CN1040763C - Larch tannin adhesive - Google Patents
Larch tannin adhesive Download PDFInfo
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- CN1040763C CN1040763C CN95105354A CN95105354A CN1040763C CN 1040763 C CN1040763 C CN 1040763C CN 95105354 A CN95105354 A CN 95105354A CN 95105354 A CN95105354 A CN 95105354A CN 1040763 C CN1040763 C CN 1040763C
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- tannin
- larch
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- phenol
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Abstract
The present invention relates to a larch tannin adhesive which is prepared from larch extract, phenol, formaldehyde, aqueous alkali and water. The raw materials are heated to 80 to 100 DEG C to carry out reaction, and the finished product can be obtained when the viscosity reaches to 200 to 800 centipoises (at 25 DEG C). The larch extract, which is the special product with low price in China, is the major raw material of the product. The larch tannin adhesive has simple production process and is suitable for industrialized large-scale production. The product is mainly used for making timber products with high added value, such as plywoods, shaving boards, fiber board, laminated sheets, etc.
Description
The present invention relates to adhesive field, or rather, relate to larch tannin adhesive, its purposes mainly is as wood adhesive, is particularly useful for the production of wood-based plate.
Present wood adhesive product mainly contains two big classes.One class is a urea aldehyde type Resin adhesive, and this class tackiness agent is non-watertight, especially is easy to ftracture because of making moist with glued board of its processing etc., seriously influences the life-span of glued board.Another kind of is phenolic resin glue, and this class tackiness agent can waterproof, but raw materials cost is higher, costs an arm and a leg.
The objective of the invention is to provide a kind of water resistance good, cohesive force is strong, and is ageing-resistant, and raw material is easy to get, and production technique is simple, and is cheap, is fit to stick with glue agent with the mass-produced wood working of technical scale.
The inventor learns through investigation, the larch extract of selling on the market in China is a kind ofly to make raw material by bark of dahurian larch, granular or the powdery product of pass through the water logging extraction, concentrate, drying and other steps being made, wherein contain the above tannin of 50 quality %, this tannin mainly is the former cyanidin of poly (Polymeric procyanidin), and " Sun Dawang writes, the vegatable tannin chemistry to belong to a kind of in the polyphenol, China Forest press, PP130-210; 374-375; 423-425, (1992) ".The inventor is through long-term experiment research, use the larch extract of China's special product and phenol, formaldehyde etc. to be main raw material, utilize tannin-P-F copolyreaction and made a kind of resin type larch tannin adhesive with the catalytic method of alkali metal hydroxide, the cohesive force of this tackiness agent is strong, water resistance is good, ageing-resistant, can replace traditional resol fully and be used to make high value added products such as outdoor grade plywood, shaving board, fiberboard, veneer sheet.Used glue applying method is identical with heat pressing process condition and resol.Through measuring, quality meets national standard fully.Because this result of study, thereby finished the present invention.
From face, the invention provides a kind of larch tannin adhesive, it is characterized in that it is made by following method: (1) composition of raw materials
Composition quality part larch extract (tannin 〉=50 quality %) 18-25 phenol 10-20 formaldehyde (aqueous solution of 37 quality %) 10-35 alkali metal hydroxide (the 40-60 quality % aqueous solution) 3-25 water 15-25
(2) operation steps
Whole 50-70% that reach cresols of phenol in the prescription are dropped in the reactor, stir, the 50-60% that under agitation adds alkali metal hydroxide aqueous solution total amount in the prescription, be warming up to 80-100 ℃, under this temperature back flow reaction 45-90 minute, add the water in the prescription and reaction mixture temperature is reduced to 50-70 ℃, add whole tannin extracts and remaining alkali metal hydroxide aqueous solution, be warming up to 80-100 ℃ again, under this temperature back flow reaction 2.5-3.5 hour, add remaining formaldehyde again, continue reaction down at 80-100 ℃, when reaction mass viscosity reaches 200-800 centipoise (25 ℃), be cooled to 20 ℃-40 ℃ rapidly, emit final resin.
In above-mentioned prescription, the tannin composition in the larch extract should be not less than 50 quality %, otherwise the performance of the product that obtains is good inadequately.Be preferably tannin 〉=58 quality %.Wherein the concentration of formaldehyde does not have particular restriction, and the 37 quality % that wherein indicate are the concentration of general industry leaf aldehyde, but its concentration is high slightly or lowly slightly also be fine, as long as convert 37 for meeting the proportional range in the prescription after the concentration of quality %.In addition, in above-mentioned prescription, the mass ratio of tannin extract and phenol is preferably (5: 5)-(7: 3).Formaldehyde solution (by 37 quality %) is preferably (3: 10)-(11: 10) to the two the ratio of total mass of tannin extract, phenol.Alkali metal hydroxide can be any one or more the mixture among KOH, NaOH, the LiOH, wherein is preferably NaOH.Its concentration is preferably the 50 quality % aqueous solution.The alkalimetal hydride aqueous solution (by 50 quality %) is preferably (1: 10)-(6: 10) to the two the ratio of total mass of tannin extract, phenol.
In above-mentioned manufacture method, also can adopt following variation scheme to product of the present invention:
(1) prescription is identical with above-mentioned prescription;
(2) operation steps
With phenol, tannin extract, the disposable adding reactor of thermonatrite metal hydroxide aqueous solution, stir, the 50-70% that adds formaldehyde then is warming up to 80-100 ℃, under this temperature back flow reaction 45-90 minute, temperature of reaction is reduced to 50-70 ℃, add remaining formaldehyde, be warming up to 80-100 ℃ again, continue reaction, when reaction mass viscosity reaches 200-800 centipoise (25 ℃), be cooled to 20 ℃-40 ℃ rapidly, emit final resin.
In addition, the present invention also provides larch tannin adhesive of the present invention making glued board, shaving board, fiberboard, the purposes of veneer sheet aspect.Its glue applying method is identical with heat pressing process condition and resol.
Compare with the analogous products resol of prior art, it is good that larch tannin adhesive of the present invention has water resistance simultaneously, and cohesive force is strong, and is ageing-resistant, and raw material is easy to get, much cheap advantages such as.
Enumerate embodiment below with further explanation the present invention.
Implementation column 1
1, composition of raw materials composition quality (kg) larch extract (tannin 〉=58 quality %) 223 phenol, 135 formaldehyde (37 quality %) 230 sodium hydrate aqueous solutions (50 quality %) 193 water 219 add up to 1000
2, operation steps
Use 1m
3Reactor.Phenol 135kg and formaldehyde 138kg are dropped in the reactor, stir, under agitation add aqueous sodium hydroxide solution 108kg, be warming up to 90 ℃, back flow reaction is 1 hour under this temperature, add entry 219kg, temperature is reduced to 50 ℃, add tannin extract 223kg and remaining aqueous sodium hydroxide solution 85kg, and temperature is brought up to 90 ℃ again, back flow reaction is 3 hours under this temperature, adds remaining formaldehyde 92kg again, keeps 20 minutes down at 90 ℃, the viscosity that this moment, sampling recorded is 500 centipoises (25 ℃), with cooling jacket temperature is reduced to 25 ℃ rapidly, emits resin, obtain rosin products 994kg altogether.
After measured, every technical indicator of product is as follows:
Solids content (quality %) 48
Density (g/cm
3) 1.20
Viscosity (centipoise) 500
PH value 11
Free-phenol (quality %)＜1.5
Basicity (quality %) 4
Can be by bromide (quality %) 15
Free formaldehyde (quality %)＜0.2
Guarantee the quality storage period (my god)＞90 (25 ℃)
Embodiment 2
1, prescription is with embodiment 1
2, operation steps
Use 1m
3Reactor.With phenol 135kg, tannin extract 223kg, water 219kg, the disposable adding reactor of aqueous sodium hydroxide solution (50 quality %) 193kg, stir, add formaldehyde (37 quality %) 161kg (account for formaldehyde total amount 70%) then, be warming up to 90 ℃.Back flow reaction is 1 hour under this temperature, be cooled to 70 ℃ then, add remaining formaldehyde 69kg again, be warming up to 90 ℃ again, continued back flow reaction 15 minutes, the viscosity that this moment, sampling recorded is 550 centipoises (25 ℃), with cooling jacket temperature is reduced to 25 ℃ rapidly, emit resin, obtain resin 995kg altogether.After measured, every index of product all meets national standard, but poorer slightly than embodiment 1.
Enumerate application examples below and explain the practical application effect of product of the present invention.
Application examples 1
The larch tannin adhesive that makes with embodiment 1 is used to make 3 layers of birch plywood.Processing condition are: veneer thickness 1.1-1.2mm, digestion time is 30 minutes after the applying glue, hot pressing pressure 1.3 MPas, 130 ℃ of temperature, 5 minutes time.Bonding strength 1.5 MPas of the product glued board that obtains, wood-breaking rate 90%.Meet the requirement of national standard fully to outdoor grade plywood.
Preferred embodiment and the application examples of making product of the present invention have been enumerated above, yet these embodiment and application examples can not be as limitations of the present invention, those skilled in the art still can make many variation schemes in spirit of the present invention and claim institute restricted portion, yet all these schemes all should be considered to belong to scope of the present invention.
Claims (5)
1, larch tannin adhesive is characterized in that, it is made by following method:
(1) composition of raw materials
Composition quality part larch extract, (tannin 〉=50 quality %) 18-25 phenol 10-20 formaldehyde, (aqueous solution of 37 quality %) 10-35 alkali metal hydroxide, (aqueous solution of 40-60 quality %) 3-25 water 15-25
(2) operation steps
Whole 50-70% that reach formaldehyde of phenol in the prescription are dropped in the reactor, stir, the 50-60% that under agitation adds alkalimetal oxide aqueous solution total amount in the prescription, be warming up to 80-100 ℃, under this temperature back flow reaction 45-90 minute, add the water in the prescription and reaction mixture temperature is reduced to 50-70 ℃, add whole tannin extracts and remaining alkali metal hydroxide aqueous solution, be warming up to 80-100 ℃ again, under this temperature back flow reaction 2.5-3.5 hour, add remaining formaldehyde again, continue reaction down at 80-100 ℃, when reaction mass viscosity reaches 200-800 centipoise (25 ℃), be cooled to 20 ℃-40 ℃ rapidly, emit final resin.
2, larch tannin adhesive as claimed in claim 1 is characterized in that, the mass ratio of tannin extract and phenol is (5: 5)-(7: 3) in its prescription.
3, larch tannin adhesive as claimed in claim 1 is characterized in that, the formaldehyde solution (by 37 quality %) in its prescription is (3: 10)-(11: 10) to the two the ratio of total mass of tannin extract, phenol.
4, larch tannin adhesive as claimed in claim 1, its spy is, and the alkali metal hydroxide in its prescription is a sodium hydroxide, and its consumption (by 50 quality %) is (1: 10)-(6: 10) to the two the ratio of total mass of tannin extract, phenol.
5, the purposes of the larch tannin adhesive of claim 1 aspect manufacturing glued board, shaving board, fiberboard, veneer sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95105354A CN1040763C (en) | 1995-05-26 | 1995-05-26 | Larch tannin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95105354A CN1040763C (en) | 1995-05-26 | 1995-05-26 | Larch tannin adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120572A CN1120572A (en) | 1996-04-17 |
| CN1040763C true CN1040763C (en) | 1998-11-18 |
Family
ID=5075499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95105354A Expired - Fee Related CN1040763C (en) | 1995-05-26 | 1995-05-26 | Larch tannin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1040763C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020957B (en) * | 2009-09-16 | 2013-04-10 | 北京化工大学 | Wood environmentally-friendly nontoxic adhesive and preparation method thereof |
| CN101870856B (en) * | 2010-06-07 | 2012-07-18 | 牙克石市拓孚林化制品有限责任公司 | Bark powder phenolic-resin adhesive and preparation method thereof |
| CN102618196B (en) * | 2011-01-27 | 2013-10-16 | 中国林业科学研究院木材工业研究所 | Biomass adhesive, preparation method of the biomass adhesive and bonded wood plate |
| FI124944B (en) | 2011-04-08 | 2015-03-31 | Upm Kymmene Corp | A method of making a binder composition, a binder composition, an adhesive composition, a layered composite structure, and uses of the binder composition and the adhesive composition |
| CN103613727B (en) * | 2013-11-29 | 2015-07-22 | 宁波中加低碳新技术研究院有限公司 | Preparation method of lignin-modified phenol aldehyde resin adhesive |
| CN107974222A (en) * | 2017-12-07 | 2018-05-01 | 广西大学 | Acacia mangiumwilld tannin extract-phenol-formaldehyde condensation copolymerization resin wood adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047105A (en) * | 1989-05-06 | 1990-11-21 | 吉林林学院 | Baking glue adhesive agent |
| CN1065476A (en) * | 1992-03-31 | 1992-10-21 | 中国林业科学研究院林产化学工业研究所 | Reactive phenolic resin is the Chinese black wattle tanning gum of linking agent |
| EP0648807A1 (en) * | 1993-10-13 | 1995-04-19 | Bakelite AG | Binding agent based on tannin |
| CN1117896A (en) * | 1995-07-11 | 1996-03-06 | 华中理工大学 | Forming technology for hollow sucker rod and mould thereof |
-
1995
- 1995-05-26 CN CN95105354A patent/CN1040763C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047105A (en) * | 1989-05-06 | 1990-11-21 | 吉林林学院 | Baking glue adhesive agent |
| CN1065476A (en) * | 1992-03-31 | 1992-10-21 | 中国林业科学研究院林产化学工业研究所 | Reactive phenolic resin is the Chinese black wattle tanning gum of linking agent |
| EP0648807A1 (en) * | 1993-10-13 | 1995-04-19 | Bakelite AG | Binding agent based on tannin |
| CN1117896A (en) * | 1995-07-11 | 1996-03-06 | 华中理工大学 | Forming technology for hollow sucker rod and mould thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120572A (en) | 1996-04-17 |
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| C14 | Grant of patent or utility model | ||
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Free format text: CORRECT: PATENTEE ADDRESS; FROM: WOOD PROCESSING AND VEGETABLE TANNIN EXTRACT INTEGRATED FACTORY, YAKESHI CITY, N TO: NEIMENGGU SENGONG RUBBER ARTICLES LIMITED LIABILITY COMPANY NEIMENGGU YAKE CITY GONGYE STREET NO.4 |
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| CP03 | Change of name, title or address |
Address after: No. 4 Industrial Street, Yakeshi, Inner Mongolia Patentee after: Sengong Tanning Extract Products Co Ltd, Inner Mongolian Autonomous Region Patentee before: Wood Processing and Vegetable Tannin Extract Integrated Factory, Yakeshi City, N |
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |