CN103467832B - Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable and preparation method thereof - Google Patents
Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable and preparation method thereof Download PDFInfo
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Abstract
Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable disclosed by the invention is by ethylene-vinyl acetate copolymer 60 ~ 80 parts, polyethylene 10 ~ 40 parts, terpolymer EP rubber 0 ~ 30 part, resin compatible agent 2 ~ 10 parts, halogen-free expansion fire retardant 35 ~ 65 parts and linking agent 0.5 ~ 2 part of blended composition, a char-forming agent component is had at least to be fusing point≤155 DEG C in its halogen-free expansion fire retardant, initial pyrolyzation temperature >=245 DEG C.The invention also discloses its preparation method.Due to the present invention introduce low melting point, high initial pyrolyzation temperature char-forming agent component can processing temperature window wide, and mate with the processing temperature of CABLE MATERIALS substrate resin, can melt in the course of processing and better dispersion, thus improve flame retarding efficiency, reduce the impact on substrate resin mechanical property, make it flame retardant properties and the mechanical property of giving CABLE MATERIALS excellence simultaneously.Preparation method of the present invention is simple, easy to operate, is easy to control and suitability for industrialized 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-resistanflexible flexible crosslinkable halogen-free flame retardant cable and preparation method thereof.
Background technology
Related data statistics display in recent years, not only because the fire electrically caused accounts for the largest percentage in all kinds of fire failure in the whole nation, and the fire failure of the comparatively large above grade electrically caused is maximum.As 2000 ~ 2008, accounted for 33% of statistics fire sum by the fire accidents electrically caused; By the electrically reason such as aging, the traffic overload of wire short-circuiting, electric wire and electrical equipment malfunction, cause cable to ignite, propagation of flame etc. and the fire caused accounts for more than 30% of fire sum, and have the trend of cumulative year after year [Li Hai river .2000-2008 whole nation fire accidents statistical study. Chinese public safety scholarly edition (Fire Science) .2010,1:64-69.].Wherein, on December 15th, 2005, there is wildfire accident in central hospital of Liaoyuan, Jilin province city, cause 39 people wrecked, direct economic loss 8,210,000 yuan, fire cause is that this hospital employs cable off quality, causes occurring in central hospital's switchgear building cable trench cable short-circuit fire and to have ignited combustiblematerials.On January 5th, 2010, it is on fire in process of production to there is cable in vertical victory underground coal mine 240 meters of, Tan Jiashan town, Xiangtan County, xiangtan, hunan province city, causes 34 miners wrecked, direct economic loss 2,962 ten thousand yuan; Point out in " reply is made to the report of investigating of three special Serious Accidents by State Council " that this fire failure immediate cause is the aging breakage of non-flame resistant cable of laying in the dark vertical in vertical three road in the middle of vertical victory colliery, short circuit is caught fire, the outer plastic pipe-covered of shot-firing cable, produce a large amount of toxic and harmful, the personnel that cause suffocate injures and deaths.A series of fire cases shows, once cause this kind of fire failure, not only cause huge property damage, also can cause great loss of life and personal injury, this just makes the research and development of the fire safety problem of electric wire and halogen-free flame-retardant wire cable and application become very important and urgent.
And the restrictive coating of conventional fire protection flame retarding electric wire all adopts is Halogen flame-retardant polymer, and Halogen flame-proofed polymer material easily decomposes a large amount of cigarette of generation and poisonous and acrid gas (as hydrogenchloride etc.) when burning, the Dioxins even producing high density had and cause " secondary disaster ", therefore national requirements is at the Olympic Sports Center, airport, station, subway, Nuclear power plants, chemical industry, the special occasions such as Highrise buildings and naval vessel must select halogen-free low-smoke flame-retardant electric wire and cable, therefore fire-retardant non-halogen of CABLE MATERIALS becomes fire-fighting technology, the inexorable trend of social development.
The more non-halogen flame-retardant cable be widely used again of current research adopts high-content metal hydroxides to be prepared from as fire retardant polyolefine, as Japanese Yasumoto(US20080029743) preparation method of a kind of CABLE MATERIALS fire retardant polyolefin of open report, be exactly at the propylene copolymer 80 parts by multistep polymerization, Low Density Polyethylene 10 parts, adds 250 parts of fire retardant Mg (OH) in the polyolefin base material of modified polypropene 10 parts composition
2make, the limiting oxygen index(LOI) (LOI) of this material is 32.0%, and elongation at break is 220%.And for example a kind of halogen-free non-phosphor flame-proof cable sheath material disclosed in CN1581369, in 100 parts of ethylene-vinyl acetate copolymers (EVA), add 130 parts of acrylic acid modified aluminium hydroxides and 30 parts of sodium oleate modified magnesium hydroxides are prepared from, the elongation of this CABLE MATERIALS is 164%, LOI is 41.2%.As can be seen here, although adopt the inorganic combustion inhibitor such as magnesium hydroxide, aluminium hydroxide can obtain good flame retardant resistance, the addition of fire retardant is very large.So high loading level will damage the processability of CABLE MATERIALS, flexibility (elongation at break), the performance such as low temperature resistant greatly, it can not have been met, and China industry standard GA306.1-2007 proposes the resistance to low temperature of flame-proof cable material explicitly calls for, and especially wherein defines elongation at break >=20% of material-15 DEG C time.
Expansion type flame retardant (IFR) is due to its special intumescent flame retardant mechanism, be widely used in the fire-retardant research of polyolefine and coating, the macromolecular material making it fire-retardant not only has anti-dropping behavior, namely 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 made up of acid source, charcoal source and source of the gas.Current 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 problem that in CABLE MATERIALS, inorganic combustion inhibitor addition is large, scientific research personnel start to attempt IFR is used for CABLE MATERIALS fire-retardant in, 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.But but there is a lot of applied defect in above-mentioned expansion type flame retardant in for polyolefin cable insulation sheath material, main manifestations for (1) each flame retardant component above-mentioned be that under CABLE MATERIALS processing temperature, (90 ~ 180 DEG C) can not melting or start the compound of thermolysis or distillation near the fusing point of flame retardant compositions self, dispersed in resin base material of fire retardant is made to become a difficult problem, (2) poor heat stability of tetramethylolmethane, initial pyrolyzation temperature is 211 DEG C, easily decompose under the processing temperature of polymkeric substance, (3) tetramethylolmethane is by force water-soluble, solubleness under room temperature is 6.8g/100ml, every employing tetramethylolmethane is caused to be that the IFR of char-forming agent all exists poor heat stability, poor water resistance, and then make by fire retardant material in use because fire retardant is separated out and water-soluble its flame retardant properties that causes there will be the problem lost gradually.For the problems referred to above, though related scientific research personnel have carried out much research, but up to now, to yet there are no about Heat stability is good and char-forming agent component has the report of halogen-free expansion fire retardant for fire-resistant cable material of melting characteristic.
Summary of the invention
The object of the invention is, for prior art Problems existing, first to provide a kind of Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable.
Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable provided by the invention, this CABLE MATERIALS forms by following component is blended by mass parts:
Wherein contained halogen-free expansion fire retardant in massfraction by the acid source of 60 ~ 77%, the charcoal source of 20 ~ 35% and 3 ~ 10% fire retarding synergist form, acid source and the charcoal source solubleness≤0.5g/100ml at 20 DEG C in water, and in charcoal source, have at least a char-forming agent component to be fusing point≤155 DEG C, the compound of initial pyrolyzation temperature >=245 DEG C, this compound is made up of following I, II structural unit represented or I, II, III structural unit represented:
The wherein structural unit number of II: the structural unit number of [I+III] be 1.33 ~ 1.67, I structural unit number be 20 ~ 100% of the structural unit number of [I+III], preferably 100%; Each structural unit or its segment formed are connected combination by carboxyl arbitrarily with hydroxy functional group.
Acid source contained by above CABLE MATERIALS is any one 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 >=700 of ammonium polyphosphate, contained charcoal source is dipentaerythritol, tripentaerythritol, 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed the esterification products and 9 of phenanthrene-succinic acid (DDP) and three (2-hydroxyethyl) chlorinated isocyanurates (THEIC), the at least one that the assorted-10-phosphinylidyne of 10-dihydro-9-oxy is mixed in the common esterification products of phenanthrene-succinic acid and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates, wherein preferably 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed the esterification products of phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates, 9, the at least one that the assorted-10-phosphinylidyne of 10-dihydro-9-oxy is mixed in the common esterification products of phenanthrene-succinic acid and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates.
Fire retarding synergist contained by 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.
Resin compatible agent contained by 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 one; Contained linking agent is any one in dicumyl peroxide (DCP), Glycerin triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), three (2-hydroxyethyl) isocyanuric acid triacrylate (THEICTA), cyanacrylate (TAIC), diacrylate-1,6-hexylene glycol ester (HDDA) or pentaerythritol triacrylate (PET3A).
The preparation method of above-mentioned Low temperature-resistanflexible flexible crosslinkable halogen-free 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-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates, terephthalic acid and catalyzer, or by phosphorous diprotic acid 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid, nitrogenous trivalent alcohol three (2-hydroxyethyl) chlorinated isocyanurates and catalyzer, according to 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy phenanthrene-succinic acid of mixing accounts for [9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid+terephthalic acid] molecular fraction be 20 ~ 100%, preferably 100%, three (2-hydroxyethyl) chlorinated isocyanurates and [9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid+terephthalic acid] the proportioning of mol ratio=1.33 ~ 1.67, adopt conventional direct esterification (200 ~ 245 DEG C, 4 ~ 10h) carry out esterification after, react through vacuum hydro-extraction and obtain fusing point≤155 DEG C, the low melting point of initial pyrolyzation temperature>=245 DEG C, high initial pyrolyzation temperature (the decomposition temperature in analyzing with TGA under nitrogen atmosphere during thermal weight loss 5wt%, T
5%, be defined as the initial pyrolyzation temperature of sample) char-forming agent, by reaction product cool, pulverize levigate sieving,
2) acid source of 60 ~ 77%, the charcoal source of 20 ~ 35% and the fire retarding synergist of 3 ~ 10% to be mixed at homogenizer and obtain halogen-free expansion fire retardant, wherein acid source and the charcoal source solubleness≤0.5g/100ml at 20 DEG C in water, have at least a char-forming agent component to be compound prepared by step 1) in charcoal source, fire retarding synergist before the esterification of step 1) or esterification terminate after add in reaction system;
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 mixes, and then mixture is added in screw extrusion press, in screw speed 20 ~ 200rpm, at temperature 90 ~ 180 DEG C, through melt extruding granulation.
The add-on of the terpolymer EP rubber that aforesaid method is used preferably 10 ~ 30 parts.
Aforesaid method acid source used is any one 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 >=700 of ammonium polyphosphate, charcoal source used is dipentaerythritol, tripentaerythritol, 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed the esterification products and 9 of phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates, the at least one that the assorted-10-phosphinylidyne of 10-dihydro-9-oxy is mixed in the common esterification products of phenanthrene-succinic acid and terephthalic acid and three (2-hydroxyethyl) chlorinated isocyanurates, wherein preferably 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed the esterification products of phenanthrene-succinic acid and three (2-hydroxyethyl) chlorinated isocyanurates, 9, the at least one that the assorted-10-phosphinylidyne of 10-dihydro-9-oxy is mixed in the common esterification products of phenanthrene-succinic acid 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 one; Linking agent used is any one in dicumyl peroxide (DCP), Glycerin triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), three (2-hydroxyethyl) isocyanuric acid triacrylate (THEICTA), cyanacrylate (TAIC), diacrylate-1,6-hexylene glycol ester (HDDA) or pentaerythritol triacrylate (PET3A).
Also can add when adopting aforesaid method to prepare CABLE MATERIALS and well known to a person skilled in the art lubricant 0.5 ~ 1 part; 0.2 ~ 1 part, oxidation inhibitor; UV light absorber 0.1 ~ 0.5 part; Colour batch 1 ~ 2 part.Lubricant wherein used can be any one 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 one 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 to introducing low melting point in Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable provided by the invention, the char-forming agent component of high initial pyrolyzation temperature, this component can processing temperature window wide and mate with the processing temperature of CABLE MATERIALS substrate resin, can melt in the CABLE MATERIALS course of processing, thus improve the dispersive ability of fire retardant systems in substrate resin, make the degree of scatter of IFR in CABLE MATERIALS substrate resin higher, distribute more even, to make in the fire-retardant efficiency improving IFR, reduce IFR to the impact of substrate resin mechanical property, finally while the flame retardant properties of giving CABLE MATERIALS excellence, the mechanical property of material is made (to comprise normal temperature, the elongation at break of material during low temperature) be obviously better than conventional flame retardant CABLE MATERIALS.
2, the IFR owing to adding in Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable provided by the invention is prepared from by the high-polymerization degree ammonium polyphosphate modifying of water tolerance splendid (solubleness≤0.5g/100ml when 20 DEG C in water) and char-forming agent and water-fast fire retarding synergist, thus not only avoid the problem that flame retardant cable goods that conventional expansion type flame retardant (as ammonium polyphosphate+tetramethylolmethane+trimeric cyanamide) water-soluble height causes make because of the precipitation of fire retardant flame retardant properties be deteriorated in wet environment, and also effectively improve the electrical insulation capability of CABLE MATERIALS goods.
3, because substrate resin used in Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable provided by the invention is the blend of EVA, PE, EPDM, their second-order transition temperature is all below-50 DEG C, thus make the resistance to low temperature of CABLE MATERIALS good, can use in severe cold area.
4, because IFR flame retarding efficiency used in Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable provided by the invention is high, addition is little, in addition in char-forming agent component containing can the component of fusion plastification at processing temperatures, thus the dispersion of fire retardant in substrate resin is not only facilitated, make the elongation of fire-resistant cable material high, and because of flexible, in using, be easy to winding, not easy to crack.
5, because the present invention introduces linking agent in preparation Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable, thus by chemically crosslinked or the cross-linking radiation of the course of processing, its heat-resistant aging and thermal shrinkage energy is 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-resistanflexible flexible crosslinkable halogen-free flame retardant cable of preparation have the features such as Halogen, nontoxic, high flame retardant, environmental protection.
Accompanying drawing explanation
Accompanying drawing is Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable prepared by the embodiment of the present invention 1, according to GB/T1040.2-2006, is prepared into 5A type standard mechanics test bars, and the environmental chamber at low temperature being placed in-20 DEG C 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
Provide embodiment below so that the invention will be further described.What be necessary to herein means out is that 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 scope.
In addition, what deserves to be explained is: 1) in following examples, the number of material is mass parts.2) fusing point of char-forming agent that prepared by following examples adopts WRX-4 micro-meldometer to measure (temperature range that fusing point here refers in particular to the temperature that temperature that material starts to melt melts completely to material); Initial pyrolyzation temperature adopts TAQ5000 type thermogravimetric analyzer, is 10 DEG C/min, measures in nitrogen atmosphere at temperature rise rate; Solubleness at room temperature measures in water.3) the limiting oxygen index(LOI) LOI of Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable for preparing of following examples is according to GB/T2406.2-2009 standard test; Vertical combustion grade is according to GB/T2408-2008 standard test; Tensile strength under room temperature and elongation at break are according to 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, be placed in the environmental chamber at low temperature of-20 DEG C carrying out stretch measure.
Embodiment 1
By 9 of 150.4g, mix phenanthrene-succinic acid, 800g tri-(2-hydroxyethyl) chlorinated isocyanurates, 288.7g terephthalic acid and 4.5g tetrabutyl titanate of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy joins in reactor, inflated with nitrogen gets rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200 ~ 240 DEG C under mechanical stirring in 2h and carry out esterification, controlling still Inner pressure is≤0.1MPa, and when the water collecting esterification generation reaches 70ml, esterification terminates; React at least 0.5h, discharging in 230 ~ 245 DEG C of vacuum hydro-extractions, pulverize levigate mistake 100 mesh sieve.Products therefrom is the common esterification products (CFA-TTD1.41) of char-forming agent DDP and terephthalic acid and THEIC, and its fusing point is 110 ~ 116 DEG C, initial pyrolyzation temperature 265 DEG C, and 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 >=700 of ammonium polyphosphate) and 50g molecular sieve, in homogenizer, mix i.e. obtained 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 screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.0%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 12.0MPa, and elongation at break is 1130%; The tensile strength of-20 DEG C is 18.0MPa, and elongation at break is 576%.
Embodiment 2
Mixed by assorted for 9, the 10-dihydro-9-oxies of 793.8g-10-phosphinylidyne phenanthrene-succinic acid, 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates and 5g tetrabutyl titanate joins in reactor, and inflated with nitrogen gets rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200 ~ 240 DEG C under mechanical stirring in 2h and carry out esterification, controlling still Inner pressure is≤0.1MPa, and when the water collecting esterification generation reaches 75ml, esterification terminates; React at least 0.5h, discharging in 230 ~ 245 DEG C of vacuum hydro-extractions, pulverize levigate mistake 100 mesh sieve.Products therefrom is the common esterification products (CFA-TD1.67) of char-forming agent DDP and THEIC, and its fusing point is 105 ~ 109 DEG C, initial pyrolyzation temperature 267 DEG C, and 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 >=700 of ammonium polyphosphate) and 40g nano imvite, in homogenizer, mix i.e. obtained 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 colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 150rpm, at screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 34.5%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 11.6MPa, and elongation at break is 1085%; The tensile strength of-20 DEG C is 17.1MPa, and elongation at break is 539%.
Embodiment 3
By 9 of 497g, mix phenanthrene-succinic acid, 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates, 238g terephthalic acid and 4.5g tetrabutyl titanate of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy joins in reactor, inflated with nitrogen gets rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200 ~ 240 DEG C under mechanical stirring in 2h and carry out esterification, controlling still Inner pressure is≤0.1MPa, and when the water collecting esterification generation reaches 95ml, esterification terminates; React at least 0.5h, discharging in 230 ~ 245 DEG C of vacuum hydro-extractions, pulverize levigate mistake 100 mesh sieve.Products therefrom is the common esterification products (CFA-TTD1.33) of char-forming agent DDP and terephthalic acid and THEIC, and its fusing point is 109 ~ 113 DEG C, initial pyrolyzation temperature 266 DEG C, and 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 >=700 of ammonium polyphosphate) and 30g molecular sieve, in homogenizer, mix i.e. obtained 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 screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 34.5%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 12.6MPa, and elongation at break is 1137%; The tensile strength of-20 DEG C is 18.5MPa, and elongation at break is 594%.
Embodiment 4
By 1000g tri-(2-hydroxyethyl) chlorinated isocyanurates (THEIC), 497g 9, mix phenanthrene-succinic acid, 238g terephthalic acid, 204g nano imvite, 4.5g tetrabutyl titanate of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy joins in reactor, inflated with nitrogen gets rid of air in kettle, is pressurized to 0.07MPa; Be warming up to 200 ~ 240 DEG C under mechanical stirring in 2h and carry out esterification, controlling still Inner pressure is≤0.1MPa, and when the water collecting esterification generation reaches 95ml, esterification terminates; React at least 0.5h, discharging in 230 ~ 245 DEG C of vacuum hydro-extractions, pulverize levigate mistake 100 mesh sieve.Products therefrom is the nano combined char-forming agent of CFA-TTD1.33/MMT, and fusing point is 111 ~ 115 DEG C, initial pyrolyzation temperature 267 DEG C, and the solubleness under room temperature in water is 0.2g/100ml.
By 120g tripentaerythritol, the nano combined char-forming agent of 90g CFA-TTD1.33/MMT, 770g epoxy resin coated ammonium polyphosphate (polymerization degree >=700 of ammonium polyphosphate) and 20g organosilicon polymer, mix i.e. obtained 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 screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 36.0%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 11.2MPa, and elongation at break is 1149%; The tensile strength of-20 DEG C 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 >=700 of ammonium polyphosphate), 50g nano layered double hydroxides and 50g organosilicon polymer, in homogenizer, mix i.e. obtained 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 screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.5%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 9.4MPa, and elongation at break is 962%; The tensile strength of-20 DEG C is 13.4MPa, and elongation at break is 467%.
MF resin Phosphate coating ammonium polyphosphate wherein used is homemade, its preparation method is as follows: prepared by (a) performed polymer: in 500ml three-necked flask, add 40g trimeric cyanamide (MEL), and be the ratio of 2:3 according to MEL and formaldehyde mole ratio, be metered into formaldehyde, after being warmed up to 80 DEG C of stirring and dissolving, adjust ph, to 8 ~ 9, obtains resin prepolymer after reaction 1h; (b) coating modification APP: in 1000ml three-necked flask, add APP140g, deionized water 600ml, stirs 10min and is uniformly dispersed, then add resin prepolymer, resin prepolymer consumption is that 3wt% measures with coating material, by phosphoric acid adjust ph to 5.5, be warmed up to 80 DEG C of reaction 2h under high-speed stirring, cooling, by product suction filtration or centrifugation, and solid product is dried at 80 ~ 105 DEG C to obtain MF resin Phosphate coating ammonium polyphosphate.
In following examples, the preparation method of MF resin-coated ammonium polyphosphate is substantially identical, adopts MEL and formaldehyde mole ratio to be that the ratio of 1:3 can obtain when just prepared by performed polymer.
Embodiment 6
By 80g char-forming agent CFA-TD1.67,162g dipentaerythritol, 658g MF resin Phosphate coating ammonium polyphosphate (polymerization degree >=700 of ammonium polyphosphate), 50g polysilsesquioxane and 50g sepiolite, in homogenizer, mix i.e. obtained 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 screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 32.0%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 9.4MPa, and elongation at break is 1023.2%; The tensile strength of-20 DEG C 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 >=700 of ammonium polyphosphate), 20g molecular sieve and 30g azo-compound, in homogenizer, mix i.e. obtained 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 colour batch are added in high-speed mixer and mix, and then mixture is added in screw extrusion press, in screw speed 200rpm, at screw rod silicon carbide 90 ~ 180 DEG C, through melt extruding granulation.
The limiting oxygen index(LOI) of this CABLE MATERIALS is 28.5%, and vertical combustion UL-94 is V-0 level; Room temperature Tensile strength is 11.1MPa, and elongation at break is 1109%; The tensile strength of-20 DEG C is 16.2MPa, and elongation at break is 567%.
6MD resin-coated ammonium polyphosphate wherein used is homemade, its preparation method is as follows: add after 600ml deionized water and stirring is uniformly dispersed in 160g APP, be that 3wt% is metered into required 6MD resin according to coating material consumption, adjust ph is to 5.5,80 DEG C of reaction 2h are warming up under high-speed stirring, cooling, by product suction filtration or centrifugation, and dries to obtain 6MD resin-coated ammonium polyphosphate at 80 ~ 105 DEG C by solid product.
Claims (6)
1. a Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable, this CABLE MATERIALS forms by following component is blended by mass parts:
Wherein contained halogen-free expansion fire retardant in massfraction by the acid source of 60 ~ 77%, the charcoal source of 20 ~ 35% and 3 ~ 10% fire retarding synergist form, acid source and the charcoal source solubleness≤0.5g/100ml at 20 DEG C in water, and in charcoal source, have at least a char-forming agent component to be fusing point≤155 DEG C, the compound of initial pyrolyzation temperature >=245 DEG C, this compound is made up of following I, II structural unit represented or I, II, III structural unit represented:
The wherein structural unit number of II: the structural unit number of [I+III] is 1.33 ~ 1.67, the structural unit number of I is 20 ~ 100% of the structural unit number of [I+III], each structural unit or its segment formed are connected combination by carboxyl arbitrarily with hydroxy functional group, acid source is melamine coated ammonium polyphosphate, epoxy resin coated ammonium polyphosphate, silane coated ammonium polyphosphate, 6MD resin-coated ammonium polyphosphate, any one in MF resin-coated ammonium polyphosphate or MF resin Phosphate coating ammonium polyphosphate, and the polymerization degree >=700 of ammonium polyphosphate, fire retarding synergist is nano imvite, carbon nanotube, nano layered double hydroxides, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, at least one in kaolin and talcum.
2. Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable according to claim 1, charcoal source contained by this CABLE MATERIALS is 9, the mix esterification products of phenanthrene-succinic acid and three (2-hydroxyethyl) isocyanuric acid ester, 9,10-dihydro-9-oxies of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy are mixed at least one that-10-phosphinylidyne is mixed in the common esterification products of phenanthrene-succinic acid and terephthalic acid and three (2-hydroxyethyl) isocyanuric acid ester.
3. Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable according to claim 1 and 2, the resin compatible agent contained by this CABLE MATERIALS is any one 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 any one in dicumyl peroxide, Viscoat 295, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1,6-hexylene glycol ester or pentaerythritol triacrylate.
4. a preparation method for Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable described in claim 1, processing step and the condition of the method are as follows:
1) by phosphorous diprotic acid 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid, nitrogenous trivalent alcohol three (2-hydroxyethyl) isocyanuric acid ester, terephthalic acid and catalyzer, or by phosphorous diprotic acid 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid, nitrogenous trivalent alcohol three (2-hydroxyethyl) isocyanuric acid ester and catalyzer, according to 9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy phenanthrene-succinic acid of mixing accounts for [9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid+terephthalic acid] molecular fraction be 20 ~ 100%, three (2-hydroxyethyl) isocyanuric acid ester and [9, assorted-10-the phosphinylidyne of 10-dihydro-9-oxy is mixed phenanthrene-succinic acid+terephthalic acid] the proportioning of mol ratio=1.33 ~ 1.67, after adopting direct esterification to carry out esterification, react through vacuum hydro-extraction and obtain fusing point≤155 DEG C, the low melting point of initial pyrolyzation temperature >=245 DEG C, the char-forming agent of high initial pyrolyzation temperature, reaction product is cooled, pulverize levigate sieving,
2) acid source of 60 ~ 77%, the charcoal source of 20 ~ 35% and the fire retarding synergist of 3 ~ 10% to be mixed at homogenizer and obtain halogen-free expansion fire retardant, wherein acid source and the charcoal source solubleness≤0.5g/100ml at 20 DEG C in water, have at least a char-forming agent component to be step 1 in charcoal source) compound prepared, fire retarding synergist or in step 1) esterification before or esterification terminate after add in reaction system;
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 mixes, and then mixture is added in screw extrusion press, in screw speed 20 ~ 200rpm, at temperature 90 ~ 180 DEG C, through melt extruding granulation
Acid source wherein used is any one 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 >=700 of ammonium polyphosphate; Fire retarding synergist used is at least one in nano imvite, carbon nanotube, nano layered double hydroxides, molecular sieve, organosilicon polymer, silica gel, azo-compound, zinc oxide, sepiolite, kaolin and talcum.
5. the preparation method of Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable according to claim 4, the method charcoal source used is 9, the mix esterification products of phenanthrene-succinic acid and three (2-hydroxyethyl) isocyanuric acid ester and 9,10-dihydro-9-oxy of the assorted-10-phosphinylidyne of 10-dihydro-9-oxy is mixed at least one that-10-phosphinylidyne mixes in the common esterification products of phenanthrene-succinic acid and terephthalic acid and three (2-hydroxyethyl) isocyanuric acid ester.
6. the preparation method of the Low temperature-resistanflexible flexible crosslinkable halogen-free flame retardant cable according to claim 4 or 5, the method resin compatible agent used is any one 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 any one in dicumyl peroxide, Viscoat 295, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, cyanacrylate, diacrylate-1,6-hexylene glycol ester or pentaerythritol triacrylate.
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