CN106397955A - Halogen-free flame-retardant coating composition for cable - Google Patents
Halogen-free flame-retardant coating composition for cable Download PDFInfo
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- CN106397955A CN106397955A CN201610791576.3A CN201610791576A CN106397955A CN 106397955 A CN106397955 A CN 106397955A CN 201610791576 A CN201610791576 A CN 201610791576A CN 106397955 A CN106397955 A CN 106397955A
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- halogen
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- free flameproof
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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
-
- 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
- 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
- H01B3/448—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 other vinyl compounds
-
- 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
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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
- 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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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention provides a halogen-free flame-retardant coating composition for a cable. The composition comprises, on the basis of the total weight of composition, 30 to 50 wt% of basic resin, 50 to 60 wt% of hydrated metal hydroxide fire retardant and 0.1 to 5.0 wt% of a flame-retardation synergist, wherein the basic resin comprises ethylene-vinyl acetate copolymer and polyolefin, and the flame-retardation synergist comprises a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DPOP) derivative. The halogen-free flame-retardant coating composition for the cable has excellent flame retardation performance and mechanical properties.
Description
Technical field
The present invention relates to the halogen-free flameproof coating composition of field of cables, more specifically cable.
Background technology
Electric wire is the wire product transmitting electromagnetic energy and conversion of electromagnetic energy, and its popularization is to weigh national economy
One of important indicator of development.As the supporting industry that national economy is maximum, the product category of electric wire is various, electric power,
All it is widely used in the industries such as communication, building, closely related with the development of national economy, thus electric wire is described as being state
The people's livelihood produce in " defeated knob ", be indispensable basic product in following electrified, informationized society.
With economic growth, the demand of electric wire constantly increases.Meanwhile, people are to electric wire quality
Require also increasingly to improve.Macromolecular material is used for manufacturing electric wire and cable jacket material always.Wherein, polrvinyl chloride is in cable row
Industry proportion is maximum, but considers environmental protection and fire safety evaluating, polrvinyl chloride oneself gradually by polyolefin or polyolefin and other
The composite of resin replaces.But these materials as the obvious problem that cable material exists be mechanical performance and heat resistance not
Good.Accordingly, it would be desirable to carry out flame-retardant modified to these materials.
In numerous electrical fire accidents, by electric wire cause countless.High polymer broadly falls into easy fuel wood substantially
Material, and polyolefinic firing resistance is poor, the limited oxygen index (LOI) of polyethylene is only 17 about, and the LOI of CABLE MATERIALS needs
Reach more than 25, this makes poly- polyolefinic range of application be restricted.Therefore, improve the resistance of polyolefin or its composite
Combustion performance is to prepare the key of CABLE MATERIALS.
Ethylene-vinyl acetate copolymer (EVA) because having the advantages that good processability, density be low, lower temperature resistance,
It is widely applied in people's social life, but EVA is inflammable, therefore its fire-retardant problem receives concern both domestic and external.
At present, domestic and international expert, using fire-retardant for inorganic combustion inhibitor EVA as research emphasis, consumes particularly in inorganic combustion inhibitor
The maximum magnesium hydroxide (MH) of amount.But MH flame retarding efficiency is low, loading reaches 60% about and just can play anti-flammability, this height
Addition can lead to the decline of system mechanical property.Therefore, in order to reduce its addition, a kind of synergistic flame retardants need to be added,
Can guarantee that while reaching fire-retardant together with magnesium hydroxide that system has preferably mechanical property again.
There is still a need for flame-retardant modified BACN or composite flame-proof are carried out with base resin to cable in prior art
System, to continue to improve the performance of resin, provides at a kind of supplement.
Content of the invention
In order to solve the above problems, inventor carries out positive research, result they find using hydrated metal hydroxide
Thing fire retardant is compounded with specific retardant synergist, can obtain the preferable non-halogen flame-retardant cable of combination property.
Therefore, in an aspect, the invention provides a kind of halogen-free flameproof coating composition of cable, comprise：Phase
For the gross weight of halogen-free flameproof coating composition, the base resin of 30-50 weight %, the hydrated metal hydrogen of 50-60 weight %
Oxide fire retardant and the retardant synergist of 0.1-5.0 weight %, wherein said base resin comprises ethene-vinyl acetate copolymerization
Thing and polyolefin, and described retardant synergist comprises 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DPOP) and spreads out
Biological.
Preferably, ethylene-vinyl acetate copolymer and polyolefinic ratio are 2:1-10:1, more preferably 2:1-4:1.
Preferably, described polyolefin be polyethylene, polypropylene or its arbitrarily combine.
It is highly preferred that described polyolefin is high density polyethylene (HDPE) (HDPE).High density polyethylene (HDPE) is cheap, is current
A kind of widely used plastics, it has minority short-chain branch structure, and degree of crystallinity height (80%-90%), melt temperature are high, strong
The advantages of spend big.
Preferably described hydration metal hydroxides fire retardant is silane coupler modified magnesium hydroxide or aluminium hydroxide.
Preferably silane coupler is KH550.After the surface of magnesium hydroxide carries out silane coupler organic-treating, magnesium hydroxide table
Face hydrophobicity strengthens, and polarity declines, and the compatibility and non-polar polymer EVA between is improved, from its fire retardant mechanism,
During high temperature, magnesium hydroxide decomposes, absorbing and cooling temperature；Discharge vapor, dilute fuel gas；The fire resistance of therefore system
It is improved.
The granularity of magnesium hydroxide or aluminium hydroxide also has an impact to fire resistance, and preferred granularity is 3000-5000 mesh.
Additionally, the modification to magnesium hydroxide or aluminium hydroxide also has active influence to the mechanical property of material.Unmodified
Magnesium hydroxide belong to inorganic matters, be difficult to obtain dispersed, through silane coupler modified hydrogen in polarity matrix resin
Magnesium oxide is had with matrix resin EVA due to possessing silane component, wherein entrained organo-functional group in its molecule well
Affinity, can cover securely on magnesium hydroxide surface, increased the affine of flame retardant of magnesium hydroxide and matrix resin EVA
Property, improve dispersion effect, thus intermolecular active force is improved in system, when external load or external force effect occur
When, there is the probability relative reduction of stress concentration in material internal, therefore the mechanical property of system is improved, particularly extension at break
The raising of rate becomes apparent from.
Preferably, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivant be 9,10- dihydro-9-oxy miscellaneous-
10- phospho hetero phenanthrene -10- oxide and the reactant of 4,4 '-dimaleoyl imino diphenyl-methane (BMI).
It is further preferred that described compositionss also comprise the compatilizer of 1-3 weight %.Compatilizer can be selected from maleic anhydride grafting
EVA, A4085, MC328 etc..
The halogen-free flameproof coating composition of the present invention can be prepared by following method：Weigh a certain amount of according to formula proportion
Hydration metal hydroxides, DPOP derivant, base resin (EVA and polyolefin), in extruder (such as banbury) plus
Enter base resin and DPOP derivant, be allowed to soften melting, until moment of torsion is stable；It is subsequently adding initiator, in sulfuration after mixing
Carry out compression molding in machine, cool down sample preparation, standby.
In a word, the fire-retardant coating composition of the present invention can be used for various electric wires, can show excellent fire-retardant
Performance and the balance of mechanical performance.
Specific embodiment
Enforcement embodiment of the present invention explained below.However, the scope of the present invention is not limited to described embodiment party
Formula, as long as not damaging purport, can carry out various changes to the present invention.Unless otherwise stated, following ratio and % divide
Do not refer to weight ratio and weight %.
The synthesis of DOPO derivant
Add equimolar DOPO and BMI heat temperature raising, stirring in the reactor, be allowed to melt, reaction temperature is 1100
DEG C, the response time is 30min, and cooling is placed in electric heating constant-temperature blowing drying box, makes solvent evaporating completely, obtain yellow transparent
Shape solid, the solid product (DB) of as halogen-free phosphorus-containing fire retardant agent, grind kept dry, chemical equation is:
DB/KH550-MH/HDPE/EVA. the preparation of CABLE MATERIALS
Weigh a certain amount of KH550-MH powder body, DB, EVA, HDPE, banbury is warming up to 140 DEG C ± 5 DEG C, addition EVA,
HDPE and DB mixture, are allowed to soften melting, until after moment of torsion is stable；It is cooled to 60 DEG C, add azobisisobutyronitrile (its interpolation
Measure 0.3% for DB addition), mixing time is 5min, is heated to 50 DEG C of 140 DEG C of scholars again, by KH550-MH2 powder body
Add banbury, continue banburying 15min, the composite after banburying passes through vulcanizing press compression molding, in upper and lower mould temperature
For 5 DEG C about chargings of 140 DEG C of scholars, preheating, after temperature constant, it is forced into 100kg/cm2, venting, continues to be forced into 100kg/cm2,
Pressurize 3-4 minute.Cooling samples, standby.
Performance test
Mechanical property
Composite sample is molded into dumbbell shaped batten according to GB/T 1040-2006 on moulding press, and the batten of cutting exists
25 DEG C, adjust 16h under the conditions of relative humidity 65%, and mechanical test is done on universal testing machine, test speed is 10mm/
min.
Vertical combustion performance is tested
Vertical combustion experiment is a kind of main method of evaluation material combustion grade, is relatively consistent with practical situation, and mould
The property intended is relatively good, and wherein flame retardant rating is divided into FV 0, FV-1, FV2 Three Estate, F V-0 fire-retardant rank highest, and fire resistance is
Excellent.
Composite sample cuts into the batten of 13mmX120mmX3 according to GB/T2918-1996, according to GB2918, will
The batten of 13mmX 120mmx3mm, in 25 DEG C of temperature, adjusts 48h under the conditions of relative humidity 50% scholar 5% respectively, fires vertical
Burn and fire resistance test is done on instrument.5 battens of every group of sample testing,
Shown in vertical combustion grade evaluation criteria following table：
Note a
Embodiment 1-4
Prepare halogen-free flameproof coating composition sample J-1, J-2, J-3 and J-4 according to above-mentioned method, wherein EVA with
The ratio of HDPE is respectively 1:1、2:1、3:1 and 4:1, DB addition is 5%, KH550-MH content and is 50% and basis
The content of resin is 45%.
Test result shows, the fire-retardant data of each embodiment is as shown in the table：
With regard to mechanical property, the tensile strength of embodiment 1-4 is respectively 14MPa, 13.6MPa, 13MPa and 11MPa, and
Elongation at break is respectively 80%, 90%, 100% and 110%.
Result shows, using specific composite flame-retardant agent system carry out flame-retardant modified cladding compositionss have excellent
Combination property.
Claims (7)
1. a kind of halogen-free flameproof coating composition of cable, comprises：
With respect to the gross weight of halogen-free flameproof coating composition, the base resin of 30-50 weight %, the hydration of 50-60 weight %
Metal hydroxide combustion inhibitor and the retardant synergist of 0.1-5.0 weight %, wherein said base resin comprises ethyl vinyl acetate second
Alkene copolymer and polyolefin, and described retardant synergist comprises 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and spreads out
Biological.
2. halogen-free flameproof coating composition according to claim 1, wherein ethylene-vinyl acetate copolymer and polyolefin
Ratio be 2:1-10:1.
3. halogen-free flameproof coating composition according to claim 1 and 2, wherein said polyolefin is polyethylene, polypropylene
Or it arbitrarily combines.
4. halogen-free flameproof coating composition according to claim 3, wherein, described polyolefin is high density polyethylene (HDPE).
5. halogen-free flameproof coating composition according to claim 1, wherein said hydration metal hydroxides fire retardant is
Silane coupler modified magnesium hydroxide or aluminium hydroxide.
6. halogen-free flameproof coating composition according to claim 1, the miscellaneous -10- phospha of wherein said 9,10- dihydro-9-oxy
Phenanthrene -10- oxide derivative is 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide and 4,4 '-dimaleoyl imino
The reactant of diphenyl-methane.
7. halogen-free flameproof coating composition according to claim 1, wherein said compositionss also comprise the phase of 1-3 weight %
Hold agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610791576.3A CN106397955A (en) | 2016-08-31 | 2016-08-31 | Halogen-free flame-retardant coating composition for cable |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610791576.3A CN106397955A (en) | 2016-08-31 | 2016-08-31 | Halogen-free flame-retardant coating composition for cable |
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| CN106397955A true CN106397955A (en) | 2017-02-15 |
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| CN201610791576.3A Pending CN106397955A (en) | 2016-08-31 | 2016-08-31 | Halogen-free flame-retardant coating composition for cable |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560144A (en) * | 2020-06-16 | 2020-08-21 | 中广核高新核材科技（苏州）有限公司 | Low-smoke halogen-free polyolefin cable material and preparation method thereof |
| KR102613586B1 (en) * | 2022-12-06 | 2023-12-14 | 주식회사 신아티앤씨 | Low Tan-delta resin composite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302661A (en) * | 1990-12-14 | 1994-04-12 | Dsm N.V. | Continuous products made of thermosettable monomers |
| CN1465616A (en) * | 2002-06-21 | 2004-01-07 | 中国科学院化学研究所 | Magnetsium hydroxide halogen-free polythene flame redardant composite material |
| CN1887892A (en) * | 2006-07-28 | 2007-01-03 | 四川东材企业集团有限公司 | No-halogen fire-proof phosphorus-containing compound with high heat stability and its prepn |
| CN102276837A (en) * | 2011-08-19 | 2011-12-14 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
-
2016
- 2016-08-31 CN CN201610791576.3A patent/CN106397955A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5302661A (en) * | 1990-12-14 | 1994-04-12 | Dsm N.V. | Continuous products made of thermosettable monomers |
| CN1465616A (en) * | 2002-06-21 | 2004-01-07 | 中国科学院化学研究所 | Magnetsium hydroxide halogen-free polythene flame redardant composite material |
| CN1887892A (en) * | 2006-07-28 | 2007-01-03 | 四川东材企业集团有限公司 | No-halogen fire-proof phosphorus-containing compound with high heat stability and its prepn |
| CN102276837A (en) * | 2011-08-19 | 2011-12-14 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHIN HSUAN LIN等: "《Synthesis and property of phosphorus-containing bismaleimide by a novel method》", 《JOURNAL OF POLYMER SCIENCE:PART A:POLYMER CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560144A (en) * | 2020-06-16 | 2020-08-21 | 中广核高新核材科技（苏州）有限公司 | Low-smoke halogen-free polyolefin cable material and preparation method thereof |
| KR102613586B1 (en) * | 2022-12-06 | 2023-12-14 | 주식회사 신아티앤씨 | Low Tan-delta resin composite |
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Application publication date: 20170215 |