CN104059321A - Weather-proof environment-friendly flame-retardant polymer material for flexible cable and preparation method thereof - Google Patents
Weather-proof environment-friendly flame-retardant polymer material for flexible cable and preparation method thereof Download PDFInfo
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- CN104059321A CN104059321A CN201310088630.4A CN201310088630A CN104059321A CN 104059321 A CN104059321 A CN 104059321A CN 201310088630 A CN201310088630 A CN 201310088630A CN 104059321 A CN104059321 A CN 104059321A
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- 239000002861 polymer material Substances 0.000 title claims abstract description 53
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 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 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 tetrabromo-benzene anhydride Chemical class 0.000 claims abstract description 34
- 230000007613 environmental effect Effects 0.000 claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 21
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims abstract description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 38
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 23
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000005060 rubber Substances 0.000 claims description 18
- 229920006132 styrene block copolymer Polymers 0.000 claims description 15
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 14
- 229920002943 EPDM rubber Polymers 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 229920001897 terpolymer Polymers 0.000 claims description 10
- 229920003987 resole Polymers 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 235000012222 talc Nutrition 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 101100136616 Arabidopsis thaliana PHT1-4 gene Proteins 0.000 claims description 4
- 229930188012 Bromoether Natural products 0.000 claims description 4
- 101100243924 Pseudomonas putida pht4 gene Proteins 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- HJCMMOODWZOXML-UHFFFAOYSA-N bromo hypobromite Chemical compound BrOBr HJCMMOODWZOXML-UHFFFAOYSA-N 0.000 claims description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LERFHXCLIVRDIK-UHFFFAOYSA-N 1,3,5-tribromo-2-ethoxybenzene Chemical compound CCOC1=C(Br)C=C(Br)C=C1Br LERFHXCLIVRDIK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 8
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 abstract description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 abstract 1
- YVVYMSXDQGDASK-UHFFFAOYSA-N 1,2,3-tribromo-4-[2-(2,3,4-tribromophenoxy)ethoxy]benzene Chemical compound BrC1=C(Br)C(Br)=CC=C1OCCOC1=CC=C(Br)C(Br)=C1Br YVVYMSXDQGDASK-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 53
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 2
- 239000004794 expanded polystyrene Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a weather-proof environment-friendly flame-retardant polymer material for a flexible cable and a preparation method thereof. The polymer material comprises the following components by weight: 100 parts of a component A, 20 to 200 parts of a component B and 50 to 130 parts of a component C, wherein the component A is TPE, the component B is TPV, the component C is a fire retardant and comprises C1 and C2, C1 is one selected from the group consisting of decabromodiphenylethane, 1,2-bis(tribromophenoxy)ethane, tetrabromobisphenol A, tetrabromo-benzene anhydride, octabromo-ether, bis(tetrabromo-o-benzene-dimethyl ether imide)ethane and hexabromocyclododecane and has a particle size in a range of 10 to 30 mu m, and C2 is one selected from the group consisting of antimony trioxide, zinc borate and zinc oxide. The polymer material provided by the invention has improved processing performance and tensile strength, high usage temperature and excellent weatherability, environmental protection performance and flame resistance and is especially applicable to outdoor usage in a severe environment.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of weather resistance environmental protection flame retardant flexible cable polymer materials and preparation method thereof.
Background technology
Electric wire is widely used in the transmission of energy and information at present, the insulation layer of the electric wire made from traditional macromolecular material or sheath, in use be easy to because circuit thermal value is excessive or short circuit etc. is former thereby burning, cause fire, European Union, many regions such as the U.S. are to electrical equipment, and wire type product is to heavy metal, and biphenyl compound etc. also limit.
All there is limitation in tradition flame-retardant polymer, the flame-retardant system of comparative maturity has following several:
(1) traditional halogen and antimony are compound system.When shortcoming is halogen flame burning, because meeting discharges dioxin, harmful to biology, therefore environment amenable electric wire will be a kind of development trend.
(2) inorganic fire-retarded system, common is magnesium hydroxide.The problem of this system is, flame retarding efficiency is low, and addition is large, and Strength retention is low.
(3) phosphorus, nitrogen compound system.This system is not suitable in non-polar material, has resistance to separating out simultaneously, the problem of poor heat resistance.
Therefore the exploitation of flexible flame retardant polymkeric substance becomes a difficult problem for global polymeric material field.
Flexible wires is an indispensable composition in cable products.The advantages such as it has flexible rolling, and under dynamic swing, resistance to fatigue is good, and low-temperature flexibility is good.In traditional flexible family, the occupation rate of PVC is the highest, but has the puzzlement of the problem such as halogen, softening agent, and EVA is also a kind of common flexible materials, but its greatest problem is: the problems such as tensile strength is low, and use temperature is on the low side.Also there is on the market the TPV fire retardant material of seeing taking PP/EPDM as base material, as the patent No. is: CN101597409A, a kind of expanding type halogen-free flame retarding thermoplastic dynamic perduren composition.The patent No. is: CN101050290A, a kind of dynamic sulfurated retardant composite material of polypropylene without halogen and preparation method thereof etc., there are good weathering resistance and good mechanical property, but the mobility that is limited to TPV is poor, after itself and fire retardant blending and modifying, easily produce and disperse bad problem, show as and occur in appearance white point and pit, thereby limited its use.And TPE fire retardant material taking SEBS as base material also occurs on the market, as the patent No. is: CN101796127A, flame-retardant thermoplastic elastomer.The patent No. is: CN102146193A, halogen-free flame-retardant thermoplastic elastomer mixture and preparation method taking SEBS as base-material.But such fire retardant material product surface greasy feeling is stronger, and ink-jet firmness is low.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of weather resistance environmental protection flame retardant flexible cable polymer materials and preparation method thereof, the blend of the TPE material of this preparation method taking SEBS as base material and the TPV material taking PP/EPDM as base material, improve processing characteristics, improve tensile strength, use temperature is higher, has good weather resistance; The halogen flame that the present invention selects is environment-friendly type, containing biphenol compound, can not discharge the harmful dioxin of biology when burning, have good water-fast, resistance to separating out and weathering resistance.
The present invention is achieved through the following technical solutions: the invention provides a kind of weather resistance environmental protection flame retardant flexible cable polymer materials, comprise each component of following weight part content,
A component: 100 parts of TPE,
B component: 20-200 part TPV,
C component: 50-130 part fire retardant;
Described TPE comprises each component of following weight part content:
(A1) thermoplastic styrene butadiene rubber SEBS100 part,
(A2) mineral oil: 100-150 part,
(A3) polypropylene: 80-200 part,
(A4) polyolefin elastomer: 0-100 part,
(A5) inorganic filler: 0-200 part;
Described TPV comprises each component of following weight part content:
(B1) polypropylene: 50-120 part,
(B2) terpolymer EP rubber: 100 parts,
(B3) resol: 2-10 part,
(B4) zinc oxide: 0-6 part;
Described C component comprises:
(C1) be selected from TDE, 1,2-two (2,4,6-tribromophenoxy) ethane, tetrabromo-bisphenol, PHT4, the eight bromo ether (one in 1.1 '-(methyl is pitched)-bis-[(3.5-dibromo) – 4 (2.3-dibromo propoxy benzene)], two (tetrabromo-phthalic dme imines) ethane, hexabromocyclododecane, selected particle diameter is 10-30 μ m, 5-200 part;
(C2) be selected from the one in antimonous oxide, zinc borate and zinc oxide, 5-200 part;
Described TPE is styrene analog thermoplastic elastomer;
Described TPV is TP-EPDM Thermoplastic elastomer-based on EPDM.
The present invention is according to the similar compatibility principle of polymkeric substance, described TPE and TPV are non-polar polymer component, so there is good compatibility, in addition, it is extremely difficult that EPDM absorbs softening oil, and the oil-extended process of having relatively high expectations, and the oil-filled convenience of SEBS, and can absorb higher multiplying power, synergy has been played in the blend of bi-material; And, the good TPE component of mobility exists with co-continuous mutually with TPV component, due to the difference of mobility, in blend melt composition viscosity gradient, dispersion to fire retardant component is more useful, has improved processing characteristics, improves tensile strength, use temperature is higher, has good weather resistance.
According to polymer materials of the present invention, preferably, the weight ratio of described component C1 and component C2 is 5:1-1:1, and component C1 and component C2 weight sum account for the 10-50% of whole polymer materials gross weight.
According to polymer materials of the present invention, further preferably, the weight ratio of described component C1 and component C2 is 3:1-2:1.
According to polymer materials of the present invention, further preferably, described component C1 and component C2 weight sum account for the 20-35% of whole polymer materials gross weight.
According to polymer materials of the present invention, it is characterized in that, described polypropylene is homopolymerization type or copoly type, its melting index is 0.5-10g/10min; Described resol is selected from the SP1045 of Sheng Laike specialization work.
According to polymer materials of the present invention, it is characterized in that, described TPE is selected from one or both in ethylene-octene copolymer, ethylene-propylene copolymer, and its Vicat softening point is not less than 70 DEG C.
According to polymer materials of the present invention, it is characterized in that, described TPE is selected from styrene block copolymer, and described styrene block copolymer is selected from one or more in styrene-butadiene-styrene, styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-ethylene-propylene-vinylbenzene.
According to polymer materials of the present invention, it is characterized in that, the tenderizer of described styrene block copolymer is selected from one or both in paraffinic base rubber oil, naphthenic rubber oil; The solubilizing agent of described styrene block copolymer is selected from one or both in the SEBS (SEBS-MAH) of maleic anhydride graft and the polypropylene (PP-MAH) of maleic anhydride graft.
According to polymer materials of the present invention, it is characterized in that, the mooney viscosity of described terpolymer EP rubber is not less than 60
mL100 DEG C of 1+4.
According to polymer materials of the present invention, it is characterized in that, described polymer materials also comprises filler, and described filler is selected from calcium carbonate, talcum, kaolin, the one in barium sulfate.
According to polymer materials of the present invention, it is characterized in that, the tensile strength of described polymer materials reaches 14.0MPa.
According to polymer materials of the present invention, it is characterized in that, described polymer materials is 136 DEG C in temperature, and the time is that 168H measures, and its stretching strength retentivity is greater than 90%.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material, preferably, A component and B component are first used after twin screw granulation and C component blend granulation again;
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material, preferably, A component, B component, and after C component single stage method co-blended, then use twin screw granulation.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material, described polymer materials, comprises each component of following weight part content,
A component: 100 parts of TPE,
B component: 20-200 part TPV,
C component: 50-130 part fire retardant;
Described TPE comprises each component of following weight part content:
(A1) SEBS100 part,
(A2) mineral oil: 100-150 part,
(A3) polypropylene: 80-200 part,
(A4) polyolefin elastomer: 0-100 part,
(A5) inorganic filler: 0-200 part;
Described TPV comprises each component of following weight part content:
(B1) polypropylene: 50-120 part,
(B2) terpolymer EP rubber: 100 parts,
(B3) resol: 2-10 part,
(B4) zinc oxide: 0-6 part;
Described C component comprises:
(C1) be selected from TDE, 1,2-two (2,4,6-tribromophenoxy) ethane, tetrabromo-bisphenol, PHT4, the eight bromo ether (one in 1.1 '-(methyl is pitched)-bis-[(3.5-dibromo) – 4 (2.3-dibromo propoxy benzene)], two (tetrabromo-phthalic dme imines) ethane, hexabromocyclododecane, selected particle diameter is 10-30 μ m, 5-200 part;
(C2) be selected from the one in antimonous oxide, zinc borate and zinc oxide, 5-200 part;
Described TPE is styrene analog thermoplastic elastomer;
Described TPV is TP-EPDM Thermoplastic elastomer-based on EPDM.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, preferably, the weight ratio of described component C1 and component C2 is 5:1-1:1, component C1 and component C2 weight sum account for the 10-50% of whole polymer materials gross weight.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, further preferably, the weight ratio of described component C1 and component C2 is 3:1-2:1.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material, further preferably, described component C1 and component C2 weight sum account for the 20-35% of whole polymer materials gross weight.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, described polypropylene is homopolymerization type or copoly type, its melting index is 0.5-10g/10min; Described resol is selected from the SP1045 of Sheng Laike specialization work.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, described TPE is selected from one or both in ethylene-octene copolymer, ethylene-propylene copolymer, and its Vicat softening point is not less than 70 DEG C.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material, it is characterized in that, described TPE is selected from styrene block copolymer, and described styrene block copolymer is selected from one or more in styrene-butadiene-styrene, styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-ethylene-propylene-vinylbenzene.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, the tenderizer of described styrene block copolymer is selected from one or both in paraffinic base rubber oil, naphthenic rubber oil; The solubilizing agent of described styrene block copolymer is selected from one or both in the SEBS (SEBS-MAH) of maleic anhydride graft and the polypropylene (PP-MAH) of maleic anhydride graft.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, the mooney viscosity of described terpolymer EP rubber is not less than 60
mL100 DEG C of 1+4.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, described polymer materials also comprises filler, and described filler is selected from calcium carbonate, talcum, kaolin, the one in barium sulfate.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, the tensile strength of described polymer materials reaches 14.0MPa.
Preparation method according to weather resistance environmental protection flame retardant flexible cable of the present invention with polymeric material,, it is characterized in that, described polymer materials is 136 DEG C in temperature, and the time is that 168H measures, and its stretching strength retentivity is greater than 90%.
A kind of polymer materials provided by the invention, it comprises the novel environment friendly halogenated flame retardant and the Sb system fire retardant that are combined in polymeric matrix, at least comprises following component A, B and C:
A component: 100 parts of TPE
A1): SEBS100 part
A2): mineral oil: 100-150 part
A3): polypropylene: 80-200 part
A4): polyolefin elastomer: 0-100 part
A5): inorganic filler: 0-200 part
B component: 20-200 part TPV
B1): polypropylene: 50-120 part
B2): terpolymer EP rubber (EPDM): 100 parts
B3): resol SP1045:2-10 part
B4): zinc oxide: 0-6 part
C component: 50-130 part
C1) TDE (TDE) or 1,2-two (2,4,6-tribromophenoxy) (1.1 '-(methyl is pitched)-bis-[(3.5-dibromo) – 4-(2.3-dibromo propoxy benzene)], two (tetrabromo-phthalic dme imines) ethane (BTBPIE), hexabromocyclododecane (HBCD), selected particle diameter is at 10-30 μ m for ethane (BTBPOE), tetrabromo-bisphenol (TBBPA), PHT4 (TBPA), eight bromo ether.
C2): antimonous oxide (Sb
2o
3) or zinc borate (ZNPB), zinc oxide (ZnO),
Wherein the weight ratio of component C1 and component C2 is 5:1 to 1:1, and the total amount of component C1 and component C2 accounts for the 10-50 % by weight of whole polymer materials,
Described polymer materials is a kind of flexible elastomer material (TPE).
In described polymer materials, the weight ratio of component C1 and component C2 is 5:1 to 1:1, is preferably 3:1 to 2:1, and the total amount of component C1 and component C2 accounts for the 10-50 % by weight of whole polymer materials, is preferably 20-35 % by weight.
Described flexible elastomer material (TPE) and (TPV) be selected from polypropylene, this polypropylene is homopolymerization type or copoly type. melting index is 0.5-10g/10min.
Described flexible elastomer material (TPE) is selected from olefin elastomer, and this elastomerics is ethylene-octene copolymer and/or ethylene-propylene copolymer. and Vicat softening point is not less than 70 DEG C.
Described flexible elastomer material (TPE) is selected from styrene block copolymer SBS(styrene-butadiene-styrene), SEBS(styrene-ethylene-butylene-styrene), SEPS(styrene-ethylene-propylene-styrene), SEEPS(styrene-ethylene-ethylene-propylene-vinylbenzene).
Described polymer materials comprises filler, and described filler is preferably from calcium carbonate, talcum, kaolin, barium sulfate.
The tenderizer of described styrene block copolymer is one or both the mixture in following material: paraffinic base rubber oil (white oil), naphthenic rubber oil, preferably white oil.
The solubilizing agent of described styrene block copolymer is one or both the mixture in following material: SEBS-MAH, PP-MAH.
The mooney viscosity of described terpolymer EP rubber is for being not less than 60.
Polymer materials of the present invention, its mode of production can be, A, two kinds of components of B are first used after twin screw granulation and C component blend granulation again, or A, B, and use twin screw granulation after the blend of C component single stage method.A kind of scheme preferably.
Beneficial effect of the present invention:
(1) blend of the TPE material of the present invention taking SEBS as base material and the TPV material taking PP/EPDM as base material, improve processing characteristics, further improve tensile strength, can reach 14MPA, use temperature is higher, can be used as 105 DEG C of lines and uses, there is good weather resistance, being specially adapted to the severe open air use the present invention of environment, to select halogen flame be environment-friendly type,, containing biphenol compound, can not discharge the harmful dioxin of biology when burning.
(2) the present invention selects by several olefin polymers, and under large inorganics adds, the more general TPE material taking SEBS as base material sees, Strength retention is good, dryer and comfortableer feel, better ink affinity.
(3) the present invention has improved the use temperature upper limit.By 136 DEG C, the mensuration of 168H, stretching strength retentivity is greater than 90%.
(4) the present invention adds man-hour doing cable extruding, has wide process window.Can be from 160 DEG C to 240 DEG C.
(5) the present invention have good water-fast, resistance to separate out etc.
(6) the present invention is a kind of flame-retardant system of expanded polystyrene veneer, becomes charcoal effective, can not drip.
(7) the present invention has good weather resistance.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Various raw materials in embodiment can be chosen the related products of multiple producers, be commercially available, easily buy.
1. proportioning raw materials
| Component (umber) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Polypropylene | 110 | 110 | 110 | 110 | 110 | 110 | 110 |
| Polyolefin elastomer | 50 | ||||||
| SEBS | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| White oil | 150 | 150 | 150 | 150 | 150 | 150 | 150 |
| Terpolymer EP rubber | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Resol | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| TDE | 180 | 180 | 180 | ||||
| Tetrabromo-bisphenol | 180 | 180 | 180 | ||||
| Hexabromocyclododecane | 180 | ||||||
| Antimonous oxide | 60 | 60 | 60 | 60 | 60 | ||
| Zinc oxide | 1 | 1 | 1 | 60 | 1 | 60 | 1 |
| SEBS-MAH | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Talcum | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Component (umber) | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| Polypropylene | 100 | 100 | 90 | 90 | 120 | 120 | 120 |
| Polyolefin elastomer | 10 | 50 | 20 | ||||
| SEBS | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| White oil | 150 | 150 | 150 | 150 | 150 | 150 | 150 |
| Terpolymer EP rubber | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Resol | 2 | 2 | 5 | 5 | 4 | 8 | 8 |
| TDE | 100 | 100 | 180 | 160 | |||
| Tetrabromo-bisphenol | 180 | 150 | 180 | ||||
| Hexabromocyclododecane | 180 | ||||||
| Antimonous oxide | 20 | 60 | 40 | 60 | 20 | ||
| Zinc oxide | 1 | 2 | 1 | 60 | 1 | 60 | 1 |
| SEBS-MAH | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Talcum | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
2. complete processing
Take feed composition by said ratio respectively, add in high-speed mixer and mix, material after mixing is sent to granulation in dual-screw pelletizer, obtain weather resistance environmental protection flame retardant flexible cable polymer materials of the present invention.Processing temperature scope: 180-220 DEG C, screw speed is: 240-350rpm.
3. performance test
To carrying out performance test by the polymer materials of above-mentioned formula system, acquired results is as following table
The blend of the TPE material of the present invention taking SEBS as base material and the TPV material taking PP/EPDM as base material as can be seen from the above table, improve processing characteristics, improve tensile strength, can reach 14MPA, use temperature is higher, can be used as 105 DEG C of lines and uses, there is good weather resistance, being specially adapted to the severe open air use the present invention of environment, to select halogen flame be environment-friendly type,, containing biphenol compound, can not discharge the harmful dioxin of biology when burning.The present invention has improved the use temperature upper limit, at 136 DEG C, and the mensuration of 168H, stretching strength retentivity is greater than 90%.
Above-described embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some changes and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention is that described claim is as the criterion.
Polymer materials and preparation method thereof for a kind of weather resistance environmental protection flame retardant flexible cable provided by the invention, (1) blend of the TPE material taking SEBS as base material and the TPV material taking PP/EPDM as base material, improve processing characteristics, further improve tensile strength, can reach 14MPA, use temperature is higher, can be used as 105 DEG C of lines uses, there is good weather resistance, being specially adapted to the severe open air use the present invention of environment, to select halogen flame be environment-friendly type,, containing biphenol compound, when burning, can not discharge the harmful dioxin of biology.
(2) the present invention selects by several olefin polymers, and under large inorganics adds, the more general TPE material taking SEBS as base material sees, Strength retention is good, dryer and comfortableer feel, better ink affinity.
(3) the present invention has improved the use temperature upper limit.By 136 DEG C, the mensuration of 168H, intensity and elongation retention are greater than 90%.
(4) the present invention adds man-hour doing cable extruding, has wide process window.Can be from 160 DEG C to 240 DEG C.
(5) the present invention have good water-fast, resistance to separate out etc.
(6) the present invention is a kind of flame-retardant system of expanded polystyrene veneer, becomes charcoal effective, can not drip.
(7) the present invention has good weather resistance.
Claims (10)
1. a weather resistance environmental protection flame retardant flexible cable polymer materials, comprises each component of following weight part content,
A component: 100 parts of TPE,
B component: 20-200 part TPV,
C component: 50-130 part fire retardant;
Described TPE comprises each component of following weight part content:
(A1) thermoplastic styrene butadiene rubber SEBS100 part,
(A2) mineral oil: 100-150 part,
(A3) polypropylene: 80-200 part,
(A4) polyolefin elastomer: 0-100 part,
(A5) inorganic filler: 0-200 part;
Described TPV comprises each component of following weight part content:
(B1) polypropylene: 50-120 part,
(B2) terpolymer EP rubber: 100 parts,
(B3) resol: 2-10 part,
(B4) zinc oxide: 0-6 part;
Described C component comprises:
(C1) be selected from TDE, 1,2-two (2,4,6-tribromophenoxy) ethane, tetrabromo-bisphenol, PHT4, the eight bromo ether (one in 1.1 '-(methyl is pitched)-bis-[(3.5-dibromo) – 4 (2.3-dibromo propoxy benzene)], two (tetrabromo-phthalic dme imines) ethane, hexabromocyclododecane, selected particle diameter is 10-30 μ m, 5-200 part;
(C2) be selected from the one in antimonous oxide, zinc borate and zinc oxide, 5-200 part;
Described TPE is styrene analog thermoplastic elastomer;
Described TPV is TP-EPDM Thermoplastic elastomer-based on EPDM.
2. polymer materials according to claim 1, is characterized in that, the weight ratio of described component C1 and component C2 is 5:1-1:1, and component C1 and component C2 weight sum account for the 10-50% of whole polymer materials gross weight.
3. polymer materials according to claim 1, is characterized in that, described polypropylene is homopolymerization type or copoly type, and its melting index is 0.5-10g/10min; Described resol is selected from the SP1045 of Sheng Laike specialization work.
4. polymer materials according to claim 1, is characterized in that, described TPE is selected from one or both in ethylene-octene copolymer, ethylene-propylene copolymer, and its Vicat softening point is not less than 70 DEG C.
5. polymer materials according to claim 1, it is characterized in that, described TPE is selected from styrene block copolymer, and described styrene block copolymer is selected from one or more in styrene-butadiene-styrene, styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-ethylene-propylene-vinylbenzene.
6. polymer materials according to claim 5, is characterized in that, the tenderizer of described styrene block copolymer is selected from one or both in paraffinic base rubber oil, naphthenic rubber oil; The solubilizing agent of described styrene block copolymer is selected from one or both in the SEBS of maleic anhydride graft and the polypropylene of maleic anhydride graft.
7. polymer materials according to claim 1, is characterized in that, the mooney viscosity of described terpolymer EP rubber is not less than 60
mL100 DEG C of 1+4.
8. polymer materials according to claim 1, is characterized in that, described polymer materials also comprises filler, and described filler is selected from calcium carbonate, talcum, kaolin, the one in barium sulfate.
9. polymer materials according to claim 1, is characterized in that, the tensile strength of described polymer materials reaches 14.0MPa; Be 136 DEG C in temperature, the time is that 168H measures, and its stretching strength retentivity is greater than 90%.
10. according to the preparation method of the polymer materials described in claim 1-9 any one, it is characterized in that, its preparation method is that in A component, A1-A5 is first made into after TPE and B B component 1-B5 are first made into TPV and uses C1-C2 blend granulation in twin screw granulation and C component again; Or A1-A5 in A component, B1-B4 in B component, and in C component after C1-C2 single stage method co-blended, then use twin screw granulation.
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