CN107841270B - Preparation method of lignin phenolic resin adhesive - Google Patents
Preparation method of lignin phenolic resin adhesive Download PDFInfo
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- CN107841270B CN107841270B CN201711212549.7A CN201711212549A CN107841270B CN 107841270 B CN107841270 B CN 107841270B CN 201711212549 A CN201711212549 A CN 201711212549A CN 107841270 B CN107841270 B CN 107841270B
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- phenolic resin
- lignin
- resin adhesive
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- 229920005610 lignin Polymers 0.000 title claims abstract description 81
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 54
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000010453 quartz Substances 0.000 claims abstract description 43
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 235000014676 Phragmites communis Nutrition 0.000 claims description 34
- 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 30
- 239000007787 solid Substances 0.000 claims description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 28
- 239000001963 growth medium Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 229910052726 zirconium Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000002893 slag Substances 0.000 claims description 23
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 22
- 239000000463 material Substances 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
- 239000002518 antifoaming agent Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 241001138370 Pleurotus pulmonarius Species 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 16
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000002609 medium Substances 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 8
- 229920000053 polysorbate 80 Polymers 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 7
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 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
- 238000007605 air drying Methods 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 235000005822 corn Nutrition 0.000 claims description 7
- 238000012258 culturing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 238000011081 inoculation Methods 0.000 claims description 7
- 238000011068 loading method Methods 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
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 235000019198 oils Nutrition 0.000 claims description 7
- 239000004576 sand 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
- 238000005406 washing Methods 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- -1 oxygen ions Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000855 fermentation Methods 0.000 abstract description 3
- 230000004151 fermentation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000004887 air purification Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 230000000813 microbial effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 description 37
- 239000002994 raw material Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 108010029541 Laccase Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compounds Of Unknown Constitution (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a lignin phenolic resin adhesive, which is prepared by using microbial fermentation to prepare activated lignin, partially substituting phenol by reacting the activated lignin with phenol, using hyperbranched polyester as a medium, and using porous material quartz powder loaded negative ion powder to react with lignin, substituting phenol and formaldehyde; the phenolic resin adhesive prepared by the invention has the advantages of high wear resistance, high curing speed, high bonding strength, very small release amount of harmful substance formaldehyde, capability of releasing negative oxygen ions when contacting air, good air purification capability, belonging to environment-friendly high polymer materials and excellent development potential.
Description
Technical Field
The invention belongs to the technical field of chemical polymer material preparation, and particularly relates to a preparation method of a lignin phenolic resin adhesive.
Background
In modern industrial production, phenol is a petrochemical raw material with large non-renewable toxicity, which is largely used in the synthesis process of phenolic resin. Therefore, it is a hot spot of research of researchers to find an environment-friendly chemical raw material which can replace phenol. Lignin is the second largest renewable resource in nature next to cellulose, and is also the largest aromatic compound produced naturally. Lignin is a three-dimensional network structure natural aromatic compound which takes phenylpropane as a structural unit and is highly crosslinked through carbon-carbon bonds and ether bonds. Because the molecules have active functional groups such as alcoholic hydroxyl, phenolic hydroxyl and the like, the structure of the adhesive is similar to that of phenolic resin, lignin can partially replace phenol to prepare the lignin modified phenolic resin adhesive, the cost can be reduced, the aim of efficiently utilizing biomass resources is fulfilled, toxic residues such as free phenol and the like of the prepared lignin modified phenolic resin adhesive are low, and the adhesive has an environmental protection significance.
The invention discloses CN201310246863.2, a method for preparing a phenolic resin adhesive by replacing phenol with organic lignin, which mainly solves the technical problem that a large amount of non-renewable petrochemical raw materials with high toxicity are used in the preparation process of the existing phenolic resin adhesive.
The invention discloses a CN201410018573.7 patent, and discloses a preparation method of a lignin-based environment-friendly phenolic resin adhesive, which comprises the following steps: step 1, carrying out quantitative analysis on hydroxyl of the lignin raw material by using a quantitative phosphorus spectrum nuclear magnetic resonance technology, and calculating the number of active sites in the lignin raw material of unit mass when reacting with formaldehyde through phenolic hydroxyl and alcoholic hydroxyl; step 2, mixing the lignin raw material and phenol to form a raw material mixture, wherein the mass ratio of the lignin raw material to the phenol is 1: 9-8: 2 during mixing; step 3, calculating the total amount of formaldehyde; and 4, mixing the raw material mixture obtained in the step 2 with formaldehyde and an alkali solution for reaction to prepare the lignin-based environment-friendly phenolic resin adhesive. The invention enables the lignin which is a byproduct in biomass refining to be utilized in a high-valued manner on the basis of solving the problems of high cost and formaldehyde pollution of the traditional lignin-based phenolic resin adhesive product, and has great economic and social significance.
The invention discloses a patent CN201510352326.5, in particular to a method for preparing a lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO, wherein the papermaking waste liquid is treated with microwave and CuO and then filtered, the pH value is adjusted to be about = 2-3 by hydrochloric acid, the obtained product is placed in an oven to stand for a period of time at a set temperature, filtered while hot, washed to be neutral, and dried to obtain acid-out lignin for later use; taking the dried lignin to partially replace phenol, and preparing the lignin-phenolic resin adhesive through phenolization, hydroxymethylation and phenolization reactions; the invention improves the substitution rate of lignin for phenol, reduces the cost and the pollution to the environment, and the adhesive has high bonding strength and low free formaldehyde content, and all the performances of the adhesive accord with the national standard.
The phenolic resin adhesive has the defects of low wear resistance, high cost, high curing temperature, long hot pressing time and the like, and on the other hand, the preparation raw materials are non-renewable petrochemical energy products and do not have environmental protection property, and the existence of formaldehyde leads to low safety of the phenolic resin.
Disclosure of Invention
Aiming at the defects of the phenolic resin adhesive prepared in the prior art, the invention provides a preparation method of a lignin phenolic resin adhesive.
The invention is realized by the following technical scheme:
a preparation method of a lignin phenolic resin adhesive comprises the following steps:
firstly, preparing activated lignin
(1) Crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 60-70%, adding tween-80 with the mass of 0.05-0.15% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 2-3 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, and continuously culturing for 12-16 days at the culture temperature of 37-45 ℃;
(2) grinding a culture medium which is mature in culture and is removed from pleurotus pulmonarius into powder, adding acetic acid until the pH value is 3-3.5, reacting for 45-60 min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 40-50 parts of water, 0.5-0.7 part of dispersing agent 5040 and 0.2-0.3 part of defoaming agent A10 in parts by weight, firstly dispersing, stirring and uniformly mixing, then adding powdered quartz ore into a ceramic lining ball mill for ball milling, controlling the solid-liquid ratio to be (2-5): 1, selecting ceramic balls with the ball-to-material ratio of (3-5): 1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, controlling the rotating speed to be 70 r/min and the ball milling time to be 3.0-4.0 h, preparing powdered quartz slurry, then adding hydroxyethyl cellulose, and preventing the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 40-50 parts of water and 5-10 parts of hydroxyethyl fiber solution in parts by weight, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of (3-5): 1, and performing ball milling for 1-2 hours to obtain negative ion agent slurry;
(3) mixing the powdered quartz slurry and the anion slurry according to the mass ratio of (12-25) to 1, adding the mixture into a sand mill, wherein the ball material ratio is (3-5): 1, grinding the zirconium balls for 30-60 min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 20-30 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting in an oil bath at the constant temperature of 210 ℃, adding trimesic acid and 0.1-0.5 part of stannous octoate; heating and stirring for 3.0-5.0 h, vacuumizing, maintaining strong stirring for reaction for 1.0-2.0 h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtering, and drying at 100 ℃ for 40-60 h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
According to the weight portion ratio, 20-30 parts of activated lignin, 24-40 parts of quartz-anion composite powder, 1-5 parts of hyperbranched polyester solid, 15-20 parts of phenol, 1-5 parts of sodium hydroxide, 20-25 parts of formaldehyde and 20-50 parts of water are uniformly mixed and added into a reactor, the temperature is increased to 80-100 ℃, and the lignin phenolic resin adhesive is obtained after a constant temperature reaction for 1-2 hours.
The solid-state fermentation of the reed residues by the pseudomonas aeruginosa and the phoenix mushroom can effectively decompose cellulose and lignin in the reed residues; the rhamnolipid generated by the fermentation of pseudomonas aeruginosa can promote the decomposition of reed residue lignin by laccase secreted by pleurotus pulmonarius, and the contents of hydroxymethyl, phenolic hydroxyl and alcoholic hydroxyl on lignin molecules are increased through activation, so that the polymerization degree of lignin and phenolic resin is increased.
The quartz main component is silicon dioxide, has porous performance, can load more negative oxygen ions, adsorbs free formaldehyde and phenol, simultaneously, the negative ion powder is contacted with moisture or oxygen in the air, releases the negative oxygen ions after ionization, and improves the air quality; the porous structure of the quartz can be combined with hyperbranched polyester, so that the polymerization degree of the phenolic resin adhesive is further improved. When the addition amount of the negative ions is between 4 and 8 percent, the formaldehyde purification rate is between 91 and 94 percent, and the purification rate changes slightly after the addition amount of the negative ions exceeds 8 percent, but the combination rate of the negative ion powder and the quartz powder is reduced along with the increase of the addition amount of the negative ion powder, so that the addition amount of the negative ion powder is preferably 4 to 8 percent.
The hyperbranched polyester has a highly branched molecular structure, multiple groups and high solubility and low viscosity, and can effectively improve the polymerization speed of the phenolic resin and the strength of the resin adhesive; meanwhile, the compound has the characteristic of various groups, so that free phenol and formaldehyde can be more combined, and the release of the phenol and the formaldehyde is reduced, so that the environmental safety is improved; on the other hand, the addition of the lignin and silicon powder composite affects the gelling performance of the phenolic resin, and the hyperbranched polyester can eliminate the effect.
As a further improvement of the invention, the pseudomonas aeruginosa in the step one (1) is activated and cultured for 12-16 h at 37 ℃ and 200rpm in an erlenmeyer flask with the liquid loading amount of 20% of the activation medium and with the inoculation amount of 5%.
As a further improvement of the invention, the activation medium is prepared by the following components with the concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L and 1.5g/L NaCl, and adjusting the pH value to 6.5-7.0.
In the optimal culture medium, the average yield of rhamnolipid obtained by the fermentation of pseudomonas aeruginosa is 30.41-34.52 g/L.
As a further improvement of the invention, the fineness of the powdered quartz ore in the step two (1) is 200-300 meshes.
The particle size of the quartz powder determines the dispersing performance and the adsorption performance, the smaller the particle size, the better the dispersion but the low adsorption capacity, so that in order to better disperse and adsorb the anion powder, the quartz powder with 200-300 meshes is best.
As a further improvement of the invention, the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid in the third step is (2-4): 1.
The molar ratio of the two monomers affects the molecular weight of the hyperbranched polyester and the hyperbranched polymer of the terminal group, when the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2:1, the polyester with high terminal group dispersibility can be obtained, and more binding sites (groups) are provided, so that the resin reaction polymerization speed, the resin strength and the wear resistance are promoted.
As a further improvement of the invention, the usage ratio of the quartz-anion composite powder to the hyperbranched polyester solid in the step four is (8-15): 1.
the content of the hyperbranched polyester affects the whole curing conversion rate of the resin, the curing conversion rate of the resin with high content is low, the bonding strength and the wear resistance of the resin with low content are low, when the content of the hyperbranched polyester is 5-15%, the curing conversion rate of the phenolic resin is 95-98%, the change rate of the wear resistance and the bonding strength is small, and the influence on the performance of the whole resin is small.
The invention has the beneficial effects that:
1. the preparation process of the invention has low requirement, does not need high-cost equipment and raw materials, and has good economic benefit;
2. the phenolic resin adhesive prepared by the invention is safe and reliable, has low formaldehyde release amount, can release beneficial negative oxygen ions, has low environmental pollution and meets the requirements of people on environment-friendly materials;
3. the phenolic resin adhesive prepared by the invention has the advantages of high abrasion resistance, high curing speed, low required hot pressing temperature, high bonding strength and excellent water and weather resistance.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Firstly, preparing activated lignin
(1) Taking and crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 60%, adding tween-80 with the mass of 0.05% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 2 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, and continuously culturing for 12 days, wherein the culture temperature is kept at 37 ℃;
the pseudomonas aeruginosa is firstly put into a conical flask with the liquid loading amount of 20% of the activation culture medium, the inoculation amount is 5%, and the pseudomonas aeruginosa is activated and cultured for 12 hours at 37 ℃ and 200 rpm; the activation medium consists of the following concentrationsThe component substances are prepared as follows: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L and 1.5g/L of NaCl, and adjusting the pH value to 6.5;
(2) grinding the culture medium which is mature in culture and is removed from the phoenix mushroom into powder, adding acetic acid until the pH value is 3, reacting for 45min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 40 parts of water, 0.5 part of a dispersing agent 5040 and 0.2 part of a defoaming agent A10 according to parts by weight, firstly dispersing, stirring and uniformly mixing, then adding 200-mesh powdered quartz ore into a ceramic lining ball mill for ball milling, controlling the solid-to-liquid ratio to be 2:1, selecting ceramic balls with the ball-to-material ratio of 3:1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, preparing powdered quartz slurry at the rotating speed of 70 revolutions per minute and the ball milling time of 3.0 hours, then adding hydroxyethyl cellulose to prevent the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 40 parts of water and 5 parts of hydroxyethyl fiber solution according to the weight part ratio, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of 3:1, and performing ball milling for 1h to obtain negative ion agent slurry;
(3) mixing powdered quartz slurry and anion slurry according to the mass ratio of 12: 1, mixing, adding into a sand mill, and adding into a ball mill according to a ball-material ratio of 3:1, grinding the zirconium balls for 30min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 20 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting the mixture in an oil bath at the temperature of 210 ℃ at constant temperature, adding trimesic acid (the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2: 1), and adding 0.1 part of stannous octoate; heating and stirring for 3.0h, vacuumizing, keeping strong stirring for reaction for 1.0h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtration, and drying at 100 ℃ for 40h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
Uniformly mixing 20 parts of activated lignin, 24 parts of quartz-anion composite powder, 3 parts of hyperbranched polyester solid, 15 parts of phenol, 1 part of sodium hydroxide, 20 parts of formaldehyde and 20 parts of water according to the parts by weight, adding the mixture into a reactor, heating to 80 ℃, and reacting at constant temperature for 1 hour to obtain the lignin phenolic resin adhesive;
example 2
Firstly, preparing activated lignin
(1) Taking and crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 70%, adding tween-80 with the mass of 0.15% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 3 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, and continuously culturing for 16 days at the culture temperature of 45 ℃;
the pseudomonas aeruginosa is firstly put into a conical flask with the liquid loading amount of 20% of the activation culture medium, the inoculation amount is 5%, and the pseudomonas aeruginosa is activated and cultured for 16 hours at 37 ℃ and 200 rpm; the activation medium is prepared from the following components in concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L NaCl 1.5g/L, adjusting pH to 7.0
(2) Grinding the culture medium which is mature in culture and is removed from the phoenix mushroom into powder, adding acetic acid until the pH value is 3.5, reacting for 60min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 50 parts of water, 0.7 part of a dispersing agent 5040 and 0.3 part of a defoaming agent A10 in parts by weight, firstly dispersing, stirring and uniformly mixing, then adding powdered quartz ore with the fineness of 300 meshes, ball-milling in a ceramic lining ball mill, controlling the solid-to-liquid ratio to be 5:1, selecting ceramic balls with the ball-to-material ratio of 5:1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, preparing powdered quartz slurry at the rotation speed of 70 r/min and the ball-milling time of 4.0h, then adding hydroxyethyl cellulose, and preventing the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 50 parts of water and 10 parts of hydroxyethyl fiber solution in parts by weight, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of 5:1, and performing ball milling for 2 hours to obtain negative ion agent slurry;
(3) mixing the powdered quartz slurry and the negative ion slurry according to the mass ratio of 25:1, adding the mixture into a sand mill, wherein the ball material ratio is 5:1, grinding the zirconium balls for 60min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 30 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting the mixture in an oil bath at the constant temperature of 210 ℃, and adding trimesic acid (the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2: 1) and 0.5 part of stannous octoate; heating and stirring for 5.0h, vacuumizing, keeping strong stirring for reaction for 2.0h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtration, and drying at 100 ℃ for 60h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
According to the weight portion ratio, 30 portions of activated lignin, 30 portions of quartz-anion composite powder, 2 portions of hyperbranched polyester solid, 20 portions of phenol, 5 portions of sodium hydroxide, 25 portions of formaldehyde and 50 portions of water are uniformly mixed and added into a reactor, the temperature is raised to 100 ℃, and the lignin phenolic resin adhesive is obtained after a constant temperature reaction for 2 hours.
Example 3
Firstly, preparing activated lignin
(1) Taking reed stems and leaves, crushing the reed stems and leaves into reed slag, watering the reed slag to moisten the reed slag until the water content is 65 percent, adding Tween-80 accounting for 0.1 percent of the mass of the reed slag, uniformly mixing the reed slag and the Tween-80, bagging the mixture, inoculating pseudomonas aeruginosa, carrying out sterile solid culture for 3 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, continuously culturing for 14 days, and keeping the culture temperature at 40 ℃;
the pseudomonas aeruginosa is firstly put into a conical flask with the liquid loading amount of 20% of the activation culture medium, the inoculation amount is 5%, and the pseudomonas aeruginosa is activated and cultured for 14 hours at 37 ℃ and 200 rpm; the activation medium is prepared from the following components in concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L NaCl and 1.5g/L NaCl, and adjusting the pH value to 6.5-7.0
(2) Grinding the culture medium which is mature in culture and is removed from the phoenix mushroom into powder, adding acetic acid until the pH value is 3.3, reacting for 50min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 45 parts of water, 0.6 part of a dispersing agent 5040 and 0.25 part of a defoaming agent A10 according to parts by weight, firstly dispersing, stirring and uniformly mixing, then adding 220-mesh powdered quartz ore into a ceramic lining ball mill for ball milling, controlling the solid-to-liquid ratio to be 3:1, selecting ceramic balls with the ball-to-material ratio of 4:1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, preparing powdered quartz slurry at the rotating speed of 70 revolutions per minute and the ball milling time of 3.5 hours, then adding hydroxyethyl cellulose to prevent the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 45 parts of water and 8 parts of hydroxyethyl fiber solution according to the weight part ratio, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of 4:1, and performing ball milling for 1.5 hours to obtain negative ion agent slurry;
(3) mixing the powdered quartz slurry and the negative ion slurry according to the mass ratio of 20:1, adding the mixture into a sand mill, wherein the ball-material ratio is 4:1, grinding the zirconium balls for 50min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 25 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting the mixture in an oil bath at the constant temperature of 210 ℃, and adding trimesic acid (the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2: 1) and 0.4 part of stannous octoate; heating and stirring for 4.0h, vacuumizing, keeping strong stirring for reaction for 1.5h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtration, and drying at 100 ℃ for 50h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
According to the weight portion ratio, 25 portions of activated lignin, 40 portions of quartz-anion composite powder, 5 portions of hyperbranched polyester solid, 17 portions of phenol, 5 portions of sodium hydroxide, 23 portions of formaldehyde and 45 portions of water are uniformly mixed and added into a reactor, the temperature is raised to 90 ℃, and the lignin phenolic resin adhesive is obtained after a constant temperature reaction for 1.5 hours.
Example 4
Firstly, preparing activated lignin
(1) Crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 62%, adding tween-80 with the mass of 0.15% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 2 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, continuously culturing for 16 days, and keeping the culture temperature at 40 ℃;
the pseudomonas aeruginosa is firstly put into a conical flask with the liquid loading amount of 20% of the activation culture medium, the inoculation amount is 5%, and the pseudomonas aeruginosa is activated and cultured for 12 hours at 37 ℃ and 200 rpm; the activation medium is prepared from the following components in concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L NaCl and 1.5g/L NaCl, and adjusting the pH value to 6.5-7.0
(2) Grinding the culture medium which is mature in culture and is removed from the phoenix mushroom into powder, adding acetic acid until the pH value is 3.3, reacting for 50min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 42 parts of water, 0.5 part of a dispersing agent 5040 and 0.3 part of a defoaming agent A10 in parts by weight, firstly dispersing, stirring and uniformly mixing, then adding 220-mesh powdered quartz ore into a ceramic lining ball mill for ball milling, controlling the solid-to-liquid ratio to be 2:1, selecting ceramic balls with the ball-to-material ratio of 5:1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, preparing powdered quartz slurry at the rotating speed of 70 revolutions per minute and the ball milling time of 3.0 hours, then adding hydroxyethyl cellulose to prevent the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 40 parts of water and 10 parts of hydroxyethyl fiber solution according to the weight part ratio, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of 5:1, and performing ball milling for 2.0 hours to obtain negative ion agent slurry;
(3) mixing the powdered quartz slurry and the negative ion slurry according to a mass ratio of 15:1, adding the mixture into a sand mill, wherein the ball material ratio is 5:1, grinding the zirconium balls for 60min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 25 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting the mixture in an oil bath at the constant temperature of 210 ℃, and adding trimesic acid (the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2: 1) and 0.4 part of stannous octoate; heating and stirring for 5.0h, vacuumizing, keeping strong stirring for reaction for 1.0h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtration, and drying at 100 ℃ for 40h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
According to the weight portion ratio, 30 portions of activated lignin, 40 portions of quartz-anion composite powder, 4 portions of hyperbranched polyester solid, 20 portions of phenol, 6 portions of sodium hydroxide, 25 portions of formaldehyde and 30 portions of water are uniformly mixed and added into a reactor, the temperature is increased to 90 ℃, and the lignin phenolic resin adhesive is obtained after a constant temperature reaction for 1.5 hours.
Example 5
Firstly, preparing activated lignin
(1) Crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 65%, adding tween-80 with the mass of 0.15% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 3 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, continuously culturing for 16 days, and keeping the culture temperature at 40 ℃;
the pseudomonas aeruginosa is firstly put into a conical flask with the liquid loading amount of 20% of the activation culture medium, the inoculation amount is 5%, and the pseudomonas aeruginosa is activated and cultured for 12 hours at 37 ℃ and 200 rpm; the activation medium is prepared from the following components in concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L and 1.5g/L of NaCl, and adjusting the pH value to 6.5;
(2) grinding the culture medium which is mature in culture and is removed from the phoenix mushroom into powder, adding acetic acid until the pH value is 3.5, reacting for 60min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 45 parts of water, 0.7 part of a dispersing agent 5040 and 0.3 part of a defoaming agent A10 in parts by weight, firstly dispersing, stirring and uniformly mixing, then adding powdered quartz ore with the fineness of 300 meshes, ball-milling in a ceramic lining ball mill, controlling the solid-to-liquid ratio to be 4:1, selecting ceramic balls with the ball-to-material ratio of 4:1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, preparing powdered quartz slurry at the rotation speed of 70 r/min and the ball-milling time of 4.0h, then adding hydroxyethyl cellulose, and preventing the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 45 parts of water and 10 parts of hydroxyethyl fiber solution in parts by weight, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of 5:1, and performing ball milling for 2 hours to obtain negative ion agent slurry;
(3) mixing powdered quartz slurry and anion slurry according to a mass ratio of 15:1, mixing, adding into a sand mill, and adding into a ball mill according to a ball-material ratio of 3:1, grinding the zirconium balls for 50min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 30 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting the mixture in an oil bath at the constant temperature of 210 ℃, and adding trimesic acid (the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid is 2: 1) and 0.5 part of stannous octoate; heating and stirring for 4.0h, vacuumizing, keeping strong stirring for reaction for 2.0h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtration, and drying at 100 ℃ for 48h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
Uniformly mixing 30 parts of activated lignin, 30 parts of quartz-anion composite powder, 3 parts of hyperbranched polyester solid, 20 parts of phenol, 5 parts of sodium hydroxide, 25 parts of formaldehyde and 40 parts of water according to parts by weight, adding the mixture into a reactor, heating to 80 ℃, and reacting at constant temperature for 1 hour to obtain the lignin phenolic resin adhesive;
the properties of the lignin phenolic adhesives prepared in examples 1-5 are shown in Table 1.
Table 1 example phenolic resin adhesive performance
As can be seen from the data in Table 1, the formaldehyde emission and the free phenol of the lignin phenolic resin adhesive prepared by the invention meet the national standard, the bonding strength meets the national requirements of I-type and II-type boards, and the lignin phenolic resin adhesive has excellent wear resistance, water resistance and weather resistance.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made thereto by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should be considered as falling within the scope of the present invention.
Claims (6)
1. The preparation method of the lignin phenolic resin adhesive is characterized by comprising the following steps:
firstly, preparing activated lignin
(1) Crushing reed stems and leaves into reed slag, watering to moisten the reed slag until the water content is 60-70%, adding tween-80 with the mass of 0.05-0.15% of the reed slag, uniformly mixing, bagging, inoculating pseudomonas aeruginosa, performing sterile solid culture for 2-3 days to obtain a culture medium, then inoculating phoenix mushroom bacteria on the culture medium, and continuously culturing for 12-16 days at the culture temperature of 37-45 ℃;
(2) grinding a culture medium which is mature in culture and is removed from pleurotus pulmonarius into powder, adding acetic acid until the pH value is 3-3.5, reacting for 45-60 min at normal temperature, and filtering to remove solid residues to obtain activated lignin;
secondly, preparing quartz-anion composite powder
(1) Mixing 40-50 parts of water, 0.5-0.7 part of dispersing agent 5040 and 0.2-0.3 part of defoaming agent A10 in parts by weight, firstly dispersing, stirring and uniformly mixing, then adding powdered quartz ore into a ceramic lining ball mill for ball milling, controlling the solid-liquid ratio to be (2-5): 1, selecting ceramic balls with the ball-to-material ratio of (3-5): 1, sequentially adding 0.3% of dispersing agent and 0.1% of defoaming agent, controlling the rotating speed to be 70 r/min and the ball milling time to be 3.0-4.0 h, preparing powdered quartz slurry, then adding hydroxyethyl cellulose, and preventing the powdered quartz slurry from settling to obtain the powdered quartz slurry;
(2) mixing 40-50 parts of water and 5-10 parts of hydroxyethyl fiber solution in parts by weight, adding negative ion powder according to the solid-liquid ratio of 1:1, then transferring to a vertical stirring mill, sequentially adding 0.3% of dispersing agent 5040 and 0.1% of defoaming agent A10 into ceramic balls with the ball-material ratio of (3-5): 1, and performing ball milling for 1-2 hours to obtain negative ion agent slurry;
(3) mixing the powdered quartz slurry and the anion slurry according to the mass ratio of (12-25) to 1, adding the mixture into a sand mill, wherein the ball material ratio is (3-5): 1, grinding the zirconium balls for 30-60 min by a wet method, putting the zirconium balls into a centrifugal tube, washing the zirconium balls for 3-4 times by deionized water, and air-drying the zirconium balls at normal temperature to obtain quartz-anion composite powder;
thirdly, preparing hyperbranched polyester
Taking 20-30 parts of 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane according to the mass part ratio, melting in an oil bath at the constant temperature of 210 ℃, adding trimesic acid and 0.1-0.5 part of stannous octoate; heating and stirring for 3.0-5.0 h, vacuumizing, maintaining strong stirring for reaction for 1.0-2.0 h, pouring into methanol for precipitation when the reaction is finished, dissolving in tetrahydrofuran for precipitation in methanol again after filtering, and drying at 100 ℃ for 40-60 h to obtain hyperbranched polyester solid;
fourthly, preparing the lignin phenolic resin adhesive
According to the weight portion ratio, 20-30 parts of activated lignin, 24-40 parts of quartz-anion composite powder, 1-5 parts of hyperbranched polyester solid, 15-20 parts of phenol, 1-5 parts of sodium hydroxide, 20-25 parts of formaldehyde and 20-50 parts of water are uniformly mixed and added into a reactor, the temperature is increased to 80-100 ℃, and the lignin phenolic resin adhesive is obtained after a constant temperature reaction for 1-2 hours.
2. The preparation method of the lignin phenolic resin adhesive according to claim 1, wherein the lignin phenolic resin adhesive comprises the following steps: and (2) firstly, performing activation culture on the pseudomonas aeruginosa for 12-16 h at 37 ℃ and 200rpm in an erlenmeyer flask with the activation culture medium liquid loading amount of 20% and the inoculation amount of 5%.
3. The preparation method of the lignin phenolic resin adhesive according to claim 1, wherein the lignin phenolic resin adhesive comprises the following steps: and (2) the fineness of the powder quartz ore in the step (1) is 200-300 meshes.
4. The preparation method of the lignin phenolic resin adhesive according to claim 1, wherein the lignin phenolic resin adhesive comprises the following steps: and the molar ratio of the 2, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane to the trimesic acid in the step three is (2-4): 1.
5. The preparation method of the lignin phenolic resin adhesive according to claim 1, wherein the lignin phenolic resin adhesive comprises the following steps: the dosage ratio of the quartz-anion composite powder to the hyperbranched polyester solid in the step four is (8-15): 1.
6. the preparation method of the lignin phenolic resin adhesive according to claim 2, wherein the lignin phenolic resin adhesive comprises the following steps: the activation medium is prepared from the following components in concentration: 30g/L of rapeseed oil, 6g/L of corn steep liquor dry powder and NaNO36g/L，K2HPO40.9g/L，NaH2PO40.6g/L，MgSO40.3g/L，CaCl20.05g/L and 1.5g/L NaCl, and adjusting the pH value to 6.5-7.0.
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| CN111909646B (en) * | 2020-08-07 | 2021-12-17 | 湖南福湘木业有限责任公司 | Mould-proof modification method for soybean-based adhesive |
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| WO2019104815A1 (en) | 2019-06-06 |
| CN107841270A (en) | 2018-03-27 |
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