CN113817260A - Special low-smoke halogen-free flame-retardant sheath material for polymer-based optical fiber and preparation method thereof - Google Patents
Special low-smoke halogen-free flame-retardant sheath material for polymer-based optical fiber and preparation method thereof Download PDFInfo
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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 80
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000013307 optical fiber Substances 0.000 title claims abstract description 56
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 239000000779 smoke Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 44
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 238000012360 testing method Methods 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 26
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 21
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 6
- -1 polyethylene maleic anhydride Polymers 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000012796 inorganic flame retardant Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000013308 plastic optical fiber Substances 0.000 claims description 4
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical group 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract 3
- 238000009472 formulation Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 6
- 229920006132 styrene block copolymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- DBKFYOISCCPYTQ-UHFFFAOYSA-K C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O Chemical compound C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O DBKFYOISCCPYTQ-UHFFFAOYSA-K 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- JBIWRUYUONRXCL-UHFFFAOYSA-N but-3-enyl trimethyl silicate Chemical compound C(=C)CCO[Si](OC)(OC)OC JBIWRUYUONRXCL-UHFFFAOYSA-N 0.000 description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- GYLXWHLPLTVIOP-UHFFFAOYSA-N ethenyl(2,2,2-trimethoxyethoxy)silane Chemical compound COC(OC)(OC)CO[SiH2]C=C GYLXWHLPLTVIOP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- 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 discloses a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by weight: ethylene-vinyl acetate copolymer: 30-60 parts of low-melting-range linear low-density polyethylene: 10-20 parts, oil-extended SEBS: 15-30 parts of a compatilizer: 10-30 parts of filler type flame retardant: 100-150 parts of aluminum phosphinate flame retardant: 10-25 parts of a silane coupling agent: 1-2 parts of silicone master batch: 2-5 parts of compound antioxidant: 0.3-0.8 part by weight, through stiring, mixing, extrusion step make, this sheath material have shrink rate low, processing temperature low, extrusion molding speed fast (not less than 200 m/min), rejection rate low, high low temperature resistant cycle good, can pass the single vertical combustion test of the fine line of optic fibre, this sheath material can be very good to protect polymer-based optic fibre from damaging, the surface of the optical cable is smooth and fine, the low smoke and zero halogen flame retardant sheath material prepared through meticulous formulation selection and processing in this invention carries on the outer sheath to process to polymer-based optic fibre, the temperature is lower, the pressure is smaller.
Description
Technical Field
The invention belongs to the field of processing of high polymer materials, relates to a sheath material and a preparation method thereof, and particularly relates to a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber and a preparation method thereof.
Background
In 1966, high roll first proposed the concept that optical fiber can be used for communication transmission, and with the development of technology, optical fiber is becoming more practical, and since the transmission loss of light in optical fiber is much lower than that of electricity in electric wire, optical fiber is more advantageous for long distance information transmission, and optical fiber and optical cable are becoming the best carriers for data transmission. The main body of the core material of the glass-based optical fiber is silicon dioxide, and a very small amount of other materials are doped in the silicon dioxide, which occupies more than 98% of the market at present, and the polymer-based optical fiber is not as good as the glass-based material in transmission characteristics, but has other advantages: they are easier to produce and more resistant to mechanical vibrations. Thus, it can be transmitted over short distances, now using the SI level, the GI level may be gradually replaced. The improved polymer-based optical fiber has larger wave width and smaller attenuation and can have certain use opportunity in a small range, the polymer-based optical fiber mainly has the advantages that the methyl methacrylate optical fiber can resist 105 degrees, the polycarbonate optical fiber can resist 125 degrees, and the polyimide optical fiber can resist 250 degrees, but the price is too high, and the market is not advantageous. Although the surface of the polymer-based optical fiber is provided with a layer of low-refractive index material, when the optical fiber is extruded into a sheath, the processing temperature and the extrusion pressure of the outer sheath are reduced as much as possible, and the shrinkage rate is small, so that the attenuation of the polymer-based optical fiber in the molding process and the later use stage is reduced, and the transmission characteristic is not influenced. With the development of 5G technology, polymer-based optical fibers have indeed found application in certain applications. Users expect that the optical fiber cable can also meet the related technical conditions of low-smoke halogen-free flame retardation, and the development of the low-smoke halogen-free flame retardation sheathing material for the polymer-based optical fiber for matching with the user requirements becomes a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to solve the technical problem that aiming at the defects in the prior art, the invention provides the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber and the preparation method thereof, the sheath material has the advantages of low shrinkage, low processing temperature, high extrusion molding speed (not less than 200 m/min), low rejection rate, good high and low temperature cycle resistance, and can pass a single vertical combustion test of an optical fiber fine wire, the sheath material can well protect the polymer-based optical fiber from being damaged, and the surface of the optical cable is smooth and fine.
The technical scheme for solving the technical problems is as follows:
a low-smoke halogen-free flame-retardant sheath material special for a polymer-based optical fiber comprises the following raw materials in parts by mass:
30-60 parts of ethylene-vinyl acetate copolymer,
10-20 parts of low-melting-range linear low-density polyethylene,
15-30 parts of oil-extended SEBS,
10-30 parts of a compatilizer,
100 portions and 150 portions of filler type flame retardant,
10-25 parts of an aluminum phosphinate flame retardant,
1-2 parts of a silane coupling agent,
2-5 parts of silicone master batch,
0.3-0.8 part of compound antioxidant.
The invention further defines the technical scheme as follows:
in the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the melt index of an ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the melt index of low-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the oil-extended SEBS is hydrogenated styrene-ethylene-butadiene-styrene copolymer, the oil-extended amount is 25-40%, and the SEBS is a linear structure with the mass ratio of styrene to butylene block copolymer in the SEBS being less than 20%.
In the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the compatilizer is one or more of polyolefin elastomer maleic anhydride graft, polyethylene maleic anhydride graft and ethylene-vinyl acetate copolymer maleic anhydride graft.
In the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the particle size of the filler type flame retardant is 0.5-5 mu m, and the filler type flame retardant is aluminum hydroxide, magnesium hydroxide inorganic flame retardant or a mixture of the aluminum hydroxide and the magnesium hydroxide inorganic flame retardant.
In the low-smoke halogen-free flame-retardant sheath material special for the polymer-based optical fiber, the particle size of the aluminum alkyl phosphinate flame retardant is 1-10 mu m, the aluminum phosphinate flame retardant is aluminum alkyl phosphinate, and preferably, the alkyl is phenyl, ethyl or butyl.
In the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, the silane coupling agent is a vinyl silane coupling agent, an aminosilane coupling agent or a mixture of the vinyl silane coupling agent and the aminosilane coupling agent;
the compound antioxidant is a mixture of a main antioxidant and an auxiliary antioxidant, and the main antioxidant comprises the following components in percentage by mass: secondary antioxidant = 1: 0.8-2, wherein: the main antioxidant is a multi-hindered phenol type serving as the main antioxidant, and the auxiliary antioxidant is a phosphite ester auxiliary antioxidant or dialkyl thiodipropionate.
In the low-smoke halogen-free flame-retardant sheath material special for the polymer-based optical fiber, the silicone master batch is a medium-high molecular weight polydimethylsiloxane dispersed master batch taking medium-high molecular weight polydimethylsiloxane or polyethylene as a carrier.
The invention also designs a preparation method of the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber, which comprises the following steps:
step (1): adding the filler type flame retardant into a high-speed mixer at the speed of 1200-1400 rpm according to the proportion, stirring at a high speed for 2-5 minutes, uniformly mixing, spraying the silane coupling agent into the high-speed mixer within 1 minute by adopting a spraying method, and continuously stirring at a high speed for 2-5 minutes to fully and uniformly mix the silane coupling agent and the filler type flame retardant to obtain a treated filler type flame retardant for later use;
step (2): adding ethylene-vinyl acetate copolymer, low-melting-range linear low-density polyethylene, oil-filled SEBS, a compatilizer, the filler type flame retardant treated in the step (1), an aluminum phosphinate flame retardant, silicone master batch and a compound antioxidant into an internal mixer, and mixing at the mixing temperature of 120-140 ℃ for 8-15 minutes;
and (3): and (3) adding the mixed material obtained in the step (2) into a double-screw/single-screw double-stage extrusion granulator, and controlling the extrusion granulation temperature at 130-145 ℃ to obtain the special low-smoke halogen-free flame-retardant sheath material for the polymer optical fiber.
The invention has the beneficial effects that:
the low-smoke halogen-free flame-retardant sheath material prepared by meticulous formula selection and processing has lower temperature and lower pressure when the outer sheath of the polymer-based optical fiber is processed, and can meet the requirement of a single vertical combustion test of a fine wire optical cable.
The optical fiber sheath material produced by optimizing the materials and the formula and adopting a proper process has the advantages of low shrinkage rate, low processing temperature, high extrusion molding speed, low influence on internal polymer optical fibers, small attenuation, small influence on the processing of the optical fibers and capability of passing a single vertical combustion test of fine optical fiber wires.
Detailed Description
Example 1
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 33): 35 parts, low melting range linear low density polyethylene: 12 parts, oil extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 15 parts of a compatilizer: ethylene-vinyl acetate copolymer maleic anhydride graft material: 12 parts, filler type flame retardant aluminum hydroxide: 100 parts of aluminum phenylphosphinate flame retardant: 12 parts of vinyl trimethoxy ethoxysilane: 1.5 parts of medium and high molecular weight polydimethylsiloxane master batch: 2.5 parts, 1010 antioxidant: 0.3 part, DLTDP: 0.3 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 2
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 33): 33 parts, low melting range linear low density polyethylene: 12 parts, oil extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 15 parts of a compatilizer: 4 parts of polyolefin elastomer maleic anhydride graft material and ethylene-vinyl acetate copolymer maleic anhydride graft material: 10 parts of filler type flame retardant aluminum hydroxide: 100 parts of aluminum ethyl phosphinate flame retardant: 11 parts of vinyltrimethoxyethoxysilane: 1.2 parts of medium and high molecular weight polydimethylsiloxane master batch: 3 parts, 1010 antioxidant: 0.3 part of + DSTDP 0.36 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 3
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 33): 35 parts, low melting range linear low density polyethylene: 12 parts, oil extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 16 parts of a compatilizer: ethylene-vinyl acetate copolymer maleic anhydride graft material: 12 parts, filler type flame retardant aluminum hydroxide: 85 parts of magnesium hydroxide: 15 parts of aluminum ethyl phosphinate flame retardant: 11 parts of vinyl trimethoxy ethoxy silane, 1.8 parts of medium and high molecular weight polydimethylsiloxane master batch: 3.5 parts, 1010 antioxidant: 0.3 part + PS168:0.27 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 4
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 28): 32 parts, low melting range linear low density polyethylene: 10 parts, oil-extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 18 parts of a compatilizer: 5 parts of polyethylene maleic anhydride grafting material and ethylene-vinyl acetate copolymer maleic anhydride grafting material: 12 parts, filler type flame retardant aluminum hydroxide: 100 parts of aluminum ethyl phosphinate flame retardant: 11 parts of vinyltrimethoxyethoxysilane: 1.2 parts of medium and high molecular weight polydimethylsiloxane master batch: 3 parts, 1076 antioxidant: 0.4 part + PS168: 0.32 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 5
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 33): 30 parts, low melting range linear low density polyethylene: 100 parts, oil extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 30 parts of a compatilizer: ethylene-vinyl acetate copolymer maleic anhydride graft material: 10 parts of filler type flame retardant aluminum hydroxide: 100 parts of aluminum phenylphosphinate flame retardant: 18 parts of vinyltrimethoxyethoxysilane: 1.5 parts of medium and high molecular weight polydimethylsiloxane: 1.8 parts, 1010 antioxidant: 0.3 part + DSTDP: 0.32 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 6
The embodiment provides a special low-smoke halogen-free flame-retardant sheath material for a polymer-based optical fiber, which comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 33): 30 parts, low melting range linear low density polyethylene: 16 parts, oil extended SEBS (styrene-ethylene-butylene-styrene block copolymer): 22 parts of a compatilizer: polyolefin elastomer graft material: 12 parts, filler type flame retardant aluminum hydroxide: 100 parts of aluminum phenylphosphinate flame retardant: 12 parts of vinyl trimethoxy ethoxysilane: 2 parts of medium and high molecular weight polydimethylsiloxane master batch: 3 parts, 1010 antioxidant: 0.3 part + DSTDP: 0.3 part.
In this embodiment: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
In this embodiment: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to the GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
In this embodiment: the oil-extended SEBS is hydrogenated styrene-butadiene-styrene copolymer with oil-extended amount of 25-40%, and is linear, and the styrene content in the styrene ethylene/butylene block copolymer is not more than 20%.
Example 7
The embodiment provides a preparation method of the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber in the embodiments 1 to 6, which specifically comprises the following steps:
step (1): adding the filler type flame retardant into a high-speed mixer at the speed of 1200-1400 rpm according to the proportion, stirring at a high speed for 2-5 minutes, uniformly mixing, spraying the silane coupling agent into the high-speed mixer within 1 minute by adopting a spraying method, and continuously stirring at a high speed for 2-5 minutes to fully and uniformly mix the silane coupling agent and the filler type flame retardant to obtain a treated filler type flame retardant for later use;
step (2): adding ethylene-vinyl acetate copolymer, low-melting-range linear low-density polyethylene, oil-filled SEBS, a compatilizer, the filler type flame retardant treated in the step (1), an aluminum phosphinate flame retardant, silicone master batch and a compound antioxidant into an internal mixer, and mixing at the mixing temperature of 120-140 ℃ for 8-15 minutes;
and (3): and (3) adding the mixed material obtained in the step (2) into a double-screw/single-screw double-stage extrusion granulator, and controlling the extrusion granulation temperature at 130-145 ℃ to obtain the special low-smoke halogen-free flame-retardant sheath material for the polymer optical fiber.
Comparative example
The sheath material of the comparative example comprises the following raw materials in parts by mass:
ethylene-vinyl acetate copolymer (EVA VA 28): 35 parts of metallocene low-density polyethylene (melting range 95-140 ℃): 12 parts, POE, i.e. ethylene-octene copolymer: 15 parts of ethylene-vinyl acetate copolymer maleic anhydride graft material: 12 parts, filler type flame retardant aluminum hydroxide: 100 parts of aluminum phenylphosphinate flame retardant: 12 parts of vinyl trimethoxy ethoxysilane: 1.5 parts of medium and high molecular weight polydimethylsiloxane: 2.5 parts, 1010 antioxidant: 0.3 part of DLTDP and 0.3 part of DLTDP.
A jacket material was prepared by the same preparation method as in example 1.
The performance indexes of the sheath materials in examples 1-6 and comparative example are shown in Table 1;
TABLE 1 indices of the respective products
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example | |
| Tensile breaking strength Mpa | 10.7 | 10.6 | 12.0 | 10.7 | 11.0 | 12.4 | 12.9 |
| Elongation at break% | 180 | 180 | 155 | 170 | 160 | 155 | 165 |
| Specific gravity of | 1.45 | 1.46 | 1.45 | 1.47 | 1.45 | 1.44 | 1.44 |
| Hardness (Shao D) | 41 | 41 | 43 | 45 | 43 | 48 | 53 |
| Oxygen index LOI% | 42 | 42 | 43 | 42 | 47 | 43 | 43 |
| Melt index g/10min | 21 | 20 | 19 | 21 | 23 | 21 | 11 |
| UL 94 V0 | By passing | By passing | By passing | By passing | By passing | By passing | By passing |
| The highest temperature is 145 DEG C | Is smooth and smooth | Is smooth and smooth | Is smooth and smooth | Is smooth and smooth | Is smooth and smooth | Is smooth and smooth | Coarse food |
| Machining Torque N M (30RPM) | 32 | 33 | 34 | 35 | 34 | 33 | 165 |
| Conclusion | Can be used | Can be used | Can be used | Can be used | Can be used | Can be used | Is not available |
Compared with the comparative example in which metallocene low-density polyethylene (melting range 95-140 ℃) and POE (ethylene-octene copolymer) are adopted as raw materials, low-melting-range linear low-density polyethylene and oil-filled SEBS are selected for the sheath material in the embodiment 1, the sheath material prepared in the embodiment 1 is high in elongation at break, smooth and available when discharged at the highest temperature of 145 ℃, the required processing torque is small, the sheath material can adapt to different machine tools, the application range is wide, the oil-filled SEBS not only has excellent aging resistance, but also has better mechanical new energy, and the mechanical property of the sheath material is obviously improved even exceeds that of vulcanized rubber in the elongation.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (10)
1. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber is characterized by comprising the following raw materials in parts by mass:
30-60 parts of ethylene-vinyl acetate copolymer,
10-20 parts of low-melting-range linear low-density polyethylene,
15-30 parts of oil-extended SEBS,
10-30 parts of a compatilizer,
100 portions and 150 portions of filler type flame retardant,
10-25 parts of an aluminum phosphinate flame retardant,
1-2 parts of a silane coupling agent,
2-5 parts of silicone master batch,
0.3-0.8 part of compound antioxidant.
2. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the melt index of the ethylene-vinyl acetate copolymer is 0.5-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, wherein, the content of vinyl acetate accounts for 18-33% of the total weight of the ethylene-vinyl acetate copolymer according to the mass ratio.
3. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the melt index of the low-melting-range linear low-density polyethylene is 3-20g/10min, and the test conditions are as follows according to GB/T3682-2000 method: the temperature is 190 ℃, the load is 2.16KG, the melting range interval is 95-115 ℃, and the DSC measurement is carried out under the test condition.
4. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the oil-extended SEBS is a hydrogenated styrene-butadiene-styrene copolymer, the oil-extended amount is 25-40%, the SEBS is linear, and the percentage content of styrene in the styrene ethylene/butylene block copolymer is not more than 20%.
5. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the compatilizer is one or more of polyolefin elastomer maleic anhydride graft, polyethylene maleic anhydride graft and ethylene-vinyl acetate copolymer maleic anhydride graft.
6. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the particle size of the filler type flame retardant is 0.5-5 mu m, and the filler type flame retardant is aluminum hydroxide, magnesium hydroxide inorganic flame retardant or a mixture of the aluminum hydroxide and the magnesium hydroxide inorganic flame retardant.
7. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the particle size of the aluminum phosphinate flame retardant is 1-10 mu m, and the aluminum phosphinate flame retardant is aluminum alkyl phosphinate.
8. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the silane coupling agent is a vinyl silane coupling agent, an aminosilane coupling agent or a mixture of the vinyl silane coupling agent and the aminosilane coupling agent;
the compound antioxidant is a mixture of a main antioxidant and an auxiliary antioxidant, and the main antioxidant comprises the following components in percentage by mass: secondary antioxidant = 1: 0.8-2, wherein: the main antioxidant is a multi-hindered phenol type serving as a main antioxidant, and the auxiliary antioxidant is a phosphite ester auxiliary antioxidant or dialkyl thiodipropionate.
9. The special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to claim 1, which is characterized in that: the silicone master batch is a medium-high molecular weight polydimethylsiloxane dispersed master batch taking medium-high molecular weight polydimethylsiloxane or polyethylene as a carrier.
10. The preparation method of the special low-smoke halogen-free flame-retardant sheath material for the polymer-based optical fiber according to any one of claims 1 to 9, which is characterized by comprising the following steps:
step (1): adding the filler type flame retardant into a high-speed mixer at the speed of 1200-1400 rpm according to the proportion, stirring at a high speed for 2-5 minutes, uniformly mixing, spraying the silane coupling agent into the high-speed mixer within 1 minute by adopting a spraying method, and continuously stirring at a high speed for 2-5 minutes to fully and uniformly mix the silane coupling agent and the filler type flame retardant to obtain a treated filler type flame retardant for later use;
step (2): adding ethylene-vinyl acetate copolymer, low-melting-range linear low-density polyethylene, oil-filled SEBS, a compatilizer, the filler type flame retardant treated in the step (1), an aluminum phosphinate flame retardant, silicone master batch and a compound antioxidant into an internal mixer, and mixing at the mixing temperature of 120-140 ℃ for 8-15 minutes;
and (3): and (3) adding the mixed material obtained in the step (2) into a double-screw/single-screw double-stage extrusion granulator, and controlling the extrusion granulation temperature at 130-145 ℃ to obtain the special low-smoke halogen-free flame-retardant sheath material for the polymer optical fiber.
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