CN107200917A - A kind of new energy high-voltage line high resistant retardant composite material and preparation method thereof - Google Patents
A kind of new energy high-voltage line high resistant retardant composite material and preparation method thereof Download PDFInfo
- Publication number
- CN107200917A CN107200917A CN201710521430.1A CN201710521430A CN107200917A CN 107200917 A CN107200917 A CN 107200917A CN 201710521430 A CN201710521430 A CN 201710521430A CN 107200917 A CN107200917 A CN 107200917A
- Authority
- CN
- China
- Prior art keywords
- parts
- composite material
- antioxidant
- new energy
- flame retardant
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 26
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 20
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 13
- 230000002902 bimodal effect Effects 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims description 53
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 43
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000155 melt Substances 0.000 claims description 17
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 15
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 11
- 229920013716 polyethylene resin Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 239000003921 oil Substances 0.000 abstract description 5
- 239000012757 flame retardant agent Substances 0.000 abstract 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- H01B3/44—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 vinyl resins; acrylic resins
- H01B3/441—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 vinyl resins; acrylic resins from alkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of new energy high-voltage line high resistant retardant composite material, by weight, the composition of raw materials of the high resistant retardant composite material includes:5 ~ 25 parts of polyvinyl resin;25 ~ 50 parts of polyolefin elastomer;30 ~ 50 parts of ethylene-vinyl acetate copolymer;8 ~ 20 parts of haloflex;30 ~ 60 parts of composite flame-retardant agent;0.2 ~ 15 part of abrasion resistant fire blocking synergist;0.7 ~ 2.5 part of antioxidant;1 ~ 2 part of lubricant;1.5 ~ 3 parts of crosslinking sensitizer.The present invention is formulated by improving, modifying agent is such as used as polyvinyl resin, haloflex using the mixture of bimodal polyethylene and high fusion index high density polyethylene (HDPE), add polyolefin elastomer and ethylene-vinyl acetate copolymer, the materials such as addition composite flame-retardant agent, fire retarding synergist, antioxidant are aided in simultaneously, so that composite of the present invention has more excellent fire resistance, it can be burnt by UL94 V0 grades, while the features such as remaining the flexibility of automotive high voltage line material, heat-resisting quantity, oil resistivity, anti-flammability, and expressing technique excellent performance.
Description
Technical Field
The invention relates to a high-flame-retardant composite material for a new energy high-voltage wire and a preparation method thereof.
Background
With the rapid development of new energy automobile production and marketing in China, the requirements of polymer composite material series products related to automobile wire harnesses are more and more urgent, different use standards such as ISO6722, GB/T1037 and the like are selected for materials for high-voltage wires according to different customer requirements, and technical characteristics such as flame retardance, tearing resistance, oil resistance, high temperature resistance, high-speed extrusion and the like become the focus and trend of the product development. At present, the materials of the high-voltage cable in the car mainly comprise radiation cross-linked polyolefin (XLPO) and thermoplastic elastomer (TPE), and compared with the thermoplastic elastomer, the radiation cross-linked polyolefin material has better anti-cracking performance and is also accepted by market customers. But because of the excellent flexibility, the flame retardant property is poor, and the flame retardant can only be burnt singly.
In the prior art, a cable material which is prepared by filling a large amount of magnesium hydroxide or aluminum hydroxide in a formula as a flame retardant has better flame retardance. The Chinese patent with publication number CN104262883A discloses a low-smoke halogen-free flame-retardant silane crosslinked cable material capable of being crosslinked at room temperature, and the cable material comprises 30-50 parts of polyolefin elastomer, 10-30 parts of linear low-density polyethylene resin, 15-30 parts of ethylene-vinyl acetate copolymer resin, 5-15 parts of functionalized polyolefin resin, 120-160 parts of flame retardant, 1.2-3 parts of unsaturated silane, 0.06-0.3 part of grafting initiator, 0.5-2 parts of antioxidant and 1.5-6 parts of processing aid, wherein a large amount of flame retardant is added into the cable material, so that the product has better flame retardance, but the addition of a large amount of flame retardant can influence other performances, and the oil resistance, flexibility and the like of the cable material can meet the use performance of a high-voltage cable and cannot be guaranteed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-flame-retardant composite material for a new energy high-voltage wire and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the high-flame-retardant composite material for the new energy high-voltage wire comprises the following raw materials in parts by weight:
wherein,
the polyethylene resin is a mixture of bimodal high-density polyethylene with a melt index of less than or equal to 1g/10min and high-density polyethylene with a melt index of more than or equal to 10g/10 min;
the polyolefin elastomer is an ethylene-octylene copolymer;
the composite flame retardant necessarily contains decabromodiphenylethane and antimony trioxide.
Preferably, the mass ratio of the bimodal high-density polyethylene with the melt index of less than or equal to 1g/10min to the high-density polyethylene with the melt index of more than or equal to 10g/10min is 1: 1 to 3. The bimodal polyethylene and the high-density polyethylene with high melt index can ensure that the material has good oil resistance and extrusion processability.
More preferably, the mass ratio of the bimodal high density polyethylene with the melt index of 1g/10min or less to the high density polyethylene with the melt index of 10g/10min or more is 1: 2.
further, the polyolefin elastomer has a hardness of 50 to 90A. Preferably, the polyolefin elastomer is compounded by 50-65A and 80-90A of ethylene-octylene copolymer, so that the material is endowed with good physical properties and excellent flexibility.
Further, the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with 15-28% of VA content and an ethylene-vinyl acetate copolymer with 35-50% of VA content according to a mass ratio of 1: 1.5-2.5.
Furthermore, the chlorinated polyethylene has a chlorine content of less than or equal to 35%, and can endow the material with good compatibility, processability and flame retardance.
Further, the composite flame retardant is a mixture of decabromodiphenylethane and antimony trioxide or a mixture of decabromodiphenylethane, antimony trioxide and magnesium hydroxide, and the mass ratio of decabromodiphenylethane to antimony trioxide is 2-4: 1. preferably, the mass ratio of the decabromodiphenylethane to the antimony trioxide is 3: 1.
further, the wear-resistant flame-retardant synergist is prepared from polytetrafluoroethylene, silicon dioxide and talcum powder according to a mass ratio of 0.1-0.5: 2-4: 5-10. The polytetrafluoroethylene is polytetrafluoroethylene powder. Preferably, the mass ratio of the polytetrafluoroethylene to the silicon dioxide to the talcum powder is 0.3: 3: 6.
further, the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant DLTP, an antioxidant 1035 and an antioxidant 1024, and the antioxidant 1035 and the antioxidant 1024 are required to be contained in the antioxidant.
Further, the lubricant is a mixture of silicone master batch, stearate and polyethylene wax.
Further, the crosslinking sensitizer is TAIC, for example TAIC powder is selected, and the effective content is more than or equal to 70%.
According to the formula, the POE and the EVA are selected as raw materials and are blended, and the POE with different hardness and the EVA with different VA content are mixed and overlapped to form a bridge, so that the physical and mechanical properties and the flexibility of the material are met.
In the invention, all the raw materials can be prepared by commercial and/or known means, and meet the requirements of standard chemical products when not particularly stated.
The invention adopts another technical scheme that: a preparation method of the high-flame-retardant composite material for the new energy high-voltage line comprises the following steps: adding polyethylene resin, polyolefin elastomer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, composite flame retardant, wear-resistant flame-retardant synergist, antioxidant, lubricant and crosslinking sensitizer into a kneading machine according to a formula, uniformly stirring, and then mixing and extruding the mixture by a double screw or an internal mixer for granulation to prepare the high-flame-retardant composite material, wherein the double screw extrusion process comprises the following steps: the temperature of the feeding section, the melting section and the die head is 120-130 ℃, 150-165 ℃, 165-175 ℃ and the banburying temperature is 150-160 ℃ in sequence.
The invention adopts another technical scheme that: the high-flame-retardant composite material is applied to a new energy high-voltage wire.
By implementing the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, by improving the formula, for example, a mixture of bimodal polyethylene and high-melt-index high-density polyethylene is used as polyethylene resin, chlorinated polyethylene is used as a modifier, a polyolefin elastomer and an ethylene-vinyl acetate copolymer are added, and meanwhile, substances such as a composite flame retardant, a flame-retardant synergist, an antioxidant and the like are added in an auxiliary manner, so that the composite material disclosed by the invention has more excellent flame retardant property, can be combusted through UL94V0 grade, and simultaneously retains the characteristics of softness, high temperature resistance, oil resistance, flame retardance and the like of an automobile high-pressure wire material, and has excellent extrusion process property.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The raw materials used in the following examples are all commercially available standard industrial products.
Example 1
The embodiment provides a high flame retardant composite material for new energy high voltage wire, and the adopted raw materials and the dosage are shown in table 1, wherein:
polyethylene resin: the polyethylene is prepared from bimodal high-density polyethylene (from northern Europe chemical industry and having a brand of FB2230) with a melt index of 0.3g/10min and high-density polyethylene (from petrochemical company and having a brand of 2909) with a melt index of 12g/10min according to the mass ratio of 1: 3, and (3).
Polyolefin elastomer: the ethylene-propylene copolymer with the hardness of 65A and the ethylene-propylene copolymer with the hardness of 87A are mixed according to the mass ratio of 1: 1.
Ethylene-vinyl acetate copolymer: the EVA material is prepared from EVA with the VA content of 18 percent and EVA with the VA content of 40 percent according to the mass ratio of 1: 2.
Chlorinated polyethylene: chlorinated polyethylene with 30% chlorine content was used.
Composite flame retardant: decabromodiphenylethane and antimony trioxide are mixed according to the mass ratio of 3: 1.
Wear-resistant flame-retardant synergist: the composite material is prepared from polytetrafluoroethylene powder, silicon dioxide and talcum powder according to the mass ratio of 0.1: 4: 9.
Antioxidant: the antioxidant 1035 and the antioxidant 1024 are mixed according to a mass ratio of 4: 1.
Lubricant: prepared from siloxane master batch (from Jiahua company, the mark is 300), magnesium stearate and polyethylene wax according to the mass ratio of 2: 1: 0.5.
Crosslinking sensitizer: TAIC powder is selected, and the effective content is 70%.
The preparation method of the high flame-retardant composite material comprises the following steps: adding polyethylene resin, a polyolefin elastomer, an ethylene-vinyl acetate copolymer, chlorinated polyethylene, a composite flame retardant, a wear-resistant flame-retardant synergist, an antioxidant, a lubricant and a crosslinking sensitizer into a kneading machine according to a formula, uniformly stirring, and then extruding and granulating the mixture by a double screw to obtain the high-flame-retardant composite material, wherein the extrusion process comprises the following steps of: the temperature of the feeding section, the melting section and the die head is 120-130 ℃, 150-165 ℃ and 165-175 ℃ in sequence.
Example 2
In this example, the raw materials and the amounts used are shown in table 1, and the raw materials other than the following are the same as those in example 1.
Polyethylene resin: prepared by mixing bimodal high-density polyethylene with a melt index of 0.3g/10min and high-density polyethylene with a melt index of 20g/10min according to a mass ratio of 1: 2.
Polyolefin elastomer: the ethylene-propylene copolymer with the hardness of 60A and the ethylene-propylene copolymer with the hardness of 82A are mixed according to the mass ratio of 5: 3, and (3).
Ethylene-vinyl acetate copolymer: the EVA material is prepared from EVA with 28% of VA content and EVA with 40% of VA content according to the mass ratio of 1: 2.5.
Chlorinated polyethylene: chlorinated polyethylene with 25% chlorine content was used.
Composite flame retardant: decabromodiphenylethane, antimony trioxide and magnesium hydroxide in a mass ratio of 3: 1: 1.
Antioxidant: the antioxidant 1035, the antioxidant 1024 and the antioxidant 168 are mixed according to the mass ratio of 2: 1: 1.
The preparation process of the high flame-retardant composite material is the same as that of example 1.
Example 3
In this example, the raw materials and the amounts used are shown in table 1, and the raw materials other than the following are the same as those in example 2.
Ethylene-vinyl acetate copolymer: the EVA material is prepared from EVA with 28% of VA content and EVA with 50% of VA content according to the mass ratio of 1: 2.
Chlorinated polyethylene: chlorinated polyethylene with a chlorine content of 35% was used.
Wear-resistant flame-retardant synergist: the composite material is prepared from polytetrafluoroethylene powder, silicon dioxide and talcum powder according to the mass ratio of 0.2: 2.5: 6.
Antioxidant: the antioxidant 1035, the antioxidant 1024, the antioxidant 1010 and the antioxidant DLTP are mixed according to the mass ratio of 2: 1: 1: 0.5.
The preparation process of the high flame-retardant composite material is the same as that of example 2.
Example 4
In this example, the raw materials and the amounts used are shown in table 1, and the raw materials other than the following are the same as those in example 2.
Polyethylene resin: prepared by mixing bimodal high-density polyethylene with a melt index of 0.8g/10min and high-density polyethylene with a melt index of 15g/10min according to a mass ratio of 1: 3, and (3).
The preparation process of the high flame-retardant composite material is the same as that of example 2.
Comparative example 1
This comparative example provides a composite material using the same raw materials and amounts as in example 2, as shown in Table 1.
The flame retardant is magnesium hydroxide.
The comparative composite was prepared as in example 2.
Comparative example 2
This comparative example provides a composite material using the same raw materials and amounts as in example 2, as shown in Table 1.
Polyethylene resin: linear low density polyethylene having a melt index of 2g/10min was used.
Chlorinated polyethylene was not added.
The comparative composite was prepared as in example 1.
TABLE 1 raw Material compositions (parts) of examples 1 to 4 and comparative examples 1 to 2
The composite materials of examples 1-4 and comparative examples 1-2 were prepared according to the standard, and the respective properties were tested, and the results are shown in table 2. For comparison, the index values specified by the materials business standards are also listed in table 2.
TABLE 2 Properties of the composites of examples 1-4 and comparative examples 1-2
The present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.
Claims (10)
1. The high-flame-retardant composite material for the new energy high-voltage wire is characterized by comprising the following raw materials in parts by weight:
5-25 parts of polyethylene resin;
25-50 parts of polyolefin elastomer;
30-50 parts of ethylene-vinyl acetate copolymer;
8-20 parts of chlorinated polyethylene;
30-60 parts of a composite flame retardant;
0.2-15 parts of a wear-resistant flame-retardant synergist;
0.7-2.5 parts of an antioxidant;
1-2 parts of a lubricant;
1.5-3 parts of a crosslinking sensitizer;
wherein,
the polyethylene resin is a mixture of bimodal high-density polyethylene with a melt index of less than or equal to 1g/10min and high-density polyethylene with a melt index of more than or equal to 10g/10 min;
the polyolefin elastomer is an ethylene-octylene copolymer;
the composite flame retardant necessarily contains decabromodiphenylethane and antimony trioxide.
2. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the mass ratio of the bimodal high-density polyethylene with the melt index of less than or equal to 1g/10min to the high-density polyethylene with the melt index of more than or equal to 10g/10min is 1: 1 to 3.
3. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the hardness of the polyolefin elastomer is 50-90A.
4. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the ethylene-vinyl acetate copolymer comprises 15-28% of VA and 35-50% of VA according to a mass ratio of 1: 1.5-2.5.
5. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the chlorinated polyethylene is chlorinated polyethylene with chlorine content less than or equal to 35%.
6. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the composite flame retardant is a mixture of decabromodiphenylethane and antimony trioxide or a mixture of decabromodiphenylethane, antimony trioxide and magnesium hydroxide, and the mass ratio of decabromodiphenylethane to antimony trioxide is 2-4: 1.
7. the high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the wear-resistant flame-retardant synergist is prepared from polytetrafluoroethylene, silicon dioxide and talcum powder according to a mass ratio of 0.1-0.5: 2-4: 5-10.
8. The high flame retardant composite material for the new energy high voltage wire according to claim 1, wherein: the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant DLTP, an antioxidant 1035 and an antioxidant 1024, and the antioxidant 1035 and the antioxidant 1024 are required to be contained.
9. The preparation method of the high flame retardant composite material for the new energy high voltage wire as claimed in any one of claims 1 to 8, wherein the preparation method comprises the following steps: adding polyethylene resin, polyolefin elastomer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, composite flame retardant, wear-resistant flame-retardant synergist, antioxidant, lubricant and crosslinking sensitizer into a kneader according to a formula proportion, uniformly stirring, and then mixing and extruding the mixture by a double screw or an internal mixer for granulation to prepare the high-flame-retardant composite material, wherein the double screw extrusion process comprises the following steps: the temperature of the feeding section, the melting section and the die head is 120-130 ℃, 150-165 ℃, 165-175 ℃ and the banburying temperature is 150-160 ℃ in sequence.
10. The use of the high flame retardant composite material according to any one of claims 1 to 8 in high voltage lines for new energy.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710521430.1A CN107200917B (en) | 2017-06-30 | 2017-06-30 | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof |
PCT/CN2018/078163 WO2019001003A1 (en) | 2017-06-30 | 2018-03-06 | High flame retardancy composite material for high voltage cable of new energy automobile, and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710521430.1A CN107200917B (en) | 2017-06-30 | 2017-06-30 | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107200917A true CN107200917A (en) | 2017-09-26 |
CN107200917B CN107200917B (en) | 2020-03-24 |
Family
ID=59910466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710521430.1A Active CN107200917B (en) | 2017-06-30 | 2017-06-30 | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN107200917B (en) |
WO (1) | WO2019001003A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108559167A (en) * | 2018-04-16 | 2018-09-21 | 南京工业大学 | Modified polyolefin elastomer functional film material with solar spectrum reflection function and preparation method thereof |
WO2019001003A1 (en) * | 2017-06-30 | 2019-01-03 | 江苏德威新材料股份有限公司 | High flame retardancy composite material for high voltage cable of new energy automobile, and preparation method thereof |
CN109233055A (en) * | 2018-08-24 | 2019-01-18 | 江苏德威新材料股份有限公司 | Automotive line low smell insulating materials and its preparation method and application suitable for cross-linking radiation |
CN109265790A (en) * | 2018-07-31 | 2019-01-25 | 江苏德威新材料股份有限公司 | A kind of vehicle-mounted Ethernet high-frequency signal cable insulating materials and its preparation method and application |
CN110105654A (en) * | 2019-04-10 | 2019-08-09 | 广东聚石化学股份有限公司 | A kind of halogen-free flameproof soft material for automobile interiors and preparation method thereof |
CN110564006A (en) * | 2019-09-11 | 2019-12-13 | 广西大学 | Flame retardant for low-density polyethylene, preparation method and application thereof |
CN110862601A (en) * | 2019-11-28 | 2020-03-06 | 江苏上上电缆集团新材料有限公司 | High-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cable and preparation method thereof |
CN112373157A (en) * | 2020-10-21 | 2021-02-19 | 永生运佳(宣城)薄膜科技有限公司 | Ultrathin EVA vacuum casting film |
CN112961420A (en) * | 2021-02-08 | 2021-06-15 | 南通第六元素材料科技有限公司 | Graphene modified high-density polyethylene composite material for carrier roller and preparation method thereof |
CN113402802A (en) * | 2021-07-09 | 2021-09-17 | 晶锋集团股份有限公司 | Cross-linked irradiation polyolefin cable material and preparation method thereof |
CN113527800A (en) * | 2021-07-05 | 2021-10-22 | 中国科学院深圳先进技术研究院 | Flame-retardant polyolefin composite material and preparation method and application thereof |
CN117126613A (en) * | 2023-10-25 | 2023-11-28 | 河北金坤工程材料有限公司 | High-strength and good-flexibility self-adhesive film plastic water stop |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103059403A (en) * | 2013-01-25 | 2013-04-24 | 天津市普立泰高分子科技有限公司 | Thermoplastic low-fume halogen-free high-flame retardance polyolefin insulation material and preparation method thereof |
CN105153528A (en) * | 2015-08-17 | 2015-12-16 | 河北新湖中利高分子材料科技有限公司 | Irradiation-crosslinked and environmental-friendly polyolefin cable material with flexibility and wear resistance and preparation method of polyolefin cable material |
CN105754179A (en) * | 2016-03-07 | 2016-07-13 | 苏州莱特复合材料有限公司 | Flame retardant HDPE cable material and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60252646A (en) * | 1984-05-30 | 1985-12-13 | Showa Electric Wire & Cable Co Ltd | Flame-retardant composition |
CN105153520A (en) * | 2015-09-25 | 2015-12-16 | 国网山东省电力公司临沂供电公司 | Cable sheath material for wind power generation |
CN107200917B (en) * | 2017-06-30 | 2020-03-24 | 江苏德威新材料股份有限公司 | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof |
-
2017
- 2017-06-30 CN CN201710521430.1A patent/CN107200917B/en active Active
-
2018
- 2018-03-06 WO PCT/CN2018/078163 patent/WO2019001003A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103059403A (en) * | 2013-01-25 | 2013-04-24 | 天津市普立泰高分子科技有限公司 | Thermoplastic low-fume halogen-free high-flame retardance polyolefin insulation material and preparation method thereof |
CN105153528A (en) * | 2015-08-17 | 2015-12-16 | 河北新湖中利高分子材料科技有限公司 | Irradiation-crosslinked and environmental-friendly polyolefin cable material with flexibility and wear resistance and preparation method of polyolefin cable material |
CN105754179A (en) * | 2016-03-07 | 2016-07-13 | 苏州莱特复合材料有限公司 | Flame retardant HDPE cable material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
吴培熙: "《聚合物共混改性原理及工艺》", 31 January 1984, 轻工业出版社 * |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019001003A1 (en) * | 2017-06-30 | 2019-01-03 | 江苏德威新材料股份有限公司 | High flame retardancy composite material for high voltage cable of new energy automobile, and preparation method thereof |
CN108559167B (en) * | 2018-04-16 | 2020-08-25 | 南京工业大学 | Modified polyolefin elastomer functional film material with solar spectrum reflection function and preparation method thereof |
CN108559167A (en) * | 2018-04-16 | 2018-09-21 | 南京工业大学 | Modified polyolefin elastomer functional film material with solar spectrum reflection function and preparation method thereof |
CN109265790A (en) * | 2018-07-31 | 2019-01-25 | 江苏德威新材料股份有限公司 | A kind of vehicle-mounted Ethernet high-frequency signal cable insulating materials and its preparation method and application |
CN109233055A (en) * | 2018-08-24 | 2019-01-18 | 江苏德威新材料股份有限公司 | Automotive line low smell insulating materials and its preparation method and application suitable for cross-linking radiation |
CN109233055B (en) * | 2018-08-24 | 2024-08-16 | 江苏德威新材料股份有限公司 | Low-odor insulating material suitable for irradiation crosslinking for automobile wire, and preparation method and application thereof |
CN110105654B (en) * | 2019-04-10 | 2021-07-30 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant soft material for automotive interior and preparation method thereof |
CN110105654A (en) * | 2019-04-10 | 2019-08-09 | 广东聚石化学股份有限公司 | A kind of halogen-free flameproof soft material for automobile interiors and preparation method thereof |
CN110564006A (en) * | 2019-09-11 | 2019-12-13 | 广西大学 | Flame retardant for low-density polyethylene, preparation method and application thereof |
CN110862601A (en) * | 2019-11-28 | 2020-03-06 | 江苏上上电缆集团新材料有限公司 | High-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cable and preparation method thereof |
CN112373157A (en) * | 2020-10-21 | 2021-02-19 | 永生运佳(宣城)薄膜科技有限公司 | Ultrathin EVA vacuum casting film |
CN112961420B (en) * | 2021-02-08 | 2022-12-16 | 南通第六元素材料科技有限公司 | Graphene modified high-density polyethylene composite material for carrier roller and preparation method thereof |
CN112961420A (en) * | 2021-02-08 | 2021-06-15 | 南通第六元素材料科技有限公司 | Graphene modified high-density polyethylene composite material for carrier roller and preparation method thereof |
CN113527800A (en) * | 2021-07-05 | 2021-10-22 | 中国科学院深圳先进技术研究院 | Flame-retardant polyolefin composite material and preparation method and application thereof |
CN113402802A (en) * | 2021-07-09 | 2021-09-17 | 晶锋集团股份有限公司 | Cross-linked irradiation polyolefin cable material and preparation method thereof |
CN117126613A (en) * | 2023-10-25 | 2023-11-28 | 河北金坤工程材料有限公司 | High-strength and good-flexibility self-adhesive film plastic water stop |
CN117126613B (en) * | 2023-10-25 | 2024-01-02 | 河北金坤工程材料有限公司 | High-strength and good-flexibility self-adhesive film plastic water stop |
Also Published As
Publication number | Publication date |
---|---|
CN107200917B (en) | 2020-03-24 |
WO2019001003A1 (en) | 2019-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107200917B (en) | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof | |
CN108017826B (en) | Flame-retardant polyethylene sheath material and preparation method thereof | |
CN103524869B (en) | The heat-resisting thermoplastic halogen-free and low-smoke flame-retardant polyolefin plastics of electric wire | |
CN103804798A (en) | Halogen-free flame retardant polyethylene sheath material applied to super high voltage cable and preparation method and application thereof | |
WO2015043122A1 (en) | Zero halogen sheath material for 125°c irradiation cross-linked epcv photovoltaics, and method for preparation thereof | |
CN103435955A (en) | Halogen-free flame retardant thermoplastic elastomer composite material and preparation method thereof | |
CN110903535A (en) | Low-smoke halogen-free flame-retardant sheath material with good cold resistance for cable and preparation method thereof | |
CN105038087A (en) | Halogen-free flame retardant high-tear-resistance wire and cable compound for electric vehicles and wire and cable production method | |
CN105504480A (en) | Oil-resistant irradiation-crosslinking low-smoke halogen-free flame-retardant polyolefin material for locomotive wires and cables | |
JP4663112B2 (en) | Flame retardant polyolefin composition | |
CN109651749A (en) | Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application | |
CN102731919B (en) | High-speed-extruding oil-proof wear-resisting irradiation crosslinking rubber material and preparation method thereof | |
CN103739928A (en) | High-performance low smoke zero halogen power cable sheath material adopting silicon resin to enhance efficiency and preparation method thereof | |
CN106928554A (en) | Cross-linking radiation high fire-retardance ethylene propylene rubber insulation material and preparation method thereof | |
CN104610646A (en) | High-temperature-resistant, anti-cracking and flame-retardant polyolefin cable material and preparation method thereof | |
CN102898715B (en) | Extremely temperature sensitive halogen-free and low smoke flame retardant plastic alloy for cables and preparation method thereof | |
CN110698770A (en) | Low-smoke halogen-free flame-retardant TPV elastomer and preparation method thereof | |
CN108164806A (en) | Locomotive engine cable irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin material and preparation method thereof | |
CN111961278A (en) | Large-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for electric wires | |
CN113912928A (en) | Halogen-free flame-retardant polyolefin cable material for automobiles and preparation method thereof | |
CN103172923B (en) | High-temperature-resistant thermoplastic flame retardant material for automotive wire and preparation method thereof | |
CN105462052A (en) | 125 DEG C irradiation crosslinking low-smoke halogen-free cable material for automotive wires and preparation method thereof | |
CN109280299B (en) | Low-smoke low-halogen PVC (polyvinyl chloride) granules and preparation method thereof | |
CN100451065C (en) | Halogen-free combustion-proof polypropylene high-speed abrasion-proof insulating material for auto initial line | |
CN108219260A (en) | A kind of halogen-free flameproof EVA thermoplastic elastic materials and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
PP01 | Preservation of patent right |
Effective date of registration: 20210122 Granted publication date: 20200324 |
|
PP01 | Preservation of patent right | ||
PD01 | Discharge of preservation of patent |
Date of cancellation: 20240122 Granted publication date: 20200324 |
|
PD01 | Discharge of preservation of patent |