CN100465220C - Halogen-free flame-proof cable sheath material - Google Patents
Halogen-free flame-proof cable sheath material Download PDFInfo
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- CN100465220C CN100465220C CNB2007100637170A CN200710063717A CN100465220C CN 100465220 C CN100465220 C CN 100465220C CN B2007100637170 A CNB2007100637170 A CN B2007100637170A CN 200710063717 A CN200710063717 A CN 200710063717A CN 100465220 C CN100465220 C CN 100465220C
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Abstract
The invention discloses a non-halogen flameproof cable jacket material formula without harming environment, which is characterized by the following: adopting ethylene-octaolefin copolymer, low-density polyethylene, ethylene-vinyl acetate copolymer as basic resin; making magnesium hydroxide as flameproof agent; using bulking graphite and organic montmorillonite as flame-proof assisting agent; adding lubricant and anti-oxidant to form the formula of cable jacket; improving extending strength to 10-14Mpa and fracture extending rate at 150-350%.
Description
Technical field
The present invention relates to a kind of is the flame-proof cable sheath material mixture of matrix resin with the polyolefine, refers more particularly to a kind of prescription of halogen-free flame-proof cable sheath material.
Background technology
Along with the enhancing of people's environmental consciousness and the appearance of corresponding environmental regulation, have macromolecular material Non-halogen Flame Retardant Technology that nontoxic, low cigarette, burning do not discharge corrosive gases and just substituting the halogen flame-retarded technology is arranged, become the main flow direction of the fire-retardant research and development of polymer materials.For a long time, polyvinyl chloride (PVC) plastics account for nearly 80% ratio in the electric wire and cable material.On the one hand contain heavy metal harmful elements such as lead, barium, tin in the PVC CABLE MATERIALS, in use harmful element dissolves gradually and flows into the river and soil causes environmental pollution; On the other hand, in many fire failures, all be, and insulating material PVC has produced gases such as having toxic hydrogenchloride and violent dense smoke and has caused that on-the-spot and the personnel's that speedily carry out rescue work is dead and wounded or disabled in combustion processes because the short circuit of electric wire causes fire.Some developed countries have formulated the new standard of cable in succession as Europe, Japan, since particularly the promulgation RoHS of European Union in 2003 instructs, and the use of halide-containings such as strict restriction PVC.
At present, people are mainly by filling a large amount of inorganic combustion inhibitor Mg (OH) in polymkeric substance
2And Al (OH)
3Prepare non-halogen flame-retardant cable, still, the existence of a large amount of mineral fillers will inevitably cause the deterioration of composite materials property.In order to reduce the content of inorganic combustion inhibitor, still simultaneously guarantee the flame retardant properties that matrix material is high again, adopt fire retarding synergist and inorganic combustion inhibitor to add in the matrix jointly usually.Red phosphorus is a kind of fire retarding synergist the most efficiently of hydrated metal oxide.But because red phosphorus easily produces the phosphine gas of severe toxicity, and red phosphorus dust explosive, therefore, red phosphorus must could use safely and effectively through surface treatment.In addition, the inherent red-purple of red phosphorus own has limited the application of the CABLE MATERIALS that contains red phosphorus greatly.And the fire-resistant cable material that contains red phosphorus all can to emit the irritating smell and the amount of being fuming during in process of production with burning in large quantities very big.
Therefore people begin one's study and seek other nontoxic fire retardants, a kind of polymer-base flame-proof composite material is disclosed in application number is 200610085561.1 patent application, this matrix material comprises polymkeric substance and expansible black lead, wherein polymkeric substance is polyethylene, polypropylene, polystyrene and cinnamic multipolymer, expansible black lead be a kind of when 280 ℃ of swelling temperatures the expandable graphite at low-temperature of allowance for expansion more than 200mL/g, its massfraction is 10%～35%.But wherein flame retardant properties only characterizes with oxygen index, and is more unilateral, and this patent do not report the mechanical property of matrix material yet, and the particle diameter of its expansible black lead and carbon content are also indeterminate.
In number of patent application was 00122157.4 open file, it came common fire retardant polyolefin with one or more combinations in expansible black lead and red phosphorus or the zinc borate to have introduced " a kind of preparation method of non-halogen flame-retardant cable ".But it is owing to have the existence of red phosphorus thereby environment is caused certain pollution.
Summary of the invention
The prescription that the purpose of this invention is to provide a kind of halogen-free flame-proof cable sheath material of environmental sound.The present invention adopts the mixture of ethylene-octene copolymer, new LDPE (film grade), ethylene-vinyl acetate copolymer as matrix resin, adopt magnesium hydroxide to do fire retardant, with expansible black lead and organo montmorillonite is fire retarding synergist, adds the prescription that lubricant and oxidation inhibitor are formed cable jacket material again.Sample with this formulation has mechanical property and flame retardant properties preferably, and its tensile strength can reach 12MPa, and elongation at break reaches more than 260, and the vertical combustion experiment can reach the FV-0 grade, and oxygen index reaches 28～30.
Concrete composition number provided by the invention following (all in mass fraction):
A) matrix resin 100
Wherein: ethylene-octene copolymer 40～98
New LDPE (film grade) 1～30
Ethylene-vinyl acetate copolymer 1～30
B) fire retardant 80～120
Wherein: magnesium hydroxide 70～100
Expansible black lead 5～20
Organo montmorillonite 2～10
C) lubricant 0～2
D) oxidation inhibitor 1～5
Screening formulation of the present invention following (all in mass fraction):
A) matrix resin 100
Wherein: ethylene-octene copolymer 50～80
New LDPE (film grade) 10～30
Ethylene-vinyl acetate copolymer 10～20
B) fire retardant 100～105
Wherein: magnesium hydroxide 90～100
Expansible black lead 5～10
Organo montmorillonite 2～5
C) lubricant 0～2
D) oxidation inhibitor 1～2
Above-mentioned cable jacket material is mixing even on mixing roll, and roller refining temperature is 150 ℃, and mixing time is 30min, make the sample that thickness is 2mm again, test its mechanical property by GB GB/T 1040-92, its tensile strength is 10.0～12.0MPa, and elongation at break is 150～260%; Carry out level-vertical combustion test according to GB GB/T 2408-1996, be respectively FH-1, the FV-0 grade.Carry out oxygen index according to GB GB2406-93 and survey, test result is 28.0～30.0.
Therein ethylene-octene copolymer is that octene content is 14～20% ethylene-octene copolymers in the prescription;
The trade mark of new LDPE (film grade) is: 11IA-1;
Ethylene-vinyl acetate copolymer is that vinyl acetate content is 18～28% ethylene-vinyl acetate copolymer;
Magnesium hydroxide is through the surface-modifying agent modification, and particle diameter is 2～4 microns a magnesium hydroxide.
Expansible black lead is: allowance for expansion is 150～250mL/g, and granularity is 0.15～0.3mm, and the pH value is 6～7, and carbon content is 90%～99% expansible black lead,
The interlamellar spacing of organic modification montmonrillonite is 2.8nm,
Lubricant is a kind of in stearic acid, Zinic stearas or the oleylamide,
Oxidation inhibitor is tetramethylolmethane-four-(3-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) ester.
Characteristics of the present invention are:
(1) the present invention is main fire retardant with magnesium hydroxide, because magnesium hydroxide is being stable below 340 ℃, its decomposition temperature is more much higher than aluminium hydroxide, and smoke density is little, therefore can make CABLE MATERIALS nonflammable, and can not emit a large amount of smog during burning.
(2) be the fire retardant synergist with expansible black lead and organic modification montmonrillonite; The fire-retardant key of expansible black lead is that it can form densification under heating condition, stable expansion charcoal layer, expansion charcoal layer has good anti-fiery ability, in fire, can resist the invasion and attack of flame, and then performance is effectively heat insulation, the oxygen barrier effect, the material between flame and the base material and the transmission of heat have been blocked, delay or suppressed the course of the thermal destruction or the thermal destruction of polymkeric substance, finally reach and stop the incendiary purpose, and have nontoxic during its burning, smoke release is low, therefore advantages such as heat release rate is low can make CABLE MATERIALS can not produce a large amount of smog and can form densification at material surface when burning, stable expansion thermal insulation layer.Organic modification montmonrillonite can form charcoal layer and silicate multilayered structure in the thermal decomposition and combustion process, play the effect of overflowing heat insulation and the prevention inflammable gas.
(3) adopt the matrix of ethene-vinyl acetate copolymer (EVA), new LDPE (film grade) (LDPE), ethylene-octene copolymer (POE) three's blend, can improve the flame retardant properties and the resistance toheat of CABLE MATERIALS biglyyer as CABLE MATERIALS.
The present invention adopts the common fire retardant polyolefin polymkeric substance of magnesium hydroxide and expansible black lead and organic modification montmonrillonite, makes high performance non-halogen flame-retardant cable.The CABLE MATERIALS that is obtained has than more excellent mechanical property and flame retardant properties.Tensile strength can reach 10～14MPa, and elongation at break reaches 150～350%, and the vertical combustion experiment can reach the FV-0 grade, and oxygen index reaches more than 29.
Embodiment:
With embodiment the inventive method is done further concrete detailed explanation below.
Embodiment 1
Adopt the ethylene-octene copolymer (octene content is 18%) of 50 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 30 parts new LDPE (film grade), 90 parts magnesium hydroxide, (its expansion multiplying power is 250 times to 10 parts of expansible black lead fire retarding synergists, particle diameter is 300 microns, carbon content is 95%), and 5 parts organic modification montmonrillonite (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, by the mechanical property of GB GB/T 1040-92 test compound material, wherein tensile strength and elongation at break are respectively 11.1MPa and 278%, and level-vertical combustion test is carried out according to GB GB/T 2408-1996, be respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.1.
Embodiment 2
Adopt the ethylene-octene copolymer (octene content is 18%) of 60 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 20 parts new LDPE (film grade), 90 parts magnesium hydroxide, (its expansion multiplying power is 250 times to 10 parts of expansible black lead retardant synergists, particle diameter is 300 microns, carbon content is 95%), and 5 parts organic modification montmonrillonite (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T 1040-92 test compound material. wherein tensile strength and elongation at break are respectively 12.3MPa and 160%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.5.
Embodiment 3
Adopt the ethylene-octene copolymer (octene content is 18%) of 70 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 10 parts new LDPE (film grade), 90 parts magnesium hydroxide, (its expansion multiplying power is 250 times to 10 parts of expansible black lead fire retarding synergists, particle diameter is 300 microns, carbon content is 95%), and 5 parts organic modification montmonrillonite (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T 1040-92 test compound material. wherein tensile strength and elongation at break are respectively 11.6MPa and 151%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.2.
Embodiment 4
Adopt the ethylene-octene copolymer (octene content is 18%) of 50 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 30 parts new LDPE (film grade), 90 parts magnesium hydroxide, (its expansion multiplying power is 250 times to 10 parts of expansible black leads, particle diameter is 300 microns, carbon content is 99%) fire retarding synergist, 2 parts of organic modification montmonrillonites (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T1040-92 test compound material. wherein tensile strength and elongation at break are respectively 11.5MPa and 169%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.0.
Embodiment 5
Adopt the ethylene-octene copolymer (octene content is 18%) of 50 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 18%), 30 parts new LDPE (film grade), 90 parts magnesium hydroxide, 10 parts of expansible black leads, 5 parts of organic modification montmonrillonites (interlamellar spacing is 2.8nm), fire retarding synergist, in two roller mills that material is mixing even, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T 1040-92 test compound material. wherein tensile strength and elongation at break are respectively 12.1MPa and 243%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.0.
Embodiment 6
Adopt the ethylene-octene copolymer (octene content is 14.5%) of 50 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 30 parts new LDPE (film grade), 90 parts magnesium hydroxide, 10 parts of expansible black lead fire retarding synergists, 5 parts of organic modification montmonrillonites (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T 1040-92 test compound material. wherein tensile strength and elongation at break are respectively 11.9MPa and 282%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.5.
Embodiment 7
Adopt the ethylene-octene copolymer (octene content is 18%) of 50 parts of weight, 20 parts ethylene-vinyl acetate copolymer (vinyl acetate content is 28%), 30 parts new LDPE (film grade), 92 parts magnesium hydroxide, 8 parts of expansible black lead fire retarding synergists, 5 parts of organic modification montmonrillonites (interlamellar spacing is 2.8nm), in two roller mills that material is mixing evenly, the roller temperature is 150 ℃, and mixing time is 30min.Compressing tablet on 160 ℃ vulcanizing press then, cold pressing, depanning, make the sample that thickness is 2mm, mechanical property by GB GB/T 1040-92 test compound material. wherein tensile strength and elongation at break are respectively 11.2MPa and 270%, level-vertical combustion test is carried out according to GB GB/T 2408-1996, is respectively FH-1, the FV-0 grade.Oxygen index is surveyed and is carried out according to GB GB2406-93, and test result is 29.3.
Claims (2)
1. a halogen-free flame-proof cable sheath material is to be mixed by matrix resin, fire retardant, lubricant, oxidation inhibitor, and in mass fraction, it is as follows specifically to fill a prescription:
A) matrix resin 100
Wherein: ethylene-octene copolymer 40～98
New LDPE (film grade) 1～30
Ethylene-vinyl acetate copolymer 1～30
B) fire retardant 80～120
Wherein: magnesium hydroxide 70～100
Expansible black lead 5～20
Organo montmorillonite 2～10
C) lubricant 0～2
D) oxidation inhibitor 1～5;
Therein ethylene-octene copolymer is that octene content is 14～20% ethylene-octene copolymers;
The trade mark of new LDPE (film grade) is: 11IA-1;
Ethylene-vinyl acetate copolymer is that vinyl acetate content is 18～28% ethylene-vinyl acetate copolymer;
Magnesium hydroxide is through the surface-modifying agent modification, and particle diameter is 2～4 microns a magnesium hydroxide;
Expansible black lead is: allowance for expansion is 150～250mL/g, and granularity is 0.15～0.3mm, and the pH value is 6～7, and carbon content is 90%～99% expansible black lead,
The interlamellar spacing of organic modification montmonrillonite is 2.8nm,
Lubricant is a kind of in stearic acid, Zinic stearas or the oleylamide,
Oxidation inhibitor is tetramethylolmethane-four-(3-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) ester.
2. halogen-free flame-proof cable sheath material according to claim 1 is characterized in that, in mass fraction, it is as follows specifically to fill a prescription:
A) matrix resin 100
Wherein: ethylene-octene copolymer 50～80
New LDPE (film grade) 10～30
Ethylene-vinyl acetate copolymer 10～20
B) fire retardant 100～105
Wherein: magnesium hydroxide 90～100
Expansible black lead 5～10
Organo montmorillonite 2～5
C) lubricant 0～2
D) oxidation inhibitor 1～2.
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| CNB2007100637170A CN100465220C (en) | 2007-02-08 | 2007-02-08 | Halogen-free flame-proof cable sheath material |
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| CNB2007100637170A CN100465220C (en) | 2007-02-08 | 2007-02-08 | Halogen-free flame-proof cable sheath material |
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| CN100465220C true CN100465220C (en) | 2009-03-04 |
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