CN115895088A - Low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material and preparation method thereof - Google Patents
Low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- 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 69
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 52
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000000779 smoke Substances 0.000 title claims abstract description 44
- 231100000053 low toxicity Toxicity 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 13
- 230000002195 synergetic effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- -1 phosphate ester Chemical class 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 16
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention relates to a low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material and a preparation method thereof, wherein the low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material comprises, by weight, 50-100 parts of ultra-high molecular weight polyethylene, 5-100 parts of a composite flame retardant, 0.01-3 parts of a coupling agent, 0.1-2 parts of a smoke suppressant and 0.1-1 part of a lubricant. Compared with the prior art, the flame-retardant ultrahigh molecular weight polyethylene composite material prepared by the invention has the advantages of low smoke, low toxicity, no halogen, good flame-retardant effect, capability of reaching UL94V-0 level, oxygen index of 32%, smoke density of 234.7 under the smokeless condition of 25kw, and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a low-smoke low-toxicity halogen-free flame retardant ultra-high molecular weight polyethylene composite material and a preparation method thereof.
Background
The ultrahigh molecular weight polyethylene (UHMWPE) is a novel thermoplastic engineering plastic with excellent comprehensive performance, and has excellent mechanical property endowed by a highly-entangled chain segment structure with extremely high molecular weight, the impact resistance of the material is at the top of the plastic, the material can still maintain toughness at-80 ℃, and the material has extremely high wear resistance, excellent stress cracking resistance and corrosion resistance, extremely low friction factor and excellent self-lubricating property. The excellent properties greatly exceed all the prior engineering plastics and some metal materials in some aspects, and the composite material is increasingly paid attention to by people and has wide application prospects in the fields of papermaking, food and beverage, mining, transportation, ceramics, machinery, textile, hydraulic and electric power and the like and geotechnical engineering construction. UHMWPE has been widely used in such areas in developed countries and regions such as abroad, germany, america, japan and europe. In China, the material also gradually enters the fields of coal mines, coal preparation plants, power plants and other industries, increasingly shows the important function of the material, and is known as a novel and astonishing efficient energy-saving material.
However, UHMWPE has the same difficult drawback to overcome as ordinary polyethylene, namely poor flame retardancy, with a Limiting Oxygen Index (LOI) of only 17.5%. Polyolefins with an oxygen index of less than 21% are flammable plastics, and thus the flame retardancy of UHMWPE greatly limits its widespread use and development. In addition, the combustion process has large heat productivity and smoke generation amount, and generates a molten drop phenomenon, thereby causing secondary fire hazard, so that the flame retardant modification of the flame retardant modified flame retardant has very important significance.
In recent years, many experts and scholars have studied flame retardancy of general-purpose plastics such as polyethylene, but there are few reports on flame retardancy of UHMWPE. Among the commonly used flame retardants, the organic flame retardants often produce a large amount of smoke when burning, and the released gas is toxic and corrosive; the inorganic flame retardant has the advantages of no toxicity, no corrosion and the like, but has poor flame retardance, and other properties of the material are greatly reduced due to the use of large dose and compatibility problems. And the amount of flame retardant varies with the type of polymer, e.g. 12% bromine organic flame retardant to 6% Sb 2 O 3 The mixed modified PE can make the oxygen index of PE reach over 27%, while the same flame retardant is used for UHMWPE, which can only make the oxygen index reach 22.7%.
Disclosure of Invention
Based on the problem of poor flame retardant property of ultra-high molecular weight polyethylene in the prior art, the invention provides a low-smoke low-toxicity halogen-free flame retardant ultra-high molecular weight polyethylene composite material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention firstly provides a low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material which comprises the following components in parts by weight:
in some embodiments of the present invention, the composite flame retardant consists of the following components in parts by weight:
in some embodiments of the present invention, the composite flame retardant has a structural formula as shown in fig. 1.
In some embodiments of the present invention, the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material comprises the following components in parts by weight:
50-100 parts of ultra-high molecular weight polyethylene, 20-70 parts of inorganic metal compound, 2-30 parts of graphene, 2-10 parts of synergistic flame retardant, 0.01-3 parts of coupling agent, 0.1-2 parts of smoke suppressant and 0.1-1 part of lubricant.
In some embodiments of the present invention, the ultra-high molecular weight polyethylene is an ultra-high molecular weight polyethylene having a viscosity average molecular weight of 100 to 1000 ten thousand, more preferably an ultra-high molecular weight polyethylene having a viscosity average molecular weight of 800 to 1000 ten thousand.
In some embodiments of the present invention, the inorganic metal compound is selected from one or more of magnesium oxide, magnesium carbonate, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, magnesium phosphate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or calcium carbonate. Preferably one or more of magnesium carbonate, calcium carbonate, aluminum hydroxide and calcium hydroxide. More preferably one or a combination of aluminum hydroxide and magnesium hydroxide, and even more preferably magnesium hydroxide.
In some embodiments of the invention, the number of graphene layers is 1 to 10.
In some embodiments of the invention, the synergistic flame retardant is one or more of phosphite, phosphate, tricresyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). More preferably DOPO.
In some embodiments of the present invention, the coupling agent is one or a combination of silane coupling agent, phthalate coupling agent, or aluminate coupling agent. More preferably a silane coupling agent. Further, the silane coupling agent is preferably a silane coupling agent having a vinyl group.
In some embodiments of the invention, the smoke suppressant is one or a combination of molybdenum disulfide, boehmite, anhydrous zinc borate, zinc stannate, and molybdenum trioxide. More preferably one or a plurality of compositions of molybdenum disulfide and anhydrous zinc borate.
In some embodiments of the present invention, the lubricant is one or more of natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax, and butyl stearate.
The invention further provides a preparation method of the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material, which comprises the following steps:
1) Respectively reacting the graphene, the inorganic metal compound and the synergistic flame retardant with the coupling agent according to parts by weight to respectively obtain coupling products with more active reaction groups;
2) Dispersing the coupling product obtained in the step 1) in a solvent according to the weight part, and stirring and reacting for a certain time to enable chemical bonds among the coupling products to be mutually crosslinked to form a three-dimensional network structure, so as to obtain the composite flame retardant with a certain reaction activity;
3) Adding the silane coupling agent, the smoke suppressant and the lubricant and the ultra-high molecular weight polyethylene into a high-speed mixer according to the parts by weight and uniformly mixing;
4) Adding the composite flame retardant obtained in the step 2) into the high-speed mixer obtained in the step 3) and uniformly mixing to obtain a mixture;
5) And (5) preparing the low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material from the mixture obtained in the step (4) by a hot press molding method.
It should be noted that, in the above preparation method, both step 1) and step 3) involve adding a coupling agent, and the coupling agent in step 1) is a coupling agent for preparing the composite flame retardant in an amount satisfying that "the composite flame retardant consists of the following components in parts by weight: 1-70 parts of inorganic metal compound, 1-30 parts of graphene, 1-70 parts of synergistic flame retardant and 0.01-3 parts of coupling agent, wherein the coupling agent in the step 3) is the coupling agent for preparing the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material, and the dosage of the coupling agent meets the requirement of the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material, and the coupling agent comprises the following components in parts by weight: 50-100 parts of ultra-high molecular weight polyethylene, 5-100 parts of composite flame retardant, 0.01-3 parts of coupling agent, 0.1-2 parts of smoke suppressant and 0.1-1 part of lubricant.
In some embodiments of the invention, in the step 5), the pressing temperature is 200-250 ℃, the pressing pressure is 2-8 MPa, and the pressure maintaining time is 10-60 min.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) According to the invention, the coupling agent is adopted to activate the flame retardant additive with a single component, the inorganic flame retardant (inorganic metal compound), the graphene and the organic flame retardant (synergistic flame retardant) are subjected to grafting reaction through the active group to form a cross-linked network structure, so that a synergistic flame retardant effect is formed, a generated carbon layer is promoted to have higher strength and better density in the combustion process, the flame retardance of the ultra-high molecular weight polyethylene material is obviously improved, and the smoke density is reduced.
2) According to the invention, graphene is added as a flame retardant, and a flame retardant effect is achieved by utilizing a labyrinth effect and a lamellar blocking effect generated by the characteristics of high specific surface area adsorption, high heat conduction, easy carbonization and the like of the graphene and a combined action of a cold trap effect and a dilution effect after an inorganic metal compound is heated and decomposed.
3) In the invention, the silane coupling agent with vinyl is used for carrying out surface modification treatment on the synergistic flame retardant, the inorganic metal compound and the graphene, so that the agglomeration effect is improved, the synergistic flame retardant, the inorganic metal compound and the graphene are better combined with the ultra-high molecular weight polyethylene and are more uniformly mixed. Therefore, the modified material can improve the flame-retardant efficiency and simultaneously give consideration to the mechanical properties of the material.
4) The invention selects the ultra-high molecular weight polyethylene with the molecular weight of 800-1000 ten thousand as the raw material, and the larger molecular weight of the ultra-high molecular weight polyethylene means that the molecular chain is longer, thereby leading the mechanical property of the composite material to be better.
5) Therefore, the invention ensures the mechanical property of the material while solving the problem of flame retardance. In addition, a small amount of lubricant is creatively added, so that the problem that the ultrahigh molecular weight polyethylene is difficult to demould in the hot press molding process is solved.
6) Compared with the prior art, the flame-retardant ultrahigh molecular weight polyethylene composite material prepared by the invention has the advantages of low smoke, low toxicity, no halogen, good flame-retardant effect, capability of reaching UL94V-0 level, oxygen index of 32%, smoke density of 234.7 under the smokeless condition of 25kw, and excellent mechanical property.
Drawings
FIG. 1 is a structural formula of the composite flame retardant.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the scope of the present invention is not limited to the examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The compositions described in examples 1 to 9 and comparative examples 1 and 2 were prepared in such a manner that the amounts of the respective components added are shown in Table 1, and the numerical values of the amounts of the respective components added shown in Table 1 are parts by weight. The performance indexes of the prepared low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material are also listed in table 1.
The preparation method of the low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material comprises the following steps:
(1) Respectively weighing graphene, an inorganic metal compound, a synergistic flame retardant and a coupling agent in proportion to react to obtain a coupling product;
(2) Respectively weighing the coupling product obtained in the step 1) in proportion, dispersing the coupling product in absolute ethyl alcohol, and stirring and reacting for 2 hours at 160 ℃ to obtain a composite flame retardant with certain reaction activity;
(3) Respectively weighing the silane coupling agent, the smoke suppressant, the lubricant and the ultra-high molecular weight polyethylene according to the proportion, adding the mixture into a high-speed mixer, and uniformly mixing the mixture for 20s at a mixing process of 500 r/min; 1500r/min,2min.
(4) Adding the composite flame retardant obtained in the step (2) into the high-speed mixer in the step (3) and uniformly mixing, wherein the mixing process is 500r/min and 20s;1500r/min,3min, to obtain the mixture.
(5) And (3) pressing the mixture obtained in the step (4) on a 160t hydraulic press by a hot press molding method to obtain the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material. The pressing temperature is 230 ℃, the pressing pressure is 5MPa, and the pressure maintaining time is 20min.
TABLE 1 compositions of the components of examples 1-9 and of crews 1, 2 and their properties
Therefore, by adopting the technical scheme of the invention, the flame retardant property is solved, and the mechanical property of the material is ensured. The flame-retardant ultrahigh molecular weight polyethylene composite material prepared in the embodiments 1-9 of the invention has the advantages of low smoke, low toxicity, no halogen, good flame-retardant effect, capability of reaching UL94V-0 level, oxygen index of 32%, smoke density of 234.7 under the smokeless condition of 25kw, and excellent mechanical property.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material is characterized by comprising the following components in parts by weight:
the composite flame retardant comprises the following components in parts by weight:
2. the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1, which is characterized by comprising the following components in parts by weight: 50-100 parts of ultra-high molecular weight polyethylene, 20-70 parts of inorganic metal compound, 2-30 parts of graphene, 2-10 parts of synergistic flame retardant, 0.01-3 parts of coupling agent, 0.1-2 parts of smoke suppressant and 0.1-1 part of lubricant.
3. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1 or 2, wherein the ultrahigh molecular weight polyethylene is ultrahigh molecular weight polyethylene having a viscosity average molecular weight of 100 to 1000 ten thousand.
4. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1 or 2, wherein the inorganic metal compound is one or more of magnesium oxide, magnesium carbonate, aluminum oxide, titanium dioxide, zinc oxide, zirconium oxide, magnesium phosphate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and calcium carbonate;
the number of the graphene layers is 1-10;
the synergistic flame retardant is one or a combination of phosphite ester, phosphate ester, tricresyl phosphate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
5. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 4, wherein the inorganic metal compound is one or a combination of aluminum hydroxide and magnesium hydroxide;
the synergistic flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
6. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1 or 2, wherein the coupling agent is one or a combination of silane coupling agent, phthalate coupling agent or aluminate coupling agent.
7. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1 or 2, wherein the coupling agent is a silane coupling agent with vinyl groups.
8. The low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 1 or 2, wherein the smoke suppressant is one or a combination of molybdenum disulfide, boehmite, anhydrous zinc borate, zinc stannate and molybdenum trioxide;
the lubricant is one or a combination of more of natural paraffin, liquid paraffin, microcrystalline paraffin, polyethylene wax and butyl stearate.
9. The preparation method of the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material as claimed in claim 1 or 2, characterized by comprising the following steps:
1) Respectively reacting the graphene, the inorganic metal compound and the synergistic flame retardant with the coupling agent according to parts by weight to respectively obtain coupling products with more active reaction groups;
2) Dispersing the coupling product obtained in the step 1) in a solvent according to the weight part, and stirring and reacting for a certain time to enable chemical bonds among the coupling products to be mutually crosslinked to form a three-dimensional network structure, so as to obtain the composite flame retardant with a certain reaction activity;
3) Adding the silane coupling agent, the smoke suppressant and the lubricant and the ultra-high molecular weight polyethylene into a high-speed mixer according to the parts by weight and uniformly mixing;
4) Adding the composite flame retardant obtained in the step 2) into the high-speed mixer obtained in the step 3) and uniformly mixing to obtain a mixture;
5) And (3) preparing the mixture obtained in the step (4) into the low-smoke low-toxicity halogen-free flame-retardant ultra-high molecular weight polyethylene composite material by a hot press molding method.
10. The preparation method of the low-smoke low-toxicity halogen-free flame-retardant ultrahigh molecular weight polyethylene composite material according to claim 9, wherein in the step 5), the pressing temperature is 200-250 ℃, the pressing pressure is 2-8 MPa, and the pressure maintaining time is 10-60 min.
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| CN118727181A (en) * | 2024-06-27 | 2024-10-01 | 南通新帝克单丝科技股份有限公司 | Low-smoke flame-retardant ultra-high molecular weight polyethylene monofilament and preparation method thereof |
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| CN106867076A (en) * | 2017-02-15 | 2017-06-20 | 九江学院 | A kind of mining Graphene enhancing dual anti-tubing preparation method of ultra-high molecular weight polyethylene |
| CN108587194A (en) * | 2018-06-11 | 2018-09-28 | 安徽国华电缆集团有限公司 | A kind of insulated cable |
| CN112376125A (en) * | 2020-08-28 | 2021-02-19 | 青岛信泰科技有限公司 | Flame-retardant high-performance ultrahigh molecular weight polyethylene composite fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106867076A (en) * | 2017-02-15 | 2017-06-20 | 九江学院 | A kind of mining Graphene enhancing dual anti-tubing preparation method of ultra-high molecular weight polyethylene |
| CN108587194A (en) * | 2018-06-11 | 2018-09-28 | 安徽国华电缆集团有限公司 | A kind of insulated cable |
| CN112376125A (en) * | 2020-08-28 | 2021-02-19 | 青岛信泰科技有限公司 | Flame-retardant high-performance ultrahigh molecular weight polyethylene composite fiber and preparation method thereof |
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| CN118727181A (en) * | 2024-06-27 | 2024-10-01 | 南通新帝克单丝科技股份有限公司 | Low-smoke flame-retardant ultra-high molecular weight polyethylene monofilament and preparation method thereof |
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