CN102367367A - Preparation method for environment-friendly starch-based binder - Google Patents
Preparation method for environment-friendly starch-based binder Download PDFInfo
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- CN102367367A CN102367367A CN2011102543278A CN201110254327A CN102367367A CN 102367367 A CN102367367 A CN 102367367A CN 2011102543278 A CN2011102543278 A CN 2011102543278A CN 201110254327 A CN201110254327 A CN 201110254327A CN 102367367 A CN102367367 A CN 102367367A
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Abstract
The invention discloses a preparation method for an environment-friendly starch-based binder. According to the method, oxidized starch and modified protein are mixed according to a mass ratio of 2:1 to 5:1; polyvinyl alcohol is added according to a mass ratio of oxidized starch to polyvinyl alcohol of 2:1 to 5:1 and uniformly mixed with oxidized starch and modified protein, and an obtained mixture is subjected to a reaction for 2 to 5 hours at a temperature of 50 to 80 DEG C; first liquid of the binder is prepared; the first liquid of the binder is taken out, an auxiliary agent is added, and the environment-friendly starch-based binder is prepared by uniformly mixing the first liquid of the binder and the auxiliary agent; the auxiliary agent is borax and/or citric acid, and the amount of the auxiliary agent accounts for 2 to 5% of the amount of dry starch base. The oxidation starch is prepared by using sodium periodate as an oxidizing agent and mixing the oxidizing agent with starch at a temperature of 20 to 50 DEG C; the raw material in the invention, starch, undergoes a chemical reaction with protein and produces firm chemical bonds, which enables a net structure of the binder to be formed; the net structure and the action of cross-linking agents allow the binder to have improved stability and enhanced water resistance; the invention enables cost to be saved and the goal of environmental protection to be realized.
Description
Technical field
The present invention relates to a kind of tackiness agent, particularly relate to a kind of preparation method of environment-friendly type starch based adhesive, this tackiness agent can be used for bonding wood materials.
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Background technology
With the synthetic macromolecule is the novel adhesive-synthetic macromolecule glue of basic substance, uses the most extensively and what have the meaning represented most is that formaldehyde is tackiness agent, comprises urea-formaldehyde resin adhesive, Phenol aldehyde resin and trimeric cyanamide.Wherein the urea-formaldehyde resin adhesive consumption is maximum, and accounting for formaldehyde is about 80% of tackiness agent consumption, accounts for 60% of wood adhesive total flow.Advantages such as this type tackiness agent is little with its molecular weight, wettability good, bonding strength height are developed rapidly, have replaced natural adhesive very soon, have captured wood adhesive market.Except that formaldehyde is tackiness agent, use more other water accacks that also comprises in the wood adhesive, like aqueous polyvinyl acetate emulsion, ACRYLIC EMULSION, urethane etc., wherein the consumption of vinyl acetate emulsion and ACRYLIC EMULSION is just in cumulative year after year.
Acrylic ester emulsion has wide material sources, pollution-free, easy synthetic characteristics, but water tolerance is relatively poor.Its major cause is to have introduced micromolecular emulsifying agent, has produced weak frictional belt, has weakened the bonding strength and the water resistance of tackiness agent.Polyurethane has that initial viscosity is good, cohesive force is strong and advantage such as water proof and wearable, but since raw material mostly from external import, cost is higher.The polyvinyl acetate glue stick is commonly called as white glue with vinyl, is a kind of thermoplasticity colloid that is obtained through polyreaction by Vinyl Acetate Monomer.Be characterized in that production technique is simple, bonding force is strong, easy to use, nontoxic pollution-frees etc. be widely used in particularly woodwork bonding of porous material, but it are water-fast, heat-resisting, frost resistance is relatively poor.Mainly be because under acid, alkaline condition, hydrolysis to a certain degree can take place the ester group on the molecular chain, generate the wetting ability hydroxyl, cause the glued membrane suction, even swelling, limited the application of polyvinyl acetate glue stick.At present, domestic aqueous polyvinyl acetate emulsion study on the modification is more, mainly concentrates on copolymerization, blend and cross-linking modified three aspects.
Urea-formaldehyde resin mainly is because after curing, still there is hydrophilic-CH in urea-formaldehyde resin in the structure than the poor water resistance of resol, melamine resin
2OH ,-OH and facile hydrolysis-the CONH-group.State, inside and outside research modification at present mainly is through adding properties-correcting agent copolymerization, blend, changing the water resistance of resin.Yet; Formaldehyde is that tackiness agent has fatal defective, because one of its main raw material is a formaldehyde, glueds joint the wood working product with it and can discharge obnoxious flavoures such as free formaldehyde inevitably in production and use; The harm producers and consumers's is healthy; Live in for a long time in the environment of high-concentration formaldehyde pollution, can produce various chronic diseases, serious can be carcinogenic.Now, environmental quality is more and more paid attention in countries in the world, and people's environmental consciousness constantly strengthens; Along with the rapid growth of China's economy, the generally raising of people's living standard, also more and more exquisite to living environment, burst size of methanal receives very big concern.
The native starch tackiness agent is so that its raw material sources are wide, cheap, production technique is simple, easy to use, environment-protecting asepsis and be widely used in many industries; Especially on Packaging Box, corrugated board production, use in a large number; But it is then rare that starch adhesive is used for timber industry, and most important reason is that the bonding strength and the water tolerance of starch adhesive is all relatively poor, utilizes its cementitious goods; Its dry strength is general and the wet tenacity wretched insufficiency can not satisfy the request for utilization of product.Because starch institute inherent wet fastness is poor, initial bonding strength is little, rate of drying is slow; Therefore, in the wood adhesive industry, seldom there is the investigator to use starch separately as the development of raw materials wood adhesive; Great majority research only is in wood adhesive such as urea-formaldehyde resin, white glue with vinyl and isocyanate adhesive, to add a certain amount of starch; Improving the over-all properties of urea-formaldehyde resin, white glue with vinyl and isocyanate adhesive, though obtained certain effect, not remarkable.External present research direction mainly is to improve its bonding strength and water tolerance, improves as adding Z 150PH, ROHM, trimeric cyanamide, urea etc.
Protein adhesive is with a kind of tackiness agent of protein as main raw material.The source of pressing protein raw material is different, can be divided into two types of animal protein tackiness agent (like blood glue, casein adhesive, osteoderm glue etc.) and vegetable protein tackiness agent (like bean powder glue, soybean glue etc.).The character of protein adhesive, because of the kind and the protein contnt of used protein raw material different.But generally speaking, the advantage of this type tackiness agent is: raw material is a renewable resources, and environment is not polluted, and impregnation equipment is simple, modulation and easy to use, and dried shape glue glued adhesion intensity is better, can satisfy the requirement of the wood-based plate and the laminated product of general indoor use.The disadvantage of this type glue is: major part is not water-fast, not anti-bacterium worm corrosion.If through modification, and add other auxiliary agent, can promote the bonding strength and the water resistance of casco.
Summary of the invention
Technical problem to be solved by this invention: a kind of environmental protection is provided, and cost is low, and water resistance is good, the preparation method of the starch-based adhesive that bounding force is strong.
The present invention is a raw material with reproducible native starch; Adopt sodium periodate oxidation to obtain Sumstar 190; Obtain the higher Sumstar 190 (DAS) of aldehyde group content (30-50%), utilize highly basic (NaOH) that soybean protein isolate (SPI) is carried out sex change simultaneously, the hydrophobic amino acid fragment in the albumen is stretched out; Weaken its wetting ability, at a certain temperature (50-80
oC) make DAS, SPI and linking agent (PVAC polyvinylalcohol) reaction; Make aldehyde radical and the amino in the albumen in the Sumstar 190 combine to form stable chemical bond on the one hand; Polyhydric Z 150PH and the former two are reacted respectively (comprise aldehyde radical-hydroxyl reaction; Reaction between amino and the hydroxyl etc.), make the bonding force in this binder molecule structure more firm, prepare have environmental protection, no aldehyde sizing agent.
The object of the invention realizes through following technical scheme:
A kind of preparation method of environment-friendly type starch based adhesive may further comprise the steps:
(1) preparation of Sumstar 190: be under 20-50 ℃ the condition, to be oxygenant with the sodium periodate in temperature, oxygenant mixes with starch, prepares the Sumstar 190 that the aldehyde radical mass content is 20-70%;
(2) preparation of modified protein: it is 8-10% that protein powder is added water configuration quality concentration, adds NaOH solution and regulates pH to 8-12, in 40-80 ℃ of waters, reacts 0.5-2h then;
(3) preparation of polyvinyl alcohol solution: Z 150PH added form mixture in the entry, the mass percent of control Z 150PH in mixture is 5-20%, dissolving, and stir;
(4) the tackiness agent preparation of liquid just: by mass ratio is 2:1 ~ 5:1, and Sumstar 190 is mixed with modified protein; Mass ratio in Sumstar 190 and Z 150PH is the ratio adding Z 150PH of 2:1 ~ 5:1, mixes, and under 50-80 ℃ of temperature, reacts 2-5h; The preparation tackiness agent is liquid just;
(5) preparation of tackiness agent: add auxiliary agent after just liquid takes out with tackiness agent, after mixing, make the environment-friendly type starch based adhesive; Said auxiliary agent is borax and/or Hydrocerol A, and auxiliary agent accounts for the 2-5% of starch butt quality.
Be further to realize the object of the invention, said prepare the aldehyde radical mass content be the Sumstar 190 of 20-70% be through with oxygenant and starch in molar ratio for 0.2:1-0.8:1 mixes, control pH=2-4, react the 1-5h realization.
Said control pH=2-4 controls through dripping hydrochloric acid solution.
The dissolving of said step (3) is in boiling water bath, to place 20-60min to realize.
The said tackiness agent just mass concentration of liquid is 10 ~ 30%.
The preferred waxy corn starch of said starch, sweet potato starch, Starch rice, wheat starch, tapioca(flour) or potato starch.
That starch has is renewable, pollution-free, cost is low, characteristics such as biodegradable; The present invention is a main raw material with starch and albumen; Through different separately denaturation methods; With they hybrid reactions according to a certain percentage, add linking agent and other auxiliary agent simultaneously then, prepare the environment-friendly type tackiness agent that meets the bonding use of wood veneer.The bad problem of water tolerance when overcoming starch and albumen and using as tackiness agent separately.
The present invention seals hydroxyl through oxidation, esterification, grafting or means such as crosslinked; Introduce other functional group; Make the hydroxy number in the whole adhesive system drop to appropriate degree and maintain enough reactive group numbers; Guarantee that the crosslinked polycondensation of the mutual generation of these reactive groups forms firm reticulated structure in the adhesive solidification process, not only can guarantee bonding strength but also can improve water-resistant capacity.
Compared with prior art, the present invention has following advantage:
(1) between raw starch of the present invention and the albumen chemical reaction takes place; Producing firm chemical bond makes tackiness agent form reticulated structure; Make it more stable; Add the effect of linking agent simultaneously, the stability of tackiness agent is strengthened, and this tackiness agent with other is different with the main bounding force that hydrogen bond and unsettled chemical bond etc. is used as tackiness agent mainly.
(2) among the present invention with the staple of dialdehyde starch as tackiness agent; Both can strengthen bonding dynamics, simultaneously can strengthen water resistance, this with the tackiness agent principle that strengthens water resistance through the adding hydrophobizing agent on different; Provide cost savings, also realized the purpose of environmental protection.
(3) dialdehyde starch also has unique anti-corrosion function among the present invention, and the addition that this can greatly reduce sanitas provides cost savings.
(4) raw material of the present invention is reproducible starch and Sunlover 10, does not have formaldehyde to produce in the reaction, also can not produce the formaldehydes objectionable impurities in the use.
(5) the present invention is main raw material with starch, and albumen proportion is lower than starch, on cost, can be effectively controlled, and has overcome the expensive shortcoming of the three-aldehyde glue on the market.
Embodiment
Below in conjunction with embodiment the present invention is further described, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1
With the sodium periodate is oxygenant; With the waxy corn starch is raw material, and the mol ratio of the two is 0.2:1, mixes the HCL regulator solution pH to 2.0 of back with 0.1N; In 20 ℃ waters, react 3h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 20% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.2kg soybean protein isolate, add 1.8L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 8, puts into 40 ℃ of water-baths then and reacts 2h, obtains the modified protein test solution after the end.
Get Z 150PH 0.2kg, stir behind the adding 3.8L zero(ppm) water, in boiling water bath, dissolve 20min, obtain polyvinyl alcohol solution then.
Get above-mentioned Sumstar 190 1kg; Made soybean protein isolate (protein content is about 91%) modification test solution 2kg above reaching mixes the two, the polyvinyl alcohol solution 4kg of configuration above adding again; In 50 ℃ of waters, react 2h after stirring, the preparation tackiness agent is liquid just; Finish the back and add borax 20g, behind the placement 30min, make the environment-friendly type starch based adhesive behind the mixing.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is 4Pa.s, has provoked thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein effective contact area of bonding plank is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
Result: utilize the program determination of GB/T9846.7-2004, ready plank is put on the clamper of omnipotent puller system, after the clamping; Set condition determination, the length upper limit of batten is 100mm, and the width upper limit is 50mm; Draw speed is 10MPa/min; After reading the pulling force registration, substitution formula P=F/S, wherein S=5 * 10
-4m
2, the shearing resistance that finally obtains year bonding plank is 3.2MPa, water-resistant capacity is 1.9MPa.This numerical value reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa), compare with simple modified starch, it is all more excellent to do wet shearing resistance, and the performance of water-fast intensity is obvious.
Present embodiment environment-friendly type starch based adhesive is compared with simple modified protein tackiness agent, and the dried wet shearing resistance difference of the two is not clearly, but the latter's cost is obviously higher.
In the composition of the environment-friendly type starch based adhesive of present embodiment only dialdehyde starch contain aldehyde radical, but most of form with acetal or semi-acetal exists, and can not form formaldehyde and discharges, its effect is in order to promote the water resistance of tackiness agent; Actual test value 0.02mg/L has reached among the GB/T9846.3-2004 standard about the burst size of methanal of I and II class wood veneer fully.
Embodiment 2:
With the sodium periodate is oxygenant; With the potato starch is raw material, and the mol ratio of the two is 0.4:1, mixes the HCL regulator solution pH to 3.0 of back with 0.1N; In 30 ℃ waters, react 3h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 40% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.3g soybean protein isolate, add 3.7L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 9, puts into 50 ℃ of water-baths then and reacts 1.5h, obtains the modified protein test solution after the end.
Get Z 150PH 0.3kg, stir behind the adding 3.7L zero(ppm) water, in boiling water bath, dissolve 30min, obtain polyvinyl alcohol solution then.
About Sumstar 190 1.2kg, above-mentioned modified protein test solution 2kg mixes the two, the polyvinyl alcohol solution 4kg that adding has been disposed, and 3h is reacted in the back that stirs in 60 ℃ of waters, finish the back and add the about 25g of borax, and behind the placement 1h, it is bonding to be used for plank behind the mixing.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is about 4.2Pa.s, has provoked significantly thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein the effective contact area of plank adherent is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
The result: utilize the program of GB/T9846.7-2004, birch lumber specifically be of a size of 3 * 2.5cm, thickness is 2mm, uses the standard coating of gluing rod according to 500-700g/m2, bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, measuring the shearing pulling force that obtains year bonding plank is 3.7MPa, and another part soaks 12h in 30 ℃ water, and behind the dry at ambient temperature 12h, measuring and obtaining shearing resistance is about 2.2MPa after the taking-up.Mechanics numerical value and burst size of methanal reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa).
Embodiment 3
With the sodium periodate is oxygenant; With the Starch rice is raw material, and the mol ratio of the two is 0.6:1, mixes the HCL regulator solution pH to 4.0 of back with 0.1N; In 30 ℃ waters, react 4h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 50% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.4g soybean protein isolate, add 4.6L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 10, puts into 60 ℃ of water-baths then and reacts 1h, obtains the modified protein test solution after the end.
Get Z 150PH 0.6kg, stir behind the adding 3.4L zero(ppm) water, in boiling water bath, dissolve 40min, obtain polyvinyl alcohol solution then.
About Sumstar 190 1.2kg, above-mentioned protein isolates test solution 2kg mixes the two then; Adding massfraction again is the above-mentioned polyvinyl alcohol solution that has disposed, and 4h is reacted in the back that stirs in 70 ℃ of waters, finishes the back and adds the about 30g of borax; After placing 1.5h behind the mixing, it is bonding to be used for plank.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is about 3.8Pa.s, has provoked thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein effective contact area of bonding plank is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
The result: utilize the program of GB/T9846.7-2004, birch lumber specifically be of a size of 3 * 2.5cm, thickness is 2mm, uses the gluing rod according to 500-700g/m
2Standard coating, bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, after the placement wherein a part to measure the shearing pulling force obtain year bonding plank be about 3.5MPa, another part soaks 12h in 30 ℃ water, measuring water-resistant capacity behind the dry at ambient temperature 12h after the taking-up is about 2.1MPa.Mechanics numerical value and burst size of methanal reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa).
Embodiment 4
With the sodium periodate is oxygenant; With the tapioca(flour) is raw material, and the mol ratio of the two is 0.8:1, mixes the HCL regulator solution pH to 5.0 of back with 0.1N; In 40 ℃ waters, react 5h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 70% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.7kg soybean protein isolate, add 6.3L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 12, puts into 80 ℃ of water-baths then and reacts 0.5h, obtains the modified protein test solution after the end.
Get Z 150PH 0.7kg, stir behind the adding 3.3L zero(ppm) water, in boiling water bath, dissolve 50min, obtain polyvinyl alcohol solution then.
About Sumstar 190 1.4kg, above-mentioned albumen test solution mixes the two, adds the polyvinyl alcohol solution that has disposed, and 5h is reacted in the back that stirs in 80 ℃ of waters, finishes the back and adds the about 35g of borax, and behind the placement 2h, it is bonding to be used for plank behind the mixing.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is about 3Pa.s, has provoked thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein effective contact area of bonding plank is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
The result: utilize the program of GB/T9846.7-2004, birch lumber specifically be of a size of 3 * 2.5cm, thickness is 2mm, uses the gluing rod according to 500-700g/m
2Standard coating, bonding back is at 1-4MPa/m
2About pressure and compacting 10min, after the placement wherein a part to measure the shearing pulling force obtain year bonding plank be about 3.1MPa, another part soaks 12h in 30 ℃ water, measuring water-resistant capacity behind the dry at ambient temperature 12h after the taking-up is about 1.8MPa.Mechanics numerical value and burst size of methanal reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa).
Embodiment 5
With the sodium periodate is oxygenant; With the wheat starch is raw material, and the mol ratio of the two is 0.25:1, mixes the HCL regulator solution pH to 3.0 of back with 0.1N; In 25 ℃ waters, react 2h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 25% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.4kg soybean protein isolate, add 4.6L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 11, puts into 70 ℃ of water-baths then and reacts 1h, obtains the modified protein test solution after the end.
Get Z 150PH 0.8kg, stir behind the adding 3.2L zero(ppm) water, in boiling water bath, dissolve 60min, obtain polyvinyl alcohol solution then.
Get about the Sumstar 190 1.6kg of above-prepared, be made into 10% milk of starch, the polyvinyl alcohol solution of configuration above adding, it is 3 that the back that stirs uses the HCl solution of 1N to regulate pH, 60
oReact about 1h under the C condition; Then with above-mentioned modified protein test solution according to a certain percentage (mass ratio 1:1) mix compositely, add the borax and the Hydrocerol A that account for Sumstar 190 butt 4.5% then and be respectively 45g, it is bonding to be used for plank behind the mixing.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is about 4.5Pa.s, has provoked thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein effective contact area of bonding plank is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
The result: utilizing the program of GB/T9846.7-2004, is sheet material with the birch, specifically is of a size of 3 * 2.5cm, and thickness is 2mm, uses the gluing rod according to 500-700g/m
2Standard coating, bonding back is at 1-4MPa/m
2About pressure and compacting 10min, after the placement wherein a part to measure the shearing pulling force obtain year bonding plank be about 4.0MPa, another part soaks 12h in 30 ℃ water, measuring water-resistant capacity behind the dry at ambient temperature 12h after the taking-up is about 2.5MPa.Mechanics numerical value and burst size of methanal reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa).
Embodiment 6
With the sodium periodate is oxygenant; With the sweet potato starch is raw material, and the mol ratio of the two is 0.3:1, mixes the HCL regulator solution pH to 3.0 of back with 0.1N; In 30 ℃ waters, react 3h; Reaction finishes the back washs respectively with zero(ppm) water and acetone, and dry back is beaten powder and can be obtained Sumstar 190, is 30% according to its aldehyde group content of determination of acid-basetitration.
Get the 0.4kg soybean protein isolate, add 5.6L zero(ppm) water mixing back and on whisking appliance, stir, utilizing the NaOH solution adjustment pH of 0.2N is 10.5, puts into 60 ℃ of water-baths then and reacts 1h, obtains the modified protein test solution after the end.
Get Z 150PH 1kg, stir behind the adding 4L zero(ppm) water, in boiling water bath, dissolve 30min, obtain polyvinyl alcohol solution then.
About Sumstar 190 2kg, configuration concentration is 10% milk of starch, adds above-mentioned polyvinyl alcohol solution 2kg, and it is 4 that the back that stirs uses the HCl solution of 1N to regulate pH, is 70 ℃ of reaction 2h down in temperature; Get top modified protein test solution, the polyvinyl alcohol solution 2kg above adding then, the back that stirs is reacted about 1h in 60 ℃ of waters; Get above-mentioned two kinds of solution then according to mass ratio 2:1 mixed, add the borax and the Hydrocerol A that account for Sumstar 190 butt quality 5% then and be respectively 50g, it is bonding to be used for plank behind the mixing.
Environment-friendly type starch based adhesive face light yellow complexion, than thickness, viscosity is about 4.7Pa.s, has provoked thread appearing with glass rod, and is better mobile when on plank, being coated with, and is easy to spread out.
Test specification:
Plank is prepared: as the carrier of tackiness agent, it is of a size of 3 * 2.5cm to choose birch (GB recommendation), and thickness is 2mm, and its moisture content of control is in 10% before using, and wherein effective contact area of bonding plank is 5mm
2
Plank is bonding: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, display the back and measure shearing resistance.
Water resistance is measured: choose the gluing rod, according to 500-700g/m
2Standard is dipped in the slurry of getting equal in quality, on the coated face of plank, is coated with evenly, and bonding back is at 1-4MPa/ m
2About pressure and compacting 10min, before measuring sample is soaked 12h in 30 ℃ water, dry at ambient temperature 12h measures shearing resistance then after the taking-up.
The result: utilize the program of GB/T9846.7-2004, birch lumber specifically be of a size of 3 * 2.5cm, thickness is 2mm, uses the gluing rod according to 500-700g/m
2Standard coating, bonding back is at 1-4MPa/m
2About pressure and compacting 10min, after the placement wherein a part to measure the shearing pulling force obtain year bonding plank be about 4.3MPa, another part soaks 12h in 30 ℃ water, measuring water-resistant capacity behind the dry at ambient temperature 12h after the taking-up is about 2.8MPa.Mechanics numerical value and burst size of methanal reached country about among the mechanics standard GB/T9846.3-2004 of wood veneer about the requirement of I and II class plywood character (>=1MPa).
The above is merely some kinds of embodiments of the present invention; It or not whole embodiment of the present invention; Those of ordinary skills, are right of the present invention and contain any equivalent transformation embodiment that technical scheme of the present invention is used through reading specification sheets of the present invention.
Claims (6)
1. the preparation method of an environment-friendly type starch based adhesive is characterized in that may further comprise the steps:
(1) preparation of Sumstar 190: be under 20-50 ℃ the condition, to be oxygenant with the sodium periodate in temperature, oxygenant mixes with starch, prepares the Sumstar 190 that the aldehyde radical mass content is 20-70%;
(2) preparation of modified protein: it is 8-10% that protein powder is added water configuration quality concentration, adds NaOH solution and regulates pH to 8-12, in 40-80 ℃ of waters, reacts 0.5-2h then;
(3) preparation of polyvinyl alcohol solution: Z 150PH added form mixture in the entry, the mass percent of control Z 150PH in mixture is 5-20%, dissolving, and stir;
(4) the tackiness agent preparation of liquid just: by mass ratio is 2:1 ~ 5:1, and Sumstar 190 is mixed with modified protein; Mass ratio in Sumstar 190 and Z 150PH is the ratio adding Z 150PH of 2:1 ~ 5:1, mixes, and under 50-80 ℃ of temperature, reacts 2-5h; The preparation tackiness agent is liquid just;
(5) preparation of tackiness agent: add auxiliary agent after just liquid takes out with tackiness agent, after mixing, make the environment-friendly type starch based adhesive; Said auxiliary agent is borax and/or Hydrocerol A, and auxiliary agent accounts for the 2-5% of starch butt quality.
2. method according to claim 1 is characterized in that: said prepare the aldehyde radical mass content be the Sumstar 190 of 20-70% be through with oxygenant and starch in molar ratio for 0.2:1-0.8:1 mixes, control pH=2-4, reaction 1-5h.
3. method according to claim 2 is characterized in that: said control pH=2-4 controls through dripping hydrochloric acid solution.
4. method according to claim 1 is characterized in that: the dissolving of said step (3) is in boiling water bath, to place 20-60min to realize.
5. method according to claim 1 is characterized in that: the said tackiness agent just mass concentration of liquid is 10 ~ 30%.
6. method according to claim 1 is characterized in that: said starch is waxy corn starch, sweet potato starch, Starch rice, wheat starch, tapioca(flour) or potato starch.
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| CN105440972A (en) * | 2015-07-31 | 2016-03-30 | 湖南工业大学 | Nano-compound biomass waterborne adhesive |
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| CN109281233A (en) * | 2018-09-12 | 2019-01-29 | 徐晨攀 | A kind of preparation method of degradable wood-plastic board |
| CN110105859A (en) * | 2019-05-28 | 2019-08-09 | 沈阳顺风新材料有限公司 | A kind of preparation method of wear-resistant paint |
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| CN114605962A (en) * | 2022-04-18 | 2022-06-10 | 北京京都大成新材料科技有限公司 | Water-resistant flexible package adhesive taking hydrolyzed collagen and oxidized starch as basic raw materials and preparation method and application thereof |
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