CN106398003A - Flame-retardant electro-conductive thermoplastic vulcanized rubber material - Google Patents
Flame-retardant electro-conductive thermoplastic vulcanized rubber material Download PDFInfo
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- CN106398003A CN106398003A CN201610985854.9A CN201610985854A CN106398003A CN 106398003 A CN106398003 A CN 106398003A CN 201610985854 A CN201610985854 A CN 201610985854A CN 106398003 A CN106398003 A CN 106398003A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a flame-retardant electro-conductive thermoplastic vulcanized rubber material. The flame-retardant electro-conductive thermoplastic vulcanized rubber material comprises ethylene propylene diene terpolymer, polypropylene, ethylene propylene terpolymer grafted maleic anhydride, ethylene-vinyl acetate rubber, talcum powder, electro-conductive materials, nanometer silicon nitride, calcium sulfate whiskers, aluminum nitride, calcium carbonate, montmorillonite, stearic acid, active zinc oxide powder, active calcium silicate, vulcanization systems, methacrylic acid, paroline, ultraviolet light absorbers, antioxidants, lubricating agents, silane coupling agents Si-69, silane coupling agents KH-550 and fire retardants. The flame-retardant electro-conductive thermoplastic vulcanized rubber material has the advantages of low surface resistance and volume resistance, high electrical conductivity, high strength and high flame retarding performance.
Description
Technical field
The present invention relates to field of rubber technology, more particularly, to a kind of flame-retardant conductive thermoplastic vulcanizate material.
Background technology
TPV includes the blend of dynamic perduren and thermoplastic polymer.This rubber can be used as thin
Crumb granule is dispersed in thermoplastic resin lipid phase.These compositionss have advantageously illustrated the many of thermo-setting elastomer
Matter, but they can be processed as thermoplastic.Because TPV advantageously can as thermoplastic
Processing, commonly used thermoplastic extrusion technology extrudes elastic article by TPV.United States Patent (USP) US4311628/
0272871A1 discloses the method preparing TPV, and described elastomer is EP rubbers, and resin is polypropylene,
Vulcanizing system is that Phenolic resin curative, two hydrated stannous chlorides prepare thermoplastic for vulcanization accelerator using dynamic vulcanization technology
Property vulcanite, but its use during there is the defect that intensity is not high, anti-flammability is less desirable；In addition, rubber
It is typically considered the material with higher electric resistivity, so rubber is often used as insulator, but in information, energy
The special dimension such as source, opto-electronic device, molecular wire and molecular device and shielding electromagnetism, non-corrosive metal (NCM) and stealth technology, past
It is less than 10 toward the resistivity needing elastomeric material6Ω m, that is, need conductive rubber, but existing TPV
Its electric conductivity of material is less desirable.
Content of the invention
The technical problem being existed based on background technology, the present invention proposes a kind of flame-retardant conductive TPV material
Material, it has relatively low sheet resistance and volume resistance, good conductivity, has the characteristics that intensity height, good flame resistance simultaneously.
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third rubber 100-250 part, polypropylene 50-100 part, grafting maleic anhydride with ethylene propylene terpolymer 3-10 part, ethylene-vinyl acetate
Rubber 3-15 part, Pulvis Talci 10-40 part, conductive material 10-30 part, nano-silicon nitride 3-15 part, calcium sulfate crystal whiskers 3-15 part, nitrogen
Change aluminum 2-10 part, Calcium Carbonate 2-10 part, montmorillonite 2-10 part, stearic acid 0.2-1 part, active Zinc Oxide 1-5 part, active calcium silicate
0.5-5 part, vulcanizing system 0.5-2.5 part, methacrylic acid 2-5 part, paraffin oil 5-15 part, UV absorbent 2-5 part, antioxygen
Agent 2-5 part, lubricant 1-3 part, silane coupler Si-69 2-5 part, silane resin acceptor kh-550 1-3.5 part, fire retardant 3-18
Part.
Preferably, described conductive material be conductive carbon nanotube, conductive black, Ni-coated graphite, silver cladding glass microballoon, poly-
One of aniline or multiple mixture；In conductive material addition system, system defines complete conductive network,
Silane coupler Si-69, the addition of silane resin acceptor kh-550 improve the interfacial interaction of conductive material and system, improve
The electric conductivity of material.
Preferably, described nano-silicon nitride is zinc methacrylate modified nano silicon nitride；Described aluminium nitride is modified nitrogen
Change aluminum, the modifying agent being adopted is one of phenolic resin, silane coupler；Described Calcium Carbonate is modified calcium carbonate, is adopted
Modifying agent is methacrylic acid；Nano-silicon nitride is through methacrylic acid zinc modification, Calcium Carbonate after acrylic modified
In addition system, during system sulfuration, vulcanizing system has caused crosslinking and methacrylic acid, the methyl of system simultaneously
Zinc acrylate resin and the graft copolymerization of ethylene propylene diene rubber, thus improve Calcium Carbonate, nano-silicon nitride to ethylene propylene diene rubber
Interface interaction, significantly improves the strengthening action to ethylene propylene diene rubber of Calcium Carbonate and nano-silicon nitride, makes the stretching of material strong
Degree, stress at definite elongation, tearing strength and elongation at break significantly improve, and change with one of phenolic resin, silane coupler simultaneously
Property aluminium nitride cooperation after so that the heat aging property of material and oil resistance is improved to some extent.
Preferably, described vulcanizing system includes vulcanizing agent and accelerator, and vulcanizing agent, the weight of accelerator are than for 2-5：1-
3；Described vulcanizing agent is sulfur, Triallyl isocyanurate, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, mistake
Oxidation tert-butyl cumyl peroxide, di-tert-butyl peroxide cumene are by weight for 0.5-1.5：0.3-1.5：3-9：3-8：2-6
Mixture；Described accelerator is Vulcanization accelerator TMTD, TM monex TM, diphenylguanidine, altax are by weight for 2-10：3-
10：1-5：The mixture of 1-3；Specifically chosen vulcanizing agent and accelerator, and have adjusted the ratio of each vulcanizing agent and accelerator,
Avoid having played synergism while bloom and recovery phenomenon, increase rate of cure, improve state of cure (vulcanization), improve
The stress at definite elongation of vulcanizate, thermostability and compression set.
Preferably, described UV absorbent be ultraviolet absorbent uv-326, in ultraviolet absorbent UV-531 one
Kind or two kinds of mixture；Described antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 626,2- sulfydryl benzo miaow
One of azoles, irgasfos 168, antioxidant DLTDP, antioxidant DTDTP or multiple mixture.
Preferably, described lubricant is pentaerythritol stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, stearic acid
One of barium or multiple mixture.
Preferably, described fire retardant is nano-aluminum hydroxide, nano-sized magnesium hydroxide, zinc, tetramethylolmethane, melamine
Amine, phosphonium flame retardant are by weight for 2-10：3-15：1-5：3-10：2-10：The mixture of 1-8.
Preferably, described phosphonium flame retardant is prepared according to following technique：Brucite is added in toluene, ultrasonic disperse
Add the toluene solution of 3- aminopropyl triethoxysilane afterwards, react 3-5h after being heated to backflow, filter after being cooled to room temperature
To material A；By material A, hydroxy benzaldehyde and dichloromethane mix homogeneously, room temperature reaction 3-6h under the protection of nitrogen, so
Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring reaction 6-10h afterwards, reaction removes dichloromethane after terminating
Alkane obtains described phosphonium flame retardant.
Preferably, in the preparation process of phosphonium flame retardant, the weight ratio of brucite and 3- aminopropyl triethoxysilane
For 5-10：1；Material A, hydroxy benzaldehyde, the weight of 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide are than for 10-
20：1-2：3-4.
Preferably, described phosphonium flame retardant is prepared according to following technique：By weight 8 parts of brucites are added 20 parts
In toluene, after ultrasonic disperse 20min, add the toluene of the 3- aminopropyl triethoxysilane that 5 parts of mass fractions are 20wt% molten
Liquid, reacts 4h after being heated to backflow, is filtrated to get material A after being cooled to room temperature；By weight by 12 parts of material A, 1.7 parts to hydroxyl
Benzaldehyde and 30 parts of dichloromethane mix homogeneously, room temperature reaction 5h under the protection of nitrogen, it is subsequently adding 3.8 parts of 9,10- bis-
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide, stirring reaction 8h, reaction removes dichloromethane after terminating and obtains described phosphorous resistance
Combustion agent.
Flame-retardant conductive thermoplastic vulcanizate material of the present invention can be prepared according to following technique：By ternary second
Third rubber, polypropylene, grafting maleic anhydride with ethylene propylene terpolymer, ethylene-vinyl acetate rubber, conductive material, Pulvis Talci, receive
Rice silicon nitride, calcium sulfate crystal whiskers, aluminium nitride, Calcium Carbonate, montmorillonite, UV absorbent, antioxidant and lubricant add banburying
In machine, banburying uniformly, is re-fed into once being plasticated in single screw extrusion machine, and wherein screw speed is 250-500r/min, once
The processing temperature plasticated is 185-200 DEG C, after pelletizing, obtains rubber master batch；Described rubber master batch and surplus stock are added
In high mixer, mix 0.2-0.5h under the speed conditions of 550-700rpm, transfer to and in double screw extruder, carry out second
Secondary plasticate, wherein screw slenderness ratio be 55-65, feeding rotating speed be 50-70rpm, screw speed be 300-500rpm, mould for the second time
The processing temperature of refining is 160-220 DEG C, tie rod, cooling, and pelletizing obtains described flame-retardant conductive thermoplastic vulcanizate material.
In its raw material of flame-retardant conductive thermoplastic vulcanizate material of the present invention, with ethylene propylene diene rubber as major ingredient, can obtain
Excellent tensile strength, bending moduluses and resistance to permanent deformation, such；In a high proportion of polypropylene addition system, multiple with ethylene propylene diene rubber
Timing, substantially improves the pliability of elastomeric material itself, and has very excellent processing characteristics, thus improving thermoplasticity sulfur
Change the performance of rubber, be simultaneously introduced grafting maleic anhydride with ethylene propylene terpolymer and ethylene-vinyl acetate rubber, itself and ternary
EP rubbers and the polyacrylic compatibility are good, and performance improves the processing characteristics of system after working in coordination with, improve the physical machine of material
Tool performance, reduces cost, obtains good Flame-Retardant and Oil-Resistant performance simultaneously；Add conductive material, so that resulting materials is had
Relatively low sheet resistance and volume resistance, with Pulvis Talci, nano-silicon nitride, calcium sulfate crystal whiskers, aluminium nitride, Calcium Carbonate, montmorillonite
After cooperation, significantly improve tensile strength, stress at definite elongation, tearing strength and the elongation at break of material, make the resistance to of material simultaneously
Heat aging performance and oil resistance are improved to some extent, the tensile strength that simultaneously compensate for causing because of the addition of fire retardant
Loss, improves the mechanical property of material, has simultaneously facilitated the one-tenth charcoal of system, improves the resistance of system with fire retardant after coordinating
Combustion property and heat stability；In silane coupler Si-69 addition system, on the one hand coordinate with silane resin acceptor kh-550, improve
The compatibility of system, on the one hand can participate in the cross-linking reaction of system, and the crosslink density that improve material improves the synthesis of material
Performance；Optimal way, in the preparation process of phosphonium flame retardant, after brucite is mixed with 3- aminopropyl triethoxysilane, leads to
Cross the condition controlling reaction, so that the hydroxyl of hydrotalcite surface and the hydroxyl of 3- aminopropyl triethoxysilane hydrolysis is there occurs instead
Should, thus the surface that amino has been incorporated into brucite has obtained material A；After material A, hydroxy benzaldehyde are mixed, material A
In amino and hydroxy benzaldehyde in carbonyl there occurs affine additive reaction, obtained siliceous imine intermediate, and 9,
After the mixing of 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide, by controlling the condition reacted, make 9,10- dihydro-9-oxy
P-H active group in miscellaneous -10- phospho hetero phenanthrene -10- oxide occurs addition anti-with the carbon-to-nitrogen double bon in siliceous imine intermediate
Should, thus by brucite, 3- aminopropyl triethoxysilane, hydroxy benzaldehyde, 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -
10- oxide is combined as a whole, and has obtained described phosphonium flame retardant, is added in system, with nano-aluminum hydroxide, nanometer hydrogen
After magnesium oxide, zinc, tetramethylolmethane, tripolycyanamide coordinate, there is cooperative effect, promoted the formation of layer of charcoal, in rubber material
Define continuously fine and close foamed char in the combustion process of material, serve heat-insulated, oxygen barrier, the effect of suppression molten drop well,
Reduce maximum HRR simultaneously, extend ignitor firing time, significantly improve the anti-flammability of material, control fire-retardant simultaneously
Content in system for the agent, prevents the generation of much higher hard phenomenon while playing potentiation.
Specific embodiment
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third 250 parts of rubber, 50 parts of polypropylene, 10 parts of grafting maleic anhydride with ethylene propylene terpolymer, 3 parts of ethylene-vinyl acetate rubber, cunning
40 parts of stone powder, 10 parts of conductive material, 15 parts of nano-silicon nitride, 3 parts of calcium sulfate crystal whiskers, 10 parts of aluminium nitride, 2 parts of Calcium Carbonate, illiteracy are de-
10 parts of soil, 0.2 part of stearic acid, active 5 parts of Zinc Oxide, 0.5 part of active calcium silicate, 2.5 parts of vulcanizing system, 2 parts of methacrylic acid,
15 parts of paraffin oil, 2 parts of UV absorbent, 5 parts of antioxidant, 1 part of lubricant, 5 parts of silane coupler Si-69, silane coupler
1 part of KH-550,18 parts of fire retardant.
Embodiment 2
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third 100 parts of rubber, 100 parts of polypropylene, 3 parts of grafting maleic anhydride with ethylene propylene terpolymer, 15 parts of ethylene-vinyl acetate rubber,
10 parts of Pulvis Talci, 30 parts of conductive material, 3 parts of nano-silicon nitride, 15 parts of calcium sulfate crystal whiskers, 2 parts of aluminium nitride, 10 parts of Calcium Carbonate, illiteracy
Take off 2 parts of soil, 1 part of stearic acid, active 1 part of Zinc Oxide, 5 parts of active calcium silicate, 0.5 part of vulcanizing system, 5 parts of methacrylic acid, stone
5 parts of wax oil, 5 parts of UV absorbent, 2 parts of antioxidant, 3 parts of lubricant, 2 parts of silane coupler Si-69, silane coupler KH-
550 3.5 parts, 3 parts of fire retardant.
Embodiment 3
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third 220 parts of rubber, 90 parts of polypropylene, 8 parts of grafting maleic anhydride with ethylene propylene terpolymer, 6 parts of ethylene-vinyl acetate rubber, cunning
37 parts of stone powder, 22 parts of conductive carbon nanotube, 5 parts of nano-silicon nitride, 11 parts of calcium sulfate crystal whiskers, 5.8 parts of aluminium nitride, Calcium Carbonate 8.3
Part, 7 parts of montmorillonite, 0.88 part of stearic acid, active 3.2 parts of Zinc Oxide, 3.7 parts of active calcium silicate, 0.9 part of vulcanizing system, methyl
4.3 parts of acrylic acid, 10 parts of paraffin oil, 4.3 parts of UV absorbent, 2.9 parts of antioxidant, 2.7 parts of pentaerythritol stearate, silicon
3.6 parts of alkane coupling agent Si-69,2.9 parts of silane resin acceptor kh-550,8.5 parts of fire retardant；
Wherein, described nano-silicon nitride is zinc methacrylate modified nano silicon nitride；Described aluminium nitride is modified nitridation
Aluminum, the modifying agent being adopted is phenolic resin；Described Calcium Carbonate is modified calcium carbonate, and the modifying agent being adopted is metering system
Acid；
Described vulcanizing system includes vulcanizing agent and accelerator, and vulcanizing agent, the weight of accelerator are than for 2：3；Described sulfuration
Agent is sulfur, Triallyl isocyanurate, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, tert-butyl peroxide
Isopropylbenzene, di-tert-butyl peroxide cumene are by weight for 0.5：1.5：3：8：2 mixture；Described accelerator is to promote
Agent TMTD, TM monex TM, diphenylguanidine, altax are by weight for 10：3：5：1 mixture；
Described UV absorbent is ultraviolet absorbent uv-326；Described antioxidant is antioxidant 1076；
Described fire retardant is nano-aluminum hydroxide, nano-sized magnesium hydroxide, zinc, tetramethylolmethane, tripolycyanamide, phosphorous resistance
Combustion agent is by weight for 2：15：1：10：2：8 mixture；
Described phosphonium flame retardant is prepared according to following technique：Brucite is added in toluene, adds after ultrasonic disperse
The toluene solution of 3- aminopropyl triethoxysilane, wherein, the weight of brucite and 3- aminopropyl triethoxysilane is than for 10：
1, react 3h after being heated to backflow, after being cooled to room temperature, be filtrated to get material A；By material A, hydroxy benzaldehyde and dichloromethane
Mix homogeneously, room temperature reaction 6h under the protection of nitrogen, it is subsequently adding 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxidation
Thing, wherein, material A, hydroxy benzaldehyde, the weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are than for 10：
2：3, stirring reaction 10h, reaction removes dichloromethane after terminating and obtains described phosphonium flame retardant.
Embodiment 4
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third 130 parts of rubber, 70 parts of polypropylene, 5.8 parts of grafting maleic anhydride with ethylene propylene terpolymer, 12 parts of ethylene-vinyl acetate rubber,
13 parts of Pulvis Talci, 11 parts of conductive black, 3 parts of Ni-coated graphite, silver 3 parts of glass microballoon of cladding, 13 parts of nano-silicon nitride, calcium sulfate are brilliant
8 parts of palpus, 8.6 parts of aluminium nitride, 4.6 parts of Calcium Carbonate, 6 parts of montmorillonite, 0.5 part of stearic acid, active 4 parts of Zinc Oxide, active calcium silicate 2
Part, 2.1 parts of vulcanizing system, 3.8 parts of methacrylic acid, 13 parts of paraffin oil, 2.9 parts of UV absorbent, 4.3 parts of antioxidant, oxygen
Change 0.8 part of polyethylene, 0.6 part of chlorinated paraffin, 0.2 part of stearic acid, silane coupler Si-694.3 part, silane resin acceptor kh-550
1.8 parts, 13 parts of fire retardant；
Wherein, described nano-silicon nitride is zinc methacrylate modified nano silicon nitride；Described aluminium nitride is modified nitridation
Aluminum, the modifying agent being adopted is silane coupler；Described Calcium Carbonate is modified calcium carbonate, and the modifying agent being adopted is metering system
Acid；
Described vulcanizing system includes vulcanizing agent and accelerator, and vulcanizing agent, the weight of accelerator are than for 5：1；Described sulfuration
Agent is sulfur, Triallyl isocyanurate, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, tert-butyl peroxide
Isopropylbenzene, di-tert-butyl peroxide cumene are by weight for 1.5：0.3：9：3：6 mixture；Described accelerator is to promote
Agent TMTD, TM monex TM, diphenylguanidine, altax are by weight for 2：10：1：3 mixture；
Described UV absorbent is ultraviolet absorbent UV-531；Described antioxidant is antioxidant 1010, antioxidant
626th, 2-mercaptobenzimidazole is by weight for 3：5：2 mixture；
Described fire retardant is nano-aluminum hydroxide, nano-sized magnesium hydroxide, zinc, tetramethylolmethane, tripolycyanamide, phosphorous resistance
Combustion agent is by weight for 10：3：5：3：10：1 mixture；
Described phosphonium flame retardant is prepared according to following technique：Brucite is added in toluene, adds after ultrasonic disperse
The toluene solution of 3- aminopropyl triethoxysilane, wherein, the weight of brucite and 3- aminopropyl triethoxysilane is than for 5：
1, react 5h after being heated to backflow, after being cooled to room temperature, be filtrated to get material A；By material A, hydroxy benzaldehyde and dichloromethane
Mix homogeneously, room temperature reaction 3h under the protection of nitrogen, it is subsequently adding 9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxidation
Thing, wherein, material A, hydroxy benzaldehyde, the weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are than for 20：
1：4, stirring reaction 6h, reaction removes dichloromethane after terminating and obtains described phosphonium flame retardant.
Embodiment 5
A kind of flame-retardant conductive thermoplastic vulcanizate material proposed by the present invention, its raw material includes by weight：Ternary second
Third 200 parts of rubber, 80 parts of polypropylene, 7 parts of grafting maleic anhydride with ethylene propylene terpolymer, 12 parts of ethylene-vinyl acetate rubber, cunning
27 parts of stone powder, silver 15 parts of glass microballoon of cladding, 12 parts of polyaniline, 11 parts of nano-silicon nitride, 12 parts of calcium sulfate crystal whiskers, aluminium nitride
8.5 parts, 7.6 parts of Calcium Carbonate, 5.8 parts of montmorillonite, 0.68 part of stearic acid, active 3.2 parts of Zinc Oxide, 4.3 parts of active calcium silicate, sulfur
2.1 parts of change system, 3.7 parts of methacrylic acid, 13 parts of paraffin oil, 3.2 parts of UV absorbent, 4 parts of antioxidant, 2 parts of lubricant,
3.5 parts of silane coupler Si-69,2.8 parts of silane resin acceptor kh-550,12 parts of fire retardant；
Wherein, described nano-silicon nitride is zinc methacrylate modified nano silicon nitride；Described aluminium nitride is modified nitridation
Aluminum, the modifying agent being adopted is phenolic resin, silane coupler is by weight for 4：3 mixture；Described Calcium Carbonate is modification
Calcium Carbonate, the modifying agent being adopted is methacrylic acid；
Described vulcanizing system includes vulcanizing agent and accelerator, and vulcanizing agent, the weight of accelerator are than for 3：2；Described sulfuration
Agent is sulfur, Triallyl isocyanurate, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, tert-butyl peroxide
Isopropylbenzene, di-tert-butyl peroxide cumene are by weight for 1：1.2：6：5：4 mixture；Described accelerator is accelerator
TMTD, TM monex TM, diphenylguanidine, altax are by weight for 6：7：2：2 mixture；
Described UV absorbent is ultraviolet absorbent uv-326, ultraviolet absorbent UV-531 is by weight for 3：2
Mixture；Described antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 626,2-mercaptobenzimidazole, antioxidant
168th, antioxidant DLTDP, antioxidant DTDTP press the mixture of any weight ratio；
Described lubricant is pentaerythritol stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate are pressed and appointed
The mixture of meaning weight ratio；
Described fire retardant is nano-aluminum hydroxide, nano-sized magnesium hydroxide, zinc, tetramethylolmethane, tripolycyanamide, phosphorous resistance
Combustion agent is by weight for 6：11：3：8：7：6 mixture；
Described phosphonium flame retardant is prepared according to following technique：By weight 8 parts of brucites are added in 20 parts of toluene,
Add the toluene solution of the 3- aminopropyl triethoxysilane that 5 parts of mass fractions are 20wt% after ultrasonic disperse 20min, be heated to
React 4h after backflow, after being cooled to room temperature, be filtrated to get material A；By weight by 12 parts of material A, 1.7 parts of hydroxy benzaldehydes
With 30 parts of dichloromethane mix homogeneously, room temperature reaction 5h under the protection of nitrogen, it is subsequently adding 3.8 parts of 9,10- dihydro-9-oxies
Miscellaneous -10- phospho hetero phenanthrene -10- oxide, stirring reaction 8h, reaction removes dichloromethane after terminating and obtains described phosphonium flame retardant.
Performance test is carried out to the flame-retardant conductive thermoplastic vulcanizate material described in embodiment of the present invention 1-5, its knot
Really as shown in the table：
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength/MPa | 18.5 | 18.7 | 18.5 | 18 | 18.8 |
| Elongation at break/% | 760 | 775 | 750 | 740 | 765 |
| Compression set/% | 9.1 | 8.4 | 8.6 | 8.8 | 8.2 |
| Volume resistance | 3×103 | 4×103 | 3×103 | 3.5×103 | 2×103 |
| Sheet resistance/Ω | 4×102 | 4×102 | 3×102 | 2×102 | 2×102 |
| Fire-retardant UL94 standard | V0 | V0 | V0 | V0 | V0 |
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.
Claims (10)
1. a kind of flame-retardant conductive thermoplastic vulcanizate material is it is characterised in that its raw material includes by weight：Ethylene-propylene-diene monomer
Glue 100-250 part, polypropylene 50-100 part, grafting maleic anhydride with ethylene propylene terpolymer 3-10 part, ethylene-vinyl acetate rubber
3-15 part, Pulvis Talci 10-40 part, conductive material 10-30 part, nano-silicon nitride 3-15 part, calcium sulfate crystal whiskers 3-15 part, aluminium nitride
2-10 part, Calcium Carbonate 2-10 part, montmorillonite 2-10 part, stearic acid 0.2-1 part, active Zinc Oxide 1-5 part, active calcium silicate 0.5-
5 parts, vulcanizing system 0.5-2.5 part, methacrylic acid 2-5 part, paraffin oil 5-15 part, UV absorbent 2-5 part, antioxidant 2-
5 parts, lubricant 1-3 part, silane coupler Si-69 2-5 part, silane resin acceptor kh-550 1-3.5 part, fire retardant 3-18 part.
2. according to claim 1 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described conductive material be lead
One of electrical carbon nanotube, conductive black, Ni-coated graphite, silver cladding glass microballoon, polyaniline or multiple mixture.
3. flame-retardant conductive thermoplastic vulcanizate material according to claim 1 or claim 2 is it is characterised in that described nano silicon nitride
Silicon is zinc methacrylate modified nano silicon nitride；Described aluminium nitride is modified aluminium nitride, and the modifying agent being adopted is phenolic aldehyde tree
One of fat, silane coupler；Described Calcium Carbonate is modified calcium carbonate, and the modifying agent being adopted is methacrylic acid.
4. according to any one of claim 1-3 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described sulfur
Change system includes vulcanizing agent and accelerator, and vulcanizing agent, the weight of accelerator are than for 2-5：1-3；Described vulcanizing agent be sulfur, three
Allyl iso cyanurate, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, t-butylcumylperoxide, two uncles
Butyl peroxy cumene is by weight for 0.5-1.5：0.3-1.5：3-9：3-8：The mixture of 2-6；Described accelerator is
Vulcanization accelerator TMTD, TM monex TM, diphenylguanidine, altax are by weight for 2-10：3-10：1-5：The mixture of 1-3.
5. according to any one of claim 1-4 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described purple
Ultraviolet absorbers are the mixture of one of ultraviolet absorbent uv-326, ultraviolet absorbent UV-531 or two kinds；Institute
Stating antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 626,2-mercaptobenzimidazole, irgasfos 168, antioxidant
One of DLTDP, antioxidant DTDTP or multiple mixture.
6. according to any one of claim 1-5 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described profit
Lubrication prescription is one of pentaerythritol stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate or multiple
Mixture.
7. according to any one of claim 1-6 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described resistance
Combustion agent is nano-aluminum hydroxide, nano-sized magnesium hydroxide, zinc, tetramethylolmethane, tripolycyanamide, phosphonium flame retardant are by weight
2-10：3-15：1-5：3-10：2-10：The mixture of 1-8.
8. according to claim 7 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described phosphonium flame retardant is pressed
It is prepared according to following technique：Brucite is added the first adding 3- aminopropyl triethoxysilane in toluene after ultrasonic disperse
Benzole soln, reacts 3-5h after being heated to backflow, is filtrated to get material A after being cooled to room temperature；By material A, hydroxy benzaldehyde and
Dichloromethane mix homogeneously, room temperature reaction 3-6h under the protection of nitrogen, it is subsequently adding 9,10- dihydro-9-oxy miscellaneous -10- phospha
Phenanthrene -10- oxide, stirring reaction 6-10h, reaction removes dichloromethane after terminating and obtains described phosphonium flame retardant.
9. according to claim 8 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that system in phosphonium flame retardant
During standby, the weight of brucite and 3- aminopropyl triethoxysilane ratio is for 5-10：1；Material A, hydroxy benzaldehyde, 9,
The weight of 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide is than for 10-20：1-2：3-4.
10. according to any one of claim 7-9 flame-retardant conductive thermoplastic vulcanizate material it is characterised in that described
Phosphonium flame retardant is prepared according to following technique：By weight 8 parts of brucites are added in 20 parts of toluene, ultrasonic disperse
The toluene solution of the 3- aminopropyl triethoxysilane that 5 parts of mass fractions are 20wt% is added after 20min, anti-after being heated to flowing back
Answer 4h, after being cooled to room temperature, be filtrated to get material A；By weight by 12 parts of material A, 1.7 parts of hydroxy benzaldehydes and 30 part two
Chloromethanes mix homogeneously, room temperature reaction 5h under the protection of nitrogen, it is subsequently adding the miscellaneous -10- phospha of 3.8 parts of 9,10- dihydro-9-oxies
Phenanthrene -10- oxide, stirring reaction 8h, reaction removes dichloromethane after terminating and obtains described phosphonium flame retardant.
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| CN107868348A (en) * | 2017-12-03 | 2018-04-03 | 深圳市罗庚电气有限公司 | A kind of high flame resistance conduction ethylene propylene diene rubber and preparation method thereof |
| CN108164839A (en) * | 2018-01-29 | 2018-06-15 | 象山杰尔德智能科技有限公司 | A kind of High-performance electroconductive rubber and preparation method thereof |
| CN109721857A (en) * | 2018-11-23 | 2019-05-07 | 东莞捷佳塑胶科技有限公司 | Improve the new auxiliary formula of TPV |
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| CN110577716A (en) * | 2019-09-23 | 2019-12-17 | 南通伟越电器有限公司 | Preparation method of high-impact-resistance polystyrene special material for television shell |
| CN111286094A (en) * | 2020-03-13 | 2020-06-16 | 泉州市华创园智能研究有限公司 | Rubber material for soles of sports shoes and preparation method thereof |
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