CN114437494A - TPE sheath material for charging cable and preparation method thereof - Google Patents
TPE sheath material for charging cable and preparation method thereof Download PDFInfo
- Publication number
- CN114437494A CN114437494A CN202210243298.3A CN202210243298A CN114437494A CN 114437494 A CN114437494 A CN 114437494A CN 202210243298 A CN202210243298 A CN 202210243298A CN 114437494 A CN114437494 A CN 114437494A
- Authority
- CN
- China
- Prior art keywords
- parts
- tpe
- charging cable
- hydroxyl
- cracking agent
- 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.)
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- 239000000463 material Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005336 cracking Methods 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 95
- -1 polypropylene Polymers 0.000 claims abstract description 73
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 56
- 239000004743 Polypropylene Substances 0.000 claims abstract description 31
- 229920001155 polypropylene Polymers 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 31
- 239000003963 antioxidant agent Substances 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 238000005469 granulation Methods 0.000 claims description 23
- 230000003179 granulation Effects 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012796 inorganic flame retardant Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 150000004646 arylidenes Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000626 sulfinic acid group Chemical group 0.000 claims description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims 1
- 125000005529 alkyleneoxy group Chemical group 0.000 claims 1
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 58
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 85
- 239000003921 oil Substances 0.000 description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 32
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 22
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 22
- 238000005520 cutting process Methods 0.000 description 22
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical group CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000227 grinding Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 17
- 229910052901 montmorillonite Inorganic materials 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 16
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 15
- 239000008116 calcium stearate Substances 0.000 description 15
- 235000013539 calcium stearate Nutrition 0.000 description 15
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000005662 Paraffin oil Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- MMKLGSAPZRJREQ-UHFFFAOYSA-N butylbenzene phosphoric acid Chemical compound C(CCC)C1=CC=CC=C1.P(O)(O)(O)=O MMKLGSAPZRJREQ-UHFFFAOYSA-N 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to the technical field of cables, in particular to a TPE (thermoplastic elastomer) sheath material for a charging cable and a preparation method thereof. The TPE sheath material for the charging cable comprises the following raw materials in parts by weight: 20-30 parts of hydrogenated styrene-butadiene block copolymer; 15-22 parts of polypropylene; 20-30 parts of a plasticizer; 3-8 parts of an ethylene-propylene copolymer; 3-8 parts of an anti-cracking agent; the anti-cracking agent is prepared from the following raw materials in parts by weight: 60-80 parts of end group functionalized hyperbranched polyphenylene oxide; 20-40 parts of hydroxyl-terminated polysiloxane; 3-5 parts of a silane coupling agent. The TPE sheath material for the charging cable disclosed by the invention takes the hydrogenated styrene-butadiene block copolymer and the polypropylene as the matrix, the plasticizer, the ethylene-propylene copolymer and the anti-cracking agent are added into the matrix, and the components are matched and act synergistically, so that the cable sheath material can ensure the original good processability and elasticity of the thermoplastic elastomer, and the anti-cracking performance of the cable sheath material is also obviously improved.
Description
Technical Field
The invention relates to the field of cables, in particular to a TPE (thermoplastic elastomer) sheath material for a charging cable and a preparation method thereof.
Background
With the increasing attention of the international society on environmental protection, the new energy automobile industry is rapidly developed aiming at various reform of the automobile industry in China, meanwhile, the market of the charging gun is also rapidly increased, the materials mainly used as the sheath material of the charging gun at present comprise three materials of TPE, TPU and cross-linked PE, wherein the TPE material has the advantages of simple preparation process, low cost, excellent elasticity and low temperature resistance, and occupies most of the share of the market.
TPE materials are various in types, but generally speaking, the TPE materials refer to thermoplastic elastomers which are blended and modified on the basis of hydrogenated styrene-butadiene copolymers, the TPE materials are stable in property, toxic substances are not contained in the material composition, and the TPE materials have the elasticity of rubber and can be recycled, so that energy is effectively saved. However, since the material structure of the cable sheath has no chemical crosslinking structure, mainly comprises a macromolecule chain entanglement point and a physical crosslinking structure, the service temperature of the cable sheath can only reach 90 ℃ at most, and after the cable sheath is prepared into the cable sheath of the charging gun, the cable sheath is subjected to the conditions of dragging, friction with the ground or a hard object, insolation and quenching, bending and folding and the like during the use process, so that many products on the market can crack under the stress or aging condition. In the face of market demands, the stress resistance and the aging cracking resistance of the TPE material are required to be further increased so as to improve the safety and the durability of the TPE material as a charging gun sheath material.
Disclosure of Invention
The invention provides a TPE sheath material for a charging cable, aiming at improving the aging and cracking resistance of the TPE sheath material for the charging cable.
In order to achieve the purpose, the invention provides a TPE sheath material for a charging cable, which comprises the following raw materials in parts by weight: 20-30 parts of hydrogenated styrene-butadiene block copolymer; 15-22 parts of polypropylene; 20-30 parts of a plasticizer; 3-8 parts of an ethylene-propylene copolymer; 3-8 parts of anti-cracking agent. The anti-cracking agent is prepared from the following raw materials in parts by weight: 60-80 parts of end group functionalized hyperbranched polyphenylene oxide; 20-40 parts of hydroxyl-terminated polysiloxane; 3-5 parts of a silane coupling agent.
The preparation method of the anti-cracking agent comprises the following steps: the raw materials in parts by weight are selected as follows: 60-80 parts of end group functionalized hyperbranched polyphenyl ether, 20-40 parts of hydroxyl-terminated polysiloxane and 3-5 parts of silane coupling agent; and mechanically stirring and blending the terminal group functionalized hyperbranched polyphenyl ether, the hydroxyl-terminated polysiloxane and the silane coupling agent for 5min, and mechanically grinding into powder to obtain the anti-cracking agent.
In the invention, the hydrogenated styrene-butadiene is a high-molecular-weight thermoplastic elastomer in a star-shaped structure, the hydrogenated styrene-butadiene block copolymer and the polypropylene are jointly used as a matrix, the plasticizer, the ethylene-propylene copolymer and the anti-cracking agent are added into the matrix, and the components are mutually matched and act synergistically, so that the cable sheath material can ensure the original good processability and elasticity of the thermoplastic elastomer, and the anti-cracking performance of the cable sheath material is also obviously improved. The TPE sheath material for the charging cable can meet thermal shock cracking resistance tests at 110-150 ℃, and cables with different specifications, which are made of the TPE sheath material, can meet the requirements of GB/T33594-2017 on various aging and cracking resistance tests of finished cables, and has excellent flame retardance and low temperature resistance. The TPE sheath material for the charging cable has the following properties: the tensile strength is 10-15MPa, the elongation at break is 300-400%, no crack is generated after thermal shock is carried out for 168 hours at 110 ℃, 130 ℃ and 150 ℃, the high-temperature pressure at 90 ℃ is less than or equal to 20%, the hardness is less than or equal to 80A, and the trouser-type tear is more than or equal to 30 kN/m; the TPE sheath material for the charging cable has no crack after being aged for 3000h at 110 ℃, 1000h at 125 ℃ and 3000h outdoors. According to the invention, the anti-cracking agent is prepared from the terminal group functionalized hyperbranched polyphenyl ether, the hydroxyl-terminated polysiloxane and the silane coupling agent, the anti-cracking agent and the hydrogenated styrene-butadiene block copolymer act synergistically, and the physical crosslinking point of the material can be greatly increased by adding a small amount of the anti-cracking agent into the hydrogenated styrene-butadiene block copolymer thermoplastic elastomer, so that the material has excellent anti-cracking performance and excellent toughness; the addition of the terminal group functionalized hyperbranched polyphenyl ether improves the cracking resistance of the TPE sheathing material, and the synergistic effect of the terminal group functionalized hyperbranched polyphenyl ether and the hydroxyl-terminated polysiloxane enhances the toughness, the impact strength and the elongation at break of the TPE sheathing material. In addition, the anti-cracking agent has good compatibility with the whole system, the risk of cracking caused by poor compatibility is avoided, and the prepared TPE sheath material for the charging cable has excellent anti-cracking, flame-retardant and low-temperature-resistant properties by compounding with other raw materials, and can be widely applied to the field of new energy charging guns.
According to the TPE sheathing compound, the solution viscosity of the hydrogenated styrene-butadiene block copolymer is 300-500cps, and the hardness is 80-85A. The hydrogenated styrene-butadiene block copolymer comprises 20-30 parts by weight of, for example: 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts or any value therebetween. Preferably, the hydrogenated styrene-butadiene block copolymer is 22 parts by weight.
According to the TPE sheath material disclosed by the invention, the weight parts of the polypropylene are 15-22 parts, for example: 15 parts, 17 parts, 19 parts, 22 parts or any value therebetween. Preferably, the weight part of the polypropylene is 18 parts.
According to the TPE sheath material, the plasticizer is used for improving the flowability of the thermoplastic elastomer and improving the processability of the thermoplastic elastomer. The weight part of the plasticizer is 20-30 parts, for example: 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts or any value therebetween. Preferably, the weight part of the plasticizer is 15 parts. The plasticizer can be one or more of white oil, naphthenic oil and paraffin oil.
According to the TPE sheath material, the melt flow rate of the ethylene-propylene copolymer is 1-3 g/min (190 ℃, 2.16kg), and the resistivity is more than or equal to 1015Ω cm, hardness 60-64A. The ethylene-propylene copolymer has excellent ozone resistance, heat resistance, weather resistance and other aging resistance, and has the characteristics of good chemical resistance, electric insulation performance, impact elasticity, low-temperature performance, low density, high filling property, hot water resistance, water vapor resistance and the like; the ethylene-propylene copolymer has the advantages of both polyethylene and polypropylene, and has better high temperature resistance and hardness than polyethylene and better impact resistance and low temperature resistance than polypropylene. The ethylene-propylene copolymer comprises 3-8 parts by weight of, for example: 3 parts, 5 parts, 7 parts, 8 parts or any value therebetween; preferably, the weight part of the ethylene propylene copolymer is 6 parts.
According to the TPE sheath material disclosed by the invention, the anti-cracking agent is a self-made anti-cracking agent, and the anti-cracking agent is 3-8 parts by weight, such as: 3 parts, 5 parts, 7 parts, 8 parts or any value therebetween. The anti-cracking agent is prepared from the following raw materials in parts by weight: 60-80 parts of end group functionalized hyperbranched polyphenylene oxide, such as 60 parts, 65 parts, 70 parts, 75 parts, 80 parts and any value therebetween; 20-40 parts of hydroxyl-terminated polysiloxane, such as: 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or any value therebetween; 3-5 parts of a silane coupling agent, such as: 3 parts, 4 parts, 5 parts or any value therebetween.
According to the TPE sheath material, the molecular weight of the terminal group functionalized hyperbranched polyphenyl ether is 2000-3000; the molecular weight of the hydroxyl-terminated polysiloxane is 2000-3000.
The structural formula of the terminal group functionalized hyperbranched polyphenylene oxide is as follows:
wherein R is1Selected from C1-C10 alkylidene or C1-C18 arylidene; x is selected from a hydrogen atom, a halogen atom or a hydroxyl group; y is1And Y2Independently selected from one of oxygen atom, allylene, epoxy, sulfinic acid group; n is more than or equal to 5 and less than or equal to 8; m is more than or equal to 5 and less than or equal to 8.
The typical structure of the terminal group functionalized hyperbranched polyphenylene ether is shown in figure 1.
The hydroxyl-terminated polysiloxane comprises the following synthetic raw materials:and, HO-R3-OH; wherein R is2Selected from any one of hydrogen atom, halogen, hydroxyl, alkyl, silyl, alkoxy, acyl or ester group, R3Selected from C1-C8 alkylene, said R3In (C) may contain an ether bond or an ester bond.
The typical structure of the hydroxyl-terminated polysiloxane is shown in FIG. 2.
According to the TPE sheathing compound, the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane (KH550), gamma- (2, 3-epoxy) propyltrimethoxysilane (KH560), vinyl trimethoxysilane (A171) and vinyl tris (2-methoxyethoxy) silane (A172).
The TPE sheath material for the charging cable also comprises the following raw materials in parts by weight: 27-42 parts of a flame retardant; 2-5 parts of a char forming agent; 0.2-1 part of a lubricant; 0.2-1 part of a light stabilizer; 0.2-1 part of antioxidant.
According to the TPE sheathing compound, the flame retardant is selected from one or more of phosphorus flame retardants, nitrogen flame retardants and inorganic flame retardants. The phosphorus flame retardant is a flame retardant with good flame retardant performance, has the advantages of no generation of corrosive gas, lasting effect, low toxicity and the like, and comprises triphenyl phosphate, ditolyl phosphate, butylbenzene phosphate, red phosphorus flame retardant, ammonium phosphate salt, ammonium polyphosphate and the like. The nitrogen flame retardant is a halogen-free environment-friendly flame retardant, has the advantages of economical use, high efficiency, excellent electrical property and mechanical property, no color change, low smoke, low corrosivity and the like, and is very effective in flame retardance when used together with various halogen derivatives, metal oxides, certain organic phosphoric acid or alkali metal and alkaline earth metal salts. The inorganic flame retardant is mainly a flame retardant system such as antimony trioxide, magnesium hydroxide, aluminum hydroxide, silicon system and the like, and has the advantages of environmental protection, low price and the like; wherein, the aluminum hydroxide is a flame retardant which integrates the functions of flame retardance, smoke suppression and filling, has no toxicity, no corrosion, good stability, no generation of toxic gas at high temperature, low price and wide source; magnesium hydroxide decomposes between 340 ℃ and 490 ℃. Good thermal stability, good flame-retardant and smoke-eliminating effects, and is especially suitable for polyolefin plastics with higher processing temperature.
According to the TPE sheath material disclosed by the invention, the flame retardant comprises the following components in parts by weight: 7-12 parts of a phosphorus flame retardant; 10-15 parts of nitrogen-based flame retardant; 10-15 parts of an inorganic flame retardant; the flame retardant is compounded and supplemented with various flame retardants, and the flame retardant performance is better than that of the flame retardant performance which is singly used. In one embodiment, the phosphorus-based flame retardant is diethyl aluminum hypophosphite (ADP), the weight part of the diethyl aluminum hypophosphite can be 7 parts, 9 parts, 11 parts, 12 parts and any value therebetween, and preferably, the weight part of the diethyl aluminum hypophosphite is 12 parts; the nitrogen flame retardant is Melamine Cyanurate (MCA), the weight parts of the melamine cyanurate can be 10 parts, 12 parts, 14 parts, 15 parts and any value therebetween, and preferably, the weight parts of the melamine cyanurate is 10 parts; the inorganic flame retardant is one or more of magnesium hydroxide, aluminum hydroxide and calcium carbonate; the weight part of the inorganic flame retardant may be 10 parts, 12 parts, 14 parts, 15 parts and any value therebetween, and preferably, the weight part of the inorganic flame retardant is 12 parts.
Preferably, the TPE sheath material for the charging cable further comprises a char-forming agent, wherein the char-forming agent has the advantages of small addition amount, high char-forming flame-retardant efficiency, no harmful compound generation during combustion, reduction of smoke density problem of the traditional flame retardant, good glossiness of a flame-retardant product, good dispersion fluidity, no white point and capability of reducing the using amount of the flame retardant; the carbon forming agent is one or more of pentaerythritol phosphate, montmorillonite, silicate and phenolic resin; the weight portion of the carbon forming agent can be 2 parts, 3 parts, 4 parts, 5 parts and any value between the two parts; preferably, the weight part of the carbon forming agent is 3 parts.
According to the TPE sheath material disclosed by the invention, the lubricant enables mixed feeding in a plasticizing state in an internal mixing process to have better compatibility and leveling property, and ensures that the sheath material is uniform in overall appearance and smooth in surface. The lubricant is not particularly limited in the invention, and may be one known to those skilled in the art, prepared by a known method or commercially available. Preferably, the lubricant is one or more of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin wax and silicone. The weight part of the lubricant may be 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part or any value therebetween, and preferably, the weight part of the lubricant is 0.5 parts.
According to the TPE sheathing compound, the light stabilizer and the antioxidant are used for inhibiting or reducing the thermal oxidation and photo-oxidation reaction speed of the sheathing compound, so that the heat resistance and the light resistance of the sheathing compound are obviously improved, and the photo-aging process of the sheathing compound is effectively prevented or delayed, thereby achieving the purpose of prolonging the service life of the sheathing compound. The light stabilizer of the present invention is not particularly limited, and may be one known to those skilled in the art, prepared by a known method or commercially available. Preferably, the light stabilizer is one or more of zinc oxide, titanium dioxide, benzophenone, salicylic acid and benzotriazole. The light stabilizer may be present in an amount of 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, or any value therebetween, preferably 0.3 parts.
The antioxidant of the present invention is not particularly limited, and may be one known to those skilled in the art, prepared by a known method or commercially available. Preferably, the antioxidant is one or more of bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1035), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), pentaerythritol tetrakis (3-laurylthiopropionate) (antioxidant TH-412S), and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098). The antioxidant may be present in an amount of 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, or any value therebetween, preferably 0.5 parts by weight.
The TPE sheath material provided by the invention comprises the following preparation steps:
s1, adding hydrogenated styrene-butadiene block copolymer, polypropylene, ethylene-propylene copolymer, plasticizer and anti-cracking agent into an internal mixer for banburying, and then crushing to obtain a crushed material.
S2, granulating the crushed material obtained in the step S1 through a double-screw extruder to obtain particles;
and S3, drying the particles obtained in the step S2 to obtain the TPE sheath material for the crack-resistant charging cable.
As a further preferred embodiment of the present invention, the preparation steps are specifically as follows:
s1, weighing the materials according to the corresponding weight parts, adding the weighed hydrogenated styrene-butadiene copolymer, polypropylene, ethylene-propylene copolymer, plasticizer, anti-cracking agent, diethyl aluminum hypophosphite, melamine urate, aluminum hydroxide, carbon forming agent, lubricant, light stabilizer and antioxidant into an internal mixer, melting and mixing uniformly, and then crushing to obtain a crushed material.
S2, enabling the obtained crushed material to pass through a material with the length-diameter ratio of (35-40): 1 extruding and granulating at 170-190 ℃ by a double-screw extruder to obtain particles.
And S3, drying the particles obtained in the step S2 at the temperature of between 80 and 90 ℃ to obtain the cracking-resistant TPE sheath material for the charging cable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the specification forming a part of the present invention are only used for providing further understanding of the present application and do not constitute a limitation of the present application.
FIG. 1 is a schematic diagram of a typical structure of an end group functionalized hyperbranched polyphenylene ether of the present invention:
FIG. 2 is a schematic diagram of a typical structure of the hydroxyl-terminated polysiloxane of the present invention.
Detailed Description
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified. Unless otherwise defined, terms used in the present specification have the same meaning as those generally understood by those skilled in the art, but in case of conflict, the definitions in the present specification shall control.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass non-exclusive inclusions, as well as non-exclusive distinctions between such terms. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting essentially of …" and "consisting essentially of …". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
All numbers or expressions referring to quantities of ingredients, process conditions, etc. used in the specification and claims are to be understood as modified in all instances by the term "about". All ranges directed to the same component or property are inclusive of the endpoints, and independently combinable. Because these ranges are continuous, they include every value between the minimum and maximum values. It should also be understood that any numerical range recited herein is intended to include all sub-ranges within that range. As used herein, "parts by weight," "parts by mass," or "parts by mass" are used interchangeably and can be any fixed weight expressed in milligrams, grams, or kilograms (e.g., 1mg, 1g, 2g, 5g, or 1kg, etc.). For example, a composition consisting of 1 part by weight of component a and 9 parts by weight of component b may be a composition consisting of 1g of component a +9 g of component b, or 10 g of component a +90 g of component b.
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Example 1
The formula is as follows:
the preparation steps are as follows:
(1) the hydroxyl-terminated polyphenyl ether, the hydroxyl-terminated dimethyl siloxane and the KH550 are mechanically stirred and blended for 5min, and then mechanically ground into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding the polypropylene, the uniformly mixed white oil, the hydrogenated styrene-butadiene block copolymer and the anti-cracking agent into an internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 2
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; and then adding the flame retardant, the polypropylene, the uniformly mixed white oil, the hydrogenated styrene-butadiene block copolymer and the anti-cracking agent into an internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 3
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite (ADP), Melamine Cyanurate (MCA) and aluminum hydroxide into a pressurized internal mixer for mixing, then adding polypropylene, white oil, hydrogenated styrene-butadiene block copolymer and anti-cracking agent which are uniformly mixed into the internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 4
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide and montmorillonite into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, cutting and crushing, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 5
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 6
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 7
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH560 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Evenly mixing paraffin oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, evenly mixed paraffin oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 160 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 35: 1, the granulation temperature is 170 ℃.
Example 8
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding ditolyl phosphate, melamine cyanurate, magnesium hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 9
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, silicate, paraffin, an antioxidant TH-412S and titanium dioxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, a hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Example 10
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 160 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 40: 1, the granulation temperature is 190 ℃.
Comparative example 1
The formula is as follows:
the preparation steps are as follows:
(1) mixing white oil and hydrogenated styrene-butadiene block copolymer (SEBS) uniformly, and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 2
The formula is as follows:
the preparation steps are as follows:
(1) the hydroxyl-terminated dimethyl siloxane and KH550 are mechanically stirred and blended for 5min, and then mechanically ground into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 3
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functionalized hyperbranched polyphenylene oxide and KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 4
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated functionalized hyperbranched polyphenylene oxide and the hydroxyl-terminated dimethyl siloxane for 5min, and mechanically grinding the mixture into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 5
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functional hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding the uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 6
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functional hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, a hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 7
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functional hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing the white oil and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials out for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 8
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functional hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, stearic acid, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, white oil and an anti-cracking agent which are uniformly mixed into the internal mixer for mixing and homogenizing, pouring out the materials when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, cutting and crushing the materials, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 9
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated functional hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 10
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; and then adding the flame retardant, the polypropylene, the uniformly mixed white oil, the hydrogenated styrene-butadiene block copolymer and the anti-cracking agent into an internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 11
The formula is as follows:
the preparation steps are as follows:
(1) mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite (ADP), Melamine Cyanurate (MCA) and aluminum hydroxide into a pressurized internal mixer for mixing, then adding polypropylene, white oil, hydrogenated styrene-butadiene block copolymer and anti-cracking agent which are uniformly mixed into the internal mixer for mixing and homogenizing, pouring out the materials for cutting and crushing when the materials are completely melted and the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Comparative example 12
The formula is as follows:
the preparation steps are as follows:
(1) firstly mechanically stirring and blending the hydroxyl-terminated hyperbranched polyphenylene oxide, the hydroxyl-terminated dimethyl siloxane and the KH550 for 5min, and then mechanically grinding into powder to obtain the anti-cracking agent for later use.
(2) Uniformly mixing white oil, hydrogenated styrene-butadiene block copolymer (SEBS) and the anti-cracking agent obtained in the step (1), and standing for 4-8 h; then adding diethyl aluminum hypophosphite, melamine cyanurate, aluminum hydroxide, montmorillonite, calcium stearate, an antioxidant 1035 and zinc oxide into a pressurized internal mixer for mixing, then adding polypropylene, uniformly mixed white oil, hydrogenated styrene-butadiene block copolymer and an anti-cracking agent into the internal mixer for mixing and homogenizing, pouring the materials for cutting and crushing when the materials are completely melted, wherein the temperature of the internal mixer is about 170 ℃, and then further granulating and homogenizing by using a double-screw extruder, wherein the length-diameter ratio of the used double screws is 38: 1, the granulation temperature is 180 ℃.
Performance testing
In order to verify the performance of the product of the invention, the TPE sheath materials prepared in the above examples and comparative examples were respectively subjected to relevant performance tests, and the specific method was as follows:
testing the physical and mechanical properties according to the standard of GB/T33594-2017;
the results of testing the TPE sheathing materials of examples 1-8 and comparative example 1 are shown in the following table.
It should be noted that, cracking at any one of the three temperatures of 110 ℃, 130 ℃ and 150 ℃ after thermal shock is regarded as unqualified, and no cracking at any of the three temperatures is regarded as qualified.
According to the test result, the anti-cracking agent can greatly improve the anti-cracking performance of the TPE sheathing material as seen from the example 5 and the comparative example 1, and the end group functionalized hyperbranched polyphenylene oxide can greatly improve the mechanical performance of the TPE sheathing material as seen from the example 5, the comparative example 2, the comparative example 3 and the comparative example 4, and the end hydroxyl polysiloxane can greatly improve the toughness and the impact resistance of the TPE sheathing material, wherein the end group functionalized hyperbranched polyphenylene oxide, the end hydroxyl polysiloxane and the silane coupling agent act synergistically to obtain the TPE sheathing material with high toughness, high impact resistance and strong anti-cracking performance; as can be seen from examples 1, 2 and 3, and comparative examples 10 and 11, the mechanical properties of the TPE sheath material are greatly affected when the weight parts of the flame retardant in the TPE sheath material for the charging cable are too large; as can be seen from example 5 and comparative example 12, the mechanical properties of the TPE sheathing material are greatly influenced by the excessive weight parts of the carbon forming agent, the lubricant, the light stabilizer and the antioxidant in the TPE sheathing material for the charging cable.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The TPE sheath material for the charging cable is characterized by comprising the following raw materials in parts by weight:
20-30 parts of hydrogenated styrene-butadiene block copolymer;
15-22 parts of polypropylene;
20-30 parts of a plasticizer;
3-8 parts of an ethylene-propylene copolymer;
3-8 parts of an anti-cracking agent;
the anti-cracking agent is prepared from the following raw materials in parts by weight:
60-80 parts of end group functionalized hyperbranched polyphenylene oxide;
20-40 parts of hydroxyl-terminated polysiloxane;
3-5 parts of a silane coupling agent.
2. The TPE sheathing compound for the charging cable as claimed in claim 1, wherein the TPE sheathing compound for the charging cable further comprises 27 to 42 parts by weight of a flame retardant.
3. The TPE sheath material for the charging cable as claimed in claim 2, wherein the flame retardant comprises the following components in parts by weight; 7-12 parts of a phosphorus flame retardant; 10-15 parts of nitrogen-based flame retardant; 10-15 parts of an inorganic flame retardant.
4. The TPE sheathing compound for the charging cable as claimed in claim 3, wherein the TPE sheathing compound for the charging cable further comprises 2-5 parts by weight of a char forming agent.
5. The TPE sheathing compound for the charging cable as claimed in claim 3, further comprising the following raw materials by weight: 0.2-1 part of a lubricant; and/or 0.2-1 part of antioxidant; and/or 0.2-1 part of light stabilizer.
6. The TPE sheathing compound for the charging cable according to claim 1, wherein the molecular weight of the terminal functionalized hyperbranched polyphenylene oxide is between 2000 and 3000; and/or the molecular weight of the hydroxyl-terminated polysiloxane is 2000-3000.
7. The TPE sheathing compound for charging cables as claimed in claim 6, wherein the terminal group functionalized hyperbranched polyphenylene oxide has the following structural formula:
wherein R is1Selected from C1-C10 alkylidene or C1-C18 arylidene; x is selected from a hydrogen atom, a halogen atom or a hydroxyl group; y is1And Y2Independently selected from one of oxygen atom, allylene, epoxy, sulfinic acid group; n is more than or equal to 5 and less than or equal to 8; m is more than or equal to 5 and less than or equal to 8.
8. The TPE sheathing compound for charging cables as claimed in any one of claims 1 to 7, wherein the hydroxyl terminated polysiloxane is synthesized from the following raw materials:
Wherein, R is2Selected from any one of hydrogen atom, halogen, hydroxyl, alkyl, silyl, alkoxy, acyl or ester group, R3Selected from C1-C10 alkylene groups and alkyleneoxy groups.
9. The preparation method of the TPE sheath material for the charging cable, which is characterized by comprising the following steps:
s1, adding a hydrogenated styrene-butadiene block copolymer, polypropylene, an ethylene-propylene copolymer, a plasticizer and an anti-cracking agent into an internal mixer for banburying, and then crushing to obtain a crushed material;
s2, granulating the crushed material obtained in the step S1 through a double-screw extruder to obtain particles;
and S3, drying the particles obtained in the step S2 to obtain the TPE sheath material for the charging cable.
10. The method according to claim 9, wherein the banburying temperature in S1 is 160 ℃ to 180 ℃; the length-diameter ratio of the screw of the twin-screw extruder in S2 is (35-40): 1, the granulation temperature of the double-screw extruder is 170-190 ℃.
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CN118256058B (en) * | 2024-05-31 | 2024-09-20 | 山东立卓睡眠科技有限公司 | Degradable TPE hollow tubular filler and preparation method thereof |
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