CN112063037A - Formula, preparation method and application of high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube - Google Patents
Formula, preparation method and application of high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
The invention discloses a formula of a high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube, which comprises the following components in parts by mass: ethylene-vinyl acetate copolymer 100-; 100 portions of modified or unmodified magnesium-containing and/or aluminum-containing compound; 5-120 parts of a flame-retardant synergist; 1-10 parts of an antioxidant; 1-10 parts of a lubricant; 1-10 parts of a coloring agent. Meanwhile, a preparation method of the high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube is also provided, and comprises the following preparation steps: s1, weighing ethylene-vinyl acetate copolymer, modified or unmodified magnesium-containing and/or aluminum-containing compound, flame retardant synergist, antioxidant, lubricant and colorant according to parts by weight; s2, uniformly stirring the materials and then banburying; then mixing and granulating; then extruding into a pipe; and (3) performing radiation crosslinking on the pipe by using an electron accelerator, and heating and expanding the pipe subjected to radiation crosslinking to obtain a finished heat-shrinkable pipe. The flame retardant grade of the heat-shrinkable tube prepared by the invention reaches the American UL224 VW-1 standard, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%.
Description
Technical Field
The invention belongs to the technical field of heat-shrinkable tubes, and relates to a formula, a preparation method and application of a high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube.
Background
The standard of the directive about the restriction of the use of certain harmful components in the electronic and electrical equipment, namely the RoHS directive, is implemented in the european union from 2006, 7 and 1, and is mainly used for standardizing the material and process standards of electronic and electrical products, so that the electronic and electrical products are more beneficial to human health and environmental protection. The purpose of this standard is to eliminate lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) in electrical and electronic products.
In order to meet the RoHS directive, manufacturers have widely used coated red phosphorus to replace polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) to produce flame retardant heat shrink tubing. Toxic irritant smoke can be released during combustion of red phosphorus, the skin and mucosa of a person are corroded, the health of the person is harmed, the red phosphorus is lapped between the positive electrode and the negative electrode of the circuit board and can generate electrochemical reaction with metal copper and metal silver on the circuit board, the positive electrode and the negative electrode of the circuit board are connected, and circuit board faults are caused. Apple company, 6 months 2007 issued the "apple halogen free specification" which limited the use of red phosphorus. In order to replace red phosphorus, manufacturers use organic phosphorus flame retardants such as diethyl aluminum hypophosphite or piperazine pyrophosphate to replace the red phosphorus, and develop halogen-free and red phosphorus-free heat-shrinkable tube products. Although the halogen-free and red-phosphorus-free product meets the requirement of no red phosphorus, in practice, the difference between red phosphorus and organic phosphorus is difficult to distinguish by wide users in the market, and great concerns still exist, so that the halogen-free and red-phosphorus-free product is difficult to open the market. The flame retardant containing no halogen or phosphorus element has extremely poor flame retardant effect and extremely high filling amount, so the development of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube with excellent mechanical property and excellent flame retardant property is extremely difficult due to the flame retardant.
Therefore, it is very necessary for those skilled in the art to provide a heat shrinkable tube which is easy to process and produce and has low cost, excellent flame retardant property, no halogen and phosphorus, and good mechanical properties.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a heat shrinkable tube which is easy to process and produce and has low cost, excellent flame retardant property, no halogen and phosphorus, and good mechanical properties.
The invention aims to provide a formula of a high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube, which adopts the following technical scheme:
the formula of the high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube comprises the following components in parts by mass:
preferably, the content of vinyl acetate, namely VA, in the ethylene-vinyl acetate copolymer is 14 wt% -40 wt%.
Further, the VA content is 18 wt% or 28 wt% or 35 wt%.
Preferably, the modified or unmodified magnesium-containing and/or aluminum-containing compound is any one or combination of aluminum hydroxide, magnesium hydroxide, modified aluminum hydroxide, magnesium-aluminum hydrate, zinc-magnesium-aluminum hydrotalcite and magnesium-aluminum silicate compound.
Further, the modified or unmodified magnesium-containing and/or aluminum-containing compound adopts modified magnesium hydroxide and/or modified aluminum hydroxide and/or magnesium aluminum hydrate.
Preferably, the flame retardant synergist is any one or combination of melamine, melamine cyanurate, dicyandiamide and organic phyllosilicate.
Further, the flame retardant synergist is melamine and/or melamine cyanurate and/or organic layered silicate.
Preferably, the antioxidant is any one or combination of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Preferably, the lubricant is any one or combination of stearic acid, zinc stearate, polyethylene wax, silicone powder, silicone master batch, oleamide and erucamide.
Further, the lubricant is silicone powder and/or silicone master batch and/or erucamide.
Preferably, the colorant is any one or combination of carbon black, graphite, organic carbon black and black master batch.
Further, the colorant is black master batch.
The second purpose of the invention is to provide a preparation method of a high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube, which comprises the following preparation steps:
s1, weighing 100-150 parts of ethylene-vinyl acetate copolymer, 100-200 parts of modified or unmodified magnesium-containing and/or aluminum-containing compound, 5-80 parts of flame retardant synergist, 1-10 parts of antioxidant, 1-10 parts of lubricant and 1-10 parts of colorant according to parts by weight;
s2, uniformly stirring the materials and then banburying; then mixing and granulating; then extruding into a pipe; and (3) performing radiation crosslinking on the pipe by using an electron accelerator, and heating and expanding the pipe subjected to radiation crosslinking to obtain a finished heat-shrinkable pipe.
Preferably, in step S2: the irradiation dose of the electron accelerator is 80-120 kGy.
Preferably, in step S2: and heating and expanding the pipe subjected to radiation crosslinking by 2-4 times at the temperature of 85-300 ℃.
The flame retardant grade of the finished product of the high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube reaches the American UL224 VW-1 standard, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%.
The invention can bring the following beneficial effects:
1) the finished product of the heat-shrinkable tube prepared by the invention does not contain halogen, phosphorus element, lead, cadmium, mercury, hexavalent chromium and other toxic and harmful substances, the flame-retardant grade reaches the American UL224 VW-1 standard, and the flame-retardant property is very excellent; moreover, the mechanical property is good, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%; meanwhile, the insulating material has excellent electrical insulating property and meets the use requirements of 300V and 600V products.
2) In the formula of the heat-shrinkable tube, proper synergistic action is exerted by selecting the components and the content, so that the magnesium-containing and/or aluminum-containing compound and the flame-retardant synergist are fully dispersed in the EVA matrix and cannot be separated out, meanwhile, the addition of the lubricant can further promote the dispersion of a formula system on a molecular structure, and the antioxidant and the colorant further promote the formula system to form a flame-retardant barrier on the molecular structure. The formula system of the invention can form a compact and continuous protective layer on EVA by using a compound containing magnesium and/or aluminum, effectively obstruct the diffusion of gas volatile matters and the energy exchange between the gas volatile matters and the combustion environment in the combustion process of the material, and effectively improve the flame-retardant effect.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will describe specific embodiments of the present invention. It is obvious that the following describes only some embodiments of the invention, from which other embodiments can be derived without inventive step for a person skilled in the art.
The following components, unless otherwise specified, are commercially available.
According to an embodiment provided by the invention, the formula of the high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube comprises the following components in parts by mass: ethylene-vinyl acetate copolymer 100-; 100 portions of modified or unmodified magnesium-containing and/or aluminum-containing compound; 5-120 parts of a flame-retardant synergist; 1-10 parts of an antioxidant; 1-10 parts of a lubricant; 1-10 parts of a coloring agent.
Wherein:
the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer is 14 wt% -40 wt%, and the flame retardant property is promoted. More preferably, the VA content is 18 wt% or 28 wt% or 35 wt%, and the flame retardant effect is more excellent.
The modified or unmodified magnesium-containing or aluminum-containing compound is any one or combination of more of aluminum hydroxide, magnesium hydroxide, modified aluminum hydroxide, magnesium-aluminum hydrate, zinc-magnesium-aluminum hydrotalcite and magnesium-aluminum silicate compounds. Preferably, the modified magnesium hydroxide and/or the modified aluminum hydroxide and/or the magnesium-aluminum hydrate are selected, specifically, the modification of the magnesium hydroxide/the aluminum hydroxide is preferably obtained by treating with a silane coupling agent, so that the dispersing performance is improved, and the compact protection of the EVA base material is effectively formed. The silane coupling agent modified magnesium hydroxide/aluminum hydroxide is directly purchased in the market.
The flame-retardant synergist is any one or combination of melamine, melamine cyanurate, dicyandiamide and organic phyllosilicate. More preferably, melamine and/or melamine cyanurate and/or an organophyllosilicate are preferred.
The antioxidant is any one or combination of more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. More preferably, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is used.
The lubricant is any one or combination of stearic acid, zinc stearate, polyethylene wax, silicone powder, silicone master batch, oleamide and erucamide. Preferably, silicone powder and/or silicone master batch and/or erucamide are used.
The colorant is any one or combination of more of carbon black, graphite, organic carbon black and black master batch. Preferably, black master is used.
According to another embodiment provided by the invention, the preparation method of the high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube comprises the following preparation steps:
s1, weighing 100-150 parts of ethylene-vinyl acetate copolymer, 100-200 parts of modified or unmodified magnesium-containing and/or aluminum-containing compound, 5-80 parts of flame retardant synergist, 1-10 parts of antioxidant, 1-10 parts of lubricant and 1-10 parts of colorant according to parts by weight;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; and (3) performing radiation crosslinking on the pipe by using an electron accelerator, and heating and expanding the pipe subjected to radiation crosslinking to obtain a finished heat-shrinkable pipe.
As a preferred embodiment, in step S2: the irradiation dose of the electron accelerator is 80-120 kGy. Preferably, the pipe after radiation crosslinking is heated and expanded by 2-4 times at the temperature of 85-300 ℃ to obtain a finished heat-shrinkable pipe.
The flame retardant grade of the finished heat-shrinkable tube prepared by the preparation method reaches the American UL224 VW-1 standard, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%. The flame retardant has excellent flame retardant property, excellent mechanical property and excellent electrical insulation property, meets the use requirements of 300V and 600V products, and can be widely applied to the industry of electronic and electrical appliances.
Several embodiments of the invention are provided below for specific applications as a verification of the effect.
S1, weighing 100-150 parts of ethylene-vinyl acetate copolymer, 200 parts of modified or unmodified magnesium-containing or aluminum-containing compound, 5-80 parts of flame retardant synergist, 1-10 parts of antioxidant, 1-10 parts of lubricant and 1-10 parts of colorant according to parts by weight;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 80-120 kGy, and the pipe subjected to radiation crosslinking is heated and expanded by 2-4 times at the temperature of 85-300 ℃ to obtain a finished heat-shrinkable pipe.
Example 1
S1, weighing 100 parts of ethylene-vinyl acetate copolymer, 110 parts of modified aluminum hydroxide, 80 parts of flame-retardant synergist melamine cyanurate, 6 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3 parts of lubricant silicone powder and 6 parts of colorant black master batch according to parts by weight;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking by an electron accelerator with the irradiation dose of 100kGy, and the pipe subjected to radiation crosslinking is heated and expanded by 2 times at the temperature of 145 ℃ to obtain a finished heat shrinkable pipe.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 11.1MPa, the elongation at break is 220%, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 2
S1, weighing 100 parts of ethylene-vinyl acetate copolymer, 110 parts of modified magnesium hydroxide, 70 parts of flame-retardant synergist melamine cyanurate, 12 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3 parts of lubricant silicone powder and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 110kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 11.7MPa, the elongation at break is 212 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 3
S1, weighing 100 parts of ethylene-vinyl acetate copolymer, 60 parts of modified aluminum hydroxide, 60 parts of modified magnesium hydroxide, 60 parts of flame-retardant synergist melamine cyanurate, 12 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3 parts of lubricant silicone powder and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 110kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 10.9MPa, the elongation at break is 205 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 4
S1, weighing 100 parts of ethylene-vinyl acetate copolymer, 30 parts of modified aluminum hydroxide, 80 parts of modified magnesium hydroxide, 70 parts of flame-retardant synergist melamine cyanurate, 15 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine, 8 parts of lubricant silicone master batch and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 90kGy, and the pipe subjected to radiation crosslinking is expanded by 3 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 10.6MPa, the elongation at break is 240 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 5
S1, weighing 100 parts of ethylene-vinyl acetate copolymer, 170 parts of modified magnesium aluminum silicate compound, 30 parts of flame-retardant synergist melamine cyanurate, 30 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine, 3 parts of lubricant silicone master batch and 2 parts of colorant carbon black according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking by an electron accelerator with the irradiation dose of 100kGy, and the pipe subjected to radiation crosslinking is expanded by 3 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 10.6MPa, the elongation at break is 236 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 6
S1, weighing 120 parts of ethylene-vinyl acetate copolymer, 150 parts of modified aluminum hydroxide, 30 parts of flame-retardant synergist melamine, 60 parts of flame-retardant synergist melamine cyanurate, 12 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 3 parts of lubricant silicone powder and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 110kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 10.8MPa, the elongation at break is 214 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 7
S1, weighing 120 parts of ethylene-vinyl acetate copolymer, 110 parts of modified magnesium hydroxide, 70 parts of flame-retardant synergist melamine cyanurate, 12 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3 parts of lubricant silicone powder and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 90kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 11.4MPa, the elongation at break is 226 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 8
S1, weighing 120 parts of ethylene-vinyl acetate copolymer, 60 parts of modified aluminum hydroxide, 60 parts of modified magnesium hydroxide, 60 parts of flame-retardant synergist melamine cyanurate, 12 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 2 parts of lubricant silicone powder and 2 parts of colorant carbon black;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 90kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 11.6MPa, the elongation at break is 275 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 9
S1, weighing 150 parts of ethylene-vinyl acetate copolymer, 60 parts of modified aluminum hydroxide, 80 parts of modified magnesium hydroxide, 80 parts of flame-retardant synergist melamine cyanurate, 35 parts of flame-retardant synergist organic layered silicate, 3 parts of antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine, 8 parts of lubricant silicone master batch and 6 parts of colorant black master batch according to the weight parts;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking by an electron accelerator with the irradiation dose of 120kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 10.8MPa, the elongation at break is 220%, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
Example 10
S1, weighing 150 parts of ethylene-vinyl acetate copolymer, 200 parts of modified magnesium aluminum silicate compound, 60 parts of flame-retardant synergist organic layered silicate, 20 parts of flame-retardant synergist melamine, 3 parts of antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 3 parts of lubricant silicone master batch and 2 parts of colorant carbon black;
s2, uniformly stirring the materials by using a high-speed stirrer and then banburying the materials by using an internal mixer; then mixing and granulating by a parallel double-screw extruder; then extruding the mixture into a pipe by using a single-screw extruder; the pipe is subjected to radiation crosslinking through an electron accelerator with the irradiation dose of 90kGy, and the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 145 ℃ to obtain a finished product of the high-flame-retardant halogen-free phosphorus-free heat shrinkable tube.
The properties are as follows: the flame retardant property passes a VW-1 test, the tensile strength is 11.1MPa, the elongation at break is 256 percent, the product does not break down under 2.5KV for 60 seconds, and the surface of the product is smooth and flat.
The embodiment is combined, so that the high-efficiency flame-retardant halogen-free phosphorus-free heat-shrinkable tube prepared by the invention is simple to prepare, low in cost and environment-friendly in process, and the flame-retardant grade reaches the American UL224 VW-1 standard on the basis of no halogen and phosphorus elements; the mechanical property is good, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%; meanwhile, the insulating material has excellent electrical insulating property, meets the use requirements of 300V and 600V products, and is widely applied to the electronic and electrical industry.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The formula of the high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube is characterized by comprising the following components in parts by mass:
2. the formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 14 wt% -40 wt%.
3. The formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the modified or unmodified magnesium-containing and/or aluminum-containing compound is any one or combination of aluminum hydroxide, magnesium hydroxide, modified aluminum hydroxide, magnesium-aluminum hydrate, zinc-magnesium-aluminum hydrotalcite and magnesium-aluminum silicate compound.
4. The formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the flame-retardant synergist is any one or combination of melamine, melamine cyanurate, dicyandiamide and organic phyllosilicate.
5. The formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the antioxidant is any one or combination of more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
6. The formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the lubricant is any one or combination of stearic acid, zinc stearate, polyethylene wax, silicone powder, silicone master batch, oleamide and erucamide.
7. The formula of the high flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 1, wherein:
the colorant is any one or combination of more of carbon black, graphite, organic carbon black and black master batch.
8. A preparation method of a high-flame-retardant halogen-free phosphorus-free heat shrinkable tube is characterized by comprising the following preparation steps:
s1, weighing 100-150 parts of ethylene-vinyl acetate copolymer, 100-200 parts of modified or unmodified magnesium-containing and/or aluminum-containing compound, 5-80 parts of flame retardant synergist, 1-10 parts of antioxidant, 1-10 parts of lubricant and 1-10 parts of colorant according to parts by weight;
s2, uniformly stirring the materials and then banburying; then mixing and granulating; then extruding into a pipe; and (3) performing radiation crosslinking on the pipe by using an electron accelerator, and heating and expanding the pipe subjected to radiation crosslinking to obtain a finished heat-shrinkable pipe.
9. The method for preparing a highly flame retardant halogen-free phosphorus-free heat shrinkable tube according to claim 8, wherein in step S2:
the irradiation dose of the electron accelerator is 80-120 kGy;
and/or;
and heating and expanding the pipe subjected to radiation crosslinking by 2-4 times at the temperature of 85-300 ℃.
10. The high-flame-retardance halogen-free phosphorus-free heat-shrinkable tube prepared by the preparation method according to claim 8 is characterized in that:
the flame retardant grade of the heat-shrinkable tube reaches the American UL224 VW-1 standard, the tensile strength is not less than 10.4MPa, and the elongation at break is not less than 200%.
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