CN104744798A - Flame-retardant cable sheathing nano-material and preparation method thereof - Google Patents

Flame-retardant cable sheathing nano-material and preparation method thereof Download PDF

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CN104744798A
CN104744798A CN201510143347.6A CN201510143347A CN104744798A CN 104744798 A CN104744798 A CN 104744798A CN 201510143347 A CN201510143347 A CN 201510143347A CN 104744798 A CN104744798 A CN 104744798A
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flame retardant
preparation
parts
retardant cable
nano material
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梁继勇
严峙胜
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ANHUI GAOGOU CABLE Co Ltd
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ANHUI GAOGOU CABLE Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
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    • 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
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08K3/20—Oxides; Hydroxides
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    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

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Abstract

The invention discloses a flame-retardant cable sheathing nano-material and a preparation method thereof. The preparation method comprises the following steps: drying the raw material ethylene-vinyl acetate copolymer for 5.5-6h at the temperature of 105 DEG C for later use, in turn adding the LDH and modified hydrotalcite at a proportion of 3phr, 6phr, 9phr and 12phr in an SHL-35 type double-screw extruder, squeezing and granulating, and adding 8-11 parts of nano-active agent, 2-6 parts of accelerant, 0.5-1.8 parts of plasticizer and 2-6 parts of anti-aging agent, setting the squeezing temperatures to 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C and 185 DEG C and the host rotary speed to 40 r/min, and performing compression moulding on the dried particle material by a press vulcanizer at the temperature of 190 DEG C. The nano-material provided by the invention cooperating with a modified fire retardant ethylene-vinyl acetate copolymer has good mechanical property, flame retardant property and heat-resistant quality.

Description

A kind of flame retardant cable outsourcing nano material and preparation method thereof
Technical field
The invention belongs to cable material technical field, particularly relate to a kind of flame retardant cable outsourcing nano material and preparation method thereof.
Background technology
Along with the development of computer techno-stress engineering, people more and more apply multiple stage computer and giant-powered computer.For the consideration to computer room safety, people progressively recognize the cable using high temperature material to make.At present, the cable being applied to this field generally uses halogen-free flame-retardant cable and silanes crosslinked cable.In halogen-free flame-retardant cable, shield semiconductors cable and two step method silanes crosslinked cable, use maximum materials to be ethylene-vinyl acetate copolymer.Ethylene-vinyl acetate copolymer is also known as ethylene-vinyl acetate copolymer resin, and molecular formula is C6H10O2, and molecular weight is 114.1424.Ethylene-vinyl acetate copolymer is obtained by ethene and vinyl acetate between to for plastic copolymerization, and polymerization process has 3 kinds.1. high pressure bulk polymerization: the pressure using more than 98MPa, produces ethylene-vinyl acetate copolymer with being similar to High-pressure Polyethylene Production method.2. pressure suspension polymerization in: the suspension stabilizer such as water and polyacrylate and VAC are made suspension, put into the reactor of removing oxygen, press-in ethene, in the presence of a free-radical initiator, at 9.8 ~ 29.4MPa(100 ~ 300KGF/cm2), be polymerized while stirring at 75 ~ 80 DEG C of temperature.3. solution polymerization process: select not produce the trimethyl carbinol of chain tra nsfer, aliphatic hydrocarbon and benzene and make solvent, make initiator with superoxide, azo-compound, 65 DEG C, copolymerization under the pressure of 7.8MPa.By ethene, vinyl acetate between to for plastic, initiator and molecular weight regulator, add in high pressure tubular reactors through compressor according to a certain ratio, polyreaction is carried out under 200 ~ 220 DEG C and 150 ~ 160MPa pressure, obtain the multipolymer containing 15% ~ 30% vinyl acetate between to for plastic, first it be separated in the high-pressure separator of 20 ~ 30MPa with unreacted gas, and unreacted gas participates in reaction again through high-pressure recycle system.Polymkeric substance is separated from light pressure separator, through extruding, pelletizing, dry ethylene-vinyl acetate copolymer product.The ethylene-vinyl acetate copolymer separated from light pressure separator is isolated after vinyl acetate between to for plastic through cooling system, and ethene participates in reaction again through low pressure recycle system.
In China, ethene and acetate ethylene copolymer, according to the difference of wherein vinyl acetate content, are divided into ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer rubber and VAE emulsion by people.The product that vinyl acetate content is less than 40% is ethylene-vinyl acetate copolymer resin; The product of vinyl acetate content 40%-70% is very pliable and tough; High resilience feature, the ethylene-vinyl acetate copolymer resin of this content range is sometimes referred to as ethylene-vinyl acetate copolymer rubber by people; Vinyl acetate content usually in emulsion state, is called VAE emulsion within the scope of 70%-95%.
Ethylene-vinyl acetate copolymer is mainly used as various film, foaming product, hot melt adhesive and polymer modifiers 2. mainly for the manufacture of thermosol.Part PVC and rubber can be replaced, also can be used for cable sheath, packaging and agricultural film, medical material, calcic-plastic composite material, laminate etc.Ethylene-vinyl acetate copolymer resin has good filler pardon and cross linkable, and the ethylene-vinyl acetate copolymer resin used in electric wire, vinyl acetate content is generally 12% ~ 24%.
At present, the class flame-retardant system be made up of acid source, charcoal source, source of the gas three basal components and Chemical expanding flame-retardant system are in the research and development application stage.Chemical expanding flame-retardant system technique functions comes from the expanding fire-proof paint occurred the thirties in 20th century.Tramm proposed first section of patent Tramm about expanding fire-proof paint and points out in the patent in 1938; the layer of charcoal of expansion can be formed at this frie retardant coating of substrate surface when heating, thus can effectively protect base material from the further burning of flame.Afterwards Olsen and Bechle employed in 1948 " expansion " one word the expansion or foamed phenomenon that occur when polymkeric substance is heated or burns are described.Jones etc. have studied the limit combustion system Multiple components role that expands in great detail, will the carbide of charcoal be provided to be referred to as charcoal source, and will the compound steeping pearl effect be caused to be referred to as foaming source.What generate acid in addition when burning is referred to as acid source.The initial stage of polymkeric substance research is applied at chemically expansible type flame-retarded technology, namely between 20 century 70s to the eighties, Camino etc., for advancing the research and development of this technology, around the application of chemically expansible type flame-retardant system in polyolefin, have carried out a series of fundamental research.Flame-retardant system wherein the most typically based on ammonium polyphosphate/tetramethylolmethane (APP/PER) flame-retardant polypropylene rare (PP).
But expansion type flame retardant great majority are still in the conceptual phase in laboratory, and do not realize suitability for industrialized production, major cause is as follows: (1) expansion type flame retardant water absorbability is strong.Such as, take APP/MEL/PER as the expansion type flame retardant of main component, between each component, more easily alcoholysis occurs, fire-retardant matrix water resisting property is declined.(2) poor compatibility of expansion type flame retardant and matrix, the insulating property of matrix and electrical property are declined, and especially mechanical property such as resistance to impact shock and tensile strength all can significantly decline.(3) relative molecular weight carved of expansion type flame-retarding is all less, than being easier to the surface moving to polymkeric substance, the thermostability of material also can be made to decline, finally causing the physical and mechanical properties of matrix and aesthetic appearance decline.(4) stoichiometric between expansion type flame retardant and matrix is still indefinite.(5) addition of expansion type flame retardant still needs larger.
Along with going deep into of research, people propose cooperative flame retardant imagination.Cooperative flame retardant refers to the flame-retardant system be made up of two kinds or two or more components, and up to the present its flame retardant effect is better than each component flame retardant effect sum, and typical cooperative flame retardant system mainly comprises that halogen phosphorus is collaborative, halogen Di collaborative, phosphorus nitrogen is collaborative.Nano material is after the eighties in 20th century, exploitation was come out, cause the very big concern of countries in the world, and research shows that nano-meter flame retardants just can make the heat release rate of system (HRR) and heat release rate peak value (PHRR) have obvious reduction under few additive.Because halogen system fire-retardant quarter is to the harm of environment, expanding fire retardant and nano-meter flame retardants receive increasing concern, and the combination of expandable flame retardant and nanotechnology, add MMT, LDH, CNT, POSS etc., while raising flame retarding efficiency, the thermostability, physical and mechanical properties etc. of flame-proofed polymer material can be improved again to some extent.So, also concentrated to the collaborative research between both.
In the research that polymer nanocomposite material is combined with expandable flame retardant, applying maximum is methyl cyclopentyl-dialkyl-tricarbon manganium (i.e. MMT).This with MMT abundance, nano-lamellar structure easier in polymer chain intercalation etc. relevant, also become the katalysis in charcoal process relevant with the thermal destruction of stratiform cinnamic acid salt pair Intumescent Retardant System.Data show, adding of MMT nanocomposite system causes the HRR of expandable flame retardant PP generally to decline.Research points out that the Synergistic Mechanisms between MMT and IFR is that the acid sites that DeR produces has strong katalysis, is conducive to the carrying out that Intumescent Retardant System oxydehydrogenation is cross-linked into charcoal process; In combustion, the restructuring of nano-complex surface forms heat-resisting silicate layer of charcoal, strengthens the iris action of layer of charcoal to oxygen and volatility product.
Adding of carbon nanotube can bring positive effect to the heat resistanceheat resistant of polymkeric substance and flame retardant properties, so the combination of it and expanding fire retardant, can reach and improve polymkeric substance and become carbonaceous amount, improve flame retardant properties, improve the performance such as thermostability and mechanics simultaneously.
Although the research of nanometer/expansion cooperative flame retardant system makes great progress; though but still have a lot of problem to be solved: (1), still the collaborative of expansion type flame retardant and nano-meter flame retardants rests on both directly blended stages at present, therefore synergy still improves a lot space; (2) mechanism that expansion/nanometer cooperative is fire-retardant is still unclear, as the quantitatively characterizing of the reacting to each other of silicate and expansion type flame-retarding and each component, carbon residue structure, silicate expansion type flame-retarding cutd open and the katalysis of polymeric matrix still very general; (3) expansion/nanometer cooperative flame-retardant system is a complicated heterogeneous system, on the impact of microtexture each other and still need further research to the relation of the final flame retardant properties of compound system when multicomponent mixture coexists.
Because the consistency of ethylene-vinyl acetate copolymer and mineral filler is good, so the fire-retardant general employing loading level of ethylene-vinyl acetate copolymer is comparatively large and have certain mineral filler fire retardant pressing down cigarette effect in prior art.Magnesium hydroxide (MH) and aluminium hydroxide (ATH) be ethylene-vinyl acetate copolymer than better suited fire retardant, but the flame retardant effect of ATH is not as good as MH.Research shows, MH has the effect promoting into charcoal to ethylene-vinyl acetate copolymer, and its ethylene-vinyl acetate copolymer residue thermostability of filling is higher.But the data of taper calorimetric show, when high addition (49%), ATH is more effective than MH, but MH can extend burning time, and ATH is not all right, and burning time even shortens when few additive.
In prior art, halogen containing flame-retardant system also has good flame retardant effect to ethylene-vinyl acetate copolymer, decabromodiphynly oxide and antimonous oxide are also with obtaining good flame retardant effect, but because bromide fire retardant can produce the shortcoming of toxic gas and dense smoke, it is also few that it applies in electric wire fire retardant material.
In view of the defect existed in above prior art, be necessary it to improve further, make it have more standby practicality, could realistic service condition.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of flame retardant cable outsourcing nano material and preparation method thereof.The mechanical property of nanometer cooperative modified flame-retardant ethylene-vinyl acetate copolymer of the present invention, flame retardant properties, resistance toheat all significantly improve.
The present invention takes following technical scheme to realize: a kind of flame retardant cable outsourcing nano material and preparation method thereof, the raw materials of described flame retardant cable outsourcing nano material comprises: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part, modified hydrotalcite (self-control) 3-5 part;
Preparation method of the present invention comprises: by for subsequent use after dry 5.5-6h at feed ethylene-vinyl acetate copolymer 105 DEG C, in SHL-35 type twin screw extruder, additional proportion is extruding pelletization after the LDH of 3phr, 6phr, 9phr, 12phr and modified hydrotalcite successively, and nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part; Extrusion temperature setting is followed successively by 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C, and engine speed is 40r/min, then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
The modified hydrotalcite preparation method that the present invention uses is:
A certain amount of magnesium aluminum-hydrotalcite is scattered in after making slurries in the deionized water of de-CO2 and water-soluble for excessive NaH2PO42H2O institute wiring solution-forming is slowly poured in slurries, heated and stirred also regulates about PH to 4.5 with dust technology, reacts 1.5 hours under reflux temperature.After naturally cooling, also filter until filtrate PH=7 with the deionized water wash product of de-CO2, then drying obtains MgAl-H2PO4-LDHs.
The modified hydrotalcite preparation method that the present invention uses can also be:
Get appropriate carbonate Intercalated (LDHs) in there-necked flask, and be scattered in there-necked flask after adding the deionized water of appropriate de-CO2 and form good slurries.By wiring solution-forming soluble in water for appropriate NaH2PO42H2O, then joined solution is slowly poured in slurries, do not stop heated and stirred, and about regulating PH value to 4.5 with rare HNO3, then be warming up to 105 DEG C of reactions, under reflux temperature, react naturally cooling after 2.5-3.0h; And also filter until the PH=7 of filtrate with the deionized water wash product of emergence work, then at 60 DEG C, in air dry oven, obtain product MgAl-H2PO4-LDHs (M-LDHs) after dry 6h.
Wherein, the embodiment of the present invention use nanoparticle active agent for MgO and Al2O3 by 2:3 part by weight mixing produce, adopt indoor temperature solid phase method prepare.
One or more mixtures that the anti-aging agent that one embodiment of the invention use is following products: antioxidant A W, anti-aging agent RD, antioxidant A, antioxidant D.
The promotor that another embodiment of the present invention uses obtains for altax and accelerant B Z mix according to the part by weight of 1:2.5.
The described softening agent that one more embodiment of the present invention uses is o-phthalic acid dibutyl ester (DOP).
The raw materials optimum weight ratio of the flame retardant cable outsourcing nano material that another embodiment of the present invention uses is: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 10 parts, promotor 5 parts, 1.2 parts, softening agent, 4 parts, anti-aging agent, modified hydrotalcite (self-control) 5 parts.
The technique effect that the present invention is useful is: the mechanical property of nanometer cooperative modified flame-retardant ethylene-vinyl acetate copolymer of the present invention, flame retardant properties, resistance toheat are all better.
Embodiment
Describe embodiments of the present invention in detail below with reference to embodiment, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
A kind of flame retardant cable outsourcing nano material and preparation method thereof, the raw materials of described flame retardant cable outsourcing nano material comprises: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part, modified hydrotalcite (self-control) 3-5 part;
Preparation method of the present invention comprises: by for subsequent use after dry 5.5-6h at feed ethylene-vinyl acetate copolymer 105 DEG C, in SHL-35 type twin screw extruder, additional proportion is extruding pelletization after the LDH of 3phr, 6phr, 9phr, 12phr and modified hydrotalcite successively, and nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part; Extrusion temperature setting is followed successively by 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C, and engine speed is 40r/min, then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
The modified hydrotalcite preparation method that the present invention uses is:
A certain amount of magnesium aluminum-hydrotalcite is scattered in after making slurries in the deionized water of de-CO2 and water-soluble for excessive NaH2PO42H2O institute wiring solution-forming is slowly poured in slurries, heated and stirred also regulates about PH to 4.5 with dust technology, reacts 1.5 hours under reflux temperature.After naturally cooling, also filter until filtrate PH=7 with the deionized water wash product of de-CO2, then drying obtains MgAl-H2PO4-LDHs.
The modified hydrotalcite preparation method that the present invention uses can also be:
Get appropriate carbonate Intercalated (LDHs) in there-necked flask, and be scattered in there-necked flask after adding the deionized water of appropriate de-CO2 and form good slurries.By wiring solution-forming soluble in water for appropriate NaH2PO42H2O, then joined solution is slowly poured in slurries, do not stop heated and stirred, and about regulating PH value to 4.5 with rare HNO3, then be warming up to 105 DEG C of reactions, under reflux temperature, react naturally cooling after 2.5-3.0h; And also filter until the PH=7 of filtrate with the deionized water wash product of emergence work, then at 60 DEG C, in air dry oven, obtain product MgAl-H2PO4-LDHs (M-LDHs) after dry 6h.
Wherein, the embodiment of the present invention use nanoparticle active agent for MgO and Al2O3 by 2:3 part by weight mixing produce, adopt indoor temperature solid phase method prepare.
Solid-phase reaction of the present invention overcomes conventional wet and prepares the agglomeration traits that magnesium oxide nanoparticle exists, and has reaction without the need to solvent, the advantage such as productive rate is high, reaction conditions is easy; And overcome that the efficiency existed in original solid-phase reaction is low, the shortcoming of the oxidizable distortion of particle.
One or more mixtures that the anti-aging agent that one embodiment of the invention use is following products: antioxidant A W, anti-aging agent RD, antioxidant A, antioxidant D.
Antioxidant A W:6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline is brown viscous liquid, and sterling is light brown sticky cylinder liquid.Nontoxic, proportion is 1.029 ~ 1.030(25 DEG C), boiling point is 169 DEG C.Benzene, acetone, dichloroethane, tetracol phenixin, industrial naptha and ethanol can be dissolved in; Water insoluble.Shelf-stable.Be the anti-ozone anti-aging agent of special efficacy, also have protective effect to flex crack and thermo-oxidative ageing.The goods used under being specially adapted to dynamic condition.
Anti-aging agent RD: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer is for amber is to canescence arborescens powder, nontoxic.Softening temperature is not less than 74 DEG C.Acetone, benzene, chloroform, dithiocarbonic anhydride can be dissolved in, be slightly soluble in petroleum hydrocarbon; Water insoluble.The oxidation that energy rejection condition is harsher, thermal ageing and Weather effect, but poor to flex crack protection effect.No blooming, there is light contamination.General amount ranges is 0.5-2 part, reaches as high as 3 compositions.
Antioxidant A: N-phenyl-α-aniline, for tawny is to purple crystal shape material, sterling is colorless plate crystal, because of containing a small amount of methyl naphthylamine and aniline, poisonous, can not with skin contact.Proportion is 1.16-1.17, and fusing point is not less than 52.0 DEG C.Be soluble in acetone, ethyl acetate, benzene, ethanol, chloroform, tetracol phenixin; Dissolve in gasoline; Water insoluble.Gradual change purple in daylight and air.Inflammable.Antioxidant A to heat, oxygen, to subdue and the solarization such as weather all has good protection effect, be the general anti-aging agent of natural rubber, synthetic rubber and reclaimed rubber.The performance that ozone-resistant is aging is had concurrently in chloroprene rubber; Also there is certain inhibition easily to disperse in dry glue to the solarization of variable valency metal ions and reclaimed rubber, be also easily scattered in water; Solubleness in rubber is up to 5%, larger than antioxidant D, and consumption is no blooming 3 ~ 4 parts time, therefore can increase consumption to improve protective benefits.
Antioxidant D is: N-Phenyl beta naphthylamine, and for light gray is to light brown powder, sterling is white powder.Proportion is 1.18, and fusing point is not less than 104 DEG C.Easy solvent is in acetone, ethyl acetate, dithiocarbonic anhydride, chloroform; Dissolve in ethanol, tetracol phenixin; Be insoluble to gasoline and water.Under air and daylight, gradually become grey black, but do not affect protection effect.Inflammable.Antioxidant D is the universal anti-aging agent of natural rubber, synthetic rubber and latex.All there is good protective effect to heat, oxygen, flex crack and general aging action, and be slightly better than antioxidant A.Also have protective effect to the ion of poisonous metal, but comparatively antioxidant A is poor.If with anti-aging agent 4040 or 4010NA and use, heat resistanceheat resistant, oxygen, flex crack and ozone-resistant aging resistance all have remarkable increase.Easily be scattered in water in dry glue.
The promotor that another embodiment of the present invention uses obtains for altax and accelerant B Z mix according to the part by weight of 1:2.5.
The described softening agent that one more embodiment of the present invention uses is o-phthalic acid dibutyl ester (DOP).Plasticizer DOP is colourless oil liquid, proportion 0.9861 (20/20), fusing point-55, and boiling point 370 (normal pressure) is water insoluble, is dissolved in ethanol, ether, the most of organic solvent of mineral wet goods.General purpose grade DOP, is widely used in the industry such as plastics, rubber, paint and emulsifying agent.DOP is universal softening agent, be mainly used in the processing of the processing of polyvinyl chloride fat, also the can be used for ground superpolymer such as resin, acetate resin, ABS resin and rubber, also can be used for making paint, dyestuff, dispersion agent etc., the PVC of DOP plasticising can be used for manufacturer's fabricate-leather, agricultural film, wrapping material, cable etc.
The raw materials optimum weight ratio of the flame retardant cable outsourcing nano material that another embodiment of the present invention uses is: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 10 parts, promotor 5 parts, 1.2 parts, softening agent, 4 parts, anti-aging agent, modified hydrotalcite (self-control) 5 parts.
The technique effect that the present invention is useful is: the mechanical property of nanometer cooperative modified flame-retardant ethylene-vinyl acetate copolymer of the present invention, flame retardant properties, resistance toheat are all better.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.

Claims (8)

1. a flame retardant cable outsourcing nano material, is characterized in that,
The raw materials of described flame retardant cable outsourcing nano material comprises: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part, self-control modified hydrotalcite 3-5 part;
The nanoparticle active agent that raw materials comprises is that MgO and Al2O3 produces by the part by weight mixing of 2:3.
2. a preparation method for flame retardant cable outsourcing nano material, is characterized in that, ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part, self-control modified hydrotalcite 3-5 part; The preparation method of described flame retardant cable outsourcing nano material comprises: by for subsequent use after dry 5.5-6h at feed ethylene-vinyl acetate copolymer 105 DEG C, in SHL-35 type twin screw extruder, additional proportion is extruding pelletization after the LDH of 3phr, 6phr, 9phr, 12phr and modified hydrotalcite successively, and nanoparticle active agent 8-11 part, promotor 2-6 part, softening agent 0.5-1.8 part, anti-aging agent 2-6 part; Extrusion temperature setting is followed successively by 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C, and engine speed is 40r/min, then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
3. the preparation method of a kind of flame retardant cable outsourcing nano material according to claim 2, it is characterized in that, described modified hydrotalcite preparation method for: a certain amount of magnesium aluminum-hydrotalcite is scattered in after making slurries in the deionized water of de-CO2 and water-soluble for excessive NaH2PO42H2O institute wiring solution-forming is slowly poured in slurries, heated and stirred also regulates about PH to 5 with dust technology, react 1.5 hours under reflux temperature, after naturally cooling, also filter until filtrate PH=7 with the deionized water wash product of de-CO2, then drying obtains MgAl-H2PO4-LDHs.
4. the preparation method of a kind of flame retardant cable outsourcing nano material according to claim 2, is characterized in that, described nanoparticle active agent adopts indoor temperature solid phase method preparation.
5. the preparation method of a kind of flame retardant cable outsourcing nano material according to claim 2, is characterized in that, described anti-aging agent is one or more mixtures of following products: antioxidant A W, anti-aging agent RD, antioxidant A, antioxidant D.
6. the preparation method of a kind of flame retardant cable outsourcing nano material according to claim 2, is characterized in that, described promotor is that altax mixes obtained with accelerant B Z according to the part by weight of 1:2.5.
7. the preparation method of a kind of flame retardant cable outsourcing nano material according to claim 2, it is characterized in that, described softening agent is o-phthalic acid dibutyl ester.
8. a kind of flame retardant cable outsourcing nano material according to claim 1, is characterized in that,
The raw materials optimum weight ratio of described flame retardant cable outsourcing nano material is: ethylene-vinyl acetate copolymer 100 parts, nanoparticle active agent 10 parts, promotor 5 parts, 1.2 parts, softening agent, 4 parts, anti-aging agent, self-control modified hydrotalcite 5 parts.
CN201510143347.6A 2015-03-30 2015-03-30 Flame-retardant cable sheathing nano-material and preparation method thereof Pending CN104744798A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1475535A (en) * 2003-03-25 2004-02-18 北京化工大学 Phosphate intercalation water talc and its preparation method and use as fire retardant
CN104183306A (en) * 2014-09-03 2014-12-03 太仓苏晟电气技术科技有限公司 Low-smoke zero-halogen and highly-flame-retardant electric wire and preparation method thereof
CN104341676A (en) * 2014-11-03 2015-02-11 安徽天元电缆有限公司 Novel low-smoke zero halogen flame-retardant cable material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1475535A (en) * 2003-03-25 2004-02-18 北京化工大学 Phosphate intercalation water talc and its preparation method and use as fire retardant
CN104183306A (en) * 2014-09-03 2014-12-03 太仓苏晟电气技术科技有限公司 Low-smoke zero-halogen and highly-flame-retardant electric wire and preparation method thereof
CN104341676A (en) * 2014-11-03 2015-02-11 安徽天元电缆有限公司 Novel low-smoke zero halogen flame-retardant cable material

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