CN117258205A - Preparation method of bio-based fire extinguishing microcapsule - Google Patents
Preparation method of bio-based fire extinguishing microcapsule Download PDFInfo
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- CN117258205A CN117258205A CN202310767583.XA CN202310767583A CN117258205A CN 117258205 A CN117258205 A CN 117258205A CN 202310767583 A CN202310767583 A CN 202310767583A CN 117258205 A CN117258205 A CN 117258205A
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- fire extinguishing
- extinguishing agent
- microcapsule
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- diisocyanate
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229920005610 lignin Polymers 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011162 core material Substances 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 16
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- -1 isocyanate compound Chemical class 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 6
- 239000008346 aqueous phase Substances 0.000 claims 2
- 238000009775 high-speed stirring Methods 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 239000008213 purified water Substances 0.000 claims 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 claims 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- KEZMBAQUUXDDDQ-UHFFFAOYSA-N CCC.N=C=O.N=C=O Chemical compound CCC.N=C=O.N=C=O KEZMBAQUUXDDDQ-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 229920001214 Polysorbate 60 Polymers 0.000 claims 1
- 229920002396 Polyurea Polymers 0.000 claims 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims 1
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007764 o/w emulsion Substances 0.000 claims 1
- 229920003226 polyurethane urea Polymers 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- WVSNNWIIMPNRDB-UHFFFAOYSA-N 1,1,1,3,3,4,4,5,5,6,6,6-dodecafluorohexan-2-one Chemical compound FC(F)(F)C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WVSNNWIIMPNRDB-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 12
- 238000010008 shearing Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- JIAFGCKUXLMTJH-UHFFFAOYSA-N hexane-1,6-diamine;hydrate Chemical compound O.NCCCCCCN JIAFGCKUXLMTJH-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0007—Solid extinguishing substances
- A62D1/0021—Microcapsules
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention discloses a preparation method of a bio-based fire extinguishing microcapsule, which mainly comprises a wall material and a core material, wherein the wall material is a bio-based composite material, the core material is a liquid fire extinguishing agent comprising tetrafluorodibromoethane, perfluoro-hexanone and homologues thereof, the bio-based composite material is prepared by carrying out interfacial polymerization reaction on lignin and polyamine at 40-50 ℃, the polymerization reaction temperature is lower than the boiling point of the core material, the fire extinguishing agent is ensured to be wrapped in the wall material in a liquid form, and the embedding rate and stability of the fire extinguishing agent are improved. When the fire extinguishing agent encounters flame, the microcapsule breaks, so that the fire extinguishing agent is released, and the effect of actively extinguishing the fire in the initial stage of the fire is achieved. The bio-based fire extinguishing microcapsule disclosed by the invention has the advantages of excellent fire extinguishing performance, stability, air tightness, environment friendliness, no toxicity and the like, and has a good application prospect.
Description
Technical Field
The invention relates to the technical field of fire extinguishing agents, in particular to a bio-based fire extinguishing microcapsule and a preparation method thereof.
Background
Fire is a common disaster, which not only causes casualties and property loss, but also causes serious environmental pollution and ecological damage, and brings direct threat to human survival. The wide use of the fire extinguishing agent can effectively prevent and control fire, protect the life and property safety of people and reduce property loss. The halogenated hydrocarbon liquid is a current common environment-friendly fire extinguishing agent, has obvious characteristics such as high efficiency, high speed, no pollution, no damage to instruments and equipment and the like, and is widely used in a plurality of important occasions. However, most halocarbon fire extinguishing agents also suffer from significant drawbacks such as low boiling point, high cost, inconvenience for storage, etc. How to improve the stability of halogenated hydrocarbon fire extinguishing agents is a current research hot spot. The halogenated hydrocarbon extinguishing agent is microencapsulated, namely the halogenated hydrocarbon extinguishing agent is used as a core material and a polymer material is used as a wall material, so that the extinguishing agent microcapsule is a very ideal choice, and the halogenated hydrocarbon extinguishing agent can be stored easily and is convenient to use. Cao Yuancheng et al disclose a patent indicating that the melamine urea formaldehyde resin is used for wrapping mixed fire extinguishing agents such as perfluoro-hexanone and heptafluorocyclopentane and is applied to fire extinguishing of lithium ion batteries, but the fire extinguishing agents prepared by the method have the defects of low loading rate, limited fire extinguishing effect and the like. The patent CN109420281a is used for adsorbing or dissolving halogenated hydrocarbon fire extinguishing agent by adding some adsorption materials such as polymer resin, fiber, inorganic filler and the like, so as to reduce the volatility of the fire extinguishing agent, however, the acting force between the materials and the fire extinguishing agent is usually weak, the stability is obviously affected, and the fire extinguishing effect is limited. Patent CN113230577a discloses a microcapsule using urea-formaldehyde resin as wall material for wrapping halogenated hydrocarbon fire extinguishing agent, however, the synthesis reaction temperature of the microcapsule needs to be controlled at 70 ℃, which is obviously higher than the boiling point (50 ℃) of the fire extinguishing agent, resulting in loss of the fire extinguishing agent. The microcapsule prepared by the reported method has the advantages of low core material loading rate, complex preparation process, poor stability, easy leakage of fire extinguishing agent in the storage process and potential risk to an ecological environment system.
Disclosure of Invention
In order to solve the technical problems, chitosan is used as a synthetic monomer, and the invention discloses a bio-based fire-extinguishing microcapsule which has the characteristics of high stability, high air tightness and the like, can effectively reduce leakage of fire extinguishing agent, and prolongs the service life of the fire-extinguishing microcapsule. In addition, the synthesis process of the microcapsule has the characteristics of green, environment protection, low price and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the shell comprises an inner layer and an outer layer, the inner layer is formed by reacting lignin with isocyanate compounds, and the outer layer is mainly polyurethane. The bio-based fire extinguishing microcapsule mainly exists in the form of fire extinguishing microcapsule powder, and can be applied to fire extinguishment of fire extinguishing patches, fire retardant cloth, fire retardant coating, lithium batteries and the like. Wherein the diameter of the bio-based fire extinguishing microcapsule is adjustable and controllable at 40-400 mu m, the core wall ratio of the microcapsule is adjustable and controllable at 1:4-9:1 for optimization, and the mass fraction of the fire extinguishing agent in the whole fire extinguishing material is 25% -90%. The fire extinguishing material can be kept stable in a conventional environment, the fire extinguishing triggering temperature is realized by regulating and controlling the wall material, the thickness and the polymer type of the microcapsule, the softening temperature of the composite material adopted in the invention is 90-150 ℃, the air permeability is less than 650mL/cm < 2 >. H, the curing shrinkage is lower than 5%, the water absorption is within 5%, the tensile strength is 9-90 MPa, and the microcapsule can soften, crack and release the fire extinguishing agent at 90-150 ℃ or when encountering open fire, thereby realizing the automatic fire extinguishing function.
The technical scheme adopted for solving the key technical problems is as follows: preparing a bio-based fire-extinguishing microcapsule taking halogenated hydrocarbon liquid as a core material, and secondarily coating the microcapsule to obtain the bio-based fire-extinguishing microcapsule taking the halogenated hydrocarbon liquid as a core component.
The invention provides a bio-based fire extinguishing microcapsule, the fire extinguishing triggering temperature is 90-150 ℃, comprising:
a capsule core comprising a mixture of one or more of tetrafluorodibromoethane, perfluoro-hexanone, and homologs thereof,
the wall material comprises two layers of shells from inside to outside: the first shell and the second shell respectively comprise a polymer material and polyurethane which are polymerized by taking lignin as a monomer, wherein:
the preferred diameter size range of the bio-based fire suppressing microcapsules is 40-400 μm (e.g., 40-150 μm, 100-200 μm, 150-300 μm, 250-400 μm). The size distribution of the bio-based fire extinguishing microcapsules can be regulated and controlled according to the needs. Compared with the existing microcapsule fire extinguishing agent, the invention selects the halogenated hydrocarbon liquid with excellent fire extinguishing effect as the fire extinguishing agent, does not need the adsorbent to adsorb the halogenated hydrocarbon liquid, has high load rate (the load rate is up to 90 percent), has green synthesis process and low cost, and is beneficial to industrialization. The bio-based fire extinguishing microcapsule has high stability and high air tightness, effectively prevents volatilization of halogenated hydrocarbon fire extinguishing agent, and can maintain excellent fire extinguishing performance in a wider temperature and humidity range.
In some embodiments, the mass ratio of the oil phase to the water phase in the step (1) is 1:5-9, the mass ratio of the liquid extinguishing agent, the polyisocyanate, the emulsifier, the lignin and the polyamine is 1:0.6-1.8:0.04-0.1:0.2-2:0.04-0.32, and the concentration of the aqueous emulsifier solution in the water phase is 0.2% -2%. The first shell and the second shell comprise polymer materials selected from lignin and polyurethane. The molecular weight of lignin is generally 1000-20000, preferably lignin molecular weight is between 1000-2000, and the speed of high-speed shearing emulsification is 500-2000 rpm. The softening point of the bio-based fire extinguishing microcapsule is 90-150 ℃; the air permeability is less than 650mL/cm < 2 >. H, the solidification shrinkage rate is lower than 5%, the water absorption rate is within 5%, the tensile strength is 9-90 MPa, and the microcapsule can soften, crack and release the fire extinguishing agent at 90-150 ℃ or when exposed fire, thereby realizing the automatic fire extinguishing function.
Next, the present invention provides a bio-based fire extinguishing microcapsule powder obtained by drying the above microcapsules.
The invention further provides a preparation method of the bio-based fire extinguishing microcapsule, which comprises the following preparation steps: forming a first layer of shell for encapsulating the halogenated hydrocarbon liquid to obtain halogenated hydrocarbon liquid microcapsules of a single layer of shell; and coating polyurethane on the first shell as a second shell to obtain the bio-based fire extinguishing microcapsule.
The present invention further provides a bio-based fire extinguishing microcapsule powder obtained by drying the above bio-based fire extinguishing microcapsule at a low temperature.
Finally, the invention provides the application of the bio-based fire-extinguishing microcapsule powder, which can be used in the preparation of fire-proof and/or fire-extinguishing products; use in the preparation of fire protection and/or extinguishing related products.
The bio-based fire suppression microcapsules of the present invention provide a number of advantages and benefits:
(1) The biological base fire-extinguishing microcapsule can be used for preparing various fire-extinguishing materials in the form of microcapsule, and compared with halogenated hydrocarbon liquid fire-extinguishing agent, the biological base fire-extinguishing microcapsule does not need a special storage container and a trigger device and is sprayed manually. The microcapsule fire extinguishing material has the advantages that the microcapsule wall is broken under the condition of a certain temperature or open flame, the halogenated hydrocarbon liquid is released, and the automatic cooling and fire extinguishing can be realized;
(2) The novel environment-friendly and efficient halogenated hydrocarbon liquid is adopted as a fire extinguishing agent, other relevant adsorbents are not needed for assisting in adsorbing the halogenated hydrocarbon liquid, the high core-wall ratio (the mass ratio of the halogenated hydrocarbon liquid to the capsule shell can reach 9:1), the shell has higher strength and lower permeability of the halogenated hydrocarbon liquid, the volatilization loss of the halogenated hydrocarbon liquid of the microcapsule at normal temperature is obviously reduced, and the microcapsule has excellent stability and service life;
(3) The lignin-based fire-extinguishing microcapsule is a product synthesized by taking degradable lignin as a raw material, which is reported and developed for the first time in China at present, has wide sources, low cost, simple process and environmental protection, and plays a great role in preventing fires, cooling and extinguishing fires and preventing fires;
(4) The fire extinguishing materials with different size ranges can be prepared, and can be applied to different fire extinguishing agents such as fire extinguishing dry powder, fire extinguishing paste, fire extinguishing coating and the like, and can also be applied to the requirements of various products such as various batteries, electric boxes, high-speed rails, aerospace, electric equipment, fire fighting and the like. The microcapsule fire extinguishing agent is gasified rapidly after fire extinguishment, and can not damage related facilities, so that the loss after fire disaster is reduced to the minimum.
Drawings
In order to clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly describe the drawings used in the description of the embodiments or the prior art, and other drawings may be obtained according to these drawings.
FIG. 1 is an infrared spectrum of microcapsules obtained in example 1: FTIR spectra of blank microcapsules (a), tetrafluorodibromoethane/microcapsules (b) and tetrafluorodibromoethane (c).
FIG. 2 is a scanning electron microscope spectrum of the microcapsule obtained in example 1: SEM of blank microcapsules (a-b) and tetrafluorodibromoethane/microcapsules (c-d).
Fig. 3 is a scanning electron microscope map after breaking the microcapsules: TG profile of blank microcapsules, tetrafluorodibromoethane and tetrafluorodibromoethane/microcapsules.
Detailed Description
The invention is described in detail below with reference to the attached drawing figures:
example 1
The preparation method of the bio-based fire extinguishing microcapsule provided by the embodiment comprises the following steps:
(1) Raw material preparation: dissolving 7.2 g tetrafluorodibromoethane and 6.3 g toluene diisocyanate in 20 mL petroleum ether, and uniformly stirring to obtain an oil phase; dissolving lignin with molecular weight of 2000 of 1.3 and g in distilled water of 200 mL, heating at constant temperature of 40 ℃ and stirring uniformly, and cooling to room temperature to obtain water phase; respectively dissolving 4 g of span80 and 4 g of Tween20 in 20 mL distilled water, and dissolving 1.32 g diethylenetriamine in 10 mL distilled water, and uniformly stirring for later use;
(2) Shearing and emulsifying the water phase at 1200 rpm, slowly adding the water phase, continuing high-speed shearing and emulsifying for 20 min, and transferring into a three-neck flask;
(3) Slowly dropwise adding a mixed solution of Span80 and Tween20 into the three-neck flask mixed system at room temperature under the condition of mechanical stirring (500 rpm), slowly dropwise adding the mixed solution at a slow speed, and continuing to react 2 h after dropwise adding is finished;
(4) Slowly dropwise adding an aqueous solution of diethylenetriamine into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (500 rpm), wherein the dropwise adding speed is one drop every three seconds, and continuing to react for 3 h after the dropwise adding is finished;
(5) Heating the mixed system obtained in the step (4) to 45 ℃, reacting 3 h, standing, suction filtering, washing with water and alcohol after the reaction is completed, and then vacuum drying at 60 ℃ for 24 h to obtain the powdery microcapsule fire extinguishing agent.
Example 2
The preparation method of the bio-based fire extinguishing microcapsule provided by the embodiment comprises the following steps:
(1) Raw material preparation: dissolving 8.3 g of perfluoro-hexanone and 4.0 g of isophorone diisocyanate in 20 mL of ethyl acetate, and uniformly stirring to obtain an oil phase; dissolving 1.62 and g alkali lignin with molecular weight of 5000 in 200 mL distilled water, heating at 45deg.C and stirring uniformly, and cooling to room temperature to obtain water phase; respectively dissolving 1.45 hexamethylenediamine in 15 mL distilled water and 12 g SDBS in 30 mL distilled water, and uniformly stirring for later use;
(2) Shearing and emulsifying the water phase at 2000 rpm, slowly adding the water phase, continuing high-speed shearing and emulsifying for 20 min, and transferring into a three-neck flask;
(3) Slowly dripping hexamethylenediamine water solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (600 rpm), wherein the dripping speed is one drop per second, and continuing to react 2 h after the dripping is finished;
(4) Slowly dripping SDBS aqueous solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (600 rpm), wherein the dripping speed is one drop per two seconds, and continuing to react 2 h after the dripping is finished;
(5) Heating the mixed system obtained in the step (4) to 45 ℃, reacting 2 h, standing, suction filtering, washing with water and alcohol after the reaction is completed, and then vacuum drying 12 h at 50 ℃ to obtain the powdery microcapsule fire extinguishing agent.
Example 3
The preparation method of the bio-based fire extinguishing microcapsule provided by the embodiment comprises the following steps:
(1) Raw material preparation: 4.5 g of 1, 2-dibromoethane and 6.4 g diphenylmethane-4, 4' -diisocyanate are dissolved in 20 mL cyclohexane and stirred uniformly to be used as an oil phase; dissolving 2.14 and g alkali lignin with molecular weight of 10000 in 200 and mL distilled water, heating at 44 ℃ and stirring uniformly, and cooling to room temperature to obtain water phase; and respectively dissolving 1.87. 1.87 g of pentanediamine in 20 mL of distilled water and 13.4 g of SMAS in 30 mL of distilled water, and uniformly stirring for later use;
(2) Shearing and emulsifying the water phase at 1500 rpm, slowly adding the water phase, continuing high-speed shearing and emulsifying for 20 min, and transferring into a three-neck flask;
(3) Slowly dripping hexamethylenediamine water solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (1200 rpm), wherein the dripping speed is one drop per second, and continuing to react for 2 h after the dripping is finished;
(4) Slowly dripping SDBS aqueous solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (1200 rpm), wherein the dripping speed is one drop per two seconds, and continuing to react 2 h after the dripping is finished;
(5) Heating the mixed system obtained in the step (4) to 47 ℃, reacting 2 h, standing, suction filtering, washing with water and alcohol after the reaction is completed, and then vacuum drying 24 h at 46 ℃ to obtain the powdery microcapsule fire extinguishing agent.
Example 4
The preparation method of the bio-based fire extinguishing microcapsule provided by the embodiment comprises the following steps:
(1) Raw material preparation: dissolving 7.6 g of perfluoro-hexanone and 6.8 g of hexamethylene diisocyanate in 20 mL of normal hexane, and uniformly stirring to obtain an oil phase; dissolving 2.43 and g alkali lignin with molecular weight of 15000 in 200 and mL distilled water, heating at 42 ℃ and uniformly stirring, and then cooling to room temperature to obtain a water phase; respectively dissolving 1.96 g diethylenetriamine in 20 mL distilled water and 13.4 g of SP20 in 30 mL distilled water, and uniformly stirring for later use;
(2) Shearing and emulsifying the water phase at 1500 rpm, slowly adding the water phase, continuing high-speed shearing and emulsifying for 20 min, and transferring into a three-neck flask;
(3) Slowly dripping hexamethylenediamine water solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (1500 rpm), wherein the dripping speed is one drop per two seconds, and continuing to react 2 h after the dripping is finished;
(4) Slowly dripping SDBS aqueous solution into the three-neck flask mixed system under the conditions of room temperature and mechanical stirring (1500 rpm), wherein the dripping speed is one drop per two seconds, and continuing to react 2 h after the dripping is finished;
(5) Heating the mixed system obtained in the step (4) to 48 ℃, reacting 2 h, standing, suction filtering, washing with water and alcohol after the reaction is completed, and then vacuum drying at 50 ℃ for 24 h to obtain the powdery microcapsule fire extinguishing agent.
Observing the microcapsule fire extinguishing agents obtained in the examples 1-4, wherein the microcapsule fire extinguishing agents are white powder, and the powder is uniform and fine; the microcapsule fire extinguishing agent obtained in example 1 was subjected to scanning electron microscopy, as shown in FIG. 2, the microcapsule fire extinguishing agent was 40-400 μm in size, and the microcapsule was broken, and the microcapsule wall thickness was 0.10-1.5. Mu.m, as shown in FIG. 2. In addition, the surface roughness of the microcapsule is moderate.
The microcapsule fire extinguishing agents obtained in examples 1-4 and the coating added with the microcapsule fire extinguishing agents were subjected to fire extinguishing experiments, and when the microcapsules are used alone or added into the coating, the fire extinguishing time is less than 20 s, so that quick fire extinguishing can be realized, the release response time of the fire extinguishing agents is short, and the effect of actively extinguishing the fire in the initial stage is achieved.
TABLE 1 implementation cases and related effects
| Description of the preferred embodiments | Coating ratio (%) | Release temperature (. Degree. C.) | Response time (seconds) | Fire extinguishing time (seconds) |
| Example 1 | 76.2 | 115～120 | 6.4 | 16.5 |
| Example 2 | 68.7 | 122～130 | 6.7 | 17.8 |
| Example 3 | 74.6 | 110～122 | 6.0 | 12.1 |
| Example 4 | 63.1 | 125～132 | 7.4 | 17.6 |
Claims (11)
1. A preparation method of a bio-based fire extinguishing microcapsule taking a liquid fire extinguishing agent as a core material is characterized by comprising the following steps of: mainly comprises the following steps: (1) preparation of aqueous phase: respectively dissolving lignin and an emulsifier in water, and stirring at normal temperature at high speed to form a uniform solution; (2) preparation of oil phase: adding an isocyanate compound and an organic solvent into a liquid fire extinguishing agent, and stirring at a high speed to form a uniform oil phase; (3) emulsification: slowly adding the oil phase mixture into the aqueous phase solution under high-speed stirring, and fully emulsifying the fire extinguishing agent under high-speed stirring to form uniform oil-in-water (O/W) emulsion; (4) interfacial polymerization: adding polyamine into the emulsion to perform polymerization reaction at a certain stirring rotation speed, performing heat preservation reaction for a certain time at normal temperature, and then heating and controlling a certain temperature to perform reaction; (5) drying: and after the reaction is finished, washing with purified water and ethanol respectively, centrifugally filtering and drying to obtain the bio-based fire extinguishing microcapsule.
2. A biobased fire extinguishing agent according to claim 1, wherein the liquid fire extinguishing agent is one or more of tetrafluorodibromoethane, perfluorinated hexanone, and homologs thereof.
3. The fire extinguishing agent according to claim 1, wherein the wall material comprises at least two shells from inside to outside, and is formed by interfacial polymerization of polyisocyanate, lignin and polyamine at a temperature range of 40-50 ℃.
4. The fire extinguishing agent according to claim 1, wherein the isocyanate compound is at least one of toluene diisocyanate, isophorone diisocyanate, propane diisocyanate, phenylene diisocyanate, naphthalene-1, 5-diisocyanate, xylylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate.
5. The bio-based fire extinguishing agent according to claim 1, wherein the lignin is an alkalized lignin, and the molecular weight is generally 1000-20000.
6. The agent of claim 1, wherein the polyamine is one or more of ethylenediamine, hexamethylenediamine, pentyenediamine, diethylenetriamine, and N, N-dimethyl 1, 3-propylenediamine.
7. The method of manufacturing according to claim 1, characterized in that: in the step 1, the emulsifier is one or more of Span80, tween20, tween60, SDS, SDBS or SMAS.
8. The method for preparing a polyurethane/polyurea composite microcapsule fire extinguishing agent according to claim 6, wherein the organic solvent in the step (1) is at least one of petroleum ether, ethyl acetate, cyclohexane and n-hexane.
9. The bio-based fire extinguishing agent according to claim 1, wherein the mass ratio of the oil phase to the water phase in the step (1) is 1:5-9, the mass ratio of the liquid fire extinguishing agent, the polyisocyanate, the emulsifier, the lignin and the polyamine is 1:0.6-1.8:0.04-0.1:0.2-2:0.04-0.32, and the concentration of the aqueous emulsifier solution in the water phase is 0.2% -2%.
10. The method for preparing the bio-based fire extinguishing microcapsule according to claim 1, wherein: the temperature of the mixed solution is 20-40 ℃, the stirring speed is 500-2000 rpm, and the stirring time is 5-30 min; the temperature of the interfacial polymerization reaction is 40-50 ℃, the thermal insulation reaction is carried out for 1-2 h, and after the reaction is finished, ethanol and purified water are respectively adopted for three times of washing.
11. The method for preparing the bio-based fire extinguishing microcapsule according to claim 1, wherein: the drying method in step 4 is vacuum reduced pressure drying or freeze drying.
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