CN115895098A - B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition and preparation method and application thereof - Google Patents
B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition and preparation method and application thereof Download PDFInfo
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- CN115895098A CN115895098A CN202211663640.1A CN202211663640A CN115895098A CN 115895098 A CN115895098 A CN 115895098A CN 202211663640 A CN202211663640 A CN 202211663640A CN 115895098 A CN115895098 A CN 115895098A
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- smoke halogen
- flame retardant
- ultraviolet crosslinking
- crosslinking low
- inorganic flame
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000004132 cross linking Methods 0.000 title claims abstract description 45
- 239000000779 smoke Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 34
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 34
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 238000009413 insulation Methods 0.000 claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000000806 elastomer Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000006078 metal deactivator Substances 0.000 claims description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003568 thioethers Chemical class 0.000 claims description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 5
- -1 3,5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 4
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- JHNMPYMTHAMTJM-UHFFFAOYSA-N phenyl-(2,3,4,5-tetramethylphenyl)methanone Chemical group CC1=C(C)C(C)=CC(C(=O)C=2C=CC=CC=2)=C1C JHNMPYMTHAMTJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 17
- 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 description 13
- 239000003063 flame retardant Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- JZHMMFMMAKFDRT-UHFFFAOYSA-N 2-(propan-2-ylideneamino)oxyacetic acid Chemical compound CC(C)=NOCC(O)=O JZHMMFMMAKFDRT-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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 group 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction 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
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KBZQKRFMZFQXHE-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C KBZQKRFMZFQXHE-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WPSPGZNUOYUBLZ-UHFFFAOYSA-N phenyl-(2,3,4,5-tetraphenylphenyl)methanone Chemical compound C1(=CC=CC=C1)C=1C(=C(C(=C(C(=O)C2=CC=CC=C2)C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 WPSPGZNUOYUBLZ-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition and a preparation method and application thereof. The insulation composition comprises the following components in parts by weight: 80-120 parts of an inorganic flame retardant; 40-60 parts of an elastomer; 1-2 parts of an antioxidant; 1-4 parts of a metal passivator; 2-6 parts of a photoinitiator; the average grain diameter of the inorganic flame retardant is 0.1-5 mu m. The insulating composition is added with an inorganic flame retardant with a specific average particle size in a system, is matched with a metal passivator to form a reticular complex, is subjected to ultraviolet crosslinking under the condition of a photoinitiator, does not need secondary irradiation crosslinking, meets B1-level flame retardance, and has good mechanical property and aging resistance.
Description
Technical Field
The invention relates to the technical field of cable insulating materials, in particular to a B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition and a preparation method and application thereof.
Background
After the time of 'Aokai problem cable' of Xian, the quality of electric wires and cables for buildings at dense places such as important public buildings and the like is widely concerned by various social circles; no. 12/2017, which is dominated by Shenyang fire-fighting research institute of Ministry of public Security, combines with units such as Chinese architectural design research institute and Chinese architectural science research institute to compile a quotation of a 'civil architecture electrical design fire-protection code' and hopes to push the standard into a mandatory execution standard, and the requirements of different places and different wires and cables for meeting the flame-retardant grade are clearly specified in the standard; among them, electric wires and cables meeting the flame retardant rating of GB/T31247B 1 are becoming the mainstream.
The cross-linked cable has excellent high temperature resistance, higher long-term service temperature and longer service life. In the prior art, radiation crosslinking is frequently adopted to prepare an insulated cable material, for example, CN 110776690A discloses a 105 ℃ B1-grade flame-retardant radiation crosslinking insulated cable material, and the obtained insulated material has low heat release, small smoke generation, good shell formation and no dripping, and can give consideration to flame retardance, mechanical properties and processability. However, since the insulation material for electric cables needs to be subjected to irradiation crosslinking, the production efficiency is relatively low and the cost is high. The ultraviolet crosslinking technology is greatly developed in the wire and cable industry in recent years due to small investment. However, in the prior art, silane is generally adopted to coat an inorganic flame retardant to improve the aging resistance of the material, while the inorganic flame retardant without coating is generally adopted, and under the condition of high addition amount, the ideal aging resistance cannot be achieved.
Disclosure of Invention
In order to overcome at least one defect in the prior art, the invention provides a B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition, wherein the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition takes an uncoated inorganic flame retardant as a raw material, and has good aging resistance and good mechanical property, and meets the requirement of B1-level flame retardance.
The invention also aims to provide a preparation method of the B1-grade ultraviolet crosslinking low-smoke halogen-free insulating composition.
The invention also aims to provide application of the B1-grade ultraviolet crosslinking low-smoke halogen-free insulation composition.
In order to achieve the purpose, the invention adopts the technical scheme that:
a B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition comprises the following components in parts by weight:
the inorganic flame retardant is an inorganic flame retardant which is not subjected to coating treatment, and the average particle size of the inorganic flame retardant is 0.1-5 mu m.
According to the invention, the metal passivator with specific content is added into the elastomer and is combined with the uncoated inorganic flame retardant with specific particle size, so that the material has weaker ultraviolet light coverage and is beneficial to ultraviolet light projection, and the metal passivator can effectively reduce the catalytic activity of metal ions in the inorganic flame retardant, so that the prepared material has better aging resistance, has better mechanical property and meets B1-level flame retardance, and the inorganic flame retardant adopted by the invention does not need coating treatment, so that the process is simple and the cost is lower.
Preferably, the metal deactivator is a hydrazide metal deactivator and/or an oxime metal deactivator.
More preferably, the metal deactivator is a hydrazide-type metal deactivator.
Specifically, the hydrazide metal passivator is N, N' -bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and/or 2,2-oxamido-bis [ ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ] propionate.
Specifically, the oxime metal passivator is dimethyl ketoxime and/or acetone carboxymethyl oxime.
Preferably, the inorganic flame retardant has an average particle diameter of 0.3 to 1.9 μm. For example, 0.3. Mu.m, 0.4. Mu.m, 0.5. Mu.m, 0.6. Mu.m, 0.7. Mu.m, 0.8. Mu.m, 0.9. Mu.m, 1.0. Mu.m, 1.1. Mu.m, 1.2. Mu.m, 1.3. Mu.m, 1.4. Mu.m, 1.5. Mu.m, 1.6. Mu.m, 1.7. Mu.m, 1.8. Mu.m, 1.9. Mu.m, and any of these values is preferably a range having an upper limit or a lower limit.
Preferably, the photoinitiator is tetramethyl-benzophenone and/or methyl o-benzoylbenzoate.
Preferably, the inorganic flame retardant is magnesium hydroxide and/or aluminum hydroxide.
Preferably, the elastomer is a polyolefin-based elastomer.
Specifically, the polyolefin elastomer is one or more of an ethylene-octene copolymer, an ethylene-vinyl acetate copolymer or an ethylene-acrylate copolymer.
Preferably, the elastomer has a density of 0.85 to 0.97g/cm 3 。
Preferably, the elastomer has a melt index of 0.5 to 10g/10min at 190 ℃ under 2.16kg test conditions. For example, 0.5g/10min, 1.0g/10min, 1.5g/10min, 2.0g/10min, 2.5g/10min, 3.0g/10min, 3.5g/10min, 4.0g/10min, 4.5g/10min, 5.0g/10min, 5.5g/10min, 6.0g/10min, 6.5g/10min, 7.0g/10min, 7.5g/10min, 8.0g/10min, 8.5g/10min, 9.0g/10min, 9.5g/10min, 10g/10min, preferably any value thereof is the upper limit or the lower limit.
Preferably, the determination standard of the melt index of the elastomer is GB/T3682-2000.
Preferably, the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition further comprises 1-5 parts of a processing aid.
Preferably, the processing aid is a lubricant.
More preferably, the lubricant is one or more of a fluorine-containing lubricant, a stearate lubricant, an ester lubricant or a silicone lubricant.
In the present invention, the antioxidant may be a commonly used antioxidant, such as hindered phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants, etc.; more preferably, a combination of antioxidants is adopted; for example, a combination of a hindered phenol type antioxidant and a phosphite type antioxidant or a combination of a hindered phenol type antioxidant, a thioether type antioxidant and a phosphite type antioxidant. Preferably, the antioxidant is a hindered phenol antioxidant and a thioether antioxidant in a mass ratio of (1-3): 1. The inventor finds that under the combination, the active free radicals generated in the aging process of the material can be better captured, so that the aging of the material is slowed down, the flame retardant property is increased, and the burning growth rate index is reduced.
Specifically, the hindered phenol antioxidant is one or more of beta (3,5 di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, tetra [ beta (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or diethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid methyl ester ].
The phosphite ester antioxidant is one or more of 2,4-di-tert-butylphenol, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite or 627A.
The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecyl dithio propyl ester.
The invention also provides a preparation method of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition, which comprises the following steps:
uniformly mixing the inorganic flame retardant, the elastomer, the antioxidant, the metal deactivator, the photoinitiator and the processing aid, and carrying out mixing and plasticizing granulation by a reciprocating machine to obtain the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition.
Preferably, the temperature of the reciprocating engine is 100 to 200 ℃.
The invention also protects the application of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition in preparing the power distribution cable.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition, which reduces the ultraviolet covering property by adding an uncoated inorganic flame retardant with a specific particle size in a base material and combining a metal passivator and a photoinitiator with specific content, does not need to modify the inorganic flame retardant, is integrated and matched with the uncoated inorganic flame retardant, and the material prepared under the condition of not adding a flame-retardant synergist meets the B1-level flame retardance, does not need secondary irradiation crosslinking, has good mechanical property and aging resistance, and improves the production efficiency.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
elastomer:
an elastomer A: ethylene-vinyl acetate copolymer, EVA00320, density 0.92g/cm 3 The melt index is 1g/10min, and the product is purchased from China petrochemical Yangzi petrochemical company, inc.;
an elastomer B: ethylene-octene copolymer, POE80, density 0.856g/cm 3 Melt index 1g/10min, available from Schumann plastics;
an elastomer C: ethylene-vinyl acetate copolymer, EVA0014, density 0.92g/cm 3 The melt index is 0.3g/10min, and the product is purchased from China petrochemical Yangzi petrochemical company, inc.;
inorganic flame retardant:
uncoated magnesium hydroxide a: an average particle size of 0.1 μm, MDH-F4, available from Liaoning Yingkou magnesium industries, ltd;
uncoated magnesium hydroxide B: average particle size of 0.3 μm, MDH-F5, available from Liaoning Yingkou magnesium industries, ltd
Uncoated magnesium hydroxide C: average particle size of 1.9 μm, MDH-F6, available from Liaoning Yingkou magnesium industries, ltd;
uncoated magnesium hydroxide D: an average particle size of 5 μm, MDH-F7, available from Liaoning Yingkou magnesium industries, ltd;
uncoated magnesium hydroxide E: an average particle size of 10 μm, MDH-F8, available from Liaoning Yingkou magnesium industries, ltd;
uncoated magnesium hydroxide F: average particle size of 0.05 μm, MDH-F9, available from Liaoning Yingkou magnesium industries, ltd;
coating magnesium hydroxide G: the magnesium hydroxide is subjected to surface coating treatment by adopting silane, and the average particle size of the coated magnesium hydroxide is 0.3 mu m and is purchased from Liaoning Yingkou magnesium industry Co., ltd;
uncoated aluminum hydroxide a: average particle size 4 μm, ATH-1, available from aluminum group, inc., china;
photoinitiator (2):
a photoinitiator A: tetraphenyl-benzophenone, CHEMCURE-PM, available from Hengqiao trade, inc. of Dongguan;
a photoinitiator B: methyl o-benzoylbenzoate, CHEMCURE-65, available from Hengqiao trade, inc. of Dongguan;
metal passivator:
metal passivator A: hydrazide type metal passivator, N, N' -bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, RIANOX MD-1024, available from Tianjin Rianlong science and technology, inc.;
and (3) metal passivator B: an oxime metal deactivator, acetone carboxymethyl oxime, available from shanghai Yi En chemistry;
antioxidant:
an antioxidant A: the hindered phenol antioxidant and the thioether antioxidant are mixed in a ratio of 1:1, preparing; wherein the hindered phenol antioxidant is antioxidant 1010, and the thioether antioxidant is antioxidant DSTDP, which are all sold in the market;
and (3) antioxidant B: antioxidant 1010, commercially available;
lubricant: silicone master batch, commercially available.
The present invention will be described in detail with reference to examples.
The following examples and comparative examples were prepared by preparing cable insulation compositions by weighing the components in the weight ratios shown in tables 1 to 3; the method comprises the following specific steps:
uniformly mixing inorganic flame retardant, elastomer, antioxidant, metal deactivator, photoinitiator and processing aid, and mixing, plasticizing and granulating at 100-200 ℃ by a reciprocating machine to obtain the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition.
Table 1 example 1-example 7B 1-stage uv cross-linking low smoke halogen-free insulation composition formulations (parts by weight)
Table 2 example 8-example 16B 1-grade uv cross-linking low smoke zero halogen insulation composition formulations (parts by weight)
TABLE 3 formulation (parts by weight) of B1 grade UV-crosslinking LSOH insulation composition for comparative examples 1 to 8
And (3) performance testing:
(1) The hot elongation property test method comprises the following steps: the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant insulation composition prepared in the above examples and comparative examples is prepared into a finished cable and tested according to GB/T2951.21-2008 standard;
the thermal elongation of the GB/T2951.21-2008 standard is less than or equal to 175 percent, wherein the lower the thermal elongation is, the higher the crosslinking degree is;
(2) Tensile strength and elongation at break test methods: the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant insulating composition prepared in the embodiment and the comparative example is prepared into a finished cable and tested according to the GB/T1040.3-2006 standard; the initial tensile strength is more than or equal to 9MPa in the GB/T1040.3-2006 standard, and the initial breaking elongation is more than or equal to 125 percent, which reaches the standard;
(3) The heat aging performance test method comprises the following steps: after the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant insulation composition prepared in the embodiment and the comparative example is subjected to ultraviolet crosslinking, the tensile strength and the elongation at break of the insulation composition reach the standards, the insulation composition is tested according to the GB/T32129-2015 standard, the change rate of the tensile strength before and after thermal aging reaches +/-25% in the GB/T32129-2015 standard, and the change rate of the elongation at break reaches +/-25%;
the B1-grade ultraviolet crosslinking low-smoke halogen-free flame-retardant insulating composition prepared in the above examples and comparative examples is prepared into finished cables according to JB/T meeting the thermal extensibility requirement and the mechanical property requirement
10491.1-2004 standard; the change rate of the tensile strength before and after thermal aging in the JB/T10491.1-2004 standard is +/-30%, and the change rate of the elongation at break reaches the standard of +/-30%;
(4) When a finished cable made of the B1-level ultraviolet crosslinking low-smoke halogen-free flame-retardant insulating composition is qualified according to heat release rate peak value, heat release total amount, smoke production total amount and combustion growth rate index in GB/T31247-2014, the material passes B1-level flame-retardant requirements; GB/T31247-2014 requires that the total heat release amount is less than or equal to 15MJ and the total smoke production amount is less than or equal to 50m 2 (ii) a The combustion growth rate index is less than or equal to 150W/s. The performance test results of the B1-grade ultraviolet crosslinking LSOH insulation compositions in the examples and comparative examples are shown in tables 4-6.
Table 4 results of performance test of examples 1 to 7
Table 5 results of performance tests of examples 8 to 16
TABLE 6 results of Performance test of comparative examples 1 to 8
As can be seen from tables 4 and 5, the change rates of the tensile strength and the elongation at break of the low-smoke halogen-free insulating composition prepared by the invention before and after aging are not more than 25%, the finished cable prepared by the invention meets B1-level flame retardance, the tensile strength after crosslinking is not less than 9MPa, the elongation at break is not less than 125%, the change rates of the tensile strength and the elongation at break are not more than 30% after thermal aging, and the thermal elongation is not more than 175%.
As can be seen from examples 1 to 4, when the average particle size of the inorganic flame retardant is 0.3 to 1.9 μm, the overall properties of the resulting material are better, the rate of change in elongation at break before and after aging of the composition and the finished cable of the material obtained in example 1 is close to the critical value, and the burn rate index of the flame retardant property of the material obtained in example 4 is close to the critical value, so that the average particle size of the inorganic flame retardant is preferably 0.3 to 1.9 μm. It can be seen from examples 2 and 8 that when the metal deactivator is a hydrazide metal deactivator, the overall performance of the prepared material is better, and the rate of change of the properties of the composition and the finished cable before and after aging is obviously better than that of the material prepared by using an oxime metal deactivator. From examples 2 and 10, it can be seen that when hindered phenolic and thioether antioxidants are used, the ratio of 1:1, the combination property of the prepared material is better, the property change rate of the composition and the finished cable prepared in the example 2 before and after aging is obviously better than that of the example 10, and the burning growth rate index in the example 10 is closer to a critical value. As can be seen from examples 2 and 16, when the melt index of the elastomer used is 0.5 to 10g/10min, the initial elongation at break of the resulting material is significantly increased, and the smoke generation amount and burn rate increase index are significantly decreased, resulting in better performance.
As can be seen from Table 6, in comparative example 1, when the amount of the elastomer used is too small, the mechanical properties of the prepared material are poor, and the initial elongation at break is only 100%, which cannot meet the performance requirements; in comparative example 2, when the amount of the inorganic flame retardant is too small, the flame retardant property of the prepared material is poor, and the B1-level flame retardance can not be met; in comparative example 3, when the amount of the inorganic flame retardant is too much, the mechanical property of the prepared material is poor, the initial elongation at break is only 80%, and the performance requirement cannot be met; in comparative example 4, when the average particle size of the inorganic flame retardant was too large, the mechanical properties of the prepared material could not be poor and could not meet the requirements; in comparative example 5, when the average particle size of the inorganic flame retardant was too small, the aging property of the prepared material was poor, and both the tensile strength change rate before and after aging and the elongation at break change rate before and after aging exceeded 30%, and the requirements were not satisfied; in comparative example 6, when the amount of the metal deactivator is small, the metal deactivator can not be matched with the inorganic flame retardant, the aging catalysis effect of metal ions in the inorganic flame retardant on the material can not be reduced, and the change rate of the tensile strength and the elongation at break of the prepared material after aging exceeds the standard; in comparative example 7, when the amount of the metal deactivator was too much, the thermal elongation of the resulting material was not satisfactory; in comparative example 8, using a coated inorganic flame retardant, the resulting material broke in cross-linking.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition is characterized by comprising the following components in parts by weight:
the inorganic flame retardant is an inorganic flame retardant which is not subjected to coating treatment, and the average particle size of the inorganic flame retardant is 0.1-5 mu m.
2. The B1-grade ultraviolet crosslinking low-smoke halogen-free insulation composition as claimed in claim 1, wherein the metal passivator is a hydrazide metal passivator and/or an oxime metal passivator.
3. The B1-grade ultraviolet light crosslinking low smoke zero halogen insulation composition of claim 1, wherein the hydrazide-type metal passivator is N, N' -bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and/or 2,2-oxamido-bis [ ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ] propionate.
4. The B1-level ultraviolet crosslinking low-smoke halogen-free insulation composition as claimed in claim 1, wherein the inorganic flame retardant is magnesium hydroxide and/or aluminum hydroxide.
5. The B1-grade ultraviolet crosslinking low-smoke halogen-free insulation composition according to claim 1, wherein the photoinitiator is tetramethyl-benzophenone and/or methyl o-benzoylbenzoate.
6. The B1-level ultraviolet crosslinking low-smoke halogen-free insulation composition as claimed in claim 1, wherein the elastomer is one or more of ethylene-octene copolymer, ethylene-vinyl acetate copolymer or ethylene-acrylate copolymer; the density of the elastomer is 0.85-0.97 g/cm 3 (ii) a The melt index of the elastomer is 0.5-10 g/10min at 190 ℃ under the test condition of 2.16 kg.
7. The B1-grade ultraviolet crosslinking low-smoke halogen-free insulation composition as claimed in claim 1, wherein the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant or thioether antioxidant.
8. The B1-level ultraviolet crosslinking low-smoke halogen-free insulation composition according to claim 1, which is characterized by further comprising 1-5 parts of a processing aid.
9. A method for preparing the B1-level ultraviolet crosslinking low-smoke zero-halogen insulation composition as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
uniformly mixing the inorganic flame retardant, the elastomer, the antioxidant, the metal deactivator, the photoinitiator and the processing aid, and carrying out mixing and plasticizing granulation by a reciprocating machine to obtain the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition.
10. Use of the B1-grade uv-crosslinked low-smoke halogen-free insulation composition according to any of claims 1 to 8 in the preparation of electrical cables.
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| CN108292539A (en) * | 2015-12-18 | 2018-07-17 | 博里利斯股份公司 | It include the cable of the foaming layer containing polyolefin polymer and foaming agent |
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