CN116262846A - Flame-retardant insulating material for cables and preparation method thereof - Google Patents
Flame-retardant insulating material for cables and preparation method thereof Download PDFInfo
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- CN116262846A CN116262846A CN202211549135.4A CN202211549135A CN116262846A CN 116262846 A CN116262846 A CN 116262846A CN 202211549135 A CN202211549135 A CN 202211549135A CN 116262846 A CN116262846 A CN 116262846A
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- magnesium hydroxide
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- flame
- chitin
- insulating material
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- 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 62
- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- 239000011810 insulating material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 95
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 56
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 56
- 229920002101 Chitin Polymers 0.000 claims description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000002156 mixing Methods 0.000 claims description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 22
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 230000006196 deacetylation Effects 0.000 claims description 18
- 238000003381 deacetylation reaction Methods 0.000 claims description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 18
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 229920013716 polyethylene resin Polymers 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000012774 insulation material Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 11
- 239000011707 mineral Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 229920003020 cross-linked polyethylene Polymers 0.000 abstract description 6
- 239000004703 cross-linked polyethylene Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical group COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 8
- 230000009970 fire resistant effect Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- MXLBKVCGLRNKBW-UHFFFAOYSA-N C(=C)OO[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C Chemical compound C(=C)OO[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C MXLBKVCGLRNKBW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- SKFYTVYMYJCRET-UHFFFAOYSA-J potassium;tetrafluoroalumanuide Chemical compound [F-].[F-].[F-].[F-].[Al+3].[K+] SKFYTVYMYJCRET-UHFFFAOYSA-J 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 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 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 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 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 230000009466 transformation Effects 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
- C08L23/06—Polyethene
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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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 invention relates to the technical field of insulating materials, and discloses a flame-retardant insulating material for cables and a preparation method thereof. The flame-retardant insulating material provided by the invention takes the crosslinked polyethylene as a matrix, and the magnesium hydroxide is compositely loaded by the organic carrier through modification, so that the agglomeration of the magnesium hydroxide is prevented, the flame-retardant performance of the insulating material is improved, and the mechanical property of the crosslinked polyethylene is further improved due to the addition of the organic carrier. The flame-retardant insulating material provided by the invention has no moisture absorption and moisture absorption problem of mineral insulating materials.
Description
Technical Field
The invention relates to the technical field of insulating materials, in particular to a flame-retardant insulating material for cables and a preparation method thereof.
Background
The cable product plays an important role in the power transmission and signal transmission of the rail transit. The national standard GB 51348-2019 (civil construction Electrical design Specification) defines that flame-retardant B1-level cables must be used in various environments; the service environment of a fire-resistant B1-class cable with a fire-resistant class B1 fire-resistant class 3h is defined in the technical requirement (trial) for the fire-resistant design of civil buildings with building height of more than 250m issued by the fire department of public security department; the test requirements of fire resistance and impact resistance and fire resistance and spraying are defined in national standard GB/T19666-2019 general rules of fire-retardant and fire-resistant wires and cables or optical cables.
For flame-retardant insulated cables, the existing products mainly comprise magnesium oxide mineral insulated cables and mica tape mineral insulated cables 2, but the 2 products are influenced by production structures and hardly meet the requirements of cable dripping indexes. The metal sheath of traditional magnesium oxide mineral insulated cable is the copper sheath, and its existence is that copper metal sheath is smooth, and the adsorption affinity is insufficient between insulating material and the metal sheath, and the cable easily drips when B1 level fire-resistant test and causes the test index unable to satisfy d0 requirement. The mica tape mineral insulated cable adopts the cladding of high temperature resistant mica tape as the flame retardant coating, and the outside squeezes insulating material again in order to insulate, but the most of mica tape mineral insulated cable is the circular telegram operation under the conflagration condition, is reserve cable in most cases, when the crowded oversheath of package or when placing for a long time, in the air gets into cable construction, the cable wets, will cause the cable unable normal use. Therefore, the conventional mineral insulated cable cannot meet all the daily requirements of the flame-retardant insulated cable.
For example, chinese patent publication No. CN 110550939B discloses an insulating material for making mineral insulated cable and a method for preparing the same. In the patent, fly ash, potassium tetrafluoroaluminate and magnesium oxide are fully and uniformly mixed, then pressed into a required shape, and then heated and calcined at 1180-1200 ℃ to obtain the mineral insulated cable. The patent preparation provides a ternary composite inorganic material composed of fly ash, potassium tetrafluoroaluminate and magnesia powder, which solves the problems of poor water absorption, poor insulation and poor uniformity of magnesia. However, in fact, due to the high self-polymerization of the fly ash, it is difficult to mix the fly ash, potassium tetrafluoroaluminate and magnesium oxide thoroughly, and if the mixture is not uniform, the prepared mineral material still has moisture absorption problem.
Therefore, in order to further improve the flame retardant property of the insulated fire-resistant cable, a new flame retardant insulating material still needs to be produced, and the requirements of the cable industry are met.
Disclosure of Invention
In order to solve the technical problems, the invention provides a flame-retardant insulating material for cables and a preparation method thereof. According to the insulating material provided by the invention, the crosslinked polyethylene is used as a matrix, and the magnesium hydroxide is subjected to composite loading by using the organic carrier through modification, so that agglomeration of the magnesium hydroxide is prevented, and the flame retardant property of the insulating material is improved. The mechanical properties of the crosslinked polyethylene are further improved due to the addition of the organic carrier.
The specific technical scheme of the invention is as follows:
on the one hand, the invention provides a flame-retardant insulating material for cables, which comprises the following components in parts by weight: 100 parts of polyethylene resin, 10-17 parts of polypropylene resin, 1.5-2 parts of cross-linking agent, 0.1-0.3 part of initiator, 25-32 parts of modified magnesium hydroxide and 0.5-1 part of catalyst. Specifically, the modified magnesium hydroxide is organic matter carrier composite connection load magnesium hydroxide.
In the flame-retardant insulating material provided by the invention, the crosslinked polyethylene is used as a matrix, the volume resistivity of the insulating material is high, and the modified magnesium hydroxide is used as a flame retardant, so that the flame-retardant performance of the insulating material is excellent. Magnesium hydroxide is often used as a flame retardant for cable insulation materials, but the magnesium hydroxide is strong in polarity and large in surface energy, and is easy to agglomerate and secondarily agglomerate in the process of adding a resin matrix material, so that the problems of incapability of playing a flame retardant effect and poor flame retardant effect are caused, and even the mechanical properties of the insulation materials are deteriorated. According to the invention, magnesium hydroxide is compounded and connected by utilizing an organic carrier structure, so that the magnesium hydroxide is uniformly dispersed in an insulating material, and the flame retardant property of the magnesium hydroxide is improved. Meanwhile, the hydrophilic problem of the magnesium hydroxide body is improved through the magnesium hydroxide structure loaded by the organic matters.
Specifically, the invention provides a preparation method of modified magnesium hydroxide, which comprises the following steps:
(1) Chitin is added into NaOH solution, naBH is added 4 And (3) performing ultrasonic treatment, reacting, washing and drying to obtain the deacetylated chitin.
Step (1) is deacetylation treatment of chitin. Adding NaBH 4 The function of (2) is to prevent chitin from depolymerizing. The ultrasonic wave can generate high-energy chemical substances, cavitation is generated, cavitation bubbles are formed in the liquid, huge energy is generated in explosion engineering, and intermolecular hydrogen bonds can be destroyed to a certain extent.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring to obtain precursor suspension.
The step (2) is the loading of magnesium hydroxide.
(3) Adding triethylenetetramine solution into the precursor suspension, heating and stirring, adding styrene and dicumyl peroxide, reacting at a constant temperature, cooling, drying and crushing to obtain the magnesium hydroxide loaded on the organic framework.
Step (3) is a further crosslinking reaction of the carrier, and the magnesium hydroxide of the primary composite organic carrier is fixed by using the crosslinking of triethylenetetramine and styrene, and the crystallization area of the chitin is damaged to a certain extent.
The invention provides modified magnesium hydroxide which takes chitin as an organic carrier matrix. The chitin molecule has many hydroxyl groups and amide groups, and many electron donors and electron acceptors, so that the chitin molecule has good conditions for becoming a connecting carrier. However, strong intermolecular and intramolecular hydrogen bonds exist between chitin chains, the chitin is pretreated in the step (1), deacetylation is carried out to improve the solubility of the chitin, the acting force of the hydrogen bonds is weakened, and conditions are prepared for loading the magnesium hydroxide in the step (2). In the step (2), sodium hydroxide is initially loaded on a chitin carrier, and then the sodium hydroxide is firmly fixed through physical winding of the crosslinking reaction in the step (3). The modified magnesium hydroxide prepared by the method provided by the application is not easy to agglomerate due to the existence of the organic carrier, and has better dispersibility in the resin insulation material.
Preferably, the concentration of the NaOH solution in the step (1) is 35-40wt%, and the mass-volume ratio of the chitin to the NaOH solution is 2-4 g/100 mL. NaBH 4 The mass ratio of the chitosan to the chitin is preferably 0.01-0.02:1.
Preferably, the time of the ultrasonic treatment in the step (1) is 1-3 hours; the reaction is a shaking table reaction at 95-100 ℃ for 2-4 hours; the deacetylation degree of the deacetylated chitin is 40-50%.
The deacetylation degree of the chitin is 40-50%, and the deacetylation degree of the chitin has a good effect on chemical bonding of an organic carrier and magnesium hydroxide. The deacetylation degree of the chitin is too small, firstly, the connection between the chitin and magnesium hydroxide is incomplete due to poor solubility, and secondly, the later cross-linking winding is not easy to carry out. The deacetylation degree of chitin is too large, the exposed amino is too much, the repulsive force on magnesium hydroxide is too large, and magnesium hydroxide cannot be loaded.
Specifically, the washing method in the step (1) is as follows: repeatedly washing the deionized water to be neutral; the drying method comprises the following steps: and (5) freeze drying.
Preferably, the mass volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the step (2) is 5-8g to 1-4g to 0.3-0.6g to 100mL; the temperature of stirring is 25-30 ℃ and the time is 3-4.5h.
Preferably, in the step (3), the mass ratio of the precursor suspension, triethylenetetramine, styrene and dicumyl peroxide is 3:0.5-0.8:3-4:0.3-0.7; heating and stirring at 95-110deg.C for 1.5-2.5 hr; the temperature of the heat preservation reaction is 75-80 ℃ and the time is 14-18h.
Preferably, the polyethylene resin has a melt index of 4.0.+ -. 0.3g/10min at 190℃and 2.16 kg. The melt index of the polypropylene resin at 190℃and 2.16kg was 2.5.+ -. 0.5g/10min.
Preferably, the cross-linking agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane and vinyl tri-tert-butyl peroxy silane.
Preferably, the initiator is dicumyl peroxide or di-tert-butyl peroxide, and the catalyst is dibutyltin dilaurate.
Specifically, the flame-retardant insulating material also comprises 0.1-0.5 part of a water scavenger, 2-5 parts of an antioxidant, 0.5-1 part of an anti-copper agent and 3-5 parts of silicone powder.
Preferably, the antioxidant is one or more of antioxidant 300, antioxidant 168, antioxidant 1010, antioxidant AT 10, antioxidant DSTP and antioxidant DLTP. The water scavenger is trimethoxy methane.
On the other hand, the invention provides a preparation method of the flame-retardant insulating material for the cable, which comprises the following steps:
s1: mixing polyethylene resin, polypropylene resin, a water removing agent and modified magnesium hydroxide, melting, adding an antioxidant, an anti-copper agent and silicone powder, and continuously mixing for 4-8min to obtain a mixed primary material;
s2: adding a cross-linking agent, an initiator and a catalyst into the mixed primary material, mixing, extruding, forming, and performing steam cross-linking for 4-12 hours at the temperature of 90-100 ℃ to obtain the flame-retardant insulating material.
Compared with the prior art, the invention has the following technical effects:
(1) The flame-retardant insulating material disclosed by the invention takes crosslinked polyethylene as a matrix and modified magnesium hydroxide as a flame retardant, and has excellent flame-retardant insulating performance.
(2) Compared with the common magnesium hydroxide flame retardant, the modified magnesium hydroxide provided by the invention can be better dispersed and distributed in the insulating material resin matrix.
(3) The flame-retardant insulating material disclosed by the invention has no moisture absorption and moisture absorption problem of the magnesium oxide mineral insulating material.
Detailed Description
The invention is further described below with reference to examples.
General examples
Preparing modified magnesium hydroxide:
(1) Adding alpha-chitin into 35-40wt% NaOH solution, adding appropriate amount of NaBH 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 2-4g to 0.02-0.04g to 100mL, ultrasonic treatment is carried out at 30 ℃ for 1-3h, shaking table reaction is carried out at 95-100 ℃ for 2-4h, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin is obtained, and the deacetylation degree of the deacetylated chitin is 40-50%.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 25-30 ℃ for 3-4.5 hours to obtain a precursor suspension, wherein the mass volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water is 5-8g:1-4g:0.3-0.6g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 95-110 ℃ and stirring for 1.5-2.5h, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to triethylenetetramine to styrene to dicumyl peroxide is 3:0.5-0.8:3-4:0.3-0.7, carrying out heat preservation reaction for 14-18h at 75-80 ℃, cooling, drying and crushing to obtain the organic frame loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing a flame-retardant insulating material:
s1: adding 100 parts of polyethylene resin, 10-17 parts of polypropylene resin, 0.1-0.5 part of trimethoxy methane and 25-32 parts of modified magnesium hydroxide according to parts by weight, mixing, melting, adding 2-5 parts of antioxidant, 0.5-1 part of copper inhibitor 1024 and 3-5 parts of silicone powder, and continuously mixing for 4-8min to obtain a mixed primary material.
S2: adding 1.5-2 parts of silane coupling agent serving as a cross-linking agent, 0.1-0.3 part of initiator dicumyl peroxide or di-tert-butyl peroxide and 0.5-1 part of catalyst dibutyltin dilaurate into a mixing initial material in a single screw extruder, and mixing, wherein the silane coupling agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane and vinyl tri-tert-butyl peroxy silane, and the temperature of each area of the single screw extruder is as follows: 125 ℃ of I, 145 ℃ of II, 165 ℃ of III, 185 ℃ of IV, 195 ℃ of V, 195 ℃ of flange, 200 ℃ of neck, 215 ℃ of nose, extrusion molding, and steam crosslinking at 90-100 ℃ for 4-12 hours to obtain the flame-retardant insulating material.
Example 1
Preparing modified magnesium hydroxide:
(1) Alpha-chitin is added into 37wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 3g:0.04g:100mL, ultrasonic treatment is carried out for 2h at 30 ℃, shaking table reaction is carried out for 3h at 98 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 48% is obtained.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 30 ℃ for 4 hours to obtain a precursor suspension, wherein the mass volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the precursor suspension is 6g:3g:0.4g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 100 ℃ and stirring for 2 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene to the dicumyl peroxide is 3:0.6:3:0.5, carrying out heat preservation reaction for 16 hours at 80 ℃, cooling, drying and crushing to obtain the organic frame loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing a flame-retardant insulating material:
s1: 100 parts of polyethylene resin, 15 parts of polypropylene resin, 0.3 part of trimethoxy methane and 30 parts of modified magnesium hydroxide are added according to parts by weight, after melting, 3 parts of antioxidant 300, 0.7 part of copper inhibitor 1024 and 4 parts of silicone powder are added for continuous mixing for 5 minutes, and a mixing initial material is obtained.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding, and steam crosslinking at 100 ℃ for 8 hours to obtain the flame-retardant insulating material.
Example 2
Preparing modified magnesium hydroxide:
(1) Alpha-chitin is added into 35wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 2g:0.02g:100mL, ultrasonic treatment is carried out for 1h at 30 ℃, shaking table reaction is carried out for 2h at 95 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 40% is obtained.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 25 ℃ for 4.5 hours to obtain a precursor suspension, wherein the mass-volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the precursor suspension is 5g:1g:0.3g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 95 ℃ and stirring for 2.5 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene to the dicumyl peroxide is 3:0.5:3:0.3, carrying out heat preservation reaction for 14 hours at 75 ℃, cooling, drying and crushing to obtain the organic frame loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing a flame-retardant insulating material:
s1: 100 parts of polyethylene resin, 10 parts of polypropylene resin, 0.1 part of trimethoxy methane and 25 parts of modified magnesium hydroxide are added according to parts by weight, after melting, 2 parts of antioxidant 168, 0.5 part of copper inhibitor 1024 and 3 parts of silicone powder are added for continuous mixing for 4 minutes, and a mixed initial material is obtained.
S2: in a single screw extruder, 1.5 parts of vinyl trimethoxy silane, 0.1 part of initiator di-tert-butyl peroxide and 0.5 part of catalyst dibutyltin dilaurate are added into the mixing initial material for mixing, and the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, forming and 90 ℃ steam crosslinking for 12 hours to obtain the flame-retardant insulating material.
Example 3
Preparing modified magnesium hydroxide:
(1) Alpha-methyl esterThe chitin is added into 40wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 4g:0.04g:100mL, ultrasonic treatment is carried out for 3h at 30 ℃, shaking table reaction is carried out for 4h at 100 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 50% is obtained.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 28 ℃ for 3 hours to obtain a precursor suspension, wherein the mass-volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the precursor suspension is 8g:4g:0.6g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 110 ℃ and stirring for 1.5 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene to the dicumyl peroxide is 3:0.8:4:0.7, carrying out heat preservation reaction for 18 hours at 80 ℃, cooling, drying and crushing to obtain the organic frame-loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing a flame-retardant insulating material:
s1: according to the weight parts, adding 100 parts of polyethylene resin, 17 parts of polypropylene resin, 0.5 part of trimethoxy methane and 32 parts of modified magnesium hydroxide, mixing, melting, adding 5 parts of antioxidant 1010, 1 part of copper inhibitor 1024 and 3-5 parts of silicone powder, and continuously mixing for 8min to obtain a mixing initial material.
S2: 2 parts of vinyl tri-tert-butyl peroxy silane, 0.3 part of initiator di-tert-butyl peroxide and 1 part of catalyst dibutyltin dilaurate are added into a mixing initial material in a single screw extruder for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, and forming and crosslinking with 100 ℃ steam for 4 hours to obtain the flame-retardant insulating material.
Example 4
Preparing modified magnesium hydroxide:
(1) Alpha-chitin is added into 40wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 3g:0.03g:100mL, ultrasonic treatment is carried out for 1h at 30 ℃, shaking table reaction is carried out for 3h at 100 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylation degree of the deacetylation chitin is 47%.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 30 ℃ for 4.5 hours to obtain a precursor suspension, wherein the mass-volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the precursor suspension is 8g:3g:0.4g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 110 ℃, stirring for 2 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene and the dicumyl peroxide is 3:0.6:4:0.4, carrying out heat preservation reaction for 16 hours at 80 ℃, cooling, drying and crushing to obtain the organic frame-loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing a flame-retardant insulating material:
s1: 100 parts of polyethylene resin, 15 parts of polypropylene resin, 0.2 part of trimethoxy methane and 32 parts of modified magnesium hydroxide are added according to parts by weight, after melting, 3 parts of antioxidant DSTP, 0.5 part of copper inhibitor 1024 and 4 parts of silicone powder are added for continuous mixing for 4 minutes, and a mixing initial material is obtained.
S2: 1.5 parts of vinyl tri-tert-butyl peroxy silane, 0.2 part of initiator di-tert-butyl peroxide and 0.5 part of catalyst dibutyltin dilaurate are added into the mixing initial material in a single screw extruder for mixing, and the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding and 95 ℃ steam crosslinking for 10 hours to obtain the flame-retardant insulating material.
Comparative example 1 (the main difference from example 1 is that 7.5 parts of magnesium hydroxide was directly added to the insulation preparation:
s1: 100 parts of polyethylene resin, 15 parts of polypropylene resin, 0.3 part of trimethoxy methane and 7.5 parts of magnesium hydroxide are added according to parts by weight, and after melting, 3 parts of antioxidant 300, 0.7 part of copper inhibitor 1024 and 4 parts of silicone powder are added for continuous mixing for 5 minutes, so as to obtain a mixed initial material.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding and 100 ℃ steam crosslinking for 8 hours to obtain the insulating material.
Comparative example 2 (the main difference from example 1 is that no crosslinking reaction was carried out in the preparation of modified magnesium hydroxide)
Preparing modified magnesium hydroxide:
(1) Alpha-chitin is added into 37wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 3g:0.04g:100mL, ultrasonic treatment is carried out for 2h at 30 ℃, shaking table reaction is carried out for 3h at 98 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 48% is obtained.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, wherein the mass volume ratio of the deacetylated chitin to the magnesium hydroxide to the sodium dodecyl benzene sulfonate to the water is 6g to 3g to 0.4g to 100mL, stirring for 4 hours at 30 ℃, separating solid, and drying to obtain modified magnesium hydroxide.
Preparing an insulating material:
s1: 100 parts of polyethylene resin, 15 parts of polypropylene resin, 0.3 part of trimethoxy methane and 22.5 parts of modified magnesium hydroxide are added according to parts by weight, after melting, 3 parts of antioxidant 300, 0.7 part of copper inhibitor 1024 and 4 parts of silicone powder are added for continuous mixing for 5 minutes, and a mixing initial material is obtained.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding, and steam crosslinking at 100 ℃ for 8 hours to obtain the flame-retardant insulating material.
Comparative example 3 (the main difference from example 1 is that 22.5 parts of chitin and 7.5 parts of magnesium hydroxide are added in the preparation of the insulating material)
Preparing an insulating material:
s1: according to the weight portions, adding 100 portions of polyethylene resin, 15 portions of polypropylene resin, 0.3 portion of trimethoxy methane, 15 portions of chitin and 7.5 portions of magnesium hydroxide, melting, adding 3 portions of antioxidant 300, 0.7 portion of copper inhibitor 1024 and 4 portions of silicone powder, and continuously mixing for 5 minutes to obtain a mixed primary material.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding, and steam crosslinking at 100 ℃ for 8 hours to obtain the flame-retardant insulating material.
Comparative example 4 (the main difference from example 1 is that 22.5 parts of a blank organic carrier and 7.5 parts of magnesium hydroxide were added to the insulation preparation)
Blank organic matter carrier preparation:
(1) Alpha-chitin is added into 37wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 3g:0.04g:100mL, ultrasonic treatment is carried out for 2h at 30 ℃, shaking table reaction is carried out for 3h at 98 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 48% is obtained.
(2) Adding triethylenetetramine solution into deacetylated chitin, heating to 100 ℃ and stirring for 2 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene and the dicumyl peroxide is 3:0.6:3:0.5, carrying out heat preservation reaction for 16 hours at 80 ℃, cooling, drying and crushing to obtain a blank organic carrier.
Preparing a flame-retardant insulating material:
s1: according to the weight portions, adding 100 portions of polyethylene resin, 15 portions of polypropylene resin, 0.3 portion of trimethoxy methane, 15 portions of blank organic carrier and 7.5 portions of magnesium hydroxide for mixing, after melting, adding 3 portions of antioxidant 300, 0.7 portion of copper inhibitor 1024 and 4 portions of silicone powder for continuous mixing for 5 minutes, and obtaining a mixing primary material.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding, and steam crosslinking at 100 ℃ for 8 hours to obtain the flame-retardant insulating material.
Comparative example 5 (the main difference from example 1 is that the degree of deacetylation of deacetylated chitin in the preparation of modified magnesium hydroxide was 65%)
Preparing modified magnesium hydroxide:
(1) Alpha-chitin is added into 50wt% NaOH solution, and proper amount of NaBH is added 4 Prevent chitin from depolymerizing, chitin and NaBH 4 The mass volume ratio of NaOH solution is 3g:0.06g:100mL, ultrasonic treatment is carried out for 3h at 30 ℃, shaking table reaction is carried out for 3h at 100 ℃, deionized water is repeatedly washed to be neutral, and freeze drying is carried out, so that the deacetylated chitin with the deacetylation degree of 65% is obtained.
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring at 30 ℃ for 4 hours to obtain a precursor suspension, wherein the mass volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water in the precursor suspension is 6g:3g:0.4g:100mL.
(3) Adding triethylenetetramine solution into the precursor suspension, heating to 100 ℃ and stirring for 2 hours, adding styrene and dicumyl peroxide, wherein the mass ratio of the precursor suspension to the triethylenetetramine to the styrene to the dicumyl peroxide is 3:0.6:3:0.5, carrying out heat preservation reaction for 16 hours at 80 ℃, cooling, drying and crushing to obtain the organic frame loaded magnesium hydroxide, namely the modified magnesium hydroxide.
Preparing an insulating material:
s1: 100 parts of polyethylene resin, 15 parts of polypropylene resin, 0.3 part of trimethoxy methane and 30 parts of modified magnesium hydroxide are added according to parts by weight, after melting, 3 parts of antioxidant 300, 0.7 part of copper inhibitor 1024 and 4 parts of silicone powder are added for continuous mixing for 5 minutes, and a mixing initial material is obtained.
S2: in a single screw extruder, adding 2 parts of vinyl triethoxysilane, 0.2 part of initiator dicumyl peroxide and 0.6 part of catalyst dibutyltin dilaurate into the mixing initial material for mixing, wherein the temperature of each zone of the single screw extruder is as follows: 125 ℃ I, 145 ℃ II, 165 ℃ III, 185 ℃ IV, 195 ℃ V, 195 ℃ flange, 200 ℃ neck, 215 ℃ head, extruding, molding, and steam crosslinking at 100 ℃ for 8 hours to obtain the flame-retardant insulating material.
Performance testing
The insulating materials prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to performance test, and the results are shown in Table 1.
TABLE 1
Data analysis
(1) As can be seen from Table 1, the insulating materials prepared in examples 1 to 4 are excellent in flame retardant property, and the vertical burning grade can reach UL94V-0 grade, and meanwhile, the insulating materials are excellent in mechanical property.
(2) Compared with the example 1, the comparative example 1 directly adds 7.5 parts of magnesium hydroxide as a flame retardant, the flame retardant grade, tensile strength and elongation at break of which are greatly reduced, which proves that the addition of the modified flame retardant provided by the invention is beneficial to improving the flame retardance of the insulating material and the mechanical property.
(3) Compared with the example 1, the modified magnesium hydroxide in the comparative example 2 does not carry out crosslinking reaction, does not carry out crosslinking of triethylenetetramine and styrene, and has slightly reduced flame retardance grade, tensile strength and elongation at break, which shows that the magnesium hydroxide is further subjected to crosslinking reaction after complexing chitin, thereby being beneficial to improving the flame retardance of the insulating material and simultaneously being beneficial to improving the mechanical property.
(4) Compared with the example 1, the preparation of the insulating material of the comparative example 3 is added with 22.5 parts of chitin and 7.5 parts of magnesium hydroxide, the flame retardant grade, the tensile strength and the breaking elongation are greatly reduced, the preparation of the insulating material of the comparative example 4 is added with 22.5 parts of blank organic matter carrier and 7.5 parts of magnesium hydroxide, the flame retardant grade is greatly reduced, the tensile strength and the breaking elongation are well maintained, and the modified flame retardant provided by the invention has the advantages that the mechanical property is acted by the chitin after the crosslinking reaction.
The polyethylene resin and polypropylene resin used in the above examples and comparative examples were the same as the raw materials. The melt index of the polyethylene resin at 190℃and 2.16kg was 4.0.+ -. 0.3g/10min, and the melt index of the polypropylene resin used at 190℃and 2.16kg was 2.5.+ -. 0.5g/10min.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides a fire-retardant insulating material for cable which characterized in that: comprises the following components in parts by weight: 100 parts of polyethylene resin, 10-17 parts of polypropylene resin, 1.5-2 parts of cross-linking agent, 0.1-0.3 part of initiator, 25-32 parts of modified magnesium hydroxide and 0.5-1 part of catalyst;
the modified magnesium hydroxide is magnesium hydroxide loaded by an organic carrier.
2. A flame retardant insulation material for cables as claimed in claim 1, wherein: the preparation method of the modified magnesium hydroxide comprises the following steps:
(1) Adding chitin into NaOH solution, adding NaBH 4 Ultrasonic treatment, reaction, washing and drying to obtain deacetylated chitin;
(2) Adding water into deacetylated chitin, adding sodium dodecyl benzene sulfonate, uniformly dispersing, adding magnesium hydroxide, and stirring to obtain precursor suspension;
(3) Adding triethylenetetramine solution into the precursor suspension, heating and stirring, adding styrene and dicumyl peroxide, carrying out heat preservation reaction, cooling, drying and crushing to obtain the organic carrier-loaded magnesium hydroxide, namely the modified magnesium hydroxide.
3. A flame retardant insulation material for cables as claimed in claim 2, wherein: in the step (1), the deacetylation degree of the deacetylated chitin is 40-50%.
4. A flame retardant insulation material for cables as claimed in claim 2, wherein: in the step (2), the mass volume ratio of the deacetylated chitin, the magnesium hydroxide, the sodium dodecyl benzene sulfonate and the water is 5-8g to 1-4g to 0.3-0.6g to 100mL.
5. A flame retardant insulation material for cables as claimed in claim 2, wherein: in the step (2), the stirring temperature is 25-30 ℃ and the stirring time is 3-4.5h.
6. A flame retardant insulation material for cables as claimed in claim 2, wherein: in the step (3), the mass ratio of the precursor suspension to triethylenetetramine to styrene to dicumyl peroxide is 3:0.5-0.8:3-4:0.3-0.7.
7. A flame retardant insulation material for cables as claimed in claim 1, wherein: in the step (3), the temperature of heating and stirring is 95-110 ℃ and the time is 1.5-2.5h.
8. A flame retardant insulation material for cables as claimed in claim 1, wherein: in the step (3), the temperature of the heat preservation reaction is 75-80 ℃ and the time is 14-18h.
9. A method of preparing a flame retardant insulating material according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
s1: mixing polyethylene resin, polypropylene resin, a water removing agent and modified magnesium hydroxide, melting, adding an antioxidant, an anti-copper agent and silicone powder, and continuously mixing to obtain a mixed primary material;
s2: adding a cross-linking agent, an initiator and a catalyst into the mixed primary material, mixing, extruding, forming and steam cross-linking to obtain the flame-retardant insulating material.
10. The method of preparing as claimed in claim 9, wherein: the temperature of the steam crosslinking is 90-100 ℃ and the time is 4-12h.
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