CN101358120B - A kind of environment-friendly alkali lignin modified phenolic resin adhesive and preparation method thereof - Google Patents
A kind of environment-friendly alkali lignin modified phenolic resin adhesive and preparation method thereof Download PDFInfo
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- CN101358120B CN101358120B CN200810198614XA CN200810198614A CN101358120B CN 101358120 B CN101358120 B CN 101358120B CN 200810198614X A CN200810198614X A CN 200810198614XA CN 200810198614 A CN200810198614 A CN 200810198614A CN 101358120 B CN101358120 B CN 101358120B
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- alkali lignin
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- lignin
- resin adhesive
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- 229920005610 lignin Polymers 0.000 title claims abstract description 103
- 239000003513 alkali Substances 0.000 title claims abstract description 92
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 76
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical group [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical class C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 abstract 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 229950011260 betanaphthol Drugs 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 23
- 235000019256 formaldehyde Nutrition 0.000 description 22
- 238000006467 substitution reaction Methods 0.000 description 12
- 239000002023 wood Substances 0.000 description 12
- 239000003292 glue Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 9
- 235000013824 polyphenols Nutrition 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000004786 2-naphthols Chemical class 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920003987 resole Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229920001732 Lignosulfonate Polymers 0.000 description 4
- 235000019357 lignosulphonate Nutrition 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- -1 phenol modified phenolic resin Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 101100518972 Caenorhabditis elegans pat-6 gene Proteins 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- OOSUHIIJYDMCCW-UHFFFAOYSA-N cyanamide;formaldehyde Chemical compound O=C.NC#N OOSUHIIJYDMCCW-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient 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
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to an environment-friendly alkali-lignin-modified phenolic resin adhesive and a preparation method thereof. The method includes the following steps: water is added into alkali lignin powder, acid is then added, and under a temperature between 100 DEG C and 120 DEG C, acidolysis lasts for one to three hours; desugarized alkali lignin is obtained; the desugarized alkali lignin powder, sodium hydroxide and water are uniformly mixed, oxidant and 2-naphthol are added for reaction, the temperature is reduced to 45 DEG C to 50 DEG C, formaldehyde and phenol are added so that polycondensation reaction occurs, and the environment-friendly alkali-lignin-modified phenolic resin adhesive is prepared. The method adopts acidolysis desugarization to reduce a great deal of alcoholic hydroxyl content in the alkali lignin and modifies the alkali lignin by alkaline hydrolysis, degradation and nucleophilic addition reaction, thus greatly increasing the chemical reaction activity of the alkali lignin, the amount of toxic phenol required in the technique of preparing modified phenolic resin is little, and the residual phenol and formaldehyde are less, so the environment-friendly alkali-lignin-modified phenolic resin adhesive has the advantages of green production technique and product properties.
Description
Technical field
The present invention relates to a kind of synvaren; Particularly relate to a kind of environment-friendly type alkali lignin modified phenolic resin adhesive and preparation method thereof; Be that the by product alkali lignin that reclaims with alkaline process is a raw material specifically; Through desugar, degraded, nucleophilic addition(Adn) and polycondensation, the preparation alkali lignin modified phenolic resin adhesive belongs to the wood adhesive technical field.
Background technology
The wood adhesive that China uses at present is main with urea-formaldehyde resin adhesive mainly, secondly is Phenol aldehyde resin and trimeric cyanamide-formaldehyde resin.But; The main raw material of these tackiness agent all derives from petrochemicals; Non-renewable its cost that causes of oil improves day by day, and will move towards exhausted inevitably, therefore; Utilize renewable raw materials to replace petroleum, the adhesive products of preparing stable performance is the key subjects that current need are faced.
The residual formaldehyde emission of formaldehydes tackiness agent is harmful, in the world today that payes attention to environment protection, can not satisfy needs of people beyond doubt, and this just requires wood adhesive to develop to low toxicity, nontoxic direction.From the eighties in 20th century, various countries stress when tackiness agent is produced, will coordinate mutually with environmental ecology.And the existence of free formaldehyde in " three aldehyde " glue is the root of the disease that causes that human body is multiple, like trachitis, asthma, dermatitis, even duration of contact long after, cause malignant tumour.Phenol toxicity residual in the phenolic glue is big, and therefore, various countries pay special attention to the strict control of content of free formaldehyde and phenol.
Xylogen is a kind of poly phenols that extensively is present in the plant soma wall, and every year can be through synthetic about 1,500 hundred million tons of photosynthesis of plants on the earth; And derive from the industrial lignin of pulping and paper-making waste liquid, and annual output is about 5,000 ten thousand tons, wherein has only less than 10% effectively to be utilized, and other major part is all burnt through soda recovery unit, has caused the huge wasting of resources.
Owing to after xylogen is activated, have the character of phenol, can nontoxic alkali lignin be substituted phenol; Simultaneously alkali lignin is prone to and formaldehyde generation crosslinking reaction, not only improves performance of products, can also catch residual formaldehyde simultaneously, plays good pushing effect for the green preparation process of synvaren and the volatilization that reduces remaining phenol and formaldehyde; Except that the Environmental Safety angle; Alkali lignin with one ton in hundreds of unit substitutes about 8000 yuan one ton phenol; Cost is reduced greatly; Therefore, the research work of carrying out alkali lignin modified phenolic resin adhesive is all significant from environmental protection and economic benefit aspect, also is the development trend of Phenol aldehyde resin.
Utilize from Pendensen in 1963 that level shaving board sticks with glue agent outside the sulphite xylogen waste liquid preparation room; And carry out suitability for industrialized production so far; Utilize xylogen to replace the production of phenol modified phenolic resin adhesive to experience, arrive the course of chemical polycondensation modification again from simple composite composite behind the physically modified.At first, people directly are mixed and made into modified phenolic resins with black liquor or rugose wood element with resol.The seventies in 20th century, the phenol of xylogen replacement 15% is processed the used for shaving board glue that the trade mark is Karatex.But because xylogen active low, the black liquor complicated component, the amount of the alternative phenol of the xylogen of the modified lignin resin Phenol aldehyde resin that this method makes is less, poor water resistance, adhesive strength be low.Foreign matter content is high in the tradition sulphate process gained xylogen, reactive behavior is low; Therefore its xylogen Pyrogentisinic Acid's in phenol resin timber adhesive substitution rate seldom surpasses 20% (massfraction); Increase xylogen Pyrogentisinic Acid's substitution rate, must at first improve the chemical reactivity of xylogen.
Patent US4769434 mixes alkali lignin behind methylolation under the alkaline condition with resol; Make lignin phenol formaldehyde resin glue; Wherein xylogen can replace 40% phenol; Because the methylolation modification of xylogen can not significantly increase lignin structure unit activity point, is difficult to increase substantially the activity of xylogen, and is not remarkable to the performance raising effect of tackiness agent.U.S. Pat 6 632 912 has been announced the lignin phenol formaldehyde resin tackiness agent that alkali lignin is processed after the phenolate modification, wherein alkali lignin replaces the ratio of phenol can reach 60%; U.S. US 5 026 808 has announced that it can improve the active site number of xylogen largely with alkali lignin and sulphur and the heating of the NaOH aqueous solution lignin modification to the demethylation of purifying, but complicated process of preparation, equipment requirements is high, and cost is also higher.
Chinese patent (CN1632030) discloses the method that sulfonated lignin and phenol, formolite reaction prepare the composite phenol formaldehyde Resin adhesive, but sulfonated lignin do not pass through activation treatment, and xylogen Pyrogentisinic Acid's substitution rate is not high; Simultaneously, sulfonated lignin are owing to relative alkali lignin, and wetting ability is stronger relatively, and therefore, the water tolerance of the Phenol aldehyde resin of this method preparation has much room for improvement.Chinese patent CN101104782A reported the sulfonated lignin that use greater than 10000 molecular weight behind methylolation with Na
3PO
4, Na
2HPO
4, urea and NaOH be prepared into auxiliary agent, auxiliary agent forms xylogen-Phenol aldehyde resin with phenol, formolite reaction again, the amount of xylogen fortified phenol is 10～30%.Chinese patent CN1854233A has reported that draft xylogen and woody xylogen, formaldehyde, aldehydes matter prepare Phenol aldehyde resin, and xylogen is 20～35% to the substitution rate of aldehydes matter.
From disclosed patent; The key of preparation lignin modification Phenol aldehyde resin is the activation treatment of xylogen; Xylogen depends on that to the substitution rate of aldehydes matter the chemical reactivity of xylogen, the activation method of the xylogen of having reported generally include methylolation, phenolate and react to remove the methyl in the xylogen under high-temperature high-pressure state with sulphur.
The defective of alkali lignin modified preparation tackiness agent is:
1. alkali lignin is the three-dimensional netted macromolecular compound with phenol type structure; Itself have certain adhesive property, but owing to contain the ehter bond of more weak chemical bond such as β-O-4 class in the structure, so its cohesive strength is lower; Therefore; Improve the cohesive strength of lignin, the problem that needs to solve is with ether bond rupture, forms the high carbon carbon chemical bond of bond energy again.
2. alkali lignin is a tridimensional network, and more phenolic hydroxyl group is wrapped in intramolecule, owing to sterically hindered reason, makes that the chemical reactivity of alkali lignin is low, causes the amount of the alternative phenol of alkali lignin when the preparation modified phenolic resins lower.
3. the residual polysaccharose substance that contains in the alkali lignin has more alcoholic extract hydroxyl group, can cause the water tolerance of lignin modification Phenol aldehyde resin to reduce, and is reflected in the cohesive strength reduction that tackiness agent hot water boils the back test.
Summary of the invention
The objective of the invention is to poor water resistance, alkali lignin Pyrogentisinic Acid's substitution rate low, residual phenol, the aldehyde more high shortcoming of the glue-line after the alkali lignin modified modified phenolic adhesive curing with respect to Phenol aldehyde resin; A kind of environment-friendly type synvaren that activation modification through alkali lignin prepares; This tackiness agent is under the prerequisite that guarantees the good physics of resol, chemical property; Increase the water tolerance of modified alkyd resin glue and Pyrogentisinic Acid's substitution rate greatly; Reduce the production cost of phenolic glue, reduce residual phenol and content of free aldehyde in the glue simultaneously.
The principle of the invention: alkali lignin through acidolysis with remove remain in the alkali lignin polysaccharide or oligose; Through modified-reaction to alkaline hydrolysis, degraded and the nucleophilic addition(Adn) of alkali lignin; The chemical reactivity of alkali lignin is improved, corresponding functioning as follows: 1. make the ortho position isoreactivity response location that is wrapped in phenolic hydroxyl group in intramolecular active reactive group such as phenolic hydroxyl group, the phenyl ring show its reactive behavior; 2. the process of degraded causes that the methoxyl group on the phenolic hydroxyl group ortho position removes in the lignin structure unit, forms active phenolic hydroxyl group, thereby the chemically reactive of alkali lignin is improved; 3. introduce strong nucleophilic reagent 2-naphthols in the C of alkali lignin structural unit α position; Use a spot of aldehydes matter to increase the active content of phenolic hydroxyl groups of alkali lignin molecule; Improve the chemical reactivity of alkali lignin greatly; Thereby improve alkali lignin Pyrogentisinic Acid's substitution rate, the corresponding amount of phenol residual in the product and formaldehyde that makes greatly reduces.
The purpose of this invention realizes through following technical measures,
A kind of preparation method of environment-friendly type alkali lignin modified phenolic resin adhesive may further comprise the steps:
(1) in the alkali lignin powder of 800 weight parts, add the water of 4500～7500 weight parts, add the acid of 15～60 weight parts again, acidolysis is 1～3 hour under 100～120 ℃ of conditions; Filter, insolubles to constant weight, obtains the alkali lignin of desugar through washing vacuum-drying; Described acid is sulfuric acid, hydrochloric acid or trifluoroacetic acid;
(2) water of alkali lignin powder 20～80 weight parts of desugar, sodium hydroxide 4～15 weight parts, 150 weight parts is added be equipped with in the reactor drum of whisking appliance and condensing surface, stir, be heated to 80～100 ℃, constant temperature stirred 1～2 hour;
(3) product of step (2) being handled is cooled to 50～80 ℃, adds the oxygenant of 1～10 weight part, and 2～10 weight parts, 2-naphthols reacted 0.5～3 hour; Said oxygenant is sodiumperoxide, potassium permanganate, Potassium Persulphate or Potassium Persulfate;
(4) product of step (3) being handled is cooled to 45～50 ℃, adds mass concentration and be 37% formaldehyde 55～85 weight parts and the phenol of 20-80 weight part, under this temperature, stirs 30 minutes; Then; Be warming up to 80～100 ℃, carried out polycondensation 1～2 hour, and then the dropping mass concentration is 37% formaldehyde 30～50 weight parts; Continue isothermal reaction 1～3 hour, make environment-friendly type alkali lignin modified phenolic resin adhesive.
The vacuum-drying of said step (1) is 40-60 ℃ of following vacuum-drying.
Said step (4) to be warming up to 80～100 ℃ be to be warming up to 80～100 ℃ with 1～2 ℃/minute speed.
The isothermal reaction of said step (4) was whenever taken out the 10ml reactant at a distance from 5～15 minutes after 1～3 hour, was cooled to 25 ℃, surveyed its viscosity; After viscosity reaches 100～400mPa.s, be cooled to room temperature rapidly, discharging.
The environment-friendly type alkali lignin modified phenolic resin adhesive of method for preparing.The alkali lignin modified phenolic resin adhesive of the present invention preparation is applicable to be included in the wood used in the wet environment, wood veneer (as: cement formwork, container bottom board etc.) that bamboo wood is manufactured various structures and shaving board etc.
The present invention compared with prior art has following outstanding advantage and effect:
1. the present invention removes polysaccharide or oligose in the alkali lignin through acid hydrolysis method, makes the alkali lignin resol of preparation have excellent water tolerance.
2. production process of the present invention adopts the alkali lignin modified preparation synvarens of method activation such as alkaline hydrolysis, degraded and nucleophilic addition, and required phenol amount is few, and production process toxicity is little, and product good water solubility, no strange taste are nontoxic, belongs to green chemical.The modified phenolic glue of processing, free-phenol≤0.1%, free formaldehyde≤0.1%, the present invention is applicable to the alkali lignin in the industrial alkali paper-making black liquor.
3. alkali lignin Pyrogentisinic Acid's of the present invention substitution rate is high.Phenol when alternative 80% weight part of xylogen still meets the requirement that GB9846-2004I class wood veneer sticks with glue agent; Therefore, alkali lignin modified phenolic resin glue of the present invention has advantage with low cost.
Embodiment
Below in conjunction with embodiment the present invention is further described, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1
The wheat straw alkali lignin that takes by weighing 800g adds 4500ml water in flask, add the trifluoroacetic acid of 15g again, and sealing was 110 ℃ of following acidolysis 1 hour.Filter, insolubles is through washing, then 50 ℃ of following vacuum-dryings to constant weight, obtain the desugar alkali lignin.
Get exsiccant desugar alkali lignin powder 20g, add the NaOH of 4g, 150g water, controlled temperature are at 80 ℃, and constant temperature stirred 1 hour; Reaction solution is cooled to 50 ℃, adds the Potassium Persulfate of 1g, 2-naphthols of 2g, reacted 0.5 hour; Reaction solution is cooled to 45 ℃, adds mass concentration and be 37% formaldehyde 55g, phenol 80g 50 ℃ of following isothermal reactions 30 minutes, is warming up to 80 ℃, isothermal reaction 1 hour with 1 ℃/minute speed again; The dropping mass concentration is 37% formaldehyde 50g, continues isothermal reaction after 2 hours, whenever takes out the 10ml reactant at a distance from 10 minutes, is cooled to 25 ℃ and surveys its viscosity, after viscosity reaches 100mPa.s, is cooled to room temperature rapidly, discharging.
Embodiment 2
The bagasse alkali-lignin that takes by weighing 800g adds 7500ml water in flask, add the sulfuric acid acid of 60g, and sealing was 120 ℃ of following acidolysis 3 hours.Filter, insolubles is through washing, then 40 ℃ of following vacuum-dryings to constant weight, obtain the desugar alkali lignin.
Get exsiccant desugar alkali lignin powder 80g, add the NaOH of 15g, 150g water, controlled temperature are at 100 ℃, and constant temperature stirred 2 hours; Reaction solution is cooled to 80 ℃, adds the sodiumperoxide of 10g, 2-naphthols of 10g, reacted 3 hours; Add reaction solution is cooled to 50 ℃; The adding mass concentration is 37% formaldehyde 80g, and phenol 80g was 50 ℃ of following isothermal reactions 30 minutes; Be warming up to 80 ℃, isothermal reaction 2 hours with 2 ℃/minute speed again; The dropping mass concentration is 37% formaldehyde 30g, continues isothermal reaction after 1 hour, whenever takes out the 10ml reactant at a distance from 5 minutes, is cooled to 25 ℃, surveys its viscosity, after viscosity reaches 400mPa.s, is cooled to room temperature rapidly, discharging.
Embodiment 3
The wheat straw alkali lignin that takes by weighing 800g adds 4500ml water in flask, add the trifluoroacetic acid of 15g again, and sealing was 110 ℃ of following acidolysis 1 hour.Filter, insolubles is through washing, then 60 ℃ of following vacuum-dryings to constant weight, obtain the desugar alkali lignin.
Get dry alkali lignin powder 40g, add the NaOH of 12g, 150g water, controlled temperature stirred 1 hour at 100 ℃; Reaction solution is cooled to 60 ℃, adds the Potassium Persulfate of 2g, 2-naphthols of 3.5g, reacted 2 hours; The adding mass concentration is 37% formaldehyde 80g, and phenol 60g was 50 ℃ of following isothermal reactions 30 minutes; Be warming up to 80 ℃, isothermal reaction 1 hour with 1 ℃/minute speed again; The dropping mass concentration is 37% formaldehyde 30g, continues isothermal reaction after 1 hour, whenever takes out a small amount of reactant at a distance from 15 minutes, is cooled to 25 ℃ and surveys its viscosity, after viscosity reaches 350mPa.s, is cooled to room temperature rapidly, discharging.
Embodiment 4
The bagasse alkali-lignin that takes by weighing 800g adds 6000ml water in flask, add the hydrochloric acid of 50g again, and sealing was 100 ℃ of following acidolysis 2 hours.Filter, insolubles is through washing, then 50 ℃ of following vacuum-dryings to constant weight, obtain the desugar alkali lignin.
Get exsiccant desugar alkali lignin powder 80g, add the NaOH of 15g, 150g water, controlled temperature are at 100 ℃, and constant temperature stirred 2 hours; Reaction solution is cooled to 80 ℃, adds the Potassium Persulfate of 5g, 2-naphthols of 3.5g, reacted 3 hours; Add reaction solution is cooled to 45 ℃; The adding mass concentration is 37% formaldehyde 80g, and phenol 20g was 50 ℃ of following isothermal reactions 30 minutes; Be warming up to 100 ℃, isothermal reaction 1 hour with 1 ℃/minute speed again; The dropping mass concentration is 37% formaldehyde 30g, continues isothermal reaction after 1 hour, whenever takes out the 10ml reactant at a distance from 10 minutes, is cooled to 25 ℃, surveys its viscosity, after viscosity reaches 350mPa.s, is cooled to room temperature rapidly, discharging.
Embodiment 5
The wheat straw alkali lignin that takes by weighing 800g adds 4500ml water in flask, add the trifluoroacetic acid of 15g again, and sealing was 110 ℃ of following acidolysis 1 hour.Filter, insolubles is through washing, then 50 ℃ of following vacuum-dryings to constant weight, obtain the desugar alkali lignin.
Get dry alkali lignin powder 60g, add the NaOH of 12g, 150g water, controlled temperature stirred 1 hour at 100 ℃; Reaction solution is cooled to 60 ℃, adds the Potassium Persulfate of 3g, 2-naphthols of 5g, reacted 2 hours; The adding mass concentration is 37% formaldehyde 80g, and phenol 40g was 50 ℃ of following isothermal reactions 30 minutes; Be warming up to 80 ℃, isothermal reaction 1.5 hours with 1 ℃/minute speed again; The dropping mass concentration is 37% formaldehyde 30g, continues isothermal reaction after 1 hour, whenever takes out a small amount of reactant at a distance from 10 minutes, is cooled to 25 ℃ and surveys its viscosity, after viscosity reaches 350mPa.s, is cooled to room temperature rapidly, discharging.
Below use a series of tests of alkali lignin remodeling synvaren of the present invention, its effect has been described.
With the modified phenolic resin adhesive of embodiment 5 preparation with press embodiment 5 but contrast, see table 1 without the cohesive strength of the modified phenolic resin adhesive of the first step acidolysis desugar Processing of Preparation.
Table 1 desugar technology is to the influence of adhesive bonds intensity
The measurement of cohesive strength is according to the I class wood veneer bond strength testing method among " mensuration of wood veneer gummed intensity " standard GB 9846.12-88 in this patent.Boil 4 hours in the boiling water owing to test specimen is placed in the testing method, therefore, the intensity of the tackiness agent of preparation can reflect the water resistance of tackiness agent under the same conditions.
Find out by table 1; Cohesive strength through the tackiness agent of patent of the present invention preparation is 1.875MPa; And the acidolysis desugar treatment step of the alkali lignin of mentioning in this preparation method; The cohesive strength of the tackiness agent of preparation is 1.737MPa, shows that alkali lignin after the acidolysis desugar is handled, improves the cohesive strength of tackiness agent; Corresponding reflecting through the acidolysis desugar handles, and the water tolerance of the tackiness agent of alkali lignin preparation is improved.This is owing to contain a large amount of hydroxyls in oligose in the alkali lignin or the high glycan, and its wetting ability causes the water tolerance of tackiness agent to reduce, and then causes the reduction of cohesive strength.Therefore, alkali lignin related in the patent of the present invention is after the acidolysis desugar is handled, and the water tolerance of the tackiness agent that helps preparing improves.
With embodiment 3 is that the alkali lignin modified phenolic resin adhesive contrast that example prepares is seen table 2 without the cohesive strength result that activation treatment modifications such as alkali lignin degraded and nucleophilic addition(Adn) prepare synvaren.
The activation of table 2 alkali lignin is to the alkali lignin modified phenolic resin adhesive Effect on Performance
In this patent content measurement of removing residue formaldehyde phenol by national standard " wood adhesive and the resin method of inspection thereof: free formaldehyde content assay method " (GB/T14074.16-93) ", " wood adhesive and the resin method of inspection thereof: free-phenol determination " (GB/T14074.13-93) carry out.
Table 2 can be known; The cohesive strength of the tackiness agent of process alkali lignin activation treatment step preparation arrives 2.176MPa; And be 1.675MPa without the cohesive strength of the tackiness agent of alkali lignin activation step preparation, show the alkali lignin activation treatment after, activity improves greatly; Thereby the cohesive strength of the tackiness agent of preparation improves greatly, residual formaldehyde, phenol content reduces greatly.
Alkali lignin Pyrogentisinic Acid's substitution rate is respectively the modified phenolic resin adhesive of 40% (embodiment 3), 80% (embodiment 4) preparation and sees table 3 with the resol that does not use alkali lignin and with the contrast of resol national standard.
The contrast of different synvaren performances of table 3 and national standard
Arrive the national standard of synvaren fully by the alkali lignin modified synvaren of the visible the present invention's preparation of table 3; Especially cohesive strength is much higher than request of national standard, and the content of removing residue formaldehyde, phenol is significantly less than request of national standard again.On the basis of other requirement of satisfying national standard; When alkali lignin Pyrogentisinic Acid's substitution rate is 40 %; The cohesive strength of the modified phenolic resin adhesive of the present invention's preparation is suitable with the intensity of pure phenolic resin tackiness agent, about 2MPa, and when alkali lignin Pyrogentisinic Acid's substitution rate is 80%; Although the cohesive strength of the tackiness agent of preparation still substantially exceeds request of national standard with respect to the low approximately 0.5MPa of pure synvaren.
Claims (5)
1. the preparation method of an environment-friendly type alkali lignin modified phenolic resin adhesive is characterized in that may further comprise the steps:
(1) in the alkali lignin powder of 800 weight parts, add the water of 4500～7500 weight parts, add the acid of 15～60 weight parts again, acidolysis is 1～3 hour under 100～120 ℃ of conditions; Filter, insolubles to constant weight, obtains the alkali lignin of desugar through washing vacuum-drying; Described acid is sulfuric acid, hydrochloric acid or trifluoroacetic acid;
(2) water of alkali lignin powder 20～80 weight parts of desugar, sodium hydroxide 4～15 weight parts, 150 weight parts is added be equipped with in the reactor drum of whisking appliance and condensing surface, stir, be heated to 80～100 ℃, constant temperature stirred 1～2 hour;
(3) product of step (2) being handled is cooled to 50～80 ℃, adds the oxygenant of 1～10 weight part, and 2～10 weight part beta naphthals reacted 0.5～3 hour; Said oxygenant is sodiumperoxide, potassium permanganate, Potassium Persulphate or Potassium Persulfate;
(4) product of step (3) being handled is cooled to 45～50 ℃, adds mass concentration and be 37% formaldehyde 55～85 weight parts and the phenol of 20-80 weight part, under this temperature, stirs 30 minutes; Then; Be warming up to 80～100 ℃, carried out polycondensation 1～2 hour, and then the dropping mass concentration is 37% formaldehyde 30～50 weight parts; Continue isothermal reaction 1～3 hour, make environment-friendly type alkali lignin modified phenolic resin adhesive.
2. the preparation method of environment-friendly type alkali lignin modified phenolic resin adhesive according to claim 1 is characterized in that, the vacuum-drying of said step (1) is 40-60 ℃ of following vacuum-drying.
3. the preparation method of environment-friendly type alkali lignin modified phenolic resin adhesive according to claim 1 is characterized in that, said step (4) to be warming up to 80～100 ℃ be to be warming up to 80～100 ℃ with 1～2 ℃/minute speed.
4. the preparation method of environment-friendly type alkali lignin modified phenolic resin adhesive according to claim 1 is characterized in that, the isothermal reaction of said step (4) was whenever taken out the 10ml reactant at a distance from 5～15 minutes after 1～3 hour, was cooled to 25 ℃, surveyed its viscosity; After viscosity reaches 100～400mPa.s, be cooled to room temperature rapidly, discharging.
5. the environment-friendly type alkali lignin modified phenolic resin adhesive of the said method of claim 1 preparation.
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| CN106478906A (en) * | 2016-10-14 | 2017-03-08 | 安徽格义循环经济产业园有限公司 | Lignin modification phenolic resin and preparation method thereof |
| CN106947419A (en) * | 2017-03-29 | 2017-07-14 | 江南大学 | A kind of synvaren of alkali lignin self-catalysis synthesis in situ and preparation method thereof |
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