CN104130733A - Preparation method of modified biomass liquefaction resin adhesive with high water resistance - Google Patents
Preparation method of modified biomass liquefaction resin adhesive with high water resistance Download PDFInfo
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- CN104130733A CN104130733A CN201410353463.6A CN201410353463A CN104130733A CN 104130733 A CN104130733 A CN 104130733A CN 201410353463 A CN201410353463 A CN 201410353463A CN 104130733 A CN104130733 A CN 104130733A
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Abstract
The invention relates to a preparation method of a modified biomass liquefaction resin adhesive with high water resistance. The method comprises the following technological steps: Step 1, preparation of a biomass phenol liquefaction product; Step 2, preparation of biomass phenol liquefaction formaldehyde resin, namely a component A; Step 3, preparation of melamine urea-formaldehyde resin, namely a component B; and Step 4, preparation of the modified biomass liquefaction resin adhesive with high water resistance. The invention has advantages as follows: the modified biomass liquefaction resin adhesive with high water resistance is stable to store; a sizing technology and a hot-pressing technology of the adhesive provided by the invention are the same as those of a traditional phenolic resin adhesive; cost is low; toxicity is low; and water-resistant bonding strength of the biomass liquefaction resin adhesive can be greatly enhanced. It shows through tests that bonding strength mean value of a poplar plywood form test piece prepared from the adhesive prepared by the method reaches more than 1.5MPa after the poplar plywood form test piece successively undergoes 4h of water boiling, 20h of drying at 63+/-2 DEG C, 4h of water boiling and natural cooling.
Description
Technical field
The present invention relates to a kind of biological materials such as Pericarppium arachidis hypogaeae, oil tea shell, tree bark powder, nut-shell that utilize and by the outer wood-based plate of Liquefaction Products in Phenol, resinifying and modification technology preparation room, use the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance.Belong to agricultural-forestry biomass comprehensive utilization and wood adhesive technical field.
Background technology
The biological materials such as Pericarppium arachidis hypogaeae, oil tea shell, tree bark powder, nut-shell all contain the compositions such as abundant xylogen, hemicellulose and the polymerization degree relatively low, they can be degraded into the small-molecule substance with reactive behavior under the liquefied catalytic effect of phenol and strong acid, and then make biomass liquefying resin adhesive with formaldehyde reaction.This class tackiness agent is compared with traditional resol, has the advantages such as the petrochemical material of saving, cost is low, toxicity is little, environmental protection, thereby has wide market development potentiality.But because biological material is in liquefaction conversion process, wherein the cellulosic degraded product of Mierocrystalline cellulose and part contains a large amount of hydrophilic radicals, these hydrophilic radicals can not participate in reacting completely in the further resinifying process with formaldehyde, thereby caused the water resistance of biomass liquefying resin adhesive not ideal enough, should not be applied to the production of outdoor enhanced water resistance structural plywood, as outdoor heavy bamboo floor, boats and ships glued board, container bottom board, railway carriage floor etc.
Summary of the invention
That the present invention proposes is a kind of preparation method of modified biomass liquefied resin tackiness agent of enhanced water resistance, its objective is and overcomes the existing above-mentioned defect of prior art, promotes biomass adhesive and leads in wood working
The commercial application in territory, improves the quality of products, and reduces products production cost.
Technical solution of the present invention: the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance, is characterized in that the method comprises following processing step:
1) preparation of biomass Liquefaction Products in Phenol thing
Biological material surface earth and foreign material are removed totally, and dry, pulverizing is powdered biomass; Powdered biomass is mixed with melting phenol, the mixture of powdered biomass and melting phenol adds inorganic middle strong acid or organic acid, at 120 ℃ ~ 140 ℃, react 1.0 ~ 2.0h, add caustic soda soln, adjust pH value to alkalescence, below reduction temperature to 40 ℃, obtain biomass Liquefaction Products in Phenol thing;
2) biomass Liquefaction Products in Phenol formaldehyde resin, the i.e. preparation of component A
Biomass Liquefaction Products in Phenol thing and formaldehyde solution are added to reactor in proportion, be warming up to 40 ~ 60 ℃ and keep 30 ~ 60min; Then continue to be warming up to 85 ~ 90 ℃, at this temperature, react 40 ~ 90min, be cooled to below 40 ℃, make biomass Liquefaction Products in Phenol formaldehyde resin, i.e. biomass liquefying resin adhesive;
3) melamine urea formaldehyde resin, the i.e. preparation of B component
In reactor, add massfraction 37% formaldehyde solution and start stirring, with NaOH solution, regulate pH value to 10 ~ 11, then add in proportion successively trimeric cyanamide, urea, methyl alcohol and polyvinyl alcohol solution, at 85 ~ 95 ℃, keep reaction 3h, when pH value is 7.2 ~ 7.6, be cooled to, below 35 ℃, make melamine urea formaldehyde resin;
4) preparation of the modified biomass liquefied resin tackiness agent of enhanced water resistance
By component A and B component by 1:(1.5 ~ 3.5) quality than under normal temperature, mix, be about to make the modified biomass liquefied resin tackiness agent of enhanced water resistance.
Advantage of the present invention: the modified biomass liquefied resin tackiness agent of the enhanced water resistance that this law makes, shelf-stable, glue-applying technique is completely identical with traditional synvaren with heat pressing process, cost is low, toxicity is little, and can significantly improve the water proof bonding strength of biomass liquefying resin adhesive.Test shows, the poplar plywood template test specimen made from the tackiness agent that this patent method makes is after boiling water boiling 4h, 63 ± 2 ℃ of dry 20h, boiling water boiling 4h, and naturally cooling, more than its bonding strength average reaches 1.5MPa.
Embodiment
The preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance, comprises following processing step:
1) preparation of biomass Liquefaction Products in Phenol thing
Biological material surface earth and foreign material are removed totally, and dry, pulverizing is powdered biomass; Powdered biomass is mixed with melting phenol, the mixture of powdered biomass and melting phenol adds inorganic middle strong acid or organic acid, at 120 ℃ ~ 140 ℃, react 1.0 ~ 2.0h, add caustic soda soln, adjust pH value to alkalescence, reduce below temperature to 40 ℃, obtain biomass Liquefaction Products in Phenol thing;
2) biomass Liquefaction Products in Phenol formaldehyde resin, the i.e. preparation of component A
Biomass Liquefaction Products in Phenol thing and formaldehyde solution are added to reactor in proportion, be warming up to 40 ~ 60 ℃ and keep 30 ~ 60min; Then continue to be warming up to 85 ~ 90 ℃, at this temperature, react 40 ~ 90min, be cooled to below 40 ℃, make biomass Liquefaction Products in Phenol formaldehyde resin, i.e. biomass liquefying resin adhesive;
3) melamine urea formaldehyde resin, the i.e. preparation of B component
In reactor, add massfraction 37% formaldehyde solution and start stirring, with NaOH solution, regulate pH value to 10 ~ 11, then add in proportion successively trimeric cyanamide, urea, methyl alcohol and polyvinyl alcohol solution, at 85 ~ 95 ℃, keep reaction 3h, when pH value is 7.2 ~ 7.6, be cooled to, below 35 ℃, make melamine urea formaldehyde resin;
4) preparation of the modified biomass liquefied resin tackiness agent of enhanced water resistance
By component A and B component by 1:(1.5 ~ 3.5) quality than under normal temperature, mix, be about to make the modified biomass liquefied resin tackiness agent of enhanced water resistance.
Biological material in described step 1) is Pericarppium arachidis hypogaeae.
Powdered biomass in described step 1) and the mass ratio of phenol are 1:(0.5 ~ 2).
Inorganic middle strong acid or organic acid in described step 1), refer to sulfuric acid, hydrochloric acid, phosphoric acid, formic acid or oxalic acid, and the consumption of acid is 6% ~ 12% of powdered biomass and phenol quality summation; Amount of caustic soda is 2 ~ 3.5 times of sour consumption.
The mass percent of the formaldehyde solution described step 2) is 37%, and biomass Liquefaction Products in Phenol thing is 1:(1.0 ~ 2.1 with the ratio of the amount of substance of formaldehyde), biomass Liquefaction Products in Phenol thing is in phenol molecular weight.
Trimeric cyanamide in described step 3) and the mass ratio of formaldehyde are 1:(3 ~ 5), urea is 1:(5 ~ 7 with the ratio of the quality of formaldehyde).
Embodiment
To the formaldehyde solution that adds 600g fluidifying peanut shell thing and 400g massfraction 37% in 1000ML reactor, start to stir, be warmed up to 50 ℃ and keep 40min, then continue to be warmed up to 87 ~ 90 ℃ of reaction 70min, the blowing of lowering the temperature when viscosity reaches 400mPa.s, makes A component;
To the formaldehyde solution that adds 500g massfraction 37% in 1000ML reactor, NaOH solution with 4g massfraction 40%, start to stir and add 190g trimeric cyanamide and 50g urea, 25g methyl alcohol, then the polyvinyl alcohol solution that adds 20g massfraction 10%, at 90 ℃, keep reaction 3h, when pH value is 7.4, be cooled to blowing below 35 ℃, make B component;
By the B component mixing and stirring of the component A of 300gd and 700g, make the modified biomass liquefied resin tackiness agent of enhanced water resistance.The solids content of this tackiness agent is 48%, is not less than 30 days storage period.
In this tackiness agent, adding massfraction is the flour of total rubber 10%, and mixing and stirring is used for producing poplar plywood (veneer thickness 2.0mm, Amount of spread 320g/m
2two-sided, unit pressure 1.0MPa, 130 ℃ of hot pressing temperatures, hot pressing time 1.2min/mm) test specimen, after boiling water boiling 4h, 63 ± 2 ℃ of dry 20h, boiling water boiling 4h, naturally cooling, detects bonding strength average and reaches 1.67MPa, and average wood-breaking rate is 80%.
Claims (8)
1. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance, is characterized in that the method comprises following processing step:
1) preparation of biomass Liquefaction Products in Phenol thing
Biological material surface earth and foreign material are removed totally, and dry, pulverizing is powdered biomass; Powdered biomass is mixed with melting phenol, the mixture of powdered biomass and melting phenol adds inorganic middle strong acid or organic acid, at 120 ℃ ~ 140 ℃, react 1.0 ~ 2.0h, add caustic soda soln, adjust pH value to alkalescence, below reduction temperature to 40 ℃, obtain biomass Liquefaction Products in Phenol thing;
2) biomass Liquefaction Products in Phenol formaldehyde resin, the i.e. preparation of component A
Biomass Liquefaction Products in Phenol thing and formaldehyde solution are added to reactor in proportion, be warming up to 40 ~ 60 ℃ and keep 30 ~ 60min; Then continue to be warming up to 85 ~ 90 ℃, at this temperature, react 40 ~ 90min, be cooled to below 40 ℃, make biomass Liquefaction Products in Phenol formaldehyde resin, i.e. biomass liquefying resin adhesive;
3) melamine urea formaldehyde resin, the i.e. preparation of B component
In reactor, add massfraction 37% formaldehyde solution and start stirring, with NaOH solution, regulate pH value to 10 ~ 11, then add in proportion successively trimeric cyanamide, urea, methyl alcohol and polyvinyl alcohol solution, at 85 ~ 95 ℃, keep reaction 3h, when pH value is 7.2 ~ 7.6, be cooled to, below 35 ℃, make melamine urea formaldehyde resin;
4) preparation of the modified biomass liquefied resin tackiness agent of enhanced water resistance
By component A and B component by 1:(1.5 ~ 3.5) quality than under normal temperature, mix, be about to make the modified biomass liquefied resin tackiness agent of enhanced water resistance.
2. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, is characterized in that the biological material in described step 1) is Pericarppium arachidis hypogaeae.
3. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, is characterized in that powdered biomass in described step 1) and the mass ratio of phenol are 1:(0.5 ~ 2).
4. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, it is characterized in that inorganic middle strong acid or organic acid in described step 1), refer to sulfuric acid, hydrochloric acid, phosphoric acid, formic acid or oxalic acid, the consumption of acid is 6% ~ 12% of powdered biomass and phenol quality summation; Amount of caustic soda is 2 ~ 3.5 times of sour consumption.
5. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, it is characterized in that described step 2) in the mass percent of formaldehyde solution be 37%, biomass Liquefaction Products in Phenol thing is 1:(1.0 ~ 2.1 with the ratio of the amount of substance of formaldehyde), biomass Liquefaction Products in Phenol thing is in phenol molecular weight.
6. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, is characterized in that trimeric cyanamide in described step 3) and the mass ratio of formaldehyde are 1:(3 ~ 5), urea is 1:(5 ~ 7 with the ratio of the quality of formaldehyde).
7. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, it is characterized in that described component A, to the formaldehyde solution that adds 600g fluidifying peanut shell thing and 400g massfraction 37% in 1000ML reactor, start and stir, be warmed up to 50 ℃ and keep 40min, then continue to be warmed up to 87 ~ 90 ℃ of reaction 70min, the blowing of lowering the temperature when viscosity reaches 400mPa.s.
8. the preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance as claimed in claim 1, it is characterized in that described B component, to the formaldehyde solution that adds 500g massfraction 37% in 1000ML reactor, NaOH solution with 4g massfraction 40%, start to stir and add 190g trimeric cyanamide and 50g urea, 25g methyl alcohol, then adds the polyvinyl alcohol solution of 20g massfraction 10%, at 90 ℃, keep reaction 3h, when pH value is 7.4, be cooled to blowing below 35 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106634745A (en) * | 2016-12-06 | 2017-05-10 | 阜阳市伟叶家具有限公司 | Anti-aging adhesive for medium-density fiber board and preparation method thereof |
| CN108424734A (en) * | 2018-04-09 | 2018-08-21 | 翟琳 | A kind of preparation method of wood-based plate adhesive |
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN108676530A (en) * | 2018-05-28 | 2018-10-19 | 福州兴创云达新材料科技有限公司 | A kind of preparation method of environment-friendly biomass adhesive |
| CN114350292A (en) * | 2021-12-28 | 2022-04-15 | 南通市锋芒复合材料科技有限公司 | Water-resistant adhesive for sand paper and preparation method thereof |
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| US3658622A (en) * | 1969-04-09 | 1972-04-25 | Georgia Pacific Corp | Process for making wood laminate |
| CN101157834A (en) * | 2007-09-17 | 2008-04-09 | 南京林业大学 | Peanut hull liquefaction and method for preparing adhesive thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634745A (en) * | 2016-12-06 | 2017-05-10 | 阜阳市伟叶家具有限公司 | Anti-aging adhesive for medium-density fiber board and preparation method thereof |
| CN108424734A (en) * | 2018-04-09 | 2018-08-21 | 翟琳 | A kind of preparation method of wood-based plate adhesive |
| CN108676530A (en) * | 2018-05-28 | 2018-10-19 | 福州兴创云达新材料科技有限公司 | A kind of preparation method of environment-friendly biomass adhesive |
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN114350292A (en) * | 2021-12-28 | 2022-04-15 | 南通市锋芒复合材料科技有限公司 | Water-resistant adhesive for sand paper and preparation method thereof |
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| CN104130733B (en) | 2016-01-06 |
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Effective date of registration: 20160329 Address after: 100080, room 18, building 1, 3 Haidian Avenue, Beijing,, Haidian District Patentee after: Beijing Sunshine International Biotechnology Service Co., Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee before: Nanjing Forestry University |