CN107778767A - A kind of preparation method of lignin phenol formaldehyde resin foamed material - Google Patents
A kind of preparation method of lignin phenol formaldehyde resin foamed material Download PDFInfo
- Publication number
- CN107778767A CN107778767A CN201711212756.2A CN201711212756A CN107778767A CN 107778767 A CN107778767 A CN 107778767A CN 201711212756 A CN201711212756 A CN 201711212756A CN 107778767 A CN107778767 A CN 107778767A
- Authority
- CN
- China
- Prior art keywords
- parts
- ratio
- lignin
- prepared
- formaldehyde resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 62
- 229920005610 lignin Polymers 0.000 title claims abstract description 59
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000004913 activation Effects 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 31
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 235000014676 Phragmites communis Nutrition 0.000 claims description 29
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 25
- 239000008187 granular material Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000001450 anions Chemical class 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000013530 defoamer Substances 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 17
- 239000010453 quartz Substances 0.000 claims description 17
- 239000002893 slag Substances 0.000 claims description 17
- 235000001674 Agaricus brunnescens Nutrition 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000001294 propane Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 11
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical compound OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 241000233805 Phoenix Species 0.000 claims description 7
- 240000008042 Zea mays Species 0.000 claims description 7
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 235000005822 corn Nutrition 0.000 claims description 7
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 238000011081 inoculation Methods 0.000 claims description 7
- 239000002054 inoculum Substances 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 claims description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 20
- 239000006260 foam Substances 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000004088 foaming agent Substances 0.000 abstract description 5
- 239000005011 phenolic resin Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 235000013312 flour Nutrition 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000000855 fermentation Methods 0.000 abstract description 2
- 230000004151 fermentation Effects 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000000813 microbial effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical class ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 description 6
- 235000019256 formaldehyde Nutrition 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 oxo phenylpropanol Chemical compound 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000004880 Polyuria Diseases 0.000 description 1
- IVJRHZRBNOWCHU-UHFFFAOYSA-N [P].COS(O)(=O)=O Chemical compound [P].COS(O)(=O)=O IVJRHZRBNOWCHU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000035619 diuresis Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 206010014599 encephalitis Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000006225 natural substrate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2361/14—Modified phenol-aldehyde condensates
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Wood Science & Technology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Microbiology (AREA)
- Virology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The present invention provides a kind of preparation method of phenol foam, by preparing activation lignin and phenol reactant part fortified phenol with microbial fermentation, using hyper-branched polyester as medium, the phenolic resin for reacting to obtain using porous material silica flour load negative ion powder and lignin fortified phenol and formaldehyde, with foaming agent, surfactant and acidic catalyst foam in mould and are prepared.Phenol foam abrasion resistance prepared by the present invention is high, with good compression strength and pliability, fire retardant performance is strong, the burst size of harmful substance formaldehyde is few simultaneously, with air contact energy releasing negative oxygen ion, with good air-filtering ability, belong to environment-friendly type macromolecule material, possess outstanding development potentiality.
Description
Technical field
The invention belongs to chemical field of polymer material preparing technology, more particularly to a kind of lignin phenol formaldehyde resin foam material
The preparation method of material.
Background technology
The densely-populated of China, groups of building are intensive, in the majority for main groups of building with multilayer and high level.2010, China
House overall floorage reaches 51,900,000,000 m2, but often it is close on 2000000000 m2Completed floor space among, only 3% or so is energy saving building,
It is to still fall within highly energy-consuming building to have 97%.According to statistics, for 10,000,000 m2New building, if realize energy-conservation 50% target,
Then every year can emission reduction CO2About 10,000 tons, according to every m2Construction area can save 30kg standard coals every year, and annual new building can
Save 300,000 tons of standard coals.It can be seen that China's building energy conservation potentiality are very big, it is light to play act foot for alleviation China's energy situation
The effect of weight, therefore building heat preservation has surprising Social benefit and economic benefit.Biomass-based material is inexpensive, it is environmentally friendly, can be again
It is raw, in nowadays oil spike, tend to energy day under the weary environment of plaque, there is the unrivaled advantage of petroleum-based products.It is raw
Material foamed material has the huge advantage of low cost, recyclable regenerative and part biodegradable, exploitation biomass bubble
Foam material has turned into the focus of various countries' research.
Reed is the widely distributed polytypic species in the whole world, in addition to forest site does not grow, the various open fields for having water source, often
The fertility extended rapidly with it, form reed community in flakes.Reed not only can the raw material of industry such as papermaking, building materials, root
It can be used as medicine, there is diuresis, removing toxic substances, refrigerant, town to vomit, the function such as anti-encephalitis, in addition to huge economic value, reed is also important
The ecological value：The reed of large area not only can adjust weather, water conservation, the good Wetland Environment formed,
There is provided and inhabit for birds, look for food, the home of breeding.Lignin is a kind of unbodied, molecule being widely present in plant
Armaticity high polymer containing oxo phenylpropanol or derivatives thereof construction unit in structure, the xylem of plant contain a large amount of wooden
Element, xylem is maintained high hardness and open up the weight of whole plant to hold.Lignin as the second largest natural substrates in ecological boundary,
Exploitation has been studied is used for every field.
Patent of invention CN201310236803.2, Urea resin foam thermal-insulation composite material and preparation method thereof, by ureaformaldehyde
Made of resin, foaming agent, surfactant, curing agent, toughener and filler.Method：First, raw material is weighed；2nd, ureaformaldehyde tree
Stirred after fat, foaming agent, surfactant mixing, add toughener stirring, add filler stirring, added curing agent stirring, obtain
To foaming body；3rd, foaming body is poured into prior preheated mold, is placed in free foaming in baking oven, foaming obtains product after terminating.
The apparent density of product of the present invention is 0.093 ~ 0.105g/cm3, and compressive strength is 170 ~ 220kPa, impact strength is 400 ~
530kPa, thermal conductivity factor are 0.028 ~ 0.036w/ (mk), and oxygen index (OI) is more than 33.3%；For building exterior wall heat preserving.The invention
Existing urea formaldehyde resin foam is solved because property is crisp, easily scaling-off, intensity is relatively low, and building thermal insulation material can not be used as containing trace formaldehyde
The technical problem used.
Patent of invention CN201210000185.7, a kind of phenol foam and preparation method thereof, by component A and B
Component forms, and wherein component A is in parts by weight by viscosity chitosan, 10-30 in 100 parts of resols, 10-20 parts
Part lignin polyether polyalcohol, 0-20 parts aluminium hydroxide, 5-10 parts surfactant, the fluorine dichloroethanes of 10-20 parts foaming agent one
（HCFC-141b）, 10-30 part diluents methyl formate composition, B component is composite toughening acidic catalyst 20-50 parts.It is prepared
The component of A, B two is well mixed by method respectively, then is poured into after being mutually mixed in mould, and being foamed at a temperature of 80 DEG C obtains phenolic aldehyde
Resin foam.A kind of phenol foam of the invention has higher while its fire retardant performance is not reduced
Compression strength and pliability, suitable for fire-protection rating require higher buildings exterior-wall heat insulation construct.
Patent of invention CN200810243419.4, the preparation method of biomass modified phenolic foam plastic,：In 100 mass
In the phenol of part, the base catalyst aqueous solution of 5 ~ 10 mass parts and the lignin of 30~60 mass parts are added, base catalyst is water-soluble
The mass percent concentration of liquid is 2 ~ 10%, 1-2h is reacted under 90~150 DEG C of reflux temperatures, then the matter of mixed liquor 72 ~ 39 is added dropwise
Part is measured, mixed liquor is made up of formaldehyde and furfural, and its mass ratio is 60 ~ 35: 40-65, reacts 2- under 90 ~ 150 DEG C of reflux temperatures
3h, reaction terminate to be neutralized with acid, the resol that solid content is 78 ~ 83% are obtained, by 100 mass parts resols
And 5 ~ 15 mass parts foaming stirred with catalyst, 1 ~ 5 mass of surface activating agent and 6 ~ 15 mass parts foaming agents, 5 ~
Foamed at 160 DEG C, obtain a kind of low stain building thermal insulation material, its performance indications reaches petroleum chemicals level.
At present, because the environment amenable demand more and more higher of people, due to the raw material used in phenolic foam
The reason for kind and technology of preparing, make not react complete free phenol and free aldehyde causes seriously to the water in environment and air
The material of pollution, addition reduction free phenol and free aldehyde causes the decline of foam performance again.
The content of the invention
The deficiency existing for the phenol foam for preparing in the prior art, the present invention provide a kind of lignin phenol
The preparation method of urea formaldehyde foamed material.
The present invention is achieved by the following technical solutions：
A kind of preparation method of lignin phenol formaldehyde resin foamed material, is prepared by following steps：
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60 ~ 70%, add reed slag
The Tween-80 of amount 0.05 ~ 0.15%, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 ~ 3 days,
Cultivation matrix is obtained, then in being inoculated with phoenix tail mushroom on cultivation matrix, is persistently cultivated 12 ~ 16 days, cultivation temperature is maintained at 37 ~ 45
℃；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3 ~ 3.5, under normal temperature
45 ~ 60min is reacted, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 ~ 50 parts of water, 0.5 ~ 0.7 part of dispersant, 5040,0.2 ~ 0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, first
It is scattered to stir and evenly mix, add powder quartz ore and ball milling is carried out into porcelain mill, control the solid-to-liquid ratio to be（2~5）:1, choose ball
Expect that ratio is（3~5）:1 Ceramic Balls, sequentially add 0.3% dispersant and 0.1% defoamer, and rotating speed is 70 revs/min, ball milling
Time is 3.0 ~ 4.0h, prepares konilite slurry, then adds hydroxyethyl cellulose, prevents the sedimentation of konilite slurry, obtains
The konilite slurry arrived；
（2）40 ~ 50 parts of water, 5 ~ 10 parts of hydroxy ethyl fiber solution mixing are taken by ratio of weight and the number of copies, by negative ion powder according to solid-to-liquid ratio
For 1:1 ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material is（3~5）:1 Ceramic Balls, sequentially add 0.3% it is scattered
The defoamer A10 of agent 5040 and 0.1%, 1 ~ 2h of ball milling, obtain anion agent slurry；
（3）It is according to mass ratio by konilite slurry and anion slurry（12~25）:1 mixing, is added to sand mill, ratio of grinding media to material
For（3~5）：1 zirconium ball 30 ~ 60min of wet grinding, is fitted into centrifuge tube, is washed with deionized 3 ~ 4 times, is air-dried under normal temperature,
Obtain quartz-anion composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 ~ 30 parts of propane, constant temperature melts in 210 DEG C of oil baths
Melt, trimesic acid is added, with 0.1 ~ 0.5 part of stannous octoate；After 3.0 ~ 5.0h of heating stirring, vacuumize and keep strong stirring
1.0 ~ 2.0h is reacted, reaction is poured into methanol and precipitated, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol while hot after terminating,
40 ~ 60h is dried at 100 DEG C, obtains hyper-branched polyester solid；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, 10 ~ 15 parts of lignin of activation is taken, quartz -12 ~ 20 parts of anion composite granule, hyper-branched polyester is solid
1 ~ 3 part of body, 8 ~ 12 parts of phenol, 1 ~ 3 part of sodium hydroxide, 10 ~ 12 parts of formaldehyde, 10 ~ 25 parts of water, 5 ~ 10 parts of Tween-80, a fluorine two
10 ~ 15 parts of chloroethanes HCFC-141b, 5 ~ 30 parts of phosphatase 11,10 ~ 15 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed and adds
In reactor accelerate stirring 10 ~ 20s after, pour into and be preheated in 80 ~ 90 DEG C of corresponding mould, at 80 ~ 90 DEG C isothermal reaction 1 ~
2h, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
Pseudomonas aeruginosa and phoenix-tail mushroom solid state fermentation reed slag, it can effectively decompose cellulose in reed slag and wooden
Element；Rhamnolipid caused by pseudomonas aeruginosa fermentation can promote decomposition of the phoenix-tail mushroom secretion laccase to reed slag lignin, living
Change and improve methylol, phenolic hydroxyl group, alcoholic extract hydroxyl group content on lignin molecule, so as to improve lignin and the phenolic resin degree of polymerization.
Quartzy main component is silica, has porous performance, can load more negative oxygen ions, adsorbs free formaldehyde
And phenol, while negative ion powder contacts with moisture in air or oxygen, releasing negative oxygen ion after ionizing, and improves air matter
Amount；The many combination hyper-branched polyesters of quartzy loose structure energy, further improve the degree of polymerization of phenol foam.It is negative
Ion addition be 4 ~ 8% between when, purifying formaldehyde rate between 91 ~ 94%, more than 8% after-purification rate change it is small, but bear from
The Percentage bound of sub- powder and silica flour reduces with the increase of negative ion powder addition, therefore is best with 4 ~ 8%.
Hyper-branched polyester has highly branched molecular structure, and radical species are more, and solubility high viscosity is low, can effectively carry
The polymerization speed of high phenolic resin, improve the intensity of resin glue；The characteristics of its radical species is more simultaneously, can more it combine free
Phenol and formaldehyde, reduce the release of phenol and formaldehyde so as to improve Environmental security；On the other hand, phenolic resin is due to lignin
With the addition of silica flour complex, gel-forming property is influenceed, this influence can be eliminated using hyper-branched polyester.
As a further improvement on the present invention, step 1（1）Described pseudomonas aeruginosa fills liquid prior to activation medium
Measure in the conical flask for 20%, inoculum concentration 5%, 37 DEG C, 12 ~ 16h of activation culture under 200rpm.
As a further improvement on the present invention, the activation medium is prepared by following density component material：Vegetable seed
Oily 30g/L, Dried Corn Steep Liquor Powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L,
CaCl20.05g/L, NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0.
In best medium, the rhamnolipid average product that pseudomonas aeruginosa ferments to obtain is 30.41 ~ 34.52g/L.
As a further improvement on the present invention, step 2（1）Described powder quartz ore fineness is 200 ~ 300 mesh.
The granule size of konilite determines its dispersive property and absorption property, and granularity is smaller to disperse better but adsorption capacity
It is low, therefore in order to preferably disperse to adsorb negative ion powder simultaneously, the silica flour using 200 ~ 300 mesh is best.
As a further improvement on the present invention, the double [4- of 2,2- described in step 3（2- hydroxy ethoxies）Phenyl] propane with
The mol ratio of benzenetricarboxylic acid is（2~4）:1.
The mol ratio of two kinds of monomers influences hyper-branched polyester molecular weight and the dissaving polymer of terminal groups, and 2,2- is double
[4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:Terminal groups dispersiveness big poly- can be obtained when 1
Ester, there are more binding sites（Group）, so as to promote the intensity of resin reaction polymerization speed and resin, anti-wear performance.
As a further improvement on the present invention, the quartz described in step 4-anion composite granule is consolidated with hyper-branched polyester
Body amount ratio is（8~15）：1.
The content of hyper-branched polyester influences resin integrally curing conversion ratio, and content high resin solidification conversion ratio is low, and content is low
Resin bonding strength and anti-wear performance are low, when hyperbranched poly ester content is 5 ~ 15%, the solidification conversion ratio of phenolic resin for 95 ~
98%, anti-wear performance and bond strength rate of change are small, overall resin property are influenceed little.
As a further improvement on the present invention, the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution sulfuric acid containing tetra methylol described in step 4
Phosphorus 60 ~ 70%.
Tetrakis hydroxymetyl phosphonium sulfuric is a kind of good fire proofing, while is overspend in the resin material that can be prepared with the present invention
Change polyester, improve the toughness of foamed material, because of the dissaving structure of hyper-branched polyester, and need not too high concentration four hydroxyls
Methylsulfuric acid phosphorus can reach fire-retardant and toughening effect, reduce cost of material.
Beneficial effects of the present invention：
1st, preparation technology of the present invention requires low, it is not necessary to high capital equipment and raw material, has good economic benefit；
2nd, the phenol foam that the present invention is prepared into is safe and reliable, and burst size of methanal is low, while can also discharge beneficial
Negative oxygen ion, environmental pollution is low, meets demand of the people to environment-friendly materials；
3rd, phenol foam abrasion resistance prepared by the present invention is high, has good compression strength and pliability, prevents fires
Fire resistance is strong, has excellent water-fast weather-resistant property.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60%, add reed slag quality
0.05% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 12 days, cultivation temperature is maintained at 37 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, it is 3 to add acetic acid to pH, is reacted under normal temperature
45min, solid residue is then filtered to remove, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 parts of water, 0.5 part of dispersant, 5040,0.2 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 200 mesh and ball milling is carried out into porcelain mill, it is 2 to control solid-to-liquid ratio:1, choose ball material
Than for 3:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）40 parts of water, the mixing of 5 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material 3:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 1h, obtain anion agent slurry；
（3）According to mass ratio it is 12 by konilite slurry and anion slurry：1 mixing, is added to sand mill, ratio of grinding media to material 3：1
Zirconium ball wet grinding 30min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.1
Part stannous octoate；After heating stirring 3.0h, vacuumize and keep strong stirring to react 1.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 40h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, take and activate 10 parts of lignin, quartz -12 parts of anion composite granule, 1 part of hyper-branched polyester solid,
8 parts of phenol, 1 part of sodium hydroxide, 10 parts of formaldehyde, 10 parts of water, 5 parts of Tween-80,10 parts of a fluorine dichloroethanes HCFC-141b, phosphorus
15 parts of acid, 10 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed after accelerating stirring 10s in addition reactor, pours into and be preheated to
In 80 DEG C of corresponding mould, the isothermal reaction 1h at 80 DEG C, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
Embodiment 2
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 70%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 45 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 16h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.5, anti-under normal temperature
60min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）50 parts of water, 0.7 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 300 mesh and ball milling is carried out into porcelain mill, it is 5 to control solid-to-liquid ratio:1, choose ball material
Than for 5:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
4.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）50 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2h, obtain anion agent slurry；
（3）According to mass ratio it is 25 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 5：1
Zirconium ball wet grinding 60min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 30 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.5
Part stannous octoate；After heating stirring 5.0h, vacuumize and keep strong stirring to react 2.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 60h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, take and activate 15 parts of lignin, quartz -20 parts of anion composite granule, 2 parts of hyper-branched polyester solid,
12 parts of phenol, 3 parts of sodium hydroxide, 12 parts of formaldehyde, 25 parts of water, 10 parts of Tween-80,15 parts of a fluorine dichloroethanes HCFC-141b,
30 parts of phosphoric acid, 15 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed after accelerating stirring 20s in addition reactor, pours into preheating
To 90 DEG C of corresponding moulds, the isothermal reaction 2h at 90 DEG C, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
Embodiment 3
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 65%, add reed slag quality
0.1% Tween-80, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, obtain cultivation base
Matter, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 14 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 14h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.3, anti-under normal temperature
50min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）45 parts of water, 0.6 part of dispersant, 5040,0.25 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 220 mesh and ball milling is carried out into porcelain mill, it is 3 to control solid-to-liquid ratio:1, choose ball material
Than for 4:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.5h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）45 parts of water, the mixing of 8 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material 4:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 1.5h, obtain anion agent slurry；
（3）According to mass ratio it is 20 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 4：1
Zirconium ball wet grinding 50min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 25 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.4
Part stannous octoate；After heating stirring 4.0h, vacuumize and keep strong stirring to react 1.5h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 50h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, take and activate 12 parts of lignin, quartz -15 parts of anion composite granule, 1 part of hyper-branched polyester solid,
10 parts of phenol, 2 parts of sodium hydroxide, 11 parts of formaldehyde, 17 parts of water, 8 parts of Tween-80,12 parts of a fluorine dichloroethanes HCFC-141b,
20 parts of phosphoric acid, 12 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed after accelerating stirring 15s in addition reactor, pours into preheating
To 85 DEG C of corresponding moulds, the isothermal reaction 1.5h at 85 DEG C, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
Embodiment 4
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 62%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.3, anti-under normal temperature
50min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）42 parts of water, 0.5 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 220 mesh and ball milling is carried out into porcelain mill, it is 2 to control solid-to-liquid ratio:1, choose ball material
Than for 5:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）40 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2.0h, obtain anion agent slurry；
（3）According to mass ratio it is 15 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 5：1
Zirconium ball wet grinding 60min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 25 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.4
Part stannous octoate；After heating stirring 5.0h, vacuumize and keep strong stirring to react 1.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 40h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, take and activate 15 parts of lignin, quartz -18 parts of anion composite granule, 1 part of hyper-branched polyester solid,
12 parts of phenol, 2 parts of sodium hydroxide, 10 parts of formaldehyde, 18 parts of water, 8 parts of Tween-80,12 parts of a fluorine dichloroethanes HCFC-141b,
20 parts of phosphoric acid, 10 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed after accelerating stirring 15s in addition reactor, pours into preheating
To 80 DEG C of corresponding moulds, the isothermal reaction 1h at 80 DEG C, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
Embodiment 5
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 65%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.5, anti-under normal temperature
60min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）45 parts of water, 0.7 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 300 mesh and ball milling is carried out into porcelain mill, it is 4 to control solid-to-liquid ratio:1, choose ball material
Than for 4:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
4.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）45 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2h, obtain anion agent slurry；
（3）According to mass ratio it is 15 by konilite slurry and anion slurry：1 mixing, is added to sand mill, ratio of grinding media to material 3：1
Zirconium ball wet grinding 50min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 30 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.5
Part stannous octoate；After heating stirring 4.0h, vacuumize and keep strong stirring to react 2.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 48h is dried at 100 DEG C, obtains hyper-branched polyester solid；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, take and activate 15 parts of lignin, quartz -15 parts of anion composite granule, 1 part of hyper-branched polyester solid,
12 parts of phenol, 2 parts of sodium hydroxide, 10 parts of formaldehyde, 16 parts of water, 10 parts of Tween-80,10 parts of a fluorine dichloroethanes HCFC-141b,
20 parts of phosphoric acid, 15 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed after accelerating stirring 20s in addition reactor, pours into preheating
To 90 DEG C of corresponding moulds, the isothermal reaction 2h at 90 DEG C, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
The gained lignin phenol formaldehyde resin foamed material of embodiment 1 ~ 5 is tested, the results are shown in Table 1.
The test result of the lignin phenol formaldehyde resin foamed material of the embodiment of the present invention of table 1
Above example is only the exemplary embodiment of the present invention, is not used in the limitation present invention, protection scope of the present invention is by weighing
Sharp claim limits.Those skilled in the art can the present invention essence and protection domain in, the present invention is made it is various modification or
Equivalent substitution, this modification or equivalent substitution also should be regarded as being within the scope of the present invention.
Claims (7)
1. a kind of preparation method of lignin phenol formaldehyde resin foamed material, it is characterised in that be prepared by following steps：
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60 ~ 70%, add reed slag
The Tween-80 of amount 0.05 ~ 0.15%, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 ~ 3 days,
Cultivation matrix is obtained, then in being inoculated with phoenix tail mushroom on cultivation matrix, is persistently cultivated 12 ~ 16 days, cultivation temperature is maintained at 37 ~ 45
℃；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3 ~ 3.5, under normal temperature
45 ~ 60min is reacted, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 ~ 50 parts of water, 0.5 ~ 0.7 part of dispersant, 5040,0.2 ~ 0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, first
It is scattered to stir and evenly mix, add powder quartz ore and ball milling is carried out into porcelain mill, control the solid-to-liquid ratio to be（2~5）:1, choose ball
Expect that ratio is（3~5）:1 Ceramic Balls, sequentially add 0.3% dispersant and 0.1% defoamer, and rotating speed is 70 revs/min, ball milling
Time is 3.0 ~ 4.0h, prepares konilite slurry, then adds hydroxyethyl cellulose, prevents the sedimentation of konilite slurry, obtains
The konilite slurry arrived；
（2）40 ~ 50 parts of water, 5 ~ 10 parts of hydroxy ethyl fiber solution mixing are taken by ratio of weight and the number of copies, by negative ion powder according to solid-to-liquid ratio
For 1:1 ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material is（3~5）:1 Ceramic Balls, sequentially add 0.3% it is scattered
The defoamer A10 of agent 5040 and 0.1%, 1 ~ 2h of ball milling, obtain anion agent slurry；
（3）It is according to mass ratio by konilite slurry and anion slurry（12~25）:1 mixing, is added to sand mill, ratio of grinding media to material
For（3~5）：1 zirconium ball 30 ~ 60min of wet grinding, is fitted into centrifuge tube, is washed with deionized 3 ~ 4 times, is air-dried under normal temperature,
Obtain quartz-anion composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 ~ 30 parts of propane, constant temperature melts in 210 DEG C of oil baths
Melt, trimesic acid is added, with 0.1 ~ 0.5 part of stannous octoate；After 3.0 ~ 5.0h of heating stirring, vacuumize and keep strong stirring
1.0 ~ 2.0h is reacted, reaction is poured into methanol and precipitated, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol while hot after terminating,
40 ~ 60h is dried at 100 DEG C, obtains hyper-branched polyester solid；
4th, lignin phenol formaldehyde resin foamed material is prepared
By ratio of weight and the number of copies, 10 ~ 15 parts of lignin of activation is taken, quartz -12 ~ 20 parts of anion composite granule, hyper-branched polyester is solid
1 ~ 3 part of body, 8 ~ 12 parts of phenol, 1 ~ 3 part of sodium hydroxide, 10 ~ 12 parts of formaldehyde, 10 ~ 25 parts of water, 5 ~ 10 parts of Tween-80, a fluorine two
10 ~ 15 parts of chloroethanes HCFC-141b, 5 ~ 30 parts of phosphatase 11,10 ~ 15 parts of the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, it is well mixed and adds
In reactor accelerate stirring 10 ~ 20s after, pour into and be preheated in 80 ~ 90 DEG C of corresponding mould, at 80 ~ 90 DEG C isothermal reaction 1 ~
2h, it is fully cured to obtain lignin phenol formaldehyde resin foamed material.
A kind of 2. preparation method of lignin phenol formaldehyde resin foamed material according to claim 1, it is characterised in that：Step
One（1）In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
12 ~ 16h of activation culture under 200rpm.
A kind of 3. preparation method of lignin phenol formaldehyde resin foamed material according to claim 1, it is characterised in that：Step
Two（1）Described powder quartz ore fineness is 200 ~ 300 mesh.
A kind of 4. preparation method of lignin phenol formaldehyde resin foamed material according to claim 1, it is characterised in that：Step
Double [the 4- of 2,2- described in three（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is（2~4）:1.
A kind of 5. preparation method of lignin phenol formaldehyde resin foamed material according to claim 1, it is characterised in that：Step
Quartz-anion composite granule described in four is with hyper-branched polyester solid amount ratio（8~15）：1.
A kind of 6. preparation method of lignin phenol formaldehyde resin foamed material according to claim 2, it is characterised in that：It is described
Activation medium is prepared by following density component material：Rapeseed oil 30g/L, Dried Corn Steep Liquor Powder 6g/L, NaNO36g/L,
K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L, NaCl 1.5g/L, adjust pH to 6.5
~ 7.0.
A kind of 7. preparation method of lignin phenol formaldehyde resin foamed material according to claim 1, it is characterised in that：Step
The tetrakis hydroxymetyl phosphonium sulfuric aqueous solution described in four contains tetrakis hydroxymetyl phosphonium sulfuric 60 ~ 70%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711212756.2A CN107778767B (en) | 2017-11-28 | 2017-11-28 | Preparation method of lignin phenolic resin foam material |
| PCT/CN2018/000047 WO2019104817A1 (en) | 2017-11-28 | 2018-01-25 | Preparation method for lignin phenolic resin foam material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711212756.2A CN107778767B (en) | 2017-11-28 | 2017-11-28 | Preparation method of lignin phenolic resin foam material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107778767A true CN107778767A (en) | 2018-03-09 |
| CN107778767B CN107778767B (en) | 2020-02-25 |
Family
ID=61430620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711212756.2A Active CN107778767B (en) | 2017-11-28 | 2017-11-28 | Preparation method of lignin phenolic resin foam material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107778767B (en) |
| WO (1) | WO2019104817A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109127076A (en) * | 2017-09-01 | 2019-01-04 | 江西理工大学 | A kind of super low energy consumption grinding process of nonferrous metals ore |
| CN111727851A (en) * | 2019-03-22 | 2020-10-02 | 东莞市乐为现代农业科技有限公司 | Naturally degradable plant seedling raising substrate and manufacturing method and application thereof |
| CN112048081A (en) * | 2020-08-19 | 2020-12-08 | 浙江工业大学 | High-strength fully-degradable lignin-based super absorbent resin and preparation method thereof |
| CN114656605A (en) * | 2022-03-23 | 2022-06-24 | 吉林大学 | Nano SiO2Preparation method of/LPF composite material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865803A (en) * | 1972-05-25 | 1975-02-11 | Westvaco Corp | Modified lignin surfactants |
| US20070105112A1 (en) * | 2003-08-11 | 2007-05-10 | Tim Hitchman | Laccases, nucleic acids encoding them and methods for making and using them |
| CN101138576A (en) * | 2007-08-15 | 2008-03-12 | 李红玉 | Codonopsis pilosula fermentation liquor and uses thereof |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 中国林业科学研究院林产化学工业研究所 | Lignin-modified phenolic foam and preparation method thereof |
| CN103361013A (en) * | 2013-08-08 | 2013-10-23 | 周广胜 | Composite phenolic glue composition and application method thereof |
| CN104817666A (en) * | 2015-05-07 | 2015-08-05 | 江苏乾翔新材料科技有限公司 | Process of making phenolic foam with insulin alkali lingin |
| CN105949955A (en) * | 2016-06-08 | 2016-09-21 | 合肥市燕美粉末涂料有限公司 | Powder coating for heating radiator surface and preparation method thereof |
| CN106589799A (en) * | 2016-12-16 | 2017-04-26 | 沙县宏盛塑料有限公司 | Lignin modified phenolic resin based composite material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817668A (en) * | 2015-05-07 | 2015-08-05 | 江苏乾翔新材料科技有限公司 | Process of making phenolic foam with corn straw alkali lingin |
| CN106632929B (en) * | 2016-09-21 | 2018-12-18 | 沈阳化工大学 | A kind of valoneaic acid dilactone copolymerization phenolic foam process for preparing resins |
| CN106966379B (en) * | 2017-03-15 | 2019-03-01 | 江南大学 | A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material |
| CN107311534A (en) * | 2017-06-29 | 2017-11-03 | 合肥达户电线电缆科技有限公司 | A kind of environment-friendly materials and preparation method thereof |
| CN107383769A (en) * | 2017-08-19 | 2017-11-24 | 天津市鑫盈保温材料有限公司 | A kind of phenol-formaldehyde resin modified foamed plastics and its preparation, application |
-
2017
- 2017-11-28 CN CN201711212756.2A patent/CN107778767B/en active Active
-
2018
- 2018-01-25 WO PCT/CN2018/000047 patent/WO2019104817A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865803A (en) * | 1972-05-25 | 1975-02-11 | Westvaco Corp | Modified lignin surfactants |
| US20070105112A1 (en) * | 2003-08-11 | 2007-05-10 | Tim Hitchman | Laccases, nucleic acids encoding them and methods for making and using them |
| CN101138576A (en) * | 2007-08-15 | 2008-03-12 | 李红玉 | Codonopsis pilosula fermentation liquor and uses thereof |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 中国林业科学研究院林产化学工业研究所 | Lignin-modified phenolic foam and preparation method thereof |
| CN103361013A (en) * | 2013-08-08 | 2013-10-23 | 周广胜 | Composite phenolic glue composition and application method thereof |
| CN104817666A (en) * | 2015-05-07 | 2015-08-05 | 江苏乾翔新材料科技有限公司 | Process of making phenolic foam with insulin alkali lingin |
| CN105949955A (en) * | 2016-06-08 | 2016-09-21 | 合肥市燕美粉末涂料有限公司 | Powder coating for heating radiator surface and preparation method thereof |
| CN106589799A (en) * | 2016-12-16 | 2017-04-26 | 沙县宏盛塑料有限公司 | Lignin modified phenolic resin based composite material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 倪文胜主编: "《保温防腐工程实用材料手册》", 31 October 2007, 山西科学技术出版社 * |
| 王松松 等: ""超支化聚酯改性酚醛树脂的制备与固化性能研究"", 《中国塑料》 * |
| 锦州市好为尔保温材料有限公司编著: "《酚醛泡沫建筑防火保温施工》", 31 January 2015, 中国建材工业出版社 * |
| 高小娥: ""漆酶活化碱木质素合成酚醛树脂的研究"", 《木材加工机械》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109127076A (en) * | 2017-09-01 | 2019-01-04 | 江西理工大学 | A kind of super low energy consumption grinding process of nonferrous metals ore |
| CN111727851A (en) * | 2019-03-22 | 2020-10-02 | 东莞市乐为现代农业科技有限公司 | Naturally degradable plant seedling raising substrate and manufacturing method and application thereof |
| CN112048081A (en) * | 2020-08-19 | 2020-12-08 | 浙江工业大学 | High-strength fully-degradable lignin-based super absorbent resin and preparation method thereof |
| CN114656605A (en) * | 2022-03-23 | 2022-06-24 | 吉林大学 | Nano SiO2Preparation method of/LPF composite material |
| CN114656605B (en) * | 2022-03-23 | 2024-04-12 | 吉林大学 | Nano SiO 2 Preparation method of LPF composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107778767B (en) | 2020-02-25 |
| WO2019104817A1 (en) | 2019-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107778767A (en) | A kind of preparation method of lignin phenol formaldehyde resin foamed material | |
| US3408316A (en) | Preformed thermal insulation material and binder for molding same | |
| CN107841270A (en) | The preparation method of lignin phenol formaldehyde resin adhesive | |
| CN109096818B (en) | Waterproof putty containing straw grass components for inner wall surface | |
| CN104357009B (en) | Lignin flame-retardant fiber board adhesive and production method thereof | |
| CN106752001A (en) | A kind of imvite modified waterproof flame-retardant type biomass board and preparation method thereof | |
| CN106675063A (en) | Lignocellulose-acrylic acid reinforced waterproof flame-retardant biomass board and preparation method thereof | |
| CN104312535B (en) | Lignin weatherability fiberboard adhesive and its production method | |
| CN113149529A (en) | Bamboo aggregate and modified straw fiber hybrid reinforced concrete sound-absorbing heat-insulating decorative multifunctional board | |
| CN103862540B (en) | Method for reinforcing and modifying bamboo willow wood | |
| CN107674465B (en) | A kind of preparation method of the environmentally friendly diatom ooze coating of enhancing | |
| CN108129867A (en) | A kind of preparation method of environmental-friendly construction material | |
| CN104293287A (en) | Lignin damp-proof fiberboard adhesive and producing method thereof | |
| CN107880818A (en) | A kind of mineral wool abatvoix formaldehydeless bio-based backboard glue and preparation method | |
| CN108101418A (en) | A kind of environmental-friendly construction material | |
| CN104403263A (en) | Toughened and reinforced phenolic foam plate | |
| CN106752004A (en) | A kind of waterproof flame-retardant type biomass board of multi-walled carbon nano-tubes activeness and quietness and preparation method thereof | |
| CN108358513A (en) | A kind of Environment-friendlywear-resistant wear-resistant heat-insulating and fire-proof composite board and preparation method thereof | |
| CN102702985A (en) | Inorganic adhesive with flame-retardant effect for plant fiber and application of inorganic adhesive | |
| CN114561189A (en) | Lignin phenolic resin dust suppressant and preparation method thereof | |
| CN106625947A (en) | Composite modifying agent added with oxide graphene modified emulsion for fast growing wood | |
| CN113213865A (en) | Autoclaved fly ash brick and preparation process thereof | |
| CN111454019B (en) | Preparation method of rural high-strength raw soil material | |
| CN112209699A (en) | Preparation method of water-resistant and anti-freezing shale ganged brick | |
| CN111978017B (en) | Bank protection engineering material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201215 Address after: 538000 Guangxi Fangchenggang Port Area East Drainage Reclamation Port Area 1 Road West Side Patentee after: Fangcheng and Hong Kong and Macao grain & Oil Industry Co.,Ltd. Address before: 530000 3205 55 Phoenix Valley Road, Qingxiu District, Nanning, Nanning, the Guangxi Zhuang Autonomous Region, China, 55 Patentee before: Huang Yu |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210728 Address after: 530012 No. 607, floor 6, haichuangmeng center, No. 10, Gehai Road, Nanning, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Shenyi Intellectual Property Operation Co.,Ltd. Address before: 538000 Guangxi Fangchenggang Port Area East Drainage Reclamation Port Area 1 Road West Side Patentee before: Fangcheng and Hong Kong and Macao grain & Oil Industry Co.,Ltd. |
|
| TR01 | Transfer of patent right |