CN114561062A - Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof - Google Patents
Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof Download PDFInfo
- Publication number
- CN114561062A CN114561062A CN202210122287.XA CN202210122287A CN114561062A CN 114561062 A CN114561062 A CN 114561062A CN 202210122287 A CN202210122287 A CN 202210122287A CN 114561062 A CN114561062 A CN 114561062A
- Authority
- CN
- China
- Prior art keywords
- parts
- loss
- shrinkable
- low
- halogen
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- 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 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 16
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 239000004611 light stabiliser Substances 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- -1 vinylsilane modified magnesium hydroxide Chemical class 0.000 claims description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- ILWVABLRFKUOOO-UHFFFAOYSA-N [3-[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxy-2,2-bis[[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxymethyl]propyl] 2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoate Chemical group CC(C(=O)OCC(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C ILWVABLRFKUOOO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001179 medium density polyethylene Polymers 0.000 claims description 3
- 239000004701 medium-density polyethylene Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 3
- 230000032683 aging Effects 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000020169 heat generation Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000004595 color masterbatch Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
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
- C08L23/04—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulating Bodies (AREA)
Abstract
The invention is suitable for the technical field of materials, and provides a low-loss halogen-free flame-retardant heat-shrinkable mother calandria and a preparation method thereof, wherein the low-loss halogen-free flame-retardant heat-shrinkable mother calandria consists of the following components in parts by weight: 100 parts of vinyl polymer, 30-70 parts of calcined kaolin, 10-20 parts of red phosphorus master batch, 20-50 parts of magnesium hydroxide, 2-5 parts of antioxidant, 0.5-3 parts of light stabilizer, 2-5 parts of crosslinking sensitizer, 2-5 parts of lubricant and 5-8 parts of master batch. The invention has excellent flame retardant property, cracking resistance, aging resistance and high and low temperature resistance, and simultaneously, the dielectric loss is less than 0.5 percent, thereby greatly reducing the energy loss caused by the dielectric loss, simultaneously reducing the heat generation of the mother calandria and improving the operation safety.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and a preparation method thereof.
Background
The busbar heat-shrinkable sleeve has wide application in transformer substations, transformers and switch cabinets, and mainly plays a main insulation protection role in tubular buses, transformers, switch cabinets and other equipment in the field of power transmission and transformation. With the construction enhancement of electric power infrastructure, the market of the busbar heat-shrinkable sleeve used for insulation protection is huge, however, the existing busbar heat-shrinkable sleeves sold in the market generally have the problems of irregularity, high dielectric loss of products, poor flame retardant property and short service life.
Disclosure of Invention
The embodiment of the invention provides a low-loss halogen-free flame-retardant heat-shrinkable female calandria, and aims to solve the problems that the existing bus heat-shrinkable tubes are irregular in difference, high in product dielectric loss, poor in flame retardant property and short in service life.
The embodiment of the invention is realized in such a way that the low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria consists of the following components in parts by weight: 100 parts of vinyl polymer, 30-70 parts of calcined kaolin, 10-20 parts of red phosphorus master batch, 20-50 parts of magnesium hydroxide, 2-5 parts of antioxidant, 0.5-3 parts of light stabilizer, 2-5 parts of crosslinking sensitizer, 2-5 parts of lubricant and 5-8 parts of master batch.
The embodiment of the invention also provides a preparation method of the low-loss halogen-free flame-retardant heat-shrinkable mother calandria, which comprises the following steps:
weighing the raw materials according to the formula of the low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria for later use;
putting vinyl polymer, calcined kaolin, red phosphorus master batch, magnesium hydroxide, antioxidant, light stabilizer, crosslinking sensitizer, lubricant and master batch into an internal mixer or a double-screw extruder, mixing and granulating, and extruding into a pipe by a single-screw extruder;
and (3) performing cobalt 60 or electron accelerator 60-120KGy radiation crosslinking treatment on the pipe, and then expanding the pipe by 2-4 times at the temperature of 85-135 ℃ to obtain the pipe.
The low-loss halogen-free flame-retardant heat-shrinkable mother calandria provided by the embodiment of the invention has excellent flame retardant property, cracking resistance, aging resistance and high and low temperature resistance, and simultaneously has the medium loss of less than 0.5%, so that the energy loss caused by the medium loss can be greatly reduced, the heat generation of the mother calandria is reduced, and the operation safety is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
The embodiment of the invention aims to solve the problems of irregular common occurrence, high medium loss of products, poor flame retardant property and short service life of the conventional busbar heat-shrinkable tube, and provides a low-loss halogen-free flame-retardant heat-shrinkable tube, which has excellent flame retardant property, cracking resistance, aging resistance and high and low temperature resistance, and simultaneously has the medium loss of less than 0.5 percent, so that the energy loss caused by the medium loss can be greatly reduced, the heat generation of the mother tube is reduced, and the operation safety is improved.
In the embodiment of the invention, the low dielectric loss halogen-free flame-retardant heat-shrinkable mother calandria consists of the following components in parts by weight: 100 parts of vinyl polymer, 30-70 parts of calcined kaolin, 10-20 parts of red phosphorus master batch, 20-50 parts of magnesium hydroxide, 2-5 parts of antioxidant, 0.5-3 parts of light stabilizer, 2-5 parts of crosslinking sensitizer, 2-5 parts of lubricant and 5-8 parts of master batch.
The ethylene-based polymer is a blend of two or more of low-density polyethylene, medium-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-octene copolymer and ethylene-propylene rubber in any mass ratio.
Wherein the red phosphorus master batch is a master batch formed by mixing microcapsule red phosphorus and ethylene-vinyl acetate copolymer, and the content of the microcapsule red phosphorus is 60%.
Wherein the magnesium hydroxide is magnesium hydroxide obtained by vinyl silane modification chemical method, and the purity is more than 96%.
Wherein the antioxidant is pentaerythritol tetrakis [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butyl) phenyl phosphite in a proportion of 3: 1 in a mass ratio.
The crosslinking sensitizer is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and triallyl isocyanurate in any mass proportion.
Wherein, the lubricant is one or more of stearic acid, zinc stearate, magnesium stearate and polyethylene wax in any mass proportion.
The embodiment of the invention also provides a preparation method of the low-loss halogen-free flame-retardant heat-shrinkable mother calandria, which comprises the following steps:
weighing the raw materials according to the formula of the low dielectric loss halogen-free flame-retardant heat-shrinkable mother calandria for later use;
putting vinyl polymer, calcined kaolin, red phosphorus master batch, magnesium hydroxide, antioxidant, light stabilizer, crosslinking sensitizer, lubricant and master batch into an internal mixer or a double-screw extruder, mixing and granulating, and extruding into a pipe by a single-screw extruder;
and (3) performing cobalt 60 or electron accelerator 60-120KGy radiation crosslinking treatment on the pipe, and then expanding the pipe by 2-4 times at the temperature of 85-135 ℃ to obtain the pipe.
Examples of certain embodiments of the invention are given below, which are not intended to limit the scope of the invention.
In addition, it is to be noted that the numerical values given in the following examples are as precise as possible, but those skilled in the art understand that each numerical value should be understood as a divisor rather than an absolutely exact numerical value due to measurement errors and experimental operational problems that cannot be avoided.
Example 1
Weighing the following raw materials according to the following formula: 60 parts of ethylene-vinyl acetate copolymer, 35 parts of ethylene-methyl acrylate copolymer, 5 parts of medium-density polyethylene, 50 parts of calcined kaolin, 10 parts of red phosphorus master batch, 50 parts of magnesium hydroxide, 1.5 parts of tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.5 part of tris (2, 4-di-tert-butyl) phenyl phosphite, 3 parts of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 3 parts of trimethylolpropane trimethacrylate, 4 parts of zinc stearate and 5 parts of master batch; mixing and granulating the raw materials by an internal mixer, and then extruding the raw materials into a pipe by a single-screw extruder; the pipe is subjected to radiation 80KGy crosslinking by a 5.0Mev electron accelerator, and the pipe subjected to radiation crosslinking is expanded by 2.5 times at the temperature of 95 ℃ to obtain the low-loss halogen-free flame-retardant heat-shrinkable mother pipe, wherein the test performance of the pipe is as follows:
dielectric loss: 0.42 percent;
flame retardancy: the flame retardant property test of UL94V-0 is passed;
tensile strength 15.6MPa, elongation at break 461%;
cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, and aging at the temperature of 120 ℃/168h without any extension of cracks;
the elongation at break is 427 percent after aging at 150 ℃/1200 h;
Aging at 120 ℃/168h, then carrying out low-temperature treatment at-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
Example 2
Weighing the raw materials according to the following formula: 42 parts of ethylene-vinyl acetate copolymer, 50 parts of ethylene-methyl acrylate copolymer, 8 parts of ethylene-octene copolymer, 30 parts of calcined kaolin, 15 parts of red phosphorus master batch, 50 parts of magnesium hydroxide, 3.75 parts of tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.25 parts of tris (2, 4-di-tert-butyl) phenyl phosphite, 0.5 part of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 4 parts of trimethylolpropane trimethacrylate, 2 parts of zinc stearate and 7 parts of color master batch; mixing and granulating the raw materials by a parallel double screw, and then extruding the mixture into a pipe by a single screw extruder; the pipe is subjected to radiation 90KGy crosslinking by a 5.0Mev electron accelerator, the pipe subjected to radiation crosslinking is expanded by 3 times at the temperature of 125 ℃, and the low-loss halogen-free flame-retardant heat-shrinkable mother calandria is obtained, and the test performance is as follows:
dielectric loss: 0.46 percent;
flame retardancy: the flame retardant property test of UL94V-0 is passed;
the tensile strength is 13.4MPa, and the elongation at break is 586%;
cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, and aging at the temperature of 120 ℃/168h without any extension of cracks;
After aging at 150 ℃/1200h, the elongation at break is 448%;
aging at 120 ℃/168h, and then processing at low temperature of-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
Example 3
Weighing the following raw materials according to the following formula: 60 parts of ethylene-methyl acrylate copolymer, 15 parts of low-density polyethylene, 25 parts of ethylene propylene rubber, 70 parts of calcined kaolin, 20 parts of red phosphorus master batch, 20 parts of magnesium hydroxide, 3 parts of tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of tris (2, 4-di-tert-butyl) phenyl phosphite, 2 parts of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 5 parts of trimethylolpropane trimethacrylate, 4 parts of zinc stearate and 8 parts of color master batch; mixing and granulating the raw materials through a mixer, and then extruding the raw materials into a pipe by using a single-screw extruder; the pipe is subjected to cobalt 60 radiation 120KGy crosslinking, and the pipe subjected to radiation crosslinking is expanded by 2.5 times at the temperature of 115 ℃ to obtain the low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria, wherein the test performance is as follows:
dielectric loss: 0.41 percent;
flame retardancy: the flame retardant property test of UL94V-0 is passed;
the tensile strength is 14.8MPa, and the elongation at break is 548 percent;
cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, and aging at the temperature of 120 ℃/168h without any extension of cracks;
After aging at 150 ℃/1200h, the elongation at break is 425%;
aging at 120 ℃/168h, then carrying out low-temperature treatment at-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
Example 4
Weighing the raw materials according to the following formula: 50 parts of ethylene-vinyl acetate copolymer, 45 parts of ethylene-methyl acrylate copolymer, 5 parts of ethylene-octene copolymer, 50 parts of calcined kaolin, 20 parts of red phosphorus master batch, 30 parts of magnesium hydroxide, 2.25 parts of tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.75 part of tris (2, 4-di-tert-butyl) phenyl phosphite, 1 part of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 2 parts of trimethylolpropane trimethacrylate, 3 parts of zinc stearate and 8 parts of color master batch; mixing and granulating the materials by parallel double screws, and then extruding the materials into a pipe by using a single-screw extruder; the pipe is subjected to radiation 60KGy crosslinking through a 3.0Mev electron accelerator, the pipe subjected to radiation crosslinking is expanded by 2 times at the temperature of 135 ℃, and the low-loss halogen-free flame-retardant heat-shrinkable mother calandria is obtained, and the test performance is as follows:
dielectric loss: 0.42 percent;
flame retardancy: the flame retardant property test of UL94V-0 is passed;
the tensile strength is 16.4MPa, and the breaking elongation is 496%;
Cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, aging at the condition of 120 ℃/168h, and ensuring that no crack extends;
after aging at 150 ℃/1200h, the elongation at break is 445 percent;
aging at 120 ℃/168h, then carrying out low-temperature treatment at-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
Example 5
Weighing the raw materials according to the following formula: 35 parts of ethylene-vinyl acetate copolymer, 60 parts of ethylene-methyl acrylate copolymer, 5 parts of ethylene-octene copolymer, 60 parts of calcined kaolin, 15 parts of red phosphorus master batch, 40 parts of magnesium hydroxide, 3 parts of tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1 part of tris (2, 4-di-tert-butyl) phenyl phosphite, 2 parts of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 4 parts of trimethylolpropane trimethacrylate, 5 parts of zinc stearate and 6 parts of color master batch; mixing and granulating the materials by an internal mixer, and then extruding the materials into a pipe by a single-screw extruder; the pipe is subjected to radiation 90KGy crosslinking by a 5.0Mev electron accelerator, and the pipe subjected to radiation crosslinking is expanded by 2.5 times at the temperature of 110 ℃ to obtain the low-loss halogen-free flame-retardant heat-shrinkable mother calandria, wherein the test performance of the low-loss halogen-free flame-retardant heat-shrinkable mother calandria is as follows:
Dielectric loss: 0.42 percent;
flame retardance: the flame retardant property test of UL94V-0 is passed;
the tensile strength is 15.2MPa, and the elongation at break is 586%;
cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, and aging at the temperature of 120 ℃/168h without any extension of cracks;
after aging at 150 ℃/1200h, the elongation at break is 489%;
aging at 120 ℃/168h, and then processing at low temperature of-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
Comparative example 1
Weighing the following raw materials according to the following formula: 85 parts of ethylene-vinyl acetate copolymer, 10 parts of low-density polyethylene, 5 parts of ethylene-octene copolymer, 20 parts of calcined kaolin, 15 parts of red phosphorus master batch, 65 parts of magnesium hydroxide prepared by a mineral method, 1.5 parts of pentaerythritol tetrakis [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 0.5 part of phenyl tris (2, 4-di-tert-butyl) phosphite, 3 parts of bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 2 parts of trimethylolpropane trimethacrylate, 2 parts of stearic acid and 5 parts of color master batch; mixing and granulating the materials by an internal mixer, and then extruding the materials into a pipe by a single-screw extruder; the pipe is subjected to 80KGy radiation crosslinking through a 5.0Mev electron accelerator, the pipe subjected to radiation crosslinking is expanded by 2.5 times at the temperature of 115 ℃, and a heat-shrinkable female comb pipe is obtained, and the test performance is as follows:
Dielectric loss: 1.22 percent;
flame retardance: the flame retardant property test of UL94V-0 is passed;
the tensile strength is 13.2MPa, and the elongation at break is 354 percent;
cutting a V-shaped notch after the copper bar of the heat-shrinkable busbar pipe sleeve is restricted and shrunk, and aging at the temperature of 120 ℃/168h without any extension of cracks;
after aging at 150 ℃/1200h, the elongation at break is 65 percent;
aging at 120 ℃/168h, and then processing at low temperature of-55 ℃/4h, and passing the power frequency withstand voltage test and the lightning impulse test.
In summary, the low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother pipe provided by the embodiment of the invention has excellent flame-retardant performance, cracking resistance, aging resistance and high and low temperature resistance, and the dielectric loss is less than 0.5%, so that the energy loss caused by the dielectric loss can be greatly reduced, the heat generation of the mother pipe is reduced, and the operation safety is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria is characterized by comprising the following components in parts by weight: 100 parts of vinyl polymer, 30-70 parts of calcined kaolin, 10-20 parts of red phosphorus master batch, 20-50 parts of magnesium hydroxide, 2-5 parts of antioxidant, 0.5-3 parts of light stabilizer, 2-5 parts of crosslinking sensitizer, 2-5 parts of lubricant and 5-8 parts of master batch.
2. The low dielectric loss halogen-free flame retardant heat shrinkable mother pipe of claim 1, wherein the vinyl polymer is a blend of two or more of low density polyethylene, medium density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-octene copolymer, ethylene-propylene rubber in any mass ratio.
3. The low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother pipe as claimed in claim 1, wherein the red phosphorus masterbatch is a masterbatch obtained by mixing microencapsulated red phosphorus with an ethylene-vinyl acetate copolymer.
4. The low dielectric loss halogen-free flame retardant heat shrinkable mother pipe as claimed in claim 1, wherein the magnesium hydroxide is vinylsilane modified magnesium hydroxide.
5. The low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria as claimed in claim 1, wherein the antioxidant is pentaerythritol tetrakis [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tris (2, 4-di-tert-butyl) phosphite in a ratio of 3: 1 in a mass ratio.
6. The low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria as claimed in claim 1, wherein the crosslinking sensitizer is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and triallyl isocyanurate in any mass ratio.
7. The low dielectric loss halogen-free flame retardant heat shrinkable mother pipe of claim 1, wherein the lubricant is one or more of stearic acid, zinc stearate, magnesium stearate, polyethylene wax in any mass ratio.
8. A preparation method of a low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria is characterized by comprising the following steps:
weighing the raw materials according to the formula of the low-loss halogen-free flame-retardant heat-shrinkable mother pipe as claimed in any one of claims 1 to 7 for later use;
putting vinyl polymer, calcined kaolin, red phosphorus master batch, magnesium hydroxide, antioxidant, light stabilizer, crosslinking sensitizer, lubricant and master batch into an internal mixer or a double-screw extruder, mixing and granulating, and extruding into a pipe by a single-screw extruder;
and (3) performing cobalt 60 or 60-120KGy radiation crosslinking treatment on the pipe, and then expanding the pipe by 2-4 times at the temperature of 85-135 ℃ to obtain the pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210122287.XA CN114561062A (en) | 2022-02-09 | 2022-02-09 | Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210122287.XA CN114561062A (en) | 2022-02-09 | 2022-02-09 | Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114561062A true CN114561062A (en) | 2022-05-31 |
Family
ID=81713536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210122287.XA Pending CN114561062A (en) | 2022-02-09 | 2022-02-09 | Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114561062A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989554A (en) * | 2022-06-16 | 2022-09-02 | 欧宝聚合物江苏有限公司 | Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432937A (en) * | 2011-08-18 | 2012-05-02 | 长园集团股份有限公司 | 1E-level K1-type halogen-free flame-retardant heat-shrinkable pipe for nuclear power plant and preparation method thereof |
| CN103183868A (en) * | 2011-12-29 | 2013-07-03 | 深圳市宏商材料科技股份有限公司 | Halogen-free flame retardant heat shirnkable sleeving and production technology |
| CN103739930A (en) * | 2014-01-10 | 2014-04-23 | 长园电子（集团）有限公司 | Halogen-free flame-retardant heat-shrinkable busbar casing and preparation method thereof |
| CN106589569A (en) * | 2016-12-28 | 2017-04-26 | 长园电子（东莞）有限公司 | Halogen-free flame-retardant adhesion-proof heat-shrinkable bush and preparation method thereof |
-
2022
- 2022-02-09 CN CN202210122287.XA patent/CN114561062A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432937A (en) * | 2011-08-18 | 2012-05-02 | 长园集团股份有限公司 | 1E-level K1-type halogen-free flame-retardant heat-shrinkable pipe for nuclear power plant and preparation method thereof |
| CN103183868A (en) * | 2011-12-29 | 2013-07-03 | 深圳市宏商材料科技股份有限公司 | Halogen-free flame retardant heat shirnkable sleeving and production technology |
| CN103739930A (en) * | 2014-01-10 | 2014-04-23 | 长园电子（集团）有限公司 | Halogen-free flame-retardant heat-shrinkable busbar casing and preparation method thereof |
| CN106589569A (en) * | 2016-12-28 | 2017-04-26 | 长园电子（东莞）有限公司 | Halogen-free flame-retardant adhesion-proof heat-shrinkable bush and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989554A (en) * | 2022-06-16 | 2022-09-02 | 欧宝聚合物江苏有限公司 | Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof |
| CN114989554B (en) * | 2022-06-16 | 2023-09-19 | 欧宝聚合物江苏有限公司 | Low-dielectric-loss halogen-free flame-retardant cable material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106633312B (en) | Oil-resistant high-temperature-resistant halogen-free flame-retardant thermal shrinkage identification tube and production method thereof | |
| CN103739930B (en) | A kind of halogen-free flameproof pyrocondensation bus-bar casing tube and its preparation method | |
| CN112321934A (en) | Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin material for 150 ℃ American standard electronic wire and preparation method thereof | |
| CN104893088A (en) | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof | |
| CN106432895A (en) | Irradiation-crosslinked halogen-free flame-retardant photovoltaic cable, and preparation method and application thereof | |
| CN102924779A (en) | Bus bar heat-shrinkable tube and preparation method thereof | |
| CN107793689A (en) | A kind of high temperature tear-proof pyrocondensation bus-bar protective sleeve material prescription and its production method | |
| CN115746445A (en) | Halogen-free low-smoke flame-retardant polyolefin sheath material and preparation method thereof | |
| CN114561062A (en) | Low-dielectric-loss halogen-free flame-retardant heat-shrinkable mother calandria and preparation method thereof | |
| CN113372644A (en) | High-flame-retardant cross-linked low-smoke halogen-free polyolefin insulating material and preparation method thereof | |
| CN114213850B (en) | High-heat-conductivity silicone rubber cable material and preparation method and application thereof | |
| CN112321955A (en) | Environment-friendly flame-retardant insulating rubber composite material and preparation method thereof | |
| CN111303528A (en) | Halogen-free low-smoke high-flame-retardant high-oxygen-insulation cable material for power cable and preparation method thereof | |
| CN111961274A (en) | Insulating material for photovoltaic cable and preparation method thereof | |
| CN109705510B (en) | Scratch-resistant and abrasion-resistant low-smoke halogen-free flame-retardant cable material for thin-wall locomotive and preparation method thereof | |
| CN113773568A (en) | Insulating material, preparation method and application thereof | |
| CN112724584A (en) | TPE sheath material for charging pile cable and preparation method thereof | |
| CN115746446A (en) | CPR-grade silane crosslinking flame-retardant polyolefin cable material for photovoltaic cable and preparation method thereof | |
| CN108485048A (en) | A kind of cable cover(ing) sizing material and preparation method thereof | |
| CN111690200A (en) | 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wire and preparation method thereof | |
| CN112521675A (en) | Insulating cold-resistant cable material and preparation method and application thereof | |
| CN112795077A (en) | Low-smoke halogen-free cable material containing rare earth synergistic flame retardant and preparation thereof | |
| CN116102815B (en) | Irradiation crosslinking high-electrical low-temperature-resistant low-smoke halogen-free insulating material, preparation method and application | |
| CN115678150B (en) | High-performance flame-retardant polyethylene sheath material and preparation method thereof | |
| CN115938661B (en) | Low-smoke halogen-free power cable and preparation process 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220531 |