CN103952118A - Modified soybean protein adhesive and preparation method thereof - Google Patents
Modified soybean protein adhesive and preparation method thereof Download PDFInfo
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- CN103952118A CN103952118A CN201310336430.6A CN201310336430A CN103952118A CN 103952118 A CN103952118 A CN 103952118A CN 201310336430 A CN201310336430 A CN 201310336430A CN 103952118 A CN103952118 A CN 103952118A
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Abstract
The invention provides a modified soy protein adhesive and a preparation method thereof. A preparation process is as below: (1) adding the defatted soybean flour, water, sodium dodecyl benzene sulfonate and alkali into a reactor, stirring for 5 min, adding ethylene glycol and silicone oil, rising the temperature to 90 DEG C, insulating and stirring for 3 h, cooling, and discharging the materials, so as to obtain a soybean protein pre-hydrolyzed solution; and (2) before usage, adding a homemade or purchased melamine-formaldehyde resin into the soybean protein pre-hydrolyzed solution as a crosslinking agent for the soybean protein, and uniformly mixing at room temperature. The modified soybean protein adhesive by the invention has simple technology, simple and flexible operation and moderate cost. The adhesive has excellent water resistant property, and a prepared poplar glued board test piece has bond strength no less than 0.7 MPa after impregnation in water at (63+/-3) DEG C for 3 h, shows no glue phenomenon, and has reached the requirements of national standard type II GB / T9846.3-2004 for glued boards.
Description
Technical field
The present invention relates to a kind of modified soy protein adhesive and preparation method thereof, this soybean albumen adhesive is mainly used on Wood-based Panel Production and Furniture manufacture, belongs to wood adhesive technical field.
Background technology
Wood adhesive is the important source material of Wood-based Panel Production, and the performance of tackiness agent has a direct impact the performance of final wood-based panel product and environment for use.At present, the tackiness agent using in wood-based panel industry is master mainly with synthetic resins type tackiness agent greatly, wherein being most widely used with " three aldehyde " glue (being urea-formaldehyde resin, resol, melamine formaldehyde resin) especially.The common feature of " three aldehyde " glue is the use of formaldehyde raw material, but toxic due to formaldehyde, the burst size of methanal how reducing in air aldehyde resin is all that timber industry is badly in need of the key technical problem solving all the time.Resin adhesive preparation technology, working conditions etc. are being carried out the improved while, the biomass wood adhesive that the nontoxic natural high molecular substance of take prepares as raw material also becomes study hotspot and the development trend in wood adhesive field gradually, soybean albumen adhesive has been that the important tackiness agent kind of a class is wherein since the nineties in last century, carried out the research work of a large amount of relevant soybean albumen adhesives both at home and abroad, and make remarkable progress, according to reports, partially modified soybean albumen adhesive has been realized industrial applications.
In crude soya bean globular protein molecule, polarity and non-polar groups most in polypeptide chain have built stable multilevel hierarchy by Fan get Hua Li, hydrogen bond, hydrophobic interaction, have formed the spheroid of fine and close combination, and bonding effect is poor.When hydrolysis or raising pH value, structural connecting key and interaction between soybean protein molecular polypeptide chain are broken, protein molecule fully disperses and launches, expose more polarity and non-polar group, can contact with timber and produce adsorption, thereby improving the bonding strength of tackiness agent.Therefore, hydrolysis or the depolymerization the first step in traditional soybean protein adhesive preparation technology normally.Afterwards, fully extended polypeptide chain is crosslinked under higher temperature and certain pressure, can again form the various valence bonds that comprise disulfide linkage, forms adhesive layer.As can be seen here, the key of soybean albumen adhesive technology of preparing is how glycinin to be carried out to appropriate modification, makes it have enough tacks, meanwhile, provides its crosslinked required functional group under certain temperature and pressure.Through the soybean protein of hydrolysis treatment, separate in advance liquid and conventionally there is good dry shape intensity, but, although because hydrolysis exposes more hydrophobic grouping, the wet shape intensity that soybean protein is separated liquid in advance makes moderate progress, according to the difference of hydrolysis process, simple hydrolysis treatment modification can not guarantee the up to standard of the wet shape intensity of soybean albumen adhesive completely.For this reason, in situation, soybean protein is separated in advance liquid and is also needed further modification mostly, and modal method of modifying is cross-linking modified.
Cross-linking modified basic thought is to utilize active group in linking agent and soybean protein molecule (as-NH
2,-OH ,-COOH ,-SH) and reaction, introduce more hydrophobic groupings, improve the water tolerance of soybean albumen adhesive.For the linking agent of modification can be before tackiness agent be used directly and soybean protein separate in advance liquid blend use, also can in soybean protein solution collecting process, add.Directly mix the linking agent using and comprise copper, chromium, zinc salt, aliphatic epoxide etc., in addition, the various aldehydes relevant to timber industry and derivative also can be used for the crosslinked of soybean protein as trishydroxymethylnitromethane, dimethylolurea, formaldehyde sodium disulfide, glutaraldehyde, hydroformylation starch, Glycerose, urea-formaldehyde resin, hydroxymethyl phenol etc.In patent ZL 200910092181.4, selected linking agent is esters of acrylic acid or acrylamides, application number is that in 201210381979.2 patent of invention, linking agent is polymethylene multi-phenenyl isocyanate, application number is to adopt multiple crosslinking agent in 201210277994.2 patent of invention, is any several mixture in urea, polyvinyl alcohol, isocyanates, acylamide polymer.If linking agent adds in soybean protein solution collecting process, be usually directed to the graft copolymerization between soybean protein and linking agent, as patent ZL 200910024411.3, ZL 200810123428.x etc.But in general, grafting, copolymerization and modification method is prepared soybean albumen adhesive method, complex manufacturing, the production of adhesive time is longer, and actual operability is not strong.
Summary of the invention
The object of the invention is to solve the technical problem of soybean albumen adhesive poor water resistance for timber industry, and a kind of soybean albumen adhesive and preparation method thereof for timber industry with better water tolerance is provided.
Modified soy protein adhesive of the present invention, is made according to following weight parts proportioning by following raw material: 80 parts of defatted soyflours, 148 ~ 320 parts, water, 0 ~ 3.2 part of Sodium dodecylbenzene sulfonate, 5.6 ~ 12 parts, alkali, 1.6 ~ 3.2 parts of ethylene glycol, 5 ~ 20 of silicone oil, 5 ~ 18 parts of linking agents.
Alkali is one or both materials in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, calcium oxide, ammoniacal liquor, alkaline sodium silicate etc.
Linking agent is melamine formaldehyde resin, and can make by oneself can be also commercial goods.Being characterized as of melamine formaldehyde resin: solids content 40% ~ 50%, viscosity (20 ℃) 65 ~ 80mPas, pH value 9.0 ~ 9.5, trimeric cyanamide and formaldehyde mole ratio M:F are 1:2 ~ 3.
The preparation method of modified soy protein adhesive of the present invention comprises two steps:
The first step: soybean protein is separated the preparation of liquid in advance.In reactor, add defatted soyflour, water, Sodium dodecylbenzene sulfonate, alkali, stir after 5 minutes, add ethylene glycol, silicone oil, in 30 ~ 60 minutes, temperature is risen to 85 ~ 95 ℃, at this temperature, stir cooling blowing 1 ~ 3 hour.
Second step: the preparation of modified soy protein adhesive.Before tackiness agent is used, by proportioning raw materials, add a certain amount of melamine formaldehyde resin, separate in advance liquid mix and blend 5 ~ 10 minutes at ambient temperature with soybean protein.
According to the source situation of linking agent melamine formaldehyde resin, sometimes also need to increase and prepare melamine formaldehyde resin step.
The method that the present invention adopts basic hydrolysis modification and blending and modifying to combine is prepared soybean albumen adhesive.Basic hydrolysis technique has been broken the sphere structure of soybean protein molecule, for interweaving of protein molecular creates conditions, dry shape Joint strength and certain water tolerance of soybean albumen adhesive have been guaranteed, blended cross linking modification afterwards further utilizes the active group of soybean protein molecule, by cross-linking modified, improved the water resistance of soybean albumen adhesive.
The invention has the advantages that:
(1) modified soy protein adhesive of the present invention has good water resistance, can be for the preparation of II class glued board.The present invention be take melamine formaldehyde resin as linking agent, and melamine formaldehyde resin itself has good water resistance, itself and the molecule crosslinked generation of reacting of soybean protein in addition, and the water resistance of soybean albumen adhesive improves obviously.Utilize soybean albumen adhesive of the present invention to prepare poplar plywood, with reference to 4.15 the II class Plywood Shear-strength method of inspection in GB GB/T 17657-1999, in the water that glued board test specimen is 63 ± 3 ℃, flood after 3 hours, in room temperature after standing 10 minutes, the shearing resistance of measured sample is greater than the 0.7MPa stipulating in GB/T 9846.3-2004, and institute's test specimens is all without the phenomenon of coming unglued.
(2) soybean albumen adhesive cost of the present invention is moderate, and burst size of methanal is low.Soybean albumen adhesive of the present invention be take defatted soyflour as main raw material, and take melamine formaldehyde resin, alkali etc. is auxiliary material.On the one hand, reduce the dependence of synthetic resins type tackiness agent to fossil resource, met environment protection and Sustainable development requirement; On the other hand, linking agent melamine formaldehyde resin is moderate, and dosage is less, does not significantly increase soybean albumen adhesive production cost.Although there is formaldehyde release And Spread of Solute in melamine formaldehyde resin, because its dosage is less, and the resin crosslinking reaction that mostly occurs greatly, the formaldehyde of soybean albumen adhesive discharges and compared with synthetic resins type tackiness agent, greatly reduces.
(3) to select melamine formaldehyde resin be linking agent to soybean albumen adhesive of the present invention.Melamine formaldehyde resin is as being a class tackiness agent kind conventional in timber industry, and most of artificial plate enterprise has correlation technique, mature preparation process, and without increasing equipment investment, be conducive to the industrial application of modified soy protein adhesive.
(4) soybean albumen adhesive preparation technology of the present invention is simple, convenient and flexible operation.Linking agent melamine formaldehyde resin can be made by oneself also commercially available.During self-control, the character that tackiness agent user can separate liquid in advance according to defatted soyflour and soybean protein, preferably suitable carbamide preparation technology.
Embodiment
Following specific embodiment is to further illustrate of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(1) in reactor, add 80 parts of defatted soy flours, 148 parts of water, 0.8 part of Sodium dodecylbenzene sulfonate, 6.4 parts of NaOH, start mechanical stirring rod, stir after 5 min, add 1.6 parts of ethylene glycol, 10 silicone oil, be warming up to 90 ℃, and keep after reaction times 3h, blowing, obtains soybean protein and separates in advance liquid after cooling.
(2) in reactor, add 150 parts of 37% formaldehyde solutions, with appropriate 30% NaOH solution, adjust pH to 9.0.Add 80 parts of trimeric cyanamides, be warming up to after 85 ℃, insulation reaction 2 hours, is cooled to 40 ℃ afterwards immediately, with NaOH solution, adjusts pH to 9.0 blowing, obtains melamine formaldehyde resin.
(3) to soybean protein, separate in advance and in liquid, add 10.7 parts of melamine formaldehyde resins, mixing and stirring.
Embodiment 2:
(1) in reactor, add 80 parts of defatted soy flours, 187 parts of water, 4.8 parts of NaOH and 1.9 parts of CaO, start mechanical stirring rod, stir after 5 min, add 1.6 parts of ethylene glycol, 10 silicone oil, be warming up to 90 ℃, and keep after reaction times 3h, blowing, obtains soybean protein and separates in advance liquid after cooling.
(2) in reactor, add 150 parts of 37% formaldehyde solutions, with appropriate 30% NaOH solution, adjust pH to 9.2.Add 95 parts of trimeric cyanamides, be warming up to after 85 ℃, insulation reaction 3 hours, after be cooled to immediately 40 ℃, with NaOH solution, adjust pH to 9.0 blowing, obtain melamine formaldehyde resin.
(3) to soybean protein, separate in advance and in liquid, add 14.2 parts of melamine formaldehyde resins, mixing and stirring.
Embodiment 3:
(1) in reactor, add 80 parts of defatted soy flours, 220 parts of water, 1.6 parts of Sodium dodecylbenzene sulfonatees, 8 parts of KOH, start mechanical stirring rod, stir after 5 min, add 3.2 parts of ethylene glycol, 10 silicone oil, be warming up to 90 ℃, and keep after reaction times 3h, blowing, obtains soybean protein and separates in advance liquid after cooling.
(2) in soybean albumen adhesive, add 17.8 parts of melamine formaldehyde resins, mixing and stirring.Wherein, melamine formaldehyde resin is commercial, is colourless transparent liquid, and solids content is 45%, and viscosity (20 ℃) is 70mPas, and pH value is 9.2, and trimeric cyanamide and formaldehyde mole ratio M/F are 1:2.67.
Experimental example
The effect test of modified soy protein adhesive of the present invention
The three layers of glued board of production of adhesive that utilize respectively embodiment of the present invention 1-3 to prepare, adopt following processing parameter:
Veneer: poplar, thickness 1.5 mm, water ratio 8% ~ 10%;
Resin added: 360g/m
2(two-sided);
Digestion time: 15 ~ 20 min;
Heat pressing process: hot pressing temperature is 160 ℃; Hot pressing pressure is 1.5MPa; Hot pressing time is 8min.
According to above-mentioned technique, prepare three layers of glued board, by dry shape and the wet shape bonding strength of GB/T 17657-1999 < < wood-based plate and face artificial board physicochemical property experimental technique > > test glued board.Wet shape bonding strength press the detection of II class glued board testing method, that is: test specimen is placed in the hot water of (63 ± 3) ℃ and floods 3h, cooling 10min at room temperature after taking-up.The performance test results of embodiment 1 ~ 3 is as shown in table 1.Detected result shows, with modified soy protein adhesive of the present invention, prepares glued board, and the dry shape of glued board and wet shape bonding strength are greater than 0.70MPa, meets the requirement of II class glued board.
Table 1 soybean albumen adhesive glued board gummed strength test result
| Test specimen | Dry shape bonding strength (MPa) | Wet shape bonding strength (MPa) |
| Embodiment 1 | 0.80 | 1.03 |
| Embodiment 2 | 1.06 | 0.94 |
| Embodiment 3 | 0.88 | 0.84 |
Claims (6)
1. a modified soy protein adhesive, is characterized in that the raw material of described soybean albumen adhesive is made according to following weight parts proportioning: 80 parts of defatted soyflours, 148 ~ 320 parts, water, 0 ~ 3.2 part of Sodium dodecylbenzene sulfonate, 5.6 ~ 12 parts, alkali, 1.6 ~ 3.2 parts of ethylene glycol, 5 ~ 20 of silicone oil, 5 ~ 18 parts of linking agents.
2. modified soy protein adhesive according to claim 1, is characterized in that described alkali is one or both materials in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, calcium oxide, ammoniacal liquor, alkaline sodium silicate etc.
3. modified soy protein adhesive according to claim 1, is characterized in that described linking agent is melamine formaldehyde resin.
4. modified soy protein adhesive according to claim 1, is characterized in that preparation method is as follows:
(1). in reactor, add defatted soyflour, water, Sodium dodecylbenzene sulfonate, alkali, stir after 5 minutes, add ethylene glycol, silicone oil, temperature is risen to 90 ℃, and insulated and stirred 1 ~ 3 hour, cooling blowing, prepares soybean protein and separates in advance liquid;
(2). before tackiness agent is used, to soybean protein, separate in advance in liquid and add linking agent, mix and blend is 5 ~ 10 minutes at ambient temperature.
5. modified soy protein adhesive preparation method according to claim 3, is characterized in that it can be also commercial goods that described melamine formaldehyde resin can be made by oneself.
6. modified soy protein adhesive preparation method according to claim 3, it is characterized in that described melamine formaldehyde resin solids content is 40% ~ 50%, viscosity (20 ℃) is 65 ~ 80mPas, and pH value is 9.0 ~ 9.5, and trimeric cyanamide and formaldehyde mole ratio M:F are 1:2 ~ 3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800911A (en) * | 2016-12-22 | 2017-06-06 | 北京林业大学 | A kind of composite modified gluing agent of MG resin plant albumen and preparation method and application |
| CN107090271A (en) * | 2017-06-23 | 2017-08-25 | 湖南省林业科学院 | A kind of soy protein adhesives and preparation method thereof |
| CN107868651A (en) * | 2017-11-27 | 2018-04-03 | 安徽颍美科技股份有限公司 | A kind of preparation method of the Waterproof corrosion type soybean albumen adhesive of the composite modified enhancing of nano-cellulose epoxy resin |
| CN113322035A (en) * | 2021-05-31 | 2021-08-31 | 江西亚太化工有限公司 | Environment-friendly modified resin and application thereof in bamboo forming |
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| CN101671534A (en) * | 2008-09-12 | 2010-03-17 | 罗门哈斯公司 | Wood adhesives comprising protein and oxazoline polymer or resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800911A (en) * | 2016-12-22 | 2017-06-06 | 北京林业大学 | A kind of composite modified gluing agent of MG resin plant albumen and preparation method and application |
| CN107090271A (en) * | 2017-06-23 | 2017-08-25 | 湖南省林业科学院 | A kind of soy protein adhesives and preparation method thereof |
| CN107090271B (en) * | 2017-06-23 | 2021-05-04 | 湖南省林业科学院 | Soybean protein adhesive and preparation method thereof |
| CN107868651A (en) * | 2017-11-27 | 2018-04-03 | 安徽颍美科技股份有限公司 | A kind of preparation method of the Waterproof corrosion type soybean albumen adhesive of the composite modified enhancing of nano-cellulose epoxy resin |
| CN113322035A (en) * | 2021-05-31 | 2021-08-31 | 江西亚太化工有限公司 | Environment-friendly modified resin and application thereof in bamboo forming |
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