CN104650441B - One kind can ceramic flame-retardant high-molecular composite and application - Google Patents

One kind can ceramic flame-retardant high-molecular composite and application Download PDF

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CN104650441B
CN104650441B CN201510113925.1A CN201510113925A CN104650441B CN 104650441 B CN104650441 B CN 104650441B CN 201510113925 A CN201510113925 A CN 201510113925A CN 104650441 B CN104650441 B CN 104650441B
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parts
antioxidant
softening point
plasticizer
low softening
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CN104650441A (en
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王玉忠
邸宏伟
邓聪
李映明
李瑞敏
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Sichuan University
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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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
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Abstract

The invention provides based on polyolefin or based on TPUE can ceramic flame-retardant high-molecular composite, the composite by weight, including following component：30 40 parts of polyolefin resin or TPUE, into 25 45 parts of porcelain filling, 20 30 parts of halogen-free flame retardants, 15 parts of synergistic flame retardant, 13 parts of plasticizer, 0.5 2 parts of antioxidant, 0.02 0.15 parts of crosslinking agent is described to include low softening point glass dust and silicate mineral filler into porcelain filling.Present invention also offers application of the composite in field of cables.Compound of the present invention can be 600 1000oThe ceramic product of densification is formed in the range of C, the ceramic product of formation has good elevated temperature strength and fire resistance, also there is good mechanical property at normal temperatures.

Description

One kind can ceramic flame-retardant high-molecular composite and application
Technical field
The invention belongs to fire resisting material field, and in particular to one kind can ceramic flame-retardant high-molecular composite.
Technical background
Chinese patent CN1095181 uses mica tape, non-ignitable silicon coating and PVC/ lanthanas/cerium oxide mixed plastic, system The high flame resistant cable of low smoke and zero halogen during into high fire resisting, high temperature resistant and burning.This patent has the disadvantage that cost is high, without into porcelain. Insulating refractory electricity is made using refractory inorganic fiber heat-barrier material and silicone-based elastomer composite in Chinese patent CN101169993 Cable.This patent has the disadvantage that cost is high, without into porcelain.Chinese patent CN1480958 is made heat-insulated resistance to of mineral matter expanding material Thermoelectricity cable, the cable can be 750oCorresponding rated voltage normal work is born in C flames 90 minutes（Meet GB12666.6 standards It is required that）Or 180 minutes（Meet the requirement of IEC331 standards）.This patent has the disadvantage complex process, without into porcelain.Chinese patent CN1710670 is made of mica tape, protective metal shell and inorganic refractory expanding material can be 800oIt is long-term in C temperature below environment The fire-resisting cable of operation.This patent has the disadvantage complex process, without into porcelain.Chinese patent CN1973019A refractory ceramic group Compound includes mineral silicate, no more than 800oAt least one inorganic phosphate of liquid phase is formed at a temperature of C, is comprised at least The polymer-based composition and use thereof in packaging of the organic polymer of 50% percentage by weight.The refractory ceramic composition is used in manufacture flame proof electrical Cable, polyurethane foam etc..This patent has the disadvantage that the ceramics strength to be formed is poor, and the temperature into porcelain requirement is high.Chinese patent CN1320556C fire-resisting cable, includes the cable of at least one conductor and at least one layer of fire resistant coating layer, and wherein fire resisting is wrapped up Layer is comprising at least one combustion reference temperature in minimum temperature T1With maximum temperature T2Between organic polymer；（At least one glass Glass material；At least one inert compound；The softening point temperature or melting temperature of wherein described inert compound are not less than 1000oC； The selection of the temperature range to make frit flow to inert compound and burned organic polymer on, so as to form solid-state Charcoal fire resistant coating layer.This patent has the disadvantage that the ceramics strength to be formed is poor, and the temperature into porcelain requirement is high, non-antiflaming property.Chinese patent 101404189B has invented a kind of fast ceramic flame-resistant cable and preparation method thereof, using ethylene-vinyl acetate copolymerization Thing EVA, LLDPE LLDPE with into porcelain filling, prepared by fire retardant, antioxidant, lubricant, coupling agent blending extrusion Fire-resisting cable material, 750oAt C and higher temperature, the CABLE MATERIALS can in 10 minutes porcelain, porcelain compound can ensure circuit 750oC-950 oNormally run more than 90 minutes under C.This patent has the disadvantage that the ceramics strength to be formed is poor, into the temperature of porcelain requirement Height, CABLE MATERIALS poor mechanical property.
In a word, in the prior art, the shortcoming of fire resisting polymer composite is that application is narrow, and cost is high, formation Ceramics strength is poor, and the temperature into porcelain requirement is high, and flame retardant effect is poor.
It would therefore be highly desirable to develop it is a kind of into porcelain temperature it is low, into porcelain effect is good, flame retardant effect is excellent and cost is low, application Extensively fire-retardant can porcelain polymer composite.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide based on polyolefin or based on polyurethane elastomer, The composite by weight, including following component：
30-40 parts of polyolefin resin or TPUE
Into 25-45 parts of porcelain filling
20-30 parts of halogen-free flame retardants
1-5 parts of synergistic flame retardant
1-3 parts of plasticizer
0.5-2 parts of antioxidant
0.02-0.15 parts of crosslinking agent
It is described to include low softening point glass dust and at least one silicate mineral filler into porcelain filling.
It is preferred that, the TPO plastics or elastomer are high density polyethylene, low density polyethylene, line Property low density polyethylene (LDPE) LLDPE, polypropylene PP, ethylene-vinyl acetate copolymer EVA, ethylene-octene copolymer POE, thermoplastic At least one of property polyurethane elastomer.
It is preferred that, the silicate mineral filler is at least one of kaolin, mica, talcum powder, wollastonite.
It is preferred that, the silicate mineral filler also includes glass fibre.
The low softening point glass dust is flint glass powder, bismuth oxide glass powder, phosphate glass powder, borate glass One kind in powder, softening point is in 300-500oBetween C.The fusing point of silicate is in 800-1500oBetween C.Wherein, low softening point glass Glass powder consumption is into the 40-75% of porcelain filling gross mass, and remaining is silicate mineral filler.
The halogen-free flame retardants is APP（APP）, APP（APP）It is poly- with carbon forming agent (CA) compound, modification Ammonium phosphate（MAPP）, hypo-aluminum orthophosphate（AP）, triphenyl phosphate（TPP）, melamine phosphate（MP）, melamine polyphosphate （MPP）, melamine pyrophosphate（MPyP）, melamine cyanurate（MCA）, 2- carboxyethyl phenyl phosphinic acid melamines Salt（CMA）, melamine hypophosphite（MHPA）, melamine phosphite（MPOA）At least one of；
The ammonium polyphosphate modifying is piperazine ammonium polyphosphate modifying, ethylenediamine ammonium polyphosphate modifying, diethylenetriamine modification One kind in APP and AEEA ammonium polyphosphate modifying；
The structural formula of the carbon forming agent is：
N is 10-20；
The mass ratio of APP and carbon forming agent is 3:1.
The synergistic flame retardant is hydrotalcite (LDH), galapectite, lead oxide (PbO), magnesia (MgO), zinc oxide (ZnO), organo montmorillonite（OMMT）, molybdenum oxide（MoO3）, antimony oxide（Sb2O3）, antimony pentoxide（Sb2O5）, Firebrake ZB（ZB）、 Lanthana（La2O3）, nickel oxide（NiO2）, zirconium oxide（ZrO2）In one kind.
Fire retardant used of the invention is halogen-free flame retardants, can be real in ratio of the present invention and synergistic flame retardant interworking The effect of existing highly effective flame-retardant.For other fire retardants, the present inventor has surprisingly found that, the resistance used in the present invention Agent is fired after with certain proportion and present invention synergistic flame retardant interworking used, can be risen in the composite porcelain of the present invention To good flame retardant effect.
The plasticizer is phthalic acid two（2-ethyl hexyl）Ester（DEHP）, dioctyl phthalate（DOP）, it is adjacent Phthalic acid di-n-octyl（DNOP or DnOP）, BBP(Butyl Benzyl Phthalate（BBP）, di-sec-octyl phthalate（DCP）, it is adjacent Dicyclo-hexyl phthlate（DCHP）, dibutyl phthalate（DBP）, diisobutyl phthalate（DIBP）, adjacent benzene two Formic acid dimethyl ester（DMP）, diethyl phthalate（DEP）, diisononyl phthalate（DINP）, phthalic acid two it is different Last of the ten Heavenly stems ester（DIDP）, chloromethoxy fatty acid ester, tributyl 2-acetylcitrate（ATBC）At least one of.
The antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 626, irgasfos 168, antioxidant DNP, antioxygen One kind in agent DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, antioxidant 300；The crosslinking agent is that peroxidating two is different Propyl benzene（DCP）, Triallyl isocyanurate（TAIC）In one kind.
Second object of the present invention is to provide based on polyolefin or based on polyurethane elastomer flame retardant cable field Using.
Beneficial effects of the present invention：
The fire resisting that the present invention is provided can ceramic flame-retardant high-molecular composite can be in 600-1000oFormed and caused in the range of C Close ceramic product, the ceramic product of formation has good elevated temperature strength and fire resistance, also has at normal temperatures good Good mechanical property；Available for ceramic flame-proof cable material.
Brief description of the drawings
Fig. 1 is the ceramic residue profile scanning electron microscope of the embodiment of the present invention 1, in figure, a1, a2, a3 be in 700oElectron microscope after C processing；B1, b2, b3 are in 800oElectron microscope after C processing；C1, c2, c3 are in 900 oAt C Electron microscope after reason；D1, d2, d3 are in 1000oElectron microscope after C processing；
Fig. 2 is the taper calorimetric result of the embodiment of the present invention 1, wherein, CF:Into porcelain filling；PHRR：Maximum heat release speed Rate；THR：Total HRR；SPR：Smoke density；ML：Mass change；Wherein, a:Maximum HRR；b:Total heat discharges Speed；c:Smoke density；d:Mass change.
Embodiment
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following examples can not Be interpreted as limiting the scope of the invention, if the person skilled in the art in the field according to the invention described above content to this hair It is bright to make some nonessential modifications and adaptations, still fall within the scope of the present invention.
Ethylene-vinyl acetate copolymer EVA used in embodiment（DUPONT, Elvax 260 ）, melt flow rate (MFR) For 6.0g/10min, VA contents, 28%.Remaining raw material is commercially available.
Embodiment 1
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant MAPP：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 part, crosslink agent DCP：0.05 part.
Embodiment 2
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant APP/CA (3/1)：28 parts, galapectite：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslinking agent DCP：0.05 part；
CA structural formula is；N is 10.
Embodiment 3
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant MCA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DNOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 4
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant CMA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DNOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 5
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire-retartant agent MP P：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DNOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 6
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant MAPP：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester：2.5 parts, hand over Join agent DCP：0.05 part.
Embodiment 7
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant APP/CA (3/1)：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester： 2.5 parts, crosslink agent DCP：0.05 part；CA structural formula is；N is 20。
Embodiment 8
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant MCA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester：2.5 parts, crosslinking Agent DCP：0.05 part.
Embodiment 9
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire retardant CMA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester：2.5 parts, crosslinking Agent DCP：0.05 part.
Embodiment 10
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：26.25 parts, E- glass fibres：8.75 Part, fire-retartant agent MP P：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester：2.5 parts, crosslinking Agent DCP：0.05 part.
Embodiment 11
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MAPP：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 12
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant APP/CA(3/1)：28 parts, galapectite：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part；
CA structural formula is；N is 15.
Embodiment 13
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MCA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 14
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant CMA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DOP
：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 15
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MPP：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 16
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MAPP：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer DOP+plasticizer chloromethoxy fatty acid ester (1：1 w/ w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 17
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant APP/CA(3/1)：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer DOP+plasticizer chloromethoxy fatty acid ester (1：1 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 18
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MCA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer DOP+plasticizer chloromethoxy fatty acid ester (1：1 w/w)： 2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 19
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant CMA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer DOP+plasticizer chloromethoxy fatty acid ester (1：1 w/w)： 2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 20
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：15 parts, fire retardant MPP：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer DOP+plasticizer chloromethoxy fatty acid ester (1：1 w/w)： 2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 21
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant MAPP：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DCHP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 22
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant APP/CA (3/1)：28 parts, galapectite：2 parts, antioxidant 1010：1 part, plasticizer DCHP：2.5 parts, crosslinking agent DCP：0.05 part.
Embodiment 23
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant MCA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DCHP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 24
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant CMA：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DCHP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 25
Ethylene-vinyl acetate copolymer EVA：35 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire-retartant agent MP P：28 parts, LDH：2 parts, antioxidant 1010：1 part, plasticizer DCHP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 26
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant MAPP：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester+plasticizer ATBC(4：6 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 27
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant APP/CA (3/1)：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester+ Plasticizer A TBC (4：6 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 28
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant MCA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester+plasticizer ATBC(4：6 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 29
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire retardant CMA：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester+plasticizer ATBC(4：6 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 30
Ethylene-vinyl acetate copolymer EVA：40 parts, low softening point glass dust：20 parts, kaolin：12 parts, wollastonite, 3 parts, fire-retartant agent MP P：22 parts, OMMT：3 parts, antioxidant 1010：1 part, plasticizer chloromethoxy fatty acid ester+plasticizer ATBC(4：6 w/w)：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 31
LLDPE LLDPE：40 parts, low softening point glass dust：12.5 parts, mica：12.5 parts, fire retardant MHPA：30 parts, OMMT：5 parts, antioxidant TPP：1 part, plasticizer DINP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 32
LLDPE LLDPE：40 parts, low softening point glass dust：15 parts, mica：15 parts, fire-retartant agent MP：29 Part, LDH：1 part, antioxidant TNP：1 part, plasticizer DINP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 33
LLDPE LDPE/HDPE (70/30)：40 parts, low softening point glass dust：12.5 parts, mica：12.5 Part, fire retardant MHPA：30 parts, OMMT：5 parts, antioxidant DCTP：1 part, plasticizer DINP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 34
LLDPE LDPE/HDPE (70/30)：40 parts, low softening point glass dust：15 parts, mica：15 parts, Fire-retartant agent MP：29 parts, LDH：1 part, antioxidant MB：1 part, plasticizer DINP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 35
Polyolefin elastomer：30 parts, low softening point glass dust：22.5 parts, mica：22.5 parts, fire retardant MyPA：20 Part, OMMT：5 parts, antioxidant DNP：1 part, plasticizer DINP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 36
Polyolefin elastomer：30 parts, low softening point glass dust：22.5 parts, mica：22.5 parts, fire-retartant agent MP：24 parts, LDH：1 part, antioxidant 626：1 part, plasticizer DIDP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 37
Polyolefin elastomer/PP (80/20)：30 parts, low softening point glass dust：22.5 parts, mica：It is 22.5 parts, fire-retardant Agent MyPA：20 parts, OMMT：5 parts, antioxidant 1010：1 part, plasticizer DIDP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 38
Polyolefin elastomer/PP (80/20)：30 parts, low softening point glass dust：22.5 parts, mica：It is 22.5 parts, fire-retardant Agent MP：24 parts, LDH：1 part, irgasfos 168：1 part, plasticizer DIDP：2.5 parts, crosslinking agent TAIC：0.05 part.
Embodiment 39
Thermoplastic polyurethane elastomer：30 parts, low softening point glass dust：22.5 parts, mica：22.5 parts, fire retardant AP：20 parts, OMMT：5 parts, antioxidant 300：0.5 part, plasticizer DOP：1 part.
Embodiment 40
Thermoplastic polyurethane elastomer：30 parts, low softening point glass dust：22.5 parts, mica：22.5 parts, fire retardant AP + fire retardant MCA (1：2 w/w)：23 parts, OMMT：2 parts, antioxidant 1076：2 parts, plasticizer DOP：3 parts.
Comparative example 1
EVA/LLDPE(70/30)：100 parts, low softening point glass dust：36 parts, E- glass fibres：54 parts, fire retardant hydrogen-oxygen Change magnesium：95 parts, melamine：10 parts, antioxidant 1010：2 parts, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Comparative example 2
EVA/LLDPE(60/40)：100 parts, low softening point glass dust：39 parts, E- glass fibres：26 parts, fire retardant hydrogen-oxygen Change magnesium：80 parts, melamine：20 parts, antioxidant 1010：2 parts, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Comparative example 3
EVA/LLDPE(60/40)：100 parts, low softening point glass dust：40 parts, E- glass fibres：40 parts, fire retardant hydrogen-oxygen Change aluminium：90 parts, Firebrake ZB：15 parts, antioxidant 1010：1 part, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Comparative example 4
EVA/LLDPE(70/30)：100 parts, low softening point glass dust：36 parts, talcum powder：54 parts, fire retardant hydroxide Aluminium：90 parts, Firebrake ZB：15 parts, antioxidant 1010：2 parts, plasticizer DOP：2.5 parts, crosslink agent DCP：0.05 part.
Embodiment 1-40 mechanical experimental results are as shown in table 1.
Table 1
By taking embodiment 1 as an example, cable preparation is used it for, as shown in table 2, ceramic residue is bent flame retardant test performance Intensity is as shown in table 3.
Table 2
UL-94 LOI
Embodiment 1 V-0 28.0
Table 3
Taper calorimetric result is as shown in Figure of description 2, and its corresponding data is shown in Table 4.
Table 4
CF:Into porcelain filling；PHRR：Maximum HRR；THR：Total HRR；SPR：Smoke density；ML：Quality Rate of change
The bending strength of comparative example 1-4 ceramic residue the results are shown in Table 5.
Table 5
From comparative example it can be seen that the bending strength of ceramics is very poor, the temperature for forming ceramics is very high.Effect is bad.

Claims (8)

1. one kind can ceramic flame-retardant high-molecular composite, it is characterised in that the composite by weight, including such as Lower component：
30-40 parts of polyolefin resin or TPUE
Into 25-45 parts of porcelain filling
20-30 parts of halogen-free flame retardants
1-5 parts of synergistic flame retardant
1-3 parts of plasticizer
0.5-2 parts of antioxidant
0.02-0.15 parts of crosslinking agent
It is described to include low softening point glass dust and silicate mineral filler into porcelain filling；
The halogen-free flame retardants is APP, APP and carbon forming agent compound, ammonium polyphosphate modifying, hypo-aluminum orthophosphate, phosphorus Triphenyl phosphate ester, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, 2- At least one of carboxyethyl phenyl phosphinic acid melamine salt, melamine hypophosphite, melamine phosphite；It is described Synergistic flame retardant is hydrotalcite, galapectite, lead oxide, magnesia, zinc oxide, organo montmorillonite, molybdenum oxide, antimony oxide, five oxygen Change one kind in two antimony, Firebrake ZB, lanthana, nickel oxide, zirconium oxide；The polyolefin resin is high density polyethylene (HDPE), low In density polyethylene, LLDPE, polypropylene, ethylene-vinyl acetate copolymer, ethylene-octene copolymer It is at least one.
2. composite according to claim 1, it is characterised in that the silicate mineral filler be kaolin, mica, At least one of talcum powder, wollastonite.
3. composite according to claim 1, it is characterised in that described also to include glass fibre into porcelain filling.
4. composite according to claim 1, it is characterised in that the low softening point glass dust accounts for into porcelain filling gross weight 40-75%.
5. composite according to claim 1, it is characterised in that the low softening point glass dust is flint glass One kind in powder, bismuth oxide glass powder, phosphate glass powder, borate glass powder, softening point is 300-500 DEG C.
6. composite according to claim 1, it is characterised in that
The ammonium polyphosphate modifying is piperazine ammonium polyphosphate modifying, ethylenediamine ammonium polyphosphate modifying, the poly- phosphorus of diethylenetriamine modification One kind in sour ammonium and AEEA ammonium polyphosphate modifying；
The structural formula of the carbon forming agent is：
N is 10-20；
The mass ratio of APP and carbon forming agent is 3:1.
7. composite according to claim 1, it is characterised in that the plasticizer be phthalic acid two (2-ethyl Oneself) ester, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, the isobutyl of phthalic acid two Ester, repefral, diethyl phthalate, diisononyl phthalate, diisooctyl phthalate, chlorine For at least one of methoxyl group fatty acid ester, tributyl 2-acetylcitrate；The antioxidant is antioxidant 1010, antioxidant 1076th, antioxidant 626, irgasfos 168, antioxidant DNP, anti-oxidant DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, anti- One kind in oxygen agent 300；The crosslinking agent is one kind in cumyl peroxide, Triallyl isocyanurate.
8. described in claim 1 it is a kind of can ceramic flame-retardant high-molecular composite flame retardant cable field application.
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