CN100381534C - Lignin Environmental-protection type adhesive and its preparing method - Google Patents
Lignin Environmental-protection type adhesive and its preparing method Download PDFInfo
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- CN100381534C CN100381534C CNB2006100765916A CN200610076591A CN100381534C CN 100381534 C CN100381534 C CN 100381534C CN B2006100765916 A CNB2006100765916 A CN B2006100765916A CN 200610076591 A CN200610076591 A CN 200610076591A CN 100381534 C CN100381534 C CN 100381534C
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- tackiness agent
- lignin
- formaldehyde
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Abstract
The present invention provides an environmental-protection type lignin adhesive agent and a preparation method thereof, which belongs to the technical field of adhesive agents. The adhesive agent is obtained by washing lignin and preparing lignin solution, and can be used for producing wood-based panels. The produced wood-based panels achieves the cheap price of urea-formaldehyde glue, favorable adhesive strength, and the favorable waterproof property of phenolic glue. The adhesive agent contains no volatilizing phenol and low free formaldehyde content, and the produced wood-based panels completely reach the E0 level standard. Adhesive agents for wood-based panels have a large market in China. When used for producing wood-based panels, the adhesive agent of the present invention can greatly consume lignin separated out of acid, and can duplicate the value of lignin. Therefore, the present invention which changes waste into valuables realizes a good method for processing large amounts of lignin residue in pulping industry and paper-making industry.
Description
Technical field
The present invention relates to a kind of lignin Environmental-protection type adhesive and preparation method thereof, belong to technical field of adhesive.
Background technology
Xylogen is as tensio-active agent, can be by modification, processing, method such as composite, produce more than 200 kind of xylogen series product, be mainly used in: resin, rubber, dyestuff, agricultural chemicals, pottery, cement, pitch, feed, water treatment, water coal oar, concrete, refractory materials, oil drilling, composite fertilizer, smelting coal, casting, tackiness agent etc., xylogen also is widely used in industrial dispersion agent and tackiness agent in addition, and its annual requirement reaches about 15～200,000 tons.
Because shaving board, slicer board and fiberboard, especially increasing sharply of medium density fibre board (MDF) output produced demand cheap, that can supply and not rely on the tackiness agent of crude oil in a large number.Xylogen is as a kind of primary timber composition, and is both non-hygroscopic also water insoluble, but in pulping process, by degraded and a series of chemical transformation, and the xylogen water soluble that becomes.
Urea-formaldehyde resin adhesive is that the raw material of urea-formaldehyde resin adhesive is easy to get by a kind of aldehyde adhesive that contains of formaldehyde and urea synthesis, and curing speed is fast, concentration height and viscosity is low, the lay up period resin property is stable, thereby can transport at a distance, good with the compatibility of water, be convenient to regulate the viscosity and the concentration of resin, cost is low, and is easy to use, excellent property, adsorptive power is strong etc., is widely used in wood working industry, and market outlook are boundless; But the arteries and veins urea formaldehyde is as made this two large problems of wood-based plate ubiquity of tackiness agent: the formaldehyde gas contaminate environment that first sheet material discharges, and residual mostly in the resin of domestic production have a higher free formaldehyde of content; It two is water tolerance, and especially resistance to boiling water is poor.
In Phenol aldehyde resin, most widely used general with the resol that phenol and formaldehyde condensation polymer form, performances such as the Joint strength of its laminated product is strong, water-fast, heat-resisting, corrosion-resistant are all fine, it is long and to shortcomings such as veneer water content requirement height that but resol exists hot pressing temperature height, time, in use be subjected to certain restriction, and because phenol is petroleum chemicals, so the price of synvaren is higher.Xylogen is a kind ofly to be only second to the cellulosic macromolecular material of content more than second, and is the unique non-oil resource that renewable compound aromatic base can be provided of nature.According to estimates, the annual whole world can generate 1,500 hundred million tons of xylogen by plant.Phenol is arranged through base and aldehyde radical in the lignin molecule, and very strong reactive behavior is arranged, can participate in the condensation cured reaction of phenol, formaldehyde under certain condition, use the lignin modification modified phenolic adhesive can save the residual volume of phenol and minimizing formaldehyde simultaneously, thereby be a kind of resol substitute that has future.
Such as the DE patent No. 3 037 992,3 621 218,3 933 279,4 020 969,4 204 793 and 4 306 439 and large quantities of patent applications such as PCT application publication number WO 93/25622, WO 94/01488, WO 95/23232 and WO 96/03546 all relate to lignin product and replace habitual PF or UF tackiness agent to be used for the application of shaving board, glued board and fiberboard as tackiness agent.When its as adhesive application the time, must be translated into a kind of insoluble substance by curing.Chemically, the curing of xylogen is a cross-linking process, and this causes between different lignin molecules or at inner new C-C and the ehter bond of forming of a macromole, intermolecular and intramolecular crosslinking reacts solubleness and the swelling that has reduced xylogen.Crosslinked in the xylogen both can be realized by condensation reaction, also can realize by the group coupled reaction.For condensation reaction, or need high temperature and long-time heating, or need mineral acid, this can cause structural changes or charing in the wood particulate.Therefore, it is crosslinked in most of the cases to carry out group coupling realization by adding xylogen linking agent, for example, adds epoxide, polyisocyanates, many alcohol, polyacrylamide, polymine and aldehyde.
Chinese patent CN98804638.5 has disclosed grass xylogen bonding quite effective between the lignin fibre material, and a kind of sheet material that does not use synthetic resin binder that replaces tackiness agent with plant class component is provided.
Chinese patent CN988033 19.4 provides a kind of tackiness agent and preparation technology thereof based on xylogen, this tackiness agent and technology are used for enzyme catalysis gummed process, tackiness agent comprises a kind of foaming mixtures from xylogen and/or carbohydrate aqeous suspension, this mixture can foam 1.1-10 times of the liquid mixture volume, and contains the oxydase of energy catalysis of phenol radical oxidation.
Chinese patent CN02112174.5 provides a kind of environment protective lignin flame redardant adhesive agent, this tackiness agent is made up of xylogen mucus, tackifier, fire retardant, stopping composition and water, specifically consist of: xylogen 30-40%, polyvinyl alcohol 2-5%, polyphosphoric acid amine 4-8%, starch 2-8%, kautschin 1-2%, surplus is a water.The characteristics of this tackiness agent are that the industrial chemicals that need not contain toxic substance comes composite adhesives, thereby can not produce objectionable impurities such as formaldehyde, and the health of protection human body has the remarkable environmental meaning.
This shows that there are a plurality of directions in the application that utilizes xylogen to carry out tackiness agent, or outstanding use properties, or the effect of outstanding environment protection, or embody value of salvaged materials, so, in the utilization of xylogen type tackiness agent, boundless prospect is arranged.
Summary of the invention
The object of the present invention is to provide a kind of lignin Environmental-protection type adhesive.
Another object of the present invention is to provide the preparation method of above-mentioned lignin Environmental-protection type adhesive.
The method of the invention is divided into the washing of xylogen, two main processes of preparation of lignin liquor, be specially: xylogen is washed with water, in the xylogen of cleaning, add NaOH solution then, pH value is controlled between the 10-11, heat simultaneously, when being heated to 80 ℃, under whipped state, drip formaldehyde solution, the formaldehyde dripping quantity is that the 1.5-1.6 of over dry lignin doubly measures, the dropping time is 2.5-3.0 hour, after formaldehyde dropwises, continues reaction 1-1.2 hour, temperature of reaction should be no more than 95 ℃ in the process, preferably is controlled at 93-95 ℃; Under whipped state, add NH then
4Cl regulates pH value, makes pH value less than 8, under 93-95 ℃, in 5-6 minute, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
Above-mentioned xylogen washes with water and should satisfy washings pH 〉=5, and colourity is below 32 times, and is preferably colourless;
Above-mentioned NaOH strength of solution is 25-35%, preferred 30%.
Above-mentioned formaldehyde solution concentration is 32-36%, is preferably 36%.
The main raw materials for production of the inventive method are the lignin acidizing separations that adopt alkaline pulping black liquor, the effect of washing, and flush away remains in the acid in the lignin on the one hand, reduces NaOH usage quantity in the production, thereby reduces production costs; Be to remain in Na in the lignin on the other hand for flush away
2SO
4, low molecule organic matter such as sugar and pectin, reduce the content of these materials, the wood-based plate that glue is made has excellent waterproof property.
The lignin of cleaning adds NaOH solution makes its pH can not be lower than 10, otherwise lignin can not all dissolve, and preferably is controlled between the 10-11, because be higher than at 11 o'clock, speed of response can seriously be affected.
The adding mode of formaldehyde and the control of temperature of reaction: the limit adds the heating of NaOH limit during the lignin formulations prepared from solutions, when being warmed up to 80 ℃, drip formaldehyde solution while stirring, do not want disposable adding, control reaction temperature is 93-95 ℃, the time that formaldehyde drips is 2.5-3.0 hour, and add-on is that the 1.5-1.6 of over dry lignin doubly measures; Formaldehyde drips the back and continues reaction 1-1.2 hour;
NH
4The adding of Cl: add NH after the lignin resinization while stirring
4Cl carries out the adjusting of pH, makes reaction pH less than 8, greater than 7.5;
The once adding of urea: 5% of adding over dry lignin urea in resinification lignin, one side is produced a kind of product that is similar to phenolic glue with the aldehyde reaction in the lignin, residual formaldehyde reaction in reacting with the preceding step on the one hand, produce urea-formaldehyde glue, thereby formaldehyde content in the reduction product improves the formaldehyde utilization ratio; The adding temperature of reaction of a urea is about 93-95 ℃, and the joining day is 5-6 minute, 0.5 hour reaction times; The secondary of urea adds: the once adding reaction of urea begins cooling after 0.5 hour, 5% of adding over dry lignin urea in the time of cooling, and the joining day was generally 10 minutes, and crucial controlled step is to have added before being cooled to 90 ℃.
The lignin acidizing separation that xylogen of the present invention produces for all alkaline pulping black liquors also is applicable to the alkali lignin that adopts membrane technique to purify simultaneously.
Tackiness agent of the present invention can be used for producing wood-based plate, and the wood-based plate that makes not only has the nominal price and the good adhesive strength of urea-formaldehyde glue, possesses the phenolic glue favorable waterproof property again; Do not contain volatile phenol; The product free formaldehyde content is extremely low, and the wood-based plate of production can reach E fully
0Grade standard.
China's wood-based plate has very big market with tackiness agent, use tackiness agent of the present invention to produce wood-based plate, not only can the mass consumption lignin acidizing separation, and xylogen is rised in value at double, turning waste into wealth, is to solve the good method that a large amount of xylogen of pulping and paper-making industry are left over.
Description of drawings
Fig. 1 is the inventive method schema.
Embodiment
Embodiment 1
Xylogen is washed with water, be washed till washings pH=5, colourity is 32 times, adding concentration then in the xylogen of cleaning is 30%NaOH solution, pH value is controlled at 10, heats simultaneously, when being heated to 80 ℃, dripping concentration under whipped state is 36% formaldehyde solution, the formaldehyde dripping quantity is 1.6 times of amounts of over dry lignin, and the dropping time is 3.0 hours, after formaldehyde dropwises, continue reaction 1.2 hours, temperature of reaction is built in 93 ℃ in the process; Under whipped state, add NH then
4Cl regulates pH value, makes pH value=7.9, under 93 ℃, in 5 minutes, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
Embodiment 2
Xylogen is washed with water, be washed till washings pH=4, colourity is at 16 times, adding concentration then in the xylogen of cleaning is 25%NaOH solution, pH value is controlled at 11, heats simultaneously, when being heated to 80 ℃, dripping concentration under whipped state is 32% formaldehyde solution, the formaldehyde dripping quantity is 1.5 times of amounts of over dry lignin, and the dropping time is 2.5 hours, after formaldehyde dropwises, continue reaction 1 hour, temperature of reaction is controlled at 95 ℃ in the process; Under whipped state, add NH then
4Cl regulates pH value, makes pH value=7.8, under 95 ℃, in 6 minutes, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
Embodiment 3
Xylogen is washed with water, washings pH=35, colourity is at 8 times, adding concentration then in the xylogen of cleaning is 35%NaOH solution, pH value is controlled between 10.5, heats simultaneously, when being heated to 80 ℃, dripping concentration under whipped state is 34% formaldehyde solution, the formaldehyde dripping quantity is 1.5 times of amounts of over dry lignin, and the dropping time is 3 hours, after formaldehyde dropwises, continue reaction 1.1 hours, temperature of reaction is controlled at 94 ℃ in the process; Under whipped state, add NH then
4Cl regulates pH value, makes pH value=7.7, under 94 ℃, in 6 minutes, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
Embodiment 4
Product to embodiment 1-3 carries out strength test, and uses 3 kinds of tackiness agents under thermocompressor pressure 1.2Mpa, and hot pressing time is 5 minutes, and temperature is carried out hot-forming under 140 ℃, obtains the shaving board test piece, measures tensile strength.
Test result such as following table:
| Solid content % | Shearing resistance MPa | Free formaldehyde content % | Test piece tensile strength MPa | Cohesive force MPa in the test piece | |
| Embodiment 1 | 45.5 | 1.80 | 0.05 | 12.9 | 0.33 |
| Embodiment 2 | 49.0 | 1.75 | 0.05 | 13.1 | 0.41 |
| Embodiment 3 | 47.9 | 1.74 | 0.06 | 12.7 | 0.39 |
From data as seen, high product performance of the present invention, and formaldehyde content is extremely low.
Claims (15)
1. lignin Environmental-protection type adhesive, it is characterized in that, described tackiness agent prepares by the following method: xylogen is washed with water, in the xylogen of cleaning, add NaOH solution then, pH value is controlled between the 10-11, heat simultaneously, when being heated to 80 ℃, under whipped state, drip formaldehyde solution, the formaldehyde dripping quantity is that the 1.5-1.6 of over dry lignin doubly measures, and the dropping time is 2.5-3.0 hour, after formaldehyde dropwises, continue reaction 1-1.2 hour, temperature of reaction should be no more than 95 ℃ in the process; Under whipped state, add NH then
4Cl regulates pH value, makes pH value less than 8, under 93-95 ℃, in 5-6 minute, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
2. tackiness agent according to claim 1 is characterized in that, in the described tackiness agent preparation, after formaldehyde dropwises, continues reaction 1-1.2 hour, and temperature of reaction is at 93-95 ℃ in the process.
3. tackiness agent according to claim 1 is characterized in that, in the preparation of described tackiness agent, the NaOH strength of solution is 25-35%.
4. tackiness agent according to claim 3 is characterized in that, described NaOH strength of solution is 30%.
5. tackiness agent according to claim 1 is characterized in that, in the preparation of described tackiness agent, formaldehyde solution concentration is 32-36%.
6. tackiness agent according to claim 5 is characterized in that, described formaldehyde solution concentration is 36%.
7. tackiness agent according to claim 1 is characterized in that, in the preparation of described tackiness agent, adds NH
4The adjusting that Cl carries out pH should make reactant pH less than 8, greater than 7.5.
8. the preparation method of a lignin Environmental-protection type adhesive is characterized in that, described method is: xylogen is washed with water, in the xylogen of cleaning, add NaOH solution then, pH value is controlled between the 10-11, heats simultaneously, when being heated to 80 ℃, under whipped state, drip formaldehyde solution, the formaldehyde dripping quantity is that the 1.5-1.6 of over dry lignin doubly measures, and the dropping time is 2.5-3.0 hour, after formaldehyde dropwises, continue reaction 1-1.2 hour, temperature of reaction should be no more than 95 ℃ in the process; Under whipped state, add NH then
4Cl regulates pH value, makes pH value less than 8, under 93-95 ℃, in 5-6 minute, adds the urea of over dry xylogen weight 5%, reacts 0.5 hour; In 10 minutes, be cooled to 90 ℃ then, add the urea of over dry xylogen weight 5% during this period, promptly get tackiness agent.
9. preparation method according to claim 8 is characterized in that, in the described method, after formaldehyde dropwises, continues reaction 1-1.2 hour, and temperature of reaction should be at 93-95 ℃ in the process.
10. method according to claim 8 is characterized in that, described xylogen washes with water and should satisfy washings pH 〉=5, and colourity is below 32 times.
11. method according to claim 8 is characterized in that, described NaOH strength of solution is 25-35%.
12. method according to claim 11 is characterized in that, described NaOH strength of solution is 30%.
13. method according to claim 8 is characterized in that, described formaldehyde solution concentration is 32-36%.
14. method according to claim 13, its feature with, described formaldehyde solution concentration is 36%.
15. method according to claim 8 is characterized in that, described adding NH
4The adjusting that Cl carries out pH should make reactant pH less than 8, greater than 7.5.
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| CN100381534C true CN100381534C (en) | 2008-04-16 |
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| CN101191038B (en) * | 2006-11-20 | 2010-05-12 | 兰州大学 | Method for preparing paper-making black liquor adhesive |
| EP2014829A1 (en) * | 2007-07-13 | 2009-01-14 | Sugar Industry Innovation Pty Ltd | A method for coating a paper product |
| CN101942068B (en) * | 2010-08-27 | 2012-09-05 | 安徽格义清洁能源技术有限公司 | Preparation method of lignin phenolic resin |
| CN102241826B (en) * | 2011-05-09 | 2013-10-16 | 北京化工大学 | Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin |
| CN102675570A (en) * | 2012-04-30 | 2012-09-19 | 苏州信邦绿色新材料科技有限公司 | Preparation method of modified lignin and starch composite material for phenolic resin adhesive |
| TWI487780B (en) * | 2012-05-03 | 2015-06-11 | Ind Tech Res Inst | Flame retardant laminate |
| CN104388044A (en) * | 2014-11-12 | 2015-03-04 | 广西南宁绿园北林木业有限公司 | High-adhesive-strength lignin fiberboard adhesive and production method thereof |
| CN105694783A (en) * | 2014-11-28 | 2016-06-22 | 广西南宁绿园北林木业有限公司 | A preparing method of a waterproof adhesive specially used for fiber boards |
| CN105694807A (en) * | 2014-11-28 | 2016-06-22 | 广西南宁绿园北林木业有限公司 | A waterproof fiber adhesive specially used for fiber boards |
| CN105619569A (en) * | 2014-11-28 | 2016-06-01 | 广西鹿寨北林胶合板有限公司 | Fiberboard |
| SE541439C2 (en) * | 2017-07-18 | 2019-10-01 | Stora Enso Oyj | Liquid lignin composition |
| CN108501478A (en) * | 2018-05-25 | 2018-09-07 | 南京林业大学 | A kind of compound laminated veneer lumber of high intensity eucalyptus poplar and its manufacturing method |
| CN109912804B (en) * | 2019-03-28 | 2021-04-02 | 南京林业大学 | Preparation method of phosphorus-nitrogen modified lignin-based intumescent flame retardant |
| CN115029104B (en) * | 2022-06-24 | 2023-04-11 | 中国林业科学研究院林产化学工业研究所 | Method for preparing lignin adhesive and product thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5230835A (en) * | 1975-09-03 | 1977-03-08 | Tokai Pulp Kk | Improved extenders for adhesives based on ureas |
| CN1069509A (en) * | 1991-08-15 | 1993-03-03 | 鞠纯衡 | Lignin modified uric-aldehyde resin and production method thereof |
| CN1594479A (en) * | 2004-07-12 | 2005-03-16 | 曲韵丰 | Method for producing composite SSL-UF urea-formaldehyde resin glue |
| CN1737030A (en) * | 2005-09-09 | 2006-02-22 | 中国林业科学研究院林产化学工业研究所 | Lignin sulfonate modified urea formaldehyde resin preparation method |
-
2006
- 2006-05-09 CN CNB2006100765916A patent/CN100381534C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5230835A (en) * | 1975-09-03 | 1977-03-08 | Tokai Pulp Kk | Improved extenders for adhesives based on ureas |
| CN1069509A (en) * | 1991-08-15 | 1993-03-03 | 鞠纯衡 | Lignin modified uric-aldehyde resin and production method thereof |
| CN1594479A (en) * | 2004-07-12 | 2005-03-16 | 曲韵丰 | Method for producing composite SSL-UF urea-formaldehyde resin glue |
| CN1737030A (en) * | 2005-09-09 | 2006-02-22 | 中国林业科学研究院林产化学工业研究所 | Lignin sulfonate modified urea formaldehyde resin preparation method |
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