CN107974037B - Application of graded lignin in preparation of phenolic foam thermal insulation material - Google Patents
Application of graded lignin in preparation of phenolic foam thermal insulation material Download PDFInfo
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- CN107974037B CN107974037B CN201711059565.7A CN201711059565A CN107974037B CN 107974037 B CN107974037 B CN 107974037B CN 201711059565 A CN201711059565 A CN 201711059565A CN 107974037 B CN107974037 B CN 107974037B
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- lignin
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- phenolic foam
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- 229920005610 lignin Polymers 0.000 title claims abstract description 129
- 239000006260 foam Substances 0.000 title claims abstract description 60
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000012774 insulation material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 33
- 239000005011 phenolic resin Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011810 insulating material Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 19
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 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 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- -1 polysiloxanes Polymers 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012466 permeate Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 7
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 7
- 238000005187 foaming Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- 239000012745 toughening agent Substances 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 230000017858 demethylation Effects 0.000 claims description 2
- 238000010520 demethylation reaction Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- RWYKESRENLAKMN-UHFFFAOYSA-N 1-[4-[1-[4-[2-[4-[5-(1,2-dihydroxypropyl)-3-(hydroxymethyl)-7-methoxy-2,3-dihydro-1-benzofuran-2-yl]-2-methoxyphenoxy]-3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)propoxy]-3-hydroxy-5-methoxyphenyl]-3-hydroxy-2-[4-[4-(4-hydroxy-3,5-dimethoxyphenyl)-1,3,3a,4,6, Chemical compound O1C=2C(OC)=CC(C(O)C(C)O)=CC=2C(CO)C1C(C=C1OC)=CC=C1OC(CO)C(C=1C=C(OC)C(O)=CC=1)OC(C(=C1)OC)=C(O)C=C1C(C(CO)OC=1C(=CC(=CC=1)C1C2COCC2C(O1)C=1C=C(OC)C(O)=C(OC)C=1)OC)OC(C(=C1)OC)=CC=C1C(O)C(CO)OC1=CC=C(C=CCO)C=C1OC RWYKESRENLAKMN-UHFFFAOYSA-N 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000004224 protection Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
Classifications
-
- 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
- C08J9/04—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- 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
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses application of lignin in preparation of a phenolic foam thermal insulation material. Compared with the prior art, the invention directly blends the graded lignin and the expandable phenolic resin to prepare the phenolic foam thermal insulation material by controlling the molecular weight of the lignin, avoids the complicated modification step in the process of preparing the phenolic resin from the lignin, saves the acid and alkali dosage, reduces the energy consumption in the modification process, can greatly improve the lignin content in the final phenolic foam thermal insulation material product, and has economical efficiency and more environmental protection. The phenolic foam heat-insulating material filled with the graded lignin has better mechanical property, thermal stability and ultraviolet aging resistance, the fineness of the foam heat-insulating material is better, the product quality reaches the national standard, and the market demand can be met.
Description
Technical Field
the invention belongs to the field of heat insulation materials, and particularly relates to application of lignin in preparation of a phenolic foam heat insulation material.
Background
the phenolic foam plastic is a novel flame-retardant, fireproof and low-smoke heat-insulating material, and is closed-cell rigid foam plastic prepared by adding a flame retardant, a smoke inhibitor, a foaming agent, a curing agent and other auxiliary agents into phenolic resin. Its outstanding features are flame-retarding, low smoke and high-temp. It can be cast and foamed in situ, and can be moulded, also can be machined, and can be made into plate material, pipe shell and various special-shaped products. The foam plastic type heat-insulating material overcomes the defects of inflammability, smoke and deformation when heated of the original foam plastic type heat-insulating material, and keeps the characteristics of light weight, convenient construction and the like of the original foam plastic type heat-insulating material.
The lignin is a natural high molecular substance which is second to cellulose in the world, 6 x 10 5 million tons of lignin are produced every year in the world, only a small part of lignin is utilized, most of lignin is directly combusted to obtain energy, and resources are greatly wasted.
CN102504477A, CN103756250A, and CN106700001A report methods of acidic or alkaline phenolization modification of lignin from different sources, and lignin phenolic resin prepared by phenolization modified lignin and used for foaming. However, the high acid (or alkali) dosage additionally added in the high-temperature phenolization, the additional energy consumption required for maintaining the high temperature, the existence of insoluble substances in the lignin phenolization liquefaction and the high viscosity of the lignin phenolic resin limit the industrial application of the lignin modified phenolic foam.
CN104403263A reports a method for mixing and foaming lignin and phenolic resin, in which a 40% solid content lignin aqueous solution is mixed and foamed with phenolic resin. However, lignin is not classified, and the physical and chemical properties of lignin with different molecular weights are greatly different, so that the mixing effect with phenolic resin is poor, and the product quality is poor.
Disclosure of Invention
The invention aims to solve the technical problem of providing an application method of lignin in preparation of a phenolic foam heat-insulating material, so as to solve the problems of poor effect and the like in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The invention protects the application of the graded lignin in preparing the phenolic foam heat-insulating material; wherein, the fractionated lignin is one of the following three lignin with molecular weight distribution ranges:
(1) Lignin with a molecular weight distribution range greater than 3000 Da;
(2) Lignin with molecular weight distribution range greater than 1000Da and less than or equal to 3000 Da;
(3) Lignin with a molecular weight distribution range of 1000Da or less.
Wherein, the fractionated lignin is prepared by the following method:
(1) Adding lignin into an alkaline aqueous solution, stirring and dissolving, and performing solid-liquid separation to obtain a lignin solution;
(2) Carrying out ultrafiltration on the lignin solution obtained in the step (1) to obtain a trapped fluid A1 and a permeate A2; nanofiltration is carried out on the permeate A2 to obtain trapped fluid B1 and permeate C1;
(3) Respectively adding acid solution into the trapped liquid A1, the trapped liquid B1 and the permeate liquid C1 obtained in the step (2), adjusting the pH value, carrying out solid-liquid separation, drying the solid part, and respectively obtaining lignin with a molecular weight distribution range of more than 3000Da, wherein the molecular weight distribution range of the lignin is more than 1000Da, and the molecular weight distribution range of the lignin is less than or equal to 3000Da and the molecular weight distribution range of the lignin is less than or equal to 1000 Da.
In the step (1), the lignin is one or a combination of more of enzymatic hydrolysis lignin, papermaking lignin, alkali lignin, organic solvent lignin, lignosulfonate and lignin modified by acylation, esterification, etherification, phenolization, alkylation and demethylation of the lignin.
In the step (1), the alkaline aqueous solution is any one or a combination of more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a rubidium hydroxide aqueous solution and a cesium hydroxide aqueous solution, and the pH value of the alkaline aqueous solution is 8-13.
In the step (1), the solid content of the lignin solution is 0.5-10 wt%.
In the step (2), the cutoff molecular weight of the ultrafiltration membrane is 3000 Da; during ultrafiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
in the step (2), the molecular weight cut-off of the nanofiltration membrane is 1000 Da; during nanofiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
In the step (3), the acid solution is any one or a combination of more of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution and an oxalic acid aqueous solution, and the acid solution is an acidic aqueous solution with pH less than 3.
in the step (3), the pH adjustment refers to adding an acid solution until the pH is 1.5-3.
Wherein, the phenolic foam thermal insulation material also comprises the following components:
phenolic resin, a foaming agent, a curing agent and a surfactant.
The weight parts of the components are as follows:
wherein, the phenolic foam thermal insulation material also comprises a flame retardant and/or a toughening agent.
the composite material also comprises the following components in parts by mass: 5-25 parts of a flame retardant and/or 5-15 parts of a toughening agent.
Wherein, the phenolic resin is an expandable phenolic resin.
wherein, the foaming agent is any one or combination of more of n-butane, n-pentane, isobutane, isopentane, cyclopentane, petroleum ether and dichloromonofluoroethane, and n-pentane is preferred.
The foaming agent is any one or combination of a plurality of benzene sulfonic acid, p-toluenesulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid, and a compound system of p-toluenesulfonic acid and phosphoric acid is preferred.
The surfactant is any one or combination of more of polysiloxane, polyoxyethylene ether, polyoxypropylene, polyoxyethylene polyoxypropylene, polyethylene sorbitan fatty acid ester and tween series, and a compound system of polysiloxane and tween series is preferred.
wherein, the flame retardant is any one or combination of more of antimony trioxide, magnesium hydroxide, aluminum hydroxide, halogenated phosphate and zinc borate, and preferably, the aluminum hydroxide.
The toughening agent is any one or a combination of more of ethylene glycol, polyethylene glycol, polyvinyl alcohol, polyester polyol, nitrile rubber, polyurethane prepolymer and epoxy resin, and a compound system of the polyethylene glycol and the polyurethane prepolymer is preferred.
The phenolic foam thermal insulation material is prepared by the following method:
The components are evenly mixed and then are foamed and heated.
The step of uniformly mixing is to uniformly mix the graded lignin and the phenolic resin into the lignin blending type phenolic resin at the rotating speed of 1000-10000 rpm, and then uniformly mix the lignin blending type phenolic resin with other components at the rotating speed of 100-1200 rpm.
Wherein the foaming temperature is 50-90 ℃ and the time is 0.5-4 h.
Has the advantages that:
The invention aims to solve the problems of high lignin modified acid-base dosage, high extra energy consumption and low lignin substitution amount in lignin phenolic foam, and provides a preparation method for preparing phenolic foam thermal insulation material by directly blending graded lignin and expandable phenolic resin through controlling the molecular weight of lignin. According to the invention, the molecular weight of lignin is controlled, and the graded lignin and the expandable phenolic resin are directly blended to prepare the phenolic foam thermal insulation material, so that the complicated modification step in the process of preparing the phenolic resin from the lignin is avoided, the acid and alkali consumption is saved, the energy consumption in the modification process is reduced, the lignin content in the final phenolic foam thermal insulation material product can be greatly increased, and the phenolic foam thermal insulation material has economical efficiency and more environmental protection property. The phenolic foam heat-insulating material filled with the graded lignin has better mechanical property, thermal stability and ultraviolet aging resistance, the fineness of the foam heat-insulating material is better, the product quality reaches the national standard, and the market demand can be met.
compared with the prior art, the invention has the following advantages:
1. compared with the traditional phenolic foam, the addition of the lignin can greatly reduce the cost of the phenolic foam, and meanwhile, the addition of the lignin improves the ultraviolet resistance and toughness of the foam and reduces the slag falling rate.
2. Compared with lignin modified phenolic foam, the method can completely save the additional acid and alkali dosage and high energy consumption in the lignin modification process. Meanwhile, the graded lignin has a net cross-linked structure and uniform molecular weight, so that the structure of the phenolic resin can be directly replaced in the phenolic resin, and the replacement amount is remarkably increased as modified lignin can only replace a phenol component. Meanwhile, the problem that the viscosity is greatly increased and foaming cannot be realized due to the addition of a large amount of lignin in the resin manufacturing process is avoided.
3. Compared with the mixing and foaming of lignin aqueous solution and phenolic resin, the invention adopts the process of directly blending the graded lignin with the phenolic resin at ultrahigh speed, and the graded lignin is more uniformly dispersed in the phenolic resin through the effect of ultrahigh-speed dispersion, homogenization and emulsification, thereby greatly increasing the substitution amount of the lignin and opening up a new way for the large-scale industrial application of the lignin.
Detailed Description
Example 1:
Weighing 100 parts by mass of hairstyle phenolic resin, 10 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 10 parts by mass of n-pentane, 14 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 3: 1), 20 parts by mass of aluminum hydroxide and 6 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Example 2:
Weighing 100 parts by mass of hairstyle phenolic resin, 20 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Example 3:
Weighing 100 parts by mass of hairstyle phenolic resin, 30 parts by mass of lignin with the molecular weight of 1000-3000, and stirring for 10min at the rotating speed of 8000rpm of an ultrahigh speed dispersion machine until the mixture is uniformly stirred. Adding tween-808 parts by mass, 10 parts by mass of n-pentane, 13 parts by mass of a curing agent (p-toluenesulfonic acid: phosphoric acid: water: 7: 3: 3), 20 parts by mass of aluminum hydroxide and 10 parts by mass of a flexibilizer (polyethylene glycol: glycerol: 1), mixing and stirring uniformly at 500rpm, introducing into a mold, curing at 80 ℃ for 2 hours, and obtaining the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Comparative example 1:
weighing 100 parts by mass of hairstyle phenolic resin, 20 parts by mass of lignin with the molecular weight less than 1000, and stirring for 10min at the rotating speed of 8000rpm of an ultra-high speed dispersion machine until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
Comparative example 2:
Weighing 100 parts by mass of hairstyle phenolic resin with the molecular weight of more than 3000 parts by mass of lignin, and stirring at the rotating speed of 8000rpm of an ultra-high speed dispersion machine for 10min until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the graded lignin filled phenolic foam thermal insulation material.
The properties of the prepared graded lignin filled phenolic foam thermal insulation material are shown in table 1.
comparative example 3:
Weighing 100 parts by mass of phenolic resin with hairstyle and 20 parts by mass of unfractionated lignin, and stirring at the rotating speed of 8000rpm of an ultra-high speed dispersion machine for 10min until the mixture is uniformly stirred. Adding tween-806 parts by mass, 8 parts by mass of n-pentane, 18 parts by mass of a curing agent (benzenesulfonic acid: phosphoric acid: water: 4: 2: 3), 20 parts by mass of aluminum hydroxide and 5 parts by mass of polyethylene glycol, uniformly mixing and stirring at 500rpm, introducing into a mold, and curing at 80 ℃ for 2 hours to obtain the unfractionated lignin filled phenolic foam thermal insulation material.
The properties of the prepared unfractionated lignin-filled phenolic foam insulation material are shown in table 1.
TABLE 1
By observing the examples 1 to 3 and the comparative example 3, the enhanced phenolic foam thermal insulation material prepared by adding the graded lignin (with the molecular weight of 1000-3000) is found to have obviously improved compression performance and tensile performance and improved oxygen index compared with the phenolic foam thermal insulation material prepared by adding the unfractionated lignin, because the graded lignin has uniform molecular weight and close physical and chemical properties, and the lignin has a rigid benzene ring structure and can enhance the performance of the foam when dispersed into the foam. Meanwhile, the heat conductivity coefficient and the smoke density of the enhanced foam heat-insulating material prepared by adding the graded lignin are not greatly floated compared with those of the phenolic resin foam heat-insulating material prepared by adding the unfractionated lignin, and the material properties are similar.
Through examples 1 to 3 and comparative examples 1 to 2, it was found that the molecular weight of the added fractionated lignin has a great influence on the properties of the phenolic foam insulation. Along with the reduction of the molecular weight of the added lignin, when the molecular weight is less than 1000, the compressive strength and the tensile strength of the phenolic foam thermal insulation material are greatly reduced, meanwhile, the heat conductivity coefficient is obviously improved, and the heat conductivity is poor. The reason is that the polymerization degree of lignin is reduced along with the reduction of the molecular weight of the lignin, and the lignin with low polymerization degree does not contribute to the performance of the phenolic foam thermal insulation material product. With the increase of the molecular weight of the added lignin, when the molecular weight is more than 3000, the oxygen index of the phenolic foam thermal insulation material is greatly reduced, and the flame retardant property is poor. This is because the hydroxymethyl content of lignin decreases with the increase in the molecular weight of lignin, the activity of lignin molecules decreases, and the increase in molecular weight causes large steric hindrance and uneven dispersion.
The enhanced phenolic foam thermal insulation material prepared by adding the graded lignin can obviously improve the compression performance, the tensile performance and the oxygen index of the foam thermal insulation material, the performances of other materials can not be reduced, and when the molecular weight of the added graded lignin is 1000-3000, the performance of the phenolic foam thermal insulation material is excellent. Meanwhile, due to the direct blending addition of the graded lignin, the cost of the phenolic foam thermal insulation material is greatly reduced, and a new way is opened up for the large-scale industrial application of the lignin.
Claims (17)
1. The application of the graded lignin in preparing phenolic foam heat-insulating materials; wherein the fractionated lignin is
lignin with molecular weight distribution range greater than 1000Da and less than or equal to 3000 Da;
Wherein, the phenolic foam thermal insulation material also comprises the following components: phenolic resin, foaming agent, curing agent and surfactant;
The phenolic foam thermal insulation material is prepared by the following method: uniformly mixing all the components, and then carrying out foaming heating;
The step of uniformly mixing is to uniformly mix the graded lignin and the phenolic resin into the lignin blending type phenolic resin at the rotating speed of 1000-10000 rpm, and then uniformly mix the lignin blending type phenolic resin with other components at the rotating speed of 100-1200 rpm;
Wherein the foaming temperature is 50-90 ℃ and the time is 0.5-4 h.
2. The use according to claim 1, wherein the fractionated lignin is prepared by the following method:
(1) Adding lignin into an alkaline aqueous solution, stirring and dissolving, and performing solid-liquid separation to obtain a lignin solution;
(2) carrying out ultrafiltration on the lignin solution obtained in the step (1) to obtain a trapped fluid A1 and a permeate A2; nanofiltration is carried out on the permeate A2 to obtain trapped fluid B1 and permeate C1;
(3) respectively adding acid solution into the trapped liquid A1, the trapped liquid B1 and the permeate liquid C1 obtained in the step (2), adjusting the pH value, carrying out solid-liquid separation, drying the solid part, and respectively obtaining lignin with a molecular weight distribution range of more than 3000Da, wherein the molecular weight distribution range of the lignin is more than 1000Da, and the molecular weight distribution range of the lignin is less than or equal to 3000Da and the molecular weight distribution range of the lignin is less than or equal to 1000 Da.
3. The use according to claim 2, wherein in the step (1), the lignin is one or more of enzymatic lignin, papermaking lignin, alkali lignin, organosolv lignin, lignosulfonate, and lignin modified by acylation, esterification, etherification, phenolization, alkylation and demethylation of the lignin.
4. The use of claim 2, wherein in step (1), the alkaline aqueous solution is any one or a combination of several of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous rubidium hydroxide solution and aqueous cesium hydroxide solution; wherein the pH value of the alkaline aqueous solution is 8-13.
5. The use according to claim 2, wherein in step (1), the lignin solution has a solid content of 0.5-10 wt%.
6. The use according to claim 2, wherein in step (2), said ultrafiltration membrane has a molecular weight cut-off of 3000 Da; during ultrafiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
7. The use according to claim 2, wherein in step (2), the nanofiltration membrane has a molecular weight cut-off of 1000 Da; during nanofiltration, the pressure is 0.1-0.6 MPa, the temperature is 20-60 ℃, and the stirring speed is 200-600 rpm.
8. The use according to claim 2, wherein in the step (3), the acid solution is any one or a combination of a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution and an oxalic acid aqueous solution; wherein the acid solution is an acidic aqueous solution with the pH value less than 3.
9. the use according to claim 2, wherein in the step (3), the pH adjustment is performed by adding an acid solution to a pH of 1.5 to 3.
10. The application of the compound as claimed in claim 1, wherein the mass parts of the components are as follows:
11. the use of claim 1, wherein the phenolic foam insulation further comprises a flame retardant and/or a toughening agent.
12. The application of the composition as claimed in claim 10, further comprising the following components in parts by mass: 5-25 parts of a flame retardant and/or 5-15 parts of a toughening agent.
13. the use according to claim 1, wherein the blowing agent is any one or a combination of n-butane, n-pentane, isobutane, isopentane, cyclopentane, petroleum ether and dichloromonofluoroethane.
14. The use of claim 1, wherein the curing agent is any one or a combination of benzene sulfonic acid, p-toluene sulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid.
15. The use according to claim 1, wherein the surfactant is any one or a combination of polysiloxanes, polyoxyethylene ethers, polyoxypropylenes, polyoxyethylene polyoxypropylenes, polyethylene sorbitan fatty acid esters, and tweens.
16. The use of claim 11, wherein the flame retardant is any one or a combination of antimony trioxide, magnesium hydroxide, aluminum hydroxide, halogenated phosphate and zinc borate.
17. The use of claim 11, wherein the toughening agent is one or more of ethylene glycol, polyethylene glycol, polyvinyl alcohol, polyester polyol, nitrile rubber, polyurethane prepolymer and epoxy resin.
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