CN115895098B - B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition and preparation method and application thereof - Google Patents
B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition and preparation method and application thereof Download PDFInfo
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- CN115895098B CN115895098B CN202211663640.1A CN202211663640A CN115895098B CN 115895098 B CN115895098 B CN 115895098B CN 202211663640 A CN202211663640 A CN 202211663640A CN 115895098 B CN115895098 B CN 115895098B
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000004132 cross linking Methods 0.000 title claims abstract description 41
- 239000000779 smoke Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 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 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 150000003568 thioethers Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 239000000155 melt Substances 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
- 238000009826 distribution Methods 0.000 claims description 2
- 238000002156 mixing Methods 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
- 238000012360 testing method Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 230000032683 aging Effects 0.000 abstract description 21
- 239000000463 material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008859 change Effects 0.000 description 12
- 239000006078 metal deactivator Substances 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000002923 oximes Chemical class 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 238000009472 formulation 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 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
- 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
- GYOZZWNPRKAISG-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C GYOZZWNPRKAISG-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect 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
- 230000007547 defect Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000006872 improvement Effects 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
- 239000005022 packaging material Substances 0.000 description 1
- 239000002530 phenolic antioxidant 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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 insulating composition comprises the following components in parts by weight: 80-120 parts of inorganic flame retardant; 40-60 parts of an elastomer; 1-2 parts of an antioxidant; 1-4 parts of metal passivating agent; 2-6 parts of photoinitiator; the average particle diameter of the inorganic flame retardant is 0.1-5 mu m. The insulating composition is added with an inorganic flame retardant with specific average particle size in a system, and is matched with a metal passivating agent to form a network complex, ultraviolet light crosslinking is performed under the condition of a photoinitiator, secondary irradiation crosslinking is not needed, and the insulating composition simultaneously meets B1-level flame retardance and has good mechanical property and ageing resistance.
Description
Technical Field
The invention relates to the technical field of cable insulation materials, in particular to a B1-level ultraviolet crosslinking low-smoke halogen-free insulation composition, a preparation method and application thereof.
Background
The cross-linked cable has excellent high temperature resistance, higher long-term use temperature and longer service life. In the prior art, radiation crosslinking is mainly adopted to prepare the insulating cable material, for example, CN 110776690A discloses a 105 ℃ B1-level flame-retardant radiation crosslinked insulating cable material, and the obtained insulating material has the advantages of low heat release amount, small smoke generation amount, good shell forming, no dripping and can be used for considering flame retardance, mechanical property and processing property. However, since the insulating material for electric cables is additionally 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 used for coating an inorganic flame retardant to improve the ageing resistance of the material, while uncoated inorganic flame retardants are generally used, and the ideal ageing resistance cannot be achieved under the condition of high addition amount of the uncoated inorganic flame retardant.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art, and provides a B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition, wherein the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition takes an inorganic flame retardant without coating as a raw material, has good ageing resistance and good mechanical property, and meets the B1-level flame retardance.
The invention further aims at providing a preparation method of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition.
The invention further aims at providing application of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition comprises the following components in parts by weight:
80-120 parts of inorganic flame retardant;
40-60 parts of an elastomer;
1-2 parts of an antioxidant;
1-4 parts of metal passivating agent;
2-6 parts of photoinitiator;
the inorganic flame retardant is an inorganic flame retardant which is not coated, and the average particle size of the inorganic flame retardant is 0.1-5 mu m.
According to the invention, the metal passivating agent with specific content is added into the elastomer and combined with the uncoated inorganic flame retardant with specific particle size, so that the material has weaker covering property to ultraviolet light, ultraviolet light projection is facilitated, the metal passivating agent can effectively reduce the catalytic activity of metal ions in the inorganic flame retardant, the prepared material has better ageing resistance, and meanwhile, the prepared material has better mechanical property and meets the B1-level flame retardance, and the inorganic flame retardant adopted by the invention does not need coating treatment, and has simple process and lower cost.
Preferably, the metal passivating agent is a hydrazide metal passivating agent and/or an oxime metal passivating agent.
More preferably, the metal deactivator is a hydrazide-based metal deactivator.
Specifically, the hydrazide metal passivating agent 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. If 0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1.0μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm, is preferred, any of the above values is the upper or lower range.
Preferably, the photoinitiator is tetramethyl-benzophenone and/or methyl o-benzoyl benzoate.
Preferably, the inorganic flame retardant is magnesium hydroxide and/or aluminum hydroxide.
Preferably, the elastomer is a polyolefin elastomer.
Specifically, the polyolefin elastomer is one or more of ethylene-octene copolymer, ethylene-vinyl acetate copolymer or ethylene-acrylic ester copolymer.
Preferably, the elastomer has a density of 0.85 to 0.97g/cm 3.
Preferably, the melt index of the elastomer is 0.5 to 10g/10min at 190℃under 2.16kg test conditions. If 0.5 g/10min、1.0 g/10min、1.5 g/10min、2.0 g/10min、2.5 g/10min、3.0 g/10min、3.5 g/10min、4.0 g/10min、4.5 g/10min、5.0 g/10min、5.5 g/10min、6.0 g/10min、6.5 g/10min、7.0 g/10min、7.5 g/10min、8.0 g/10min、8.5 g/10min、9.0 g/10min、9.5 g/10min、10 g/10min, is preferred, any of the above values is the upper or lower range.
Preferably, the melt index of the elastomer is measured in GB/T3682-2000.
Preferably, the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition further comprises 1-5 parts of processing aid.
Preferably, the processing aid is a lubricant.
More preferably, the lubricant is one or more of fluorine-containing lubricant, stearate lubricant, ester lubricant or silicone lubricant.
In the present invention, the antioxidant may be a commonly used antioxidant such as hindered phenol antioxidant, phosphite antioxidant, thioether antioxidant, etc.; more preferably, an antioxidant combination is adopted; for example, it is a combination of both 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 hindered phenol antioxidant and thioether antioxidant with the mass ratio of (1-3): 1. The inventor finds that under the combination, 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 combustion growth rate is exponentially reduced.
Specifically, the hindered phenol antioxidant is one or more of beta (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate or 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) propionate ] pentaerythritol ester or diethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] methyl ester.
The phosphite antioxidant is one or more of 2, 4-di-tert-butylphenol, bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol phosphite or 627A.
The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecyl thiopropyl.
The invention also provides a preparation method of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition, which comprises the following steps:
Inorganic flame retardant, elastomer, antioxidant, metal passivator, photoinitiator and processing aid are uniformly mixed, and the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition is obtained through mixing, plasticizing and granulating by a reciprocating machine.
Preferably, the temperature of the reciprocating machine is 100-200 ℃.
The invention also protects the application of the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition in the preparation of the electric 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 is prepared by adding an uncoated inorganic flame retardant with specific particle size into a base material, combining a metal passivating agent with specific content and a photoinitiator, reducing the ultraviolet light covering property, avoiding modifying the inorganic flame retardant, and matching the inorganic flame retardant, the photoinitiator and the metal passivating agent as a whole, wherein 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 ageing resistance, and improves the production efficiency.
Detailed Description
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 apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The following examples and comparative examples were prepared from the following raw materials:
An elastomer:
Elastomer a: ethylene-vinyl acetate copolymer, EVA 00320, density 0.92g/cm 3, melt index 1g/10min, available from China petrochemical, yangzi petrochemical Co;
elastomer B: ethylene-octene copolymer, POE80, density 0.856 g/cm 3, melt index 1g/10min, available from Shulman plastics company;
elastomer C: ethylene-vinyl acetate copolymer, EVA 0014, density of 0.92 g/cm 3, melt index of 0.3g/10min, available from China petrochemical, yangzi petrochemical Co., ltd;
Inorganic flame retardant:
Uncoated magnesium hydroxide a: the average particle size was 0.1 μm, MDH-F4, available from Liaoning Yingkou magnesium Co., ltd;
uncoated magnesium hydroxide B: average particle size of 0.3 μm, MDH-F5, available from Liaoning Yingkou magnesium Co Ltd
Uncoated magnesium hydroxide C: the average particle size was 1.9 μm, MDH-F6, available from Liaoning Yingkou magnesium Co., ltd;
uncoated magnesium hydroxide D: the average particle size was 5 μm, MDH-F7, available from Liaoning Yingkou magnesium Co., ltd;
Uncoated magnesium hydroxide E: the average particle size was 10 μm, MDH-F8, available from Liaoning Yingkou magnesium Co., ltd;
Uncoated magnesium hydroxide F: the average particle size was 0.05 μm, MDH-F9, available from Liaoning Yingkou magnesium Co., 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 the magnesium hydroxide is purchased from Liaoning Yingkou magnesium industry Co;
Uncoated aluminium hydroxide a: the average particle size was 4 μm, ATH-1, available from China aluminum industry group Co., ltd;
and (3) a photoinitiator:
Photoinitiator a: tetraphenyl-benzophenone CHEMCURE-PM, purchased from dongguan Hengqiao trade limited;
Photoinitiator B: methyl o-benzoyl benzoate, CHEMCURE-65, purchased from Dongguan Hengqiao trade limited;
Metal passivating agent:
metal deactivator a: hydrazide metal deactivator, N, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, RIANOX MD-1024, available from Tianjin An Long technologies Co., ltd;
metal passivating agent B: oxime metal deactivators, acetone carboxymethyl oxime, purchased from Shanghai Yi En chemistry;
An antioxidant:
Antioxidant A: hindered phenolic antioxidants and thioether antioxidants in the following ratio 1:1 proportion; wherein, the hindered phenol antioxidant is antioxidant 1010, the thioether antioxidant is antioxidant DSTDP, and the hindered phenol antioxidant and the thioether antioxidant are all sold in the market;
and (3) an antioxidant B: antioxidant 1010, commercially available;
and (3) a lubricant: silicone master batches, commercially available.
The present invention will be described in detail with reference to examples.
The following examples and comparative examples each prepared a cable insulation composition by the following method, and the components were weighed according to the weight ratios of tables 1 to 3; the method comprises the following specific steps:
Inorganic flame retardant, elastomer, antioxidant, metal passivator, photoinitiator and processing aid are uniformly mixed, and are mixed, plasticized and granulated by a reciprocating machine at 100-200 ℃ to obtain the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition.
Table 1 formulation (parts by weight) of the B1 ultraviolet crosslinking Low-smoke halogen-free insulation composition of examples 1 to 7
Table 2 formulation (parts by weight) of the B1 ultraviolet crosslinking low smoke halogen-free insulation composition of examples 8 to 16
Table 3 formulation (weight portion) of B1-grade ultraviolet light crosslinking low smoke halogen-free insulating composition of comparative examples 1-8
Performance test:
Thermal elongation performance test method: the B1-grade ultraviolet crosslinking low-smoke halogen-free flame retardant insulating composition prepared in the examples and the comparative examples is prepared into a finished cable which is tested according to GB/T2951.21-2008 standard; the thermal elongation rate is less than or equal to 175 percent in GB/T2951.21-2008 standard, wherein the lower the thermal elongation rate is, the higher the crosslinking degree is; tensile strength and elongation at break test method: the B1-grade ultraviolet crosslinking low-smoke halogen-free flame retardant insulating composition prepared in the examples and the comparative examples is prepared into a finished cable which is tested according to GB/T1040.3-2006 standard; the initial tensile strength is more than or equal to 9MPa in GB/T1040.3-2006 standard, and the initial elongation at break is more than or equal to 125 percent and reaches the standard; the thermal ageing performance test method comprises the following steps: the B1-level ultraviolet crosslinking low-smoke halogen-free flame retardant insulating compositions prepared in the examples and the comparative examples are subjected to ultraviolet crosslinking, and then tested according to GB/T32129-2015 standard, wherein the tensile strength change rate before and after heat aging is +/-25% and the elongation at break change rate is +/-25% and reach the standard; the B1-level ultraviolet light crosslinking low-smoke halogen-free flame retardant insulating composition prepared in the embodiment and the comparative example is prepared into a finished cable, and the finished cable meets the thermal extension performance requirement and the mechanical performance requirement and is tested according to JB/T10491.1-2004 standard; the tensile strength change rate before and after heat aging is within +/-30% and the elongation at break change rate is within +/-30% in JB/T10491.1-2004 standard; when the B1-level ultraviolet crosslinking low-smoke halogen-free flame-retardant insulating composition is prepared into a finished cable and the heat release rate peak value, the total heat release amount, the total smoke generation amount and the combustion growth rate index in GB/T31247-2014 are all qualified, the material passes the B1-level flame-retardant requirement; in GB/T31247-2014, the total heat release amount is less than or equal to 15MJ, and the total smoke yield is less than or equal to 50m 2
; The combustion growth rate index is less than or equal to 150W/s. The results of the performance test of the B1 uv-crosslinking low smoke halogen-free insulating compositions in examples and comparative examples are shown in tables 4 to 6.
Table 4 results of the performance tests of examples 1 to 7
TABLE 5 results of Performance test of examples 8-16
TABLE 6 results of Performance test of comparative examples 1 to 8
As can be seen from tables 4 and 5, the low smoke halogen-free insulating composition prepared by the invention has the change rate of tensile strength and elongation at break not more than 25% before and after aging, the finished cable prepared by the composition 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 rate of the tensile strength and the elongation at break is not more than 30% after heat aging, and the thermal elongation is not more than 175%.
As can be seen from examples 1 to 4, when the average particle diameter of the inorganic flame retardant is 0.3 to 1.9. Mu.m, the overall properties of the obtained material are better, the composition of the material obtained in example 1 and the rate of change of elongation at break before and after aging of the finished cable are close to the critical value, and the flame retardant property of the material obtained in example 4 has a combustion growth rate index close to the critical value, so that the average particle diameter of the inorganic flame retardant is preferably 0.3 to 1.9. Mu.m. As can be seen from examples 2 and 8, when the metal passivating agent is a hydrazide metal passivating agent, the prepared material has better comprehensive performance, and the change rate of the performance of the composition and the finished cable before and after aging is obviously better than that of the material prepared by adopting an oxime metal passivating agent. It can be seen from examples 2 and 10 that when hindered phenol-based antioxidants and thioether-based antioxidants are used, the following are used at 1: when the antioxidant is composed of 1 proportion, the comprehensive performance of the prepared material is better, the performance change rate of the composition prepared in the example 2 and the finished cable before and after aging is obviously better than that of the composition prepared in the example 10, and the combustion 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 0.5-10 g/10min, the initial elongation at break of the prepared material is significantly improved, the smoke yield and the burning growth rate index are significantly reduced, and the performance is better.
As can be seen from Table 6, in comparative example 1, when the elastomer amount is too small, the mechanical properties of the prepared material are poor, the initial elongation at break is only 100%, and the performance requirements cannot be satisfied; 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-grade flame retardant cannot be satisfied; in comparative example 3, when the amount of the inorganic flame retardant is too large, 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 diameter of the inorganic flame retardant is too large, the mechanical properties of the prepared material cannot be poor, and the requirements cannot be met; in comparative example 5, when the average particle diameter of the inorganic flame retardant is too small, the aging performance of the prepared material is poor, and the change rate of the tensile strength before and after aging and the change rate of the elongation at break before and after aging both exceed 30% and do not meet the requirements; in comparative example 6, when the metal deactivator is used in a small amount, the metal deactivator cannot be matched with the inorganic flame retardant, the aging catalysis effect of metal ions in the inorganic flame retardant on the material cannot be reduced, and the tensile strength and the elongation at break change rate of the prepared material after aging exceed the standards; in comparative example 7, when the metal deactivator is used in an excessive amount, the thermal elongation of the resulting material does not satisfy the requirement; in comparative example 8, a coated inorganic flame retardant was used, and the resulting material was broken in crosslinking.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
1. The B1-level ultraviolet light 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 coated, and the average particle size of the inorganic flame retardant is 0.1-5 mu m; the metal passivating agent is N, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine; the B1-level ultraviolet crosslinking low-smoke halogen-free insulating composition does not contain a flame retardant synergist; the elastomer is one or more of ethylene-octene copolymer, ethylene-vinyl acetate copolymer or ethylene-acrylic ester copolymer.
2. The B1-stage ultraviolet light crosslinking low smoke zero halogen insulation composition of claim 1, wherein the inorganic flame retardant is magnesium hydroxide and/or aluminum hydroxide.
3. The B1-stage uv-crosslinking low smoke halogen-free insulation composition of claim 1, wherein the photoinitiator is tetramethyl-benzophenone and/or methyl o-benzoyl benzoate.
4. The B1 stage uv crosslinked low smoke halogen free insulation composition of claim 1 wherein the elastomer has a density of 0.85 to 0.97g/cm 3; the melt index of the elastomer under the test condition of 2.16kg at 190 ℃ is 0.5-10 g/10min.
5. The B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition according to claim 1, wherein the antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants and thioether antioxidants.
6. The B1-stage uv-crosslinked low smoke halogen-free insulation composition of claim 1, further comprising 1-5 parts of a processing aid.
7. The method for preparing the B1-stage ultraviolet crosslinking low-smoke halogen-free insulating composition as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
Inorganic flame retardant, elastomer, antioxidant, metal passivator, photoinitiator and processing aid are uniformly mixed, and the B1-level ultraviolet light crosslinking low-smoke halogen-free insulating composition is obtained through mixing, plasticizing and granulating by a reciprocating machine.
8. Use of the B1-stage uv-cross-linked low smoke halogen-free insulation composition according to any one of claims 1-6 in the preparation of an electrical distribution cable.
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| CN112759821A (en) * | 2020-12-28 | 2021-05-07 | 金发科技股份有限公司 | Ultraviolet crosslinking type low-smoke halogen-free polyolefin and preparation method and application thereof |
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| CN113480797A (en) * | 2021-07-08 | 2021-10-08 | 合肥工业大学 | Pre-crosslinking-resistant one-step silane crosslinked polyethylene insulating material for cables of 35kV and below, and environment-friendly preparation method and application thereof |
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| CN112759821A (en) * | 2020-12-28 | 2021-05-07 | 金发科技股份有限公司 | Ultraviolet crosslinking type low-smoke halogen-free polyolefin and preparation method and application thereof |
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