CN102618196B - Biomass adhesive, preparation method of the biomass adhesive and bonded wood plate - Google Patents
Biomass adhesive, preparation method of the biomass adhesive and bonded wood plate Download PDFInfo
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Abstract
The invention discloses a preparation method of a biomass adhesive. The preparation method comprises the following steps of 1, carrying out a first contact of oil tea cake, an alkali and water to obtain a first contact product and 2, carrying out a second contact of the first contact product, one or more phenols and one or more aldehydes under the condition of polycondensation to obtain a second contact product having viscosity of 500 to 5000 centipoises. The invention also provides the biomass adhesive obtained by the preparation method. The invention further provides a bonded wood plate. The bonded wood plate comprises at least two single plates and at least one biomass adhesive layer sandwiched between adjacent two of the at least two single plates and is characterized in that the biomass adhesive layer is prepared from the biomass adhesive by curing under the condition of hot-pressing. The biomass adhesive obtained by the preparation method has good fluidity and water-resistant bonding strength.
Description
Technical field
The present invention relates to a kind of preparation method of biomass adhesive and biomass adhesive and the glued wood that is prepared by the method, particularly, relate to a kind of preparation method of biomass adhesive, a kind of biomass adhesive and a kind of glued wood that uses this biomass adhesive preparation by the method preparation.
Background technology
Be accompanied by the shortage of forest resource decrease and timber, glued wood has become the important materials of Furniture manufacture and interior decoration.Prepare the used tackiness agent of all kinds of glued woods and be mainly three urea formaldehydes that comprise urea-formaldehyde resin, resol and terpolycyantoamino-formaldehyde resin, but there is the defective of the objectionable impuritiess such as release formaldehyde in three urea formaldehydes, and three urea formaldehydes mostly to adopt Nonrenewable resources be that raw material synthesizes.In recent years, for environmental protection and the reproducible requirement of resource that reaches present promotion, use the glued wood of biomass adhesive preparation to be widely applied.
At present, biomass adhesive for the preparation of glued wood mainly comprises protein and starch adhesive, but flowability and the water tolerance of these two kinds of sizing agents are relatively poor, bonding strength is lower and the shelf lives is shorter, the more important thing is that representational protein and starch adhesive need to soybean and food starch as raw material, have higher preparation cost.
Summary of the invention
For the flowability that overcomes existing biomass adhesive with water tolerance is relatively poor, bonding strength is lower and the shelf lives is shorter, and the higher defective of preparation cost, the invention provides a kind of preparation method of biomass adhesive, a kind of biomass adhesive and a kind of glued wood that uses this biomass adhesive preparation by the method preparation.
The present inventor finds that the albumen, plant amylum, fiber and the tannin that contain in the cake of camellia oleifera seeds are the desirable feedstock of preparation biomass adhesive, therefore use cake of camellia oleifera seeds partially or completely to substitute the performance that biomass in the existing biomass adhesive can improve biomass adhesive, finished thus the present invention.
According to the preparation method of biomass adhesive provided by the present invention, the method may further comprise the steps:
(1) cake of camellia oleifera seeds is carried out first with alkali and water and contacts, obtain first the contact after product;
(2) in the presence of polycondensation catalyst, the product after the first contact is carried out second with phenol and aldehyde and contacts under the polycondensation condition, obtain viscosity and be the product after second of 500-5000 centipoise contacts.
The present invention also provides the biomass adhesive by the method preparation.
The present invention further provides a kind of glued wood, this glued wood comprises two-layer at least veneer and the adhesive layer between the adjacent two layers veneer, it is characterized in that, described adhesive layer is the cured product of biomass adhesive under hot pressing condition for preparing as stated above.
The tackiness agent that the method according to this invention prepares has preferably I generic request that mobile (viscosity is not more than 6000 centipoises), water proof bonding strength reach GB/T 9846.3-2004 GB regulation, can at room temperature store 2 months has no significant effect performance, and has lower preparation cost.Simultaneously, glued wood burst size of methanal provided by the invention meets the E0 level requirement of GB/T 9846.3-2004 GB regulation.
In addition, method of the present invention has solved the recycling problem of the waste material of cake of camellia oleifera seeds after as the tea seed oil expression on the other hand, therefore in the preparation cost that has reduced biomass adhesive, has improved the economic worth of oil tea crop.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
According to the preparation method of biomass adhesive provided by the present invention, the method may further comprise the steps:
(1) cake of camellia oleifera seeds is carried out first with alkali and water and contacts, obtain first the contact after product;
(2) in the presence of polycondensation catalyst, the product after the first contact is carried out second with phenol and aldehyde and contacts under the polycondensation condition, obtain viscosity and be the product after second of 500-5000 centipoise contacts.
Need to prove, cake of camellia oleifera seeds of the present invention refers to residual solid matter after the Extraction oil of seed tea-seed oil of oil tea (Camellia oleifera), wherein, the technique of kind, the place of production and the extraction camellia seed oil of oil tea, water content and the oleaginousness of cake of camellia oleifera seeds all there is not specific requirement.For example, can be commercially available from the unit of various operation oil tea related productss, the oleaginousness of cake of camellia oleifera seeds can be less than 12 % by weight, and the fineness of cake of camellia oleifera seeds can be less than 200 orders.In order further to improve the bonding strength of biomass adhesive, the oleaginousness of preferred described cake of camellia oleifera seeds is more preferably less than 3 % by weight less than 10 % by weight.
Among the present invention, cake of camellia oleifera seeds is contacted with alkali in the presence of water first, product after will contacting again is in order to make cake of camellia oleifera seeds activate comparatively fully to expose the polycondensation active group with the purpose that phenol contacts with aldehyde, compare with directly cake of camellia oleifera seeds being contacted with aldehyde with phenol, improved the bonding strength of biomass adhesive; Compare with directly cake of camellia oleifera seeds being contacted with aldehyde with alkali, phenol, further improved the bonding strength of biomass adhesive.
Preparation method according to biomass adhesive provided by the present invention, wherein, in step (1), with respect to the water of 1 weight part, the consumption of cake of camellia oleifera seeds does not have special requirement, so long as can get final product in water by the Uniform Dispersion cake of camellia oleifera seeds, in order to improve the performance of tackiness agent, under the preferable case, be the 0.2-1.2 weight part, more preferably the 0.3-1 weight part.
Wherein, water with respect to 1 weight part, the consumption of alkali does not have special requirement yet, get final product so long as be conducive to improve dispersed in water of cake of camellia oleifera seeds and make cake of camellia oleifera seeds activate comparatively fully to expose the polycondensation active group, in order to improve the performance of tackiness agent, under the preferable case, the consumption of alkali is so that the pH value of the product of described the first contact is 8.5-10.5, further the consumption of preferred bases is so that the pH value of the product of described the first contact is 9-10, and most preferably the consumption of alkali is so that the pH value of the product of described the first contact is 9.4-9.6.
Wherein, the selection of described alkali does not have special requirement, get final product so long as can be conducive to improve the dispersiveness of cake of camellia oleifera seeds in water, can be various water miscible mineral alkalis and/organic bases, for example, described alkali can be in the materials such as sodium hydroxide, potassium hydroxide, ammoniacal liquor and hydrated barta one or more.
Wherein, in step (1), the condition of described the first contact has no particular limits, get final product so long as cake of camellia oleifera seeds can be well-dispersed in the water, in order to improve the performance of tackiness agent, under the preferable case, the condition of described the first contact comprises: the Contact Temperature of the first contact is 10-50 ℃, more preferably 20-40 ℃, be 10-100 minute the duration of contact of the first contact, more preferably 30-80 minute.
Wherein, in step (2), with respect to the described first product that contacts of 1 weight part, the consumption of phenol, aldehyde and polycondensation catalyst has no particular limits, as long as can make the viscosity of the product after the second contact reach the 500-5000 centipoise, in order to improve the performance of tackiness agent, under the preferable case, with respect to the described first product that contacts of 1 weight part, the consumption of phenol is the 0.05-0.35 weight part, the consumption of aldehyde is the 0.04-0.17 weight part, and the consumption of polycondensation catalyst is the 0.005-0.1 weight part; Further under the preferable case, the consumption of phenol is the 0.1-0.2 weight part, and the consumption of aldehyde is the 0.06-0.13 weight part, and the consumption of polycondensation catalyst is the 0.01-0.05 weight part.
Wherein, in step (2), the condition of described polycondensation has no particular limits, as long as can make the viscosity of the product after the second contact reach the 500-5000 centipoise, in order to improve the performance of tackiness agent, under the preferable case, the condition of described polycondensation comprises: the pH value of polycondensation is 10-11.5, more preferably 10.5-11; The temperature of polycondensation is 80-95 ℃, more preferably 85-90 ℃; The time of polycondensation is 1-3 hour, more preferably 1.5-2.5 hour.
Need to prove, the product that viscosity obtained above reaches after second of 500-5000 centipoise contacts namely can use as biomass adhesive.
In order further to improve the over-all properties of tackiness agent, the present invention provides a kind of preferred implementation especially.In this preferred implementation, to viscosity obtained above reach the 500-5000 centipoise second the contact after product in add filler.
Particularly, according to this preferred implementation, the preparation method of biomass adhesive provided by the present invention also comprises: the product of described the second contact is mixed with filler, so that the viscosity of mixed material is the 1000-6000 centipoise.
Wherein, described filler can be selected from one or more in cake of camellia oleifera seeds, dregs of beans, flour and the food starch, the preferred oil tea-cake dregs.
Wherein, with respect to the described second product that contacts of 1 weight part, the consumption of filler is the 0.1-0.5 weight part, more preferably the 0.15-0.4 weight part.
When described filler was cake of camellia oleifera seeds, the used oil tea-cake dregs was preferably 1 with weight ratio as the cake of camellia oleifera seeds of filler in the step (1): 0.5-3, more preferably 1: 1-2.With direct whole cake of camellia oleifera seeds is compared for the preparation of the first mixture, can further be improved the bonding strength of biomass adhesive.
Wherein, the condition of described mixing comprises: the temperature of mixing is 70-95 ℃, and more preferably 75-95 ℃, the time of mixing is 5-60 minute, more preferably 15-30 minute.
Preparation method according to biomass adhesive provided by the present invention, wherein, described phenol and aldehyde have no particular limits, can be the known selection of preparation biomass adhesive, for example, described phenol can be phenol, ortho-cresol, meta-cresol, p-cresol, 2,6-xylenol, 4-tertiary butyl phenol, the different octyl phenol of 4-, 4-p-phenyl phenol, 4-phenol in the ninth of the ten Heavenly Stems, 2, one or more in 2-two (4-hydroxyphenyl) propane and the Resorcinol; Described aldehyde can be in formaldehyde, Paraformaldehyde 96, acetaldehyde and the oxalic dialdehyde one or more; For the production cost that reduces tackiness agent and improve its performance, under the preferable case, described phenol is phenol, and described aldehyde is formaldehyde.
Need to prove, when aldehyde of the present invention is chosen as formaldehyde, can add concentration greater than the formalin of 30 % by weight, and this moment aldehyde consumption in the amount of wherein formaldehyde.
According to the preparation method of biomass adhesive provided by the present invention, wherein, described polycondensation catalyst has no particular limits, and can be the known selection of preparation biomass adhesive, and for example, described polycondensation catalyst can contain sodium hydroxide.Under the preferable case, in described polycondensation catalyst, the content of sodium hydroxide is the 55-100 % by weight, more preferably the 60-90 % by weight.
In order further to improve the over-all properties of tackiness agent, the present invention provides a kind of preferred implementation especially.In this preferred implementation, described polycondensation catalyst contains sodium hydroxide and component A, and described component A is selected from one or more in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide and the yellow soda ash; With respect to the sodium hydroxide of 1 weight part, the consumption of component A is the 0.1-0.7 weight part, more preferably the 0.2-0.6 weight part.
Based on aforesaid method, the present invention further provides a kind of biomass adhesive by the aforesaid method preparation.
Based on aforesaid method and tackiness agent, the present invention also provides a kind of glued wood, this glued wood comprises two-layer at least veneer and the adhesive layer between the adjacent two layers veneer, it is characterized in that, described adhesive layer is by the cured product of biomass adhesive under hot pressing condition of aforesaid method preparation.
Wherein, the weight of adhesive layer does not have special requirement, can be known selection in the glued wood preparation, in order to improve the performance of glued wood, under the preferable case, in the usage quantity of tackiness agent, the weight of every square metre of described adhesive layer is 110-190g, more preferably 140-150g.
Wherein, described hot pressing condition does not have special requirement, can be known selection in the glued wood preparation, in order to improve the performance of glued wood, under the preferable case, described hot pressing condition comprises: hot pressing pressure is 0.7-1.4MPa, more preferably 0.9-1.2MPa, hot pressing temperature is 120-150 ℃, more preferably 130-140 ℃; With respect to the plank of per 1 centimetre of total thickness, hot pressing time is 3-20 minute, more preferably 5-15 minute.
Need to prove, the viscosity of liquid is under 25 ℃ among the present invention, and according to the numerical value that the method for GB/T 14074-2006 regulation is measured, the volume of gas and liquid is the numerical value under the standard state.
Below, by the further illustrated in greater detail the present invention of embodiment, but scope of the present invention is not limited in following examples.
Embodiment 1
In the flask of 1.5L, add the 140g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, at room temperature, stirred 20 minutes, add alkali (sodium hydroxide) in the whipping process so that the product pH value after stirring is 9.5, obtain the first product of contact P1.
Then, the concentration that adds 165g in the first product of contact P1 is formalin, 100g phenol and the 9.8g polycondensation catalyst of 37 % by weight (7g sodium hydroxide and 2.8g yellow soda ash mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, keep and stirred 120 minutes, obtain the product Q1 of the second contact.The viscosity of product Q1 under 25 ℃ that records the second contact is 4000 centipoises.
Be to add 210 gram fillers (cake of camellia oleifera seeds identical with above-mentioned source) among the second product of contact Q1 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 30 minutes, obtain product T1.Recording the viscosity of product T1 under 25 ℃ is 5500 centipoises.
Be that 0.1 square metre and thickness are the product T1 that the two sides of 0.5 centimetre poplar plate respectively applies 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, and use thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W1.
Embodiment 2
In the flask of 1.5L, add the 120g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, in room temperature with under stirring, contact 25 minutes, add alkali (sodium hydroxide) in the contact process so that the product pH value after the contact is 9.2, obtain the first product of contact P2.
Then, the concentration that adds 180g in the first product of contact P2 is formalin, 100g phenol and the 21g polycondensation catalyst of 37 % by weight (15g sodium hydroxide and 6g zinc oxide mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 100 minutes, obtain the product Q2 of the second contact.The viscosity of product Q2 under 25 ℃ that records the second contact is 3000 centipoises.
Be to add 240 gram fillers (cake of camellia oleifera seeds identical with above-mentioned source) among the second product of contact Q2 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 15 minutes, obtain product T2.Recording the viscosity of product T2 under 25 ℃ is 4500 centipoises.
Be that 0.1 square metre and thickness are the product T2 that the two sides of 0.5 centimetre poplar plate respectively applies 14 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 10 minutes under the condition of 140 ℃ of hot pressing temperatures and pressure 1.2MPa, obtain glued wood W2.
Embodiment 3
In the flask of 1.5L, add the 160g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, in room temperature with under stirring, contact 20 minutes, add alkali (sodium hydroxide) in the contact process so that the product pH value after the contact is 9.7, obtain the first product of contact P3.
Then, the concentration that adds 170g in the first product of contact P3 is formalin, 100g phenol and the 21g polycondensation catalyst of 37 % by weight (15g sodium hydroxide and 6g magnesium oxide mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 120 minutes, obtain the product Q3 of the second contact.The viscosity of product Q3 under 25 ℃ that records the second contact is 3500 centipoises.
Be to add 240 gram fillers (cake of camellia oleifera seeds identical with above-mentioned source) among the second product of contact Q3 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 15 minutes, obtain product T3.Recording the viscosity of product T3 under 25 ℃ is 5000 centipoises.
Be that 0.1 square metre and thickness are the product T3 that the two sides of 0.5 centimetre poplar plate respectively applies 13 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 9 minutes under the condition of 130 ℃ of hot pressing temperatures and pressure 1.0MPa, obtain glued wood W3.
Embodiment 4
In the flask of 1.5L, add the 120g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, at room temperature, stirred 20 minutes, add alkali (yellow soda ash) in the whipping process so that the product pH value after stirring is 9.5, obtain the first product of contact P4.
Then, in the first product of contact P4, add 60g acetaldehyde, 100g p-cresol and 9.8g polycondensation catalyst (7g sodium hydroxide and 2.8g yellow soda ash mix) and add simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 120 minutes, obtain the product Q4 of the second contact.The viscosity of product Q4 under 25 ℃ that records the second contact is 4000 centipoises.
Be to add 240 gram fillers (dregs of beans, (available from Shandong Rong Feng biotechnology development corporation, Ltd.)) among the second product of contact Q4 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 30 minutes, obtain product T4.Recording the viscosity of product T4 under 25 ℃ is 5500 centipoises.
Be that 0.1 square metre and thickness are the product T4 that the two sides of 0.5 centimetre poplar plate respectively applies 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W4.
Embodiment 5
In the flask of 1.5L, add the 200g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, in room temperature with under stirring, contact 20 minutes, add alkali (sodium hydroxide) in the contact process so that the product pH value after the contact is 9.7, obtain the first product of contact P5.
Then, the concentration that adds 170g in the first product of contact P5 is formalin, 100g phenol and the 21g polycondensation catalyst of 37 % by weight (15g sodium hydroxide and 6g magnesium oxide mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 120 minutes, obtain the product Q5 of the second contact.The viscosity of product Q5 under 25 ℃ that records the second contact is 3500 centipoises.
Be that 0.1 square metre and thickness are the product Q5 that the two sides of 0.5 centimetre poplar plate respectively applies the second contact of 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W5.
Comparative Examples 1
In the flask of 1.5L, add 140g dregs of beans (available from Shandong Rong Feng biotechnology development corporation, Ltd.) and 400g water, at room temperature, stirred 20 minutes, and added alkali (sodium hydroxide) in the whipping process so that the product pH value after stirring is 9.5, obtain the first product of contact P6.
Then, the concentration that adds 165g in the first product of contact P6 is formalin, 100g phenol and the 9.8g polycondensation catalyst of 37 % by weight (7g sodium hydroxide and 2.8g yellow soda ash mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 120 minutes, obtain the product Q6 of the second contact.The viscosity of product Q6 under 25 ℃ that records the second contact is 3500 centipoises.
Be to add 210 gram fillers (dregs of beans identical with above-mentioned source) among the second product of contact Q6 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 30 minutes, obtain product T5.Recording the viscosity of product T5 under 25 ℃ is 4500 centipoises.
Be that 0.1 square metre and thickness are the product T5 that the two sides of 0.5 centimetre poplar plate respectively applies the second contact of 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W6.
Comparative Examples 2
In the flask of 1.5L, add 140g cake of camellia oleifera seeds (available from available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness≤3 % by weight) and 400g water, at room temperature, stirred 20 minutes, obtain product P 7.
Then, the concentration that adds 165g in product P 7 is formalin, 100g phenol and the 9.8g polycondensation catalyst of 37 % by weight (7g sodium hydroxide and 2.8g yellow soda ash mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, kept 120 minutes, obtain the product Q7 of the second contact.The viscosity of product Q7 under 25 ℃ that records the second contact is 6000 centipoises.
Be to add 210 gram fillers (cake of camellia oleifera seeds identical with above-mentioned source) among the second product of contact Q7 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 30 minutes, obtain product T6.Recording the viscosity of product T6 under 25 ℃ is 8500 centipoises.
Be that 0.1 square metre and thickness are the product T6 that the two sides of 0.5 centimetre poplar plate respectively applies the second contact of 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, use simultaneously thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W7.
Embodiment 6
In the flask of 1.5L, add the 140g cake of camellia oleifera seeds (available from Subtropical Zone Forestry Inst., Chinese Academy of Forest Science, oleaginousness 8.6 % by weight) and 400g water, at room temperature, stirred 20 minutes, add alkali (sodium hydroxide) in the whipping process so that the product pH value after stirring is 9.5, obtain the first product of contact P8.
Then, the concentration that adds 165g in the first product of contact P8 is formalin, 100g phenol and the 9.8g polycondensation catalyst of 37 % by weight (7g sodium hydroxide and 2.8g yellow soda ash mix) and adds simultaneously alkali (sodium hydroxide) so that the pH value is 10.5-11, then under 85-90 ℃ temperature, keep and stirred 120 minutes, obtain the product Q8 of the second contact.The viscosity of product Q8 under 25 ℃ that records the second contact is 3200 centipoises.
Be to add 210 gram fillers (cake of camellia oleifera seeds identical with above-mentioned source) among the second product of contact Q8 of 85-90 ℃ in temperature, and under 85-90 ℃ temperature, kept 30 minutes, obtain product T7.Recording the viscosity of product T7 under 25 ℃ is 4800 centipoises.
Be that 0.1 square metre and thickness are the product T7 that the two sides of 0.5 centimetre poplar plate respectively applies 14.5 grams at an area, then making its every one side and an area is that 0.1 square metre and thickness are that 0.5 centimetre poplar plate is fitted, and use thermocompressor hot pressing 5 minutes under the condition of 135 ℃ of hot pressing temperatures and pressure 1.1MPa, obtain glued wood W8.
Test case
The the second product of contact Q1-Q8 that obtains according to method test implementation example 1-6 and the Comparative Examples 1-2 of GB/T 14074-2006 regulation and bonding strength, package stability and the free formaldehyde content of product T1-T7, the results are shown in Table 1.
Table 1
Water proof bonding strength and the burst size of methanal of the glued wood W1-W8 that obtains according to method test implementation example 1-6 and the Comparative Examples 1-2 of GB/T 17657-1999 regulation, the results are shown in Table 2.
Table 2
Above data show, tackiness agent provided by the invention have preferably mobile (viscosity is not more than 6000 centipoises), water proof bonding strength reach GB/T 9846.3-2004 GB regulation I class plate (〉=0.7MPa) require, can at room temperature store 2 months performance is had no significant effect, and have lower preparation cost.Simultaneously, glued wood burst size of methanal provided by the invention meets the E0 level (≤0.5mg/L) requirement of GB/T 9846.3-2004 GB regulation.
Claims (10)
1. the preparation method of a biomass adhesive, the method may further comprise the steps:
(1) cake of camellia oleifera seeds is carried out first with alkali and water and contacts, obtain first the contact after product;
(2) in the presence of polycondensation catalyst, the product after the first contact is carried out second with phenol and aldehyde and contacts under the polycondensation condition, obtain viscosity and be the product after second of 500-5000 centipoise contacts;
Wherein, in step (1), with respect to the water of 1 weight part, the consumption of cake of camellia oleifera seeds is the 0.2-1.2 weight part, and the consumption of alkali is so that the pH value of the product of described the first contact is 8.5-10.5;
The condition of described the first contact comprises: the Contact Temperature of the first contact is 10-50 ℃, and be 10-100 minute the duration of contact of the first contact;
Wherein, in step (2), with respect to the described first product that contacts of 1 weight part, the consumption of phenol is the 0.05-0.35 weight part, and the consumption of aldehyde is the 0.04-0.17 weight part, and the consumption of polycondensation catalyst is the 0.005-0.1 weight part;
The condition of described polycondensation comprises: the pH value of polycondensation is 10-11.5, and the temperature of polycondensation is 80-95 ℃, and the time of polycondensation is 1-3 hour.
2. method according to claim 1, wherein, in step (1), with respect to the water of 1 weight part, the consumption of cake of camellia oleifera seeds is the 0.3-1 weight part, the consumption of alkali is so that the pH value of the product of described the first contact is 9-10.
3. method according to claim 1 and 2, wherein, in step (2), the described first product that contacts with respect to 1 weight part, the consumption of phenol is the 0.1-0.2 weight part, and the consumption of aldehyde is the 0.06-0.13 weight part, and the consumption of polycondensation catalyst is the 0.01-0.05 weight part.
4. method according to claim 1 and 2, wherein, described method also comprises: the product of described the second contact is mixed with filler, so that the viscosity of mixed material is the 1000-6000 centipoise, described filler is selected from one or more in cake of camellia oleifera seeds, dregs of beans, flour and the food starch.
5. method according to claim 4, wherein, with respect to the product of described second contact of 1 weight part, the consumption of filler is the 0.1-0.5 weight part; The condition of described mixing comprises: the temperature of mixing is 70-95 ℃, and the time of mixing is 5-60 minute.
6. the described method of any one according to claim 1-2 and in 5, wherein, described phenol is phenol, ortho-cresol, meta-cresol, p-cresol, 2,6-xylenol, 4-tertiary butyl phenol, the different octyl phenol of 4-, 4-p-phenyl phenol, 4-phenol in the ninth of the ten Heavenly Stems, 2, one or more in 2-two (4-hydroxyphenyl) propane and the Resorcinol; Described aldehyde is one or more in formaldehyde, Paraformaldehyde 96, acetaldehyde and the oxalic dialdehyde.
7. the described method of any one according to claim 1-2 and in 5, wherein, described polycondensation catalyst contains sodium hydroxide and component A, and described component A is selected from one or more in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide and the yellow soda ash; And in the described polycondensation catalyst, with respect to the sodium hydroxide of 1 weight part, the consumption of component A is the 0.1-0.7 weight part.
8. biomass adhesive by the preparation of the described method of any one among the claim 1-7.
9. glued wood, this glued wood comprises two-layer at least veneer and the adhesive layer between the adjacent two layers veneer, it is characterized in that, described adhesive layer is the cured product of biomass adhesive under hot pressing condition, and described biomass adhesive is the biomass adhesive with the described method preparation of any one among the claim 1-7.
10. glued wood according to claim 9, wherein, in the usage quantity of tackiness agent, the weight of every square metre of described adhesive layer is 280-300g; Described hot pressing condition comprises: hot pressing pressure is 0.9-1.2MPa, and hot pressing temperature is 130-140 ℃; With respect to the plank of per 1 centimetre of total thickness, hot pressing time is 5-15 minute.
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CN1120572A (en) * | 1995-05-26 | 1996-04-17 | 内蒙古牙克石木材加工栲胶联合厂 | Larch tannin adhesive |
CN1207114A (en) * | 1995-11-06 | 1999-02-03 | 河野刚 | Adhesive and boards made by using the same |
CN1554724A (en) * | 2003-12-23 | 2004-12-15 | 中国林业科学研究院木材工业研究所 | Process for preparing liquefied wood phenolic adhesive |
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CN1120572A (en) * | 1995-05-26 | 1996-04-17 | 内蒙古牙克石木材加工栲胶联合厂 | Larch tannin adhesive |
CN1207114A (en) * | 1995-11-06 | 1999-02-03 | 河野刚 | Adhesive and boards made by using the same |
CN1554724A (en) * | 2003-12-23 | 2004-12-15 | 中国林业科学研究院木材工业研究所 | Process for preparing liquefied wood phenolic adhesive |
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Dong-bin Fan et al..Evaluation of Forestry Residue-Source Oil-Tea Cake as an Extender for Phenol-Formaldehyde Plywood Adhesive.《FOREST PRODUCTS JOURNAL》.2010,第60卷(第7/8期),第610-614页. |
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