CN114686121A - Biomass adhesive and preparation method and application thereof - Google Patents
Biomass adhesive and preparation method and application thereof Download PDFInfo
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- CN114686121A CN114686121A CN202011600076.XA CN202011600076A CN114686121A CN 114686121 A CN114686121 A CN 114686121A CN 202011600076 A CN202011600076 A CN 202011600076A CN 114686121 A CN114686121 A CN 114686121A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 239000002028 Biomass Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 91
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- -1 amide compound Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 229920002472 Starch Polymers 0.000 claims abstract description 12
- 239000008107 starch Substances 0.000 claims abstract description 12
- 235000019698 starch Nutrition 0.000 claims abstract description 12
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 150000002978 peroxides Chemical class 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 12
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229940043350 citral Drugs 0.000 claims description 6
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- MQBIZQLCHSZBOI-UHFFFAOYSA-N 4-(4-Methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde Chemical compound CC(C)=CCCC1=CCC(C=O)CC1 MQBIZQLCHSZBOI-UHFFFAOYSA-N 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000007031 hydroxymethylation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Forests & Forestry (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a biomass adhesive and a preparation method and application thereof. The preparation method of the biomass adhesive comprises the following steps: (1) carrying out oxidative ammonolysis reaction on lignin to prepare a mixed material A; (2) in a solvent, reacting the mixed material A, starch, an initiator and a dispersant, mixing with polyvinyl alcohol, and aging to prepare a mixed material B; (3) the mixed material C and a catalyst are subjected to a first reaction, and then, the mixed material C and a coupling agent and an amide compound are subjected to a second reaction to obtain the catalyst; wherein the mixed material C is a mixture of the mixed material B, phenol, aldehyde and an alkaline compound. The formaldehyde release amount of the biomass adhesive prepared by the invention is less than or equal to 0.05mg/L, so that the environment-friendly adhesive with low formaldehyde or no formaldehyde release is prepared, and is safe and pollution-free, and the environment and personnel safety are protected; low cost, good bonding strength and excellent application performance.
Description
Technical Field
The invention relates to a biomass adhesive and a preparation method and application thereof.
Background
The rapid development of the current artificial board industry leads to the increase of the demand of adhesives for artificial boards. The phenolic glue has the advantages of high bonding strength, good durability, weather resistance, water resistance, strong aging resistance and the like, and is widely applied to the artificial board industry, but the phenolic glue has the defects of high formaldehyde release amount, high cost, large brittleness and the like. To ameliorate these deficiencies of phenolic adhesives, researchers have been looking for certain renewable feedstock modified phenolic resins. The industrial lignin is a natural high molecular polymer which has wide sources, low price and aromatic structure. At present, phenolic resin is modified by hydroxymethylation, demethylation, phenolization and the like of lignin, so that the cost is reduced, the defects of high brittleness and the like are overcome, and the formaldehyde release amount is reduced, but is still more than or equal to 0.1 percent. For example, the chinese patent application CN108003822A is a method for preparing phenolic adhesive by hydroxymethylation of modified lignin, although the cost is reduced, the formaldehyde emission is still 0.06-0.14 mg/L, the average is 0.1mg/L, and the adhesive strength is up to the standard, but still in a low standard state.
Therefore, there is a need in the art to develop an environment-friendly adhesive with low formaldehyde emission and good bonding strength.
Disclosure of Invention
The invention aims to overcome the defects of high formaldehyde release amount, high cost, unsatisfactory bonding strength and the like of adhesives in the prior art, and provides a biomass adhesive, and a preparation method and application thereof. The formaldehyde release amount of the biomass adhesive prepared by the invention is less than or equal to 0.05mg/L, so that the environment-friendly adhesive with low formaldehyde or no formaldehyde release is prepared, and is safe and pollution-free, and the environment and personnel safety are protected; low cost, good bonding strength and excellent application performance.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a preparation method of a biomass adhesive, which comprises the following steps:
(1) carrying out oxidative ammonolysis reaction on lignin to prepare a mixed material A;
(2) in a solvent, reacting the mixed material A, starch, an initiator and a dispersant, mixing with polyvinyl alcohol, and aging to obtain a mixed material B;
(3) the mixed material C and a catalyst are subjected to a first reaction, and then, the mixed material C and a coupling agent and an amide compound are subjected to a second reaction to obtain the catalyst; wherein the mixed material C is a mixture of the mixed material B, phenol, aldehyde and an alkaline compound.
In step (1), the preparation method of lignin can be conventional in the art, and preferably comprises the following steps: and (3) preserving the heat of the papermaking black liquor, and adjusting the pH value of the system to 3-4.
The papermaking black liquor can be waste water produced in the alkaline pulping process commonly referred to in the papermaking field, for example, the papermaking black liquor produced in the papermaking process of Shandong solar control stock group.
The solid content of the papermaking black liquor can be conventional in the art, and generally can be 15-20%, and preferably 18-20%. In the invention, the solid content generally refers to the mass percentage of dry materials prepared by removing the solvent from the papermaking black liquor in the papermaking black liquor.
The papermaking black liquor can be other residual materials except sulfate pulp in the sulfate pulp preparation process, and is generally prepared by the following steps: cooking wood, a sodium hydroxide aqueous solution with the concentration of 0.5-1.5 mol/L and a sodium sulfide aqueous solution with the concentration of 0.1-0.3 mol/L, blowing, recovering steam, and washing to obtain sulfate paper pulp; the rest materials except the sulfate paper pulp are the papermaking black liquor.
Wherein, the temperature of the heat preservation can be the temperature which is conventional in the operation in the field, and is preferably 50-60 ℃.
The time for heat preservation can be the time of the operation routine in the field, preferably 1-3 h, more preferably 2-3 h.
The condition and the method for adjusting the pH value of the system to 3-4 can be conventional in the field, and generally can be adding an acidic pH value regulator. The acidic pH regulator can be an acidity regulator with a pH value less than 7, which is conventionally used in the field, and can be one or more of aqueous sulfuric acid solution, aqueous hydrochloric acid and aqueous acetic acid solution, preferably aqueous sulfuric acid solution. The concentration of the acidic pH adjustor can be conventional in the art and can generally be from 30 wt% to 60 wt%.
Wherein, preferably, the pH value of the system is adjusted to 3.5-3.7.
And adjusting the pH value of the system to 3-4, and then further filtering and collecting a filter cake and/or washing. The washing conditions and methods may be conventional in the art and may generally be washed until the eluate is neutral. The wash solution used in the washing process may be conventional in the art and may typically be water and/or ethanol, preferably water.
In step (1), the oxidative ammonolysis reaction may be a process in which carbonyl groups and carboxyl groups in the lignin are covalently reacted with ammonia, which is conventionally considered by those skilled in the art, and preferably comprises the following steps: and (3) carrying out oxidative ammonolysis reaction on the lignin, an aminating agent, an oxidant and N, N-dimethylformamide, filtering, and collecting a filter cake to obtain a mixed material A.
Wherein, the aminating agent can be an agent which is used conventionally in the field and can make the lignin and the N, N-dimethylformamide generate amine compounds, and generally can be one or more of ammonia, liquid ammonia, urea and ammonium salt, and preferably ammonia. The ammonium salt is preferably ammonium bicarbonate. The ammonia may be added in the form of aqueous ammonia as is conventional in the art, and the concentration of the aqueous ammonia may be conventional in the art, preferably 25 wt% to 30 wt%. The percentage is the percentage of the mass of ammonia in the ammonia water to the total mass of the ammonia water.
Wherein, the oxidant can be an oxidant conventionally used in the field, and can be one or more of peroxide, oxygen, hypochlorous acid and hypochlorite generally, and is preferably peroxide. The peroxide is preferably hydrogen peroxide. The hypochlorite is preferably sodium hypochlorite.
When the oxidizing agent is the hydrogen peroxide, the hydrogen peroxide may be added as an aqueous hydrogen peroxide solution as is conventional in the art. Wherein, the mass percentage of the hydrogen peroxide in the aqueous hydrogen peroxide solution can be conventional in the field, and is preferably 20-30%.
Wherein the mass ratio of said lignin to said aminating agent may be conventional in the art, preferably 1: (0.5 to 1.5), preferably 1: 0.9.
wherein the mass ratio of the lignin to the oxidant can be conventional in the art, and is preferably (6-17): 1, more preferably (10 to 13.3): 1.
wherein the mass ratio of the lignin to the N, N-dimethylformamide can be conventional in the art, and is preferably 1: (1 to 4), more preferably 1: (1.2 to 1.7), more preferably 1: (1.2-1.3).
In the step (1), the temperature of the oxidative ammonolysis reaction may be a temperature conventional in the art, preferably 40 to 80 ℃, and more preferably 50 to 80 ℃.
In the step (1), the time of the oxidative ammonolysis reaction can be the time conventional in the field, and is preferably 30-50 min.
In the step (2), the mixed material A can further comprise a drying operation before use.
The conditions and methods for drying may be conventional in the art, and may generally be carried out in an oven.
Wherein, the drying temperature can be the temperature which is conventional in the operation in the field, and is preferably 80-100 ℃.
The drying time can be the time of the operation routine in the field, preferably 3-5 h, and more preferably 4-5 h.
In step (2), the initiator may be a reagent which is conventionally used in the art and can initiate the grafting reaction of the material a, the starch and the polyvinyl alcohol, preferably an inorganic peroxide initiator and/or an azo initiator, and more preferably an inorganic peroxide initiator. The inorganic peroxide initiator is preferably ammonium persulfate and/or potassium persulfate, more preferably ammonium persulfate. The azo-based initiator is preferably azobisisobutyronitrile.
In the step (2), the dispersant may be a dispersant conventionally used in the field of adhesives, preferably an anionic surfactant, more preferably one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium hexadecyl sulfonate, and further more preferably sodium dodecyl sulfate.
In step (2), the solvent may be a solvent capable of completely dissolving all the raw materials in the reaction in the prior art, and may be an aqueous solution of N, N-dimethylformamide. The mass percentage of the N, N-dimethylformamide in the aqueous solution of N, N-dimethylformamide may be conventional in the art, and is preferably 4% to 8%, more preferably 5% to 8%.
In the step (2), the number average molecular weight of the polyvinyl alcohol may be conventional in the art, and is preferably 18 to 20 ten thousand.
In the step (2), the mass ratio of the dry material of the mixed material a to the starch can be conventional in the art, and is preferably 1: (0.125-0.5), preferably 1: (0.2 to 0.35), for example, 1: 0.25. in the present invention, the dry material of the mixed material a may be a material remaining after the mixed material a is dried, which is conventionally considered by those skilled in the art.
In the step (2), the mass ratio of the dry material of the mixed material a to the initiator can be conventional in the art, and is preferably 1: (0.12 to 0.7), preferably 1: (0.4-0.5).
In the step (2), the mass ratio of the dry material of the mixed material a to the dispersant can be conventional in the art, and is preferably 1: (0.0001 to 0.005), preferably 1: (0.0005-0.001).
In the step (2), the mass ratio of the dry material of the mixed material a to the polyvinyl alcohol may be conventional in the art, and is preferably 1: (0.02 to 0.1), preferably 1: (0.031-0.079), and more preferably 1: (0.042-0.079).
In the step (2), the reaction temperature may be a temperature conventional in the field, and is preferably 50 to 80 ℃.
In the step (2), the reaction time may be a time conventionally used in the field, and is preferably 1 to 3 hours, and more preferably 2 to 3 hours.
In step (2), the conditions and methods of aging may be conventional in the art, and may be generally static.
In the step (2), the aging time can be the conventional time in the field, and the material prepared after the reaction in the system can be reacted with the polyvinyl alcohol completely, preferably 5-8 h.
In step (3), the catalyst may be a catalyst which is conventionally used in the art and can catalyze a crosslinking reaction, preferably a metal oxide catalyst, more preferably one or more of zinc oxide, titanium oxide, tin oxide, and α -iron oxide, and further more preferably zinc oxide.
In the step (3), the amide-based compound may be an amide-based compound which is conventionally used in the art and can undergo a crosslinking reaction with the phenol and the aldehyde, preferably one or more of acrylamide, polyacrylamide and carbamide, and more preferably acrylamide.
In the step (3), the coupling agent may be a coupling agent conventionally used in the field of adhesives, preferably one or more of a silane coupling agent, a polyisocyanate coupling agent and a phthalate coupling agent, and more preferably a silane coupling agent.
Among them, the silane coupling agent is preferably one or more of vinyltriethoxysilane, vinyltrimethoxysilane and gamma-methacryloxytrimethoxysilane, and more preferably vinyltrimethoxysilane.
In the step (3), the phenol may be a phenol conventionally used in the field of adhesives, and is preferably one or more of phenol, meta alkyl substituted phenol and para alkyl substituted phenol, wherein alkyl in the meta alkyl substituted phenol and the para alkyl substituted phenol is C1～C4An alkyl group; the phenol is more preferably phenol. The meta-alkyl substituted phenol is preferably meta-cresol and/or cardanol. The para-alkyl substituted phenol is preferably 4-tert-butylcatechol and/or 4-tert-butylphenol, more preferably 4-tert-butylphenol.
In the step (3), the aldehyde may be an aldehyde conventionally used in the field of adhesives, preferably formaldehyde and/or an aldehyde compound having a double bond in the molecular formula, and more preferably formaldehyde. The aldehyde compound containing a double bond in the molecular formula is preferably one or more of citral, cinnamaldehyde and citral, and more preferably citral.
In the step (3), the basic compound may be one conventionally used in the art for catalyzing condensation reaction, and preferably, one or more of alkali metal hydroxide, alkali metal carbonate and alkali metal sulfite. The alkali metal hydroxide is preferably one or more of barium hydroxide, sodium hydroxide and calcium hydroxide, more preferably sodium hydroxide. The alkali metal carbonate compound is preferably sodium carbonate and/or sodium bicarbonate. The alkali metal sulfite compound is preferably sodium sulfite.
In step (3), the preparation method of the mixed material C may be conventional in the art, and generally comprises the following steps: and uniformly mixing the mixed material B, the phenol, the aldehyde and the alkaline compound. Wherein, the mixing time can be conventional in the field, and can be generally 20-30 min.
In the step (3), the mass ratio of the mixed material B to the phenol may be conventional in the art, and is preferably 1: (0.3 to 0.7), preferably 1: (0.4-0.52), for example, 1: 0.51.
in the step (3), the mass ratio of the mixed material B to the aldehyde may be conventional in the art, and is preferably 1: (0.1 to 0.3), preferably 1: (0.16-0.27).
In the step (3), the mass ratio of the mixed material B to the basic compound may be conventional in the art, and is preferably 1: (0.1 to 0.27), preferably 1: (0.12-0.15).
In the step (3), the mass ratio of the mixture C to the catalyst may be conventional in the art, and is preferably 1: (0.1 to 0.35), more preferably 1: (0.15 to 0.2), for example, 1: 0.17.
in the step (3), the mass ratio of the mixture C to the coupling agent may be conventional in the art, and is preferably 1: (0.03-0.2), preferably 1: (0.03 to 0.06), for example, 1: 0.05.
in the step (3), the mass ratio of the mixture C to the amide compound may be conventional in the art, and is preferably 1: (0.08-0.3), preferably 1: (0.09-0.1).
In the step (3), the temperature of the first reaction may be a temperature conventional in the field, preferably 70 to 90 ℃, and more preferably 70 to 80 ℃.
In the step (3), the time of the first reaction may be a time conventionally used in this type of reaction in the field, and is preferably 1 to 3 hours, and more preferably 2 to 3 hours.
In the step (3), the temperature of the second reaction may be a temperature conventional in the field, and is preferably 60 to 80 ℃.
In the step (3), the time of the second reaction can be the time of the reaction of the kind conventional in the art, preferably 20 to 50min, and more preferably 30 to 50 min.
In the step (3), the operation of the second reaction may further include a cooling operation, which may be generally cooling to room temperature.
In the present invention, the terms "first" and "second" in the first reaction and the second reaction have no special meaning, and only the order of the reactions is shown here.
The invention provides a biomass adhesive, which is prepared by the preparation method of the biomass adhesive.
The invention also provides application of the biomass adhesive as an adhesive in the field of artificial boards.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: according to the invention, lignin is modified and grafted with starch, and the coupling agent is utilized to better combine the phenolic glue and the modified lignin of the grafted starch, so that the novel biomass adhesive is prepared. The formaldehyde release amount of the biomass adhesive prepared by the invention is less than or equal to 0.05 percent, so that the environment-friendly adhesive with low formaldehyde or no formaldehyde release is prepared, and is safe and pollution-free, and the environment and personnel safety are protected; the cost is low, the bonding strength is good, and the application performance is excellent; the lignin can be extracted from the papermaking black liquor, so that the cost is further reduced, and the waste is changed into valuable.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The preparation method of the papermaking black liquor used in the following examples comprises the following steps: wood, 0.5mol/L sodium hydroxide aqueous solution and 0.1mol/L sodium sulfide aqueous solution are steamed and boiled, blown, steam is recycled, and sulfate pulp is obtained by washing; the rest materials except the sulfate paper pulp are papermaking black liquor.
Example 1
(1) Firstly, putting 1L of papermaking black liquor into a container, adding water to adjust the solid content to be 15%, starting stirring, heating to 50 ℃, and preserving heat for 2 hours at the temperature; adding a 30 wt% sulfuric acid aqueous solution to adjust the pH value of the system to 3.5, stirring for 30min, and then carrying out suction filtration to collect a filter cake; and washing the filter cake with 500mL of pure water;
(2) mixing the filter cake prepared in the step (1) with 30 wt% ammonia water, wherein the mass ratio of the filter cake to the ammonia water is 1: 3; transferring into a container, adding 30 wt% of hydrogen peroxide, wherein the mass ratio of the filter cake to the hydrogen peroxide is 3:1, adding 140mL of N, N-dimethylformamide, and uniformly stirring, wherein the mass ratio of the lignin to the N, N-dimethylformamide is 1: 1.7, heating in a water bath at 50 ℃ for 30min, carrying out suction filtration, drying a filter cake in an oven at 100 ℃ for 5h, and finally crushing to obtain a dried mixed material A;
(3) soaking 100g of dried mixed material A, 25g of starch, 50g of ammonium persulfate, 0.1g of sodium dodecyl sulfate and 5% by mass of N, N-dimethylformamide aqueous solution, heating in a water bath at 80 ℃ for 2h, adding 100mL of 3% by mass of polyvinyl alcohol aqueous solution, wherein the mass ratio of the dried mixed material A to the polyvinyl alcohol is 1: 0.031, the polyvinyl alcohol number average molecular weight is 18 ten thousand, age 8 hours after stiring, make mixed supplies B;
(4) and (3) mixing the mixed material B prepared in the step (3) with 100mL of 4-tert-butylphenol, 80mL of liquid caustic soda with the mass percent of 32% and 30mL of myrac aldehyde, and uniformly stirring, wherein the mass ratio of the mixed material B to the 4-tert-butylphenol is 1: 0.52, the mass ratio of the mixed material B to the alkaline compound is 1: 0.15, wherein the mass ratio of the mixed material B to the myrac aldehyde is 1: 0.16; heating to 80 ℃, and adding 30g of zinc oxide to perform catalytic reaction for 2 hours; and (3) cooling, adding 10g of silane coupling agent vinyl trimethoxy silane and 20g of acrylamide, stirring for 30min at 80 ℃, cooling and discharging to obtain the biomass adhesive.
Example 2
(1) Firstly, putting 2L of papermaking black liquor into a container, adding water to adjust the solid content to be 20%, starting stirring, heating to 50 ℃, and preserving heat for 2 hours at the temperature; adding a 30 wt% sulfuric acid aqueous solution to adjust the pH value of the system to 3, stirring for 30min, and then performing suction filtration to collect a filter cake; and flushing the filter cake with 800mL of pure water;
(2) mixing the filter cake prepared in the step (1) with 30 wt% ammonia water, wherein the mass ratio of the filter cake to the ammonia water is 1: 3; transferring into a container, adding 30 wt% of hydrogen peroxide, wherein the mass ratio of the filter cake to the hydrogen peroxide is 3:1, adding 200mL of N, N-dimethylformamide, and uniformly stirring, wherein the mass ratio of the lignin to the N, N-dimethylformamide is 1: 1.3, heating in a water bath at 50 ℃ for 30min, carrying out suction filtration, drying a filter cake in an oven at 100 ℃ for 4h, and finally crushing to obtain a dried mixed material A;
(3) soaking 100g of dried mixed material A, 35g of starch, 40g of ammonium persulfate, 0.05g of sodium dodecyl sulfate and 5% by mass of N, N-dimethylformamide aqueous solution, heating in a water bath at 80 ℃ for 2h, adding 80mL of 5% by mass of polyvinyl alcohol aqueous solution, wherein the mass ratio of the dried mixed material A to the polyvinyl alcohol is 1: 0.042, the number average molecular weight of polyvinyl alcohol is 20 ten thousand, and the mixture is aged for 8 hours after being evenly stirred to prepare a mixed material B;
(4) and (3) mixing the mixed material B prepared in the step (3) with 80mL of 4-tert-butylphenol, 60mL of liquid caustic soda with the mass percentage of 32% and 50mL of myrac aldehyde, and uniformly stirring, wherein the mass ratio of the mixed material B to the 4-tert-butylphenol is 1: 0.4, the mass ratio of the mixed material B to the alkaline compound is 1: 0.1, wherein the mass ratio of the mixed material B to the myrac aldehyde is 1: 0.27; heating to 80 ℃, and adding 35g of zinc oxide to perform catalytic reaction for 2 hours; and (3) cooling, adding 8g of silane coupling agent vinyl trimethoxy silane and 20g of acrylamide, stirring for 30min at 80 ℃, cooling and discharging to obtain the biomass adhesive.
Example 3
(1) Firstly, putting 2L of papermaking black liquor into a container, adding water to adjust the solid content to be 18%, starting stirring, heating to 50 ℃, and preserving heat for 2 hours at the temperature; adding a 30 wt% sulfuric acid aqueous solution to adjust the pH value of the system to 3.7, stirring for 30min, and then performing suction filtration to collect a filter cake; washing the filter cake with 1000mL of pure water;
(2) mixing the filter cake prepared in the step (1) with 30 wt% ammonia water, wherein the mass ratio of the filter cake to the ammonia water is 1: 3; transferring into a container, adding 30 wt% of hydrogen peroxide, wherein the mass ratio of the filter cake to the hydrogen peroxide is 4:1, adding 180mL of N, N-dimethylformamide, and uniformly stirring, wherein the mass ratio of the lignin to the N, N-dimethylformamide is 1: 1.2, heating in a water bath at 50 ℃ for 30min, carrying out suction filtration, drying a filter cake in an oven at 100 ℃ for 5h, and finally crushing to obtain a dried mixed material A;
(3) soaking 200g of dried mixed material A, 40g of starch, 80g of ammonium persulfate, 0.1g of sodium dodecyl sulfate and 5% by mass of N, N-dimethylformamide aqueous solution, heating in a water bath at 80 ℃ for 2h, adding 150mL of 5% by mass of polyvinyl alcohol aqueous solution, wherein the mass ratio of the dried mixed material A to the polyvinyl alcohol is 1: 0.079, the number average molecular weight of polyvinyl alcohol is 20 ten thousand, and the mixture is aged for 8 hours after being evenly stirred to prepare a mixed material B;
(4) and (4) mixing the mixed material B prepared in the step (3) with 180mL of 4-tert-butylphenol, 120mL of liquid caustic soda with the mass percent of 32% and 40mL of myrac aldehyde, and uniformly stirring, wherein the mass ratio of the mixed material B to the 4-tert-butylphenol is 1: 0.5, the mass ratio of the mixed material B to the alkaline compound is 1: 0.1, wherein the mass ratio of the mixed material B to the myrac aldehyde is 1: 0.1; heating to 80 ℃, and adding 50g of zinc oxide to perform catalytic reaction for 2 hours; and (3) cooling, adding 10g of silane coupling agent vinyl trimethoxy silane and 30g of acrylamide, stirring for 30min at 80 ℃, cooling and discharging to obtain the biomass adhesive.
Comparative example 1
(1) Firstly, putting 2L of papermaking black liquor into a container, adding water to adjust the solid content to be 18%, starting stirring, heating to 50 ℃, and preserving heat for 2 hours at the temperature; adding a 30 wt% sulfuric acid aqueous solution to adjust the pH value of the system to 3.7, stirring for 30min, and then performing suction filtration to collect a filter cake; washing the filter cake with 1000mL of pure water;
(2) mixing the mixed filter cake prepared in the step (1) with 180mL of 4-tert-butylphenol, 120mL of 32 mass percent liquid caustic soda and 40mL of myrac aldehyde, and uniformly stirring; heating to 80 ℃, and adding 50g of zinc oxide to perform catalytic reaction for 2 hours; and (3) cooling, adding 10g of silane coupling agent vinyl trimethoxy silane and 30g of acrylamide, stirring for 30min at 80 ℃, cooling and discharging to obtain the biomass adhesive.
Comparative example 2
Compared with the example 1, the difference is only that the adding sequence in the step (3) is different, specifically, 100g of the mixed material A, 25g of starch, 50g of ammonium persulfate, 0.1g of sodium dodecyl sulfate, 5 mass percent of N, N-dimethylformamide aqueous solution and 3 mass percent of polyvinyl alcohol aqueous solution are taken, soaked, heated in 80 ℃ water bath for 2 hours, stirred uniformly and aged for 8 hours, and the mixed material B is prepared.
Effect example 1
The biomass adhesive prepared in the embodiments 1-3 and the comparative examples 1-2 is blended with filler flour, and the mass ratio of the biomass adhesive to the filler flour is 1: 0.2, uniformly coating the mixed materials on a plate, and performing double-sided sizing, wherein the sizing amount is 330g/m2Pressing the plate in a plate pressing machine, and cold pressing for 1-1.5 h at room temperature under the pressure of 1 MPa; hot pressing at 100-150 deg.c for 10-15 min under 1 MPa; and then putting the sample into an oven with the temperature of 60-75 ℃ for curing for 10-15 min to prepare the sample to be detected. Sampling and detecting formaldehyde release amount data according to the national standard GBT 20974-2014 standard, wherein the specification of the formaldehyde release amount measurement sample is 15 cm-5 cm; and detecting the bonding strength according to the national standard GB/T17657-2013, wherein the specifications of bonding strength test samples are as follows: 10cm by 2.5 cm; the results are shown in Table 1 below.
TABLE 1
| Numbering | Bonding strength/MPa | Formaldehyde emission mg/L |
| Example 1 | 1.33 | 0.01 |
| Example 2 | 1.54 | 0.02 |
| Example 3 | 1.78 | 0.01 |
| Comparative example 1 | 1.15 | 0.35 |
| Comparative example 2 | 1.19 | 0.22 |
The effect data show that all performances of the biomass adhesive prepared by the invention meet the national standard requirements. The biomass adhesive disclosed by the invention is wide in raw material source and low in price, and can change waste into valuable and improve the resource utilization rate.
The above description is only a part of the embodiments of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still belong to the technical scheme scope of the present invention; paper waste, in addition to including what is mentioned in the claims, also relates to other waste produced by the paper making process.
Claims (10)
1. The preparation method of the biomass adhesive is characterized by comprising the following steps of:
(1) carrying out oxidative ammonolysis reaction on lignin to prepare a mixed material A;
(2) in a solvent, reacting the mixed material A, starch, an initiator and a dispersant, mixing with polyvinyl alcohol, and aging to obtain a mixed material B;
(3) the mixed material C and a catalyst are subjected to a first reaction, and then, the mixed material C and a coupling agent and an amide compound are subjected to a second reaction to obtain the catalyst; wherein the mixed material C is a mixture of the mixed material B, phenol, aldehyde and an alkaline compound.
2. The preparation method of the biomass adhesive according to claim 1, wherein in the step (1), the preparation method of the lignin comprises the following steps: the papermaking black liquor is subjected to heat preservation, and the pH value of a system is adjusted to 3-4;
preferably, the solid content of the papermaking black liquor is 15-20%, and more preferably 18-20%;
preferably, the temperature of the heat preservation is 50-60 ℃;
preferably, the heat preservation time is 2-3 h;
preferably, the method for adjusting the pH value of the system to 3-4 is to add an acidic pH value regulator; the acidic pH value regulator is preferably one or more of aqueous sulfuric acid solution, aqueous hydrochloric acid and aqueous acetic acid solution, and is more preferably aqueous sulfuric acid solution; the concentration of the acidic pH value regulator is preferably 30-60 wt%;
preferably, the pH value of the system is adjusted to 3.5-3.7;
preferably, the operation of adjusting the pH value of the system to 3-4 further comprises the operation of filtering and collecting a filter cake and/or washing; the washing liquid used in the washing process is preferably water and/or ethanol, more preferably water.
3. The preparation method of the biomass adhesive according to claim 1, wherein in the step (1), the oxidative ammonolysis reaction comprises the following steps: carrying out oxidative ammonolysis reaction on the lignin, an aminating agent, an oxidant and N, N-dimethylformamide, filtering, and collecting a filter cake to obtain a mixed material A;
preferably, the aminating agent is one or more of ammonia, liquid ammonia, urea and ammonium salt, more preferably ammonia; the ammonium salt is preferably ammonium bicarbonate; preferably, the ammonia is added in the form of ammonia water, and the concentration of the ammonia water is 25 wt% -30 wt%;
preferably, the oxidizing agent is one or more of peroxide, oxygen, hypochlorous acid and hypochlorite, more preferably peroxide; the peroxide is preferably hydrogen peroxide; the hypochlorite is preferably sodium hypochlorite;
when the oxidizing agent is the hydrogen peroxide, the hydrogen peroxide is added in the form of an aqueous hydrogen peroxide solution, and the mass percentage of the hydrogen peroxide in the aqueous hydrogen peroxide solution is preferably 20 to 30 percent;
preferably, the mass ratio of the lignin to the aminating agent is 1: (0.5 to 1.5), preferably 1: 0.9;
preferably, the mass ratio of the lignin to the oxidant is (6-17): 1, more preferably (10 to 13.3): 1;
preferably, the mass ratio of the lignin to the N, N-dimethylformamide is 1: (1 to 4), more preferably 1: (1.2 to 1.7), more preferably 1: (1.2-1.3).
4. The preparation method of the biomass adhesive according to claim 1, wherein in the step (1), the temperature of the oxidative ammonolysis reaction is 40-80 ℃, preferably 50-80 ℃;
and/or in the step (1), the time of the oxidative ammonolysis reaction is 30-50 min.
5. The preparation method of the biomass adhesive according to claim 1, wherein in the step (2), the mixed material A further comprises a drying operation before use; the drying temperature is preferably 80-100 ℃; the drying time is preferably 3 to 5 hours, more preferably 4 to 5 hours;
and/or, in the step (2), the initiator is an inorganic peroxide initiator and/or an azo initiator, and is preferably an inorganic peroxide initiator;
and/or, in the step (2), the dispersant is an anionic surfactant, preferably one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium hexadecyl sulfonate, and more preferably sodium dodecyl sulfate;
and/or, in the step (2), the solvent is N, N-dimethylformamide aqueous solution; the mass percentage of the N, N-dimethylformamide in the N, N-dimethylformamide aqueous solution is preferably 4-8%, more preferably 5-8%;
and/or, in the step (2), the number average molecular weight of the polyvinyl alcohol is 18 to 20 ten thousand;
and/or in the step (2), the mass ratio of the dry material of the mixed material A to the starch is 1: (0.125-0.5), preferably 1: (0.2 to 0.35), preferably 1: 0.25;
and/or in the step (2), the mass ratio of the dry material of the mixed material A to the initiator is 1: (0.12 to 0.7), preferably 1: (0.4-0.5);
and/or in the step (2), the mass ratio of the dry material of the mixed material A to the dispersing agent is 1: (0.0001 to 0.005), preferably 1: (0.0005 to 0.001)
And/or in the step (2), the mass ratio of the dry material of the mixed material A to the polyvinyl alcohol is 1: (0.02 to 0.1), preferably 1: (0.031-0.079), preferably 1: (0.042-0.079);
and/or in the step (2), the reaction temperature is 50-80 ℃;
and/or in the step (2), the reaction time is 1-3 h, preferably 2-3 h;
and/or in the step (2), the aging time is 5-8 h.
6. The preparation method of the biomass adhesive according to claim 5, wherein the inorganic peroxide initiator is ammonium persulfate and/or potassium persulfate, preferably ammonium persulfate;
and/or the azo initiator is azobisisobutyronitrile.
7. The method for preparing the biomass adhesive according to any one of claims 1 to 6, wherein in the step (3), the catalyst is a metal oxide catalyst, preferably one or more of zinc oxide, titanium oxide, tin oxide and alpha-iron oxide, and more preferably zinc oxide;
and/or, in the step (3), the amide-type compound is one or more of acrylamide, polyacrylamide and carbamide, preferably acrylamide;
and/or, in the step (3), the coupling agent is one or more of a silane coupling agent, a polyisocyanate coupling agent and a phthalate coupling agent, preferably a silane coupling agent;
and/or in the step (3), the phenol is one or more of phenol, m-alkyl substituted phenol and p-alkyl substituted phenol, and the alkyl in the m-alkyl substituted phenol and the p-alkyl substituted phenol is C1～C4An alkyl group, preferably phenol;
and/or, in the step (3), the aldehyde is formaldehyde and/or an aldehyde compound containing double bonds in the molecular formula, preferably formaldehyde;
and/or, in the step (3), the alkaline compound is one or more of alkali metal hydroxide, alkali metal acid compound and alkali metal sulfurous acid compound;
and/or, in the step (3), the preparation method of the mixed material C comprises the following steps: uniformly mixing the mixed material B, the phenol, the aldehyde and the alkaline compound;
and/or in the step (3), the mass ratio of the mixed material B to the phenol is 1: (0.3 to 0.7), preferably 1: (0.4 to 0.52), preferably 1: 0.51;
and/or in the step (3), the mass ratio of the mixed material B to the aldehyde is 1: (0.1 to 0.3), preferably 1: (0.16 to 0.27);
and/or in the step (3), the mass ratio of the mixed material B to the alkaline compound is 1: (0.1 to 0.27), preferably 1: (0.12-0.15);
and/or in the step (3), the mass ratio of the mixed material C to the catalyst is 1: (0.1 to 0.35), preferably 1: (0.15-0.2), more preferably 1: 0.17;
and/or in the step (3), the mass ratio of the mixed material C to the coupling agent is 1: (0.03-0.2), preferably 1: (0.03-0.06), preferably 1: 0.05;
and/or in the step (3), the mass ratio of the mixed material C to the amide compound is 1: (0.08 to 0.3), preferably 1: (0.09-0.1);
and/or, in the step (3), the temperature of the first reaction is 70-90 ℃, preferably 70-80 ℃;
and/or in the step (3), the time for the first reaction is 1-3 h, preferably 2-3 h;
and/or in the step (3), the temperature of the second reaction is 60-80 ℃;
and/or, in the step (3), the time of the second reaction is 20-50 min, preferably 30-50 min;
and/or, in the step (3), the operation of the second reaction is further followed by an operation of reducing the temperature, preferably to room temperature.
8. The method for preparing the biomass adhesive according to claim 7, wherein the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane and gamma-methacryloxytrimethoxysilane, preferably vinyltrimethoxysilane;
and/or the meta-alkyl substituted phenol is m-cresol and/or cardanol;
and/or the para-alkyl substituted phenol is 4-tert-butyl catechol and/or 4-tert-butyl phenol, preferably 4-tert-butyl phenol;
and/or the aldehyde compound containing double bonds in the molecular formula is one or more of citral, cinnamaldehyde and citral, preferably citral;
and/or, the alkali metal hydroxide is one or more of barium hydroxide, sodium hydroxide and calcium hydroxide, preferably sodium hydroxide;
and/or, the alkali metal acid compound is sodium carbonate and/or sodium bicarbonate;
and/or, the alkali metal sulfite compound is sodium sulfite;
and/or in the preparation method of the mixed material C, the mixing time is 20-30 min.
9. The biomass adhesive is characterized by being prepared by the preparation method of the biomass adhesive as claimed in any one of claims 1 to 8.
10. The application of the biomass adhesive as claimed in claim 9 in the field of artificial boards as an adhesive.
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| CN202011600076.XA CN114686121B (en) | 2020-12-29 | Biomass adhesive and preparation method and application thereof |
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| CN202011600076.XA CN114686121B (en) | 2020-12-29 | Biomass adhesive and preparation method and application thereof |
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| CN114686121B CN114686121B (en) | 2024-06-28 |
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| CN116144289A (en) * | 2023-02-07 | 2023-05-23 | 大连工业大学 | Biological aldehyde group modified polyvinyl alcohol adhesive and application thereof in preparation of medium-density chipboard |
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