CN106519460A - Flame-retardant thermoplastic vulcanized rubber material - Google Patents
Flame-retardant thermoplastic vulcanized rubber material Download PDFInfo
- Publication number
- CN106519460A CN106519460A CN201610985568.2A CN201610985568A CN106519460A CN 106519460 A CN106519460 A CN 106519460A CN 201610985568 A CN201610985568 A CN 201610985568A CN 106519460 A CN106519460 A CN 106519460A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame
- vulcanized rubber
- rubber material
- thermoplastic vulcanized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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 thermoplastic vulcanized rubber material. Raw materials of the flame-retardant thermoplastic vulcanized rubber material include ethylene propylene terpolymer, polypropylene, methyl-phenyl-vinyl silicone, montmorillonite, kaolin, cerium dioxide, white carbon black, zirconium oxide, aramid fiber, tetra-needle like ZnO whiskers, titanate coupling agent modified calcium sulfate whiskers, phenolic resin, pulverous coal, activated zinc oxide powder, nanosilicon dioxide, fire retardant, a vulcanizing agent, glutamic acid dithiocarbamic lanthanum, paraffin oil, an ultraviolet light absorber, an antioxidant and a lubricant. The flame-retardant thermoplastic vulcanized rubber material which is put forward has the beneficial effects of being high in strength, good in fire resistance, high in durability and good in tenacity.
Description
Technical field
The present invention relates to technical field of rubber material, more particularly to a kind of flame-proofed thermoplastic vulcanized rubber material.
Background technology
TPV includes the blend of dynamic perduren and thermoplastic polymer.The rubber can be used as thin
Crumb particle is dispersed in thermoplastic resin lipid phase.These compositions have advantageously illustrated many property of thermo-setting elastomer
Matter, but they can be processed as thermoplastic.As TPV can advantageously as thermoplastic
Processing, commonly used thermoplastic extrusion technology extrude elastic article by TPV.United States Patent (USP) US4311628/
0272871A1 discloses the method for 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 using dynamic vulcanization technology for vulcanization accelerator
Property vulcanized rubber, but which is present during use, and intensity is not high, the defect that anti-flammability is less desirable.
The content of the invention
Based on the technical problem that background technology is present, the present invention proposes a kind of flame-proofed thermoplastic vulcanized rubber material, its
Have the advantages that intensity height, good flame resistance, durability be strong, toughness is good.
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
Glue 120-250 parts, polypropylene 120-250 parts, phenyl siloxane rubber 20-50 parts, montmorillonite 10-40 parts, kaolin 3-15 parts, dioxy
Change cerium 3-15 parts, white carbon 10-35 parts, zirconium oxide 2-15 parts, aramid fiber 3-15 parts, four acicular type zinc oxide crystal whisker 3-18 parts,
Titanate coupling agent modified calcium sulfate crystal whiskers 1-5 parts, phenolic resin 2-10 parts, flyash 3-12 parts, active Zinc Oxide 1-5 parts,
Nano silicon 2-10 parts, fire retardant 40-60 parts, vulcanizing agent 1-3 parts, glutamic acid aminodithioformic acid lanthanum 0.2-1.5 parts,
Paraffin oil 20-50 parts, ultra-violet absorber 1.5-5 parts, antioxidant 1.5-5 parts, lubricant 1-3 parts.
Preferably, in its raw material, ethylene propylene diene rubber, polypropylene, the weight ratio of phenyl siloxane rubber are 150-200：150-
200：30-40.
Preferably, the montmorillonite is modified montmorillonoid；The modified montmorillonoid is prepared according to following technique：By season
During penta tetrol adds dichloromethane, POCl3 is stirring evenly and then adding into, wherein, pentaerythrite with the mol ratio of POCl3 is
1：2-3, reacts 3-5h after being warming up to 35-40 DEG C, after reaction terminates, Jing is filtered, washs, is dried to obtain material A；By montmorillonite plus
Enter in toluene, ultrasonic disperse uniformly adds the toluene solution of silane coupler KH-540 afterwards, wherein, montmorillonite and silane coupler
The weight ratio of KH-540 is 20-35：1-2, stirring reaction 3-5h after being warming up to 95-105 DEG C, reaction are cooled to 30-35 after terminating
DEG C, material A is subsequently adding, wherein, material A is 1 with the mol ratio of silane coupler KH-540：2-3, stirring reaction 3-5h, instead
After should terminating, Jing is filtered, is washed, being dried to obtain the modified montmorillonoid.
Preferably, the fire retardant is formed by organic fire-retardant and inorganic combustion inhibitor compounding, and organic fire-retardant accounts for fire-retardant
The 60-80% of agent gross weight, inorganic combustion inhibitor account for the 20-40% of fire retardant gross weight；The organic fire-retardant is melamine
The mixture of the one or two kinds of in phosphate, phosphorus nitrogen silicon fire retardant；The inorganic combustion inhibitor is aluminium hydroxide, hydroxide
The mixture of one or more in magnesium, microencapsulated powder oil, zinc stannate, Firebrake ZB.
Preferably, the following technique of the phosphorus nitrogen silicon fire retardant is prepared：Beta-schardinger dextrin is added in toluene, ultrasound
The toluene solution of 3- aminopropyl triethoxysilanes is added after dispersion, 3-5h is reacted after being heated to backflow, is cooled to room temperature and obtains
Material A；Material A, parahydroxyben-zaldehyde and dichloromethane are well mixed, the room temperature reaction 3-6h under the protection of nitrogen, then
Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring reaction 6-10h, reaction to remove solvent after terminating to obtain
The phosphorus nitrogen silicon fire retardant；
In the preparation process of phosphorus nitrogen silicon fire retardant, after beta-schardinger dextrin is mixed with 3- aminopropyl triethoxysilanes, lead to
The condition of control reaction is crossed, the hydroxyl and the hydroxyl of 3- aminopropyl triethoxysilanes hydrolysis for making beta-schardinger dextrin surface there occurs instead
Should, the surface that amino has been incorporated into beta-schardinger dextrin has been obtained into material A；After by material A, parahydroxyben-zaldehyde mixing, in material A
Amino and parahydroxyben-zaldehyde in carbonyl there occurs affine addition reaction, obtained siliceous imine intermediate, with 9,10-
After the mixing of dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrenes -10- oxides, by the condition for controlling reaction, make 9,10- dihydro-9-oxies it is miscellaneous -
There is addition reaction with the carbon-to-nitrogen double bon in siliceous imine intermediate in the P-H active groups in 10- phospho hetero phenanthrene -10- oxides,
So as to by beta-schardinger dextrin, 3- aminopropyl triethoxysilanes, parahydroxyben-zaldehyde, the miscellaneous -10- phospho hetero phenanthrenes of 9,10- dihydro-9-oxies -
10- oxides are combined as a whole, and have obtained the phosphorus nitrogen silicon fire retardant, as organic fire-retardant addition system in, with nothing
After machine fire retardant coordinates, with cooperative effect, the formation of layer of charcoal is promoted, has defined in the combustion process of elastomeric material continuous
Fine and close foamed char, serves good heat-insulated, oxygen barrier, suppresses the effect of molten drop, while maximum HRR is reduced,
Ignitor firing time is extended, the anti-flammability of material is significantly improved, while controlling content of the fire retardant in system, increasing is being played
Pretend with while prevent the generation of much higher hard phenomenon.
Preferably, in the preparation process of phosphorus nitrogen silicon fire retardant, the weight of beta-schardinger dextrin and 3- aminopropyl triethoxysilanes
Amount is than being 5-10：1；The weight ratio of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of material A, parahydroxyben-zaldehyde, 9,10- dihydro-9-oxies
For 10-20：1-2：3-4.
Preferably, the vulcanizing agent is 2,5- dimethyl -2, and bis--(t-butyl peroxy) hexanes of 5-, tert-butyl peroxide are different
Propyl benzene, cumyl peroxide, peroxidized t-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate,
BMI is 3-15 by weight：2-10：3-15：2-15：3-15：3-10：2-8：The mixture of 1-5；
With 2,5- dimethyl -2, bis--(t-butyl peroxy) hexanes of 5-, t-butylcumylperoxide, peroxidating diisopropyl
Benzene, peroxidized t-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate, BMI are sulfuration
Agent, and the ratio of vulcanizing agent is controlled, under the facilitation of glutamic acid aminodithioformic acid lanthanum, hence it is evident that accelerate system
Curingprocess rate, and the crosslinking degree and uniform performance of cross-linked material are efficiently controlled, give vulcanizate excellent elongation rate of tensile failure
And tearing strength, while improve the heatproof air aging performance of sizing material.
Preferably, the ultra-violet absorber be ultraviolet absorbent uv-326, in ultraviolet absorbent UV-531 one
Kind or two kinds of mixture；The antioxidant is antioxidant 1076, antioxidant 1010, antioxidant 626,2- sulfydryl benzo miaows
One or more mixture in azoles, irgasfos 168, antioxidant DLTDP, antioxidant DTDTP.
Preferably, the lubricant is pentaerythrite stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, stearic acid
Barium, oleamide are 2-10 by weight：2-8：4-12：2-10：1-5：The mixture of 2-10.
Flame-proofed thermoplastic vulcanized rubber material of the present invention can be prepared according to following technique：By ethylene-propylene-diene monomer
Glue, polypropylene, phenyl siloxane rubber, montmorillonite, kaolin, ceria, white carbon, zirconium oxide, aramid fiber, the oxidation of four needle-likes
Zinc whisker, titanate coupling agent modified calcium sulfate crystal whiskers, phenolic resin, flyash, fire retardant, ultra-violet absorber, antioxidant
Banburying in banbury is added uniformly, to carry out plasticating in being re-fed into single screw extrusion machine for the first time, wherein screw speed with lubricant
For 200-400r/min, the processing temperature plasticated for the first time is 160-180 DEG C, after pelletizing, obtains rubber master batch；By the rubber
During master batch and surplus stock add high mixer, mix 0.2-0.4h under the speed conditions of 500-600rpm, transfer to double spiral shells
Plasticated in bar extruder for the second time, wherein screw slenderness ratio is 55-65, and feeding rotating speed is 50-70rpm, and screw speed is
300-500rpm, the processing temperature plasticated for the second time are 160-220 DEG C, and tie rod, cooling, pelletizing obtain the flame-proofed thermoplastic
Vulcanized rubber material.
Flame-proofed thermoplastic vulcanized rubber material of the present invention, with ethylene propylene diene rubber as major ingredient, has gained elastomeric material
Excellent tensile strength, bending modulus and cross-linked polymeric degree, significantly improve the resistance to permanent deformation, such of elastomeric material and are processed into
Type performance, while polypropylene and phenyl siloxane rubber are added, by controlling polypropylene, phenyl siloxane rubber and ethylene propylene diene rubber
Ratio, makes the performance of three act synergistically, and gives the excellent oil resistivity of elastomeric material, heat resistance and anti-flammability, while and
Improve cold resistance and the ozone aging resistance of the diaphragm, weatherability and the resistance to low temperature of material；Add montmorillonite, its with kaolin,
Ceria, white carbon, zirconium oxide, aramid fiber, four acicular type zinc oxide crystal whisker, titanate coupling agent modified calcium sulfate crystal whiskers,
Phenolic resin, flyash, nano silicon define aggregation and filler network in system after coordinating, and significantly improve material
The tensile strength of material, tearing strength, elongation at break, and the hydrophobicity and processing fluidity of material are improved, improve material
Anti-flammability；In the preparation process of modified montmorillonoid, first with pentaerythrite and POCl3 as raw material, by controlling reaction
Condition, make the hydroxyl in pentaerythrite there occurs reaction with POCl3, during reaction, control pentaerythrite and
The molar ratio of POCl3 has obtained chloride material A；With montmorillonite and silane coupler KH-540 as raw material, control anti-
The condition answered, makes the hydroxyl on montmorillonite surface and the hydroxyl of silane coupler KH-540 hydrolysis there occurs reaction, so as to by primary amine
Base has been incorporated into the surface of montmorillonite, and after mixing with material A afterwards, the chlorine in material A is there occurs with the amino on montmorillonite surface
Reaction, has obtained modified illiteracy and has taken off so as to pentaerythrite, POCl3, montmorillonite and silane coupler KH-540 are combined as a whole
Soil, is added in system, on the one hand, which is coordinated with filler, gives elastomeric material excellent intensity, serves significant reinforcement
Effect, while because pentaerythrite, POCl3, montmorillonite and silane coupler are connected as one by which, in addition system, with
Fire retardant gives the excellent anti-flammability of elastomeric material and heat resistance after coordinating；Glutamic acid aminodithioformic acid lanthanum is added, its
There are to rubber good promotion functions, the speed of sulfuration is accelerated, the process of sulfuration is improve, while the nano-silica for adding
The fillers such as SiClx, white carbon have activation to glutamic acid aminodithioformic acid lanthanum, reduce the activation energy of system, make sulphur
Change reaction to be easier to make for, while in glutamic acid aminodithioformic acid lanthanum addition system, with the scattered effect of promotion filler,
Improve the strengthening action of filler.
Performance test is carried out to flame-proofed thermoplastic vulcanized rubber material of the present invention, its result is as follows：Stretching
Intensity is 20-23.8MPa, and elongation at break is 770-810%, and compression set is 5-6.2%, and fire-retardant UL94 standards reach
V0 grades.
Specific embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
250 parts of glue, 120 parts of polypropylene, 20 parts of phenyl siloxane rubber, 40 parts of montmorillonite, 3 parts of kaolin, 15 parts of ceria, white carbon 10
Part, 15 parts of zirconium oxide, 3 parts of aramid fiber, 18 parts of four acicular type zinc oxide crystal whisker, 1 part of titanate coupling agent modified calcium sulfate crystal whiskers,
10 parts of phenolic resin, 3 parts of flyash, active 5 parts of Zinc Oxide, 2 parts of nano silicon, 60 parts of fire retardant, 1 part of vulcanizing agent, paddy
1.5 parts of propylhomoserin aminodithioformic acid lanthanum, 20 parts of paraffin oil, 5 parts of ultra-violet absorber, 1.5 parts of antioxidant, 3 parts of lubricant.
Embodiment 2
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
120 parts of glue, 0 part of polipropene 25,50 parts of phenyl siloxane rubber, 10 parts of montmorillonite, 15 parts of kaolin, 3 parts of ceria, white carbon 35
Part, 2 parts of zirconium oxide, 15 parts of aramid fiber, 3 parts of four acicular type zinc oxide crystal whisker, 5 parts of titanate coupling agent modified calcium sulfate crystal whiskers,
2 parts of phenolic resin, 12 parts of flyash, active 1 part of Zinc Oxide, 10 parts of nano silicon, 40 parts of fire retardant, 3 parts of vulcanizing agent, paddy
0.2 part of propylhomoserin aminodithioformic acid lanthanum, 50 parts of paraffin oil, 1.5 parts of ultra-violet absorber, 5 parts of antioxidant, 1 part of lubricant.
Embodiment 3
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
200 parts of glue, 150 parts of polypropylene, 30 parts of phenyl siloxane rubber, 30 parts of montmorillonite, 7 parts of kaolin, 10 parts of ceria, white carbon 19
Part, 10 parts of zirconium oxide, 8 parts of aramid fiber, 15 parts of four acicular type zinc oxide crystal whisker, titanate coupling agent modified calcium sulfate crystal whiskers 3.2
Part, 6.5 parts of phenolic resin, 5.9 parts of flyash, active 4 parts of Zinc Oxide, 5.8 parts of nano silicon, 60 parts of fire retardant, sulfuration
1.8 parts of agent, 1.3 parts of glutamic acid aminodithioformic acid lanthanum, 30 parts of paraffin oil, 4 parts of ultra-violet absorber, 3.5 parts of antioxidant, profit
2.4 parts of lubrication prescription；
Wherein, the montmorillonite is modified montmorillonoid；The modified montmorillonoid is prepared according to following technique：By season penta
During tetrol adds dichloromethane, POCl3 is stirring evenly and then adding into, wherein, pentaerythrite is 1 with the mol ratio of POCl3：
3,5h is reacted after being warming up to 35 DEG C, after reaction terminates, Jing is filtered, washs, is dried to obtain material A；Montmorillonite is added in toluene,
Ultrasonic disperse uniformly adds the toluene solution of silane coupler KH-540 afterwards, wherein, montmorillonite is with silane coupler KH-540's
Weight ratio is 20：2, stirring reaction 5h after being warming up to 95 DEG C, reaction are cooled to 30 DEG C after terminating, and are subsequently adding material A, wherein,
Material A is 1 with the mol ratio of silane coupler KH-540：3, stirring reaction 3h, reaction terminate after Jing filter, it is washing, dry
To the modified montmorillonoid；
The fire retardant is formed by organic fire-retardant and inorganic combustion inhibitor compounding, and organic fire-retardant accounts for fire retardant gross weight
80%, inorganic combustion inhibitor accounts for the 20% of fire retardant gross weight；The organic fire-retardant is phosphorus nitrogen silicon fire retardant；The inorganic resistance
It is 4 by weight that combustion agent is magnesium hydroxide, microencapsulated powder oil：5 mixture；
The following technique of the phosphorus nitrogen silicon fire retardant is prepared：Beta-schardinger dextrin is added in toluene, after ultrasonic disperse
The toluene solution of 3- aminopropyl triethoxysilanes is added, wherein, the weight of beta-schardinger dextrin and 3- aminopropyl triethoxysilanes
Than for 5：1,5h is reacted after being heated to backflow, be cooled to room temperature and obtain material A；By material A, parahydroxyben-zaldehyde and dichloromethane
It is well mixed, the room temperature reaction 3h under the protection of nitrogen, is subsequently adding the miscellaneous -10- phospho hetero phenanthrenes -10- oxidations of 9,10- dihydro-9-oxies
Thing, wherein, material A, parahydroxyben-zaldehyde, the weight ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are 20：
1：4, stirring reaction 6h, reaction remove solvent after terminating and obtain the phosphorus nitrogen silicon fire retardant；
The vulcanizing agent be 2,5- dimethyl -2, bis--(t-butyl peroxy) hexanes of 5-, t-butylcumylperoxide, mistake
Oxidation diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate, span carry out acyl
Imines is 15 by weight：2：15：2：15：3：8：1 mixture；
The ultra-violet absorber is ultraviolet absorbent UV-531；The antioxidant is antioxidant 1076；
The lubricant is pentaerythrite stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate, oleic acid
Acid amides is 2 by weight：8：4：10：1：10 mixture.
Embodiment 4
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
150 parts of glue, 200 parts of polypropylene, 40 parts of phenyl siloxane rubber, 18 parts of montmorillonite, 11 parts of kaolin, 5 parts of ceria, white carbon 30
Part, 6 parts of zirconium oxide, 12 parts of aramid fiber, 10 parts of four acicular type zinc oxide crystal whisker, titanate coupling agent modified calcium sulfate crystal whiskers 4.5
Part, 5.8 parts of phenolic resin, 7 parts of flyash, active 3.2 parts of Zinc Oxide, 7 parts of nano silicon, 55 parts of fire retardant, vulcanizing agent
2.5 parts, 0.7 part of glutamic acid aminodithioformic acid lanthanum, 40 parts of paraffin oil, 3.2 parts of ultra-violet absorber, 4.3 parts of antioxidant, profit
1.5 parts of lubrication prescription；
Wherein, the montmorillonite is modified montmorillonoid；The modified montmorillonoid is prepared according to following technique：By season penta
During tetrol adds dichloromethane, POCl3 is stirring evenly and then adding into, wherein, pentaerythrite is 1 with the mol ratio of POCl3：
2,3h is reacted after being warming up to 40 DEG C, after reaction terminates, Jing is filtered, washs, is dried to obtain material A；Montmorillonite is added in toluene,
Ultrasonic disperse uniformly adds the toluene solution of silane coupler KH-540 afterwards, wherein, montmorillonite is with silane coupler KH-540's
Weight ratio is 35：1, stirring reaction 3h after being warming up to 105 DEG C, reaction are cooled to 35 DEG C after terminating, and are subsequently adding material A, wherein,
Material A is 1 with the mol ratio of silane coupler KH-540：2, stirring reaction 5h, reaction terminate after Jing filter, it is washing, dry
To the modified montmorillonoid；
The fire retardant is formed by organic fire-retardant and inorganic combustion inhibitor compounding, and organic fire-retardant accounts for fire retardant gross weight
60%, inorganic combustion inhibitor accounts for the 40% of fire retardant gross weight；The organic fire-retardant is melamine phosphate, the resistance of phosphorus nitrogen silicon
Combustion agent is 4 by weight：3 mixture；The inorganic combustion inhibitor is aluminium hydroxide；
The following technique of the phosphorus nitrogen silicon fire retardant is prepared：Beta-schardinger dextrin is added in toluene, after ultrasonic disperse
The toluene solution of 3- aminopropyl triethoxysilanes is added, wherein, the weight of beta-schardinger dextrin and 3- aminopropyl triethoxysilanes
Than for 10：1,3h is reacted after being heated to backflow, be cooled to room temperature and obtain material A；By material A, parahydroxyben-zaldehyde and dichloromethane
Alkane is well mixed, the room temperature reaction 6h under the protection of nitrogen, is subsequently adding the miscellaneous -10- phospho hetero phenanthrenes -10- oxygen of 9,10- dihydro-9-oxies
Compound, wherein, material A, parahydroxyben-zaldehyde, the weight ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are
10：2：3, stirring reaction 10h, reaction remove solvent after terminating and obtain the phosphorus nitrogen silicon fire retardant；
The vulcanizing agent be 2,5- dimethyl -2, bis--(t-butyl peroxy) hexanes of 5-, t-butylcumylperoxide, mistake
Oxidation diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate, span carry out acyl
Imines is 3 by weight：10：3：15：3：10：2：5 mixture；
The ultra-violet absorber is ultraviolet absorbent uv-326；The antioxidant is antioxidant 1010, antioxidant 626
It is 4 by weight：1 mixture；
The lubricant is pentaerythrite stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate, oleic acid
Acid amides is 10 by weight：2：12：2：5：2 mixture.
Embodiment 5
A kind of flame-proofed thermoplastic vulcanized rubber material proposed by the present invention, its raw material include by weight：Ethylene-propylene-diene monomer
180 parts of glue, 180 parts of polypropylene, 35 parts of phenyl siloxane rubber, 30 parts of montmorillonite, 11 parts of kaolin, 8 parts of ceria, white carbon 28
Part, 12 parts of zirconium oxide, 12 parts of aramid fiber, 12 parts of four acicular type zinc oxide crystal whisker, titanate coupling agent modified calcium sulfate crystal whiskers 3.8
Part, 8.5 parts of phenolic resin, 10 parts of flyash, active 3 parts of Zinc Oxide, 7 parts of nano silicon, 50 parts of fire retardant, vulcanizing agent
2.6 parts, 1.2 parts of glutamic acid aminodithioformic acid lanthanum, 35 parts of paraffin oil, 4.3 parts of ultra-violet absorber, 4.2 parts of antioxidant, profit
2.6 parts of lubrication prescription；
Wherein, the montmorillonite is modified montmorillonoid；The modified montmorillonoid is prepared according to following technique：By season penta
During tetrol adds dichloromethane, POCl3 is stirring evenly and then adding into, wherein, pentaerythrite is 1 with the mol ratio of POCl3：
2.8,4h is reacted after being warming up to 38 DEG C, after reaction terminates, Jing is filtered, washs, is dried to obtain material A；Montmorillonite is added into toluene
In, ultrasonic disperse uniformly adds the toluene solution of silane coupler KH-540 afterwards, wherein, montmorillonite and silane coupler KH-540
Weight ratio be 27：1.6, stirring reaction 4h after being warming up to 100 DEG C, reaction are cooled to 32 DEG C after terminating, and are subsequently adding material A,
Wherein, material A and the mol ratio of silane coupler KH-540 are 1：2.6, stirring reaction 4h, reaction terminate after Jing filter, washing,
It is dried to obtain the modified montmorillonoid；
The fire retardant is formed by organic fire-retardant and inorganic combustion inhibitor compounding, and organic fire-retardant accounts for fire retardant gross weight
70%, inorganic combustion inhibitor accounts for the 30% of fire retardant gross weight；The organic fire-retardant is melamine phosphate, the resistance of phosphorus nitrogen silicon
Combustion agent is 4 by weight：6 mixture；The inorganic combustion inhibitor is aluminium hydroxide, magnesium hydroxide, microencapsulated powder oil, stannic acid
The mixture of zinc, Firebrake ZB by any weight ratio；
The following technique of the phosphorus nitrogen silicon fire retardant is prepared：Beta-schardinger dextrin is added in toluene, after ultrasonic disperse
The toluene solution of 3- aminopropyl triethoxysilanes is added, wherein, the weight of beta-schardinger dextrin and 3- aminopropyl triethoxysilanes
Than for 7：1,4h is reacted after being heated to backflow, be cooled to room temperature and obtain material A；By material A, parahydroxyben-zaldehyde and dichloromethane
It is well mixed, the room temperature reaction 5h under the protection of nitrogen, is subsequently adding the miscellaneous -10- phospho hetero phenanthrenes -10- oxidations of 9,10- dihydro-9-oxies
Thing, wherein, material A, parahydroxyben-zaldehyde, the weight ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are 13：
1.6：3.2, stirring reaction 8h, reaction remove solvent after terminating and obtain the phosphorus nitrogen silicon fire retardant；
The vulcanizing agent be 2,5- dimethyl -2, bis--(t-butyl peroxy) hexanes of 5-, t-butylcumylperoxide, mistake
Oxidation diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate, span carry out acyl
Imines is 11 by weight：7：10：10：12：8：6：3.8 mixture；
The lubricant is pentaerythrite stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate, oleic acid
Acid amides is 7 by weight：5：10：6：3：7 mixture.
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, should all be included within the scope of the present invention.
Claims (9)
1. a kind of flame-proofed thermoplastic vulcanized rubber material, it is characterised in that its raw material includes by weight：Ethylene propylene diene rubber
120-250 parts, polypropylene 120-250 parts, phenyl siloxane rubber 20-50 parts, montmorillonite 10-40 parts, kaolin 3-15 parts, titanium dioxide
Cerium 3-15 parts, white carbon 10-35 parts, zirconium oxide 2-15 parts, aramid fiber 3-15 parts, four acicular type zinc oxide crystal whisker 3-18 parts, titanium
The coupling agent modified calcium sulfate crystal whiskers 1-5 parts of acid esters, phenolic resin 2-10 parts, flyash 3-12 parts, active Zinc Oxide 1-5 parts, receive
Rice silica 2-10 parts, fire retardant 40-60 parts, vulcanizing agent 1-3 parts, glutamic acid aminodithioformic acid lanthanum 0.2-1.5 parts, stone
Wax oil 20-50 parts, ultra-violet absorber 1.5-5 parts, antioxidant 1.5-5 parts, lubricant 1-3 parts.
2. flame-proofed thermoplastic vulcanized rubber material according to claim 1, it is characterised in that in its raw material, ethylene-propylene-diene monomer
Glue, polypropylene, the weight ratio of phenyl siloxane rubber are 150-200：150-200：30-40.
3. flame-proofed thermoplastic vulcanized rubber material according to claim 1 or claim 2, it is characterised in that the montmorillonite is modified
Montmorillonite；The modified montmorillonoid is prepared according to following technique：Pentaerythrite is added in dichloromethane, after stirring
POCl3 is added, wherein, pentaerythrite is 1 with the mol ratio of POCl3：2-3, reacts 3-5h after being warming up to 35-40 DEG C,
After reaction terminates, Jing is filtered, washs, is dried to obtain material A；Montmorillonite is added in toluene, ultrasonic disperse uniformly adds silane afterwards
The toluene solution of coupling agent KH-540, wherein, montmorillonite is 20-35 with the weight ratio of silane coupler KH-540：1-2, heats up
Stirring reaction 3-5h to after 95-105 DEG C, reaction are cooled to 30-35 DEG C after terminating, and are subsequently adding material A, wherein, material A and silicon
The mol ratio of alkane coupling agent KH-540 is 1：2-3, stirring reaction 3-5h, reaction terminate after Jing filters, wash, be dried to obtain described in
Modified montmorillonoid.
4. the flame-proofed thermoplastic vulcanized rubber material according to any one of claim 1-3, it is characterised in that the fire retardant
Formed by organic fire-retardant and inorganic combustion inhibitor compounding, and organic fire-retardant accounts for the 60-80% of fire retardant gross weight, it is inorganic fire-retarded
Agent accounts for the 20-40% of fire retardant gross weight；The organic fire-retardant is melamine phosphate, the one kind in phosphorus nitrogen silicon fire retardant
Or two kinds of mixture；The inorganic combustion inhibitor is aluminium hydroxide, magnesium hydroxide, microencapsulated powder oil, zinc stannate, Firebrake ZB
In one or more of mixture.
5. flame-proofed thermoplastic vulcanized rubber material according to claim 4, it is characterised in that the phosphorus nitrogen silicon fire retardant
Following technique is prepared：Beta-schardinger dextrin is added the first for adding 3- aminopropyl triethoxysilanes in toluene after ultrasonic disperse
Benzole soln, reacts 3-5h after being heated to backflow, is cooled to room temperature and obtains material A；By material A, parahydroxyben-zaldehyde and dichloromethane
Alkane is well mixed, the room temperature reaction 3-6h under the protection of nitrogen, is subsequently adding the miscellaneous -10- phospho hetero phenanthrenes -10- of 9,10- dihydro-9-oxies
Oxide, stirring reaction 6-10h, reaction remove solvent after terminating and obtain the phosphorus nitrogen silicon fire retardant.
6. flame-proofed thermoplastic vulcanized rubber material according to claim 5, it is characterised in that in the preparation of phosphorus nitrogen silicon fire retardant
During, beta-schardinger dextrin is 5-10 with the weight ratio of 3- aminopropyl triethoxysilanes：1；Material A, parahydroxyben-zaldehyde, 9,
The weight ratio of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 10- dihydro-9-oxies is 10-20：1-2：3-4.
7. the flame-proofed thermoplastic vulcanized rubber material according to any one of claim 1-6, it is characterised in that the vulcanizing agent
For 2,5- dimethyl -2, bis--(t-butyl peroxy) hexanes of 5-, t-butylcumylperoxide, cumyl peroxide, peroxidating
T-butyl perbenzoate, benzoyl peroxide, sulphur, Triallyl isocyanurate, BMI are 3-15 by weight：
2-10：3-15：2-15：3-15：3-10：2-8：The mixture of 1-5.
8. the flame-proofed thermoplastic vulcanized rubber material according to any one of claim 1-7, it is characterised in that the ultraviolet
Absorbent is ultraviolet absorbent uv-326, the mixture of one or two kinds of in ultraviolet absorbent UV-531；It is described anti-
Oxygen agent is antioxidant 1076, antioxidant 1010, antioxidant 626,2-mercaptobenzimidazole, irgasfos 168, antioxidant DLTDP, anti-
One or more mixture in oxygen agent DTDTP.
9. the flame-proofed thermoplastic vulcanized rubber material according to any one of claim 1-8, it is characterised in that the lubricant
It is 2- by weight for pentaerythrite stearate, oxidic polyethylene, chlorinated paraffin, stearic acid, barium stearate, oleamide
10：2-8：4-12：2-10：1-5：The mixture of 2-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610985568.2A CN106519460A (en) | 2016-11-09 | 2016-11-09 | Flame-retardant thermoplastic vulcanized rubber material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610985568.2A CN106519460A (en) | 2016-11-09 | 2016-11-09 | Flame-retardant thermoplastic vulcanized rubber material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106519460A true CN106519460A (en) | 2017-03-22 |
Family
ID=58350339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610985568.2A Pending CN106519460A (en) | 2016-11-09 | 2016-11-09 | Flame-retardant thermoplastic vulcanized rubber material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519460A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751007A (en) * | 2016-11-09 | 2017-05-31 | 安徽中翰高分子科技有限公司 | A kind of high-strength low-density thermoplastic vulcanizate material and preparation method thereof |
| CN106977825A (en) * | 2017-04-28 | 2017-07-25 | 国网河南唐河县供电公司 | A kind of cold resistant cable material and preparation method thereof |
| CN107564606A (en) * | 2017-08-23 | 2018-01-09 | 江苏浦漕科技股份有限公司 | A kind of copper core aluminium sheath inorganic insulation flexible fire-retardant cable |
| CN107857938A (en) * | 2017-11-29 | 2018-03-30 | 宁波海雨新材料科技有限公司 | A kind of halogen-free anti-flaming polypropylene material and its preparation method and application |
| CN108314899A (en) * | 2018-02-07 | 2018-07-24 | 缪琼 | A kind of nano-meter flame retardants preparation method |
| CN109535560A (en) * | 2018-11-29 | 2019-03-29 | 袁进 | A kind of TPV material and preparation method thereof haveing excellent performance |
| CN111944244A (en) * | 2020-08-20 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-temperature-resistant low-smoke halogen-free flame-retardant insulating material and preparation method thereof |
| CN111941941A (en) * | 2020-06-29 | 2020-11-17 | 安徽浩天新型材料有限公司 | High-flame-retardant silicone rubber glass fiber braided tube |
| CN112216433A (en) * | 2020-09-27 | 2021-01-12 | 安徽龙庵电缆集团有限公司 | High-flame-retardance medium-voltage fire-resistant cable and preparation method thereof |
| CN112441593A (en) * | 2020-12-15 | 2021-03-05 | 山东海螺型材有限责任公司 | Preparation method of surface hydrophobic modified anhydrous nano zinc borate |
| CN113387365A (en) * | 2021-07-19 | 2021-09-14 | 安徽瑞联节能科技股份有限公司 | Method for organically modifying nano silicon dioxide aerogel |
| CN113717443A (en) * | 2021-09-28 | 2021-11-30 | 四川轻化工大学 | Modified beta-cyclodextrin-DOPO composite material and preparation method thereof |
| CN115594978A (en) * | 2022-10-29 | 2023-01-13 | 江苏加富新材料科技有限公司（Cn） | High-voltage-resistant insulating rubber plate and preparation method thereof |
| CN115651522A (en) * | 2022-12-28 | 2023-01-31 | 广州豫顺新材料有限公司 | Polyurethane coating containing nano silicon dioxide based flame retardant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376665A (en) * | 2008-09-29 | 2009-03-04 | 四川东材科技集团股份有限公司 | Phosphaphenanthrene flame-retardant compound containing s-triazine structure, and preparation and use thereof |
| CN101987902A (en) * | 2009-07-31 | 2011-03-23 | 索肯（上海）科技有限公司 | Halogen-free thermoplastic elastomer and manufacturing method thereof and environment-friendly electric wires and cables using halogen-free thermoplastic elastomer |
| CN102070667A (en) * | 2010-12-30 | 2011-05-25 | 上海交通大学 | Organosilicon compound containing phosphorus and nitrogen and preparation method thereof |
-
2016
- 2016-11-09 CN CN201610985568.2A patent/CN106519460A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376665A (en) * | 2008-09-29 | 2009-03-04 | 四川东材科技集团股份有限公司 | Phosphaphenanthrene flame-retardant compound containing s-triazine structure, and preparation and use thereof |
| CN101987902A (en) * | 2009-07-31 | 2011-03-23 | 索肯（上海）科技有限公司 | Halogen-free thermoplastic elastomer and manufacturing method thereof and environment-friendly electric wires and cables using halogen-free thermoplastic elastomer |
| CN102070667A (en) * | 2010-12-30 | 2011-05-25 | 上海交通大学 | Organosilicon compound containing phosphorus and nitrogen and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 欧育湘主编: "《阻燃剂》", 30 September 2009, 国防工业出版社 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751007A (en) * | 2016-11-09 | 2017-05-31 | 安徽中翰高分子科技有限公司 | A kind of high-strength low-density thermoplastic vulcanizate material and preparation method thereof |
| CN106751007B (en) * | 2016-11-09 | 2019-07-02 | 安徽中翰高分子科技有限公司 | A kind of high-strength low-density thermoplastic vulcanizate material and preparation method thereof |
| CN106977825A (en) * | 2017-04-28 | 2017-07-25 | 国网河南唐河县供电公司 | A kind of cold resistant cable material and preparation method thereof |
| CN107564606A (en) * | 2017-08-23 | 2018-01-09 | 江苏浦漕科技股份有限公司 | A kind of copper core aluminium sheath inorganic insulation flexible fire-retardant cable |
| CN107857938A (en) * | 2017-11-29 | 2018-03-30 | 宁波海雨新材料科技有限公司 | A kind of halogen-free anti-flaming polypropylene material and its preparation method and application |
| CN108314899A (en) * | 2018-02-07 | 2018-07-24 | 缪琼 | A kind of nano-meter flame retardants preparation method |
| CN109535560A (en) * | 2018-11-29 | 2019-03-29 | 袁进 | A kind of TPV material and preparation method thereof haveing excellent performance |
| CN111941941A (en) * | 2020-06-29 | 2020-11-17 | 安徽浩天新型材料有限公司 | High-flame-retardant silicone rubber glass fiber braided tube |
| CN111944244A (en) * | 2020-08-20 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-temperature-resistant low-smoke halogen-free flame-retardant insulating material and preparation method thereof |
| CN112216433A (en) * | 2020-09-27 | 2021-01-12 | 安徽龙庵电缆集团有限公司 | High-flame-retardance medium-voltage fire-resistant cable and preparation method thereof |
| CN112216433B (en) * | 2020-09-27 | 2022-06-14 | 安徽龙庵电缆集团有限公司 | High-flame-retardance medium-voltage fire-resistant cable and preparation method thereof |
| CN112441593A (en) * | 2020-12-15 | 2021-03-05 | 山东海螺型材有限责任公司 | Preparation method of surface hydrophobic modified anhydrous nano zinc borate |
| CN112441593B (en) * | 2020-12-15 | 2022-07-12 | 山东海螺型材有限责任公司 | Preparation method of surface hydrophobic modified anhydrous nano zinc borate |
| CN113387365A (en) * | 2021-07-19 | 2021-09-14 | 安徽瑞联节能科技股份有限公司 | Method for organically modifying nano silicon dioxide aerogel |
| CN113717443A (en) * | 2021-09-28 | 2021-11-30 | 四川轻化工大学 | Modified beta-cyclodextrin-DOPO composite material and preparation method thereof |
| CN115594978A (en) * | 2022-10-29 | 2023-01-13 | 江苏加富新材料科技有限公司（Cn） | High-voltage-resistant insulating rubber plate and preparation method thereof |
| CN115594978B (en) * | 2022-10-29 | 2024-03-05 | 江苏加富新材料科技有限公司 | High-voltage-resistant insulating rubber plate and preparation method thereof |
| CN115651522A (en) * | 2022-12-28 | 2023-01-31 | 广州豫顺新材料有限公司 | Polyurethane coating containing nano silicon dioxide based flame retardant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106519460A (en) | Flame-retardant thermoplastic vulcanized rubber material | |
| CN101704976B (en) | Low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof | |
| JP5753497B2 (en) | CROSSLINKABLE RUBBER COMPOSITION, USE THEREOF, PRODUCTED RUBBER GRANES, AND METHOD OF PREPARING AND INJECTION MOLDING THE RUBBER GRANES | |
| CN105111694B (en) | Cross-linkable composition, by its obtainable thermoplastic elastomer (TPE) and their purposes | |
| US5171787A (en) | Silicone-based composite rubber composition and uses thereof | |
| CN101208187B (en) | Process for preparing thermoplastic elastomers by dynamic vulcanization | |
| CN101925639B (en) | Surface-treated fiber, resin composition, and molded article of composition | |
| CN106398003A (en) | Flame-retardant electro-conductive thermoplastic vulcanized rubber material | |
| CN105820438B (en) | A kind of motor turning dust cover thermoplastic vulcanizate material and preparation method thereof | |
| JPS61276846A (en) | Glass fiber reinforced polypropylene resin composition | |
| US20180163901A1 (en) | Hoses, compositions, and methods of making the same | |
| CN105482266A (en) | Thermoplastic vulcanized rubber material for automobile steering device dust-proof cover and preparation method of thermoplastic vulcanized rubber material | |
| DE112008003343B4 (en) | Rubber composition for a breaker topcoat | |
| CN104918997A (en) | Polybutylene terephthalate resin composition, and molded article | |
| CN1082073A (en) | Glass fibre enhanced propylene polymer graft composition | |
| CN106750860A (en) | A kind of high temperature resistant halogen-free flame-retardant thermoplastic elastomer (TPE) and preparation method thereof | |
| JPH0277459A (en) | Fiber-reinforced polypropylene composition having high melt flow | |
| CN107603112A (en) | A kind of high-performance high ferro outer hood elastomeric material and its compression molding preparation method | |
| CN105694224A (en) | Heat-resistant thermoplastic elastomer and preparation method thereof | |
| CN106574080A (en) | Crosslinkable nitrile rubber composition and crosslinked rubber product | |
| CN101889052B (en) | Polyvinyl alcohol fiber-containing polyolefin resin composition and molded article thereof | |
| CN106700976A (en) | Thermoplastic vulcanized rubber material serving as bonding base material | |
| TWI810466B (en) | Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article | |
| CN115260658A (en) | Polypropylene composite material applied to household electrical appliance products and preparation method thereof | |
| KR100366229B1 (en) | Silica Compound with Silica dispersion agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |