CN104497964A - Formaldehyde-free defatted soy flour-based adhesive for fiberboard and preparation method of adhesive - Google Patents
Formaldehyde-free defatted soy flour-based adhesive for fiberboard and preparation method of adhesive Download PDFInfo
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- CN104497964A CN104497964A CN201410801962.7A CN201410801962A CN104497964A CN 104497964 A CN104497964 A CN 104497964A CN 201410801962 A CN201410801962 A CN 201410801962A CN 104497964 A CN104497964 A CN 104497964A
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Abstract
The invention discloses a formaldehyde-free defatted soy flour-based adhesive for a fiberboard and a preparation method of the adhesive. The formaldehyde-free defatted soy flour-based adhesive is prepared from 45-65 parts of protein substances, 0.5-5 parts of basic compounds, 0.5-5 parts of an emulsifier and 35-55 parts of a crosslinking enhancer as raw materials. The preparation method comprises the following steps of dispersing, cross-linking and carrying out spray drying. The formaldehyde-free defatted soy flour-based adhesive has the advantages that the product is high in quality and free of formaldehyde; main raw materials are derived from renewable substances, the problem of formaldehyde pollution in use of the adhesive is completely solved and meanwhile, the practical performances such as water resistance and bonding strength of the adhesive are ensured; and the preparation method is simple, convenient to operate and high in production efficiency and very long curing time is not required.
Description
Technical field
The present invention relates to a kind of adhesion agent for artificial board, specifically a kind of fibre board use is without aldehyde defatted soy flour base adhesive and preparation method thereof, belongs to adhesion agent for artificial board field.
Background technology
Along with the sustainable and stable development of the industry such as raising and building, decorations, packaging, Furniture manufacture of living standards of the people, China's wood-based plate output increases rapidly.Wood-based plate ultimate production, glued board output, furniture output, wood floors output occupy first place in the world position for years.2013, China's wood-based plate ultimate production 2.72 hundred million m
3, account for 50% of Gross World Product.On average 9m is produced by tackiness agent per ton
3wood-based plate calculates, and China's wood adhesive consumption about 3,000 ten thousand tons (solids content 50%) in 2013, wherein urea-formaldehyde resin and modified product thereof account for more than 80% of tackiness agent ultimate production, occupy an leading position.Why urea-formaldehyde resin adhesive can use in a large number in timber industry, is that such as raw material is sufficient, cheap, good water solubility, glue-line are of light color because it has the incomparable advantage of other resins.But urea-formaldehyde resin also has some shortcomings significantly, except ageing resistance is poor, poor water resistance, can not for the preparation of except outdoor use wood-based plate, its fatal shortcoming is that the wood-based plate gluedd joint exists Form aldehyde release problem.Along with people's quality of life improves, healthy and environmental consciousness strengthens, and people are more and more main can release formaldehyde to urea-formaldehyde resin adhesive in preparation and use procedure, and it glueds joint wood-based plate also constantly can discharge formaldehyde in the process used, pollute human settlement, infringement people are healthy.The tackiness agent generally adopted in Wood-based Panel Production is formaldehyde system synthetic resins, mainly urea-formaldehyde resin and modified product thereof.Although through effort for many years, China's adhesive of artificial board production level has had large increase, wood-based plate and goods environmental protection characteristic thereof are greatly improved, but the wood-based plate that many enterprises produce and goods (furniture, timber floor and Indoor Wooden finishing material etc.) thereof still also exist comparatively serious Form aldehyde release problem, are the main sources of formaldehyde pollution in room air pollution.
In addition, the adhesive of artificial board generally adopted at present also all also exists the fossil resource Dependence Problem of raw material, does not meet the requirement of Sustainable development.
Name is called " adhesion agent for artificial board, its preparation method and utilize its glued board ", and application number be " 201310744731.2 " Chinese invention patent provides a kind of adhesion agent for artificial board, and its preparation method and utilize the glued board of this tackiness agent; The raw material of described adhesion agent for artificial board comprises: dispersion medium, protein matter, basic cpd and crosslinking enhancer; Described crosslinking enhancer is furfuryl alcohol furfural type furane resin; But due to adopt crosslinking enhancer be furfuryl alcohol furfural type furane resin, therefore, quality product is poor, and quality is not high.
Summary of the invention
In order to solve the problem, the present invention devises a kind of fibre board use without aldehyde defatted soy flour base adhesive and preparation method thereof, quality product is high, not containing formaldehyde, main raw material derives from renewable material, thoroughly solve the problem of formaldehyde pollution when using tackiness agent, ensure that again the Practical Performances such as the water tolerance of tackiness agent and bonding strength simultaneously; Preparation method is simple, and does not need set time of growing very much, and easy to operate, production efficiency is high.
Technical scheme of the present invention is:
Fibre board use is without aldehyde defatted soy flour base adhesive, and the raw material primarily of following weight part is prepared from:
Protein matter 45 ~ 65 parts, basic cpd 0.5 ~ 5 part, emulsifying agent 0.5 ~ 5 part, crosslinking enhancer 35 ~ 55 parts.
Preferably, protein matter 50 ~ 60 parts, basic cpd 0.5 ~ 4 part, emulsifying agent 0.5 ~ 4 part, crosslinking enhancer 40 ~ 50 parts.Protein matter more preferably 55 ~ 60 parts, basic cpd 1 ~ 3 part, emulsifying agent 1 ~ 3 part, crosslinking enhancer 40 ~ 45 parts.
Wherein, described crosslinking enhancer is protein-reacting ethylene oxide thing.This reactant can obtain at synthetic.Its acting as in the present invention: form active group on the higher reactant of the degree of branching and protein and react and increase tackiness agent cross-linking density and improve water-fast bonding property.
The present invention is the performance utilizing hydroxyl in resin structure, aldehyde radical, epoxy group(ing) isoreactivity group, by improving the water-fast bonding property of protein adhesive with protein-active group chemical crosslinking reaction, and formaldehydeless release, environmental protection, without the application of anticorrosion anti-acid-basicity energy.
Described protein matter is degreasing soybean protein, dregs of beans albumen, soybean meal protein or cottonseed meal etc.; Be preferably degreasing soybean protein, and form is preferably powdery, i.e. degreasing soybean protein powder.Protein matter, especially degreasing soybean protein powder, acting as in the present invention: as mainly glueing joint composition.
Described basic cpd is sodium carbonate, sodium hydroxide or potassium hydroxide, is preferably sodium carbonate.Basic cpd, especially sodium carbonate, acting as in the present invention: make protein denaturation exposed inner active group.
Described emulsifying agent is polyvinyl alcohol, polyoxyethylene glycol, OP-10 or polyacrylamide; Be preferably polyacrylamide.Emulsifying agent acting as in the present invention: make protein molecule and cross-linker molecules distribution more even, increase tackiness agent temperature flowing.
Above-mentioned fibre board use, without the preparation method of aldehyde defatted soy flour base adhesive, comprises the following steps:
(1) disperse: weigh each material composition according to above-mentioned weight proportion, then make protein matter, basic cpd and emulsifying agent be dispersed in dispersion medium, obtain mixture;
(2) crosslinked: to be added crosslinking enhancer in the mixture that step (1) is obtained and stir;
(3) spraying dry: it is powdery that the product obtained after step (2) being stirred carries out spraying dry, namely obtains product of the present invention.
Wherein, the dispersion medium in described step (1) is deionized water, and consumption is 200 ~ 260 parts.
In described step (1), after basic cpd, protein matter, emulsifying agent are stirred after joining dispersion medium, by the mixture (comprising basic cpd, protein matter, emulsifying agent, dispersion medium) of acquisition at 40 ~ 80 DEG C, be incubated 1 ~ 3 hour; Preferably 40 ~ 60 DEG C of insulations;
In described step (2), when the mixture that step (1) obtains is cooled to 35 ~ 45 DEG C, adds dispersion medium and crosslinking enhancer, and stir.
Described crosslinking enhancer is protein-reacting ethylene oxide thing.Its synthesis technique is: stir after the polymine of 33 parts by weight of soybean protein, 5 weight and the mixing of 100 weight part dispersion medium, then add 5 weight part highly basic compounds and stir; In reaction unit, be heated to 90 ~ 95 DEG C, after slowly instilling the oxyethane of 20 weight, be cooled to 60 ~ 75 DEG C and add 6 weight part highly basic compounds, be cooled to 40 ~ 45 DEG C of dischargings, spraying dry is powdery solid and get final product;
Wherein, described highly basic compounds is sodium hydroxide or potassium hydroxide; Further, described highly basic compounds to be mass concentration be 40% the aqueous solution;
In described soy-protein, the mass percentage of albumen is greater than 55%;
The mass concentration of described oxyethane is 99.5%;
Described dispersion medium is deionized water;
Described reaction unit is reactor.
Wherein, described dispersion medium is water, preferred softening water.It sticks with glue in agent prescription as tackiness agent provides decentralized environment at wood-based plate of the present invention; Cost is low, and security is high and effective, also utilizes the later stage dry.
The resin added of invention adhesive is the 12-20% of dry fiber weight.
Process of Applying Glue is: first spray into after dry fiber and adhesive powder mixing and stirring the water accounting for gross weight 12-20%, is preferably the water of 14-19%, rear assembly hot pressing, hot pressing temperature 170 DEG C, hot pressing time 70s/mm.
Invention formulation is not containing formaldehyde, and main raw material derives from renewable material, is that a kind of environment friendly artificial board sticks with glue agent; Thoroughly solve the problem of formaldehyde pollution when using tackiness agent, ensure that again the Practical Performances such as the water tolerance of tackiness agent and bonding strength simultaneously; Compared to the prior art, each component serves and acts synergistically well, and effect is strengthened simultaneously; Preparation method is simple, and does not need set time of growing very much, and easy to operate, production efficiency is high; Utilize resources synthetically on the whole, meets environment protection and continuable development principle, has a good application prospect.
The invention has the advantages that:
1) with protein matter, especially defatted soybean protein powder is as the raw material of adhesion agent for artificial board, not containing free formaldehyde, there is not Form aldehyde release problem during for glueing joint wood-based plate, the formaldehyde pollution problem in the room air that thorough solution wood-based plate brings.
2) protein matter is as the reproducible resource of one, as the main raw material of tackiness agent, contributes to solving the exhausted problem using synthesis fossil feedstock in conventional artificial's board adhesive, meets environment protection and continuable development principle;
3) tackiness agent obtained utilizes protein matter to process, and effectively make use of soyabean processing residuum, utilize resources synthetically, save production cost, improve value-added content of product;
4) adopt protein-reacting ethylene oxide thing to be crosslinking enhancer, solve the problem of common soybean glue stick poor water resistance, the water-fast requirement of adhesion agent for artificial board can be met, ensure that the Practical Performances such as the bonding strength of tackiness agent; And the fiberboard obtained by production of adhesive of the present invention reaches II class plate standard-required in GB;
5) adopt protein-reacting ethylene oxide thing crosslinking enhancer, its main raw material soybean protein dregs of rice derive from soybean extract oil residuum, contribute to solving the exhausted problem using synthesis fossil feedstock in common adhesives, meet environment protection and continuable development principle.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Except as otherwise noted, the percentage ratio adopted in the present invention is weight percentage.
Defatted soybean protein powder is purchased from Xiangchi Grain and Oil Co., Ltd., Shandong, and oxyethane is purchased from Nanjing Ke Zheng Chemical Co., Ltd..
The present invention's sodium carbonate used is Powdered.
Protein used in the present invention-reacting ethylene oxide thing, its synthesis technique is: stir after the polymine of 33 parts by weight of soybean protein, 5 weight and the mixing of 100 weight part softening waters, then add 5 parts by weight of sodium hydroxide and stir; Be heated to 90 ~ 95 DEG C, after slowly instilling the oxyethane of 20 weight, be cooled to 60 ~ 75 DEG C and add 6 parts by weight of sodium hydroxide, be cooled to 40 ~ 45 DEG C of dischargings, spraying dry is powdery solid and get final product.The protein obtained-reacting ethylene oxide beyond the region of objective existence is seen as yellowish white pulverulent solids.
The unclassified stores used in the present invention is the conventional material that can commercially obtain.
In the present invention, unit " part " or " weight part " refer to kilogram, gram etc., can be determined on a case-by-case basis.
embodiment 1
1) get the raw materials ready by following weight:
Softening water 230 kg
Sodium carbonate 1 kg
Polyacrylamide 1kg
Defatted soybean protein powder 60 kg
Protein-reacting ethylene oxide thing 40 kg;
2) in the reactor being furnished with agitator, thermometer and condensing works, stir after sodium carbonate and defatted soybean protein powder are added softening water;
3) mixture of the sodium carbonate of acquisition, defatted soybean protein powder and softening water is heated to 42 ~ 46 DEG C, is incubated 3 hours;
4) mixture that upper step obtains is cooled to 35 DEG C, obtains uniform soybean protein mucus;
5) protein-reacting ethylene oxide is added in the soybean protein mucus of upper step gained, stir, rear spray dried into powder form solid, make wood-based plate soybean glue stick.
The performance quality index of the tackiness agent obtained is in table 1.
embodiment 2
1) get the raw materials ready by following weight:
Softening water 240 kg
Sodium carbonate 2 kg
Polyacrylamide 2kg
Defatted soybean protein powder 58 kg
Protein-reacting ethylene oxide thing 42 kg;
2) in the reactor being furnished with agitator, thermometer and condensing works, stir after sodium carbonate and defatted soybean protein powder are added softening water;
3) mixture of the sodium carbonate of acquisition, defatted soybean protein powder and softening water is heated to 48 ~ 51 DEG C, is incubated 4 hours;
4) mixture that upper step obtains is cooled to 40 DEG C, obtains uniform soybean protein mucus;
5) protein-reacting ethylene oxide is added in the soybean protein mucus of upper step gained, stir, rear spray dried into powder form solid, make wood-based plate soybean glue stick.
The performance quality index of the tackiness agent obtained is in table 1.
embodiment 3
1) get the raw materials ready by following weight:
Softening water 245 kg
Sodium carbonate 3 kg
Polyacrylamide 2.5kg
Defatted soybean protein powder 55 kg
Protein-reacting ethylene oxide thing 45 kg;
2) in the reactor being furnished with agitator, thermometer and condensing works, stir after sodium carbonate and defatted soybean protein powder are added softening water;
3) mixture of the sodium carbonate of acquisition, defatted soybean protein powder and softening water is heated to 58 ~ 60 DEG C, is incubated 5 hours;
4) mixture that upper step obtains is cooled to 45 DEG C, obtains uniform soybean protein mucus;
5) protein-reacting ethylene oxide is added in the soybean protein mucus of upper step gained, stir, rear spray dried into powder form solid, make wood-based plate soybean glue stick.
The performance quality index of the tackiness agent obtained is in table 1.
In table 1, water content " % " is mass percentage, and pH value is for being made into pH when massfraction is 10% strength solution.
Table 1: the performance quality index of tackiness agent
As can be seen from Table 1: the tackiness agent water ratio obtained by embodiment 1 ~ 3 is low, pH value, in alkalescence, not containing formaldehyde, can store 1 year.
experimental example
Adopt the embodiment of the present invention 1 ~ 3 and reference examples 1 ~ 3(to adopt soybean protein mucus in embodiment 1 ~ 3 as tackiness agent respectively, namely do not add crosslinking enhancer) corresponding product to manufacture 10mm(thick) × 450(is long) × 450mm(is wide) fiberboard.
By following processes for forming cellulose plate:
Applying glue: mixed with rubber powder by dry fiber, resin added is the 12-20% of dry fiber weight, is uniformly mixed, and sprays into 14-20% water, assembly hot pressing.
Preload pressure and time: precompressed 10 minutes, pressure 1.0 MPa.
Hot pressing pressure: 1.1 MPa, hot pressing temperature is 160 ~ 170 DEG C, and hot pressing time is 70 s/mm.
Carry out Performance Detection by GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental technique " detection method to the fibreboard product produced, detected result is in table 2.
Table 2: the formaldehyde glueing joint glued board releases content and bonding strength
The burst size of methanal of national regulation, II class glued board standard: E0 standard≤5mg/100g, this is environmental protection highest standard; E1 standard is 5-9mg/100g; E2 standard is 9-30mg/100g.
Experimental result shows, the fiberboard that the formaldehydeless soybean glue stick of the present invention manufactures, and burst size of methanal all very low (and being timber body Form aldehyde release), well below the higher limit of the environmental protection highest standard of national regulation burst size of methanal; The internal bond strength of fiberboard is at more than 0.8MPa, and MOR is at more than 30MPa, and water sucting thickness expands below 10%, reaches acceptable end product standard in GB (MOR >=23MPa, internal bond strength >=0.65MPa, water sucting thickness expands≤10%); And do not add crosslinking enhancer, can not glue together well, fiberboard internal bond strength can be caused not up to standard, water-swelling is defective.
In the present invention, raw materials used being during this area produces commonly uses raw material, all can obtain from market, and can not have an impact for production result; The various equipment adopted in the present invention, are the conventional equipment used in the production technique of this area, and the operation of each equipment, parameter etc. all conveniently operate and carry out, and there is no special feature.
Claims (10)
1. fibre board use is without aldehyde defatted soy flour base adhesive, it is characterized in that, the raw material primarily of following weight part is prepared from:
Protein matter 45 ~ 65 parts, basic cpd 0.5 ~ 5 part, emulsifying agent 0.5 ~ 5 part, crosslinking enhancer 35 ~ 55 parts.
2. fibre board use according to claim 1 is without aldehyde defatted soy flour base adhesive, it is characterized in that: described crosslinking enhancer is protein-reacting ethylene oxide thing.
3. fibre board use according to claim 1 is without aldehyde defatted soy flour base adhesive, it is characterized in that: described protein matter is degreasing soybean protein, dregs of beans albumen, soybean meal protein or cottonseed meal.
4. fibre board use according to claim 1 is without aldehyde defatted soy flour base adhesive, it is characterized in that: described basic cpd is sodium carbonate, sodium hydroxide or potassium hydroxide.
5. fibre board use according to claim 1 is without aldehyde defatted soy flour base adhesive, it is characterized in that: described emulsifying agent is polyvinyl alcohol, polyoxyethylene glycol, OP-10 or polyacrylamide; Be preferably polyacrylamide.
6. the fibre board use as described in claim 1-5 any one, without a preparation method for aldehyde defatted soy flour base adhesive, is characterized in that, comprises the following steps:
(1) disperse: weigh each material composition according to above-mentioned weight proportion, then make protein matter, basic cpd and emulsifying agent be dispersed in dispersion medium, obtain mixture;
(2) crosslinked: to be added crosslinking enhancer in the mixture that step (1) is obtained and stir;
(3) spraying dry: it is powdery that the product obtained after step (2) being stirred carries out spraying dry, namely obtains product of the present invention.
7. preparation method according to claim 6, is characterized in that: the dispersion medium in described step (1) is deionized water, and consumption is 200 ~ 260 parts.
8. preparation method according to claim 6, is characterized in that: in described step (1), by the mixture of acquisition at 40 ~ 80 DEG C, is incubated 1 ~ 3 hour.
9. preparation method according to claim 6, is characterized in that: in described step (2), when the mixture that step (1) obtains is cooled to 35 ~ 45 DEG C, adds dispersion medium and crosslinking enhancer, and stirs.
10. preparation method according to claim 6, is characterized in that: described crosslinking enhancer is protein-reacting ethylene oxide thing; Its synthesis technique is: stir after the polymine of 33 parts by weight of soybean protein, 5 weight and the mixing of 100 weight part dispersion medium, then add 5 weight part highly basic compounds and stir; In reaction unit, be heated to 90 ~ 95 DEG C, after slowly instilling the oxyethane of 20 weight, be cooled to 60 ~ 75 DEG C and add 6 weight part highly basic compounds, be cooled to 40 ~ 45 DEG C of dischargings, spraying dry is powdery solid and get final product.
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Cited By (7)
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| CN105838100A (en) * | 2016-05-31 | 2016-08-10 | 何松 | Fiber wood with formaldehyde purification function and method for preparing fiber wood |
| CN106085349A (en) * | 2016-07-19 | 2016-11-09 | 宁波朴锐环保科技有限公司 | The preparation technology of a kind of decorative panel, decorative panel stick with glue agent and preparation technology thereof |
| CN106367021A (en) * | 2016-09-13 | 2017-02-01 | 南京小豆芽木业有限公司 | Formaldehyde-free adhesive and preparation method and application thereof |
| CN110343505A (en) * | 2018-04-02 | 2019-10-18 | 广西大学 | A kind of soyabean protein adhesive for plywood and preparation method thereof |
| CN110475823A (en) * | 2017-02-10 | 2019-11-19 | 恩里科·坎蒂 | Natural glue and thus obtained composite materials for bonding any kind of biomass and countless obsolete materials |
| CN110510984A (en) * | 2019-09-03 | 2019-11-29 | 胡铁军 | A kind of A grades is prevented fires except aldehyde carbon plate and preparation method thereof |
| CN116083050A (en) * | 2023-01-03 | 2023-05-09 | 四川大学 | Novel soybean meal adhesive and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |