CN109971065A - Low smoke and zero halogen ceramic polyolefin refractory insulation material - Google Patents

Low smoke and zero halogen ceramic polyolefin refractory insulation material Download PDF

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Publication number
CN109971065A
CN109971065A CN201711456957.7A CN201711456957A CN109971065A CN 109971065 A CN109971065 A CN 109971065A CN 201711456957 A CN201711456957 A CN 201711456957A CN 109971065 A CN109971065 A CN 109971065A
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parts
insulation material
low smoke
zero halogen
refractory insulation
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张家宏
单永东
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Zhongguang Nuclear High-Tech Nuclear Material Technology (suzhou) Co Ltd
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Zhongguang Nuclear High-Tech Nuclear Material Technology (suzhou) Co Ltd
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Publication of CN109971065A publication Critical patent/CN109971065A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • 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
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention discloses a kind of low smoke and zero halogen ceramic polyolefin refractory insulation material, it is characterised in that: is grouped as by the group of following parts by weight: 30 ~ 50 parts of metallocene PE, 30 ~ 50 parts of ethylene-alpha-octylene copolymers, 10 ~ 20 parts of high-density polyethylene resin, maleic anhydride are grafted 5 ~ 10 parts of amorphous polyolefin, 10 ~ 20 parts of pentaerythrite, 6 ~ 13 parts of boron carbide, 16 ~ 23 parts of silicon carbide, 60 ~ 80 parts of nano-aluminum hydroxide, 20 ~ 30 parts of shepardite, talcum powder, antioxidant, silane coupling agent, neopelex, lubricant silicone master batch；Tensile strength >=15MPa of the metallocene PE, elongation at break >=500%；The melt flow rate (MFR) of the ethylene-alpha-octylene copolymers is 1 ~ 5 g/10min.The present invention is transformed into hard ceramic protective layer by porcelain after meeting high temperature kindling, and has certain mechanical strength, ensure that wire and cable route operates normally.

Description

Low smoke and zero halogen ceramic polyolefin refractory insulation material
Technical field
The present invention relates to Halogen-free flame retardant sheath material technical field more particularly to a kind of low smoke and zero halogen ceramic polyolefin fire resistings Insulation Material.
Background technique
Ceramic fluidized polymer refractory material be using polymer as matrix, and be added a certain proportion of ceramic powder, fluxing agent and With the advanced composite material (ACM) of fire resisting function prepared by other auxiliary agents.The material at normal temperature have good flexibility and Mechanical performance is transformed into hard ceramic protective layer by porcelain after meeting high temperature kindling, and the protective layer has certain machine Tool intensity.
Both at home and abroad although the research of this respect can be traced in the 1930s, but develop slowly always, until in recent years to can The research of ceramic fire-resisting cable just increased, ceramic fire-resisting cable just become fire-resisting cable field research hotspot it One.Studied in ceramic fluidized polymer refractory material at present it is more be Ceramic silicon rubber, but Ceramic silicon rubber electricity Shortcoming present in cable material is: when and also needing by vulcanization process in use, need to squeeze out by dedicated Rubber Extruder Vulcanizing treatment is carried out, thus technique is relative complex, restricted application；If silicone rubber belt is made in CABLE MATERIALS, and in electricity Line is wrapped to outside cable core during cable processing, then production efficiency is low and at high cost, is unfavorable for industrial amplification production. The ceramic polyolefin refractory material for this purpose, researcher begins one's study, and in the selection of ceramic material, formula design, ceramic Exploration of Mechanism, structural characterization and industrial application etc. achieve certain achievement.
Summary of the invention
The object of the present invention is to provide a kind of low smoke and zero halogen ceramic polyolefin refractory insulation material, the low smoke and zero halogen ceramics Polyolefin refractory insulation material has property identical with common wiring cable insulation in room temperature, and extrusion processing technology is simple, Equipment requirement is low, and mounting and installation is convenient, is transformed into hard ceramic protective layer by porcelain after meeting high temperature kindling, and have one Fixed mechanical strength ensure that wire and cable route operates normally.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of low smoke and zero halogen ceramic polyolefin is resistance to Fiery Insulation Material is grouped as by the group of following parts by weight:
30 ~ 50 parts of metallocene PE,
30 ~ 50 parts of ethylene-alpha-octylene copolymers,
10 ~ 20 parts of high-density polyethylene resin,
Maleic anhydride is grafted 5 ~ 10 parts of amorphous polyolefin,
10 ~ 20 parts of pentaerythrite,
6 ~ 13 parts of boron carbide,
16 ~ 23 parts of silicon carbide,
60 ~ 80 parts of nano-aluminum hydroxide,
20 ~ 30 parts of shepardite,
10 ~ 20 parts of talcum powder,
0.5 ~ 2 part of antioxidant,
0.5 ~ 2 part of silane coupling agent,
2 ~ 4 parts of neopelex,
2 ~ 6 parts of lubricant silicone master batch；
Tensile strength >=15MPa of the metallocene PE, elongation at break >=500%；
The melt flow rate (MFR) of the ethylene-alpha-octylene copolymers is 1 ~ 5 g/10min, elongation at break >=600%；
Fusing point >=125 DEG C of the high-density polyethylene resin；
The grafting rate of the maleic anhydride grafting amorphous polyolefin is 1.0% ~ 1.5%, and melt index is 1 ~ 10g/10min；
Microhardness >=5800kg/mm of the boron carbide2；
Content of magnesia >=64.5% of the shepardite, content≤1.0% of calcium oxide；
Active matter content >=90% of the neopelex, inorganic salt content≤3%, pH value are 8 ~ 9.
The further improved technical solution of above-mentioned technical proposal is as follows:
1. in above scheme, the metallocene PE is in SP5040, SP4020, SP1071C of Mitsui production One kind, or for Dow Chemical production 5815, one of 4404G.
2. in above scheme, the ethylene-α-pungent hydrocarbon copolymer be DOW Chemical production 8100,8130,8150, 8200, one of 8400,8450,8452,8480.
3. in above scheme, the high density polyethylene (HDPE) is the DGDK-3364NT of DOW Chemical production, Exxon Mobil The one kind for the DGDA6098 that the HMA-016 of production, Qilu Petrochemical produce.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1. boron carbide is added in CABLE MATERIALS, silicon carbide, receives for low smoke and zero halogen ceramic polyolefin refractory insulation material of the present invention Rice aluminium hydroxide, shepardite, talcum powder compound system as ceramics at porcelain filling, it is good with ceramic performance, after sintering Ceramic shell bending strength is high, crust is very rigid, closely knit, and when having flame, nonflame for 600 ~ 1500 DEG C, molten drop, does not take off It falls, not will cause spot fire, hard ceramic-like armour body can be burnt into, temperature is higher, the ceramic-like armour body after time longer burning Harder, residue is ceramic inorganic object, and section can generate uniform micropore, can play extraordinary heat-insulated, cooling, fire resisting Effect, smoke amount is low when burning, Halogen, nontoxic, tasteless, passes through ROHS test stone.
2. low smoke and zero halogen ceramic polyolefin refractory insulation material of the present invention selects the metallocene PE of special parameter 30 ~ 50 parts, ethylene-α -30 ~ 50 parts of pungent hydrocarbon copolymer, 10 ~ 20 parts of high-density polyethylene resin, maleic anhydride grafting is amorphous poly- 5 ~ 10 parts of alkene are used as basis material, fill out with what boron carbide, silicon carbide, nano-aluminum hydroxide, shepardite, talcum powder formed at porcelain Material mixing, make each component have good compatibility, make material have excellent mechanical performance, tensile strength be greater than 10.0MPa, Elongation at break is greater than 160%；Electrical insulation capability is excellent under room temperature, dielectric strength >=28KV/mm, and volume resistivity >=1.0 × 1015Ω·cm。
3. low smoke and zero halogen ceramic polyolefin refractory insulation material of the present invention selects the surfactant of special parameter, and Silane coupling agent and lubricant silicone master batch are equipped with as processing aid system, can be squeezed out with thermoplasticity thin-walled, processing technology is good, With simple process, equipment requirement is low, mounting and installation is convenient, overcomes ceramic rubber cable material in amplification production process Disadvantage is an important directions of cable material development both at home and abroad at present.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment 1 ~ 4: a kind of low smoke and zero halogen ceramic polyolefin refractory insulation material is grouped as, such as table 1 by the group of following parts by weight It is shown:
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Metallocene PE 35 45 40 50
Ethylene-alpha-octylene copolymers 45 35 35 30
High-density polyethylene resin 10 15 15 10
Maleic anhydride is grafted amorphous polyolefin 10 5 10 10
Pentaerythrite 15 20 10 15
Boron carbide 7 10 12 9
Silicon carbide 22 16 20 18
Nano-aluminum hydroxide 60 70 75 80
Shepardite 25 22 26 24
Talcum powder 12 16 15 14
Antioxidant 1 1.2 1.4 1.1
Silane coupling agent 0.6 0.8 1.2 1.4
Neopelex 3.0 3.2 3.1 3.5
Lubricant silicone master batch 2.3 3.5 2.8 3.1
Above-mentioned metallocene PE, tensile strength >=15MPa, elongation at break >=500%；
The melt flow rate (MFR) of above-mentioned ethylene-alpha-octylene copolymers is 1 ~ 5 g/10min, elongation at break >=600%；
Fusing point >=125 DEG C of above-specified high density polyvinyl resin；
The grafting rate of above-mentioned maleic anhydride grafting amorphous polyolefin is 1.0% ~ 1.5%, and melt index is 1 ~ 10g/10min；
Microhardness >=5800kg/mm of above-mentioned boron carbide2；
Content of magnesia >=64.5% of above-mentioned shepardite, content≤1.0% of calcium oxide；
Above-mentioned neopelex, active matter content >=90%, inorganic salt content≤3%, pH value are 8 ~ 9；
Wherein the metallocene PE in above-described embodiment 1 ~ 4 is respectively SP5040, SP4020 of Mitsui production, SP1071C, beauty The 5815 of state's DOW Chemical production.
Ethylene-the α-pungent hydrocarbon copolymer in above-described embodiment 1 ~ 4 be respectively DOW Chemical production 8150,8200, 8450、8480。
The high density polyethylene (HDPE) in above-described embodiment 1 ~ 4 is respectively DGDK-3364NT, Ai Ke of DOW Chemical production The DGDK-3364NT that the HMA-016 of gloomy Mobil production, DGDA6098, the DOW Chemical of Qilu Petrochemical production produce.
The low smoke and zero halogen ceramic polyolefin refractory insulation material that above-described embodiment 1 ~ 4 is obtained passes through experimental test, has Performance indicator such as the following table 2:
Table 2
In about 2.5mm2Copper core on squeeze into a kind of low smoke and zero halogen ceramic polyolefin hot-face insulation of the invention of about 1mm thickness Material, GB/T19216.21-2003 carries out route integrality fire resistance test according to national standards, and test result is as shown in table 3 below:
Table 3
It is obtained from table 2 and 3, low smoke and zero halogen ceramic polyolefin refractory insulation material of the present invention has the advantage that
(1) there is good mechanical property, tensile strength is greater than 10.0MPa, elongation at break is greater than 160%；
(2) electrical insulation capability is excellent under room temperature, dielectric strength >=28KV/mm, volume resistivity >=1.0 × 1015Ω·cm；
(3) smoke amount is low when burning, Halogen, nontoxic, tasteless, passes through ROHS test stone；
(4) ceramic fire resistance is good, and boron carbide, silicon carbide, nano-aluminum hydroxide, shepardite, talcum are added in CABLE MATERIALS For the compound system of powder as ceramics at porcelain filling, ceramic buckling of shells intensity is high, is all larger than 7.0MPa, crusts very hard Firmly, closely knit, temperature is higher, the ceramic-like armour body after time longer burning is harder, and residue is ceramic inorganic object, ablation rear surface Completely, without bright slight crack, and section can generate uniform micropore, can play extraordinary heat-insulated, cooling, fire resisting effect；
(5) processing technology is good, have squeeze out processing technology it is simple, equipment requirement is low, mounting and installation is convenient, overcome ceramic rubber Disadvantage of the glue CABLE MATERIALS in amplification production process is an important directions of cable material development both at home and abroad at present.
Low smoke and zero halogen ceramic polyolefin refractory insulation material of the present invention, for immediate product, present invention tool Smoke amount is low when having under good mechanical property, room temperature excellent electrical insulation capability, burning, Halogen, nontoxic, tasteless, is examined by ROHS Standard, ceramic performance are good, ceramic bending strength is high, crust speed is fast, and investing temperature is low, crust very rigid, closely knit, In the case of 600 ~ 1500 DEG C have flame, nonflame, molten drop, is not fallen off, and not will cause spot fire, can be burnt into hard ceramic-like armour Body, temperature is higher, the ceramic-like armour body after time longer burning is harder, and residue is ceramic inorganic object, ablation rear surface is complete, Without bright slight crack, and section can generate uniform micropore, can play extraordinary heat-insulated, cooling, fire resisting effect, can pass through country's mark Quasi- fire resisting test.The CABLE MATERIALS has property identical with common wiring cable insulation, extrusion processability energy in room temperature Good, equipment requirement is low, and mounting and installation is convenient, is transformed into hard ceramic protective layer by porcelain after meeting high temperature kindling, and have There is certain mechanical strength, can guarantee the normal operation of wire and cable route.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (4)

1. a kind of low smoke and zero halogen ceramic polyolefin refractory insulation material, it is characterised in that: be grouped as by the group of following parts by weight:
30 ~ 50 parts of metallocene PE,
30 ~ 50 parts of ethylene-alpha-octylene copolymers,
10 ~ 20 parts of high-density polyethylene resin,
Maleic anhydride is grafted 5 ~ 10 parts of amorphous polyolefin,
10 ~ 20 parts of pentaerythrite,
6 ~ 13 parts of boron carbide,
16 ~ 23 parts of silicon carbide,
60 ~ 80 parts of nano-aluminum hydroxide,
20 ~ 30 parts of shepardite,
10 ~ 20 parts of talcum powder,
0.5 ~ 2 part of antioxidant,
0.5 ~ 2 part of silane coupling agent,
2 ~ 4 parts of neopelex,
2 ~ 6 parts of lubricant silicone master batch；
Tensile strength >=15MPa of the metallocene PE, elongation at break >=500%；
The melt flow rate (MFR) of the ethylene-alpha-octylene copolymers is 1 ~ 5 g/10min, elongation at break >=600%；
Fusing point >=125 DEG C of the high-density polyethylene resin；
The grafting rate of the maleic anhydride grafting amorphous polyolefin is 1.0% ~ 1.5%, and melt index is 1 ~ 10g/10min；
Microhardness >=5800kg/mm of the boron carbide2；
Content of magnesia >=64.5% of the shepardite, content≤1.0% of calcium oxide；
Active matter content >=90% of the neopelex, inorganic salt content≤3%, pH value are 8 ~ 9.
2. low smoke and zero halogen ceramic polyolefin refractory insulation material according to claim 1, it is characterised in that: the cyclopentadienyl gold Belong to one of SP5040, SP4020, SP1071C that polyethylene is Mitsui production, or is produced for Dow Chemical 5815, one of 4404G.
3. low smoke and zero halogen ceramic polyolefin refractory insulation material according to claim 1, it is characterised in that: the ethylene- The pungent hydrocarbon copolymer of α-is one of 8100,8130,8150,8200,8400,8450,8452,8480 of DOW Chemical production.
4. low smoke and zero halogen ceramic polyolefin refractory insulation material according to claim 1, it is characterised in that: the high density Polyethylene is the DGDK-3364NT of DOW Chemical production, the HMA-016 of Exxon Mobil production, Qilu Petrochemical produce One kind of DGDA6098.
CN201711456957.7A 2017-12-28 2017-12-28 Low smoke and zero halogen ceramic polyolefin refractory insulation material Pending CN109971065A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300480A (en) * 2020-11-17 2021-02-02 苏州亨利通信材料有限公司 Ceramic polyolefin and preparation method thereof
WO2022135250A1 (en) * 2020-12-21 2022-06-30 金发科技股份有限公司 Alloy material having ceramicized surface, preparation method therefor and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348627A (en) * 2015-11-13 2016-02-24 苏州希普拉斯新材料有限公司 Ceramifying polyolefin fireproof cable material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348627A (en) * 2015-11-13 2016-02-24 苏州希普拉斯新材料有限公司 Ceramifying polyolefin fireproof cable material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300480A (en) * 2020-11-17 2021-02-02 苏州亨利通信材料有限公司 Ceramic polyolefin and preparation method thereof
WO2022135250A1 (en) * 2020-12-21 2022-06-30 金发科技股份有限公司 Alloy material having ceramicized surface, preparation method therefor and application thereof

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