CN113980358A - Lignin/halloysite nano hybrid material, preparation method thereof and application thereof in phenolic foam thermal insulation material - Google Patents
Lignin/halloysite nano hybrid material, preparation method thereof and application thereof in phenolic foam thermal insulation material Download PDFInfo
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- CN113980358A CN113980358A CN202111191575.2A CN202111191575A CN113980358A CN 113980358 A CN113980358 A CN 113980358A CN 202111191575 A CN202111191575 A CN 202111191575A CN 113980358 A CN113980358 A CN 113980358A
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- lignin
- halloysite
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- phenolic foam
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- 229920005610 lignin Polymers 0.000 title claims abstract description 95
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 68
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000006260 foam Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012774 insulation material Substances 0.000 title abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 29
- 229920001568 phenolic resin Polymers 0.000 claims description 29
- 239000005011 phenolic resin Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002071 nanotube Substances 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 5
- 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 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 235000013824 polyphenols Nutrition 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 229930040373 Paraformaldehyde Natural products 0.000 description 20
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- 238000001816 cooling Methods 0.000 description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 14
- -1 p-hydroxyphenyl Chemical group 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000002156 mixing Methods 0.000 description 7
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- 230000008901 benefit Effects 0.000 description 6
- 239000011121 hardwood Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000002893 slag Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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Abstract
The invention discloses a lignin/halloysite nano hybrid material, a preparation method thereof and application thereof in phenolic foam thermal insulation materials, wherein the lignin/halloysite nano hybrid material is a nano tubular structure formed by coating demethylated lignin on halloysite, the length of the tube is 0.5-5 mu m, and the outer diameter of the tube is 20-100 nm. According to the invention, the lignin/halloysite nano hybrid material is prepared by activating lignin and modifying halloysite nanotubes, and the hybrid material can be used for preparing a phenolic foam thermal insulation material in situ, has excellent compatibility and reactivity with a phenolic foam matrix, and effectively improves the mechanical, thermal insulation and flame retardant properties of phenolic foam.
Description
Technical Field
The invention belongs to the field of heat insulation materials, and particularly relates to a lignin/halloysite nano hybrid material, a preparation method thereof and application thereof in a phenolic foam heat insulation material.
Background
The phenolic foam is a universal rigid foam plastic, has the most prominent characteristics of flame retardancy, low smoke, high-temperature creep resistance, excellent barrier property, corrosion resistance, high modulus, light weight, convenient construction and the like, and is widely applied to the fields of buildings, mining, petrochemical industry, vehicles, ships, aerospace industry and the like as a heat-insulating material. The preparation of phenolic foam generally comprises two steps, wherein the first step is the synthesis of phenolic resin, namely, phenol and formaldehyde are catalyzed to be condensed under alkaline conditions to obtain resol with proper foaming viscosity and solid content, and the second step is the foaming of phenolic resin, namely, processing aids such as surfactant, foaming agent, curing agent and the like are added into the resol, and the phenolic foam is obtained through high-temperature foaming molding. The phenolic foam has the characteristics of high brittleness and easy surface abrasion, a reinforcing or toughening component can be introduced in the preparation process of the foam to improve the mechanical property of the phenolic foam, an organic component with a flexible group such as cardanol can be introduced to improve the toughness of the phenolic foam, but the hardness and the flame retardance of the phenolic foam are sacrificed to a certain extent, and the nano material is uniformly dispersed in the phenolic foam, so that the mechanical strength of the phenolic foam can be improved on the basis of keeping the flame retardance of the phenolic foam, but the key problem to be solved is how to realize the nano-scale dispersion of the nano material. Therefore, the invention provides a lignin/halloysite nano hybrid material, a preparation method thereof and application thereof in phenolic foam thermal insulation materials so as to effectively solve the technical problems.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a lignin/halloysite nano hybrid material aiming at the defects of the prior art.
The technical problem to be solved by the invention is to provide a preparation method of the lignin/halloysite nano hybrid material.
The invention further aims to solve the technical problem of providing the application of the lignin/halloysite nano hybrid material.
The invention idea is as follows: lignin is an important component of cell walls of terrestrial plants, the content of the lignin is only second to cellulose, and wastes generated in the paper making and biorefinery industries at present contain a large amount of lignin which is often combusted for energy supply or directly discharged, so that serious resource waste and environmental pollution are caused, and a high-value utilization way of the lignin is urgently needed to be found. The lignin is a polyphenol natural polymer, is a three-dimensional reticular molecular structure formed by connecting three phenylpropane units of guaiacyl (G), syringyl (S) and p-hydroxyphenyl (H) through C-O-C and C-C bonds, has the reaction activity similar to phenol, and can be used as a phenol substitute to participate in the synthesis reaction of phenolic resin. Demethylating reaction is carried out on methoxy groups in the G and S structural units, so that the content of phenolic hydroxyl groups and phenolic aldehyde condensation active sites of lignin can be improved, and meanwhile, catechol groups are generated. The invention provides a new idea of demethylation lignin modification of halloysite nanotubes, obtains a lignin-coated halloysite nano hybrid material, uses the lignin-coated halloysite nano hybrid material for in-situ synthesis of phenolic resin to participate in phenolic condensation reaction, can effectively improve the dispersibility of nano materials in the phenolic resin, obtains a phenolic foam thermal insulation material with excellent mechanical, thermal insulation and flame retardant properties, and simultaneously achieves the purposes of efficiently utilizing biomass resources and improving the ecological environmental protection benefits of the phenolic foam material.
In order to solve the first technical problem, the invention discloses a lignin/halloysite nano hybrid material which is a nano tubular structure formed by coating the halloysite with demethylated lignin, wherein the length of the nano tubular structure is 0.5-5 mu m, and the outer diameter of the nano tubular structure is 20-100 nm.
In order to solve the second technical problem, the invention discloses a preparation method of the lignin/halloysite nano hybrid material, which comprises the step of carrying out a first reaction on demethylated lignin, halloysite and a first organic solvent to obtain a solution containing the lignin/halloysite nano hybrid material.
The preparation method of the demethylated lignin comprises the step of carrying out a second reaction on lignin, a second organic solvent, a hydrobromic acid aqueous solution and hexadecyl trimethyl ammonium bromide to separate out a precipitate, wherein the obtained precipitate is the demethylated lignin.
The lignin is any one or combination of more of herbaceous lignin, hardwood lignin and softwood lignin, and preferably herbaceous lignin.
Wherein the second organic solvent is any one or a combination of more of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Wherein the concentration of the hydrobromic acid aqueous solution is 40-56%, and preferably 48%.
Wherein the lignin, the second organic solvent, the hydrobromic acid aqueous solution and the hexadecyl trimethyl ammonium bromide are 10 parts by weight: (50-200): (20-50): (0.1-0.5).
Wherein the second reaction is carried out at 80-100 ℃ for 1-4 h.
And after the second reaction is finished, cooling the reaction liquid to room temperature, adding water to separate out a precipitate, carrying out centrifugal separation, washing the precipitate with water, and drying to obtain the demethylated lignin.
Wherein the removal rate of methyl in the demethylated lignin is 5-30%.
Wherein the halloysite is of a nano-tubular structure, and the outer diameter of the halloysite is 10-100 nm.
Wherein the first organic solvent is any one or a combination of more of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Wherein the weight parts of the demethylated lignin, the halloysite and the first organic solvent are 10: (50-200): (5-20).
Wherein the first reaction is carried out at 50-100 ℃ for 12-24 h.
And after the first reaction is finished, cooling the reaction liquid to room temperature, carrying out centrifugal separation, washing the precipitate with water, and drying to obtain the lignin/halloysite nano hybrid material.
In order to solve the third technical problem, the invention also discloses application of the lignin/halloysite nano hybrid material in preparation of phenolic resin.
The preparation method of the phenolic resin comprises the following steps:
(1) reacting phenol, water, NaOH, paraformaldehyde and lignin/halloysite nano hybrid materials;
(2) and (2) adding paraformaldehyde into the reactant obtained in the step (1) in several times, reacting and cooling to obtain the phenolic resin.
In the step (1), the weight parts of the phenolic aldehyde, the water, the NaOH and the paraformaldehyde are 100: (20-40) parts of: (2-4) parts: (20-30).
In the step (1), the lignin/halloysite nanometer hybrid material and phenol are in parts by weight (0.1-2): 100 parts.
In the step (1), the reaction is carried out for 0.5-1 h at 70-90 ℃ with stirring.
In the step (2), the weight parts of the paraformaldehyde and the phenol are (20-30): 100 parts.
In the step (2), the reaction is carried out for 0.5-1.5 h at the temperature of 70-90 ℃ by stirring.
The invention further discloses an application of the lignin/halloysite nano hybrid material in preparation of phenolic foam, or an application of the phenolic resin in preparation of phenolic foam, wherein the application comprises the steps (3) of uniformly mixing the phenolic resin, a surfactant, a foaming agent and a curing agent, and heating and foaming to obtain the phenolic foam besides the steps (1) and (2).
In the step (3), the surfactant is any one or a combination of more of polysiloxane, polyoxyethylene ether, polyoxypropylene, polyoxyethylene polyoxypropylene, polyethylene sorbitan fatty acid, polydimethylsiloxane and tween series.
In the step (3), the foaming agent is any one or a combination of more of n-pentane, n-butane, isopentane, petroleum ether, a polyvinyl alcohol aqueous solution and diisopropyl ether, and n-pentane is preferred.
In the step (3), the curing agent is any one or a combination of sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, benzenesulfonic acid and p-toluenesulfonic acid.
In the step (3), the weight parts of the phenolic resin, the surfactant, the foaming agent and the curing agent are 100: (2-10) parts of: (5-15) parts of: (15-25).
In the step (3), the heating foaming is carried out for 0.5-3 h at 70-90 ℃.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) according to the invention, G, S units in lignin molecules have ortho methoxy substituted phenolic hydroxyl groups, and the ortho methoxy groups can generate new phenolic hydroxyl groups through demethylation reaction, so that on one hand, the number of active sites capable of participating in phenolic aldehyde condensation reaction in the lignin is increased, on the other hand, a catechol group is formed, aluminosilicate nano clay such as halloysite nanotube can be covalently modified, and the lignin-coated halloysite nano hybrid material is obtained, and is used for in-situ synthesis of phenolic resin, can participate in phenolic aldehyde condensation reaction, and can realize nanoscale dispersion, so that the mechanical, thermal insulation and flame retardant properties of phenolic foam are effectively improved, and the problem of poor foam performance in the prior art is solved.
(2) Compared with unmodified lignin, the demethylated lignin contains catechol groups, so that the halloysite nanotube can be covalently modified to form a chemically stable organic-inorganic nano hybrid structure.
(3) Compared with pure halloysite, the lignin-modified halloysite has the advantages that the dispersibility in phenol is greatly improved, and the compatibility of the nano material and phenolic resin is improved.
(4) The surface of the lignin/halloysite nano hybrid material contains lignin molecules, and the lignin molecules can participate in the polymerization reaction of the phenolic resin in situ, so that organic and inorganic components are firmly connected through chemical bonds.
(5) The lignin/halloysite nanometer hybrid material has the function of a heterogeneous nucleating agent in the foaming process of the phenolic resin, improves the stability of the bubble nucleation and growth process, and is beneficial to forming a uniform and compact foam structure, thereby improving the closed cell rate and the heat insulation performance of the phenolic foam.
(6) The lignin/halloysite nano hybrid material has a high length-diameter ratio, a rigid framework is formed in the pore wall of the phenolic foam, and the mechanical strength of the phenolic foam can be effectively improved and the slag falling rate can be reduced only by adding a small amount of nano hybrid material.
(7) The lignin/halloysite nano hybrid material improves the flame retardance of phenolic foam, is beneficial to blocking the migration of combustible molecules in the combustion process and improves the oxygen index.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a transmission electron microscope image of the lignin/halloysite hybrid nanomaterial obtained in example 1 and example 2.
FIG. 2 is a thermogravimetric analysis diagram of the lignin/halloysite nano-hybrid materials obtained in example 1 and example 2.
FIG. 3 is a scanning electron micrograph of the phenolic foam insulation obtained in example 3 and comparative example 1.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are commercially available; the parts are parts by weight unless otherwise specified.
The detection method of each parameter in the following examples is as follows: properties of the foam: national standard GBT 20974-2014.
The paraformaldehyde is added twice in 13.58 parts of paraformaldehyde in each time in the following examples, namely 13.58 parts of paraformaldehyde is added firstly, and 13.58 parts of paraformaldehyde is added after 20 min.
Example 1:
(1) dissolving 10 parts of herbal lignin in 100 parts of N, N-dimethylformamide, adding 34 parts of a 48% hydrobromic acid aqueous solution and 0.2 part of hexadecyl trimethyl ammonium bromide, stirring and reacting at 90 ℃ for 1.5h, cooling to room temperature after the reaction is finished, adding water to precipitate, performing centrifugal separation, and washing the precipitate with water to obtain demethylated herbal lignin;
(2) dissolving 10 parts of demethylated herbaceous lignin in 100 parts of organic solvent, adding 7.5 parts of halloysite, stirring and reacting at 50 ℃ for 24 hours, cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, and washing the precipitate with water to obtain the herbaceous lignin/halloysite nano hybrid material.
Example 2:
(1) dissolving 10 parts of hardwood lignin in 100 parts of N, N-dimethylformamide, adding 34 parts of a 48% hydrobromic acid aqueous solution and 0.2 part of hexadecyl trimethyl ammonium bromide, stirring and reacting at 90 ℃ for 1.5h, cooling to room temperature after the reaction is finished, adding water to precipitate, performing centrifugal separation, and washing the precipitate with water to obtain demethylated hardwood lignin;
(2) dissolving 10 parts of demethylated hardwood lignin in 100 parts of organic solvent, adding 7.5 parts of halloysite, stirring and reacting at 50 ℃ for 24 hours, cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, and washing the precipitate with water to obtain the hardwood lignin/halloysite nano hybrid material.
Through nuclear magnetic resonance analysis, the methyl removal rate of lignin in the lignin/halloysite nano hybrid materials obtained in the embodiments 1 and 2 is respectively 21.4% and 13.7%, the content of phenolic hydroxyl groups is respectively 19.0% and 15.0% higher than that of unmodified lignin, catechol groups are formed, the halloysite nano hybrid materials have the capability of covalently modifying halloysite, a transmission electron microscope photo (figure 1) shows that the surfaces of halloysite nanotubes are coated by lignin, thermogravimetric analysis (figure 2) shows that the content of lignin in the lignin/halloysite nano hybrid materials is respectively 16.45% and 9.36%, and experimental results prove that the demethylation modification effect of herbal lignin is better and the modification capability of halloysite is stronger.
Example 3:
(1) adding 30 parts of water, 3.3 parts of NaOH, 27.15 parts of paraformaldehyde and 0.4 part of herbal lignin/halloysite nano hybrid material into 100 parts of phenol, and stirring and reacting at 70 ℃ for 0.5 h;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
Example 4:
(1) adding 30 parts of water, 3.3 parts of NaOH, 27.15 parts of paraformaldehyde and 0.4 part of hardwood lignin/halloysite nano hybrid material into 100 parts of phenol, and stirring and reacting at 70 ℃ for 0.5 h;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
Comparative example 1:
(1) adding 30 parts of water, 3.3 parts of NaOH and 27.15 parts of paraformaldehyde into 100 parts of phenol, and stirring and reacting at 70 ℃ for 0.5 h;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
Comparative example 2:
(1) adding 30 parts of water, 3.3 parts of NaOH, 27.15 parts of paraformaldehyde and 0.4 part of halloysite nanotube into 100 parts of phenol, and stirring and reacting at 70 ℃ for 0.5 h;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
Comparative example 3:
(1) adding 30 parts of water, 3.3 parts of NaOH, 27.15 parts of paraformaldehyde and 0.4 part of demethylated herbal lignin obtained in the step (1) of the example 1 into 100 parts of phenol, and stirring and reacting for 0.5h at 70 ℃;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
Comparative example 4:
(1) adding 30 parts of water, 3.3 parts of NaOH, 27.15 parts of paraformaldehyde, 0.065 part of demethylated herbaceous lignin obtained in the step (1) of the example 1 and 0.335 part of halloysite nanotubes into 100 parts of phenol, and stirring and reacting for 0.5h at 70 ℃;
(2) further adding 27.15 parts of paraformaldehyde twice, stirring and reacting at 90 ℃ for 1h, cooling to 70 ℃, stirring and reacting for 0.5h, and cooling to obtain phenolic resin;
(3) adding 3.5 parts of surfactant DC-193, 8 parts of n-pentane and 20 parts of p-toluenesulfonic acid into 100 parts of phenolic resin, uniformly mixing, introducing into a mold, heating and foaming at the foaming temperature of 80 ℃ for 1.25 hours to obtain the phenolic foam heat-insulating material.
The phenolic foam thermal insulation materials obtained in examples 3-4 and comparative examples 1-2 were tested for mechanical properties, thermal conductivity and oxygen index, and the results are shown in table 1.
TABLE 1
Compared with the phenolic foam of comparative examples 1-4, the phenolic foam thermal insulation material modified by the lignin/halloysite nano hybrid material in the examples 3 and 4 has the advantages of improved compressive strength and bending strength and reduced slag falling rate, which shows that the mechanical property of the phenolic foam is obviously improved, and the surface wear resistance is enhanced, which shows that the lignin/halloysite nano hybrid material has the functions of enhancing and toughening the phenolic foam matrix. Meanwhile, the thermal conductivity coefficient of the phenolic foam modified by the lignin/halloysite nano hybrid material is reduced, and the oxygen index is increased, which shows that the barrier property and the flame retardant property of the phenolic foam are improved, and the improvement is related to the formation of a more uniform and compact foam structure by the phenolic foam, as reflected by a foam scanning electron microscope photo and the average size of foam holes in fig. 3. The experiment results show that the lignin/halloysite nano hybrid material can efficiently improve the comprehensive performance of the phenolic foam thermal insulation material, and has good market application prospect.
The invention provides a lignin/halloysite nanometer hybrid material, a preparation method thereof, and an idea and a method for application in a phenolic foam thermal insulation material, and a method and a way for realizing the technical scheme are many. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The lignin/halloysite nano hybrid material is characterized in that the lignin/halloysite nano hybrid material is a nano tubular structure formed by coating the demethylated lignin on halloysite, the length of the pipe is 0.5-5 mu m, and the outer diameter of the pipe is 20-100 nm.
2. The method for preparing the lignin/halloysite hybrid nanomaterial as claimed in claim 1, wherein the method comprises the step of carrying out a first reaction on demethylated lignin, halloysite and a first organic solvent to obtain a solution containing the lignin/halloysite hybrid nanomaterial.
3. The method of claim 2, wherein the demethylated lignin is prepared by a second reaction of lignin, a second organic solvent, an aqueous hydrobromic acid solution, and cetyltrimethylammonium bromide to precipitate a precipitate, and the precipitate is demethylated lignin.
4. The preparation method according to claim 3, wherein the weight parts of the lignin, the second organic solvent, the aqueous hydrobromic acid solution and the hexadecyl trimethyl ammonium bromide are 10: (50-200): (20-50): (0.1-0.5).
5. The method according to claim 3, wherein the second reaction is carried out at 80-100 ℃ for 1-4 hours.
6. The method of claim 2, wherein the weight parts of the demethylated lignin, halloysite and the first organic solvent are 10: (50-200): (5-20).
7. The method according to claim 2, wherein the first reaction is carried out at 50-100 ℃ for 12-24 hours.
8. A phenolic resin prepared from the lignin/halloysite nano-hybrid material of claim 1.
9. The application of the lignin/halloysite nanometer hybrid material as claimed in claim 8, wherein the weight parts of the lignin/halloysite nanometer hybrid material and phenol are (0.1-2): 100 parts.
10. Use of the lignin/halloysite nanohybrid material according to claim 1 or the phenolic resin according to claim 8 for the preparation of phenolic foams.
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