CN105906914A - High-strength inorganic hydroxide flame-retardant polyethylene sheath martial for refrigerator power line and preparing method thereof - Google Patents

High-strength inorganic hydroxide flame-retardant polyethylene sheath martial for refrigerator power line and preparing method thereof Download PDF

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Publication number
CN105906914A
CN105906914A CN201610431790.8A CN201610431790A CN105906914A CN 105906914 A CN105906914 A CN 105906914A CN 201610431790 A CN201610431790 A CN 201610431790A CN 105906914 A CN105906914 A CN 105906914A
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Prior art keywords
magnesium hydroxide
red phosphorus
hydroxide
flame
polyethylene sheath
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CN201610431790.8A
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Chinese (zh)
Inventor
林文树
林文禄
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Tianzhang City Fu Da Electronics Co Ltd
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Tianzhang City Fu Da Electronics Co Ltd
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Priority to CN201610431790.8A priority Critical patent/CN105906914A/en
Publication of CN105906914A publication Critical patent/CN105906914A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • H01B3/44—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 vinyl resins; acrylic resins
    • H01B3/441—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 vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-strength inorganic hydroxide flame-retardant polyethylene sheath martial for a refrigerator power line. Nano-magnesium hydroxide is subjected to silane surface modification and then serves as a flame retardant, so that the hydrophobicity of magnesium hydroxide is relieved to some extent, the compatibility of magnesium hydroxide in a polymer is improved, and the effects of improving the mechanical performance and fire retardance of the material are achieved; red phosphorus is subjected to encapsulation modification, so that the problem that red phosphorus is likely to absorb moisture and poor in safety is relieved; encapsulation-modified red phosphorus forms phosphoric acid or metaphosphoric acid when heated and then forms strong dehydrant polymetaphosphate, so that decomposition of magnesium hydroxide is accelerated, and synergistic flame retardation is achieved. Besides, inorganic filler bull bone powder is subjected to chemical surface modification, so that the compatibility of inorganic filler bull bone powder in a polymer is improved, and the mechanical strength and abrasion resistance of the product are improved; through compatibility of the material and other effective auxiliaries such as alkali-free glass fibers, the obtained polyethylene sheath material is high in strength; a brominated flame retardant is replaced with inorganic hydroxide (a zero-halogen flame retardant), so that the polyethylene sheath material meets the requirements for environmental friendliness and zero halogen.

Description

A kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material and preparation method thereof.
Background technology
It is known that power line is the electric wire of transmission electric current, wherein sheath is the indispensable structure division of power line, plays the effect of protection wire insulation, it is ensured that the energising safety of power line, allows conductor and the medium such as water, air completely cut off, it is to avoid leaky occur.The sheath of refrigerator power cord can be divided into oversheath and inner sheath, and oversheath also referred to as protects sheath, is the outmost one layer of sheath of refrigerator power cord, and this layer of oversheath plays a part to protect power line.High density polyethylene (HDPE) (HDPE) is the general-purpose plastics being most widely used, because its good electrical insulating property, mechanical performance, dielectric properties, easy machine-shaping, heat-resisting cold-resistant and chemical-resistance are applied to making refrigerator power cord protective cover material, but owing to the performances such as the low easy firing of the oxygen index (OI) of HDPE, ageing resistance and flexible resistance are low, therefore, it is carried out the meaning that the performances such as fire-retardant, aging resistance and flexible resistance are modified having particular importance.
Having halogen fire retardant is the fire retardant being currently mainly applied to HDPE, has the most fire-retardant and mechanical property, but because the hazardness of environment is the most gradually eliminated by it.Magnesium hydroxide is a kind of novel halogen-free flame-retardant agent in recent years developed, and has the advantages such as decomposition temperature height, Heat stability is good, has been widely used in plastic material.But its flame retarding efficiency is relatively low, often need to add in a large number, and poor with polymer compatibility, dispersion inequality, it is difficult to independent use.Although nano-sized magnesium hydroxide surface area is big, improves its degree that is uniformly dispersed in macromolecular material to a certain extent, but still fail to reach desirable.Magnesium hydroxide surface modifying can be improved to a certain extent the hydrophobicity of magnesium hydroxide, thus improve its compatibility in the material, and reach to improve the mechanics of materials and the effect of anti-flammability." surface modification impact on nano-sized magnesium hydroxide/high-density polyethylene composite material " literary composition is by silane coupler, magnesium stearate and titanate esters surface modification magnesium hydroxide blending HDPE respectively, result shows: high density polyethylene (HDPE) anti-flammability is improved less by silane coupler, magnesium stearate and titanate esters modified magnesium hydroxide, but beneficially raising system mechanical property.Considering combination property, silane coupler is best surface modifying agent, and when consumption is the 3.5% of magnesium hydroxide quality, system oxygen index (OI), hot strength, elongation at break and impact strength are respectively increased about 8%, 30%, 6% and 18%.
But, in literary composition, only anti-flammability to HDPE has carried out modification, and flame retardant effect is general, and along with the fast development of science and technology, the performance such as wear-resisting, anticorrosion, the oil resistant of existing refrigerator power cord protective cover material the most more and more cannot meet the demand in market.High-density polyethylene modified method also has a lot, and more conventional is is filled with enhancing modified to it, filling-modified can be divided into inorganic filler and organic filler by filler modified kind.Consider that conventional is addition inorganic filler to high density polyethylene (HDPE) from environmental protection, such as calcium carbonate, Pulvis Talci, glass microballoon, Muscovitum etc., although the intensity improving material can be played, rigidity, the effect of the performances such as dimensional stability, but these inorganic filler relative densities are bigger, add and polymer makes the composite prepared relatively denser, product quality is caused to rise, and the compatibility is bad between inorganic filler and organic polyethylene, need inorganic material is carried out surface modification, just can preferably be combined with matrix, preparation technology is complex, relatively costly.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material, is prepared by the raw materials in: high density polyethylene (HDPE) 100, acrylic resin 8-9, nano-sized magnesium hydroxide 18-20, blanc fixe 1-2, red phosphorus 7-8, alkali-free glass fibre 2-3, Os Bovis seu Bubali powder 11-13, Semen Maydis oil 6-8, decabromodiphenyl oxide 4-5, ethylene bis stearamide 2-3, dimethyl itaconate 3-5, silane coupler KH-560 0.6-0.8.
The manufacture method of described a kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material, comprises the following steps:
(1) nano-sized magnesium hydroxide, silane coupler KH-560 are put in high-speed mixer, after addition blanc fixe processes 30 minutes under the conditions of 100 DEG C, put into vacuum drying oven in placing 3-4 hour at 80 DEG C；
(2) by red phosphorus, dimethyl itaconate stirring and evenly mixing, put in high-speed mixer, add acrylic resin and stir, be cooled to room temperature and add decabromodiphenyl oxide ultrasonic grinding 2-3 hour, obtain encapsulated modified red phosphorus；
(3) Os Bovis seu Bubali powder sprays after high-temperature process concentrated sulfuric acid solution sulfonation in a nitrogen environment that mass concentration is 98% process 15-20 minute, filtration with hot wash to without SO42–, add Semen Maydis oil, ethylene bis stearamide magnetic agitation 2-3 hour, dry；
(4) high density polyethylene (HDPE) is put in 105-110 DEG C of drying in baking oven, put into and high-speed mixer adds step (1), (2), (3) material and other residual components mix homogeneously, use double screw extruder extruding pelletization, discharging.
The invention have the advantage that the present invention nano-sized magnesium hydroxide surface is carried out silane-modified after as fire retardant, improve the hydrophobicity of magnesium hydroxide to a certain extent, improve its compatibility in the polymer, and reach to improve the mechanics of materials and the effect of anti-flammability, encapsulated for red phosphorus modification is improved the easy moisture absorption of red phosphorus, the problem of poor stability, encapsulated modified red phosphorus is by thermosetting phosphoric acid, Metaphosphoric acid, and then form the poly-Metaphosphoric acid of strong dehydrant, accelerate the decomposition of magnesium hydroxide, serve cooperative flame retardant effect；Inorganic filler Os Bovis seu Bubali powder surface is also carried out chemical modification by the present invention, improve its compatibility in the polymer, improve mechanical strength and the wearability of product, and other effective auxiliary agent alkali-free glass fibres of compatibility etc., the polyethylene sheath material intensity prepared is high, bromide fire retardant is replaced so that it is meet the requirement of green Halogen with inorganic hydroxide (halogen-free flame retardants).
Detailed description of the invention
A kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material, is prepared by the raw materials in: high density polyethylene (HDPE) 100, acrylic resin 8, nano-sized magnesium hydroxide 18, blanc fixe 1, red phosphorus 7, alkali-free glass fibre 2, Os Bovis seu Bubali powder 11, Semen Maydis oil 6, decabromodiphenyl oxide 4, ethylene bis stearamide 2, dimethyl itaconate 3, silane coupler KH-560 0.6。
The manufacture method of described a kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material, comprises the following steps:
(1) nano-sized magnesium hydroxide, silane coupler KH-560 are put in high-speed mixer, after addition blanc fixe processes 30 minutes under the conditions of 100 DEG C, put into vacuum drying oven in placing 3-4 hour at 80 DEG C；
(2) by red phosphorus, dimethyl itaconate stirring and evenly mixing, put in high-speed mixer, add acrylic resin and stir, be cooled to room temperature and add decabromodiphenyl oxide ultrasonic grinding 2-3 hour, obtain encapsulated modified red phosphorus；
(3) Os Bovis seu Bubali powder sprays after high-temperature process concentrated sulfuric acid solution sulfonation in a nitrogen environment that mass concentration is 98% process 15-20 minute, filtration with hot wash to without SO42 –, add Semen Maydis oil, ethylene bis stearamide magnetic agitation 2-3 hour, dry；
(4) high density polyethylene (HDPE) is put in 105-110 DEG C of drying in baking oven, put into and high-speed mixer adds step (1), (2), (3) material and other residual components mix homogeneously, use double screw extruder extruding pelletization, discharging.
The oxygen index (OI) of refrigerator power cord flame-retardant polyethylene sheathing material, hot strength, elongation at break and the impact strength that utilize the present invention to prepare are respectively increased about 16%, 36%, 11% and 22%.

Claims (2)

1. a high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material, it is characterized in that, be prepared by the raw materials in: high density polyethylene (HDPE) 100, acrylic resin 8-9, nano-sized magnesium hydroxide 18-20, blanc fixe 1-2, red phosphorus 7-8, alkali-free glass fibre 2-3, Os Bovis seu Bubali powder 11-13, Semen Maydis oil 6-8, decabromodiphenyl oxide 4-5, ethylene bis stearamide 2-3, dimethyl itaconate 3-5, silane coupler KH-560 0.6-0.8。
The manufacture method of a kind of high-intensity inorganic hydroxide refrigerator power cord flame-retardant polyethylene sheathing material the most according to claim 1, it is characterised in that comprise the following steps:
(1) nano-sized magnesium hydroxide, silane coupler KH-560 are put in high-speed mixer, after addition blanc fixe processes 30 minutes under the conditions of 100 DEG C, put into vacuum drying oven in placing 3-4 hour at 80 DEG C；
(2) by red phosphorus, dimethyl itaconate stirring and evenly mixing, put in high-speed mixer, add acrylic resin and stir, be cooled to room temperature and add decabromodiphenyl oxide ultrasonic grinding 2-3 hour, obtain encapsulated modified red phosphorus；
(3) Os Bovis seu Bubali powder sprays after high-temperature process concentrated sulfuric acid solution sulfonation in a nitrogen environment that mass concentration is 98% process 15-20 minute, filtration with hot wash to without SO42–, add Semen Maydis oil, ethylene bis stearamide magnetic agitation 2-3 hour, dry；
(4) high density polyethylene (HDPE) is put in 105-110 DEG C of drying in baking oven, put into and high-speed mixer adds step (1), (2), (3) material and other residual components mix homogeneously, use double screw extruder extruding pelletization, discharging.
CN201610431790.8A 2016-06-17 2016-06-17 High-strength inorganic hydroxide flame-retardant polyethylene sheath martial for refrigerator power line and preparing method thereof Withdrawn CN105906914A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105086071A (en) * 2015-08-20 2015-11-25 晶锋集团股份有限公司 Ultraviolet-resistant cable material for outdoor appliances and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105086071A (en) * 2015-08-20 2015-11-25 晶锋集团股份有限公司 Ultraviolet-resistant cable material for outdoor appliances and preparation method thereof

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