CN110746646A - Biomass-based flame retardant and preparation method thereof - Google Patents
Biomass-based flame retardant and preparation method thereof Download PDFInfo
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- CN110746646A CN110746646A CN201910871693.4A CN201910871693A CN110746646A CN 110746646 A CN110746646 A CN 110746646A CN 201910871693 A CN201910871693 A CN 201910871693A CN 110746646 A CN110746646 A CN 110746646A
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- flame retardant
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- based flame
- aminophenol
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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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000012141 vanillin Nutrition 0.000 claims abstract description 18
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract 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 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a biomass-based flame retardant and a preparation method thereof, wherein the preparation method comprises the following steps: s1: under magnetic stirring, dissolving vanillin in tetrahydrofuran, wherein the concentration of the prepared vanillin solution is 0.1-0.5mol/L, dropwise adding dichlorodimethylsilane under the condition of introducing nitrogen, and reacting at 50-80 ℃ for 2-8h to obtain a product I; s2: under magnetic stirring, mixing the product I and aminophenol/primary aminophenol according to a molar ratio of 1:2-5, dissolving in absolute ethyl alcohol, reacting at 50-80 ℃ for 4-8h, filtering out a product, washing the obtained product with deionized water, and drying at 50-80 ℃ in vacuum to constant weight to obtain a product II; s3: dissolving DOPO in dichloromethane, then adding azodiisobutyronitrile, and then adding the product in S2 under the protection of inert gas to obtain the biomass-based flame retardant III. The preparation method has simple process, green and renewable raw materials, is beneficial to reducing the consumption of the organic phosphorus flame retardant on non-renewable petroleum and coal resources, and has application prospect.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a biomass-based flame retardant and a preparation method thereof.
Background
The polymer material is one of three traditional materials, and is applied to various fields of national economy and people's life. With the high concern of people on safety and sustainable development, the high molecular flame retardant material becomes an important content of material research and development. However, the polymer material itself does not have good flame retardancy.
The Intumescent Flame Retardant (IFR) is a flame retardant taking phosphorus and nitrogen as main components, and the flame retardant foams and expands when being heated, so the intumescent flame retardant is called as the intumescent flame retardant and is an environment-friendly flame retardant with higher flame retardant efficiency. Due to the unique flame retardant mechanism, good flame retardant, smoke suppression and anti-dripping effects, the IFR has wide application prospect and is one of the most active research fields of flame retardants since the 90 s of the 20 th century. However, most of the production raw materials of the flame retardant are from non-renewable petrochemical resources, and if the raw materials are partially replaced by chemicals derived from biomass resources, the sustainable development of 'green' in the field of flame retardance is facilitated.
The flame retardant prepared by using biomass as a raw material just meets the trend of safety, environmental protection and sustainability, but most biomass materials have insufficient heat resistance, and most of biomass-based flame retardants have low efficiency and cannot meet the use requirement of the flame retardant.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the biomass-based flame retardant and the preparation method thereof, so that the flame retardant is green and renewable, and the flame retardant efficiency of high polymer materials such as polycarbonate, epoxy resin and the like can be effectively improved.
The biomass-based flame retardant provided by the invention comprises the following chemical structures of a flame retardant (III):
the preparation method of the biomass-based flame retardant provided by the invention comprises the following steps:
s1: dissolving vanillin in tetrahydrofuran, and then adding dichlorodimethylsilane for reaction to obtain a product (I);
s2: dissolving the product in S1 in absolute ethyl alcohol, and then adding aminophenol or primary aminophenol to react to obtain a product (II);
s3: dissolving 9, 10-dihydro-9, 10-oxa-10-phosphaphenanthrene-10-oxide (DOPO) in dichloromethane, adding Azodiisobutyronitrile (AIBN), and adding the product in S2 under the protection of inert gas to obtain the biomass-based flame retardant (III).
Preferably, the vanillin in S1 is derived from a biomass resource.
Preferably, the specific steps of S1 are: under magnetic stirring, dissolving vanillin in tetrahydrofuran to prepare vanillin solution with the concentration of 0.1-0.5mol/L, adding dichlorodimethylsilane dropwise under the condition of introducing nitrogen, and reacting at 50-80 ℃ for 2-8h to obtain the product (I).
Preferably, the chemical structure of the product (i) is:
preferably, the vanillin solution further comprises an amine acid scavenger.
Preferably, the acid scavenger is an organic amine acid scavenger.
Preferably, the organic amine acid-binding agent is one or more of triethylamine, diethylamine, pyridine and aminopyridine.
Preferably, the molar ratio of dichlorodimethylsilane to vanillin in S1 is 1: 2-5.
Preferably, the specific steps of S2 are: under magnetic stirring, mixing the product (I) and aminophenol/primary aminophenol in a molar ratio of 1:2-5, dissolving in absolute ethanol, reacting at 50-80 ℃ for 4-8h, filtering out the product, washing the obtained product with deionized water, and drying at 50-80 ℃ in vacuum to constant weight to obtain the product (II).
Preferably, the aminophenol is 4-hydroxyaniline and the primary aminophenol is dopamine;
preferably, the chemical structure of the product (ii) is:
preferably, the specific steps of S3 are: under the protection of nitrogen, the DOPO and the product (II) are dissolved in CH according to the mol ratio of 2-5:12Cl2Adding AIBN with the concentration of 0.001-0.01mol/L, and reacting for 2-8h at the temperature of 50-80 ℃ to obtain the biomass-based flame retardant (III).
The invention provides an application of a biomass-based flame retardant in a thermoplastic polymer.
Preferably, the thermoplastic polymer comprises polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethylmethacrylate, polyamide, polycarbonate, or a terephthalate-based thermoplastic polyester.
The invention provides an application of a biomass-based flame retardant in thermosetting resin.
Preferably, the thermosetting resin is epoxy resin or polyurethane, and the biomass-based flame retardant and the epoxy resin or the polyurethane can be used as a curing agent or an auxiliary agent.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the invention provides a biomass phosphorus-nitrogen-silicon-containing multi-element intumescent flame retardant, which combines the excellent reaction performance of vanillin, aminophenol/primary aminophenol and the flame retardant advantages of intumescent flame retardant elements, can be independently used as an intumescent flame retardant for application without being compounded with other flame retardants, and can be used as an additive type and reactive type flame retardant with good compatibility and an ideal adhesive flame retardant coating due to the existence of catechol groups in molecules.
(2) The flame retardant formed by mixing a plurality of components in the prior art has the limitations of uneven dispersion of each component, insufficient compatibility of each component with a matrix material and the like, but the flame retardant combining a plurality of elements into one molecule only needs to consider the compatibility of one flame retardant component with the matrix material, and has relatively stronger operability.
(3) The invention provides a multi-element intumescent flame retardant based on biomass resources, which has better market prospect and sustainable development advantage compared with the flame retardant derived from non-renewable petrochemical resources.
(4) The flame retardant of the invention has hydroxyl groups, is particularly suitable for polylactic acid, epoxy resin and similar systems, and has better flame retardant property.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum (a) and a phosphorus spectrum (b) of a biomass-based flame retardant in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a biomass-based flame retardant in example 1 of the present invention;
FIG. 3 is an SEM image of a carbon layer of a biomass-based flame retardant composite epoxy resin after combustion in example 1 of the invention;
FIG. 4 is a digital photograph of a residual carbon layer from combustion of biomass-based flame retardant composite epoxy resin in example 1 of the present invention;
FIG. 5 is a pressure-tension curve diagram of the biomass-based flame retardant composite epoxy resin in example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
First, 15mmol of vanillin was dissolved in 150mL of THF at room temperature, 3mL of triethylamine was injected into the flask using a syringe, and after stirring for 10min, 7.5mmol of dichlorodimethylsilane was slowly injected into the flask using a syringe. Stirring and reacting at 50 ℃ for 2 hours, pouring the reaction mixture into n-hexane at 0 ℃, filtering, washing the precipitate with deionized water, and drying in vacuum at 50 ℃ to obtain an intermediate product (I).
Then, under the protection of nitrogen, 0.1mol (12.21g) of the intermediate product (I) is dissolved in 500m1 of absolute ethyl alcohol, 0.2mo1 of dopamine is slowly dropped into the solution prepared above, the product is filtered after heating reflux reaction for 4 hours, the obtained solid is washed by deionized water and dried in vacuum at 50 ℃ to constant weight, and the product (II) is obtained;
finally, product (II) (0.1mol) was dissolved in absolute ethanol (100 ml) in N2Adding 0.2mol of DOPO and 0.1mmol of AIBN under protection, stirring and refluxing at 50 ℃ for 2h, and cooling to room temperature. Filtration and washing of the precipitate with dichloromethane followed by vacuum drying at 50 ℃ for 12 hours gave biomass-based flame retardant (III).
Referring to a in FIG. 1, which is a nuclear magnetic resonance hydrogen spectrum of the biomass-based flame retardant prepared in this example, 8.92ppm was assigned to phenolic hydroxyl groups (Ar-OH), 7.30ppm, 6.73ppm and 6.69ppm were assigned to H on benzene rings, 3.74ppm was assigned to H on methoxy groups, and 1.13ppm was assigned to H on methyl groups on silanes.
Referring to b in FIG. 1, which is the NMR spectrum of the biomass-based flame retardant prepared in this example, a sharp peak at 15.83ppm was observed, indicating that there is only one phosphorus atom in the molecular structure, consistent with theory.
See FIG. 2, 3571cm-1Belongs to N-H, 3219-3342cm-1Belongs to phenolic hydroxyl Ar-OH, 3106cm-1Belonging to the aromatic ring C-H), 2962and2869cm-1Belong to- CH 31612,1580,1515 and 1359cm-1Belongs to an aromatic ring; 1466cm-1Belongs to (P-C); 1247cm-1To (P ═ O); 1153cm-1Belongs to (Si-O-C); 912 and 914cm-1Belongs to (P-O-C).
As can be seen from the above figures, the product prepared in this example is the target product.
In order to determine the morphology of the carbon residue, SEM analysis was performed on the carbon residue, and it can be seen from FIG. 3 that the carbon layer was not sufficiently formed without adding the flame retardant of the present invention and was macroporous. In contrast, the coverage and continuity of the char layer with 5% flame retardant addition was improved. The carbon layer has good compactness and continuity, and is beneficial to reducing the transfer of gas and heat in the combustion process. These results again demonstrate the effectiveness of the flame retardant application of the present invention in carbon layer formation, ultimately improving the flame retardant effectiveness of the polymeric substrate.
The expansion by heating is the most obvious characteristic of the intumescent flame retardant, a porous foam carbon layer formed by the expansion by heating can play a flame retardant role in a condensed phase, and the expansion degree is one of the main bases of the flame retardant effect of the intumescent flame retardant. As can be seen from FIG. 4, the addition of the flame retardant of the present invention achieves a greater swell height and the expanded residue not only better inhibits the release of volatile fuels, but also further insulates and protects the interior substrate from fire.
FIG. 5 illustrates that the addition of the flame retardant of the present invention reduces the elongation at break of the substrate, increasing and then decreasing the tensile strength to the substrate.
The limiting oxygen index refers to the minimum oxygen content necessary to maintain stable combustion of the target material in an oxygen-nitrogen mixture under specified conditions. The high oxygen index indicates that the material is not easy to burn, so that the measurement of the oxygen index of the material can theoretically determine the flame retardant effect of the flame retardant material.
The flammability UL-94 rating is widely used, and is often used as a flammability standard for plastic materials to evaluate the ability of the material to extinguish after being ignited, which is a test method for vertical burning. UL-94V-O assessment method: the sample quickly self-extinguished after the flame was removed from the ignition until no flaming melt dropped within a certain time interval (i.e., the flaming melt dropped on a cotton pad located one foot below the test sample and did not bow | burn the cotton). UL-94V-1 is similar to the assessment method for V-0, except that the self-extinguishing time is different. The required self-extinguishing time of V-1 is relatively long. This test requires that the droplets falling on the cotton pad do not ignite the cotton. UL-94V-2 is identical to V-1 except that it allows burning droplets to ignite the cotton below.
The flame retardant effect of the product prepared in the embodiment in polycarbonate and DGEBA epoxy resin is examined through oxygen index and vertical combustion performance, wherein the oxygen index is less than 21 and is flammable material, the oxygen index has self-extinguishing property between 22 and 26, the oxygen index is more than 27 and is nonflammable material, the vertical combustion method comprises three grades V-0, V-1 and V-2, the grade V-0 is the best grade which can be achieved by the material, and the evaluation standard of the grade of the material is based on the combustion time from the moment that a vertically placed sample is removed to the moment that the sample is self-extinguished.
And testing the limiting oxygen index of the sample according to GB/T2406-2008 'Plastic burning performance test method-oxygen index method'. The flame retardant and the polymer base material are uniformly mixed in different proportions, extruded by an extruder to prepare a sample strip with the diameter of 3mm, and the flame retardant property of the sample strip is tested, wherein the test result is shown in table 1.
TABLE 1 flame retardant Effect of flame retardant polycarbonate
TABLE 2 flame retardant DGEBA epoxy resin combustion parameters
TABLE 3 thermal Properties of flame retardant DGEBA epoxy resin
TABLE 4 mechanical Properties of flame retardant DGEBA epoxy resin
As can be seen from tables 1-4, the flame retardant of the present application exhibits very good tensile strength (80MPa) and modulus (2709MPa) when applied to an epoxy resin, which are much higher than those of a bisphenol A epoxy resin (Dow DER331) measured under the same conditions (76MPa) and modulus (1893 MPa). The flame retardant property is excellent, two applied base materials (polycarbonate and epoxy resin) reach the UL-94V-0 industrial flame retardant level, and the limited oxygen index reaches 30%; meanwhile, no black smoke is generated in the epoxy resin in a combustion experiment, and a large amount of black smoke is generated by the bisphenol A epoxy resin, so that the flame retardant disclosed by the invention has a smoke suppression effect. Through a thermal weight loss experiment and analysis of the morphology and structural components of the carbon layer after a flame-retardant experiment, the excellent flame retardance of the carbon layer is mainly found out as follows: the biomass-based multi-element flame retardant has excellent expansion char forming capability, and a formed char layer is very compact, so that the flame retardant can play a very good role in heat insulation and oxygen isolation, and further combustion of internal materials is prevented.
Example 2
First, 75mmol of vanillin was dissolved in 150mL of THF at room temperature, 3mL of triethylamine was injected into the flask using a syringe, and after stirring for 10min, 15mmol of dichlorodimethylsilane was slowly injected into the flask using a syringe. Stirring and reacting at 80 ℃ for 8 hours, pouring the reaction mixture into n-hexane at 0 ℃, filtering, washing the precipitate with deionized water, and drying in vacuum at 80 ℃ to obtain an intermediate product (I).
Then, under the protection of nitrogen, 0.1mol (12.21g) of the intermediate product (I) is dissolved in 500m1 of absolute ethyl alcohol, 0.5mo1 of 4-hydroxyaniline is slowly dropped into the prepared solution, the product is filtered after heating reflux reaction for 8 hours, the obtained solid is washed by deionized water and dried in vacuum at 80 ℃ to constant weight, and the product structure (II) is obtained;
finally, product (II) (0.1mol) was dissolved in absolute ethanol (100 ml) in N2Adding 0.5mol of DOPO and 1mmol of AIBN under protection, stirring and refluxing at 80 ℃ for 8h, and cooling to room temperature. Filtration and washing of the precipitate with dichloromethane followed by vacuum drying at 50 ℃ for 12 hours gave biomass-based flame retardant (III).
Example 3
First, 20mmol of vanillin was dissolved in 100mL of THF at room temperature, 3mL of triethylamine was injected into the flask using a syringe, and after stirring for 10min, 5mmol of dichlorodimethylsilane was slowly injected into the flask using a syringe. Stirring and reacting at 60 ℃ for 5 hours, pouring the reaction mixture into n-hexane at 0 ℃, filtering, washing the precipitate with deionized water, and drying in vacuum at 60 ℃ to obtain an intermediate product (I).
Then, under the protection of nitrogen, 0.1mol (12.21g) of the intermediate product (I) is dissolved in 500m1 of absolute ethyl alcohol, 0.4mo1 of dopamine is slowly dropped into the solution prepared above, the product is filtered after heating reflux reaction for 5 hours, the obtained solid is washed by deionized water and dried in vacuum at 60 ℃ to constant weight, and the product structure (II) is obtained;
finally, product (II) (0.1mol) was dissolved in absolute ethanol (100 ml) in N2Adding 0.5mol of DOPO and 1mmol of AIBN under protection, stirring and refluxing at 80 ℃ for 8h, and cooling to room temperature. Filtration and washing of the precipitate with dichloromethane followed by vacuum drying at 50 ℃ for 12 hours gave biomass-based flame retardant (III).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The biomass-based flame retardant is characterized in that the chemical structure of the flame retardant III is as follows:
2. the preparation method of the biomass-based flame retardant of claim 1, which is characterized by comprising the following steps:
s1: dissolving vanillin in tetrahydrofuran, and then adding dichlorodimethylsilane for reaction to obtain a product I;
s2: dissolving the product in S1 in absolute ethyl alcohol, and then adding aminophenol or primary aminophenol for reaction to obtain a product II;
s3: dissolving 9, 10-dihydro-9, 10-oxa-10-phosphaphenanthrene-10-oxide in dichloromethane, adding azodiisobutyronitrile, and adding the product in S2 under the protection of inert gas to obtain a biomass-based flame retardant III.
3. The method of claim 2, wherein vanillin in S1 is derived from biomass resources.
4. The preparation method of the biomass-based flame retardant of claim 2, wherein the specific steps of S1 are as follows: under magnetic stirring, dissolving vanillin in tetrahydrofuran to prepare vanillin solution with the concentration of 0.1-0.5mol/L, adding dichlorodimethylsilane dropwise under the condition of introducing nitrogen, and reacting at 50-80 ℃ for 2-8h to obtain a product I;
preferably, the chemical structure of the product I is:
5. the method of claim 4, wherein the vanillin solution further comprises an amine acid scavenger;
preferably, the acid-binding agent is an organic amine acid-binding agent;
preferably, the organic amine acid-binding agent is one or more of triethylamine, diethylamine, pyridine and aminopyridine.
6. The method for preparing biomass-based flame retardant of claim 2, wherein the molar ratio of dichlorodimethylsilane to vanillin in S1 is 1: 2-5.
7. The preparation method of the biomass-based flame retardant of claim 2, wherein the specific steps of S2 are as follows: under magnetic stirring, mixing the product I and aminophenol/primary aminophenol according to a molar ratio of 1:2-5, dissolving in absolute ethyl alcohol, reacting at 50-80 ℃ for 4-8h, filtering out a product, washing the obtained product with deionized water, and drying at 50-80 ℃ in vacuum to constant weight to obtain a product II;
preferably, the aminophenol is 4-hydroxyaniline and the primary aminophenol is dopamine;
preferably, the chemical structural formula of the product II is shown in the specification
8. The preparation method of the biomass-based flame retardant of claim 2, wherein the specific steps of S3 are as follows: under the protection of nitrogen, 9, 10-dihydro-9, 10-oxa-10-phosphaphenanthrene-10-oxide and the product II are dissolved in CH according to the mol ratio of 2-5:12Cl2Adding azodiisobutyronitrile with the concentration of 0.001-0.01mol/L, and reacting at 50-80 ℃ for 2-8h to obtain the biomass-based flame retardant III.
9. Use of a biomass-based flame retardant according to claim 1 in thermoplastic polymers;
preferably, the thermoplastic polymer comprises polypropylene, polyethylene, polyvinyl chloride, polystyrene, polymethylmethacrylate, polyamide, polycarbonate, or a terephthalate-based thermoplastic polyester.
10. Use of the biomass-based flame retardant of claim 1 in thermosetting resins;
preferably, the thermosetting resin is an epoxy resin or a polyurethane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940375A (en) * | 2021-01-13 | 2021-06-11 | 东莞市道尔新材料科技有限公司 | Organic phosphorus flame-retardant master batch and preparation method thereof |
| CN113929968A (en) * | 2021-11-02 | 2022-01-14 | 合肥学院 | Resveratrol-based flame retardant and preparation method and application thereof |
| CN115073686A (en) * | 2022-06-28 | 2022-09-20 | 河北大学 | Preparation method of bio-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin |
| CN116284757A (en) * | 2023-03-10 | 2023-06-23 | 吉林大学 | High-strength chemically-stable flame-retardant closed-loop recycled plastic and preparation and recycling methods thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
| CN105801867A (en) * | 2016-04-14 | 2016-07-27 | 浙江大学宁波理工学院 | Expansive type flame retardant based on biomass structure and preparation method of expansive type flame retardant |
| CN107011499A (en) * | 2017-04-18 | 2017-08-04 | 中国科学院宁波材料技术与工程研究所 | The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application |
| WO2018095362A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Phosphaphenanthrene-structure reactive fire retardant and application thereof |
| CN109096472A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of application of novel P-N-Si cooperative resistance combustion epoxy curing agent in epoxy-resin systems |
-
2019
- 2019-09-16 CN CN201910871693.4A patent/CN110746646B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
| CN105801867A (en) * | 2016-04-14 | 2016-07-27 | 浙江大学宁波理工学院 | Expansive type flame retardant based on biomass structure and preparation method of expansive type flame retardant |
| WO2018095362A1 (en) * | 2016-11-23 | 2018-05-31 | 厦门大学 | Phosphaphenanthrene-structure reactive fire retardant and application thereof |
| CN107011499A (en) * | 2017-04-18 | 2017-08-04 | 中国科学院宁波材料技术与工程研究所 | The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application |
| CN109096472A (en) * | 2018-07-27 | 2018-12-28 | 武汉工程大学 | A kind of application of novel P-N-Si cooperative resistance combustion epoxy curing agent in epoxy-resin systems |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940375A (en) * | 2021-01-13 | 2021-06-11 | 东莞市道尔新材料科技有限公司 | Organic phosphorus flame-retardant master batch and preparation method thereof |
| CN113929968A (en) * | 2021-11-02 | 2022-01-14 | 合肥学院 | Resveratrol-based flame retardant and preparation method and application thereof |
| CN113929968B (en) * | 2021-11-02 | 2023-01-13 | 合肥学院 | Resveratrol-based flame retardant and preparation method and application thereof |
| CN115073686A (en) * | 2022-06-28 | 2022-09-20 | 河北大学 | Preparation method of bio-based flame-retardant smoke suppressant containing vanillin and flame-retardant epoxy resin |
| CN115073686B (en) * | 2022-06-28 | 2023-07-21 | 河北大学 | Preparation method of vanillin-containing bio-based flame-retardant smoke suppressant and flame-retardant epoxy resin |
| CN116284757A (en) * | 2023-03-10 | 2023-06-23 | 吉林大学 | High-strength chemically-stable flame-retardant closed-loop recycled plastic and preparation and recycling methods thereof |
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