CN106317601A - Cross-linking and flame-retardant cable cladding material - Google Patents

Cross-linking and flame-retardant cable cladding material Download PDF

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Publication number
CN106317601A
CN106317601A CN201610791553.2A CN201610791553A CN106317601A CN 106317601 A CN106317601 A CN 106317601A CN 201610791553 A CN201610791553 A CN 201610791553A CN 106317601 A CN106317601 A CN 106317601A
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China
Prior art keywords
cross
covering material
fire
resistant cable
cable covering
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Pending
Application number
CN201610791553.2A
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Chinese (zh)
Inventor
应国军
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Yuyao City Kai Rui Electronics Co Ltd
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Yuyao City Kai Rui Electronics Co Ltd
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Priority to CN201610791553.2A priority Critical patent/CN106317601A/en
Publication of CN106317601A publication Critical patent/CN106317601A/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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Insulated Conductors (AREA)

Abstract

The invention provides a cross-linking and flame-retardant cable cladding material. The cross-linking and flame-retardant cable cladding material is prepared from 40-100 parts by weight of cross-linking basic resin, 80-140 parts by weight of a hydrous metal hydroxide flame retardant, 1-5 parts by weight of a peroxide cross-linking agent and 0.1-0.7 parts by weight of an antioxidant, wherein the antioxidant contains hindered polyhydric phenol antioxidant. The cross-linking and flame-retardant cable cladding material has excellent flame retardance and mechanical properties.

Description

Cross-linked fire-resistant cable covering material
Technical field
The present invention relates to the fire-retardant of polymeric material, more specifically cross-linked fire-resistant cable covering material.
Background technology
In order to meet the safety requirements of electric wiring, the fire-retardant problem of electric wire increasingly causes the concern of people, electricity The fire-retardant research of line cable has become a comprehensive developing direction of cable industry, the wires and cables industry need to fire-retardant aspect Ask particularly pertinent.The supplier of the most existing plurality of wire cable material, such as Dupond, Union Carbide, Alpha Gary, BASF, Bayer, Borealis, Exxon and Shell Chemicals etc..Occur in that on market multiple use (building, Communication, traffic, railway etc.) halogen-free flame-retardant wire cable product.Britain is sent out since London imperial family subway station bitterness fire incident After life, relevant departments explicit order public arena must use LSZH (the low smoke zero meeting technical specification Halogen) CABLE MATERIALS.
The appearance of modern computer network has driven the quick of LAN (local area network, LAN) Development, so cause to data cable crave for.Under important events, LSZH will become the first-selection of cable material.Nuclear industry It it is one of field promoting the use of Halogen product the earliest.The specifications of cables that CERN formulates is expressly provided and is entered The precondition in this field must be Halogen, without sulfur, low-smoke low-toxicity, low corrosion.Owing to the electrical property of data cable is much better than electricity Words cable, next step development, LAN cable will enter the telephone system of interior of building, be in great demand.According to estimates, often Platform computer averagely needs the LAN cable of 100m.
Electric wire plastics mainly include polrvinyl chloride (PVC), polyolefin (such as polyethylene, polypropylene), fluoroplastics etc.. Substantial amounts of corrosive gas and dense smoke is released, danger when polyvinyl chloride cable and some other Halogen cable materials are due to burning And the life security of people, so low smoke, zero halogen cable is widely used in recent years.Therefore the substitute of PVC is sought, Advance interior of building city electrical wiring (220/240V), Telephone Cable data cable non-halogen oneself is extremely urgent.2001 Year, set up FROOC (Fire Retardant Olefinic Cable Compounds) association in Europe, it is therefore intended that push away The dynamic development working in coordination with the line cable industry based on halogen-free polyolefin CABLE MATERIALS.
Sub polyethylene is low-density, high density and crosslinking three kinds, has the electric property of excellence, tolerance to cold, chemical resistance, Cable insulation can be made.Ethene-vinyl acetate copolymer (EVA) has superior pliability, optical property, resistance to low temperature because of it And environmental stress crack resistance, and be widely used in electric wire, expanded material, functional greenhouse film, packaging film, PUR and The fields such as toy.But EVA is the same with most polymers, easily burn, and thermal discharge is big, the amount of being fuming is big, and release has poison Body, so that the research using Halogen, low cigarette, the environment friendly flame retardant of low toxicity to prepare fire-retardant EVA composite is increasingly drawn Play the attention of people.
About cross-linked polyolefin, crosslinking technological is one of important means improving its temperature resistant grade.Molecule is made by crosslinking Being bonded between main chain, the linear structure making macromolecule original is transformed into tridimensional network, is significantly improving polyolefine material While heat resistance etc., damage the electrical insulation capability of its excellence, mechanical performance hardly.Therefore, to polyolefin crosslinking technological Research be constantly subjected to the extensive concern of researcher.Recently, the research of irradiation cross-linking low smoke halogen-free fire retardant polyolefin cable material is subject to Arrive extensive attention, use cross-linking radiation to make the temperature resistant grade of low smoke halogen-free fire retardant polyolefin cable material from 70 DEG C of original raisings To 125 DEG C, the highest.In multiple cross-linking method, the chemical crosslinking with peroxide as cross-linking agent because of have strong adaptability, The advantages such as crosslinked products performance is good and obtain commercial Application widely.
But, in prior art, the research about chemical crosslinking low smoke halogen-free fire retardant polyolefin cable material is relatively fewer.Cause This, it is still desirable to the chemical crosslinking cable covering material of improvement, to continue to improve its performance, provide at a kind of supplementing.
Summary of the invention
In order to solve the problems referred to above, inventor carries out positive research, result they find to use specific crosslinked resin Formula, it is possible to obtain combination property preferable cross-linked fire-resistant cable covering material.
Therefore, in an aspect, the invention provides a kind of cross-linked fire-resistant cable covering material, comprise: 40-100 weight The crosslinking base resin of amount part, the hydration metal hydroxides fire retardant of 80-140 weight portion, the peroxide of 1-5 weight portion are handed over Connection agent and the antioxidant of 0.1-0.7 weight portion, wherein said antioxidant packages contains polynary hindered phenol type antioxidant.Such as, cross-linking agent Benzoyl peroxide (DCP) can be used.
Preferably, polynary hindered phenol type antioxidant is four ((3,5-di-t-butyl-4-carboxyl propanoic acid) pentaerythritol esters.
Polyolefin is susceptible to thermo-oxidative ageing in processing with during using, and adding antioxidant in system is having of preventing Effect means.But the mechanism preventing macromolecular chain from degrading due to antioxidant antioxidation is to decompose the free radical of generation in capture system With active component labile on stable main polymer chain.This just will necessarily dissociate in generation caused to peroxide cross-linking agent Base has the effect terminating closing, and makes the cross-linking efficiency of peroxide decline.Therefore, the consumption of antioxidant is controlled by the present invention 0.1-0.7 weight portion.When the amount of antioxidant is less than 0.1 weight portion, it is impossible to play sufficiently effect.Amount when antioxidant During more than 0.7 weight portion, crosslinking degree can be caused to reduce.
The cross-linked fire-resistant cable covering material of the present invention can also comprise the retardant synergist of 0.1-5.0 weight portion.
Preferably, described base resin comprises polyolefin-vinyl acetate (EVA) copolymer composite resin or EPDM Rubber-polyolefin composite resin.
Preferably, described polyolefin be polyethylene, polypropylene or its combine arbitrarily.
It is highly preferred that described polyolefin is linear low density polyethylene (LLDPE).
In one example, described covering material also comprises the compatilizer of 2-10 weight portion.Compatilizer can be selected from Malaysia Anhydride grafting modified polyethylene, the ethylene-vinyl acetate copolymer of modified by maleic acid anhydride graft or its combination in any.
Preferably, the cross-linked fire-resistant cable covering material of the present invention also comprises the retardant synergist of 0.1-5.0 weight %.
Preferably, described retardant synergist is selected from microencapsulation red phosphorus, APP, montmorillonite or its combination in any.
As an example, the preparation technology of the cross-linked fire-resistant cable covering material of the present invention enters according to flow process shown in Fig. 1 OK.
The flame retardant cable covering material of the present invention has fire resistance and the mechanical property of improvement.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow process of cross-linked fire-resistant cable covering material of the present invention.
Detailed description of the invention
Enforcement embodiment of the present invention explained below.But, the scope of the present invention is not limited to described embodiment party Formula, as long as not damaging purport, can carry out various change to the present invention.Unless otherwise stated, following ratio and % divide Do not refer to weight ratio and weight %.
The preparation of fire-resistant cable material
Technique shown in Fig. 1 is used to prepare fire-resistant cable material.
Mechanics Performance Testing
By the mechanical performance of GB/T2951.5-94 test material, sample uses I type dumbbell test piece, and draw speed is 250mm/min.Tensile strength is calculated as follows.
σ t = p b × d
In formula: p is that sample is stretched to load maximum during fracture；B is specimen width；D is sample thickness.
ϵ t = L - L 0 L 0 × 100 %
In formula, L0For the original gauge length of sample；L is sample fracture markers wire spacing.
Limited oxygen index is tested
Limited oxygen index (Limited Oxygen Index, LOI) refers under prescribed conditions, and sample is in oxygen, nitrogen mixing Minimum oxygen concentration required during maintenance smooth combustion in air-flow, generally carrys out table with the percent that oxygen is shared in mixed gas Show.During test, sample is vertically loaded on specimen holder, bottom combustion barrel, is passed through oxygen, nitrogen mixed gas, with lighter from upper extreme point Combustion sample, changes oxygen concentration in mixed gas, till flame front reaches the graticule of sample just.Thus oxymeter Calculate material oxygen index (OI), and with the arithmetic mean of instantaneous value of 3 result of the tests as measured value.The combustibility evaluating plastics with LOI is first Being proposed equal to 1966 by American scholar Fenimore before this, U.S. material was with test association (ASTM) based on this later Having formulated test method and the standard ASTM D2863-1970 of LOI, International Organization for Standardization has also formulated corresponding testing standard ISO4589, the national standard of China is GB-2406.The specimen size used in this test is 100X6.5X3mm, by ASTM D2863-77 standard is tested on HC-2 type oxygen index instrument.
Computing formula is as follows:
L O I = [ O 2 ] [ O 2 ] + [ N 2 ] × 100 %
In formula: O2For oxygen flow (liter/min)；[N2] it is nitrogen flow (liter/min).The arithmetic equal value of three result of the tests Being the oxygen index (OI) of this material, data retain after decimal one.
Comparative example and embodiment
Preparing the flame retardant cable covering material of comparative example 1 and embodiment 1 in a manner mentioned above, wherein comparative example 1 uses: 44 "-thiobis (the 6-tert-butyl group-3-methylphenol) (antioxidant 300), and embodiment 1 uses four ((3,5-di-t-butyl-4-carboxylics Base propanoic acid) pentaerythritol ester) (antioxidant 1010).Performance test is carried out according to above-mentioned method.
As a result, when gel content is zero, resin system adds the oxygen index (OI) after antioxidant 300 more than adding antioxygen Oxygen index (OI) after agent 1010；After chemical crosslinking, along with the increase of gel content, add the resin system of antioxidant 1010 relatively low Gel content time oxygen index (OI) quickly raise, be increased to 33.2% from 28.0%, then with gel content increase the most lentamente Rise, declined when gel content is 83%.And add the resin system of antioxidant 300 in higher oxygen index (OI) position On quickly dropped, be reduced to 26.4% from 30.1%, the most slightly raise.The decline of antioxidant 300 is likely due to The synergism quickly destroyed when its antioxidant is under chemical crosslinking effect thus have impact between antioxidant and fire retardant Reason.
It can be seen that in the material system of crosslinked halogen-free flame-retardant, the selection of antioxidant is except to consider whether beneficially Thermo-oxidative ageing, simultaneously it is also contemplated that antioxidant whether chemically-resistant crosslinking.Polynary hindered phenol type antioxidant is more suitable for being chemically crosslinked Antioxidant, under suitable gel content, polynary hindered phenol type kind antioxidant and fire retardant have certain synergism, make oxygen Index raises.
About comparative example 1 and the mechanical performance of embodiment 1, result shows: through 135 DEG C, the hot air aging of 168 hours The retention rate of after-drawing intensity and elongation at break is more than 80%, all meets index.

Claims (9)

1. a cross-linked fire-resistant cable covering material, comprises:
Crosslinking base resin, the hydration metal hydroxides fire retardant of 80-140 weight portion, the 1-5 weight portion of 40-100 weight portion Peroxide cross-linking agent and the antioxidant of 0.1-0.7 weight portion, wherein said antioxidant packages contain polynary hindered phenol type antioxidant.
Cross-linked fire-resistant cable covering material the most according to claim 1, also comprises the fire-resistant synergistic of 0.1-5.0 weight portion Agent.
Cross-linked fire-resistant cable covering material the most according to claim 1, wherein said base resin comprises polyolefin-acetic acid Ethylene copolymer composite resin or ethylene propylene diene rubber-polyolefin composite resin.
Cross-linked fire-resistant cable covering material the most according to claim 3, wherein said polyolefin be polyethylene, polypropylene or It combines arbitrarily.
Cross-linked fire-resistant cable covering material the most according to claim 4, wherein, described polyolefin is that linea low density gathers Ethylene.
6. according to the cross-linked fire-resistant cable covering material described in any one in claim 1-5, wherein said polynary hindered phenol Type antioxidant is four ((3,5-di-t-butyl-4-carboxyl propanoic acid) pentaerythritol esters.
Cross-linked fire-resistant cable covering material the most according to claim 1, wherein said covering material also comprises 2-10 weight The compatilizer of part.
Cross-linked fire-resistant cable covering material the most according to claim 7, wherein said compatilizer is grafted selected from maleic anhydride Modified polyethylene, the ethylene-vinyl acetate copolymer of modified by maleic acid anhydride graft or its combination in any.
Cross-linked fire-resistant cable covering material the most according to claim 2, wherein retardant synergist is selected from microencapsulation red phosphorus, gathers Ammonium phosphate, montmorillonite or its combination in any.
CN201610791553.2A 2016-08-31 2016-08-31 Cross-linking and flame-retardant cable cladding material Pending CN106317601A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101597395A (en) * 2009-06-24 2009-12-09 上海至正道化高分子材料有限公司 A kind of fireproofing cable material without halide and preparation method thereof
CN103012940A (en) * 2012-09-29 2013-04-03 深圳市沃尔核材股份有限公司 High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material
CN103360712A (en) * 2013-08-06 2013-10-23 河南久通电缆有限公司 High-temperature resistant wear-resistant irradiation cross-linked regenerated-polyolefin/nano-magnesium-hydroxide halogen-free flame-retardant environmental-friendly cable material with high electric properties and production method of the cable material
CN103450544A (en) * 2013-08-07 2013-12-18 合肥安聚达新材料科技有限公司 Low-smoke, halogen-free and flame-retardant irradiation crosslinking polyolefin composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101597395A (en) * 2009-06-24 2009-12-09 上海至正道化高分子材料有限公司 A kind of fireproofing cable material without halide and preparation method thereof
CN103012940A (en) * 2012-09-29 2013-04-03 深圳市沃尔核材股份有限公司 High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material
CN103360712A (en) * 2013-08-06 2013-10-23 河南久通电缆有限公司 High-temperature resistant wear-resistant irradiation cross-linked regenerated-polyolefin/nano-magnesium-hydroxide halogen-free flame-retardant environmental-friendly cable material with high electric properties and production method of the cable material
CN103450544A (en) * 2013-08-07 2013-12-18 合肥安聚达新材料科技有限公司 Low-smoke, halogen-free and flame-retardant irradiation crosslinking polyolefin composite material and preparation method thereof

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