CN105111394A - High-activity lignin phenol-formaldehyde resin adhesive and preparation method therefor - Google Patents
High-activity lignin phenol-formaldehyde resin adhesive and preparation method therefor Download PDFInfo
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Abstract
The invention provides a high-activity lignin phenol-formaldehyde resin adhesive. According to the high-activity lignin phenol-formaldehyde resin adhesive, a lignin biomacromolecule raw material is dissolved and degraded by adopting an alkaline dispersant, methoxyl groups on lignin are efficiently removed by a demethylating composite catalyst (strong-nucleophile combination), and meanwhile, more phenolic hydroxyl groups can be produced on a benzene ring by adopting a reduction protecting agent under the condition of not introducing nitrogen gas. Compared with the existing patented methods, oil-bath and high-temperature conditions and high-pressure reactors are not needed, the nitrogen gas is not required to be introduced to carry out protection, and the preparation process is simpler and more feasible. The reaction is stable and is easy to control, industrial production is facilitated, the formaldehyde release of plywood reaches E0 level, and the bonding strength meets the requirements of national I-class boards, so that a new way is provided for the development of environment-friendly biomass-based wood adhesives and the resource utilization of wastes.
Description
Technical field
The present invention relates to chemical field, specifically, relate to a kind of highly active lignin phenol formaldehyde resin sizing agent and preparation method thereof.
Background technology
Wood-based plate is the model of timber efficiency utilization, is the main development direction of countries in the world timber industry for many years always.China's wood-based plate and furniture, floor turnout occupy first place in the world for years nearly ten years, all account for 50% of Gross World Product.China's wood-based plate output about 2.9 billion cubic meter in 2014, needs based Wood Adhesives to reach more than 1,500 ten thousand tons.At present, China's wood-based plate production capacity is seriously superfluous, product structure is single, of low grade, more than 95% wood-based plate gluedd joint for amino resin (being mainly urea-formaldehyde resin and modified product thereof), can only be used for furniture, floor and indoor decorating, the tackiness agent that water-fast, weather-proof Wood-based Panel Production uses is mainly resol.And the phenol that the main Price-dependent of phenolic resin starting material is higher, thus limit its widespread use.In recent years, scientific research personnel is devoted to develop that the price such as xylogen is lower, the biomass material Some substitute phenol of wide material sources, and preparation price has more advantage, modified phenolic resin adhesive of good performance.
Xylogen is the three-dimensional space net structure polymer of height cladodification, and this unformed supramolecular structure is primarily of pockwood fundamental mode, Syringa oblata Lindl. fundamental mode and be formed by connecting by the chemical bond of more than ten types is random to oxybenzene fundamental mode three kinds of phenylpropyl alcohol structural units.Because its supramolecular structure is complicated, molecular structure is random, active group is less and sterically hindered comparatively large, cause its higher value application difficulty larger.The more avtive spot of xylogen does not come out or is occupied by other groups, and larger is sterically hindered, and making the reactive behavior of xylogen lower, causing when preparing phenolic resin adhesive, the amount that xylogen substitutes phenol is lower.The gordian technique that based Wood Adhesives prepared by lignin modification resol is the activation treatment of xylogen.The xylogen activation method reported comprises methylolation, phenolate modification and demethylation reaction.
From rear lignin molecule structural changes before modified, hydroxymethylation and phenolate reaction do not increase lignin molecule avtive spot quantity, are only increased the activity in original site.As patent ZL201310082995.6 (CN103131022A) adopts the method for phenolate modification, xylogen macromole generation phenolate is degraded, obtains xylogen phenolate product, may be used for preparing lignin modification resol.And patent ZL200810198614.X (CN101358120A) adopts alkaline hydrolysis, degraded, nucleophilic addition, namely hydroxymethylation carries out modification to alkali lignin, prepares alkali lignin modified phenolic resin sizing agent with phenol, formaldehyde copolymer.
And demethylation reaction had both added avtive spot quantity on lignin molecule turn increases active site activity.Analyze from composition principle, demethylation modification technology is the most remarkable to xylogen activation effect.But it is pointed out that prior art is high-temperature and high-pressure conditions, passing into nitrogen as under shielding gas condition, and the demethylation reaction under catalyst action.In xylogen demethylation study on the modification, publication number is that CN102936323A patent application adopts phenolic compound as solvent, then nucleophilic reagent (oxyhydroxide, sulfide, sulfohydrate, sulphite, hydrosulphite, vitriol, hydrosulfate, H2S, H2SO3, H2SO4) is added, by the α ~ aryl ethers in xylogen, α ~ alkyl oxide, phenolic β ~ aryl ethers, containing the ether bond rupture in the non-phenolic β ~ aryl ethers of α ~ alcoholic extract hydroxyl group and methyl aryl ether, xylogen macromole is degraded preferably.Patent ZL201110150520.7 (CN102250363A) adopts the organic solvent such as mercaptan and dimethyl formamide lignin dissolution to be obtained alcohol dissolubility xylogen, and adds basic catalyst and carry out demethylation reaction in organic solvent.Reaction needs under nitrogen protection, reacts, temperature 80 ~ 150 DEG C, react 1 ~ 3 hour in oil bath, and be diluted with water to pH=2 after reaction terminates, centrifugation obtains Demethylated lignin.Equally, patent ZL201410086068.6 (CN104293258A) discloses a kind of papermaking wastewater first to carry out concentrating to obtain concentrating spent liquor, and add the vulcanizing agents such as sodium sulphite, lithium sulfide, ammonium sulfide and carry out demethoxylation process, obtain demethoxylated waste liquid, last and phenol formaldehyde (PF) reacts the method preparing resol and the tackiness agent adopting the method to produce, and the temperature of wherein demethylation process is at 240 ~ 260 DEG C.
Be not difficult to find out thus, prior art is high-temperature and high-pressure conditions, is passing into nitrogen as under shielding gas condition, and the demethylation reaction under catalyst action, operating procedure is complicated, and cost is higher, and commercial viability is lower.And because xylogen supramolecular structure is complicated, molecular structure is random, active group is less and sterically hindered comparatively large, making the reactive behavior of xylogen lower, causing when preparing phenolic resin adhesive, the amount that xylogen substitutes phenol is lower.
Summary of the invention
In order to solve problems of the prior art, the object of this invention is to provide a kind of highly active lignin phenol formaldehyde resin sizing agent and preparation method thereof.
In order to realize the object of the invention, first the present invention provides a kind of highly active lignin phenol formaldehyde resin sizing agent, and its preparation method comprises the steps:
1) xylogen condition of normal pressure demethylation pre-treatment:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed stir, add demethylation composite catalyst (strong nucleophilic reagent combination), reduction protection agent and water high-speed stirring again afterwards, carry out demethylation process;
2) synthesis of Resin adhesive:
Phenol is added, first formaldehyde solution and water after reducing stir speed (S.S.), under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
3) in reactor, add second batch formaldehyde solution and first basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
4) in reactor, add the 3rd batch of formaldehyde solution and second batch basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
5) in reactor, add formaldehyde trapping agent, under 65 ~ 75 DEG C of conditions, be cooled to 20 ~ 40 DEG C of dischargings after reaction 10 ~ 20min, obtain highly active lignin phenol formaldehyde resin sizing agent.
Further, described step 1) be:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed mechanical stirring; stir speed (S.S.) 1000 ~ 1200r/min; stir 20 ~ 40min; afterwards demethylation composite catalyst (strong nucleophilic reagent combination), reduction protection agent and water are added reactor under 90 ~ 95 DEG C of conditions; high speed machine stirs; stir speed (S.S.) 1000 ~ 1200r/min, carries out demethylation processing reaction 50 ~ 80min.
Further, described step 2) be:
Phenol is added, first formaldehyde solution and water after stir speed (S.S.) being reduced to 200 ~ 400r/min, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min.
Further, the mass substitution rate of xylogen Pyrogentisinic Acid is 10% ~ 50%; Alkaline dispersing agent add-on is 10% ~ 20% of xylogen raw materials quality; Demethylation composite catalyst add-on is 5% ~ 15% of xylogen raw materials quality; Reduction protection agent add-on is 1% ~ 5% of xylogen raw materials quality; Two batches of basic solutions add that total mass is phenol and xylogen raw material total mass 10% ~ 20%, and two batches of basic solutions successively add mass ratio is 1:2; Water add-on controls 42% ~ 52% with the solid content meeting whole system.Control the additional proportion of formaldehyde: at the end of second step is reinforced, the mass ratio of formaldehyde solution/(phenol+xylogen raw material) is 0.2 ~ 0.38; At the end of 3rd step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.4 ~ 0.7; At the end of 4th step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.8 ~ 1.0.
Further, described xylogen raw material is the one in papermaking alkali xylogen, sulfonated lignin, enzymic hydrolysis xylogen and organic solvent xylogen.
Further, described alkaline dispersing agent is organic bases, is selected from the one in sodium methylate, sodium tert-butoxide and triethylamine.
Further, described demethylation composite catalyst (strong nucleophilic reagent combination) is made up of inorganic sulphide reagent and organic sulfide reagent, described inorganic sulphide reagent is any one in sulphur, S-WAT and Sodium sulfhydrate, described organic sulfide reagent is any one in sodium methyl mercaptide, benzyl sulfhydrate and n-dodecyl mereaptan, and the mass ratio of inorganic sulphide reagent and organic sulfide reagent is 1:1 ~ 3:1.
Further, described reduction protection agent is strong reductant, is selected from the one in sodium borohydride, hydrazine hydrate and lithium aluminum hydride.
Further, the described basic solution one that to be sodium hydroxide, potassium hydroxide and concentration be in the baryta water of 40%.
Present invention also offers a kind of preparation method of highly active lignin phenol formaldehyde resin sizing agent, specifically comprise the steps:
1) xylogen condition of normal pressure demethylation pre-treatment:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed stir, add demethylation composite catalyst (strong nucleophilic reagent combination), reduction protection agent and water high-speed stirring again afterwards, carry out demethylation process;
2) synthesis of Resin adhesive:
Phenol is added, first formaldehyde solution and water after reducing stir speed (S.S.), under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
3) in reactor, add second batch formaldehyde solution and first basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
4) in reactor, add the 3rd batch of formaldehyde solution and second batch basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
5) in reactor, formaldehyde trapping agent is added, under 65 ~ 75 DEG C of conditions, reaction 10 ~ 20min; Be cooled to 20 ~ 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Beneficial effect of the present invention is:
The present invention adopts organic bases xylogen good solvent to dissolve xylogen supramolecule complex construction; and realize initial breakdown by high speed machine stirring; efficiently deviate from the methoxyl group on xylogen by demethylation composite catalyst (strong nucleophilic reagent combination), adopt reduction protection agent making phenyl ring to generate more phenolic hydroxyl group under passing into condition of nitrogen gas simultaneously.Compared with prior art, do not need oil bath hot conditions and autoclave, without the need to passing into nitrogen protection, preparation technology is simple possible more.Reacting balance is easy to control, easy suitability for industrialized production, and glued board burst size of methanal reaches E0 level, and bonding strength reaches the requirement of national I class plate, for the exploitation of environment friendly biological matter base timber adhesive and the recycling of waste provide new approach.
The present invention adopts multicomponent system Molecular Structure Design technology, by process parameter optimizings such as differential responses stage mol ratio, temperature of reaction, reaction times, the high mixture ratio realizing the low cost raw materials such as the regulation and control of biomass-based molecular resin amount and xylogen uses, and wherein the substitution rate of xylogen Pyrogentisinic Acid is 10% ~ 50%.According to Beijing area market quotes in 2015: phenol market value 11000 yuan/ton; And xylogen market value 800 ~ 2000 yuan/ton.The present invention makes full use of lignin portion and substitutes phenol and prepare xylogen high mixture ratio modified phenolic resin adhesive, has certain environment and economy and is worth.
Embodiment
Xylogen raw material used in following examples is commercial obtaining, without the need to through extracting and pre-treatment; Alkaline dispersing agent is organic bases as the one in sodium methylate, sodium tert-butoxide, triethylamine; The assembly that demethylation composite catalyst (strong nucleophilic reagent combination) is inorganic sulphide reagent and organic sulfide reagent, inorganic sulphide reagent is: any one in sulphur, S-WAT, Sodium sulfhydrate, and organic sulfide reagent comprises: any one of sodium methyl mercaptide, benzyl sulfhydrate, n-dodecyl mereaptan; Reduction protection agent is strong reductant as the one in sodium borohydride, hydrazine hydrate, lithium aluminum hydride; Basic solution is the one in the aqueous solution of sodium hydroxide, potassium hydroxide, hydrated barta 40% concentration.About concentration of formaldehyde: existing commercially available formaldehyde solution concentration is all between 35 ~ 37%wt, and the concentration of the formaldehyde solution mentioned in embodiment is 36.8%wt.Phenol is commercially available analytical pure, and massfraction is 99%.In addition, the proportionlity in the present invention, as: the mass substitution rate of xylogen Pyrogentisinic Acid is 10% ~ 50%, that is: tree bark powder/(xylogen+phenol)=0.1 ~ 0.5; Alkaline dispersing agent add-on is 10% ~ 20% of lignin quality, that is: alkaline dispersing agent/xylogen=0.1 ~ 0.2 etc.
Under a kind of xylogen condition of normal pressure, demethylation modification is prepared the method preparation process of Phenolic resin wood adhesive and is: 1) xylogen demethylation pre-treatment: by xylogen raw material, alkaline dispersing agent and water add reactor high speed mechanical stirring, stir speed (S.S.) 1000 ~ 1200r/min, stir 20 ~ 40min, lignin molecule is made fully to discongest in the basic conditions and localized degradation, add demethylation composite catalyst (strong nucleophilic reagent combination) afterwards, reduction protection agent and water add reactor under 90 ~ 95 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1000 ~ 1200r/min, carry out demethylation processing reaction 50 ~ 80min, 2) synthesis of Resin adhesive: stir speed (S.S.) is reduced to 200 ~ 400r/min and adds phenol, first formaldehyde solution and water, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min, 3) in reactor, add second batch formaldehyde solution and first basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min, 4) in reactor, add the 3rd batch of formaldehyde solution and second batch basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min, 5) in reactor, formaldehyde trapping agent is added, under 65 ~ 75 DEG C of conditions, reaction 10 ~ 20min, be cooled to 20 ~ 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
The mass substitution rate of above-mentioned xylogen Pyrogentisinic Acid is 10% ~ 50%; Alkaline dispersing agent add-on is 10% ~ 20% of lignin quality; Demethylation composite catalyst add-on is 5% ~ 15% of lignin quality; Reduction protection agent add-on is 1% ~ 5% of lignin quality; Two batches of basic solutions add that total mass is phenol and xylogen total mass 10% ~ 20%, and two batches of basic solutions add mass ratio is 1:2; Water add-on controls 42% ~ 52% with the solid content meeting whole system.Control the additional proportion of formaldehyde: at the end of second step is reinforced, the mass ratio of formaldehyde solution/(phenol+xylogen raw material) is 0.2 ~ 0.38; At the end of 3rd step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.4 ~ 0.7; At the end of 4th step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.8 ~ 1.0.
Embodiment 1
1) 94g papermaking alkali xylogen, 10g sodium methylate and 70g water are added 1000mL reactor high speed mechanical stirring, stir speed (S.S.) 1000r/min, stir 20min, add 9g sulphur afterwards and 5g sodium methyl mercaptide, 1g sodium borohydride and 10g water add reactor under 93 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1000r/min, carries out demethylation processing reaction 50min;
2) 94g phenol is added 1000mL reactor, stir speed (S.S.) is reduced to 250r/min, 67.6g formaldehyde solution and 10g water, under 85 DEG C of conditions, and reaction 60min;
3) in reactor, add the NaOH solution of 43.3g formaldehyde solution and 4.3g40%wt concentration, under 85 DEG C of conditions, reaction 60min;
4) in reactor, add the NaOH solution of 70.6g formaldehyde solution and 8.6g40%wt concentration, under 85 DEG C of conditions, reaction 50min;
5) in reactor, 2.1g urea is added, under 75 DEG C of conditions, reaction 10min; Be cooled to 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Compacting poplar three-layer glued board, tests its performance, the results are shown in table 1.
Embodiment 2
1) 94g papermaking alkali xylogen, 15g sodium tert-butoxide and 70g water are added 1000mL reactor high speed mechanical stirring, stir speed (S.S.) 1000r/min, stir 20min, add 7g S-WAT afterwards and 7g benzyl sulfhydrate, 2g hydrazine hydrate and 10g water add reactor under 90 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1000r/min, carries out demethylation processing reaction 50min;
2) 94g phenol is added 1000mL reactor, stir speed (S.S.) is reduced to 200r/min, 68.5g formaldehyde solution and 8g water, under 80 DEG C of conditions, and reaction 50min;
3) in reactor, add the NaOH solution of 41g formaldehyde solution and 4.3g40%wt concentration, under 80 DEG C of conditions, reaction 50min;
4) in reactor, add the NaOH solution of 72g formaldehyde solution and 8.6g40%wt concentration, under 80 DEG C of conditions, reaction 60min;
5) in reactor, 2.0g urea is added, under 65 DEG C of conditions, reaction 10min; Be cooled to 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Compacting poplar three-layer glued board, tests its performance, the results are shown in table 1.
Embodiment 3
1) 94g sulfonated lignin, 10g sodium methylate and 65g water are added 1000mL reactor high speed mechanical stirring, stir speed (S.S.) 1100r/min, stir 30min, add 9g Sodium sulfhydrate afterwards and 5 n-dodecyl mereaptan, 4g lithium aluminum hydride and 15g water add reactor under 90 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1100r/min, carries out demethylation processing reaction 60min;
2) 94g phenol is added 1000mL reactor, stir speed (S.S.) is reduced to 300r/min, 66.8g formaldehyde solution and 10g water, under 75 ~ 85 DEG C of conditions, and reaction 60min;
3) in reactor, add the NaOH solution of 45g formaldehyde solution and 4.3g40%wt concentration, under 75 ~ 85 DEG C of conditions, reaction 60min;
4) in reactor, add the NaOH solution of 71g formaldehyde solution and 8.6g40%wt concentration, under 75 ~ 85 DEG C of conditions, reaction 60min;
5) in reactor, 1.7g urea is added, under 65 ~ 75 DEG C of conditions, reaction 10 ~ 20min; Be cooled to 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Compacting poplar three-layer glued board, tests its performance, the results are shown in table 1.
Embodiment 4
1) 94g enzymic hydrolysis xylogen, 15g triethylamine and 70g water are added 1000mL reactor high speed mechanical stirring, stir speed (S.S.) 1000r/min, stir 40min, add 7g sulphur afterwards and 7g n-dodecyl mereaptan, 3g sodium borohydride and 5g water add reactor under 90 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1000r/min, carries out demethylation processing reaction 50min;
2) 94g phenol is added 1000mL reactor, stir speed (S.S.) is reduced to 200r/min, 68.2g formaldehyde solution and 10g water, under 80 DEG C of conditions, and reaction 50min;
3) in reactor, add the NaOH solution of 42g formaldehyde solution and 4.3g40%wt concentration, under 80 DEG C of conditions, reaction 50min;
4) in reactor, add the NaOH solution of 71g formaldehyde solution and 8.6g40%wt concentration, under 80 DEG C of conditions, reaction 55min;
5) in reactor, 2.1g urea is added, under 70 DEG C of conditions, reaction 10 ~ 20min; Be cooled to room temperature discharging afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Compacting poplar three-layer glued board, tests its performance, the results are shown in table 1.
Embodiment 5
1) 94g organic solvent xylogen, 15g triethylamine and 70g water are added 1000mL reactor high speed mechanical stirring, stir speed (S.S.) 1200r/min, stir 30min, add 9g S-WAT afterwards and 5g sodium methyl mercaptide, 1g hydrazine hydrate and 10g water add reactor under 90 DEG C of conditions, high speed machine stirs, stir speed (S.S.) 1000r/min, carries out demethylation processing reaction 70min;
2) 94g phenol is added 1000mL reactor, stir speed (S.S.) is reduced to 400r/min, 67.6g formaldehyde solution and 10g water, under 85 DEG C of conditions, and reaction 80min;
3) in reactor, add the NaOH solution of 43.3g formaldehyde solution and 4.3g40%wt concentration, under 85 DEG C of conditions, reaction 80min;
4) in reactor, add the NaOH solution of 70.6g formaldehyde solution and 8.6g40%wt concentration, under 85 DEG C of conditions, reaction 80min;
5) in reactor, 2.5g urea is added, under 75 DEG C of conditions, reaction 20min; Be cooled to room temperature discharging afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
Compacting poplar three-layer glued board, tests its performance, the results are shown in table 1.
Table 1 tree bark powder, urea modified phenolic resin sizing agent and plywood character thereof
| Label | Resin | Xylogen Pyrogentisinic Acid substitution rate | Bonding strength/MPa | Qualification rate/% | Burst size of methanal/mg/L |
| Blank sample 1 | PF | 50％ | 1.25 | 100 | 0.4 |
| Blank sample 2 | LPF | 50％ | 0.94 | 100 | 0.9 |
| Embodiment 1 | LPF～S | 50％ | 0.95 | 100 | 0.5 |
| Embodiment 2 | LPF～NaSH | 50％ | 1.00 | 100 | 0.7 |
| Embodiment 3 | LPF～Na 2SO 3 | 50％ | 1.15 | 100 | 0.4 |
| Embodiment 4 | LPF ~ n-dodecyl mereaptan | 50％ | 1.01 | 100 | 0.8 |
| Embodiment 5 | LPF～CH 3SNa | 50％ | 1.05 | 100 | 0.7 |
Above-mentioned blank sample 1 (PF resin) is common commercial phenolic resin, and blank sample 2 (LPF resin) is not for adopt demethylation modified technique, and alkali lignin raw material directly substitutes lignin phenol formaldehyde resin sizing agent prepared by phenol.
Above-mentioned glued board is poplar three-layer glued board.Veneer spread is 250 ~ 300g/m
2, preload pressure 0.8MPa, precompressed 30min, hot pressing temperature 135 DEG C, hot pressing pressure 1.0MPa, hot pressing time 6min.
The detection of above-mentioned Resin adhesive: bonding strength is pressed type Ⅰ plywood method in GB/T9846 ~ 2004 and detected; The condensed steam water that burst size of methanal is pressed in GB/T17657 ~ 1996 detects.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a highly active lignin phenol formaldehyde resin sizing agent, it is characterized in that, its preparation method comprises the steps:
1) xylogen condition of normal pressure demethylation pre-treatment:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed stir, add demethylation composite catalyst, reduction protection agent and water high-speed stirring again afterwards, carry out demethylation process;
2) synthesis of Resin adhesive:
Phenol is added, first formaldehyde solution and water after reducing stir speed (S.S.), under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
3) in reactor, add second batch formaldehyde solution and first basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
4) in reactor, add the 3rd batch of formaldehyde solution and second batch basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
5) in reactor, add formaldehyde trapping agent, under 65 ~ 75 DEG C of conditions, be cooled to 20 ~ 40 DEG C of dischargings after reaction 10 ~ 20min, obtain highly active lignin phenol formaldehyde resin sizing agent.
2. sizing agent according to claim 1, is characterized in that, described step 1) be:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed mechanical stirring; stir speed (S.S.) 1000 ~ 1200r/min; stir 20 ~ 40min; afterwards demethylation composite catalyst, reduction protection agent and water are added reactor under 90 ~ 95 DEG C of conditions; high speed machine stirs; stir speed (S.S.) 1000 ~ 1200r/min, carries out demethylation processing reaction 50 ~ 80min.
3. sizing agent according to claim 1, is characterized in that, described step 2) be:
Phenol is added, first formaldehyde solution and water after stir speed (S.S.) being reduced to 200 ~ 400r/min, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min.
4. the sizing agent according to any one of claims 1 to 3, is characterized in that, the mass substitution rate of xylogen Pyrogentisinic Acid is 10% ~ 50%; Alkaline dispersing agent add-on is 10% ~ 20% of xylogen raw materials quality; Demethylation composite catalyst add-on is 5% ~ 15% of xylogen raw materials quality; Reduction protection agent add-on is 1% ~ 5% of xylogen raw materials quality; Two batches of basic solutions add that total mass is phenol and xylogen raw material total mass 10% ~ 20%, and two batches of basic solutions successively add mass ratio is 1:2; Water add-on controls 42% ~ 52% with the solid content meeting whole system; Control the additional proportion of formaldehyde: at the end of second step is reinforced, the mass ratio of formaldehyde solution/(phenol+xylogen raw material) is 0.2 ~ 0.38; At the end of 3rd step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.4 ~ 0.7; At the end of 4th step is reinforced, the mass ratio of accumulative formaldehyde solution/(phenol+xylogen raw material) added is 0.8 ~ 1.0.
5. sizing agent according to claim 4, is characterized in that, described xylogen raw material is the one in papermaking alkali xylogen, sulfonated lignin, enzymic hydrolysis xylogen and organic solvent xylogen.
6. sizing agent according to claim 4, is characterized in that, described alkaline dispersing agent is organic bases, is selected from the one in sodium methylate, sodium tert-butoxide and triethylamine.
7. sizing agent according to claim 4, it is characterized in that, described demethylation composite catalyst is made up of inorganic sulphide reagent and organic sulfide reagent, described inorganic sulphide reagent is any one in sulphur, S-WAT and Sodium sulfhydrate, described organic sulfide reagent is any one in sodium methyl mercaptide, benzyl sulfhydrate and n-dodecyl mereaptan, and the mass ratio of inorganic sulphide reagent and organic sulfide reagent is 1:1 ~ 3:1.
8. sizing agent according to claim 4, is characterized in that, described reduction protection agent is strong reductant, is selected from the one in sodium borohydride, hydrazine hydrate and lithium aluminum hydride.
9. sizing agent according to claim 4, is characterized in that, the described basic solution one that to be sodium hydroxide, potassium hydroxide and concentration be in the baryta water of 40%.
10. a preparation method for highly active lignin phenol formaldehyde resin sizing agent, is characterized in that, specifically comprise the steps:
1) xylogen condition of normal pressure demethylation pre-treatment:
Xylogen raw material, alkaline dispersing agent and water are added reactor high speed stir, add demethylation composite catalyst, reduction protection agent and water high-speed stirring again afterwards, carry out demethylation process;
2) synthesis of Resin adhesive:
Phenol is added, first formaldehyde solution and water after reducing stir speed (S.S.), under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
3) in reactor, add second batch formaldehyde solution and first basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
4) in reactor, add the 3rd batch of formaldehyde solution and second batch basic solution, under 75 ~ 85 DEG C of conditions, reaction 50 ~ 80min;
5) in reactor, formaldehyde trapping agent is added, under 65 ~ 75 DEG C of conditions, reaction 10 ~ 20min; Be cooled to 20 ~ 40 DEG C of dischargings afterwards, obtain highly active lignin phenol formaldehyde resin sizing agent.
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| CN105754527A (en) * | 2016-03-21 | 2016-07-13 | 常州大学 | Phenolic resin adhesive containing demethylated lignin and preparation method of phenolic resin adhesive |
| CN105960988A (en) * | 2016-05-11 | 2016-09-28 | 丁广礼 | Deep pool lotus rhizome planting method |
| CN107177026A (en) * | 2017-06-22 | 2017-09-19 | 南京工业大学 | A kind of resorcinol phenol formaldehyde resin adhesive of lignin-base containing demethylation and preparation method thereof |
| CN109135862A (en) * | 2018-07-09 | 2019-01-04 | 安徽大地节能科技有限公司 | A kind of biomass fuel binder and preparation method thereof |
| CN110041481A (en) * | 2019-05-22 | 2019-07-23 | 南京林业大学 | A kind of demethylation lignin phenol formaldehyde resin adhesive modified using halogen acid |
| CN111040689A (en) * | 2019-12-24 | 2020-04-21 | 江南大学 | Long-chain alkylphenol and phenol synergistic modified lignin-based phenolic resin adhesive |
| CN111100581A (en) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111205798A (en) * | 2020-03-10 | 2020-05-29 | 江南大学 | Lignin pyrolytic phenol-based resin adhesive and preparation method thereof |
| CN111793456A (en) * | 2020-07-20 | 2020-10-20 | 广西众人投资有限公司 | Lignin modified phenolic glue and preparation method thereof |
| CN114316898A (en) * | 2021-10-21 | 2022-04-12 | 西南林业大学 | Preparation method of hyperbranched polyamine modified lignin adhesive |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250088A (en) * | 1979-08-20 | 1981-02-10 | American Can Company | Demethylated lignin and process |
| US5026808A (en) * | 1989-04-03 | 1991-06-25 | Colorado State University Research Foundation | Method for recovering and using lignin in adhesive resins by extracting demethylated lignin |
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN102250363A (en) * | 2011-06-07 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Modification method of lignin |
| CN103130972A (en) * | 2011-11-28 | 2013-06-05 | 济南圣泉集团股份有限公司 | Thermoplastic phenolic resin and preparation method thereof |
| CN104293258A (en) * | 2014-03-10 | 2015-01-21 | 黄淮学院 | Method for resource utilization of papermaking waste liquid, and adhesive produced by the same |
-
2015
- 2015-08-18 CN CN201510509679.1A patent/CN105111394B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250088A (en) * | 1979-08-20 | 1981-02-10 | American Can Company | Demethylated lignin and process |
| US5026808A (en) * | 1989-04-03 | 1991-06-25 | Colorado State University Research Foundation | Method for recovering and using lignin in adhesive resins by extracting demethylated lignin |
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN102250363A (en) * | 2011-06-07 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Modification method of lignin |
| CN103130972A (en) * | 2011-11-28 | 2013-06-05 | 济南圣泉集团股份有限公司 | Thermoplastic phenolic resin and preparation method thereof |
| CN104293258A (en) * | 2014-03-10 | 2015-01-21 | 黄淮学院 | Method for resource utilization of papermaking waste liquid, and adhesive produced by the same |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754527A (en) * | 2016-03-21 | 2016-07-13 | 常州大学 | Phenolic resin adhesive containing demethylated lignin and preparation method of phenolic resin adhesive |
| CN105960988A (en) * | 2016-05-11 | 2016-09-28 | 丁广礼 | Deep pool lotus rhizome planting method |
| CN107177026A (en) * | 2017-06-22 | 2017-09-19 | 南京工业大学 | A kind of resorcinol phenol formaldehyde resin adhesive of lignin-base containing demethylation and preparation method thereof |
| CN107177026B (en) * | 2017-06-22 | 2019-03-05 | 南京工业大学 | One kind resorcinol phenol formaldehyde resin adhesive of lignin-base containing demethylation and preparation method thereof |
| CN109135862A (en) * | 2018-07-09 | 2019-01-04 | 安徽大地节能科技有限公司 | A kind of biomass fuel binder and preparation method thereof |
| CN110041481A (en) * | 2019-05-22 | 2019-07-23 | 南京林业大学 | A kind of demethylation lignin phenol formaldehyde resin adhesive modified using halogen acid |
| CN110041481B (en) * | 2019-05-22 | 2022-03-15 | 南京林业大学 | Demethylated lignin phenolic resin adhesive modified by halogen acid |
| CN111100581B (en) * | 2019-12-02 | 2020-11-06 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111100581A (en) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111040689A (en) * | 2019-12-24 | 2020-04-21 | 江南大学 | Long-chain alkylphenol and phenol synergistic modified lignin-based phenolic resin adhesive |
| US11214716B2 (en) | 2020-03-10 | 2022-01-04 | Jiangnan University | Phenol-based resin adhesive from lignin pyrolysis and its preparation method |
| CN111205798A (en) * | 2020-03-10 | 2020-05-29 | 江南大学 | Lignin pyrolytic phenol-based resin adhesive and preparation method thereof |
| CN111793456A (en) * | 2020-07-20 | 2020-10-20 | 广西众人投资有限公司 | Lignin modified phenolic glue and preparation method thereof |
| CN114316898A (en) * | 2021-10-21 | 2022-04-12 | 西南林业大学 | Preparation method of hyperbranched polyamine modified lignin adhesive |
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