CN115403674B - Biomass-based enhanced flame retardant, and preparation method and application thereof - Google Patents
Biomass-based enhanced flame retardant, and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 94
- 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 92
- 239000002028 Biomass Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 16
- 241001553178 Arachis glabrata Species 0.000 claims abstract description 16
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 16
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 16
- 235000020232 peanut Nutrition 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- RRDGKBOYQLLJSW-UHFFFAOYSA-N bis(2-ethylhexyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)CC2OC21 RRDGKBOYQLLJSW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 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 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- IEJMXUUZAXGOAU-UHFFFAOYSA-N 5-oxido-6H-benzo[c]chromen-5-ium Chemical compound C1=CC=CC=2C3=CC=CC=C3C[O+](C12)[O-] IEJMXUUZAXGOAU-UHFFFAOYSA-N 0.000 abstract 1
- -1 aminosiloxane Chemical class 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000779 smoke Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910014572 C—O—P Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08L2201/22—Halogen free composition
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a biomass-based enhanced flame retardant, and a preparation method and application thereof. The agricultural product waste peanut shell is taken as a raw material, carbonized in concentrated sulfuric acid, dried and ground, reacted with epichlorohydrin, and then added with aminosiloxane, 9, 10-dihydro-9, 10-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to obtain the biomass-based phosphorus, nitrogen and silicon-containing multielement synergistic enhanced flame retardant. The preparation method disclosed by the application is simple in process, green and renewable in raw materials, beneficial to reducing the consumption of the organic phosphorus flame retardant on nonrenewable petroleum and coal resources, and good in application prospect.
Description
Technical Field
The application relates to the technical field of preparation of flame retardant materials, in particular to a biomass-based enhanced flame retardant, and a preparation method and application thereof.
Background
Along with the improvement of people's fire-proof consciousness, the requirements on the flame retardant property of the material are also improved, and a nontoxic, halogen-free and environment-friendly flame retardant system is widely paid attention to. The traditional phosphate flame retardant does not have reactive groups, and has the problems of high volatility, poor compatibility and the like when the traditional phosphate flame retardant is used for preparing flame-retardant high polymer materials, and generally leads to a certain reduction in tensile strength of a matrix material.
The biomass polymer material is a novel material synthesized by using renewable biomass through biological, physical or chemical methods and the like, and is widely focused in the flame-retardant field due to the characteristics of green, environment-friendly, renewable, biodegradable and the like. Many biomass materials are natural carbon sources, and can replace pentaerythritol and the like in the traditional intumescent flame retardant system to form a novel intumescent flame retardant system. Therefore, improving the mechanical properties of polymeric materials by introducing novel flame retardants of the environmentally friendly biomass-based type is a hotspot of current research.
Chinese patent CN105219038A discloses a thermoplastic elastomer polyether ester of an intumescent flame retardant with b-cyclodextrin as carbon source and a preparation method thereof, wherein the intumescent flame retardant system consists of an organic hypophosphite flame retardant (acid source), melamine flame retardant (air source) and b-cyclodextrin (carbon source), and the method uses a blending formula system of various flame retardants, which is easy to cause compatibility problem. Chinese patent CN104559100a discloses a functional cyclodextrin flame-retardant polylactic acid composite material and a preparation method thereof, however, the flame retardant structure invented by the method only contains phosphorus-containing groups suitable for being used as acid sources, and lacks an air source structure containing nitrogen groups, so that the flame retardant efficiency is lower.
In recent years, cellulose Nanofibers (CNF) isolated from plants are considered as one of the most potential polymer reinforcing materials due to their excellent mechanical strength and rigidity and high aspect ratio. Peanut shell is an agricultural product waste, and cellulose is an important component in peanut shell components, and has wide application in the fields of food packaging materials, biological fuels, pharmacy and the like due to the excellent performance of nanocellulose. However, there is no report of biomass-based enhanced flame retardants using peanut shells as a raw material.
Disclosure of Invention
The technical problems to be solved are as follows: the traditional phosphate flame retardant in the prior art does not have reactive groups, and has the problems of high volatility, poor compatibility, unfriendly environment and the like when being used for preparing flame-retardant polymer materials, so the application adopts peanut shells as raw materials, provides an environment-friendly biomass-based enhanced flame retardant and a preparation method thereof, combines the reactive property, carbon forming property, structural strength of cellulose and flame retarding advantages of phosphorus, nitrogen and silicon in peanut shell components, can be independently used as an intumescent flame retardant, and can be used as an additive flame retardant and a reactive flame retardant with good compatibility and also can be used as an ideal mechanical strength enhanced flame retardant due to existence of molecular hydroxyl groups, silica groups, amino groups and cellulose frameworks.
The technical scheme is as follows:
specifically, the application provides the following technical scheme:
a biomass-based enhanced flame retardant, the chemical structural formula of the biomass-based enhanced flame retardant DSP is:
the preparation method of the biomass-based enhanced flame retardant comprises the following specific steps:
(1) Drying peanut shells, mechanically crushing, adding particles with the particle size smaller than 2.0mm into concentrated sulfuric acid, fully magnetically stirring under the high-temperature condition, washing the reaction product with water to be neutral, drying to be constant weight, and grinding to the particle size smaller than 2mm to obtain a product PS, wherein the structural formula is as follows:
(2) Dispersing the PS product obtained in the step (1) into deionized water, adding a solvent, adjusting the pH value of the solution to 12, heating, adding Epoxy Chloropropane (ECH) for reaction, centrifugally separating, washing with deionized water, and vacuum drying to obtain the E-PS product, wherein the specific synthetic route is as follows:
(3) Dissolving the product E-PS obtained in the step (2) in N, N-dimethylacetamide (DMAc), heating, adding DOPO, stirring for reaction for 3-5 h, cooling, and adding 3-aminopropyl triethoxysilane (APTES, M) under the protection of inert gas n 221) stirring and reacting for 12h, washing by adopting methanol and distilled water in sequence after centrifugal separation, and drying at high temperature under vacuum condition to obtain the biomass-based enhanced flame retardant.
Further, the preparation method of the biomass-based enhanced flame retardant comprises the steps of (1) setting the liquid-solid ratio of concentrated sulfuric acid to peanut shells at (5-10), setting the concentration of concentrated sulfuric acid at 60-98wt%, setting the high-temperature reaction temperature at 80-100deg.C, setting the magnetic stirring rotation speed at 5000-8000rpm, and setting the stirring time at 10-24 h.
Further, in the preparation method of the biomass-based enhanced flame retardant, the concentration of the PS dispersion liquid in the step (2) is 1.0wt%, the solvent is NaOH solution with the concentration of 1.0mol/L, the heating reaction temperature is 60-100 ℃, the mass ratio of ECH to PS is 10-15:1, and the reaction time is 10-24 hours.
Further, in the preparation method of the biomass-based enhanced flame retardant, in the step (3), the liquid-solid ratio of DMAc to E-PS is 8-15:1 mL/g, and the solution heating reaction temperature is as follows: 150 ℃, the mass ratio of DOPO to E-PS is 5:1, and the molar ratio of DOPO to APTES is 2:1, the cooling temperature is 30 ℃, the inert gas is nitrogen, the drying temperature is 60 ℃ under the vacuum condition, and the drying time is 24 hours.
The application also discloses application of the biomass-based enhanced flame retardant in polyurethane, nylon 6, polycarbonate, polylactic acid and epoxy resin materials.
The beneficial effects are that:
compared with the prior art, the application has the following advantages:
1. the application provides a biomass phosphorus, nitrogen and silicon-based multi-element intumescent flame retardant, which combines the reactivity, carbon forming performance and structural strength of cellulose in peanut shell components and the flame retardant advantages of phosphorus, nitrogen and silicon, can be independently used as an intumescent flame retardant, and can be used as an additive flame retardant and a reactive flame retardant with good compatibility and an ideal mechanical strength enhancement flame retardant due to existence of molecular hydroxyl groups, siloxyl groups, amino groups and cellulose skeletons.
2. The flame retardant formed by mixing the components in the prior art has the limitations of uneven dispersion of each component, mismatching of compatibility of each component with a matrix material and the like, and the flame retardant integrating multiple elements into one molecule only needs to consider the compatibility of one flame retardant with the matrix material, so that the flame retardant has stronger operability relatively.
3. The application provides an enhanced multi-element synergistic intumescent flame retardant based on biomass resources, which has better market prospect and sustainable development advantage compared with flame retardants derived from non-renewable petrochemical resources.
4. The flame retardant has hydroxyl and silicon oxygen groups, is particularly suitable for polylactic acid, epoxy resin and similar systems, and has better flame retardant property.
Drawings
FIG. 1 is an infrared spectrum of a flame retardant of the present application;
FIG. 2 is an X-ray photoelectron spectrum (XPS) of a flame retardant of the present application;
FIG. 3 is a digital photograph (a 1, b 1) and electronic scanning electron microscope (a 2, b 2) of the epoxy resin and the flame retardant resin added after combustion;
fig. 4 is a graph of tensile strength and elongation at break of an epoxy resin with a flame retardant added.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the application, but are not intended to limit the application in any way.
Example 1
The preparation method of the biomass-based enhanced flame retardant comprises the following specific steps:
(1) Drying peanut shells, mechanically crushing, screening 2g of particles with the particle size smaller than 2.0mm, adding the particles into 10mL of 60% sulfuric acid, heating the solution to 80 ℃, reacting for 24 hours under magnetic stirring, washing the reaction product with water to be neutral, drying to constant weight, and grinding the reaction product into powder with the particle size smaller than 2mm to obtain a product PS; structural formula:
(2) Dispersing 1.0g of the PS product obtained in the step (1) into 100mL of deionized water, using 1.0mol/L NaOH as a solvent, adjusting the pH value of the solution to 12, heating to 60 ℃, adding 10g of Epichlorohydrin (ECH) for reaction for 24 hours, centrifugally separating, washing with deionized water, and vacuum drying to obtain the E-PS product; the specific synthetic route is as follows:
(3) 2.0g of the product E-PS obtained in step (2) was dissolved in 20mLN, N-dimethylacetamide (DMAc), the solution was heated to 150℃and 10g (0.046 mol) of DOPO (M) n =216) stirring and reacting for 3h, slowly cooling to 30 ℃, adding 3-aminopropyl triethoxysilane (APTES, M) under nitrogen condition n =221) 5.0g, stirring and reacting for 12h, centrifugally separating, washing by adopting methanol and distilled water in sequence, and vacuum drying at 60 ℃ for 24h to obtain the biomass-based enhanced flame retardant.
As shown in FIG. 1, it can be seen from the infrared spectrogram that 3454cm -1 The broader peak is the stretching vibration absorption peak of hydroxyl-OH and the stretching vibration peak of N-H bond, 2976cm -1 The peak at the position is the C-H bond vibration absorption peak of methylene, and the strong telescopic vibration absorption peak of C=C double bond is 1637cm -1 1468cm at -1 The stretching vibration peak of the C-N bond is positioned, and the P=O bond is positioned at 1302cm -1 Has stronger stretching vibration peak, si-O-C bond is 1140cm -1 The data above indicate that the target product DSP is produced.
As shown in fig. 2, X-ray photoelectron spectroscopy (XPS) showed that the product DSP contains C, O, N, P and Si elements. C (C) 1s The peak of the spectrum at 284.6 eV is attributed to C-C and C-HBond, peak at 286.0eV is assigned to C-OH, C-O-P and C-N. Furthermore, the peak at 288.9 is due to the C-Si structure. At N 1s In the spectrum, a peak at 400.2eV may correspond to N. In Si 2p In the spectra, peaks at 101.6 and 102.2eV are assigned to Si-C and Si-O bonds, respectively. The above results further demonstrate successful synthesis of the target product DSP.
(4) Application result description
TABLE 1 flame retardant Properties of flame retardant for epoxy resins EP
The flame retardant properties of the samples were determined using Limiting Oxygen Index (LOI) and UL-94 vertical burning test. The results are shown in Table 1. Pure epoxy resin sample S 0 The LOI value of (2) was only 22.1%. As the content of the flame retardant DSP increases, the LOI value gradually increases, and only 1.0wt% of the DSP is added to the sample S 1 The LOI value of (2) increases to 24.6; however, sample S 1 Fails the UL-94 burn test. Sample S when the DSP content increased to 5.0% 5 The LOI value of (C) increased to 29.1 and passed the UL-94V-1 rating test. The LOI value of the sample, such as S, can be further improved by increasing the mass fraction of the DSP in the matrix 15 The LOI value for the sample (15 wt% DSP) reached a maximum of 34.2, while the sample reached the UL-94 highest V-0 level. The UL-94 vertical burning test result shows that the UL-94 grade of the epoxy resin hot solid is obviously improved along with the increase of the DSP content. Meanwhile, compared with pure EP, the thermosetting resin modified by DSP has no dripping phenomenon in the UL-94 vertical burning test, which shows that the flame retardant property of the EP matrix is obviously improved. In addition, the carbon residue rate data of the combustion shows that the carbon residue rate of the sample can be improved along with the increase of the mass fraction of the DSP. The carbon residue rate is increased from 15.2 of pure EP to S 15 29.3, demonstrating that the incorporation of DSP inhibits further decomposition of the matrix material, exhibiting good char formation ability. Thus, DSP is a high-efficiency flame retardant with a multielement synergistic effect on EP.
TABLE 2 Combustion parameters of flame retardant DSP for epoxy resins EP
From Table 2 we can see that pure EP without flame retardant burns rapidly after ignition, its heat release rate is 743kW/m 2 As the DSP content increased, the heat release rate of the sample decreased, and when the flame retardant addition amount reached 15%, sample S 15 Is reduced to 607kW/m 2 . Therefore, it can be inferred that the DSP decomposes on the surface of the sample during the combustion process to form a dense carbon residue layer, which can effectively block heat and combustible gas from entering the sample internal matrix. As can be seen from the variation of the total heat release THR data, the THR of pure EP at the end of combustion was 77.3MJ/m 2 THR gradually decreases with increasing content of the flame retardant DSP, and S is added when the addition amount of the flame retardant is 15% 15 THR decreases to 34.4MJ/m 2 . The results show that after the DSP is added into the matrix, the flame propagation speed is obviously slowed down. The main reason is that the introduction of phosphorus, nitrogen and silicon elements in the system can promote the formation of a synergistic phosphorus/nitrogen/silicon carbon residue layer in the combustion process, thereby effectively limiting the spread of flame.
The toxic gases and fumes in a fire are severely life threatening, and therefore the fume performance of the flame retardant is considered an important parameter. As can be seen from Table 2, the smoke yield SPR value of pure EP is 0.29m 2 And/s. And S is 15 SPR value of 0.18m 2 S, far below pure EP. Thus, the introduction of DSP in the EP matrix can effectively reduce the generation of smoke during combustion. Furthermore, as can be seen from Table 2, with the addition of DSP, the total smoke yield TSR value was significantly reduced, and the pure EP total smoke yield TSP value was 31.3m 2 Sample S/kg 15 The total smoke yield TSR of (C) is reduced to 17.9m 2 /kg. Therefore, the introduction of phosphorus, nitrogen and silicon can effectively promote the formation of a protective carbon layer on the surface of the system, and the initially formed compact carbon layer is beneficial to inhibiting the combustion intensity and reducing the release amount of smoke.
To further elucidate the relationship between the flame retarding mechanism and the morphology of carbon residue, cone calorimetry was used on sample S 15 And the microscopic morphology of the pure epoxy resin EP burning carbon residue are observed by a scanning electron microscope. As is evident from the photograph of fig. 3a1Pure EP was almost burnt out after the cone calorimetric test, leaving only a small amount of carbon residue. However, S 15 The sample produced more carbon residue, the overall structure of which is shown in fig. 3b 1. It is clear from the SEM image that the surface of the pure EP residue is not only very rough, but also is covered with a large number of small holes of different sizes. This phenomenon can be explained: a large amount of gas is generated during the combustion process, and thus, a large number of holes are generated during the release of the generated gas. In contrast, sample S15, with the addition of flame retardant, exhibited a more compact and smooth char layer, such that a continuous and stable char layer structure could act as a protective barrier, effectively inhibiting heat transfer between the bulk gas phase and the substrate, thereby preventing further combustion of the inner substrate. In addition, the so dense coke layer structure also inhibits the release of combustible volatiles into the gas phase. In summary, the introduction of the flame retardant DSP helps to improve the flame retardancy and thermal stability of the EP matrix. To further determine the effect of the flame retardant of the application on the mechanical properties of the EP matrix, all samples were tested for tensile strength and elongation at break. As shown in FIG. 4, the tensile strength of EP was 59.06MPa and the elongation at break was 8.50%. The addition of the DSP improves the tensile strength of the epoxy EP material. The tensile strength of the flame retardant sample at 20% added was 75.41MPa. The increase in tensile strength may be due to the flame retardant containing a rigid DOPO structure. The elongation at break slightly decreases with the increase of the DSP content of the flame retardant, but the elongation at break slowly increases with the increase of the addition amount, and when the content of the flame retardant is 15%, the maximum elongation at break is 8.61%, and the content of the flame retardant is continuously increased, so that the elongation at break decreases. This is probably due to the dispersibility and interfacial effect of the flame retardant in the matrix EP. The flame retardant structure contains a DOPO structure which is large in volume and strong in rigidity, so that molecular movement is limited. In contrast, the uniform dispersion and strong interfacial adhesion of the peanut shell matrix in the flame retardant are beneficial to the effective transfer of external load from the polymer matrix to the cellulose chains in the high-strength peanut shell matrix, so that the mechanical property of the epoxy resin is effectively improved. When the flame retardant content reaches 20%, the elongation at break is slightly reduced. This may be due to the aggregation of the flame retardant at high levels.Therefore, after the DSP is introduced, the mechanical property of the epoxy resin EP is improved well.
Example 2
The preparation method of the biomass-based enhanced flame retardant comprises the following specific steps:
(1) Drying peanut shells, mechanically crushing, screening 2g of particles with the particle size smaller than 2.0mm, adding the particles into 10mL of 60% sulfuric acid, heating the solution to 60 ℃, reacting for 24 hours under magnetic stirring, washing the reaction product with water to be neutral, drying to constant weight, and grinding the reaction product into powder with the particle size smaller than 2mm to obtain a product PS; structural formula:
(2) Dispersing 1.0g of the PS product obtained in the step (1) into 100mL of deionized water, using 1.0mol/L NaOH as a solvent, adjusting the pH value of the solution to 12, heating to 60 ℃, adding 10g of Epichlorohydrin (ECH) for reaction for 24 hours, centrifugally separating, washing with deionized water, and vacuum drying to obtain the E-PS product; the specific synthetic route is as follows:
(3) Dissolving 2.0g of the product E-PS obtained in the step (2) in 20mLN, N-dimethylacetamide (DMAc), heating the solution to 150 ℃, adding 10g (0.046 mol) of DOPO, stirring and reacting for 3 hours, slowly cooling to 30 ℃, and adding 3-aminopropyl triethoxysilane (APTES, M) under the condition of introducing nitrogen n =221) 5.0g, stirring and reacting for 12h, centrifugally separating, washing by adopting methanol and distilled water in sequence, and vacuum drying at 60 ℃ for 24h to obtain the biomass-based enhanced flame retardant DSP.
Example 3
The preparation method of the biomass-based enhanced flame retardant comprises the following specific steps:
(1) Drying peanut shells, mechanically crushing, screening 2g of particles with the particle size smaller than 2.0mm, adding the particles into 20mL of 98% sulfuric acid, heating the solution to 80 ℃, reacting for 24 hours under magnetic stirring, washing the reaction product with water to be neutral, drying to constant weight, and grinding the reaction product into powder with the particle size smaller than 2mm to obtain a product PS; structural formula:
(2) Dispersing 2.0g of the PS product obtained in the step (1) into 200mL of deionized water, using 1.0mol/L NaOH as a solvent, adjusting the pH value of the solution to 12, heating to 100 ℃, adding 30g of Epichlorohydrin (ECH) for reaction for 10 hours, centrifugally separating, washing with deionized water, and vacuum drying to obtain the E-PS product; the specific synthetic route is as follows:
(3) Dissolving 2.0g of the product E-PS obtained in the step (2) in 30mLN, N-dimethylacetamide (DMAc), heating the solution to 150 ℃, adding 10g (0.046 mol) of DOPO, stirring and reacting for 3 hours, slowly cooling to 30 ℃, and adding 3-aminopropyl triethoxysilane (APTES, M) under the condition of introducing nitrogen n =221) 5.0g, stirring and reacting for 12h, centrifugally separating, washing by adopting methanol and distilled water in sequence, and vacuum drying at 60 ℃ for 24h to obtain the biomass-based enhanced flame retardant.
Claims (4)
1. The preparation method of the biomass-based enhanced flame retardant is characterized in that the chemical structural formula of the biomass-based enhanced flame retardant DSP is as follows:；
the preparation method of the biomass-based enhanced flame retardant comprises the following specific steps: (1) Drying peanut shells, carrying out mechanical crushing, screening out particles with the particle size smaller than 2.0mm, adding the particles into concentrated sulfuric acid, carrying out sufficient magnetic stirring under the high-temperature condition, washing a reaction product with water to be neutral, drying to constant weight, and grinding the reaction product into powder with the particle size smaller than 2mm to obtain a product PS, wherein the structural formula is as follows:
；
(2) Dispersing the PS product obtained in the step (1) into deionized water, adding a solvent, adjusting the pH value of the solution to 12, heating, adding epichlorohydrin ECH for reaction, centrifugally separating, washing with deionized water, and vacuum drying to obtain the E-PS product, wherein the specific synthetic route is as follows:；
(3) Dissolving the product E-PS obtained in the step (2) in N, N-dimethylacetamide DMAc, heating, adding DOPO, stirring and reacting for 3-5 hours, cooling, adding 3-aminopropyl triethoxysilane APTES under the protection of inert gas, stirring and reacting for 12 hours, centrifugally separating, washing by adopting methanol and distilled water in sequence, and drying at high temperature under vacuum condition to obtain the biomass-based enhanced flame retardant.
2. The method for preparing the biomass-based enhanced flame retardant according to claim 1, wherein the method comprises the following steps: the liquid-solid ratio of the concentrated sulfuric acid to the peanut shell in the step (1) is (5-10), the concentration of the concentrated sulfuric acid is 60-98 wt%, the reaction temperature is 80-100 ℃, the magnetic stirring rotating speed is 5000-8000rpm, and the stirring time is 10-24 h.
3. The method for preparing the biomass-based enhanced flame retardant according to claim 1, wherein the method comprises the following steps: in the step (2), the concentration of the PS dispersion liquid is 1.0-wt%, the solvent is NaOH solution with the concentration of 1.0mol/L, the heating reaction temperature is 60-100 ℃, the mass ratio of ECH to PS is 10-15:1, and the reaction time is 10-24 h.
4. The method for preparing the biomass-based enhanced flame retardant according to claim 1, wherein the method comprises the following steps: in the step (3), the liquid-solid ratio of DMAc to E-PS is 8-15:1 mL/g, and the solution heating reaction temperature is as follows: 150 ℃, the mass ratio of DOPO to E-PS is 5:1, and the molar ratio of DOPO to APTES is 2:1, the cooling temperature is 30 ℃, the inert gas is nitrogen, the drying temperature is 60 ℃ under the vacuum condition, and the drying time is 24 hours.
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