CN104710682A - Method for preparing nano fire-retardant material for cable wrapping - Google Patents
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- 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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- 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
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- C08K9/02—Ingredients treated with inorganic substances
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- 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
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- 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 method for preparing a nano fire-retardant material for cable wrapping. The method comprises the steps: drying a raw material, namely Eva, for 6 hours at the temperature of 80 DEG C for later use, sequentially adding LDH, of which the ratio is 3phr, 6phr, 9phr and 12phr respectively, and modified hydrotalcite into a twin-screw extruder SHL-35, then, carrying out extrusion granulation, and adding 1-4 parts of an anti-aging agent, 1-3 parts of an accelerant, 0.6-1.5 parts of a plasticizer and 5-11 parts of a nano activator, wherein the extrusion temperature is set to be 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C and 185 DEG C sequentially, and the revolution rate of a principal machine is 40 revolutions per minute; then, carrying out compacting molding on the dried granular material with a plate vulcanizing machine at the temperature of 190 DEG C. According to the method, the mechanical properties, flame retardance and heat resistance of nano synergistic-modified flame-retardant EVA are relatively good.
Description
Technical field
The present invention relates to cable material technical field, particularly a kind of preparation method of the flame retardant nano-materials for cable outsourcing.
Background technology
Along with the development of computer techno-stress engineering, for the consideration to computer room safety, people use halogen-free flame-retardant cable and silanes crosslinked cable more and more.Because EVA resin has good filler pardon and cross linkable, therefore use more in halogen-free flame-retardant cable, shield semiconductors cable and two step method silanes crosslinked cable.In addition, EVA resin is also applied to the sheath making some special cables.The EVA resin used in electric wire, vinyl acetate content is generally 12% ~ 24%.
The classification of fire retardant can be divided into halogen system, organophosphorus system and halogen phosphorus system, silicon system, high purity alumina-magnesia, molybdenum system, boron system, nitrogen system etc. according to element kind.Halogenated flame retardant for a long time high with its flame retarding efficiency, consumption is few, price is low and well-known.Since first Europe in 1986 find that polybromodiphenyl ether, the two benzdioxan of tetrabromo and the two cumarones of tetrabromo etc. contained in the product that the burning of brominated system produces belong to carcinogenic substance, the situation that Halogen flame-retardant system rules all the land receives stern challenge, and employing bittern-free flame-proof material and product have been the fact of trend of the times.The promulgation of European Union's two instructions " instruction of waste electronic electrical equipment " (WEEE) and " forbidding Hazardous Substances Directive in electronic and electrical equipment " (RoHS) accelerates this process.Inorganic combustion inhibitor (boron system, silicon system etc.) although have low toxicity, anti-corruption candle property, inexpensive, the advantage such as low cigarette in combustion processes, but but there are some very serious shortcomings, as low flame retarding efficiency and thermostability, the physical and mechanical properties of material is caused and worsens largely.People are devoted to the research and development of environmentally friendly fire retardant in recent years, and its focus mainly concentrates on chemically expansible flame-retardant system and nano flame retardant system.
Eva: ethylene-vinyl acetate copolymer, English abbreviation: EVA, coding: 1314, molecular formula: (C2H4) x. (C4H6O2) y, chemical property: commodity polymer polymkeric substance.Ethene and acetate ethylene copolymer are most important products in ethylene copolymer, general are referred to as EVA abroad.But in China, ethene and acetate ethylene copolymer, according to the difference of wherein vinyl acetate content, are divided into EVA resin, EVA rubber and VAE emulsion by people.The product that vinyl acetate content is less than 40% is EVA resin; The product of vinyl acetate content 40% ~ 70% is very pliable and tough; High resilience feature, the EVA resin of this content range is sometimes referred to as EVA rubber by people; Vinyl acetate content usually in emulsion state, is called VAE emulsion in 70% ~ 95% scope.
The content of the vinyl acetate between to for plastic in EVA lower than 20% time, at this moment just can be used as plastics and use.EVA has good resistance to low temperature, its heat decomposition temperature is lower, is about about 230 DEG C, along with the increase of molecular weight, the softening temperature of EVA rises, processibility and plastic surface luster property decline, but intensity increases, and impelling strength and environmental stress crack resistance improve, the chemical-resistant resistance of EVA, oil-proofness aspect are than PE, PVC is slightly poor, and with the increase of vinyl acetate content, changes more obvious.
EVA resin is ethylene-vinyl acetate copolymer, and general vinyl acetate between to for plastic (VA) content is 5% ~ 40%.Compared with polyethylene, EVA owing to introducing Vinyl Acetate Monomer in molecular chain, thus reduce high-crystallinity, improve snappiness, shock resistance, filler intermiscibility and heat seal performance, be widely used in the fields such as foaming shoe material, functional greenhouse film, packing film, hot melt adhesive, electric wire and toy.In general, the performance of EVA resin depends primarily on the content of vinyl acetate between to for plastic on molecular chain.
Chemically expansible type fire-retardant (int μm of escent flame retardant) system originates from traditional what is called " three sources ": i.e. a class flame-retardant system of acid source, charcoal source, source of the gas three basal components formations.Chemically expansible type flame-retarded technology originates 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).
Although the synthesis report of expansion type flame retardant is a lot of at present, great majority are still in the conceptual phase in laboratory, do not realize suitability for industrialized production, and 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.
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 was opened from the eighties in 20th century. after question generation, 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.
Expansion/nanometer cooperative fire-retardant representative be the research being applied to APP/PER system about molecular sieve.The molecular sieve of research discovery 1 % ~ 1.5 % content can make the LOI of expansion type flame-retarding PP, PE, PS of interpolation 30%APP/PER and the rare based polyalcohol of second improve 2 ~ 20.
In the research that polymer nanocomposite material is combined with expandable flame retardant, applying maximum is 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 EVA and mineral filler is good, so the fire-retardant general employing loading level of EVA 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 EVA 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 EVA, and its EVA 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 EVA, decabromodiphynly oxide and antimonous oxide with obtaining good flame retardant effect, but the shortcoming of toxic gas and dense smoke can be produced due to bromide fire retardant, and it is also few that it applies in electric wire fire retardant material.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of nano flame retardant cable material and Application and preparation thereof.The mechanical property of nanometer cooperative modified flame-retardant EVA of the present invention, flame retardant properties, resistance toheat are all better.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of the flame retardant nano-materials for cable outsourcing,
The raw materials of the described flame retardant nano-materials for cable outsourcing comprises: EVA, modified hydrotalcite, anti-aging agent, promotor, softening agent, nanoparticle active agent;
Preparation method comprises: raw material Eva is for subsequent use after dry 6h at 80 DEG C, extruding pelletization add LDH and modified hydrotalcite successively in SHL-35 type twin screw extruder after, and anti-aging agent, promotor, softening agent, nanoparticle active agent; Extrusion temperature setting is followed successively by: 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C; Engine speed is 40r/min; Then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
Described modified hydrotalcite can be LDHs.
Described nanoparticle active agent can comprise in following reagent one or more: MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, alum, kaolin.
Described modified hydrotalcite is preferably M-LDHs.
Described anti-aging agent can be 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline.
Described anti-aging agent also can be: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.
Described anti-aging agent can also be: N-phenyl-α-aniline.
Described promotor can be one or more in following product: promotor T, altax, accelerant B Z.
Described softening agent can be o-phthalic acid dibutyl ester.
For solving the problems of the technologies described above, present invention also offers and a kind ofly as described in aforementioned any one, prepare the application in cable outsourcing material for the preparation method of the flame retardant nano-materials of cable outsourcing.
For solving the problems of the technologies described above, invention further provides a kind of nanometer cooperative modified flame-retardant EVA cable material.
The preparation of modified hydrotalcite LDHs
A certain amount of magnesium aluminum-hydrotalcite is scattered in the deionized water of de-CO2 and makes excessive NaH after slurries
2pO
42H
2o water-soluble institute wiring solution-forming is slowly poured in slurries, and heated and stirred also regulates about pH to 4.5 with dust technology, reacts 1.5 hours under reflux temperature.After naturally cooling, with de-CO
2deionized water wash product and filter until filtrate pH=7, then drying obtains LDHs.
The preparation of modified hydrotalcite M-LDHs
Get appropriate carbonate Intercalated (LDHs) in there-necked flask, and add appropriate de-CO
2deionized water after be scattered in there-necked flask and form good slurries.By appropriate NaH
2pO
42H
2o wiring solution-forming soluble in water, then slowly pours into joined solution in slurries, does not stop heated and stirred, and regulates PH value to about 4-5 with rare HNO3, is then warming up to 100 DEG C-105 DEG C reactions, reacts naturally cooling after 2.5h under reflux temperature.And with removing CO
2deionized water wash product and filter until the pH=7 of filtrate, then at 60 DEG C, in air dry oven, obtain product MgAl-H after dry 6h
2pO
4-LDHs (M-LDHs).
As shown in Figure 1, for providing to obtain the TEM photo of two kinds of hydrotalcites (LDHs and M-LDHs) in the embodiment of the present invention, can find out that LDHs is obvious class hexagon, M-LDHs is rotund sheet material, before modified, the pattern of LDHs and M-LDHs changes, and the size of sheet surfaces is probably 50-150nm.
The anti-aging agent that the present invention uses can be: 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline.Its trade name is antioxidant A W.Antioxidant A W 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.
The anti-aging agent that the present invention uses can also be: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.Trade name is anti-aging agent RD.Anti-aging agent RD be amber 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.
Anti-aging agent of the present invention can be again: N-phenyl-α-aniline.Trade name is antioxidant A.Antioxidant A be tawny 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.
Anti-aging agent of the present invention also can be: N-Phenyl beta naphthylamine.Trade name is antioxidant D.Antioxidant D is light grey to light brown powder, and 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 the embodiment of the present invention uses is one or more in following product: promotor T, altax, accelerant B Z.
Softening agent of the present invention can be: 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.
Softening agent of the present invention can also be: DEDB.DEDB and polyvinyl chloride and the rare multipolymer of vinyl chloride acetic acid second, the poly-rare good intermiscibility of acetic acid second, also and polyvinyl chloride, polymethyl acrylate, polyvinyl alcohol butyral, Nitrocellulose, N-BUTYL ACETATE Mierocrystalline cellulose and ethyl cellulose etc. mix.DEDB lighter color, plasticizing efficiency are high, intermiscibility good, volatility is low, exudative low, thermally-stabilised index is high, cold-resistant water-fast extraction, not oxidizable and volatilization, excellent electrical properties, weighting agent capacity greatly, goods luminance brightness high.Be widely used in PVC plastic particle, non-filling calendered film, leatheroid, CABLE MATERIALS, sheet material, sheet material, soft or hard tubing, sole material, rubber-plastic strip, foamed material, film, paint, rubber, synthetic glass, printing-ink, plastipaste, acetate emulsion tackiness agent etc.Be the one that softening agent industry price is minimum, can significantly reduce rubber product cost.
Softening agent of the present invention also can be: Octyl adipate.Its chemistry is by name: hexanodioic acid 2121 ethylhexyl, molecular formula is C
22h
42o
4, Octyl adipate is colorless and odorless transparent oily liquid, can be dissolved in most of organic solvents such as ethanol, ether, acetone, acetic acid, be slightly soluble in ethylene glycol, water insoluble.But the volatility of Octyl adipate is large, and there is certain deficiency the aspects such as water tolerance, transport property, insulativity.Octyl adipate is normal and phthalate is composite, is applied to cold-resistant agricultural film, cable coating layer, leatheroid, sheet material, outdoor water pipe and Frozen Food Packaging film etc.Octyl adipate can also as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polystyrene, vinylchlorid one acetic acid butylene copolymer.At present, di-n-hexyl adipate is also widely used in polyvinyl butyral resin film.In addition, in many countries, legal its can be used as the softening agent of food, medical packaging plastics.
Softening agent of the present invention can be again: di-n-hexyl adipate.Di-n-hexyl adipate is the cold resisting type softening agent that consumption is maximum in the world.N-octyl-n-decyl adipate, colourless transparent liquid is by hexanodioic acid and the n-Octanol of straight chain, the straight chain type binary acid mixed ester of nonylcarbinol lactate synthesis; N-octyl-n-decyl adipate is dissolved in mineral oil, gasoline and most of organic solvent, insoluble or be slightly soluble in glycerine, glycols and some amine, is the straight chain type cold-resistant plasticizer of excellent property.Compared with hexanodioic acid branched-chain alcoho, there is better resistance to low temperature, and volatilization loss, thermotolerance and photostabilization, water-extraction resistance etc. are also excellent compared with side chain alcohol ester.When it and phthalic ester shares time, polyvinyl chloride Vinyl Acetate Copolymer Emulsion performance can be improved, be widely used for the cold resistant plasticizer of polyvinyl acetate (PVA), polystyrene, polymethylmethacrylate, nitrocellulose, ethyl cellulose and rubber.
Softening agent of the present invention can be: butyl benzyl phthalate (Butyl benzyl phthalate) molecular weight 312.40.Character: colourless transparent oil liquid.Relative density (25 DEG C/4 DEG C) 1.116 ,-35 DEG C, zero pour, boiling point 370 DEG C. flash-point (opening) 19 9 DEG C. specific refractory power 1.535. viscosity (25 DEG C) 41.5mPas, is dissolved in organic solvent and hydro carbons.Water insoluble.Flammable.Micro-poison.With most of rubber and resin compatible good. solvation is strong, the softening agent of, oil resistant extractable heat-resisting as water tolerance.
Softening agent of the present invention can also be: cold resistant plasticizer DOS.Dioctyl sebacate (DOS), formal name used at school: sebacic acid two (2-ethyl hexyl) ester molecule formula: C26H50O4.Cold resistant plasticizer DOS is colourless or pale yellow transparent oily liquids, zero pour-48 ° of C, boiling point: 256 ° of C (0.67Kpa), point of ignition 257-263 ° C, viscosity 25mPa.s (20 ° of C), refractive index 1.449-1.451 (25 ° of C), can be dissolved in the organic solvents such as hydro carbons, alcohols, ketone, ester class, chlorinated hydrocarbon, be insoluble to di-alcohols and water.Cold resistant plasticizer DOS is the excellent cold resistant plasticizer of a kind of polyvinyl chloride, and plasticizing efficiency is high, and volatility is low, therefore except having excellent low temperature cold tolerance, has again good thermotolerance, can use at a higher temperature.The weathering resistance of this product is better, and electrical insulation properties is also more excellent, normal and phthalate use, is specially adapted to the goods such as cold-resistant electric wire and CABLE MATERIALS, leatheroid, film, sheet material, sheet material.Cold resistant plasticizer DOS can as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polymethylmethacrylate, polystyrene, vinyl chloride copolymer.
The nanoparticle active agent that raw materials comprises is one or more in following compounds (or mixture): MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, AlN, ZnO, KAl (SO
4)
212H
2o(alum), Al
2o
3-2SiO
2-2H
2o(kaolin).
The MgO that the embodiment of the present invention uses is nano-MgO particle.
The present embodiment adopts indoor temperature solid phase method to prepare MgO particle.
The concrete grammar that the present embodiment indoor temperature solid phase method prepares MgO particle is preferably: by MgCI solution and Na2CO3(raw material mass mixture ratio 1:1.2) solution, with PVA solution (polyvinyl alcohol solution) for properties-correcting agent, reaction produces precipitation MgCO3 precipitation, then, under 75 ~ 85 DEG C of constant temperature, the mode transformed by precipitation obtains alkali formula carbon formula magnesium presoma.50 ~ 60 DEG C of standing alkali formula carbon formula magnesium presoma precipitation 24-30 hour.Finally pass at Ar air-flow, temperature is calcination under the condition of 600 ~ 650 DEG C, obtains nano-MgO particle.Adopt PVA as polymeric surface active agent, control the reunion of particle, obtained nano-MgO particle dispersion is better, and be cubic structure, substantially spherical in shape, its particle diameter is 25-35nm.
The technique effect that the present invention is useful is: the mechanical property of nanometer cooperative modified flame-retardant EVA of the present invention, flame retardant properties, resistance toheat are all better.
Accompanying drawing explanation
Fig. 1 is the TEM photo of two kinds of hydrotalcites (LDHs and M-LDHs) described in the embodiment of the present invention;
Fig. 2 is the digital photo of test materials described in the embodiment of the present invention in 400 DEG C of retort furnaces after heating flame 30min;
Fig. 3 for described in the embodiment of the present invention without the stress-strain(ed) curve of any surface-treated magnesium hydroxide.
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.
One embodiment of the invention provides a kind of preparation method of the flame retardant nano-materials for cable outsourcing,
The raw materials of the described flame retardant nano-materials for cable outsourcing comprises: EVA, modified hydrotalcite, anti-aging agent, promotor, softening agent, nanoparticle active agent;
Preparation method comprises: raw material Eva is for subsequent use after dry 6h at 80 DEG C, extruding pelletization add LDH and modified hydrotalcite successively in SHL-35 type twin screw extruder after, and anti-aging agent, promotor, softening agent, nanoparticle active agent; Extrusion temperature setting is followed successively by: 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C; Engine speed is 40r/min; Then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
Described modified hydrotalcite can be LDHs.
Described nanoparticle active agent can comprise in following reagent one or more: MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, alum, kaolin.
Described modified hydrotalcite is preferably M-LDHs.
Described anti-aging agent can be 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline.
Described anti-aging agent also can be: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.
Described anti-aging agent can also be: N-phenyl-α-aniline.
Described promotor can be one or more in following product: promotor T, altax, accelerant B Z.
Described softening agent can be o-phthalic acid dibutyl ester.
Another embodiment of the present invention provides a kind ofly is preparing the application in cable outsourcing material for the preparation method of the flame retardant nano-materials of cable outsourcing as described in aforementioned any one.
Embodiment of the present invention raw material:
EVA (Elvax
360) 1000 parts: Dupont, melt flow rate (MFR) is 2 g/10 min, and density is 0.948g/cm
3, self-control modified hydrotalcite 10-30 part, anti-aging agent 1-4 part, promotor 1-3 part, softening agent 0.6-1.5 part, nanoparticle active agent 5-11 part.
The preparation method of modified hydrotalcite LDHs
Magnesium aluminum-hydrotalcite is scattered in de-CO
2deionized water in make slurries after, by NaH
2pO
42H
2the water-soluble supersaturated solution that is made into of O is slowly poured in slurries, and heated and stirred also regulates pH to 4.2 ~ 4.3 with dust technology, reacts 1.5 hours under reflux temperature.After naturally cooling, with de-CO
2deionized water wash product and filter until filtrate pH=7, then drying obtains carbonate Intercalated (LDHs).
The preparation method of modified hydrotalcite M-LDHs
Get carbonate Intercalated (LDHs) in there-necked flask, and add de-CO
2deionized water after be scattered in there-necked flask and form good slurries.By NaH
2pO
42H
2o is soluble in water is made into saturated solution, is then slowly poured in slurries by joined solution, does not stop heated and stirred, and uses rare HNO
3regulate PH value to 4.8 ~ 5.0, be then warming up to 100 DEG C-105 DEG C reactions, under reflux temperature, react naturally cooling after 2.5h.And with removing CO
2deionized water wash product and filter until the pH=7 of filtrate, then at 60 DEG C, in air dry oven, obtain product MgAl-H after dry 6h
2pO
4-lDHs (M-LDHs).
As shown in Figure 1, for providing to obtain the TEM photo of two kinds of hydrotalcites (LDHs and M-LDHs) in the embodiment of the present invention, can find out that LDHs is obvious class hexagon, M-LDHs is rotund sheet material, before modified, the pattern of LDHs and M-LDHs has certain change, and the size of sheet surfaces is probably 50-150nm.
The anti-aging agent that one embodiment of the invention uses is: 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline, its trade name is antioxidant A W.Antioxidant A W 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.
The anti-aging agent that another embodiment of the present invention uses is: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.Trade name is anti-aging agent RD.Anti-aging agent RD be amber 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.
The anti-aging agent that yet another embodiment of the invention uses is: N-phenyl-α-aniline.Trade name is antioxidant A.Antioxidant A be tawny 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.
The anti-aging agent that further embodiment of this invention uses is: N-Phenyl beta naphthylamine.Trade name is antioxidant D.Antioxidant D is light grey to light brown powder, and 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 the embodiment of the present invention uses is one or more in following product: promotor T, altax, accelerant B Z.
The softening agent that one embodiment of the 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 softening agent that another embodiment of the present invention uses is: DEDB.DEDB and polyvinyl chloride and the rare multipolymer of vinyl chloride acetic acid second, the poly-rare good intermiscibility of acetic acid second, also and polyvinyl chloride, polymethyl acrylate, polyvinyl alcohol butyral, Nitrocellulose, N-BUTYL ACETATE Mierocrystalline cellulose and ethyl cellulose etc. mix.DEDB lighter color, plasticizing efficiency are high, intermiscibility good, volatility is low, exudative low, thermally-stabilised index is high, cold-resistant water-fast extraction, not oxidizable and volatilization, excellent electrical properties, weighting agent capacity greatly, goods luminance brightness high.Be widely used in PVC plastic particle, non-filling calendered film, leatheroid, CABLE MATERIALS, sheet material, sheet material, soft or hard tubing, sole material, rubber-plastic strip, foamed material, film, paint, rubber, synthetic glass, printing-ink, plastipaste, acetate emulsion tackiness agent etc.Be the one that softening agent industry price is minimum, can significantly reduce rubber product cost.
The softening agent that yet another embodiment of the invention uses is: Octyl adipate.Its chemistry is by name: hexanodioic acid 2121 ethylhexyl, molecular formula is C
22h
42o
4, Octyl adipate is colorless and odorless transparent oily liquid, can be dissolved in most of organic solvents such as ethanol, ether, acetone, acetic acid, be slightly soluble in ethylene glycol, water insoluble.But the volatility of Octyl adipate is large, and there is certain deficiency the aspects such as water tolerance, transport property, insulativity.Octyl adipate is normal and phthalate is composite, is applied to cold-resistant agricultural film, cable coating layer, leatheroid, sheet material, outdoor water pipe and Frozen Food Packaging film etc.Octyl adipate can also as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polystyrene, vinylchlorid one acetic acid butylene copolymer.At present, di-n-hexyl adipate is also widely used in polyvinyl butyral resin film.In addition, in many countries, legal its can be used as the softening agent of food, medical packaging plastics.
The softening agent that further embodiment of this invention uses is: di-n-hexyl adipate.Di-n-hexyl adipate is the cold resisting type softening agent that consumption is maximum in the world.N-octyl-n-decyl adipate, colourless transparent liquid is by hexanodioic acid and the n-Octanol of straight chain, the straight chain type binary acid mixed ester of nonylcarbinol lactate synthesis; N-octyl-n-decyl adipate is dissolved in mineral oil, gasoline and most of organic solvent, insoluble or be slightly soluble in glycerine, glycols and some amine, is the straight chain type cold-resistant plasticizer of excellent property.Compared with hexanodioic acid branched-chain alcoho, there is better resistance to low temperature, and volatilization loss, thermotolerance and photostabilization, water-extraction resistance etc. are also excellent compared with side chain alcohol ester.When it and phthalic ester shares time, polyvinyl chloride Vinyl Acetate Copolymer Emulsion performance can be improved, be widely used for the cold resistant plasticizer of polyvinyl acetate (PVA), polystyrene, polymethylmethacrylate, nitrocellulose, ethyl cellulose and rubber.
The softening agent that further embodiment of this invention uses is: butyl benzyl phthalate (Butyl benzyl phthalate) molecular weight 312.40.Character: colourless transparent oil liquid.Relative density (25 DEG C/4 DEG C) 1.116 ,-35 DEG C, zero pour, boiling point 370 DEG C. flash-point (opening) 19 9 DEG C. specific refractory power 1.535. viscosity (25 DEG C) 41.5mPas, is dissolved in organic solvent and hydro carbons.Water insoluble.Flammable.Micro-poison.With most of rubber and resin compatible good. solvation is strong, the softening agent of, oil resistant extractable heat-resisting as water tolerance.
The softening agent that further embodiment of this invention uses is: cold resistant plasticizer DOS.Dioctyl sebacate (DOS), formal name used at school: sebacic acid two (2-ethyl hexyl) ester molecule formula: C
26h
50o
4.Cold resistant plasticizer DOS is colourless or pale yellow transparent oily liquids, zero pour-48 ° of C, boiling point: 256 ° of C (0.67Kpa), point of ignition 257-263 ° C, viscosity 25mPa.s (20 ° of C), refractive index 1.449-1.451 (25 ° of C), can be dissolved in the organic solvents such as hydro carbons, alcohols, ketone, ester class, chlorinated hydrocarbon, be insoluble to di-alcohols and water.Cold resistant plasticizer DOS is the excellent cold resistant plasticizer of a kind of polyvinyl chloride, and plasticizing efficiency is high, and volatility is low, therefore except having excellent low temperature cold tolerance, has again good thermotolerance, can use at a higher temperature.The weathering resistance of this product is better, and electrical insulation properties is also more excellent, normal and phthalate use, is specially adapted to the goods such as cold-resistant electric wire and CABLE MATERIALS, leatheroid, film, sheet material, sheet material.Cold resistant plasticizer DOS can as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polymethylmethacrylate, polystyrene, vinyl chloride copolymer.
The nanoparticle active agent that raw materials comprises is one or more in following compounds (or mixture): MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, AlN, ZnO, KAl (SO
4)
212H
2o(alum), Al
2o
3-2SiO
2-2H
2o(kaolin).
The MgO that the embodiment of the present invention uses is nano-MgO particle.
Nano-powder material industrialized producing technology requires that preparation method is simple, and production cost is suitable for, and reproducible, powder granularity is even, product purity is high, reunion degree is low.Method about nano magnesia synthesis in prior art is a lot, but in fact can be applied to industrial less.One is because problems such as equipment, cost, raw material, scale, investments; Two is that some technique is still in the laboratory study stage, and realize suitability for industrialized production and have any problem, even some may not realize suitability for industrialized production.
The present embodiment adopts indoor temperature solid phase method to prepare MgO particle.
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.
The concrete grammar that the present embodiment indoor temperature solid phase method prepares MgO particle is: by MgCI solution and Na
2cO
3(raw material mass mixture ratio 1:1.2) solution, with PVA solution (polyvinyl alcohol solution) for properties-correcting agent, reaction produces precipitation MgCO
3precipitation, then under 75 ~ 85 DEG C of constant temperature, the mode transformed by precipitation obtains alkali formula carbon formula magnesium presoma.50 ~ 60 DEG C of standing alkali formula carbon formula magnesium presoma precipitation 24-30 hour.Finally pass at Ar air-flow, temperature is calcination under the condition of 600 ~ 650 DEG C, obtains nano-MgO particle.Adopt PVA as polymeric surface active agent, control the reunion of particle, obtained nano-MgO particle dispersion is better, and be cubic structure, substantially spherical in shape, its particle diameter is 25-35nm.
The Si that the embodiment of the present invention uses
3n
4for nano silicon nitride silicon grain, meet following index:
the Si that the embodiment of the present invention uses
3n
4it can also be highly heat-conductive silicon nitride.Common silicon nitride has randomly-oriented sintering structure.Highly heat-conductive silicon nitride adds kind of crystal grain (diameter 1 μm, long 3-4 μm) at material powder (particle diameter less than 1 μm), makes the sub-orientations of this all crystal grain, forms the fibrous silicon nitride structure reaching 100 μm with orientation.Due to the formation of filamentary structure, thermal conductivity presents each diversity, and on oriented structure direction, thermal conductivity is 120w/ (mK), is 3 times of common silicon nitride, is equivalent to the thermal conductivity of steel.
The BN that the embodiment of the present invention uses is nano silicon nitride boron particles, meets following index:
| Median size (nm) | Purity (%) | Specific surface area (m2/g) | Volume density (g/cm3) | Density (g/cm3) | Crystal formation | Appearance color |
| <120 | >99.9 | >19 | 0.30 | 2.25 | Six sides | Black |
The embodiment of the present invention use high purity carbon dust be: Dongguan pull together produce 10000 high-purity carbon dusts.Performance index are:
| Fixed carbon: | 99.99% | Specification: | 10000 orders |
| The trade mark: | 18925457433 | Moisture: | 0.015% |
| Turgidity: | 1-2 doubly | Screen overflow granularity: | 0.0006% |
| Ash content: | 0.85 | Volatile matter: | 0.01％ |
| Screen underflow granularity: | 0.0005% |
The AlN filler that the embodiment of the present invention uses is: AlN whisker and AlN particle do filler.In the embodiment of the present invention, using EVA as matrix, less than 5 μm AlN whiskers and AlN particle-filled, obtain the matrix material of high flame retardant rate, AlN whisker and AlN particle ratio (mass ratio) are l:20 ~ 30.Invention further contemplates the confounding effect of filler and coupling agent to the impact of the fire-retardant rate of matrix material.By AlN whisker and the AlN mix particles of adequate rate, give matrix material comparatively high flame retardant rate than independent whisker and particle.
The ZnO that the embodiment of the present invention uses is: nano granular of zinc oxide.Its performance index are:
The embodiment of the present invention use nano zine oxide, for above-mentioned: 1 class nano-ZnO, 2 class nano-ZnOs, 3 class nano-ZnOs, in one.
The preparation of Eva matrix material
By EVA (Elvax
360, Dupont is tested) 1000 parts for subsequent use after dry 8h at 75 DEG C.Modified hydrotalcite 10-30 part is added successively in SHL-35 type twin screw extruder, anti-aging agent 1-4 part, promotor 1-3 part, softening agent 0.6-1.5 part, extruding pelletization after nanoparticle active agent 5-11 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 by dried pellet at 190 DEG C with vulcanizing press compression moulding and with after the obtained required testing standard sample of universal sampling machine, the flame retardant properties of exosyndrome material, thermal characteristics and crystal property etc.
Experimental group form:
Performance test and sign
The LOI of limiting oxygen index(LOI) (LOI) sample tests according to GB GB/T 2406-1993, concrete sample size is long 70 × 6.5 × 3 (± 0.1) mm3, when sample burning times is less than 3min or burning length little 50mm, the threshold concentration of the nitrogen carrier of oxygen needed for representing with oxygen purity is the limiting oxygen index(LOI) of material.
Horizontal vertical burning grade (UL-94)
Carry out vertical combustion performance according to GB GB/T 2408-1996 to PP matrix material to test, sample size is 130 × 13 × 3mm
3.5 samples at least tested by each sample, classified estimation the combustionproperty of recording materials.
Fig. 2 gives the digital photo of test materials in 400 DEG C of retort furnaces after heating flame 30min; As can be seen from Fig. 2, pure Eva only has a small amount of black carbon residue to remain, and extravagant area is very big; Eva/LDHs sample produces a loose greyish white carbon residue structure, the reduction compared with pure Eva of extravagant area; Eva/M-LDHs sample produces a carbon residue structure of relatively more compacting greyish white, and extravagant area reduces further.LDHs and M-LDHs can suppress its curtain coating in the process of polymer combustion, and the carbon residue area that M-LDHs is formed is less, and structure is finer and close, and compared with LDHs, it has better provide protection.
Mechanics Performance Testing
After the EVA matrix material of sulfidization molding is placed at room temperature 3 days, making 5B type dumbbell shaped batten (following standard GB/T 1040-2006) with sampling machine, on universal testing machine, do Mechanics Performance Testing with the speed of 200 mm/min.
Flame retardant properties is tested
After the EVA matrix material of sulfidization molding is placed at room temperature 3 days, cut into batten respectively according to GB GB/T 2408.96, vertical combustion instrument does flame retardant properties test.
Vertical combustion: UL.94 (plastics)
The flame retardant rating at the most end in HB:UL94 standard.Require the sample for 3 to 13 mm thick, combustionvelocity is less than 40 millimeters of per minutes; Be less than the sample of 3 mm thick, combustionvelocity is less than 70 millimeters of per minutes; Or extinguish before the mark of 100 millimeters.
V_2: after carrying out twice combustion testings of 10 seconds to sample, flame extinguished in 60 seconds.Combustionmaterial can be had to fall down.
V-1: after carrying out twice combustion testings of 10 seconds to sample, flame extinguished in 60 seconds.Combustionmaterial can not be had to fall down.
V-0: after carrying out twice combustion testings of 10 seconds to sample, flame extinguished in 30 seconds.Combustionmaterial can not be had to fall down.
Thermal characteristics
After the EVA matrix material of sulfidization molding is placed at room temperature 3 days, get and on thermal analyzer, do thermolysis test (TG) in right amount, test condition is pure nitrogen gas, and temperature rise rate is 20 degrees celsius/minute.And with pure Eva as a reference.
Fig. 3 shows the stress-strain(ed) curve of the pure Eva without any process.We can draw from curve, and from the trend of whole curve, stress increases along with the growth of Eva amount of tension.Within the scope of elongation 0-2cm, its stress has almost no change, and from 2cm, its stress parabolically form increases.When elongation is 14cm, reach stress maximum value 140N.
Following table shows the impact of different experiments group on fracture tensile strength and elongation at break:
| Experimental group | I | II | III | IV | V | VI | Control group |
| Elongation at break % | 123.4 | 319.2 | 260.7 | 179.2 | 48.4 | 86.2 | 20.1 |
| Fracture tensile strength MPa | 15.4 | 12.7 | 12.7 | 12.6 | 11.7 | 11.5 | 10.3 |
Upper table shows the fire-retardant EVA of different experiments group to the impact of the change of its elongation at break.Obviously, the fracture tensile strength between each experimental group and pure Eva control group and elongation at break difference obvious.
After the EVA matrix material of sulfidization molding is placed at room temperature 3 days, cut into 150 × 150x3mm batten respectively according to GB GB/T 2408-96, vertical combustion instrument does flame retardant properties test, and result is as follows:
| Experimental group | Control group | I | II | III | IV | V | VI |
| Average burning time first time (S) | 4 | 3 | 2 | 0 | 2 | 3 | 4 |
| Second time average burning time (S) | 36(molten drop) | 53 | 33 | 3 | 14 | 44 | 56 |
| Fire-retardant rank | Without rank | V-2 | V-1 | V-0 | V-0 | V-1 | V-2 |
Upper table lists the result of the fire-retardant EVA vertical combustion of different experiments group.Control group first time the average burning time be 4s, second time burning time within the 36th second, just produce molten drop, and mean time 36s, do not reach fire-retardant rank; Experimental group I average burning time first time is 3s, but second time average burning time 53S, and flame retardant properties is slightly poor is V-2 rank; Experimental group II average burning time first time is 2s, and at second time 33S combustion time, flame retardant grade is V-1 rank; Its flame retardant properties of experimental group III is best, and twice average burning time summation only has 3S, reaches V-0 rank; Experimental group IV average burning time first time is 2s, and the second time average burning time is 14s, and fire-retardant rank reaches V-0 rank; Experimental group V average burning time first time is 3S, and at second time 44S combustion time, flame retardant grade is V-1 rank; Experimental group VI average burning time first time is 4s, but second time average burning time 56S, be V-2 rank for flame retardant properties is slightly poor.
The above results illustrates the fire retardant cooperative flame retardant of the present invention's six groups of experimental formulas, effectively can improve flame retarding efficiency, reduces molten drop phenomenon when amount of flame-retardant agent and polymer materials burning; And the flame retardant properties of fire retardant material can be improved to a certain extent.
All above-mentioned this intellecture properties of primary enforcement, not setting restriction this product innovation of other forms of enforcement and/or novel method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on product innovation of the present invention.
Claims (10)
1., for a preparation method for the flame retardant nano-materials of cable outsourcing, it is characterized in that,
The raw materials of the described flame retardant nano-materials for cable outsourcing comprises: EVA, modified hydrotalcite, anti-aging agent, promotor, softening agent, nanoparticle active agent;
Preparation method comprises: raw material Eva is for subsequent use after dry 6h at 80 DEG C, extruding pelletization add LDH and modified hydrotalcite successively in SHL-35 type twin screw extruder after, and anti-aging agent, promotor, softening agent, nanoparticle active agent; Extrusion temperature setting is followed successively by: 180 DEG C, 185 DEG C, 195 DEG C, 195 DEG C, 185 DEG C; Engine speed is 40r/min; Then dried pellet is used vulcanizing press compression moulding at 190 DEG C.
2. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described modified hydrotalcite is LDHs.
3., according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described nanoparticle active agent comprise in following reagent one or more: MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, alum, kaolin.
4. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described modified hydrotalcite is M-LDHs.
5. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described anti-aging agent is 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline.
6. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described anti-aging agent is: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.
7. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described anti-aging agent is: N-phenyl-α-aniline.
8. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described promotor is one or more in following product: promotor T, altax, accelerant B Z.
9. according to claim 1 for the preparation method of the flame retardant nano-materials of cable outsourcing, it is characterized in that, described softening agent is o-phthalic acid dibutyl ester.
10. according to any one of claim 1 ~ 9, preparing the application in cable outsourcing material for the preparation method of the flame retardant nano-materials of cable outsourcing for one kind.
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|---|---|---|---|---|
| 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 |
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| 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 |
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