CN117362803A - Flame-retardant PE composite material - Google Patents
Flame-retardant PE composite material Download PDFInfo
- Publication number
- CN117362803A CN117362803A CN202311414716.1A CN202311414716A CN117362803A CN 117362803 A CN117362803 A CN 117362803A CN 202311414716 A CN202311414716 A CN 202311414716A CN 117362803 A CN117362803 A CN 117362803A
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- China
- Prior art keywords
- flame
- retardant
- mica powder
- parts
- styrene
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 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 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 239000010445 mica Substances 0.000 claims abstract description 60
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 60
- 239000004698 Polyethylene Substances 0.000 claims abstract description 59
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims abstract description 29
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 13
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 claims description 9
- CTYWXRDQWMRIIM-BQYQJAHWSA-N (e)-3-(3,5-ditert-butyl-4-hydroxyphenyl)prop-2-enoic acid Chemical compound CC(C)(C)C1=CC(\C=C\C(O)=O)=CC(C(C)(C)C)=C1O CTYWXRDQWMRIIM-BQYQJAHWSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 8
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- YPJHXRAHMUKXAE-UHFFFAOYSA-N 3-diethoxyphosphorylprop-1-ene Chemical compound CCOP(=O)(CC=C)OCC YPJHXRAHMUKXAE-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- -1 Polyethylene Polymers 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention relates to the technical field of composite materials, and discloses a flame-retardant PE composite material, which comprises the following raw materials: low density polyethylene, modified styrene-isoprene block copolymer, flame-retardant mica powder, lubricant, plasticizer, ultraviolet absorber and antioxidant; wherein the modified styrene-isoprene block copolymer is a styrene-isoprene block copolymer with quaternary ammonium groups in the structure; the flame-retardant mica powder is mica powder coated with phosphate groups on the surface; the PE composite material prepared by the invention has excellent heat resistance and flame retardant property, can exert long-acting flame retardant effect in case of fire, and additionally endows the composite material with antibacterial property, so that the composite material can exert antibacterial effect for a long time, and the application field of the composite material is widened.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a flame-retardant PE composite material.
Background
Polyethylene is a high molecular material with good chemical stability, no odor and no toxicity, is widely applied to the fields of film materials, packaging materials, pipes, power industry and the like, plays a role in protecting products and controlling quality, but has low toughness, poor high temperature resistance and no flame retardant property, so that the polyethylene material is difficult to process, is easy to generate fire in a dry environment or under unexpected conditions, can lose the protection effect on the products and also brings irrecoverable loss, and in addition, the packaging material not only needs to have good blocking and fresh-keeping effects, but also needs to ensure that foods are not corroded by microorganisms to cause food spoilage, and the polyethylene material does not have antibacterial capability, so that the development of the polyethylene material in the food packaging field is limited.
In order to obtain more excellent performance of polyethylene, people often carry out modification treatment on the polyethylene, for example, the patent with the publication number of CN111234343B discloses a modified regenerated PE nano composite material and a preparation method thereof, and the recycled polyethylene is taken as a main material, PE new materials, filling agents, reinforcing agents, toughening agents, cross-linking agents, antioxidants, plasticizers, lubricants and colorants are taken as auxiliary materials, and the main materials and the auxiliary materials are subjected to melt blending and then pelleting to obtain the modified regenerated PE nano composite material, so that the prepared composite material has excellent tensile strength and impact strength, strong toughness, safety and environmental protection and great popularization value, but the material does not have the functions of antibiosis and flame retardance, has potential safety hazards during manufacturing and storage, and simultaneously limits the development of the composite material in the field of food packaging.
Disclosure of Invention
The invention aims to provide a flame-retardant PE composite material, which solves the following technical problems: (1) The common PE material has poor flame retardant property and potential safety hazard; (2) The common PE material has poor heat resistance and poor toughness; (3) The common PE material has no antibacterial property and has limited application field.
The aim of the invention can be achieved by the following technical scheme:
the flame-retardant PE composite material comprises the following raw materials in parts by weight: 50-70 parts of low-density polyethylene, 8-10 parts of modified styrene-isoprene segmented copolymer, 3-6 parts of flame-retardant mica powder, 0.5-1 part of lubricant, 1-3 parts of plasticizer, 0.5-2 parts of ultraviolet absorber and 1-2 parts of antioxidant; the modified styrene-isoprene block copolymer is a styrene-isoprene block copolymer with quaternary ammonium groups in the structure; the flame-retardant mica powder is mica powder coated with phosphate groups on the surface.
Further, the lubricant is any one of stearic acid, ethylene bis stearamide and paraffin; the plasticizer is any one of dibutyl phthalate, dioctyl phthalate, dibutyl sebacate and dioctyl sebacate; the ultraviolet absorbent is any one of benzophenone and 2-aminobenzophenone; the antioxidant is any one of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid.
Further, the preparation method of the modified styrene-isoprene block copolymer comprises the following steps:
s1, placing a styrene-isoprene segmented copolymer in toluene, fully mixing, adding formic acid, heating to 55-65 ℃, dropwise adding hydrogen peroxide for 30-40min, adding ethanol for condensation after the reaction is completed, filtering, washing and vacuum drying after the condensation is completed to obtain an epoxidized styrene-isoprene segmented copolymer;
s2, placing the epoxidized styrene-isoprene segmented copolymer in cyclohexane, adding 2-hydroxy-N, N, N-trimethyl ethyl ammonium chloride and the catalyst (1), heating to 60-70 ℃ to react for 3-5h, cooling to room temperature, filtering, washing and drying in vacuum to obtain the modified styrene-isoprene segmented copolymer.
Through the technical scheme, under the action of formic acid and hydrogen peroxide, double bonds in the structure of the styrene-isoprene block copolymer are oxidized into epoxy groups to obtain the epoxidized styrene-isoprene block copolymer, and then under the action of the catalyst (1), the hydroxy in the 2-hydroxy-N, N, N-trimethyl ethyl ammonium chloride structure and the epoxy groups in the epoxidized styrene-isoprene block copolymer structure undergo ring opening reaction to obtain the modified styrene-isoprene block copolymer. The modified styrene-isoprene segmented copolymer has lower glass transition temperature and crystallinity, can interact with polyethylene molecular chains when being added into a composite material to form a three-dimensional network structure, and can generate synergistic effect with a plurality of benzene rings existing in the composite material to enhance the heat resistance of polyethylene.
Further, in the step S1, the mass fraction of the hydrogen peroxide is 30-40%.
Further, in step S2, the catalyst (1) is tetrabutylammonium bromide.
Further, the preparation method of the flame-retardant mica powder comprises the following steps:
SS1, placing mica powder into deionized water, performing ultrasonic dispersion for 10-15min, introducing nitrogen, adding methacrylic acid-2-isocyanic acid ethyl ester and a catalyst (2), heating to 60-70 ℃ for reaction for 2-3h, cooling to room temperature, filtering, washing and drying in vacuum to obtain modified mica powder;
and SS2, placing the modified mica powder and diethyl allylphosphonate in butyl acetate, fully mixing, introducing nitrogen, adding an initiator, heating to 50-70 ℃ for reaction for 3-5h, cooling to room temperature, filtering, washing and drying in vacuum to obtain the flame-retardant mica powder.
According to the technical scheme, under the action of the catalyst (2), isocyanate groups in the methacrylic acid-2-isocyanate structure react with hydroxyl groups on the surface of mica powder to obtain modified mica powder, under the action of the initiator, alkenyl groups in the allyl diethyl phosphonate structure react with alkenyl groups on the surface of the modified mica powder in a free radical polymerization way, and the surface of the mica powder is coated with polyphosphate groups to form flame-retardant mica powder. The flame-resistant mica powder is coated with the polyphosphate, so that the dispersibility of the flame-resistant mica powder in the composite material can be enhanced, agglomeration phenomenon is not easy to occur, meanwhile, the polyphosphate can volatilize at high temperature to produce gas-phase flame retardation, and a compact protective layer can be produced to slow down the spread of flame.
Further, in step SS1, the catalyst (2) is any one of stannous octoate and dibutyltin dilaurate.
Further, in step SS2, the initiator is any one of dicumyl peroxide and benzoyl peroxide.
Further, the preparation method of the PE composite material comprises the following steps:
adding low-density polyethylene, flame-retardant mica powder, a modified styrene-isoprene block copolymer, a lubricant, a plasticizer, an ultraviolet absorber and an antioxidant in parts by weight into a high-speed mixer, setting the rotating speed to be 200-300r/min, and mixing for 1-2 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the screw rotating speed to be 300-500r/min, extruding and granulating at the working temperature of the extrusion section to be 160-180 ℃ to obtain the PE composite material.
The invention has the beneficial effects that:
according to the invention, the prepared modified styrene-isoprene segmented copolymer and the flame-retardant mica powder participate in the preparation process of the PE composite material, so that the prepared PE composite material has excellent heat resistance and flame retardance, can exert a long-acting flame retardance effect in case of fire, reduces potential safety hazards, and additionally endows the PE composite material with antibacterial property, so that the PE composite material can exert a long-term antibacterial effect, and the application field of the composite material is widened.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of mica powder, modified mica powder and flame-retardant mica powder in example 1 of the present invention;
FIG. 2 is a scanning electron microscope analysis of PE composite in example 1 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of modified styrene-isoprene Block copolymer
S1, placing 2g of styrene-isoprene segmented copolymer in 60ml of toluene, fully mixing, adding 4ml of formic acid, heating to 55 ℃, dropwise adding 10ml of hydrogen peroxide with the mass fraction of 30%, controlling the dropwise adding time to be 30min, adding 5ml of ethanol for condensation after the reaction is completed, filtering, washing and vacuum drying after the condensation is completed, so as to obtain the epoxidized styrene-isoprene segmented copolymer;
s2, placing 2g of the epoxidized styrene-isoprene segmented copolymer in 50ml of cyclohexane, adding 1g of 2-hydroxy-N, N, N-trimethyl ethyl ammonium chloride and 0.05g of tetrabutylammonium bromide, heating to 60 ℃ for reaction for 3 hours, cooling to room temperature, filtering, washing and drying in vacuum to obtain the modified styrene-isoprene segmented copolymer.
Using an EA2400II type element analyzer to analyze the content of three elements of hydrocarbon and nitrogen of the epoxidized styrene-isoprene block copolymer and the modified styrene-isoprene block copolymer, wherein the content of carbon element in the epoxidized styrene-isoprene block copolymer is 77.7%, the content of hydrogen element is 6.8%, and the epoxidized styrene-isoprene block copolymer does not contain nitrogen element; in the modified styrene-isoprene block copolymer, the content of carbon element is 67.9%, the content of hydrogen element is 5.6%, and the content of nitrogen element is 5.1%; compared with the two, the content of carbon element and hydrogen element in the modified styrene-isoprene segmented copolymer is reduced, and nitrogen element is increased, which indicates that the ring-opening reaction of the epoxidized styrene-isoprene segmented copolymer and 2-hydroxy-N, N, N-trimethyl ethyl ammonium chloride occurs.
2. Preparation of flame-retardant mica powder
SS1, placing 2g of mica powder into 100ml of deionized water, dispersing for 10min by ultrasonic, introducing nitrogen, adding 1.5ml of methacrylic acid-2-isocyanic acid ethyl ester and 0.03g of stannous octoate, heating to 60 ℃ for reaction for 2h, cooling to room temperature, filtering, washing and drying in vacuum to obtain modified mica powder;
SS2, placing 2g of modified mica powder and 1.8ml of diethyl allylphosphonate in 120ml of butyl acetate, fully mixing, introducing nitrogen, adding 0.08g of dicumyl peroxide, heating to 50 ℃ for reaction for 3 hours, cooling to room temperature, filtering, washing and drying in vacuum to obtain flame-retardant mica powder.
Characterization of mica powder, modified mica powder and flame-retardant mica powder by infrared spectrum, wherein 3251cm of the infrared spectrum of the mica powder -1 The absorption peak of hydroxyl is 1021cm -1 The absorption peak of the silica bond is shown; in the infrared spectrum of the modified mica powder, 3065cm -1 Is an absorption peak of 1719cm of carbon-carbon hydrogen bond in carbon-carbon double bond -1 The absorption peak of carbon-oxygen double bond in carbamate shows that hydroxyl on the surface of mica powder reacts with 2-isocyanatoethyl methacrylate; in the infrared spectrum of the flame-retardant mica powder, 3065cm -1 The absorption peak of the carbon-hydrogen bond in the carbon-carbon double bond is basically disappeared, 1278cm -1 Where there is an adsorption of the phosphorus-oxygen double bond in the phosphate groupAnd (3) collecting peaks to show that the alkenyl groups on the surface of the modified mica powder and the alkenyl groups in the structure of the diethyl allylphosphonate undergo free radical polymerization reaction.
3. Preparation of PE composite
Adding 50 parts of low-density polyethylene, 8 parts of modified styrene-isoprene block copolymer, 3 parts of flame-retardant mica powder, 0.5 part of stearic acid, 1 part of dibutyl phthalate, 0.5 part of diphenyl ketone and 1 part of 3, 5-di-tert-butyl-4-hydroxybenzoic acid into a high-speed mixer, setting the rotating speed to 200r/min, and mixing for 1h to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 300r/min, extruding and granulating at the working temperature of an extrusion section of 160 ℃, and obtaining the PE composite material.
The morphology of the PE composite material is analyzed by a scanning electron microscope, and as can be seen from FIG. 2, the PE composite material is composed of a three-dimensional network structure which is connected with each other, and is caused by the fact that the modified styrene-isoprene segmented copolymer and polyethylene molecular chains are mutually entangled to form the three-dimensional network structure.
Example 2
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 9 parts of modified styrene-isoprene segmented copolymer, 5 parts of flame-retardant mica powder, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Wherein, the preparation method of the modified styrene-isoprene block copolymer and the flame-retardant mica powder is the same as that of the example 1.
Example 3
Preparation of PE composite
Step one, adding 70 parts of low-density polyethylene, 10 parts of modified styrene-isoprene segmented copolymer, 6 parts of flame-retardant mica powder, 1 part of ethylene bis stearamide, 3 parts of dibutyl sebacate, 2 parts of 2-aminobenzophenone and 2 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 300r/min, and mixing for 2 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to be 500r/min, extruding and granulating at the working temperature of the extrusion section of 180 ℃ to obtain the PE composite material.
Wherein, the preparation method of the modified styrene-isoprene block copolymer and the flame-retardant mica powder is the same as that of the example 1.
Comparative example 1
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 5 parts of flame-retardant mica powder, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Wherein, the preparation method of the flame-retardant mica powder is the same as that of the example 1.
Comparative example 2
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 9 parts of modified styrene-isoprene segmented copolymer, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Wherein the preparation method of the modified styrene-isoprene block copolymer is the same as in example 1.
Comparative example 3
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Comparative example 4
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 9 parts of styrene-isoprene segmented copolymer, 5 parts of flame-retardant mica powder, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Wherein, the preparation method of the flame-retardant mica powder is the same as that of the example 1.
Comparative example 5
Preparation of PE composite
Step one, adding 60 parts of low-density polyethylene, 9 parts of modified styrene-isoprene segmented copolymer, 5 parts of mica powder, 0.8 part of paraffin, 2 parts of dioctyl phthalate, 1 part of 2-aminobenzophenone and 1.5 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid into a high-speed mixer, setting the rotating speed to 250r/min, and mixing for 1.5 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the rotating speed of the screw to 400r/min, extruding and granulating at the working temperature of an extrusion section of 170 ℃ to obtain the PE composite material.
Wherein the preparation method of the modified styrene-isoprene block copolymer is the same as in example 1.
Performance detection
Tabletting the PE composite prepared in the examples 1-3 and the comparative examples 1-5 to prepare samples meeting the specification; performing antibacterial property detection on the sample by referring to a standard GB/T31402-2015; the flexural modulus of elasticity of the samples was tested with reference to standard GB/T9341-2008; testing the Vicat softening temperature of the sample by referring to GB/T1633-2000, and judging the high temperature resistance of the sample; the oxygen index of a sample is measured according to the reference standard GB/T2406.2-2009, and the flame retardant property of the sample is judged; the specific detection results are shown in the following table:
as can be seen from the above table, the samples prepared in examples 1 to 3, comparative examples 1 to 5 have excellent high temperature resistance, toughness, flame retardance and antibacterial property, the samples prepared in comparative examples 1 and 3 are not added with the modified styrene-isoprene block copolymer, so that toughness is poor, and do not have antibacterial property, the samples prepared in comparative example 1 have good high temperature resistance and excellent flame retardance, because the flame-resistant mica powder is added to the material, the samples prepared in comparative example 4 are not added with the styrene-isoprene block copolymer, toughness is strong, high temperature resistance is good, but the copolymer is not modified, so that the samples have poor antibacterial property, almost no antibacterial effect, the samples prepared in comparative example 2 and comparative example 3 are not added with the flame-resistant mica powder, but the samples prepared in comparative example 2 are added with the modified styrene-isoprene block copolymer, so that toughness is strong and excellent antibacterial property, the samples prepared in comparative example 5 are directly added with the mica powder, the mica powder is not modified, the mica powder is produced in the material, and the flame-resistant property is poor, but the flame-resistant property is poor, and the flame-resistant property is generally poor, and the flame-resistant property is caused by the fact that the flame-resistant property is poor.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.
Claims (9)
1. The flame-retardant PE composite material is characterized by comprising the following raw materials in parts by weight: 50-70 parts of low-density polyethylene, 8-10 parts of modified styrene-isoprene segmented copolymer, 3-6 parts of flame-retardant mica powder, 0.5-1 part of lubricant, 1-3 parts of plasticizer, 0.5-2 parts of ultraviolet absorber and 1-2 parts of antioxidant; the modified styrene-isoprene block copolymer is a styrene-isoprene block copolymer with quaternary ammonium groups in the structure; the flame-retardant mica powder is mica powder coated with phosphate groups on the surface.
2. The flame-retardant PE composite according to claim 1, wherein the lubricant is any one of stearic acid, ethylene bis stearamide and paraffin wax; the plasticizer is any one of dibutyl phthalate, dioctyl phthalate, dibutyl sebacate and dioctyl sebacate; the ultraviolet absorbent is any one of benzophenone and 2-aminobenzophenone; the antioxidant is any one of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylic acid.
3. The flame-retardant PE composite of claim 1, characterized in that the preparation method of the modified styrene-isoprene block copolymer comprises the following steps:
s1, placing a styrene-isoprene segmented copolymer in toluene, fully mixing, adding formic acid, heating to 55-65 ℃, dropwise adding hydrogen peroxide for 30-40min, adding ethanol for condensation after the reaction is completed, filtering, washing and vacuum drying after the condensation is completed to obtain an epoxidized styrene-isoprene segmented copolymer;
s2, placing the epoxidized styrene-isoprene segmented copolymer in cyclohexane, adding 2-hydroxy-N, N, N-trimethyl ethyl ammonium chloride and the catalyst (1), heating to 60-70 ℃ to react for 3-5h, cooling to room temperature, filtering, washing and drying in vacuum to obtain the modified styrene-isoprene segmented copolymer.
4. A flame resistant PE composite according to claim 3, characterized in that in step S1 the mass fraction of hydrogen peroxide is 30-40%.
5. A flame resistant PE composite according to claim 3, characterized in that in step S2 the catalyst (1) is tetrabutylammonium bromide.
6. The flame-retardant PE composite according to claim 1, wherein the preparation method of the flame-retardant mica powder comprises the following steps:
SS1, placing mica powder into deionized water, performing ultrasonic dispersion for 10-15min, introducing nitrogen, adding methacrylic acid-2-isocyanic acid ethyl ester and a catalyst (2), heating to 60-70 ℃ for reaction for 2-3h, cooling to room temperature, filtering, washing and drying in vacuum to obtain modified mica powder;
and SS2, placing the modified mica powder and diethyl allylphosphonate in butyl acetate, fully mixing, introducing nitrogen, adding an initiator, heating to 50-70 ℃ for reaction for 3-5h, cooling to room temperature, filtering, washing and drying in vacuum to obtain the flame-retardant mica powder.
7. The flame-retardant PE composite according to claim 6, wherein in step SS1, the catalyst (2) is any one of stannous octoate and dibutyltin dilaurate.
8. The flame-retardant PE composite according to claim 6, wherein in step SS2, the initiator is any one of dicumyl peroxide and benzoyl peroxide.
9. The flame resistant PE composite of claim 1, characterized in that the method for preparing the PE composite comprises the steps of:
adding low-density polyethylene, flame-retardant mica powder, a modified styrene-isoprene block copolymer, a lubricant, a plasticizer, an ultraviolet absorber and an antioxidant in parts by weight into a high-speed mixer, setting the rotating speed to be 200-300r/min, and mixing for 1-2 hours to obtain a mixed base material;
and step two, transferring the mixed base material into a double-screw extruder, setting the screw rotating speed to be 300-500r/min, extruding and granulating at the working temperature of the extrusion section to be 160-180 ℃ to obtain the PE composite material.
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