PTFE-type or SAN-type anti-dripping agent.
Preferably, the lubricant is one or more of stearic acid, stearic acid amide, oleic acid amide, calcium stearate, zinc stearate and polyethylene wax.
The invention also provides a preparation method of the halogen-free flame-retardant high glow wire high CTI unattended electric appliance polypropylene material, which comprises the following steps:
(1) mixing polypropylene resin, a halogen-free flame retardant, a compatilizer, an antioxidant, an auxiliary agent and a lubricant to obtain a mixed component;
(2) and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
Preferably, the extrusion temperature of each zone of the parallel twin-screw extruder in the step (2) is respectively as follows: a first area: 120 ℃ and 160 ℃, and a second zone: 170 ℃ and 180 ℃, three zones: 180 ℃ and 187 ℃, four zones: 185 ℃ and 190 ℃ and a five-zone: 185 ℃ and 192 ℃ and a six-zone: 188-: 178 ℃ and 190 ℃ and eight zones: 170 ℃ and 185 ℃.
Preferably, the degree of vacuum is-0.06-0.1 MPa.
Preferably, the screw speed is 200-450 rpm.
The beneficial technical effects of the invention are as follows:
(1) by compounding various halogen-free flame retardants, the flame retardant generates a carbon layer to isolate air and block heat conduction and heat radiation when the polypropylene material is combusted, and the flame retardant decomposes and releases generated non-combustible gas to achieve the effect of isolating air; the polypropylene material disclosed by the invention is free from halogen, so that the prepared material is free from toxic and waste gas during the flame retardant process, the flame retardant process is shorter, and the halogen-free environment-friendly material is truly realized.
(2) According to the invention, the hydrolysis-resistant glass short fiber is added, so that the reinforcement effect on the matrix is exerted to the greatest extent, the compatilizer is added, the compatibility of the glass fiber and the polypropylene matrix is improved, the toughness and the strength performance of the product are improved, the polypropylene material has excellent flame retardant property, and the mechanical strength is greatly improved.
(3) The Glow Wire Ignition Temperature (GWIT) of the halogen-free flame-retardant high-glow-wire high-CTI unattended electric appliance polypropylene material is up to 870 ℃, the Glow Wire Flammability Index (GWFI) of the glow wire is up to 960 ℃, the mechanical property is excellent, the preparation process is simple, the halogen-free environment-friendly effect is realized, the halogen-free and environment-friendly material standard of customers is met, and the cost is low; the components of the invention are mature materials, are convenient for large-scale popularization and use, and can meet the application requirements of a plurality of fields such as automobiles, electronics, household appliances, chemical engineering, buildings and the like.
Detailed Description
Example 1
A halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following components in parts by weight:
the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, methyl dimethyl phosphate and DOPO according to the weight ratio of 0: 3: 3: 6: 6: 6, and the components are compounded in proportion.
The compatilizer is polypropylene-maleic acid glycoside copolymer.
The antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
The auxiliary agent is an antibacterial agent, an anti-UV agent and a nucleating agent (the mass ratio is 2: 1: 2).
The antibacterial agent is nano zinc oxide.
The anti-UV agent is chlorobenzotriazole.
The nucleating agent is talcum powder mixed with alumina (the mass ratio is 1: 3).
The lubricant is stearic acid amide.
A preparation method of a halogen-free flame-retardant high glow wire high CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following steps:
(1) respectively drying the polypropylene resin, the halogen-free flame retardant, the compatilizer, the antioxidant, the auxiliary agent and the lubricant for 8 hours at 80 ℃ to ensure that the water content is less than 0.5 percent, thus obtaining the dried components;
(2) weighing the dried components in parts by weight, adding the components into a high-speed mixer, and mixing for 6min, wherein the rotating speed of the high-speed mixer is 1000rpm, so as to obtain mixed components;
(3) and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
The extrusion temperature of each zone of the parallel double-screw extruder in the step (3) is respectively as follows: a first area: 140 ℃ and a second zone: 170 ℃ and three zones: 180 ℃ and four zones: 185 ℃ and five zones: 190 ℃ and six zones: 195 ℃, seven regions: 190 ℃ and eight regions: 185 ℃ C.
The vacuum degree is-0.06-0.1 Mpa, and the screw rotating speed is 300 rpm.
Example 2
A halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following components in parts by weight:
the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, methyl dimethyl phosphate and DOPO according to the weight ratio of 1: 2: 3: 8: 8: 6, and the components are compounded in proportion.
The compatilizer is a polypropylene-maleic acid glycoside copolymer mixed styrene-maleic anhydride copolymer (mass ratio is 1: 2).
The antioxidant is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
The auxiliary agent is an antibacterial agent, an anti-UV agent and a nucleating agent (the mass ratio is 2: 1: 2).
The antibacterial agent is nano copper oxide.
The anti-UV agent is hydroxybenzophenone.
The nucleating agent is talcum powder mixed montmorillonite (the mass ratio is 1: 4).
The lubricant is calcium stearate.
A preparation method of a halogen-free flame-retardant high glow wire high CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following steps:
(1) respectively drying the polypropylene resin, the halogen-free flame retardant, the compatilizer, the antioxidant, the auxiliary agent and the lubricant for 6 hours at 90 ℃ to ensure that the water content is less than 0.5 percent, and obtaining the dried components;
(2) weighing the dried components in parts by weight, adding the components into a high-speed mixer, and mixing for 6min, wherein the rotating speed of the high-speed mixer is 1500rpm, so as to obtain mixed components;
(3) and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
The extrusion temperature of each zone of the parallel double-screw extruder in the step (3) is respectively as follows: a first area: 135 ℃ and a second zone: 175 ℃, three zones: 183 ℃ C., four zones: 188 ℃, five zones: 190 ℃ and six zones: 195 ℃, seven regions: 185 ℃ and eight regions: 180 ℃ is carried out.
The vacuum degree is-0.06-0.1 Mpa, and the screw rotating speed is 350 rpm.
Example 3
A halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following components in parts by weight:
the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, methyl dimethyl phosphate and DOPO according to the weight ratio of 0: 5: 5: 8: 8: 8, and the components are compounded in a ratio of.
The compatilizer is ethylene propylene diene monomer-maleic anhydride copolymer.
The antioxidant is pentaerythritol ester mixed dilauryl thiodipropionate (mass ratio of 2: 3).
The auxiliary agent is an antibacterial agent, an anti-UV agent, a nucleating agent and an anti-dripping agent (the mass ratio is 2: 1: 2: 1).
The antibacterial agent is nano zinc oxide.
The UV resistant agent is hydroxyphenyl benzotriazole mixed with hydroxyphenyl triazine (the mass ratio is 4: 5).
The nucleating agent is kaolin mixed calcium carbonate (the mass ratio is 1: 2).
The anti-dripping agent PTFE type anti-dripping agent.
The lubricant is polyethylene wax.
A preparation method of a halogen-free flame-retardant high glow wire high CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following steps:
(1) respectively drying the polypropylene resin, the halogen-free flame retardant, the compatilizer, the antioxidant, the auxiliary agent and the lubricant for 10 hours at 75 ℃ to ensure that the water content is less than 0.5 percent, thus obtaining the dried components;
(2) weighing the dried components in parts by weight, adding the components into a high-speed mixer, and mixing for 10min, wherein the rotating speed of the high-speed mixer is 600rpm, so as to obtain mixed components;
(3) and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
The extrusion temperature of each zone of the parallel double-screw extruder in the step (3) is respectively as follows: a first area: 150 ℃ and a second zone: 180 ℃ and three zones: 187 ℃, four zones: 190 ℃ and five regions: 192 ℃ and six zones: 190 ℃ and seven regions: 185 ℃ and eight regions: 175 ℃.
The vacuum degree is-0.06-0.1 Mpa, and the screw rotating speed is 400 rpm.
Example 4
A halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following components in parts by weight:
the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, methyl dimethyl phosphate and DOPO according to the weight ratio of 2: 4: 4: 7: 8: 8, and the components are compounded in a ratio of.
The compatilizer is a polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer.
The antioxidant is trilauryl tris (2, 4-di-tert-butylphenyl) phosphite mixed thiodipropionate (mass ratio is 1: 1).
The auxiliary agent is an antibacterial agent, an anti-UV agent, a nucleating agent and an anti-dripping agent (the mass ratio is 2: 1: 2: 1).
The antibacterial agent is nano copper oxide.
The anti-UV agent is chloro-benzotriazole mixed with 2-hydroxy-4-octoxy benzophenone (the mass ratio is 1: 1).
The nucleating agent is sodium phenylphosphinate.
The anti-dripping agent PTFE type anti-dripping agent.
The lubricant is stearic acid.
A preparation method of a halogen-free flame-retardant high glow wire high CTI (comparative tracking index) polypropylene material for an unattended electric appliance comprises the following steps:
(1) respectively drying the polypropylene resin, the halogen-free flame retardant, the compatilizer, the antioxidant, the auxiliary agent and the lubricant at 75 ℃ for 12 hours to enable the water content of the polypropylene resin to be less than 0.5%, and obtaining the dried components;
(2) weighing the dried components in parts by weight, adding the components into a high-speed mixer, and mixing for 10min, wherein the rotating speed of the high-speed mixer is 500rpm, so as to obtain mixed components;
(3) and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
The extrusion temperature of each zone of the parallel double-screw extruder in the step (3) is respectively as follows: a first area: 120 ℃ and a second zone: 180 ℃ and three zones: 185 ℃ and four zones: 190 ℃ and five regions: 192 ℃ and six zones: 190 ℃ and seven regions: 186 ℃ and eight regions: 178 ℃.
The vacuum degree is-0.06-0.1 Mpa, and the screw rotating speed is 250 rpm.
The performance of the halogen-free flame-retardant high-glow-wire high-CTI unattended electric appliance polypropylene material prepared in the examples 1 to 4 was tested, and the obtained results are shown in Table 1. Wherein the tensile strength is measured according to ASTM-D638, the flexural modulus is measured according to ASTM-D790, the notched impact strength is measured according to ASTM-D256, the flame retardancy is measured according to UL40, and the GWIT, GWFI and hot-bulb indentation are measured according to IEC 60695.
Table 1 examples 1-4 of the performance test results of the polypropylene material for halogen-free flame-retardant high glow-wire high CTI unattended electric appliances prepared in examples 1-4
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 |
| Tensile strength (Mpa) | 182.6 | 198.1 | 201.2 | 196.7 |
| Flexural modulus (Mpa) | 255.3 | 279.9 | 283.6 | 276.3 |
| Notched impact strength (kJ/m)2) | 6.7 | 7.8 | 8.3 | 7.9 |
| Flame retardancy of 1.6mm | V-0 | V-0 | V-0 | V-0 |
| GWIT(℃) | 850 | 855 | 865 | 870 |
| GWFI(℃) | 950 | 955 | 960 | 960 |
| Hot ball indentation (mm) | 1.58 | 1.57 | 1.52 | 1.53 |
The above examples are given for the purpose of illustrating the invention clearly and not for the purpose of limiting the same, and it will be apparent to those skilled in the art that, in light of the above description, numerous modifications and variations can be made in the form and details of the embodiments of the invention described herein, and it is not intended to be exhaustive or to limit the invention to the precise forms disclosed.
Claims (10)
1. The halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended electric appliance is characterized by comprising the following components in parts by weight:
2. the halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended electric appliance according to claim 1, which is characterized by comprising the following components in parts by weight:
3. the halogen-free flame retardant high glow wire high CTI unattended appliance polypropylene material according to claim 1, wherein the halogen-free flame retardant is one or more of poly ammonium polyphosphate, expanded graphite, melamine phosphate, zinc borate, ammonium polyphosphate, triglycidyl isocyanurate, tricresyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tributyl phosphate, trioctyl phosphate, cresyl diphenyl phosphate, N-p-phenylenediamine (2-hydroxy) dibenzyl tetraethyl phosphate, dimethyl methyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
4. The halogen-free flame retardant high glow wire high CTI unattended appliance polypropylene material according to claim 1, wherein the halogen-free flame retardant is prepared from expanded graphite, ammonium polyphosphate, triglycidyl isocyanurate, N-p-phenylenediamine (2-hydroxy) tetraethyl dibenzyl phosphate, dimethyl methyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a weight ratio of 0-5: 2-6: 2-6: 4-10: 4-10: 0-8 percent of the total weight.
5. The halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended electric appliance according to claim 1, wherein the glass fiber is hydrolysis-resistant glass fiber.
6. The halogen-free flame retardant high glow wire high CTI unattended appliance polypropylene material according to claim 1, wherein the compatilizer is one or more of polypropylene-maleic acid glycoside copolymer, styrene-maleic anhydride copolymer, polyethylene octene copolymer elastomer-maleic anhydride copolymer, ethylene propylene diene monomer rubber-maleic anhydride copolymer and polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer.
7. The halogen-free flame-retardant high-glow-wire high-CTI unattended electric appliance polypropylene material according to claim 1, wherein the antioxidant is one or more of a hindered phenol antioxidant, a phosphite antioxidant and a thioether antioxidant.
8. The halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended appliance according to claim 1, wherein the auxiliary agent is one or more of an antibacterial agent, an anti-UV (ultraviolet) agent, a nucleating agent and an anti-dripping agent.
9. The halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for the unattended electric appliance according to claim 1, wherein the lubricant is one or more of stearic acid, stearic acid amide, oleic acid amide, calcium stearate, zinc stearate and polyethylene wax.
10. The preparation method of the halogen-free flame-retardant high glow wire high CTI unattended electric appliance polypropylene material according to any one of claims 1 to 9, characterized by comprising the following steps:
mixing polypropylene resin, a halogen-free flame retardant, a compatilizer, an antioxidant, an auxiliary agent and a lubricant to obtain a mixed component;
and adding the obtained mixed components into a parallel double-screw extruder, adding glass fibers into a side feeding port of the parallel double-screw extruder, and sequentially extruding, cooling and granulating to obtain the halogen-free flame-retardant high-glow-wire high-CTI polypropylene material for the unattended electric appliance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325163.6A CN111004441A (en) | 2019-12-20 | 2019-12-20 | Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325163.6A CN111004441A (en) | 2019-12-20 | 2019-12-20 | Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111004441A true CN111004441A (en) | 2020-04-14 |
Family
ID=70116942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911325163.6A Pending CN111004441A (en) | 2019-12-20 | 2019-12-20 | Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004441A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115667388A (en) * | 2020-05-28 | 2023-01-31 | 三菱化学株式会社 | Resin composition and molded article |
| CN116948494A (en) * | 2023-06-20 | 2023-10-27 | 广东傲博新材料有限公司 | Insulating flame-retardant corrosion-resistant powder coating for battery and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050994A (en) * | 2011-01-18 | 2011-05-11 | 广东聚石化学股份有限公司 | High-voltage breakdown resisting halogen-free precipitate-free antiflaming PP (Polypropylene) for electronic/electric apparatus components |
| CN102492218A (en) * | 2011-11-29 | 2012-06-13 | 深圳市科聚新材料有限公司 | Halogen-free expansion type flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
| CN102492219A (en) * | 2011-11-30 | 2012-06-13 | 深圳市科聚新材料有限公司 | High glow-wire reinforced polypropylene material and its preparation method |
| CN102775680A (en) * | 2012-07-17 | 2012-11-14 | 上海日之升新技术发展有限公司 | Halogen-free flame-retardant polypropylene composition with high glowing wires and high CTI (comparative tracking index) and preparation method thereof |
| CN102942739A (en) * | 2012-12-04 | 2013-02-27 | 上海日之升新技术发展有限公司 | High-CTI (Creepage Tracking Index) high-GWIT (Glow-Wire Ignition Temperature) environmental-friendly flame-retardant glass fiber reinforced PP (Polypropylene) material and preparation method thereof |
| CN102964688A (en) * | 2012-12-04 | 2013-03-13 | 上海日之升新技术发展有限公司 | Environment-friendly and flame-retardant glass fiber reinforced PP (polypropylene)/PA (polyamide) 11 alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value and preparation method thereof |
| CN103160025A (en) * | 2013-02-27 | 2013-06-19 | 广东聚石化学股份有限公司 | High-glowing filament anti-soaking separate-out-free halogen-free inflaming retarding polypropylene materials and preparation method thereof |
| CN103756152A (en) * | 2014-02-13 | 2014-04-30 | 广东聚石化学股份有限公司 | Halogen-free flame retardant polypropylene composite material for coil skeleton and preparation method thereof |
| CN105199219A (en) * | 2015-09-17 | 2015-12-30 | 苏州新区佳合塑胶有限公司 | Stretch-proof polypropylene composite material |
| CN106995559A (en) * | 2017-04-18 | 2017-08-01 | 广东圆融新材料有限公司 | UL94 5VA grades a kind of high GWIT RPPs composition and preparation method thereof |
| CN107418047A (en) * | 2017-06-02 | 2017-12-01 | 中山康诺德新材料有限公司 | A kind of High glow wire halogen-free flame retardant polyolefin composition and preparation method |
| CN107446236A (en) * | 2017-08-17 | 2017-12-08 | 合肥会通新材料有限公司 | A kind of high glow-wire environment friendly halogen-free fireproof fiber glass reinforced polypropylene material and preparation method thereof |
| CN108084564A (en) * | 2017-12-26 | 2018-05-29 | 重庆普利特新材料有限公司 | A kind of high flame retardant, high oxygen index (OI) halogen-free anti-flaming polypropylene material and preparation method thereof |
-
2019
- 2019-12-20 CN CN201911325163.6A patent/CN111004441A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050994A (en) * | 2011-01-18 | 2011-05-11 | 广东聚石化学股份有限公司 | High-voltage breakdown resisting halogen-free precipitate-free antiflaming PP (Polypropylene) for electronic/electric apparatus components |
| CN102492218A (en) * | 2011-11-29 | 2012-06-13 | 深圳市科聚新材料有限公司 | Halogen-free expansion type flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
| CN102492219A (en) * | 2011-11-30 | 2012-06-13 | 深圳市科聚新材料有限公司 | High glow-wire reinforced polypropylene material and its preparation method |
| CN102775680A (en) * | 2012-07-17 | 2012-11-14 | 上海日之升新技术发展有限公司 | Halogen-free flame-retardant polypropylene composition with high glowing wires and high CTI (comparative tracking index) and preparation method thereof |
| CN102942739A (en) * | 2012-12-04 | 2013-02-27 | 上海日之升新技术发展有限公司 | High-CTI (Creepage Tracking Index) high-GWIT (Glow-Wire Ignition Temperature) environmental-friendly flame-retardant glass fiber reinforced PP (Polypropylene) material and preparation method thereof |
| CN102964688A (en) * | 2012-12-04 | 2013-03-13 | 上海日之升新技术发展有限公司 | Environment-friendly and flame-retardant glass fiber reinforced PP (polypropylene)/PA (polyamide) 11 alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value and preparation method thereof |
| CN103160025A (en) * | 2013-02-27 | 2013-06-19 | 广东聚石化学股份有限公司 | High-glowing filament anti-soaking separate-out-free halogen-free inflaming retarding polypropylene materials and preparation method thereof |
| CN103756152A (en) * | 2014-02-13 | 2014-04-30 | 广东聚石化学股份有限公司 | Halogen-free flame retardant polypropylene composite material for coil skeleton and preparation method thereof |
| CN105199219A (en) * | 2015-09-17 | 2015-12-30 | 苏州新区佳合塑胶有限公司 | Stretch-proof polypropylene composite material |
| CN106995559A (en) * | 2017-04-18 | 2017-08-01 | 广东圆融新材料有限公司 | UL94 5VA grades a kind of high GWIT RPPs composition and preparation method thereof |
| CN107418047A (en) * | 2017-06-02 | 2017-12-01 | 中山康诺德新材料有限公司 | A kind of High glow wire halogen-free flame retardant polyolefin composition and preparation method |
| CN107446236A (en) * | 2017-08-17 | 2017-12-08 | 合肥会通新材料有限公司 | A kind of high glow-wire environment friendly halogen-free fireproof fiber glass reinforced polypropylene material and preparation method thereof |
| CN108084564A (en) * | 2017-12-26 | 2018-05-29 | 重庆普利特新材料有限公司 | A kind of high flame retardant, high oxygen index (OI) halogen-free anti-flaming polypropylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张书华 等: "《高性能电缆材料及其应用技术》", 30 November 2015, 上海交通大学出版社 * |
| 杨桂生编著: "《工程塑料》", 31 December 2017, 中国铁道出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115667388A (en) * | 2020-05-28 | 2023-01-31 | 三菱化学株式会社 | Resin composition and molded article |
| CN116948494A (en) * | 2023-06-20 | 2023-10-27 | 广东傲博新材料有限公司 | Insulating flame-retardant corrosion-resistant powder coating for battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160025B (en) | High-glowing filament anti-soaking separate-out-free halogen-free inflaming retarding polypropylene materials and preparation method thereof | |
| CN101293983B (en) | Expansion flame-proof polypropelene composition and preparation method thereof | |
| CN107286563B (en) | Intumescent flame retardant for ABS electrical switch outer cover and preparation and application thereof | |
| CN109721768B (en) | Halogen-free phosphorus-nitrogen composite flame retardant and halogen-free flame retardant thermoplastic polymer containing same | |
| CN108250572B (en) | UL94-5 VA-capable high-flame-retardant photo-thermal-aging-resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN102964667B (en) | Halogen-free flame-retardant polyethylene composite material and preparation method thereof | |
| CN110885498A (en) | Flame-retardant toughened polypropylene material and preparation method thereof | |
| CN107141591A (en) | A kind of few additive halogen-free anti-flaming polypropylene material and preparation method thereof | |
| CN101817972A (en) | Flame-retardant enhanced PBT material and preparation method thereof | |
| CN111333960A (en) | Antimony-free flame-retardant polypropylene composition and preparation method thereof | |
| CN103602061A (en) | High glow-wire ignition temperature halogen-free flame-retardant reinforced nylon composite and preparation method thereof | |
| CN110591152A (en) | Flame-retardant stabilizer, halogen-free flame-retardant glass fiber reinforced polypropylene and preparation method thereof | |
| CN101469096A (en) | Flame-retardant polypropylene film material | |
| CN115505172B (en) | Halogen-free flame retardant, and preparation method and application thereof | |
| CN102863691A (en) | Polypropylene composite material and preparation method thereof | |
| CN105418967B (en) | Organic materials as flame retardant and flame retardant synergists | |
| CN115558181B (en) | Flame-retardant master batch and preparation method and application thereof | |
| CN111004441A (en) | Halogen-free flame-retardant high-glow-wire high-CTI (comparative tracking index) polypropylene material for unattended electric appliance and preparation method thereof | |
| CN115260754A (en) | High-toughness halogen-free flame-retardant PA66 material and preparation method thereof | |
| CN111635587A (en) | High-reinforcement, low-fuming, halogen-free and environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN103740038A (en) | High-glossiness halogen-free flame-retardant ABS material and preparation method thereof | |
| CN108467547A (en) | A kind of converter environment-protection flame-proof electrostatic resistance polypropylene composition and preparation method thereof | |
| CN111748156A (en) | Halogen-free flame-retardant mineral powder reinforced polypropylene composition | |
| CN109957246A (en) | Charging pile high CTI organic phosphonate fire-retardant nylon and preparation method thereof | |
| CN109721854B (en) | Scratch-resistant PP composite material for socket and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200414 |