CN114316417A - Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof - Google Patents
Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof Download PDFInfo
- Publication number
- CN114316417A CN114316417A CN202111447906.4A CN202111447906A CN114316417A CN 114316417 A CN114316417 A CN 114316417A CN 202111447906 A CN202111447906 A CN 202111447906A CN 114316417 A CN114316417 A CN 114316417A
- Authority
- CN
- China
- Prior art keywords
- parts
- halogen
- flame
- free high
- retardant polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 62
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 abstract description 45
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 21
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 230000002902 bimodal effect Effects 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 9
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims abstract description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 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 claims description 2
- 238000002485 combustion reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 230000006750 UV protection Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Abstract
The invention discloses a halogen-free high-flame-retardant polyolefin sheath material, which comprises the following components in parts by weight: 30-50 parts of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 10-20 parts of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 10-15 parts of ethylene-octene copolymer, 20-25 parts of bimodal polyethylene resin, 13-18 parts of maleic anhydride grafting compatilizer, 170-190 parts of inorganic halogen-free flame retardant, 3-5 parts of melamine urate, 3-5 parts of phosphorus flame retardant, 1-2 parts of lubricant, 1-1.5 parts of antioxidant, 1-2 parts of silane coupling agent, 3-5 parts of ultraviolet-resistant auxiliary agent and toner. In addition, the invention also discloses a preparation method of the halogen-free high-flame-retardant polyolefin sheath material.
Description
Technical Field
The invention relates to a polyethylene sheath material, in particular to a halogen-free high-flame-retardant polyolefin sheath material and a preparation method thereof.
Background
The low-smoke halogen-free high-flame-retardant polyolefin sheath material is an environment-friendly flame-retardant optical cable sheath material developed for meeting the requirements of low smoke, halogen-free, non-toxicity, good flame-retardant property and ultraviolet resistance, and is a particle material prepared by taking polyolefin resin as a base material, taking inorganic flame-retardant materials such as aluminum hydroxide, melamine uronate and the like as flame retardants, and assisting an antioxidant, a lubricant and an ultraviolet-resistant auxiliary agent through blending, banburying plasticization, twin-screw extrusion and granulation.
However, the existing polyethylene sheath material for the indoor optical cable has the following defects: 1. the mechanical property and the cracking resistance of the sheath material are greatly reduced due to the addition of a large amount of inorganic flame retardant, so that after the molded butterfly-shaped optical cable is subjected to high-low temperature cycle experiments, the suspension wires and the subunits of the optical cable are easy to crack, and the sheath deforms to cause unqualified optical fiber signal attenuation; 2. the ultraviolet resistance of the optical cable sheath material can not meet the requirement; 3. the common material has poor carbon forming property and self-extinguishing property during combustion, and the smoke generated during combustion has high density.
Disclosure of Invention
The invention aims to: overcomes at least one defect in the prior art and provides a halogen-free high flame-retardant polyolefin sheath material and a preparation method thereof.
In order to achieve the purpose, the invention provides a halogen-free high-flame-retardant polyolefin sheath material, which comprises the following components in parts by weight: 30-50 parts of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 10-20 parts of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 10-15 parts of ethylene-octene copolymer, 20-25 parts of bimodal polyethylene resin, 13-18 parts of maleic anhydride grafting compatilizer, 170-190 parts of inorganic halogen-free flame retardant, 3-5 parts of melamine urate, 3-5 parts of phosphorus flame retardant, 1-2 parts of lubricant, 1-1.5 parts of antioxidant, 1-2 parts of silane coupling agent and 3-5 parts of ultraviolet-resistant auxiliary agent.
According to one embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the melt index of the ethylene-octene copolymer is 0.3-0.7g/10min, the maleic anhydride grafted compatilizer is maleic anhydride grafted polyethylene copolymer, and the grafting rate is 0.5-1.0%.
According to an embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the phosphorus-based flame retardant is aluminum hypophosphite.
According to one embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the inorganic halogen-free flame retardant is aluminum hydroxide, and the average particle size D50 is 1.6-2.3 μm.
According to one embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the lubricant is silicone master batch with siloxane content of 50% and polyethylene wax.
According to one embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the antioxidant comprises a primary antioxidant of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and a secondary antioxidant of dilauryl thiodipropionate.
According to an embodiment of the halogen-free high flame retardant polyolefin sheathing compound, the anti-ultraviolet auxiliary agent is 2-hydroxy-4-octyloxy benzophenone, hindered amine, white zinc oxide powder, titanium dioxide or a combination thereof.
In order to achieve the above object, the present invention also provides a preparation method of the halogen-free high flame retardant polyolefin sheath material, which comprises the following steps:
s1: according to the weight content, 13-15 wt% of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 3-5 wt% of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 3-5 wt% of ethylene-octene copolymer, 6-8 wt% of bimodal polyethylene resin, 5-8 wt% of maleic anhydride grafted polyethylene copolymer, 60-65 wt% of aluminum hydroxide, 2-5 wt% of melamine urate, 2-5 wt% of phosphorus flame retardant, 0.2-0.45 wt% of antioxidant, 0.5-1 wt% of lubricant, 0.4-0.6 wt% of silane coupling agent and 0.9-1.5 wt% of anti-ultraviolet auxiliary agent are sequentially put into a pressure internal mixer for premixing to obtain a uniformly mixed material;
s2: pressurizing and banburying the material premixed in the step S1 for 13-15min, wherein the pressure is 0.55-0.65MPa, and the banburying temperature needs to reach 160-165 ℃, so as to obtain a banburied material mass;
s3: the material mass subjected to banburying in the step S2 enters a double-cone feeding bin, and then is subjected to double-screw extrusion, single-screw extrusion, die head granulation and air cooling conveying and cooling in sequence; and
s4: and (4) taking out the materials by using a bag containing aluminum foil, sampling, inspecting, weighing and packaging.
According to one embodiment of the preparation method of the halogen-free high-flame-retardant polyolefin sheath material, the temperature of each region of the twin-screw extrusion processing is respectively 100 ℃ of 120-; the temperature of each zone of the single-screw extrusion processing is respectively 100-110-135 ℃, and the allowable deviation value is +/-10 ℃.
Compared with the prior art, the halogen-free high-flame-retardant polyolefin sheath material and the preparation method thereof have the following advantages:
the cabling adopting the halogen-free high flame-retardant polyolefin sheath material meets the requirements of bundled D-type combustion, the combustion light transmittance is more than or equal to 50 percent, and the single vertical combustion pass rate is more than 90 percent; the halogen-free high-flame-retardant polyolefin sheath material disclosed by the invention has the ultraviolet resistance which meets the ANSL/UL 1581-containing 2013 standard (the sunlight aging resistance is 720h, and the retention rate of the tensile strength and the elongation at break after aging is not less than 80%); the finished cable adopting the halogen-free high flame-retardant polyolefin sheath material meets the series requirements of cracking resistance.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a halogen-free high-flame-retardant polyolefin sheath material, which comprises the following components in parts by weight: 30-50 parts of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 10-20 parts of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 10-15 parts of ethylene-octene copolymer, 20-25 parts of bimodal polyethylene resin, 13-18 parts of maleic anhydride grafting compatilizer, 170-190 parts of inorganic halogen-free flame retardant, 3-5 parts of melamine urate, 3-5 parts of phosphorus flame retardant, 1-2 parts of lubricant, 1-1.5 parts of antioxidant, 1-2 parts of silane coupling agent and 3-5 parts of ultraviolet-resistant auxiliary agent.
Specifically, in the ethylene-vinyl acetate copolymer, the ethylene-vinyl acetate copolymer with 28 wt% of VA accounts for 13-15 wt%, and the ethylene-vinyl acetate copolymer is from Exxon Mobil with a melt index of 2.5-4.0g/10min, a tensile strength of 22-27MPa and an elongation at break of 600-900% determined by a GB/T3682-2000 method; the ethylene-vinyl acetate copolymer with 18 wt% of VA accounts for 3-5 wt%, and the melt index measured by GB/T3682-2000 method is 1.2-2.0g/10 min; the tensile strength is 19-22MPa, and the elongation at break is 600-900%. The EVA dosage of the two types of VA with different contents is the most suitable proportion, and the EVA dosage is matched with each other, so that the coating effect, the material flowability and the anti-cracking performance of the resin to the powder can be considered, and the mechanical property of the sheath material can be improved.
Specifically, the ethylene-octene copolymer is NX series of Korean SK chemical company or Sabic company of Sabite, and the melt index measured by GB/T3682-2000 method is 0.3-0.7g/10 min; the tensile strength is 10-15MPa, and the breaking elongation is 700-900%.
Specifically, the bimodal polyethylene resin is FB series of northern Europe chemical industry company, and the melt index measured by GB/T3682-2000 method is 0.2-0.6g/10 min; the tensile strength is 30-35MPa, and the breaking elongation is 500-700%.
Specifically, the maleic anhydride grafted compatilizer is a maleic anhydride grafted polyethylene copolymer (PE-G-MAH), the grafting rate is 0.5-1.0%, and the melt index measured by a GB/T3682-2000 method is 0.3-0.8G/10 min; the tensile strength is 20-24MPa, and the breaking elongation is 600-800%.
Specifically, the inorganic halogen-free flame retardant is home-made aluminum hydroxide, the average particle size D50 is 1.6-2.3 μm, and the specific gravity is 2.4g/cm 3.
Specifically, the melamine urate is MCA which is a domestic flame retardant, and the phosphorus flame retardant is aluminum hypophosphite which is a domestic phosphorus flame retardant.
Specifically, the lubricant is silicone master batch with the siloxane content of 50% and polyethylene wax.
Specifically, the antioxidant comprises a main antioxidant of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and an auxiliary antioxidant of dilauryl thiodipropionate.
Specifically, the anti-ultraviolet auxiliary agent is 2-hydroxy-4-octyloxy benzophenone, hindered amine, white zinc oxide powder, titanium dioxide or a combination thereof, and the silane coupling agent is Japanese wisdom rope S-230.
The preparation method of the halogen-free high flame retardant polyolefin sheathing compound of the invention is described in detail with reference to the following examples.
Example 1
S1: sequentially adding 50 parts by weight of ethylene-vinyl acetate copolymer with the VA content of 28 wt%, ethylene-vinyl acetate copolymer with the VA content of 18 wt%, 5 parts by weight of ethylene-octene copolymer, 20 parts by weight of bimodal polyethylene resin, 15 parts by weight of maleic anhydride grafted polyethylene copolymer compatilizer, 180 parts by weight of aluminum hydroxide flame retardant, 5 parts by weight of melamine urate, 5 parts by weight of phosphorus flame retardant, 1.5 parts by weight of antioxidant, 1.5 parts by weight of lubricant, 1.5 parts by weight of silane coupling agent and 4 parts by weight of ultraviolet-resistant auxiliary agent into a pressurized internal mixer for premixing to obtain a uniformly mixed material;
s2: pressurizing and banburying the material premixed in the step S1 for 13-15min, wherein the pressure is 0.55-0.65MPa, and the banburying temperature needs to reach 160-165 ℃, so as to obtain a banburied material mass;
s3: the material mass subjected to banburying in the step S2 enters a double-cone feeding bin, and then is subjected to double-screw extrusion, single-screw extrusion, die head granulation and air cooling conveying and cooling in sequence; and
s4: and (4) taking out the materials by using a bag containing aluminum foil, sampling, inspecting, weighing and packaging.
The double-screw extrusion processing and the single-screw extrusion processing are operated in a subarea mode, the temperature of each area of the double-screw extrusion processing is respectively 100 ℃ in 120-125-110-105-110-, and the allowable deviation value is +/-10 ℃; the temperature of each zone of the single-screw extrusion processing is respectively 100-110-135 ℃, and the allowable deviation value is +/-10 ℃.
Example 2
Example 2 is essentially the same as example 1, except that: the components and the proportions of the components are different, and the components and the proportions of the components in example 2 are shown in table 1.
Example 3
Example 3 is essentially the same as example 1, except that: the components and the proportions of the components are different, and the proportions of the components and the components in example 3 are shown in table 1.
Comparative examples 1 to 3
Comparative examples 1-3 are essentially the same as example 1, except that: the components and the proportions of the components are different, and the components and the proportions of the components in comparative examples 1 to 3 are shown in table 1.
Table 1 examples 1-3 comparative examples 1-3 each component and their ratio
Mechanical property detection
The halogen-free high flame-retardant polyolefin sheath materials of examples 1-3 and comparative examples 1-3 were tested for mechanical properties according to the methods and standards shown in Table 2, and the test results are shown in Table 3.
TABLE 2 test standards for halogen-free highly flame-retardant polyolefin sheathing materials of examples 1 to 3 and comparative examples 1 to 3
Table 3 mechanical test results of halogen-free highly flame-retardant polyolefin sheathing materials of examples 1 to 3 and comparative examples 1 to 3
In the prior art, the addition of the inorganic flame-retardant filler can greatly deteriorate the mechanical property of matrix resin, because the compatibility between the inorganic flame-retardant filler and the matrix resin is poor, even if the filler is subjected to surface treatment, the phenomenon of uneven dispersion among the matrix resin still exists, the bonding force of the aggregated inorganic filler and the matrix resin is weakened, the mechanical property is greatly reduced, the strength and the toughness of the material are reduced, and the formed butterfly-shaped optical cable is easy to crack in the high-low temperature circulation process.
It can be seen from tables 1 to 3 that the halogen-free high flame retardant polyolefin sheath material of the present invention reduces the amount of PE resin, changes bimodal polyethylene with better crack resistance to the polyethylene, increases the amount of EVA and POE resin to make the matrix resin have better coating effect, and simultaneously adds silane coupling agent for modification and filler surface treatment to increase the interface strength.
Combustion Performance and extrusion Performance testing
The halogen-free high flame-retardant polyolefin sheath materials of examples 1-3 and comparative examples 1-3 were tested for flammability according to the methods and criteria shown in table 4, using a length-diameter ratio of 25: the extrusion performance test was carried out on 65 machines (low smoke zero halogen special screw) of 1, the extrusion temperature was 135-165 ℃, and the test results are shown in Table 5.
TABLE 4 flammability test standards for halogen-free highly flame retardant polyolefin sheathing materials of examples 1-3 and comparative examples 1-3
TABLE 5 test results of flammability and extrusion Properties of the halogen-free highly flame-retardant polyolefin sheath materials of examples 1-3 and comparative examples 1-3
The halogen-free high flame-retardant polyolefin sheath materials of examples 1 to 3 and comparative examples 1 to 3 were subjected to D-burn performance test as shown in Table 6, and the test results are shown in Table 6.
TABLE 6D flammability results of halogen-free highly flame retardant polyolefin jacket materials of examples 1-3 and comparative examples 1-3
The common flame-retardant optical cable sheath material mostly adopts calcium carbonate and inorganic red phosphorus flame retardant, is easy to drip and generate a large amount of black smoke in the single vertical combustion and bundled combustion processes, and does not meet the requirement of light transmittance. Referring to tables 4 to 6, the halogen-free high flame retardant polyolefin sheath material of the present invention employs aluminum hydroxide with better flame retardancy and phosphate flame retardant with better char formation, and simultaneously adds synergistic nitrogen flame retardant, so that no drop occurs during combustion, single-piece, bundled combustion and light transmittance are ensured, cabling satisfies bundled D-type combustion, the combustion light transmittance is not less than 50%, and the single-piece vertical combustion pass rate is more than 90%. The extrusion production speed reaches 100m/min, and the practical use requirement is met. In addition, the color and the mechanical property of the material are ensured by adopting a compound mode of the ultraviolet absorbent and the ultraviolet screening agent, and the ANSL/UL 1581-containing 2013 standard (sunlight aging resistance is 720h, and the retention rate of the tensile strength and the elongation at break after aging is not less than 80 percent) is met.
In combination with the above detailed description of the present invention, it can be seen that, compared with the prior art, the halogen-free high flame retardant polyolefin sheath material and the preparation method thereof of the present invention have the following advantages:
the cabling adopting the halogen-free high flame-retardant polyolefin sheath material meets the requirements of bundled D-type combustion, the combustion light transmittance is more than or equal to 50 percent, and the single vertical combustion pass rate is more than 90 percent; the halogen-free high-flame-retardant polyolefin sheath material disclosed by the invention has the ultraviolet resistance which meets the ANSL/UL 1581-containing 2013 standard (the sunlight aging resistance is 720h, and the retention rate of the tensile strength and the elongation at break after aging is not less than 80%); the finished cable adopting the halogen-free high flame-retardant polyolefin sheath material meets the series requirements of cracking resistance.
The present invention can be modified and adapted appropriately from the above-described embodiments, according to the principles described above. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The halogen-free high-flame-retardant polyolefin sheath material is characterized by comprising the following components in parts by weight: 30-50 parts of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 10-20 parts of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 10-15 parts of ethylene-octene copolymer, 20-25 parts of bimodal polyethylene resin, 13-18 parts of maleic anhydride grafting compatilizer, 170-190 parts of inorganic halogen-free flame retardant, 3-5 parts of melamine urate, 3-5 parts of phosphorus flame retardant, 1-2 parts of lubricant, 1-1.5 parts of antioxidant, 1-2 parts of silane coupling agent and 3-5 parts of ultraviolet-resistant auxiliary agent.
2. The halogen-free high flame retardant polyolefin sheath material according to claim 1, wherein the ethylene-octene copolymer has a melt index of 0.3-0.7g/10min, and the bimodal polyethylene resin has a melt index of 0.3-0.8g/10 min.
3. The halogen-free high-flame-retardant polyolefin sheathing compound as claimed in claim 1, wherein the phosphorus-based flame retardant is aluminum hypophosphite.
4. The halogen-free high-flame-retardant polyolefin sheathing compound as claimed in claim 1, wherein the maleic anhydride grafted compatibilizer is a maleic anhydride grafted polyethylene copolymer, and the grafting ratio is 0.5-1.0%.
5. The halogen-free high-flame-retardant polyolefin sheathing compound as claimed in claim 1, wherein the inorganic halogen-free flame retardant is aluminum hydroxide, and the average particle diameter D50 is 1.6-2.3 μm.
6. The halogen-free high-flame-retardant polyolefin sheath material according to claim 1, wherein the lubricant is silicone master batch with siloxane content of 50% and polyethylene wax.
7. The halogen-free high-flame-retardant polyolefin sheathing compound as claimed in claim 1, wherein the antioxidant comprises a primary antioxidant of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and a secondary antioxidant of dilauryl thiodipropionate.
8. The halogen-free high-flame-retardant polyolefin sheath material as claimed in claim 1, wherein the anti-ultraviolet auxiliary agent is 2-hydroxy-4-octoxybenzophenone, hindered amine, white zinc oxide powder, titanium dioxide or a combination thereof.
9. The preparation method of the halogen-free high flame retardant polyolefin sheathing compound according to any one of claims 1 to 8, comprising the steps of:
s1: according to the weight content, 13-15 wt% of ethylene-vinyl acetate copolymer with 28 wt% of VA content, 3-5 wt% of ethylene-vinyl acetate copolymer with 18 wt% of VA content, 3-5 wt% of ethylene-octene copolymer, 6-8 wt% of bimodal polyethylene resin, 5-8 wt% of maleic anhydride grafted polyethylene copolymer, 60-65 wt% of aluminum hydroxide, 2-5 wt% of melamine urate, 2-5 wt% of phosphorus flame retardant, 0.2-0.45 wt% of antioxidant, 0.5-1 wt% of lubricant, 0.4-0.6 wt% of silane coupling agent and 0.9-1.5 wt% of anti-ultraviolet auxiliary agent are sequentially put into a pressure internal mixer for premixing to obtain a uniformly mixed material;
s2: pressurizing and banburying the material premixed in the step S1 for 13-15min, wherein the pressure is 0.55-0.65MPa, the banburying temperature is 160-165 ℃, and a banburied material mass is obtained;
s3: the material mass subjected to banburying in the step S2 enters a double-cone feeding bin, and then is subjected to double-screw extrusion, single-screw extrusion, die head granulation and air cooling conveying and cooling in sequence; and
s4: and (4) taking out the materials by using a bag containing aluminum foil, sampling, inspecting, weighing and packaging.
10. The method as claimed in claim 9, wherein the temperature of each region of the twin-screw extrusion process is 100 ℃ for 120-; the temperature of each zone of the single-screw extrusion processing is respectively 100-110-135 ℃, and the allowable deviation value is +/-10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111447906.4A CN114316417A (en) | 2021-11-30 | 2021-11-30 | Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111447906.4A CN114316417A (en) | 2021-11-30 | 2021-11-30 | Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114316417A true CN114316417A (en) | 2022-04-12 |
Family
ID=81048097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111447906.4A Pending CN114316417A (en) | 2021-11-30 | 2021-11-30 | Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316417A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975281A (en) * | 2022-12-27 | 2023-04-18 | 新远东电缆有限公司 | Ultraviolet light shielding polyolefin material, preparation method and application thereof |
| CN116199959A (en) * | 2022-12-02 | 2023-06-02 | 中广核拓普（湖北）新材料有限公司 | Flame-retardant polyethylene sheath material and preparation method thereof |
| CN115975281B (en) * | 2022-12-27 | 2024-04-30 | 新远东电缆有限公司 | Ultraviolet light shielding polyolefin material, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073780A (en) * | 2013-01-25 | 2013-05-01 | 杭州双马高分子材料科技有限公司 | Low-smoke, zero-halogen and high-flame-retardant polyolefin sheath material and preparation method thereof |
| CN104262773A (en) * | 2014-10-17 | 2015-01-07 | 上海至正道化高分子材料股份有限公司 | Oil-resistant and cold-resistant LSOH (Low Smoke Zero Halogen) cable material with high fire retardancy and preparation method thereof |
| CN104893088A (en) * | 2015-06-17 | 2015-09-09 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof |
| CN109627567A (en) * | 2018-12-29 | 2019-04-16 | 上海至正道化高分子材料股份有限公司 | A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material and preparation method thereof |
| CN110903535A (en) * | 2019-11-22 | 2020-03-24 | 上海至正道化高分子材料股份有限公司 | Low-smoke halogen-free flame-retardant sheath material with good cold resistance for cable and preparation method thereof |
| CN112759819A (en) * | 2020-12-28 | 2021-05-07 | 中广核拓普（湖北）新材料有限公司 | High-flame-retardance high-light-transmittance low-smoke halogen-free cable material and preparation method thereof |
| CN113527798A (en) * | 2021-06-21 | 2021-10-22 | 杭州永通新材料有限公司 | Special halogen-free low-smoke flame-retardant polyolefin sheath material for B1-grade cable |
-
2021
- 2021-11-30 CN CN202111447906.4A patent/CN114316417A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073780A (en) * | 2013-01-25 | 2013-05-01 | 杭州双马高分子材料科技有限公司 | Low-smoke, zero-halogen and high-flame-retardant polyolefin sheath material and preparation method thereof |
| CN104262773A (en) * | 2014-10-17 | 2015-01-07 | 上海至正道化高分子材料股份有限公司 | Oil-resistant and cold-resistant LSOH (Low Smoke Zero Halogen) cable material with high fire retardancy and preparation method thereof |
| CN104893088A (en) * | 2015-06-17 | 2015-09-09 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof |
| CN109627567A (en) * | 2018-12-29 | 2019-04-16 | 上海至正道化高分子材料股份有限公司 | A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material and preparation method thereof |
| CN110903535A (en) * | 2019-11-22 | 2020-03-24 | 上海至正道化高分子材料股份有限公司 | Low-smoke halogen-free flame-retardant sheath material with good cold resistance for cable and preparation method thereof |
| CN112759819A (en) * | 2020-12-28 | 2021-05-07 | 中广核拓普（湖北）新材料有限公司 | High-flame-retardance high-light-transmittance low-smoke halogen-free cable material and preparation method thereof |
| CN113527798A (en) * | 2021-06-21 | 2021-10-22 | 杭州永通新材料有限公司 | Special halogen-free low-smoke flame-retardant polyolefin sheath material for B1-grade cable |
Non-Patent Citations (2)
| Title |
|---|
| 史新影;周桓;: "磷系阻燃剂中次磷酸盐的应用研究进展", no. 09, pages 106 * |
| 郭正波;夏利平;何正宏;黄安民;: "阻燃热塑性聚酯弹性体复合材料制备及性能", no. 04, pages 21 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116199959A (en) * | 2022-12-02 | 2023-06-02 | 中广核拓普（湖北）新材料有限公司 | Flame-retardant polyethylene sheath material and preparation method thereof |
| CN115975281A (en) * | 2022-12-27 | 2023-04-18 | 新远东电缆有限公司 | Ultraviolet light shielding polyolefin material, preparation method and application thereof |
| CN115975281B (en) * | 2022-12-27 | 2024-04-30 | 新远东电缆有限公司 | Ultraviolet light shielding polyolefin material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104893088B (en) | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof | |
| CN112321934B (en) | Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin material for 150 ℃ American standard electronic wire and preparation method thereof | |
| CN104403190A (en) | Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof | |
| CN110903535A (en) | Low-smoke halogen-free flame-retardant sheath material with good cold resistance for cable and preparation method thereof | |
| CN109627567A (en) | A kind of B1 grades of fire-retardant irradiated crosslinking low-smoke and halogen-free insulated cable material and preparation method thereof | |
| CN103897256A (en) | High-speed low-shrink low-smoke zero-halogen tight-buffered material used for 4G optical cable and preparation method of high-speed low-shrink low-smoke zero-halogen tight-buffered material | |
| CN102250409A (en) | Synergistic flame-retardant low-smoke halogen-free polyolefin cable material and preparation method thereof | |
| CN109627568B (en) | Polyolefin cable sheath material and preparation method thereof | |
| CN103881229A (en) | High-flame-retardant and halogen-free polyolefin cable material and preparation method thereof | |
| CN108948476B (en) | Halogen-free flame-retardant polyethylene material and preparation method thereof | |
| CN114656712A (en) | Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof | |
| CN102898715B (en) | Extremely temperature sensitive halogen-free and low smoke flame retardant plastic alloy for cables and preparation method thereof | |
| CN112321945B (en) | Precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| JP6353045B2 (en) | Flexible flame retardant thermoplastic composition with high thermomechanical strength, especially for electrical cables | |
| CN1793212A (en) | Low smoke non-halogen fire retarding expansive polyolefins electronic wire material and preparation process thereof | |
| CN114316417A (en) | Halogen-free high-flame-retardant polyolefin sheath material and preparation method thereof | |
| CN114044954A (en) | Flame-retardant polyethylene material and preparation method and application thereof | |
| CN108164806A (en) | Locomotive engine cable irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin material and preparation method thereof | |
| CN111303528A (en) | Halogen-free low-smoke high-flame-retardant high-oxygen-insulation cable material for power cable and preparation method thereof | |
| CN112759821B (en) | Ultraviolet crosslinking type low-smoke halogen-free polyolefin and preparation method and application thereof | |
| CN103804835A (en) | Halogen-free flame retardant thermoplastic elastomer cable material and preparation method thereof | |
| CN100451065C (en) | Halogen-free combustion-proof polypropylene high-speed abrasion-proof insulating material for auto initial line | |
| CN109280256B (en) | Low-VOC halogen-free flame-retardant polyolefin cable material for locomotive | |
| CN114656706A (en) | Halogen-free flame-retardant polyethylene sheath material and preparation method thereof | |
| CN114276610A (en) | Low-hardness low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |