CN103467832A - Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof - Google Patents
Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material. The low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material is obtained through mixing 60-80 parts of an ethylene-vinyl acetate copolymer, 10-40 parts of polyethylene, 0-30 parts of ternary ethylene propylene rubber, 2-10 parts of a resin compatilizer, 35-65 parts of a halogen-free expanded flame retardant and 0.5-2 parts of a crosslinking agent, wherein at least one charring agent component in the halogen-free expanded flame retardant has a melting point of 155DEG C or less and an initial pyrolysis temperature of 245DEG C or less. The invention also discloses a preparation method of the cable material. The processing temperature of the introduced low-melting-point high-initial-pyrolysis-temperature charring agent component has a wide window and is matched with the processing temperature of a cable material matrix resin, so the charring agent component can be fused and well dispersed in the processing process, thereby the flame retardation efficiency is improved, the influences on the mechanical performances of the matrix resin are reduced, and the cable material has an excellent flame retardation performance and excellent mechanical performances. The preparation method has the advantages of simplicity, convenient operation, easy control and easy industrial production.
Description
Technical field
The invention belongs to non-halogen flame-retardant cable and preparing technical field thereof, specifically, the present invention relates to a kind of low temperature resistant flexible crosslinkable non-halogen flame-retardant cable and preparation method thereof.
Background technology
Related data in recent years statistics shows, in all kinds of fire failures in the whole nation, not only because the electric fire caused accounts for the largest percentage, and the fire failure of the large above grade of electric initiation is maximum.As 2000～2008, by the electric fire accidents caused, account for 33% of statistics fire sum; By electric reasons such as aging, the traffic overload of wire short-circuiting, electric wire and electrical equipment malfunctions, cause that cable ignites, propagation of flame etc. and the fire that causes accounts for more than 30% of fire sum, and have cumulative year after year trend [the fire accidents statistical study of the Li Hai river .2000-2008 whole nation. Chinese public safety scholarly edition (Fire Science) .2010,1:64-69.].Wherein, on December 15th, 2005, the wildfire accident occurs in Liaoyuan, Jilin province city central hospital, cause 39 people wrecked, 8,210,000 yuan of direct economic losses, the fire cause is that this hospital has been used cable off quality, causes in central hospital's switchgear building cable trench occurring the cable short circuit combustiblematerials that ignited on fire.On January 5th, 2010, lower 240 meters of Tan Jiashan town, Xiangtan County, xiangtan, hunan province city vertical victory coal mine is in production process that cable occurs is on fire, causes 34 miners wrecked, 2,962 ten thousand yuan of direct economic losses; Point out that this fire failure immediate cause is the aging breakage of non-flame retardant cable of laying in the vertical three dark vertical in road of centre, vertical victory colliery in " State Council to three special Serious Accidents the report of investigating make reply ", short circuit is caught fire, the outer plastic pipe-covered of shot-firing cable, produce a large amount of toxic and harmfuls, the personnel that the cause injures and deaths of suffocating.A series of fire cases shows, once cause this class fire failure, not only cause huge property damage, also can cause great loss of life and personal injury, this just makes the fire safety problem of electric wire and research and development and the application of halogen-free flame-retardant wire cable become very important and urgent.
And the restrictive coating of fire protection flame retarding electric wire commonly used all adopts, it is the Halogen flame-retardant polymer, and the Halogen flame-proofed polymer material easily decomposes in when burning and generates a large amount of cigarettes and poisonous and acrid gas (as hydrogenchloride etc.), the Dioxins that even produces high density had and cause " secondary disaster ", native land man requires at the Olympic Sports Center, airport, station, subway, Nuclear power plants, chemical industry, the special occasions such as Highrise buildings and naval vessel must be selected halogen-free low-smoke flame-retardant electric wire and cable, so fire-retardant non-halogen fire-fighting technology that become of CABLE MATERIALS, the inexorable trend of social development.
The more non-halogen flame-retardant cable be widely used again of research at present adopts high-content metal oxyhydroxide to be prepared from as the fire retardant polyolefine, as Japanese Yasumoto(US20080029743) a kind of CABLE MATERIALS of open report preparation method of fire retardant polyolefin, be exactly 80 parts of the propylene copolymers by multistep polymerization, 10 parts of Low Density Polyethylenes, add 250 parts of fire retardant Mg (OH) in the polyolefin base material of 10 parts of compositions of modified polypropene
2make, the limiting oxygen index(LOI) of this material (LOI) is 32.0%, and elongation at break is 220%.The disclosed a kind of halogen-free non-phosphor flame-proof cable sheath material of CN1581369 and for example, in 100 parts of ethylene-vinyl acetate copolymers (EVA), to have added 130 parts of acrylic acid modified aluminium hydroxides and 30 parts of sodium oleate modified magnesium hydroxides to be prepared from, the elongation of this CABLE MATERIALS is that 164%, LOI is 41.2%.As can be seen here, although adopt the inorganic combustion inhibitors such as magnesium hydroxide, aluminium hydroxide can obtain flame retardant resistance preferably, the addition of fire retardant is very large.So high loading level will damage the processability, flexibility (elongation at break) of CABLE MATERIALS, the performance such as low temperature resistant greatly, make it can not to have met explicitly calling for that China industry standard GA306.1-2007 proposes the resistance to low temperature of flame-proof cable material, especially wherein stipulated the elongation at break of material in the time of-15 ℃ >=20%.
Expansion type flame retardant (IFR) is due to its special intumescent flame retardant mechanism, be widely used in the fire-retardant research of Polyolefin and coating, make its fire-retardant macromolecular material not only there is anti-molten drop behavior, long-time or repeated exposure still has fabulous resistivity in flame, and also there is Halogen, without advantages such as antimony, low toxicity, low cigarette, non-corrosiveness gases, be described as the revolution of flame-retarded technology.IFR is comprised of acid source, charcoal source and source of the gas.At present application the most ripe and widely expansion type flame retardant surely belong to conventional expansion type flame retardant system: ammonium polyphosphate+tetramethylolmethane (+trimeric cyanamide).In order to solve the large problem of inorganic combustion inhibitor addition in CABLE MATERIALS, the scientific research personnel starts to attempt by IFR fire-retardant for CABLE MATERIALS, as CN101481475 discloses a kind of ultraviolet crosslinked expansion type flame-retardant polyolefin cable insulation sheath material, the expanding halide-free fire-retardant used in this sheath material is just ammonium polyphosphate+tetramethylolmethane (+trimeric cyanamide), or ammonium polyphosphate+macro molecular triazine series, or melamine salt of pentaerythritol phosphate compounds.Yet but there are a lot of applied defects in above-mentioned expansion type flame retardant for polyolefin cable insulation sheath material, main manifestations is that under the CABLE MATERIALS processing temperature, (90～180 ℃) can not melting or near start thermolysis or distillation the fusing point of flame retardant compositions self compound for (1) above-mentioned each fire retardant component, make dispersed the become difficult problem of fire retardant in resin base material, (2) poor heat stability of tetramethylolmethane, initial heat decomposition temperature is 211 ℃, under the processing temperature of polymkeric substance, easily decompose, (3) tetramethylolmethane is water-soluble strong, solubleness under room temperature is 6.8g/100ml, cause the IFR that every employing tetramethylolmethane is char-forming agent all to have poor heat stability, poor water resistance, and then make in use due to fire retardant, to be separated out with water-soluble its flame retardant properties that causes and there will be gradually the problem of losing by fire retardant material.For the problems referred to above, though the related scientific research personnel have carried out much research, but up to now, yet there are no about Heat stability is good and char-forming agent component and there is the report of the halogen-free expansion fire retardant of melting characteristic for fire-resistant cable material.
Summary of the invention
The objective of the invention is the problem existed for prior art, at first a kind of low temperature resistant flexible crosslinkable non-halogen flame-retardant cable is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned low temperature resistant flexible crosslinkable non-halogen flame-retardant cable.
Low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention, this CABLE MATERIALS is comprised of following component blend by mass parts:
Wherein contained halogen-free expansion fire retardant is comprised of 60～77% acid source, 20～35% charcoal source and 3～10% fire retarding synergist in massfraction, acid source and the charcoal source solubleness≤0.5g/100ml in water under 20 ℃, and having a char-forming agent component in the charcoal source at least is fusing point≤155 ℃, the compound of initial heat decomposition temperature >=245 ℃, the structural unit that the structural unit that this compound is meaned by following I, II or I, II, III mean forms:
The structural unit number of II wherein: the structural unit number of [I+III] is 1.33～1.67,20～100% of the structural unit number that the structural unit number of I is [I+III], preferably 100%; The segment of each structural unit or its formation is connected arbitrarily combination by carboxyl with hydroxy functional group.
The contained acid source of above CABLE MATERIALS is any in melamine coated ammonium polyphosphate, epoxy resin coated ammonium polyphosphate, silane coated ammonium polyphosphate, 6MD resin-coated ammonium polyphosphate, MF resin-coated ammonium polyphosphate or MF resin Phosphate coating ammonium polyphosphate, and the polymerization degree of ammonium polyphosphate >=700, contained charcoal source is dipentaerythritol, tripentaerythritol, 9, the esterification products and 9 of assorted phenanthrene-succinic acid (DDP) and three (2-hydroxyethyl) chlorinated isocyanurates (THEIC) of mix-10-phosphinylidyne of 10-dihydro-9-oxy, at least one in the common esterification products of the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates, wherein preferably 9, the esterification products of assorted phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 9, at least one in the common esterification products of the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates.
The contained fire retarding synergist of above CABLE MATERIALS is at least one in nano imvite, carbon nanotube, nano layered double hydroxides, polysilsesquioxane, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, kaolin and talcum.
The contained resin compatible agent of above CABLE MATERIALS is ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid copolymer (EAA), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride graft EVA(EVA-g-MAH) or maleic anhydride graft SBS (SEBS-g-MAH) in any; Contained linking agent is dicumyl peroxide (DCP), Glycerin triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), three (2-hydroxyethyl) isocyanuric acid triacrylate (THEICTA), cyanacrylate (TAIC), diacrylate-1, any in 6-hexylene glycol ester (HDDA) or pentaerythritol triacrylate (PET3A).
The preparation method of above-mentioned low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention, processing step and the condition of the method are as follows:
1) by phosphorous diprotic acid 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates, terephthalic acid and catalyzer, perhaps by phosphorous diprotic acid 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates and catalyzer, according to 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy accounts for [9, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-succinic acid of 10-phosphinylidyne+terephthalic acid] molecular fraction be 20～100%, preferably 100%, three (2-hydroxyethyl) chlorinated isocyanurates and [9, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-succinic acid of 10-phosphinylidyne+terephthalic acid] the proportioning of mol ratio=1.33～1.67, adopt (200～245 ℃ of conventional direct esterifications, 4～10h) after carrying out esterification, react and obtain fusing point≤155 ℃ through vacuum hydro-extraction, the low melting point of initial heat decomposition temperature>=245 ℃, high initial heat decomposition temperature (decomposition temperature during thermal weight loss 5wt% under nitrogen atmosphere in analyzing with TGA, T
5%, be defined as the initial heat decomposition temperature of sample) char-forming agent, reaction product is cooling, pulverize levigate sieving,
2) 60～77% acid source, 20～35% charcoal source and 3～10% fire retarding synergist are mixed and obtain halogen-free expansion fire retardant at homogenizer, acid source and the charcoal source solubleness≤0.5g/100ml in water under 20 ℃ wherein, having a char-forming agent component in the charcoal source at least is compound prepared by step 1), fire retarding synergist or before the esterification of step 1) or during esterification adds reaction system after finishing;
3) by mass parts, 60～80 parts of ethylene-vinyl acetate copolymers, 10～40 parts of polyethylene, 0～30 part of terpolymer EP rubber, 2～10 parts of resin compatible agent, 35～65 parts of halogen-free expansion fire retardants and 0.5～2 part of linking agent are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 20～200rpm, at 90～180 ℃ of temperature, through melt extruding granulation, get final product.
Preferably 10～30 parts of the add-ons of the terpolymer EP rubber that aforesaid method is used.
Aforesaid method acid source used is any in melamine coated ammonium polyphosphate, epoxy resin coated ammonium polyphosphate, silane coated ammonium polyphosphate, 6MD resin-coated ammonium polyphosphate, MF resin-coated ammonium polyphosphate or MF resin Phosphate coating ammonium polyphosphate, and the polymerization degree of ammonium polyphosphate >=700, charcoal source used is dipentaerythritol, tripentaerythritol, 9, the esterification products and 9 of assorted phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates of mix-10-phosphinylidyne of 10-dihydro-9-oxy, at least one in the common esterification products of the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates, wherein preferably 9, the esterification products of assorted phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 9, at least one in the common esterification products of the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates.
Aforesaid method fire retarding synergist used is at least one in nano imvite, carbon nanotube, nano layered double hydroxides, polysilsesquioxane, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, kaolin and talcum.
Aforesaid method resin compatible agent used is ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid copolymer (EAA), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride graft EVA(EVA-g-MAH) or maleic anhydride graft SBS (SEBS-g-MAH) in any; Linking agent used is dicumyl peroxide (DCP), Glycerin triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), three (2-hydroxyethyl) isocyanuric acid triacrylate (THEICTA), cyanacrylate (TAIC), diacrylate-1, any in 6-hexylene glycol ester (HDDA) or pentaerythritol triacrylate (PET3A).
Also can add and well known to a person skilled in the art 0.5～1 part of lubricant while adopting aforesaid method to prepare CABLE MATERIALS; 0.2～1 part, oxidation inhibitor; 0.1～0.5 part of UV light absorber; 1～2 part of colour batch.Wherein lubricant used can be any in stearic acid, calcium stearate, Zinic stearas, stearylamide, butyl stearate, polyethylene wax or silicone oil; Oxidation inhibitor can be antioxidant 1010 and the irgasfos 168 of mass ratio 4:1; UV light absorber can be any in UV-9, UV-531, UV-326, UV-327, UV Absorber BAD or UV light absorber triazine 5; Colour batch is commercially available various colour batches.
The present invention compared with prior art, has the following advantages:
1, owing in low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention, having introduced low melting point, the char-forming agent component of high initial heat decomposition temperature, but the processing temperature window of this component is wide and with the processing temperature of CABLE MATERIALS substrate resin coupling, can in the CABLE MATERIALS course of processing, melt, thereby improved the dispersive ability of fire retardant systems in substrate resin, make the degree of scatter of IFR in the CABLE MATERIALS substrate resin higher, distribute more even, so that in the fire-retardant efficiency that improves IFR, reduce the impact of IFR on the substrate resin mechanical property, final in the flame retardant properties of giving the CABLE MATERIALS excellence, make the mechanical property of material (comprise normal temperature, the elongation at break of material during low temperature) obviously be better than conventional fire-resistant cable material.
2, because the IFR added in low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention is prepared from by the high-polymerization degree ammonium polyphosphate modifying of water tolerance splendid (20 ℃ time solubleness≤0.5g/100ml) in water and char-forming agent and water-fast fire retarding synergist, thereby the flame retardant cable goods of not only having avoided the water-soluble height of conventional expansion type flame retardant (as ammonium polyphosphate+tetramethylolmethane+trimeric cyanamide) to cause make the problem of flame retardant properties variation in wet environment because of separating out of fire retardant, and also effectively improve the electrical insulation capability of CABLE MATERIALS goods.
3, due to blend that in low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention, substrate resin used is EVA, PE, EPDM, their second-order transition temperature is all below-50 ℃, thereby make the resistance to low temperature of CABLE MATERIALS good, can use at severe cold area.
4, because IFR flame retarding efficiency used in low temperature resistant flexible crosslinkable non-halogen flame-retardant cable provided by the invention is high, addition is little, in the char-forming agent component, contain can be at the component of fusion plastification under processing temperature in addition, thereby not only promoted the dispersion of fire retardant in substrate resin, make the elongation of fire-resistant cable material high, and because of flexible, in use, be easy to reel, not easy to crack.
5, because the present invention has introduced linking agent in the low temperature resistant flexible crosslinkable non-halogen flame-retardant cable of preparation, thereby chemically crosslinked or the cross-linking radiation of the course of processing be can pass through, its heat-resistant aging and heat-resisting shrinkage improved.
6, preparation method provided by the invention is simple, easy to operate, be easy to control and suitability for industrialized production, in production process, non-corrosiveness gas and refuse produce, and make the low temperature resistant flexible crosslinkable non-halogen flame-retardant cable of preparation have the characteristics such as Halogen, nontoxic, high flame retardant, environmental protection.
The accompanying drawing explanation
The low temperature resistant flexible crosslinkable non-halogen flame-retardant cable that accompanying drawing is the embodiment of the present invention 1 preparation, according to GB/T1040.2-2006, be prepared into 5A type standard mechanics test bars, and the environmental chamber at low temperature that is placed in-20 ℃ carries out the curve that Elongation test obtains.The CABLE MATERIALS that as can be seen from Figure prepared by the present invention also has very high tensile strength and high elongation at break at low temperatures, shows that material has good resistance to low temperature.
Embodiment
Below provide embodiment so that the invention will be further described.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
In addition, what deserves to be explained is: 1) in following examples, the umber of material is mass parts.The fusing point of the char-forming agent that 2) prepared by following examples is (the fusing point here refers in particular to the temperature range that material starts the temperature that the temperature of fusing melts fully to material) that adopts that the WRX-4 micro-meldometer measures; Initial heat decomposition temperature is to adopt TAQ5000 type thermogravimetric analyzer, at temperature rise rate, is 10 ℃/min, in nitrogen atmosphere, measures; Solubleness is at room temperature measured in water.The limiting oxygen index(LOI) LOI of the low temperature resistant flexible crosslinkable non-halogen flame-retardant cable that 3) prepared by following examples is according to the GB/T2406.2-2009 standard test; The vertical combustion grade is according to the GB/T2408-2008 standard test; Tensile strength under room temperature and elongation at break are according to the GB/T1040.2-2006 standard test; Tensile strength under low temperature and elongation at break are according to GB/T1040.2-2006, are prepared into 5A type standard mechanics test bars, and to be placed in the environmental chamber at low temperature of-20 ℃ stretch measures.
Embodiment 1
By 9 of 150.4g, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 800g tri-(2-hydroxyethyl) chlorinated isocyanurates, 288.7g terephthalic acid and 4.5g tetrabutyl titanate join in reactor, inflated with nitrogen is got rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200～240 ℃ in 2h and carry out esterification under mechanical stirring, controlling still Inner pressure is≤0.1MPa that, when the water of collecting the esterification generation reaches 70ml, esterification finishes; React at least 0.5h in 230～245 ℃ of vacuum hydro-extractions, discharging, pulverize levigate mistake 100 mesh sieves.The common esterification products (CFA-TTD1.41) that products therefrom is char-forming agent DDP and terephthalic acid and THEIC, its fusing point is 110～116 ℃, 265 ℃ of initial heat decomposition temperatures, the solubleness under room temperature in water is 0.4g/100ml.
By 350g char-forming agent CFA-TTD1.41,600g melamine coated ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700) and 50g molecular sieve, mix in homogenizer and make halogen-free expansion fire retardant (5-1).
First 80 parts of EVA, 20 parts of PE, 2 parts of EEA, 45 parts of halogen-free expansion fire retardants (5-1), 0.5 part of TMPTA, 0.5 part of stearic acid, 0.2 part of oxidation inhibitor, 0.1 part of ultraviolet absorbent UV-531 and 1 part of colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 120rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.0%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 12.0MPa, and elongation at break is 1130%; The tensile strength of-20 ℃ is 18.0MPa, and elongation at break is 576%.
Embodiment 2
By 9 of 793.8g, the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates and 5g tetrabutyl titanate join in reactor, and inflated with nitrogen is got rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200～240 ℃ in 2h and carry out esterification under mechanical stirring, controlling still Inner pressure is≤0.1MPa that, when the water of collecting the esterification generation reaches 75ml, esterification finishes; React at least 0.5h in 230～245 ℃ of vacuum hydro-extractions, discharging, pulverize levigate mistake 100 mesh sieves.The common esterification products (CFA-TD1.67) that products therefrom is char-forming agent DDP and THEIC, its fusing point is 105～109 ℃, 267 ℃ of initial heat decomposition temperatures, the solubleness under room temperature in water is 0.5g/100ml.
By 240g char-forming agent CFA-TD1.67,720g silane coated ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700) and 40g nano imvite, mix in homogenizer and make halogen-free expansion fire retardant (5-2).
First 80 parts of EVA, 15 parts of PE, 5 parts of PE-g-MAH, 45 parts of halogen-free expansion fire retardants (5-2), 2 parts of THEICTA, 1 part of calcium stearate, 0.5 part of oxidation inhibitor, 0.5 part of UV light absorber UV-327 and 1 part of colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 150rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 34.5%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 11.6MPa, and elongation at break is 1085%; The tensile strength of-20 ℃ is 17.1MPa, and elongation at break is 539%.
Embodiment 3
By 9 of 497g, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates, 238g terephthalic acid and 4.5g tetrabutyl titanate join in reactor, inflated with nitrogen is got rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200～240 ℃ in 2h and carry out esterification under mechanical stirring, controlling still Inner pressure is≤0.1MPa that, when the water of collecting the esterification generation reaches 95ml, esterification finishes; React at least 0.5h in 230～245 ℃ of vacuum hydro-extractions, discharging, pulverize levigate mistake 100 mesh sieves.The common esterification products (CFA-TTD1.33) that products therefrom is char-forming agent DDP and terephthalic acid and THEIC, its fusing point is 109～113 ℃, 266 ℃ of initial heat decomposition temperatures, the solubleness under room temperature in water is 0.2g/100ml.
By 242g char-forming agent CFA-TTD1.33,81g char-forming agent CFA-TD1.67,647g silane coated ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700) and 30g molecular sieve, mix in homogenizer and make halogen-free expansion fire retardant (5-3).
First 70 parts of EVA, 15 parts of PE, 10 parts of EPDM, 5 parts of PE-g-MAH, 45 parts of halogen-free expansion fire retardants (5-3), 1 part of TMPTMA, 0.5 part of Zinic stearas, 1 part of oxidation inhibitor, 0.2 part of ultraviolet absorbent uv-326 and 2 parts of colour batches are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 100rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 34.5%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 12.6MPa, and elongation at break is 1137%; The tensile strength of-20 ℃ is 18.5MPa, and elongation at break is 594%.
Embodiment 4
By 9 of 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates (THEIC), 497g, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, 238g terephthalic acid, 204g nano imvite, 4.5g tetrabutyl titanate join in reactor, inflated with nitrogen is got rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200～240 ℃ in 2h and carry out esterification under mechanical stirring, controlling still Inner pressure is≤0.1MPa that, when the water of collecting the esterification generation reaches 95ml, esterification finishes; React at least 0.5h in 230～245 ℃ of vacuum hydro-extractions, discharging, pulverize levigate mistake 100 mesh sieves.Products therefrom is the nano combined char-forming agent of CFA-TTD1.33/MMT, and fusing point is 111～115 ℃, 267 ℃ of initial heat decomposition temperatures, and the solubleness under room temperature in water is 0.2g/100ml.
By the 120g tripentaerythritol, the nano combined char-forming agent of 90g CFA-TTD1.33/MMT, 770g epoxy resin coated ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700) and 20g organosilicon polymer mix and make halogen-free expansion fire retardant (5-4) in homogenizer.
First 60 parts of EVA, 10 parts of PE, 30 parts of EPDM, 10 parts of resin compatible agent EVA-g-MAH, 65 parts of halogen-free expansion fire retardants (5-4), 2 parts of crosslink agent DCPs, 1 part of polyethylene wax, 1 part of oxidation inhibitor, 0.5 part of UV light absorber triazine 5 and 2 parts of colour batches are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 20rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 36.0%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 11.2MPa, and elongation at break is 1149%; The tensile strength of-20 ℃ is 17.3MPa, and elongation at break is 575%.
Embodiment 5
By 80g char-forming agent CFA-TD1.67,162g dipentaerythritol, 658g MF resin Phosphate coating ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700), 50g nano layered double hydroxides and 50g organosilicon polymer, mix in homogenizer and make halogen-free expansion fire retardant (5-5).
First 60 parts of EVA, 40 parts of PE, 10 parts of resin compatible agent EAA, 55 parts of halogen-free expansion fire retardants (5-5), 1 part of linking agent TAIC, 1 part of silicone oil, 0.5 part of oxidation inhibitor, 0.5 part of ultraviolet absorbent uv-326 and 1 part of colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 50rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.5%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 9.4MPa, and elongation at break is 962%; The tensile strength of-20 ℃ is 13.4MPa, and elongation at break is 467%.
Wherein MF resin Phosphate coating ammonium polyphosphate used is homemade, its preparation method is as follows: (a) performed polymer preparation: in the 500ml three-necked flask, add 40g trimeric cyanamide (MEL), and the ratio that is 2:3 according to MEL and formaldehyde mole ratio, be metered into formaldehyde, after being warmed up to 80 ℃ of stirring and dissolving, regulate pH value to 8～9, after reaction 1h, make resin prepolymer; (b) coat modification APP: in the 1000ml three-necked flask, add APP140g, deionized water 600ml, stir 10min and be uniformly dispersed, and then adds resin prepolymer, the resin prepolymer consumption be take coating material as the 3wt% metering, with phosphorus acid for adjusting pH value to 5.5, be warmed up to 80 ℃ of reaction 2h under high-speed stirring, cooling, by product suction filtration or centrifugation, and solid product is dried under 80～105 ℃ to obtain to MF resin Phosphate coating ammonium polyphosphate.
In following examples, the preparation method of MF resin-coated ammonium polyphosphate is basic identical, when just prepared by performed polymer, adopts the ratio that MEL and formaldehyde mole ratio are 1:3 to obtain.
Embodiment 6
By 80g char-forming agent CFA-TD1.67,162g dipentaerythritol, 658g MF resin Phosphate coating ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700), 50g polysilsesquioxane and 50g sepiolite, mix in homogenizer and make halogen-free expansion fire retardant (5-6).
First 60 parts of EVA, 20 parts of PE, 20 parts of EPDM, 10 parts of resin compatible agent EAA, 55 parts of halogen-free expansion fire retardants (5-6), 1 part of linking agent TAIC, 1 part of silicone oil, 0.5 part of oxidation inhibitor, 0.5 part of ultraviolet absorbent uv-326 and 1 part of colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 80rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.0%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 9.4MPa, and elongation at break is 1023.2%; The tensile strength of-20 ℃ is 14.0MPa, and elongation at break is 503%.
Embodiment 7
By 100g char-forming agent CFA-TD1.67,222g dipentaerythritol, 628g6MD resin-coated ammonium polyphosphate (polymerization degree of ammonium polyphosphate >=700), 20g molecular sieve and 30g azo-compound, mix in homogenizer and make halogen-free expansion fire retardant (5-7).
First 80 parts of EVA, 10 parts of PE, 10 parts of EPDM, 2 parts of resin compatible agent SEBS-g-MAH, 35 parts of halogen-free expansion fire retardants (5-7), 0.5 part of linking agent PET3A, 0.5 part of lubricant stearylamide, 0.5 part of oxidation inhibitor, 0.3 part of UV light absorber UV-9 and 1 part of colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 200rpm, at 90～180 ℃ of the interval temperature of screw rod, through melt extruding granulation, get final product.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 28.5%, and vertical combustion UL-94 is the V-0 level; Under room temperature, tensile strength is 11.1MPa, and elongation at break is 1109%; The tensile strength of-20 ℃ is 16.2MPa, and elongation at break is 567%.
Wherein 6MD resin-coated ammonium polyphosphate used is homemade, its preparation method is as follows: after adding the 600ml deionized water and stirring to be uniformly dispersed in 160g APP, according to the coating material consumption, be that 3wt% is metered into required 6MD resin, regulate pH value to 5.5, be warming up to 80 ℃ of reaction 2h under high-speed stirring, cooling by product suction filtration or centrifugation, and is dried solid product to obtain 6MD resin-coated ammonium polyphosphate under 80～105 ℃.
Claims (10)
1. a low temperature resistant flexible crosslinkable non-halogen flame-retardant cable, this CABLE MATERIALS is comprised of following component blend by mass parts:
Wherein contained halogen-free expansion fire retardant is comprised of 60～77% acid source, 20～35% charcoal source and 3～10% fire retarding synergist in massfraction, acid source and the charcoal source solubleness≤0.5g/100ml in water under 20 ℃, and having a char-forming agent component in the charcoal source at least is fusing point≤155 ℃, the compound of initial heat decomposition temperature >=245 ℃, the structural unit that the structural unit that this compound is meaned by following I, II or I, II, III mean forms:
The structural unit number of II wherein: the structural unit number of [I+III] is 1.33～1.67,20～100% of the structural unit number that the structural unit number of I is [I+III], and the segment of each structural unit or its formation is connected arbitrarily combination by carboxyl with hydroxy functional group.
2. low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 1, the contained acid source of this CABLE MATERIALS is any in melamine coated ammonium polyphosphate, epoxy resin coated ammonium polyphosphate, silane coated ammonium polyphosphate, 6MD resin-coated ammonium polyphosphate, MF resin-coated ammonium polyphosphate or MF resin Phosphate coating ammonium polyphosphate, and the polymerization degree of ammonium polyphosphate >=700; Contained charcoal source is dipentaerythritol, tripentaerythritol, 9, at least one in the common esterification products of the esterification products of assorted phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates of mix-10-phosphinylidyne of 10-dihydro-9-oxy and the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 9,10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates.
3. low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 1 and 2, the contained fire retarding synergist of this CABLE MATERIALS is at least one in nano imvite, carbon nanotube, nano layered double hydroxides, polysilsesquioxane, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, kaolin and talcum.
4. low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 1 and 2, the contained resin compatible agent of this CABLE MATERIALS is any in ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme or maleic anhydride graft SBS; Contained linking agent is dicumyl peroxide, Glycerin triacrylate, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1, any in 6-hexylene glycol ester or pentaerythritol triacrylate.
5. low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 3, the contained resin compatible agent of this CABLE MATERIALS is any in ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme or maleic anhydride graft SBS; Contained linking agent is dicumyl peroxide, Glycerin triacrylate, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1, any in 6-hexylene glycol ester or pentaerythritol triacrylate.
6. the preparation method of the described low temperature resistant flexible crosslinkable non-halogen flame-retardant cable of claim 1, processing step and the condition of the method are as follows:
1) by phosphorous diprotic acid 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates, terephthalic acid and catalyzer, perhaps by phosphorous diprotic acid 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates and catalyzer, according to 9, assorted phenanthrene-the succinic acid of mix-10-phosphinylidyne of 10-dihydro-9-oxy accounts for [9, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-succinic acid of 10-phosphinylidyne+terephthalic acid] molecular fraction be 20～100%, three (2-hydroxyethyl) chlorinated isocyanurates and [9, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-succinic acid of 10-phosphinylidyne+terephthalic acid] the proportioning of mol ratio=1.33～1.67, after adopting direct esterification to carry out esterification, react and obtain fusing point≤155 ℃ through vacuum hydro-extraction, the low melting point of initial heat decomposition temperature >=245 ℃, the char-forming agent of high initial heat decomposition temperature, reaction product is cooling, pulverize levigate sieving,
2) 60～77% acid source, 20～35% charcoal source and 3～10% fire retarding synergist are mixed and obtain halogen-free expansion fire retardant at homogenizer, acid source and the charcoal source solubleness≤0.5g/100ml in water under 20 ℃ wherein, having a char-forming agent component in the charcoal source at least is compound prepared by step 1), fire retarding synergist or before the esterification of step 1) or during esterification adds reaction system after finishing;
3) by mass parts, 60～80 parts of ethylene-vinyl acetate copolymers, 10～40 parts of polyethylene, 0～30 part of terpolymer EP rubber, 2～10 parts of resin compatible agent, 35～65 parts of halogen-free expansion fire retardants and 0.5～2 part of linking agent are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 20～200rpm, at 90～180 ℃ of temperature, through melt extruding granulation, get final product.
7. the preparation method of low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 6, the method acid source used is any in melamine coated ammonium polyphosphate, epoxy resin coated ammonium polyphosphate, silane coated ammonium polyphosphate, 6MD resin-coated ammonium polyphosphate, MF resin-coated ammonium polyphosphate or MF resin Phosphate coating ammonium polyphosphate, and the polymerization degree of ammonium polyphosphate >=700; Charcoal source used is dipentaerythritol, tripentaerythritol, 9, at least one in the common esterification products of the esterification products of assorted phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates of mix-10-phosphinylidyne of 10-dihydro-9-oxy and the assorted phenanthrene-succinic acid of mix-10-phosphinylidyne of 9,10-dihydro-9-oxy and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates.
8. according to the preparation method of the described low temperature resistant flexible crosslinkable non-halogen flame-retardant cable of claim 6 or 7, the method fire retarding synergist used is at least one in nano imvite, carbon nanotube, nano layered double hydroxides, polysilsesquioxane, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, kaolin and talcum.
9. according to the preparation method of the described low temperature resistant flexible crosslinkable non-halogen flame-retardant cable of claim 6 or 7, the method resin compatible agent used is any in ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme or maleic anhydride graft SBS; Linking agent used is dicumyl peroxide, Glycerin triacrylate, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1, any in 6-hexylene glycol ester or pentaerythritol triacrylate.
10. the preparation method of low temperature resistant flexible crosslinkable non-halogen flame-retardant cable according to claim 8, the method resin compatible agent used is any in ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, maleic anhydride grafted polyethylene, maleated ethylene vinyl acetate copolyme or maleic anhydride graft SBS; Linking agent used is dicumyl peroxide, Glycerin triacrylate, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1, any in 6-hexylene glycol ester or pentaerythritol triacrylate.
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