CN112812508A - Flame-retardant TPEE material for automobile cable and preparation method thereof - Google Patents

Flame-retardant TPEE material for automobile cable and preparation method thereof Download PDF

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CN112812508A
CN112812508A CN202011524531.2A CN202011524531A CN112812508A CN 112812508 A CN112812508 A CN 112812508A CN 202011524531 A CN202011524531 A CN 202011524531A CN 112812508 A CN112812508 A CN 112812508A
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flame
retardant
tpee
master batch
flame retardant
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苏迎旭
王彬
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Jiangyin Excen Broaden Polymer Co ltd
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Jiangyin Excen Broaden Polymer Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Abstract

The invention discloses a flame-retardant TPEE material for automobile cables, which comprises the following raw materials in parts by weight: 70-80 parts of TPEE, 10-30 parts of flame-retardant master batch, 0.5-1 part of OP wax, 0.5-3 parts of internal lubricant, 0.5-1 part of antioxidant, 0.5-1 part of anti-dripping agent and 0.1-0.5 part of antiozonant. The invention provides a preparation method of a flame-retardant TPEE material for automobile cables. The compatibility between the flame retardant and the TPEE is increased by adding the flame-retardant master batch; adding a lubricant OP wax to reduce the precipitation of a flame retardant, reduce the degradation of the material in the extrusion process and improve the uniformity of each component in a material system; the internal lubricant is added, so that the current situation that the surface of the material is not smooth after the flame retardant is added is improved, the viscosity of the TPEE is reduced, and the fluidity of the TPEE material is improved; the flame-retardant master batch, the OP wax and the internal lubricant have synergistic effect, so that the uniformity of the flame-retardant effect is greatly improved, and the flame-retardant master batch is better suitable for automobile cables.

Description

Flame-retardant TPEE material for automobile cable and preparation method thereof
Technical Field
The invention relates to the technical field of TPEE composite materials, in particular to a flame-retardant TPEE material for automobile cables and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is widely used as an insulating material for electric wires and cables because of its good mechanical properties, tensile strength, impact strength and excellent dielectric properties. However, in the use process of the existing cable, the phenomenon of spontaneous combustion easily occurs due to the generation of a large amount of heat caused by resistance, flame cannot be quickly extinguished in the combustion process, so that the cable is seriously damaged, and along with the long-time sunlight exposure of the cable, the problems of poor heat resistance, poor aging resistance and the like of PVC (polyvinyl chloride) can cause the decomposition of PVC, the discoloration is caused, and the physical and mechanical properties are also quickly reduced. In practical application, additives such as high-temperature-resistant stabilizers and flame retardants are often added to stabilize and improve the stability to light and heat and the flame retardant effect; however, due to the addition of a large amount of additives, additives or flame retardant substances are precipitated as the service life is normal, and the flame retardant effect of the cable is lost and uneven, so that a composite material for the cable, which is resistant to high and low temperatures, stable in flame retardant performance and low in material cost, is needed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a flame-retardant TPEE material for automobile cables, which has excellent high-low temperature resistance, reduces the precipitation of a flame retardant and has stable flame retardant property.
The invention also aims to provide a preparation method of the flame-retardant TPEE material for the automobile cable.
In order to achieve the purpose, the invention provides a flame-retardant TPEE material for automobile cables, which comprises the following raw materials in parts by weight: 70-80 parts of TPEE, 10-30 parts of flame-retardant master batch, 0.5-1 part of OP wax, 0.5-3 parts of internal lubricant, 0.5-1 part of antioxidant, 0.5-1 part of anti-dripping agent and 0.1-0.5 part of antiozonant. TPEE (thermoplastic polyester elastomer) is a block copolymer, which is formed by alternately arranging amorphous aliphatic polyester or polyether soft segments and aromatic polyester hard segments to form a two-phase structure, wherein the hard segments are crystallized to play a role in physical crosslinking and stabilize the size of a product, and the soft segments are amorphous to endow polymers with high resilience. TPEE has both the flexibility and elasticity of rubber, and the rigidity and easy processability of thermoplastics. However, TPEE is extremely easily combustible, has a Limited Oxygen Index (LOI) of only about 19%, and drips during combustion, and drips during a fire to cause a risk of spreading a flame or burning, and therefore, a flame retardant needs to be additionally added; if the flame retardant is directly added, the flame retardant is not uniformly mixed in the processing and manufacturing process, and the flame retardant is easily separated out, so that the flame retardant effect is poor. The compatibility between the flame retardant and the TPEE is increased by adding the flame-retardant master batch; adding a lubricant OP wax to reduce the precipitation of a flame retardant, reduce the degradation of the material in the extrusion process and improve the uniformity of each component in a material system; the internal lubricant is added, so that the current situation that the surface of the material is not smooth after the flame retardant is added is improved, the viscosity of the TPEE is reduced, and the fluidity of the TPEE material is improved; however, the more the addition amount of the OP wax and the internal lubricant is, the better the OP wax is, and the OP wax is added into a TPEE system, which is beneficial to the dispersion of the flame-retardant master batch; but the viscosity of the TPEE system is reduced while the OP wax is added, so that the shearing force which can be transferred to the surface of the flame-retardant master batch in the processing process is greatly reduced, and the dispersion of the flame retardant is not favorable. Therefore, the proportion of the flame-retardant master batch, the OP wax and the internal lubricant in the whole TPEE system is obtained according to a plurality of tests; the flame-retardant master batch, the OP wax and the internal lubricant act synergistically, so that the uniformity of the flame-retardant effect is greatly improved.
The preferable technical scheme is that the flame-retardant master batch comprises, by mass, 5% -10% of TPEE, 40% -45% of polylactic acid, 40% -50% of a main flame retardant and 5% -10% of a synergistic flame retardant. In the flame-retardant master batch, a small amount of TPEE, polylactic acid with excellent compatibility, a main flame retardant and a synergistic flame retardant are added for blending and granulation, so that the dispersibility and compatibility of the main flame retardant and the synergistic flame retardant in a TPEE material system are obviously improved, the flame-retardant uniformity of the main flame retardant and the synergistic flame retardant in the subsequent use process is further improved, and the precipitation effect of the flame retardant is reduced.
In order to further improve the uniformity of the flame retardant effect and reduce the precipitation of the flame retardant, a more preferable technical scheme is that the viscosity of the TPEE is 1.25-1.3, and the hardness is 50-72D. The TPEE with proper viscosity and hardness is selected, so that a good stable and balanced flame retardant effect can be formed among the TPEE, the added OP wax, the internal lubricant and the flame retardant master batch, the viscosity of a TPEE system can not be reduced in a transition manner, the TPEE is balanced, and in addition, the high and low temperature resistance of the material can be improved by selecting the TPEE with proper viscosity and hardness.
Further preferred technical scheme is that the internal lubricant is lipid internal lubricant; the antiozonant is 3, 9-di-3-cyclohexene-1-yl-2, 4,8, 10-tetraoxaspiro [5.5] undecane. The lipid internal lubricant has the characteristics of low melting point and low viscosity, can quickly wet the particle surface, and improves the dispersibility of the particles.
The further preferable technical scheme is that the main flame retardant is melamine phosphate and/or melamine polyphosphate, and the synergistic flame retardant is one or more of zinc borate, zirconium phosphate and organic montmorillonite.
The further preferable technical scheme is that the antioxidant comprises one or more of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 164; the anti-dripping agent is polytetrafluoroethylene with the molecular weight of 400-500 ten thousand.
The invention provides a preparation method of a flame-retardant TPEE material for automobile cables, which comprises the following steps:
s1: preparing a flame-retardant master batch: firstly, weighing TPEE, PLA, a main flame retardant and a synergistic flame retardant according to the mass percentage of a flame-retardant master batch formula, then drying the TPEE and the PLA in a vacuum drying oven at 45 ℃ for 12 hours, then placing the TPEE, the PLA, the main flame retardant and the synergistic flame retardant into an internal mixer for blending according to the mass percentage, adding the well-mixed materials from a feed inlet of a double-screw extruder, extruding and granulating to obtain flame-retardant master batches;
s2: drying the base material: weighing TPEE required in the flame-retardant TPEE material, adding the TPEE into a reaction kettle, and drying for 1h at 120 ℃, wherein the rotating speed of the reaction kettle is 3.5-4 rpm/min;
s3: and (3) mixing auxiliary materials: weighing the flame-retardant master batch obtained in the step S1, weighing OP wax, an internal lubricant, an antioxidant, an anti-dripping agent and an antiozonant, adding the materials into a high-speed mixer, and mixing for 0.5-1h at 120-150 ℃;
s4: and (4) sequentially putting the mixture obtained in the step (S2) and the step (S3) into a weightless scale, feeding the mixture into a screw extruder through a main feeding system of the double-screw extruder, blending, melting and granulating to obtain the flame-retardant TPEE material for the automobile, and cooling and packaging the finished product.
The invention has the advantages and beneficial effects that: the compatibility between the flame retardant and the TPEE is increased by adding the flame-retardant master batch; adding a lubricant OP wax to reduce the precipitation of a flame retardant, reduce the degradation of the material in the extrusion process and improve the uniformity of each component in a material system; the internal lubricant is added, so that the current situation that the surface of the material is not smooth after the flame retardant is added is improved, the viscosity of the TPEE is reduced, and the fluidity of the TPEE material is improved; however, the more the addition amount of the OP wax and the internal lubricant is, the better the OP wax is, and the OP wax is added into a TPEE system, which is beneficial to the dispersion of the flame-retardant master batch; but the viscosity of the TPEE system is reduced while the OP wax is added, so that the shearing force which can be transferred to the surface of the flame-retardant master batch in the processing process is greatly reduced, and the dispersion of the flame retardant is not favorable. Therefore, the proportion of the flame-retardant master batch, the OP wax and the internal lubricant in the whole TPEE system is obtained according to a plurality of tests; the flame-retardant master batch, the OP wax and the internal lubricant act synergistically, so that the uniformity of the flame-retardant effect is greatly improved; the TPEE with proper viscosity and hardness is selected, so that a better stable and balanced flame retardant effect can be formed with the added OP wax, the internal lubricant and the flame retardant master batch, the viscosity of a TPEE system can not be reduced in a transition manner, and the TPEE can reach balance, and in addition, the high and low temperature resistance of the material can be improved by selecting the TPEE with proper viscosity and hardness; the flame-retardant TPEE material for the automobile cable provided by the invention has the advantages of excellent high-low temperature resistance, reduction of precipitation of a flame retardant and stable flame-retardant property, and the flame-retardant grade of the TPEE material reaches UL-94VO grade, so that the TPEE material can be better suitable for the automobile cable.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The invention relates to a flame-retardant TPEE material for automobile cables, which comprises the following raw materials in parts by weight: 75 portions of TPEE with the viscosity of 1.25 to 1.3 and the hardness of 50 to 72D, 20 portions of flame-retardant master batch, 0.75 portion of OP wax, 1.8 portions of internal lubricant, 0.75 portion of antioxidant, 0.75 portion of polytetrafluoroethylene with the molecular weight of 400 to 500 ten thousand and 0.3 portion of antiozonant.
The internal lubricant is lipid internal lubricant lubde; the antiozonant is 3, 9-di-3-cyclohexene-1-yl-2, 4,8, 10-tetraoxaspiro [5.5] undecane.
A preparation method of a flame-retardant TPEE material for automobile cables comprises the following steps:
s1: preparing a flame-retardant master batch: weighing 7.5 parts of TPEE, 42.5 parts of PLA, 45 parts of main flame retardant and 5 parts of synergistic flame retardant according to the formula mass percentage of the flame-retardant master batch, drying the weighed TPEE and PLA in a vacuum drying oven at 45 ℃ for 12 hours, then placing the TPEE, the PLA, the main flame retardant and the synergistic flame retardant into an internal mixer according to the mass percentage for blending, adding the well-mixed materials from a feed inlet of a double-screw extruder, extruding and granulating to obtain the flame-retardant master batch;
s2: drying the base material: weighing 75 parts of TPEE required by the flame-retardant TPEE material, adding the TPEE material into a reaction kettle, and drying for 1h at 120 ℃, wherein the rotating speed of the reaction kettle is 3.5-4 rpm/min;
s3: and (3) mixing auxiliary materials: adding 20 parts of the flame-retardant master batch obtained in the step S1, 0.75 part of OP wax, 1.8 parts of internal lubricant, 0.75 part of antioxidant, 0.75 part of anti-dripping agent and 0.3 part of antiozonant into a high-speed mixer and mixing for 0.5-1h at the temperature of 120-;
s4: and (4) sequentially putting the mixture obtained in the step (S2) and the step (S3) into a weightless scale, feeding the mixture into a screw extruder through a main feeding system of the double-screw extruder, blending, melting and granulating to obtain the flame-retardant TPEE material for the automobile, and cooling and packaging the finished product.
The main flame retardant is melamine phosphate and melamine polyphosphate, the weight ratio is 1:1, and the synergistic flame retardant is zinc borate.
Example 2
The invention relates to a flame-retardant TPEE material for automobile cables, which comprises the following raw materials in parts by weight: 75 portions of TPEE with the viscosity of 1.25 to 1.3 and the hardness of 50 to 72D, 20 portions of flame-retardant master batch, 0.75 portion of OP wax, 1.8 portions of lubde internal lubricant, 0.75 portion of antioxidant, 0.75 portion of polytetrafluoroethylene with the molecular weight of 400 to 500 ten thousand and 0.3 portion of antiozonant.
The internal lubricant is lipid internal lubricant lubde; the antiozonant is 3, 9-di-3-cyclohexene-1-yl-2, 4,8, 10-tetraoxaspiro [5.5] undecane.
A preparation method of a flame-retardant TPEE material for automobile cables comprises the following steps:
s1: preparing a flame-retardant master batch: firstly, weighing 10 parts of TPEE, 45 parts of PLA, 40 parts of main flame retardant and 5 parts of synergistic flame retardant according to the formula mass percentage of the flame-retardant master batch, then drying the weighed TPEE and PLA in a vacuum drying oven at 45 ℃ for 12 hours, then placing the TPEE, the PLA, the main flame retardant and the synergistic flame retardant into an internal mixer according to the mass percentage for blending, adding the well-mixed materials from a feed inlet of a double-screw extruder, extruding and granulating to obtain the flame-retardant master batch;
s2: drying the base material: weighing 75 parts of TPEE required by the flame-retardant TPEE material, adding the TPEE material into a reaction kettle, and drying for 1h at 120 ℃, wherein the rotating speed of the reaction kettle is 3.5-4 rpm/min;
s3: and (3) mixing auxiliary materials: adding 20 parts of the flame-retardant master batch obtained in the step S1, 0.75 part of OP wax, 1.8 parts of internal lubricant, 0.75 part of antioxidant, 0.75 part of anti-dripping agent and 0.3 part of antiozonant into a high-speed mixer and mixing for 0.5-1h at the temperature of 120-;
s4: and (4) sequentially putting the mixture obtained in the step (S2) and the step (S3) into a weightless scale, feeding the mixture into a screw extruder through a main feeding system of the double-screw extruder, blending, melting and granulating to obtain the flame-retardant TPEE material for the automobile, and cooling and packaging the finished product.
The main flame retardant is melamine phosphate and melamine polyphosphate, the weight ratio is 1:1, and the synergistic flame retardant is zirconium phosphate.
Example 3
The invention relates to a flame-retardant TPEE material for automobile cables, which comprises the following raw materials in parts by weight: 75 portions of TPEE with the viscosity of 1.25 to 1.3 and the hardness of 50 to 72D, 20 portions of flame-retardant master batch, 0.75 portion of OP wax, 1.8 portions of lubde internal lubricant, 0.75 portion of antioxidant, 0.75 portion of polytetrafluoroethylene with the molecular weight of 400 to 500 ten thousand and 0.3 portion of antiozonant.
The internal lubricant is lipid internal lubricant lubde; the antiozonant is 3, 9-di-3-cyclohexene-1-yl-2, 4,8, 10-tetraoxaspiro [5.5] undecane.
A preparation method of a flame-retardant TPEE material for automobile cables comprises the following steps:
s1: preparing a flame-retardant master batch: firstly weighing 5 parts of TPEE, 40 parts of PLA, 50 parts of main flame retardant and 5 parts of synergistic flame retardant according to the formula mass percentage of the flame-retardant master batch, then drying the weighed TPEE and PLA in a vacuum drying oven at 45 ℃ for 12 hours, then placing the TPEE, the PLA, the main flame retardant and the synergistic flame retardant into an internal mixer according to the mass percentage for blending, adding the well-mixed materials from a feed inlet of a double-screw extruder, extruding and granulating to obtain the flame-retardant master batch;
s2: drying the base material: weighing 75 parts of TPEE required by the flame-retardant TPEE material, adding the TPEE material into a reaction kettle, and drying for 1h at 120 ℃, wherein the rotating speed of the reaction kettle is 3.5-4 rpm/min;
s3: and (3) mixing auxiliary materials: adding 20 parts of the flame-retardant master batch obtained in the step S1, 0.75 part of OP wax, 1.8 parts of internal lubricant, 0.75 part of antioxidant, 0.75 part of anti-dripping agent and 0.3 part of antiozonant into a high-speed mixer and mixing for 0.5-1h at the temperature of 120-;
s4: and (4) sequentially putting the mixture obtained in the step (S2) and the step (S3) into a weightless scale, feeding the mixture into a screw extruder through a main feeding system of the double-screw extruder, blending, melting and granulating to obtain the flame-retardant TPEE material for the automobile, and cooling and packaging the finished product.
The main flame retardant is melamine phosphate and melamine polyphosphate, the weight ratio is 1:1, and the synergistic flame retardant is organic montmorillonite.
Example 4
Example 4 is different from example 3 in that a flame retardant TPEE material for automobile cables comprises the following raw materials in parts by weight: 70 portions of TPEE with the viscosity of 1.25 to 1.3 and the hardness of 50 to 72D, 10 portions of flame-retardant master batch, 0.5 portion of OP wax, 0.5 portion of lubde internal lubricant, 0.5 portion of antioxidant and 0.5 portion of polytetrafluoroethylene with the molecular weight of 400 to 500 ten thousand.
Example 5
The difference between the embodiment 5 and the embodiment 3 is that the flame-retardant TPEE material for the automobile cable comprises the following raw materials in parts by weight: 80 parts of TPEE with the viscosity of 1.25-1.3 and the hardness of 50-72D, 30 parts of flame-retardant master batch, 1 part of OP wax, 3 parts of lubde internal lubricant, 1 part of antioxidant and 1 part of anti-dripping agent.
The tensile strength of the cable TPEE materials of the above examples 1-5 was more than 30Mpa, the oxygen index was more than 30%, the flame retardancy reached the UL-94V0 rating, and no dripping occurred.
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 technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. The flame-retardant TPEE material for the automobile cable is characterized by comprising the following raw materials in parts by weight: 70-80 parts of TPEE, 10-30 parts of flame-retardant master batch, 0.5-1 part of OP wax, 0.5-3 parts of internal lubricant, 0.5-1 part of antioxidant, 0.5-1 part of anti-dripping agent and 0.1-0.5 part of antiozonant.
2. The flame-retardant TPEE material for the automobile cable according to claim 1, wherein the flame-retardant master batch comprises 5-10% of TPEE, 40-45% of polylactic acid, 40-50% of main flame retardant and 5-10% of synergistic flame retardant in percentage by mass.
3. The flame retardant TPEE material for automobile cables as claimed in claim 2, wherein the TPEE has a viscosity of 1.25-1.3 and a hardness of 50-72D.
4. The flame retardant TPEE material for automobile cables as claimed in claim 3, wherein the internal lubricant is a lipid internal lubricant; the antiozonant is 3, 9-di-3-cyclohexene-1-yl-2, 4,8, 10-tetraoxaspiro [5.5] undecane.
5. The flame-retardant TPEE material for the automobile cables as claimed in claim 4, wherein the main flame retardant is melamine phosphate and/or melamine polyphosphate, and the synergistic flame retardant is one or more of zinc borate, zirconium phosphate and organic montmorillonite.
6. The flame-retardant TPEE material for automobile cables as claimed in claim 5, wherein the antioxidant comprises one or more of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 164; the anti-dripping agent is polytetrafluoroethylene with the molecular weight of 400-500 ten thousand.
7. A method for preparing the flame retardant TPEE material for the automobile cable according to any one of claims 1 to 6, which comprises the following steps:
s1: preparing a flame-retardant master batch: firstly, weighing TPEE, PLA, a main flame retardant and a synergistic flame retardant according to the mass percentage of a flame-retardant master batch formula, then drying the TPEE and the PLA in a vacuum drying oven at 45 ℃ for 12 hours, then placing the TPEE, the PLA, the main flame retardant and the synergistic flame retardant into an internal mixer for blending according to the mass percentage, adding the well-mixed materials from a feed inlet of a double-screw extruder, extruding and granulating to obtain flame-retardant master batches;
s2: drying the base material: weighing TPEE required in the flame-retardant TPEE material, adding the TPEE into a reaction kettle, and drying for 1h at 120 ℃, wherein the rotating speed of the reaction kettle is 3.5-4 rpm/min;
s3: and (3) mixing auxiliary materials: weighing the flame-retardant master batch obtained in the step S1, weighing OP wax, an internal lubricant, an antioxidant, an anti-dripping agent and an antiozonant, adding the materials into a high-speed mixer, and mixing for 0.5-1h at 120-150 ℃;
s4: and (4) sequentially putting the mixture obtained in the step (S2) and the step (S3) into a weightless scale, feeding the mixture into a screw extruder through a main feeding system of the double-screw extruder, blending, melting and granulating to obtain the flame-retardant TPEE material for the automobile, and cooling and packaging the finished product.
CN202011524531.2A 2020-12-22 2020-12-22 Flame-retardant TPEE material for automobile cable and preparation method thereof Pending CN112812508A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025401A (en) * 1996-07-12 1998-01-27 Toyobo Co Ltd Flame-retardant polyester elastomer composition
CN102757622A (en) * 2011-04-27 2012-10-31 合肥杰事杰新材料股份有限公司 Low-smoke halogen-free flame-retardant thermoplastic polyester elastomer and preparation method thereof
CN103980675A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 3D printing aromatic polyester material and preparation method
CN106398128A (en) * 2016-08-31 2017-02-15 贵州国塑科技管业有限责任公司 Halogen-free and flame-retardant long glass fiber reinforced TPEE composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025401A (en) * 1996-07-12 1998-01-27 Toyobo Co Ltd Flame-retardant polyester elastomer composition
CN102757622A (en) * 2011-04-27 2012-10-31 合肥杰事杰新材料股份有限公司 Low-smoke halogen-free flame-retardant thermoplastic polyester elastomer and preparation method thereof
CN103980675A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 3D printing aromatic polyester material and preparation method
CN106398128A (en) * 2016-08-31 2017-02-15 贵州国塑科技管业有限责任公司 Halogen-free and flame-retardant long glass fiber reinforced TPEE composite material and preparation method thereof

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