CN112280160A - Irradiation crosslinking thermal shrinkage material and preparation method thereof - Google Patents
Irradiation crosslinking thermal shrinkage material and preparation method thereof Download PDFInfo
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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
- C08L23/08—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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- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
The invention discloses an irradiation crosslinking heat shrinkable material and a preparation method thereof, the technical scheme of the invention adopts ethylene-vinyl acetate copolymer with high VA content, ethylene-vinyl acetate copolymer with low VA content, specific rubber, ethylene-acrylate copolymer, metal hydroxide flame retardant, nitrogen-phosphorus flame retardant, microencapsulated red phosphorus flame retardant and antioxidant as raw materials, the proportion of the raw materials is reasonably set, the raw materials are mutually matched and have synergistic action, unexpected technical effect is obtained, and the irradiation crosslinking heat shrinkable material has the following characteristics at the same time: (1) high flame retardance: the flame retardant rating can reach the flame retardant rating of US UL224 VW-1; (2) the processing and forming are easy; (3) low temperature (below 90 ℃) shrinkage; (4) the tensile strength is high, and the elongation at break is large; (5) the thermal stability is good.
Description
Technical Field
The invention relates to the technical field of heat shrinkable tubes, in particular to an irradiation crosslinking heat shrinkable material and a preparation method thereof.
Background
The heat shrinkable material is a functional polymer material prepared by taking a rubber plastic material as a base material and mixing, molding, crosslinking, heating, expanding, cooling and shaping by utilizing the principle of 'elastic memory' of a high polymer. Since the development of the middle of the fifties of the last century to date, heat-shrinkable materials have become important functional materials and are widely used in the fields of sealing and corrosion prevention of chemical engineering and petroleum pipelines, joint insulation protection of household appliances, control cables, national defense communication and power cables, shielding connection of electrical components, insulation sealing and the like.
CN1760997A discloses an environment-friendly halogen-free flame-retardant heat-shrinkable tube. The heat-shrinkable tubing is prepared by mixing, granulating, extruding and molding, radiating, crosslinking and expanding and shaping ethylene-vinyl acetate copolymer, silicon rubber, microcapsule red phosphorus, phosphorus-nitrogen flame retardant, inorganic flame retardant, lubricant, antioxidant, color master batch and light stabilizer. It has good flame retardancy but poor low-temperature shrinkage properties.
CN1357572A discloses a method for preparing a heat-shrinkable tube from a trans-polyisoprene blend, which comprises the steps of adding an antioxidant, a flame retardant and a processing aid into trans-polyisoprene (TPI) and an ethylene-vinyl acetate copolymer (EVA30/10), blending, extruding the tube, irradiating the tube by cobalt 60, expanding, cooling and shaping. The prepared heat shrinkable tube can be completely shrunk at 70 ℃, and the long-term use temperature reaches 105 ℃. It has good low-temperature shrinkage properties but poor flame retardancy.
CN1266867A discloses a low-smoke halogen-free flame-retardant radiation crosslinking polyolefin heat shrinkable material shrinkable at lower temperature (less than or equal to 90 ℃). The flame-retardant and flame-retardant composite material is prepared by mixing, extruding and granulating ethylene-vinyl acetate copolymer, ethylene propylene diene monomer, antioxidant, halogen-free flame retardant, smoke suppressor, lubricant and crosslinking aid, extruding into a pipe, and performing radiation crosslinking. It has poor flame retardancy and low tensile strength.
CN106188868A discloses a halogen-free flame-retardant low-temperature shrinkable tube and a preparation method thereof, the halogen-free flame-retardant low-temperature shrinkable tube comprises the following components in parts by weight: 50-80 parts of polypropylene, 10-40 parts of olefin-acrylate copolymer, 5-10 parts of melamine flame retardant, 0.5-5 parts of nano active calcium carbonate, 0.5-5 parts of lubricant and 0.5-5 parts of antioxidant. The halogen-free flame-retardant low-temperature shrinkable heat shrinkable tube overcomes the problem of high response temperature (above 120 ℃), and can realize complete shrinkage at a low temperature (below 90 ℃). But it has poor flame retardancy and poor thermal stability.
CN101885917A discloses a silicone heat-shrinkable sleeve and a preparation method thereof, which is prepared from methyl vinyl silicone rubber crude rubber, ethylene-methyl methacrylate copolymer, an antioxidant and a lubricant, and the method comprises the following steps: the material is prepared by high-temperature mixing, extrusion molding to form a tubular object, and processes such as electron irradiation crosslinking, expansion, shaping and the like. The large-caliber silicone resin soft heat-shrinkable tubing manufactured by the invention has the characteristics of good thermal stability, low hardness and low-temperature shrinkage, can be used for occasions requiring environment-friendly soft heat-shrinkable tubing with low-temperature shrinkage, and has good industrialization prospect. However, it has the disadvantage of difficult preforming and low processing efficiency.
CN100369968C discloses an irradiation cross-linking low-smoke halogen-free phosphorus-free nanometer flame-retardant heat-shrinkable material, which comprises the following components: ethylene-vinyl acetate copolymer, ethylene-octene copolymer, polymer compatilizer, organic silicon polymer, composite antioxidant, nano magnesium hydroxide flame retardant, surface activated superfine aluminum hydroxide or magnesium hydroxide, lubricant, sensitizer and the like, and is prepared by mixing, stirring, extruding, drawing, air cooling, granulating, irradiating, expanding, stretching, cooling and sizing. The heat shrinkable material has excellent flame retardant effect, does not contain halogen-containing flame retardant and phosphorus-containing flame retardant, is an environment-friendly product, has little influence on the ecological environment and human health after the material is processed, used and discarded, has wide application, simple and easy preparation method, easily obtained raw materials and low price, and is suitable for industrial production. But the tensile strength of the product is generally lower (9-11MPa), and the requirement of low-temperature shrinkage cannot be met.
CN102766293A discloses an irradiation crosslinking low-smoke halogen-free red phosphorus-free flame retardant material, which comprises: 10-80 parts by weight of ethylene-vinyl acetate copolymer; 5-30 parts by weight of ethylene-octene copolymer and/or ethylene-butene copolymer and/or ethylene-propylene-diene monomer; 0-100 parts by weight of polyethylene; 1-20 parts by weight of a polymer compatibilizer; 0.5-10 parts by weight of an organosilicon polymer; 1-10 parts of a composite antioxidant; 0-200 parts by weight of aluminum hydroxide and/or magnesium hydroxide and/or modified aluminum hydroxide and/or modified magnesium hydroxide; 0.1-100 parts of high molecular weight ammonium polyphosphate and/or 0.1-50 parts of phosphate flame retardant and/or 0.1-50 parts of melamine cyanurate, and the flame retardant can reach the American UL224VW-1 standard when applied to heat-shrinkable sleeves, and the flame retardant grade can reach the American UL1581VW-1 standard when applied to electric wires and cables, does not contain halogen or red phosphorus, and is environment-friendly. But the complete shrinkage temperature of the prepared heat-shrinkable tubing is 115-125 ℃, and the requirement of low-temperature shrinkage cannot be met.
However, in the process of implementing the embodiments of the present application, the inventors of the present application found that the above-mentioned technology has at least the following technical problems: the heat shrinkable material in the prior art is difficult to simultaneously combine high flame retardance, good processing formability, low-temperature (below 90 ℃) shrinkability, excellent mechanical property and thermal stability.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention mainly aims to provide a radiation crosslinking heat shrinkable material and a preparation method thereof, and the radiation crosslinking heat shrinkable material has the characteristics of high flame retardance, easiness in processing and forming, low-temperature (below 90 ℃) shrinkage, high tensile strength, large elongation at break and good thermal stability.
The technical problem to be solved by the invention is realized by the following technical scheme:
in one aspect of the invention, the invention provides a radiation crosslinking heat shrinkable material, which comprises the following raw materials in parts by weight:
15-100 parts of ethylene-vinyl acetate copolymer with high VA content, 1-50 parts of ethylene-vinyl acetate copolymer with low VA content, 1-30 parts of rubber, 1-50 parts of ethylene-acrylate copolymer, 5-120 parts of metal hydroxide flame retardant, 1-50 parts of nitrogen-phosphorus flame retardant, 3-30 parts of microencapsulated red phosphorus flame retardant and 0.5-5 parts of antioxidant.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28-40%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 15-20%; the rubber is at least one of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene rubber (SBR), Butadiene Rubber (BR), nitrile rubber (NBR) and Natural Rubber (NR).
Optionally, the ethylene-acrylate copolymer is at least one of ethylene-methacrylate, ethylene-ethyl acrylate, and ethylene-butyl acrylate; the ethylene-acrylate copolymer has a melt index of 0.5 to 6g/10min at 190 ℃ under a pressure of 2.16 kg.
Optionally, the metal hydroxide flame retardant is at least one of magnesium hydroxide, aluminum hydroxide, modified magnesium hydroxide, and modified aluminum hydroxide.
Optionally, the nitrogen-phosphorus flame retardant is at least one of melamine cyanurate and phosphinate.
Optionally, the Shore hardness of the rubber is less than or equal to 80; the Mooney viscosity of the styrene-butadiene rubber (SBR), the Butadiene Rubber (BR), the nitrile-butadiene rubber (NBR) and the Natural Rubber (NR) is ML (1+4) at 100 ℃ of 20-50.
Optionally, the metal hydroxide flame retardant has an average particle size D50 of less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
Optionally, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DSTP, antioxidant DLTP, antioxidant CPL, antioxidant 1035, antioxidant 300 and antioxidant 330.
Optionally, 0-5 parts of a lubricant is further included; the lubricant is at least one of ethylene bis stearamide, stearic acid lubricant and silicon-containing lubricant, and the silicon-containing lubricant is silicone oil, silicone rubber, silicone powder and silicone master batch.
Optionally, the lubricant is at least one of ethylene bis stearamide, a stearic acid based lubricant.
Optionally, the color masterbatch also comprises 0-10 parts of carbon black and/or color masterbatch.
In another aspect of the present invention, the present invention provides a method for preparing the above radiation cross-linking heat shrinkable material, comprising the steps of:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 5 to 10 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 20 to 80 ℃; then extruding, drawing and air-cooling and granulating the mixture at the temperature of 100-160 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 100-160 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 4-12 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 100-360 ℃ by using expansion equipment; and (6) cooling and shaping.
Optionally, in the extruding step, adding a hot melt adhesive for extruding together; or, after the expanding step, gluing the inner wall of the pipe.
The invention has the following beneficial effects:
the technical scheme of the invention adopts ethylene-vinyl acetate copolymer with high VA content, ethylene-vinyl acetate copolymer with low VA content, specific rubber, ethylene-acrylate copolymer, metal hydroxide flame retardant, nitrogen-phosphorus flame retardant, microencapsulated red phosphorus flame retardant and antioxidant as raw materials, reasonably sets the proportion of the raw materials, and the raw materials are matched with each other, has synergistic effect, obtains unexpected technical effect, and ensures that the irradiation crosslinking heat shrinkable material has the following characteristics at the same time: (1) high flame retardance: the flame retardant grade can reach the flame retardant grade of US UL224VW-1, and the halogen-free flame retardant avoids the generation of toxic hydrogen halide gas and smoke by halogen-containing materials during combustion when the traditional halogen-containing irradiation crosslinking flame retardant material is in fire; (2) easy machine-shaping: the irradiation crosslinking heat shrinkable material is easier to process by using the existing method, can be extruded and expanded to be processed and molded by using a general pipe processing method, and has high finished product shrinkage; (3) low temperature (below 90 ℃) shrinkage: the shrinkage temperature of the irradiation crosslinking thermal shrinkage material is low, the heating shrinkage at 78-90 ℃ can be realized, and the irradiation crosslinking thermal shrinkage material is suitable for occasions where high-temperature heating shrinkage cannot be realized and occasions where hot water is used for heating shrinkage; (4) high tensile strength and large elongation at break: the irradiation crosslinking heat shrinkable material has the tensile strength of more than 12MPa at normal temperature and the elongation at break of 400-600 percent; (5) the thermal stability is good: after the irradiation crosslinking thermal contraction material is thermally aged at 158 ℃ for 168 hours, the tensile strength is kept above 12MPa, and the elongation at break is above 300%.
The irradiation crosslinking thermal contraction material of the invention has simple preparation method, easily obtained raw materials and low price, and is suitable for industrial production.
Detailed Description
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
Unless otherwise defined, terms used in the present specification have the same meaning as those generally understood by those skilled in the art, but in case of conflict, the definitions in the present specification shall control.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
All numbers or expressions referring to quantities of ingredients, process conditions, etc. used in the specification and claims are to be understood as modified in all instances by the term "about". All ranges directed to the same component or property are inclusive of the endpoints, and independently combinable. Because these ranges are continuous, they include every value between the minimum and maximum values. It should also be understood that any numerical range recited herein is intended to include all sub-ranges within that range.
As used herein, "parts by weight" or "parts by weight" are used interchangeably and can be any fixed weight expressed in milligrams, grams, or kilograms (e.g., 1mg, 1g, 2g, 5g, or 1kg, etc.). For example, a composition consisting of 1 part by weight of component a and 9 parts by weight of component b may be a composition consisting of 1g of component a +9 g of component b, or 10 g of component a +90 g of component b.
As described in the background art, the prior art has the problem that the heat shrinkable material is difficult to simultaneously combine high flame retardancy, good processability, low-temperature (below 90 ℃) shrinkability, excellent mechanical properties and thermal stability. In order to solve the technical problems, the invention provides a radiation crosslinking heat shrinkable material and a preparation method thereof.
In a first aspect, a radiation crosslinking heat shrinkable material comprises the following raw materials in parts by weight:
15-100 parts of ethylene-vinyl acetate copolymer with high VA content, 1-50 parts of ethylene-vinyl acetate copolymer with low VA content, 1-30 parts of rubber, 1-50 parts of ethylene-acrylate copolymer, 5-120 parts of metal hydroxide flame retardant, 1-50 parts of nitrogen-phosphorus flame retardant, 3-30 parts of microencapsulated red phosphorus flame retardant and 0.5-5 parts of antioxidant.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28-40%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 15-20%; the rubber is at least one of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene rubber (SBR), Butadiene Rubber (BR), nitrile rubber (NBR) and Natural Rubber (NR).
The technical scheme of the invention adopts ethylene-vinyl acetate copolymer with high VA content, ethylene-vinyl acetate copolymer with low VA content, specific rubber, ethylene-acrylate copolymer, metal hydroxide flame retardant, nitrogen-phosphorus flame retardant, microencapsulated red phosphorus flame retardant and antioxidant as raw materials, reasonably sets the proportion of the raw materials, and the raw materials are matched with each other, has synergistic effect, obtains unexpected technical effect, and ensures that the irradiation crosslinking heat shrinkable material has the following characteristics at the same time: (1) high flame retardance: the flame retardant grade can reach the flame retardant grade of US UL224VW-1, and the halogen-free flame retardant avoids the generation of toxic hydrogen halide gas and smoke by halogen-containing materials during combustion when the traditional halogen-containing irradiation crosslinking flame retardant material is in fire; (2) easy machine-shaping: the irradiation crosslinking thermal contraction material is easier to process by using the existing method, can be extruded and expanded by using a general pipe processing method, and has high yield; (3) low temperature (below 90 ℃) shrinkage: the shrinkage temperature of the irradiation crosslinking thermal shrinkage material is low, the heating shrinkage at 78-90 ℃ can be realized, and the irradiation crosslinking thermal shrinkage material is suitable for occasions where high-temperature heating shrinkage cannot be realized and occasions where hot water is used for heating shrinkage; (4) high tensile strength and large elongation at break: the irradiation crosslinking heat shrinkable material has the tensile strength of more than 12MPa at normal temperature and the elongation at break of 400-600 percent; (5) the thermal stability is good: after the irradiation crosslinking thermal contraction material is thermally aged at 158 ℃ for 168 hours, the tensile strength is kept above 12MPa, and the elongation at break is above 300%.
It should be noted that the technical effect of the present invention is the sum of synergistic effects of all technical features, and all raw materials have certain inherent correlation, and are not simple superposition of the effects of individual technical features.
High VA content ethylene-vinyl acetate copolymer and low VA content ethylene-vinyl acetate copolymer
In the present invention, the high VA content ethylene-vinyl acetate copolymer is 15 to 100 parts by weight, for example, 15 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, and any value therebetween.
The weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28-40%, such as 28%, 30%, 32%, 34%, 36%, 38%, 40% and any value between the two.
In the present invention, the ethylene-vinyl acetate copolymer having a low VA content is 1 to 50 parts, for example, 1 part, 5 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and any value therebetween.
The ethylene-vinyl acetate copolymer with low VA content has the weight percentage of VA of 15-20%, such as 15%, 16%, 17%, 18%, 19%, 20% and any value in between.
Rubber composition
In the present invention, the rubber is 1 to 30 parts by weight, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts and any value therebetween.
When the rubber is two or more selected from the above specific choices, the present invention does not have any particular limitation on the ratio of each substance, and the rubber may be mixed in any ratio.
The Shore hardness of the rubber is less than or equal to 80; the Mooney viscosity of the styrene-butadiene rubber (SBR), the Butadiene Rubber (BR), the nitrile-butadiene rubber (NBR) and the Natural Rubber (NR) is ML (1+4) at 100 ℃ of 20-50.
The inventor finds that not all the rubber can be compounded with other raw materials to simultaneously have the characteristics of high flame retardance, easy processing and forming, low-temperature (below 90 ℃) shrinkage, high tensile strength, large elongation at break and good thermal stability, and only the specific type of rubber is compounded with other raw materials to simultaneously have the characteristics of high flame retardance, easy processing and forming, low-temperature (below 90 ℃) shrinkage, high tensile strength, large elongation at break and good thermal stability.
Ethylene-acrylic ester copolymer
In the present invention, the ethylene-acrylic acid ester copolymer is 1 to 50 parts by weight, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and any value therebetween.
The ethylene-acrylate copolymer of the present invention is not particularly limited, and may be prepared by a known method or may be commercially available, as long as it is an ethylene-acrylate copolymer known to those skilled in the art. Preferably, the ethylene-acrylate copolymer is at least one of ethylene-methacrylate, ethylene-ethyl acrylate, and ethylene-butyl acrylate.
When the ethylene-acrylic acid ester copolymer is two or more selected from the above specific choices, the present invention does not have any particular limitation on the ratio of each substance, and the ethylene-acrylic acid ester copolymer may be mixed in any ratio.
In the invention, the melt index of the ethylene-acrylate copolymer is 0.5-6 g/10min at 190 ℃ and under 2.16kg pressure.
Flame retardant
In the present invention, the metal hydroxide flame retardant is 5 to 120 parts by weight, for example, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, and any value therebetween.
In the present invention, the nitrogen-phosphorus flame retardant is 1 to 50 parts by weight, for example, 1 part, 5 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and any value therebetween.
In the present invention, the microencapsulated red phosphorus flame retardant is used in an amount of 3 to 30 parts by weight, for example, 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, and any value therebetween.
Because of the adoption of the microencapsulated red phosphorus flame retardant, the water-absorbing agent is not easy to absorb moisture and hydrolyze, and the safety is greatly improved.
In the invention, the metal hydroxide flame retardant is at least one of magnesium hydroxide, aluminum hydroxide, modified magnesium hydroxide and modified aluminum hydroxide.
In the present invention, the specific preparation method of the modified magnesium hydroxide and the modified aluminum hydroxide is not particularly limited, and may be a conventional modification method when used as a flame retardant, and the modified magnesium hydroxide is a surfactant-modified magnesium hydroxide and the modified aluminum hydroxide is a surfactant-modified aluminum hydroxide, for example.
In the invention, the nitrogen-phosphorus flame retardant is at least one of melamine cyanurate and phosphinate.
In the present invention, the average particle diameter D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
With the increasing use of heat shrinkable materials, electrical fire accidents frequently occur, and the problem of flame retardancy of heat shrinkable materials gradually draws attention from countries around the world. Therefore, the heat shrinkable material must have flame retardancy or flame retardancy, and the heat shrinkable material is made of a polymer material having flame retardancy, so that the corresponding polymer material is subjected to flame retardant modification in the production of the heat shrinkable tube. Most of flame-retardant heat-shrinkable materials in the prior art are halogen-containing, and although the flame-retardant heat-shrinkable materials have a certain flame-retardant effect, when a fire disaster occurs, the burning heat-shrinkable materials still generate toxic gas and smoke, so that the smooth operation of disaster relief work is influenced, and 'second disaster' is caused to lives and properties. Therefore, the development of an environmentally friendly, highly flame retardant, halogen-free flame retardant heat shrinkable material is urgently required.
According to the invention, the metal hydroxide flame retardant, the nitrogen-phosphorus flame retardant and the microencapsulated red phosphorus flame retardant are compounded to serve as the flame retardant, so that the flame retardant property of the thermal contraction material can be greatly improved, and the halogen-free flame retardant is not contained, so that the phenomenon that the halogen-containing material generates toxic hydrogen halide gas and smoke during combustion when the traditional halogen-containing irradiation crosslinking flame retardant material is in a fire disaster is avoided, the heating and smoke quantity in the combustion process is low, the harm to the environment and human bodies is small, and the environment-friendly low-smoke halogen-free flame retardant pollution-free cleaning product is provided.
In the invention, from the consideration of comprehensive performance of the whole technical scheme, based on the mutual influence and cooperation with other materials, the metal hydroxide flame retardant, the nitrogen-phosphorus flame retardant and the microencapsulated red phosphorus flame retardant are selected to be compounded to be used as the flame retardant, the flame retardant has good compatibility with other raw materials, each component is synergistic, the influence on mechanical properties is small, the flame retardant has high flame retardant property, and the flame retardant property can pass UL224VW-1 level.
Antioxidant agent
By adding the antioxidant, the invention can delay or inhibit the oxidation process of the raw materials and prolong the service life of the heat shrinkable material.
In the present invention, the antioxidant is 0.5 to 5 parts by weight, for example, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, and any value therebetween.
The antioxidant of the present invention is not particularly limited, and may be one known to those skilled in the art, prepared by a known method or commercially available. Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DSTP, antioxidant DLTP, antioxidant CPL, antioxidant 1035, antioxidant 300 and antioxidant 330.
Lubricant agent
As a further improvement, the lubricant further comprises 0-5 parts of lubricant, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts and any value in between.
The lubricant of the present invention is not particularly limited, and may be one known to those skilled in the art, prepared by a known method or commercially available. Preferably, the lubricant is at least one of ethylene bis stearamide, a stearic acid type lubricant and a silicon-containing lubricant. More preferably, the lubricant is at least one of ethylene bis stearamide and a stearic acid type lubricant.
The silicon-containing lubricant may be, for example, silicone oil, silicone rubber, silicone powder, or silicone master batch, but is not limited thereto.
The stearic acid-based lubricant may be exemplified by zinc stearate, but is not limited thereto.
Carbon black and/or color masterbatch
As a further improvement, the color masterbatch also comprises 0-10 parts of carbon black and/or color masterbatch, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and any value between the parts.
In a second aspect, there is provided a method for preparing the radiation cross-linking heat shrinkable material of the first aspect, comprising the steps of:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 5 to 10 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 20 to 80 ℃; then extruding, drawing and air-cooling and granulating the mixture at the temperature of 100-160 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 100-160 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 4-12 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 100-360 ℃ by using expansion equipment; and (6) cooling and shaping.
Further, in the extrusion step, adding hot melt adhesive for extrusion; or, after the expanding step, gluing the inner wall of the pipe.
The irradiation crosslinking thermal contraction material is easier to process by using the existing method, can be extruded and expanded by using a general pipe processing method, and has high yield.
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to specific examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Examples 1 to 6 and comparative examples 1 to 7 were prepared according to the formulations shown in Table 1, respectively.
TABLE 1
Example 1
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
60 parts of ethylene-vinyl acetate copolymer with high VA content, 10 parts of ethylene-vinyl acetate copolymer with low VA content, 28 parts of rubber, 2 parts of ethylene-acrylate copolymer, 90 parts of metal hydroxide flame retardant, 15 parts of nitrogen-phosphorus flame retardant, 10 parts of microencapsulated red phosphorus flame retardant and 1 part of antioxidant.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 18 percent; the rubber is hydrogenated styrene-butadiene-styrene block copolymer (SEBS); the ethylene-acrylate copolymer is ethylene-methacrylate; the metal hydroxide flame retardant is magnesium hydroxide and aluminum hydroxide; the nitrogen-phosphorus flame retardant is phosphinate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is 1010; the lubricant is ethylene bis stearamide.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 8 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 60 ℃; then extruding, drawing, air-cooling and granulating the mixture at 120 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 120 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 8 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 250 ℃ by using expansion equipment; and (6) cooling and shaping.
Example 2
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
75 parts of ethylene-vinyl acetate copolymer with high VA content, 30 parts of ethylene-vinyl acetate copolymer with low VA content, 15 parts of rubber, 10 parts of ethylene-acrylate copolymer, 78 parts of metal hydroxide flame retardant, 1 part of nitrogen-phosphorus flame retardant, 12 parts of microencapsulated red phosphorus flame retardant, 3 parts of antioxidant, 4 parts of lubricant and 5 parts of carbon black and/or color master batch.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 30%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 18 percent; the rubber is styrene-isoprene-styrene block copolymer (SIS) and Natural Rubber (NR); the ethylene-acrylate copolymer is ethylene-butyl acrylate; the metal hydroxide flame retardant is magnesium hydroxide; the nitrogen-phosphorus flame retardant is melamine cyanurate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is an antioxidant 1076; the lubricant is zinc stearate.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 8 minutes at a high speed, wherein the temperature of the materials is controlled within 50 ℃; then extruding, drawing, air-cooling and granulating the mixture at the temperature of 150 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 150 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 6 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at 180 ℃ by using expansion equipment; and (6) cooling and shaping.
Example 3
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
15 parts of ethylene-vinyl acetate copolymer with high VA content, 50 parts of ethylene-vinyl acetate copolymer with low VA content, 30 parts of rubber, 50 parts of ethylene-acrylate copolymer, 75 parts of metal hydroxide flame retardant, 5 parts of nitrogen-phosphorus flame retardant, 20 parts of microencapsulated red phosphorus flame retardant, 0.5 part of antioxidant, 3 parts of lubricant and 10 parts of carbon black and/or color master batch.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 40%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 15%; the rubber is styrene-butadiene-styrene block copolymer (SBS); the ethylene-acrylate copolymer is ethylene-ethyl acrylate; the metal hydroxide flame retardant is aluminum hydroxide; the nitrogen-phosphorus flame retardant is melamine cyanurate and phosphinate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is antioxidant DSTP; the lubricant is silicone oil.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 5 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 20 ℃; then extruding, drawing, air-cooling and granulating the mixture at the temperature of 100 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 100 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 4 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 100 ℃ by using expansion equipment; and (6) cooling and shaping.
Example 4
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
90 parts of ethylene-vinyl acetate copolymer with high VA content, 20 parts of ethylene-vinyl acetate copolymer with low VA content, 1 part of rubber, 5 parts of ethylene-acrylate copolymer, 60 parts of metal hydroxide flame retardant, 25 parts of nitrogen-phosphorus flame retardant, 15 parts of microencapsulated red phosphorus flame retardant, 2.5 parts of antioxidant, 2 parts of lubricant and 4 parts of carbon black and/or color master batch.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 20%; the rubber is Styrene Butadiene Rubber (SBR); the ethylene-acrylate copolymer is ethylene-ethyl acrylate; the metal hydroxide flame retardant is modified magnesium hydroxide; the nitrogen-phosphorus flame retardant is melamine cyanurate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is 1010 and CPL; the lubricant is ethylene bis stearamide and zinc stearate.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 10 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 80 ℃; then extruding, drawing, air-cooling and granulating the mixture at 160 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 160 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 12 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 360 ℃ by using expansion equipment; and (6) cooling and shaping.
Example 5
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
100 parts of ethylene-vinyl acetate copolymer with high VA content, 40 parts of ethylene-vinyl acetate copolymer with low VA content, 5 parts of rubber, 30 parts of ethylene-acrylate copolymer, 120 parts of metal hydroxide flame retardant, 30 parts of nitrogen-phosphorus flame retardant, 3 parts of microencapsulated red phosphorus flame retardant, 2 parts of antioxidant, 5 parts of lubricant and 3 parts of carbon black and/or color master batch.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 35%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 16%; the rubber is styrene-butadiene-styrene block copolymer (SBS) and cis-Butadiene Rubber (BR); the ethylene-acrylate copolymer is ethylene-methacrylate; the metal hydroxide flame retardant is modified aluminum hydroxide; the nitrogen-phosphorus flame retardant is phosphinate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is antioxidant 300 and antioxidant 330; the lubricant is zinc stearate.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 5 minutes at a high speed, wherein the temperature of the materials is controlled within 70 ℃; then extruding, drawing, air-cooling and granulating the mixture at 120 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 120 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 10 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at 260 ℃ by using expansion equipment; and (6) cooling and shaping.
Example 6
A radiation crosslinking heat shrinkable material is prepared from the following raw materials in parts by weight:
80 parts of ethylene-vinyl acetate copolymer with high VA content, 1 part of ethylene-vinyl acetate copolymer with low VA content, 10 parts of rubber, 1 part of ethylene-acrylate copolymer, 5 parts of metal hydroxide flame retardant, 50 parts of nitrogen-phosphorus flame retardant, 30 parts of microencapsulated red phosphorus flame retardant, 5 parts of antioxidant, 1 part of lubricant and 1 part of carbon black and/or color master.
Wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 38%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 18 percent; the rubber is Styrene Butadiene Rubber (SBR); the ethylene-acrylate copolymer is ethylene-methacrylate and ethylene-ethyl acrylate; the metal hydroxide flame retardant is modified magnesium hydroxide and modified aluminum hydroxide; the nitrogen-phosphorus flame retardant is melamine cyanurate.
The average particle size D50 of the metal hydroxide flame retardant is less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
The antioxidant is 1010 and 330; the lubricant is ethylene bis stearamide.
The preparation method of the irradiation crosslinking heat shrinkable material comprises the following steps:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 10 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 80 ℃; then extruding, drawing and air-cooling and granulating the mixture at 140 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 140 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 5 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at 180 ℃ by using expansion equipment; and (6) cooling and shaping.
Comparative example 1
Based on example 2, except that no high VA content ethylene-vinyl acetate copolymer was used.
Comparative example 2
Based on example 2, except that 52.5 parts of high VA content ethylene-vinyl acetate copolymer and 52.5 parts of low VA content ethylene-vinyl acetate copolymer were used, respectively.
Comparative example 3
Based on example 2, except that the rubber was a silicone rubber.
Comparative example 4
Based on example 2, except that no ethylene-acrylate copolymer was used.
Comparative example 5
Based on example 2, except that no metal hydroxide flame retardant was used.
Comparative example 6
Based on example 2, except that no nitrogen-phosphorus flame retardant was used.
Comparative example 7
Based on example 2, except that microencapsulated red phosphorus flame retardant was not used.
In order to verify the performance of the products of the present invention, the products prepared in examples 1 to 6 and comparative examples 1 to 7 were tested for their respective properties by the following specific methods, and the specific test results are shown in table 2:
tensile strength: the test method refers to test standard ASTM D2671, and the index requirement is more than or equal to 10.4 MPa;
elongation at break: the test method refers to test standard ASTM D2671, and the index requirement is more than or equal to 200%;
and (3) testing thermal stability: the test method refers to a test standard ASTM D2671, and the index requires that after 168 hours of heat aging at 158 ℃, the tensile strength is kept above 7.3MPa, and the elongation at break is above 100%;
volume resistivity: the test method refers to test standard IEC93, and index requirement is not less than 1 x 1014ΩΩcm；
And (3) insulating and voltage-withstanding test: the test method refers to test standard UL 224;
and (3) cold bending test: the test method refers to test standard UL224, and the index is required to be at-30 deg.C, and after 1hr, the product is bent without crack;
flame retardancy (VW-1 vertical Combustion test): the test method refers to test standard UL 224.
TABLE 2
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.
Claims (10)
1. The radiation crosslinking heat shrinkable material is characterized by comprising the following raw materials in parts by weight:
15-100 parts of ethylene-vinyl acetate copolymer with high VA content, 1-50 parts of ethylene-vinyl acetate copolymer with low VA content, 1-30 parts of rubber, 1-50 parts of ethylene-acrylate copolymer, 5-120 parts of metal hydroxide flame retardant, 1-50 parts of nitrogen-phosphorus flame retardant, 3-30 parts of microencapsulated red phosphorus flame retardant and 0.5-5 parts of antioxidant;
wherein the weight percentage content of VA in the ethylene-vinyl acetate copolymer with high VA content is 28-40%; the weight percentage content of VA in the ethylene-vinyl acetate copolymer with low VA content is 15-20%; the rubber is at least one of hydrogenated styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene rubber, nitrile rubber and natural rubber.
2. The radiation crosslinked heat shrinkable material of claim 1, wherein the ethylene-acrylate copolymer is at least one of ethylene-methacrylate, ethylene-ethyl acrylate, ethylene-butyl acrylate; the ethylene-acrylate copolymer has a melt index of 0.5 to 6g/10min at 190 ℃ under a pressure of 2.16 kg.
3. The radiation crosslinked heat shrinkable material of claim 1, wherein the metal hydroxide flame retardant is at least one of magnesium hydroxide, aluminum hydroxide, modified magnesium hydroxide, and modified aluminum hydroxide.
4. The radiation crosslinked heat shrinkable material of claim 1, wherein the nitrogen-phosphorus flame retardant is at least one of melamine cyanurate and phosphinate.
5. The radiation crosslinked heat shrinkable material of claim 1, wherein the metal hydroxide flame retardant has an average particle diameter D50 of less than 10 μm; the average particle size D50 of the nitrogen-phosphorus flame retardant is less than 10 μm; the average grain diameter D50 of the microencapsulated red phosphorus flame retardant is less than 50 mu m, and the phosphorus content is more than 80 percent.
6. The radiation crosslinked heat shrinkable material of claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DSTP, antioxidant DLTP, antioxidant CPL, antioxidant 1035, antioxidant 300, and antioxidant 330.
7. The radiation crosslinked heat shrinkable material of claim 1, further comprising 0 to 5 parts of a lubricant; the lubricant is at least one of ethylene bis stearamide, stearic acid lubricant and silicon-containing lubricant.
8. The radiation crosslinked heat shrinkable material of claim 1, further comprising 0 to 10 parts of carbon black and/or color masterbatch.
9. The method for producing the radiation crosslinked heat shrinkable material of any one of claims 1 to 8, comprising the steps of:
and (3) processing the master batch: weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, and stirring the raw materials for 5 to 10 minutes at a high speed, wherein the temperature of the materials is controlled within the range of 20 to 80 ℃; then extruding, drawing and air-cooling and granulating the mixture at the temperature of 100-160 ℃ by using a double-screw extruder to obtain master batches;
an extrusion step: extruding the master batch into a tube at the temperature of 100-160 ℃ through single screw extrusion to obtain an extruded tube;
an irradiation step: irradiating the extruded pipe by an electron accelerator or a cobalt source, wherein the irradiation dose is 4-12 Mrad;
an expansion step: expanding the irradiated pipe by 1-3 times at the temperature of 100-360 ℃ by using expansion equipment; and (6) cooling and shaping.
10. The method for producing a radiation crosslinked heat shrinkable material of claim 9, further comprising, in the extruding step, adding a hot melt adhesive to extrude together; or, after the expanding step, gluing the inner wall of the pipe.
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