CN113336908A - Branched polymer-urea-glyoxal copolycondensation resin, preparation method and application thereof - Google Patents
Branched polymer-urea-glyoxal copolycondensation resin, preparation method and application thereof Download PDFInfo
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- C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
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- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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Abstract
The invention provides a branched polymer-urea-glyoxal copolycondensation resin and a preparation method thereof, wherein the preparation method comprises the following steps: the method comprises the following steps: making branched polyethyleneimine and urea undergo the process of grafting reaction to obtain graft-modified branched polyethyleneimine polymerization product, and recording said product as HPEIU-1800; step two: and (3) mixing the glyoxal aqueous solution with urea, adjusting the pH value to 7.5-8.0, heating and preserving heat for reaction, adding the HPEIU-1800 synthesized in the step one, and continuing heating and preserving heat for reaction to obtain a target product. Due to the introduction of the branched polymer, the obtained resin has excellent bonding strength and water resistance. And the synthetic raw materials do not use formaldehyde and organic solvents, and the resin does not release formaldehyde and has excellent environmental protection. The invention also provides application of the resin in wood adhesives.
Description
Technical Field
The invention relates to the technical field of chemical synthetic resin, in particular to branched polymer-urea-glyoxal copolycondensation resin, a preparation method of the resin and application of the resin in wood adhesive.
Background
The artificial board is used as an important way for improving the utilization rate of wood, and under the existing process conditions, the artificial board is a wood product which is formed by processing wood or wood fiber as a raw material into a certain unit and then hot-pressing the unit under the action of an adhesive and other additives. The adhesive is an important index for determining the quality of the artificial board. At present, the adhesives used for producing the artificial boards generally mainly comprise synthetic resins taking formaldehyde as a raw material, and the resins have excellent bonding strength and durability, but the only deficiency is that the products have formaldehyde release. In order to solve the problem of formaldehyde pollution, a great deal of effort is also put on by experts and scholars, and certain effect is achieved. It is worth noting that since chemically synthetic resins are mainly gelled by organic chemical reactions, there are inevitably reversible reactions of varying degrees. Therefore, it is difficult to solve the problem by using formaldehyde as a basic material for resin synthesis. In addition, people increasingly demand green and environment-friendly products, so that an effective method is to abandon formaldehyde and find a formaldehyde substitute for resin synthesis, and attempts are made to find that glyoxal has the most development potential. One is that glyoxal has functions and properties similar to formaldehyde, while the functionality is twice that of formaldehyde; secondly, the toxicity and volatility are much lower than those of formaldehyde; finally, the price is low, and the method is a mature chemical raw material.
Based on the above consideration, the performance of the resin prepared by using glyoxal instead of formaldehyde and adopting a formaldehyde resin synthesis process is far from the expected result. The reason is that when the glyoxal is used for replacing formaldehyde synthetic resin in the existing process route, the function of the glyoxal is not fully utilized, the crosslinking degree of the synthetic resin is not enough, a compact crosslinking system is difficult to form, and the resin performance is poor, particularly the water resistance is almost no.
Based on the previous research results, the copolymer resin generated by glyoxal and other monomers has the advantages of simple production process, energy conservation and excellent comprehensive performance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a branched polymer-urea-glyoxal copolycondensation resin, a preparation method of the resin and application of the resin in wood adhesives. In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a branched polymer-urea-glyoxal copolycondensation resin, which is obtained by carrying out copolycondensation reaction on branched polyethyleneimine (HPEI), urea (U) and glyoxal.
The invention also relates to a preparation method of the branched polymer-urea-glyoxal copolycondensation resin, which comprises the following steps:
the method comprises the following steps: making branched polyethyleneimine and urea undergo the process of grafting reaction to obtain graft-modified branched polyethyleneimine polymerization product, and recording said product as HPEIU-1800;
preferably, the branched polyethyleneimine has an average molecular weight of 1800.
Preferably, the molar ratio of the branched polyethyleneimine to the urea is 1 (6-10).
Preferably, the reaction temperature in the first step is 95-100 ℃, and the reaction time is 1-3 hours.
Step two: and (3) mixing the glyoxal aqueous solution with urea, adjusting the pH value to 7.5-8.0, heating and preserving heat for reaction, adding the HPEIU-1800 synthesized in the step one, and continuing heating and preserving heat for reaction to obtain a target product.
Preferably, the mass concentration of the glyoxal water solution is 40%.
Preferably, the molar ratio of the glyoxal to the urea added in the second step is 1 (1.6-1.8).
Preferably, the molar ratio of the glyoxal in the second step to the sum of the urea in the first step and the urea in the second step is 1 (1.4-1.6).
Preferably, the pH value is adjusted by using an alkaline solution, wherein the alkaline solution is at least one of sodium hydroxide and potassium hydroxide aqueous solution, and the mass concentration of the compound in water is 30-40%.
Preferably, the temperature of the two times of heating and heat preservation is 55-65 ℃ and the time is 1-1.5 hours.
The invention also relates to application of the branched polymer-urea-glyoxal copolycondensation resin prepared by the method in wood adhesives.
The invention has the beneficial effects that:
(1) the invention provides a branched polymer-urea-glyoxal copolycondensation resin, which is a water-based thermosetting resin, and the water resistance of the synthesized branched polymer-urea-glyoxal copolycondensation resin is remarkably improved by introducing HPEI polymer, so that the use requirements of III-type plywood in the latest standard can be met.
(2) The invention also provides a preparation method of the resin, and the method has the advantages of simple process, lower synthesis reaction temperature and obvious energy-saving effect. And the rubber can be smoothly butted with the existing industrialized rubber making equipment, and a good foundation is laid for industrialized popularization. And the preparation process does not use organic solvent, phenols and formaldehyde. Compared with the existing adhesive for wood, the adhesive has the outstanding characteristics of green, environmental protection and the like.
(3) The invention also provides the application of the synthesized resin in wood bonding, no additional curing agent or organic auxiliary agent is needed to be added in practical use, and crosslinking curing can be carried out under reasonable hot pressing process conditions to generate bonding strength, which is beneficial to controlling the resin cost and is a prominent characteristic different from the existing resin.
Drawings
FIG. 1 is a graph of the molecular weight distribution of branched polyethyleneimine (HPEI) from example 1;
FIG. 2 is a graph showing the molecular weight distribution of the graft-modified branched polyethyleneimine polymerization product (HPEIU-1800) according to example 1;
FIG. 3 is a graph of the molecular weight distribution of the reaction product of urea and glyoxal in comparative example 1;
FIG. 4 is a graph of the molecular weight distribution of the branched polymer-urea-glyoxal resin of example 1;
FIG. 5 is a FT-IR test chart of the branched polymer-urea-glyoxal copolycondensation resin in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a branched polymer-urea-glyoxal copolycondensation resin which is obtained by carrying out copolycondensation reaction on branched polyethyleneimine (HPEI), urea (U) and glyoxal.
In order to fully exert the advantages of the glyoxal and obviously improve the water resistance of the resin, the applicant adopts branched polyethyleneimine (HPEI) to carry out blending modification on the urea-glyoxal resin, and finds that the addition of the HPEI can obviously improve the water resistance of a cured resin system, thereby indicating that the HPEI can effectively improve the crosslinking degree of the resin system. But the shortage is that the dosage of HPEI is relatively high, which can increase the production cost of the resin system and is not beneficial to large-scale industrial production and popularization. Repeated trials and experimental comparisons show that the structural advantages and the functional group advantages of the HPEI can be fully utilized by adopting the resin integrated synthesis process, the bonding strength and the water resistance of the resin are greatly improved, and the production cost of the resin can be considered. The following is the structural formula of HPEI:
reaction of HPEI with Urea, first of all the amino groups (-NH) in HPEI2) Deamination reaction with the amino group in urea converts the amino group in HPEI into the amino group at the end of urea, which is equivalent to converting the environment of the amino group. The reason for this is that the reaction rate between glyoxal and the amino group in HPEI is too fast, and the gel reaction can occur rapidly at room temperature without time and space for operation. After the conversion, the aldehyde group in the glyoxal and the amino group of the urea and partial imino (-NH) in the unreacted HPEI are subjected to mutual crosslinking reaction, so that the HPEI can be smoothly introduced into a resin structural system to obtain a target product.
The embodiment of the invention also provides a preparation method of the branched polymer-urea-glyoxal copolycondensation resin, which comprises the following steps:
the method comprises the following steps: making branched polyethyleneimine and urea undergo the process of grafting reaction to obtain graft-modified branched polyethyleneimine polymerization product, and recording said product as HPEIU-1800;
further, HPEI is generally distinguished by average molecular weight, with commercially available HPEI products having average molecular weights of 600, 800, 1800, 1, 7, etc. The HPEI is a commercial product, is a light yellow viscous liquid in appearance, has the purity of more than 95 percent and the pH value of 10-12, and is stored at normal temperature.
The branched polyethyleneimine employed in the present invention has an average molecular weight of 1800. The introduction of HPEI is due to the fact that the crosslinking degree of urea-glyoxal copolycondensation resin (GU resin for short) is too low to form sufficient cohesive force. If the molecular weight of the branched polyethyleneimine is too small, the crosslinking degree of a system in a resin structure of a product is still insufficient, and sufficient cohesive force is difficult to form after curing, so that the use requirement cannot be met; if the average molecular weight of the branched polyethyleneimine is too high, the cost is too high, and the polymerization process is difficult to control.
In one embodiment of the invention, the molar ratio of the branched polyethyleneimine to the urea is 1 (6-10). If the addition amount of the HPEI is too large, gelation reaction can be quickly carried out in the step two, and a stable adhesive cannot be synthesized; if the urea is added in an excessive amount, the polymerized product of the HPEIU-1800 synthesized in the step (1) is unstable, and the subsequent reaction can not be carried out.
In one embodiment of the present invention, the reaction temperature in the first step is 95 to 100 ℃ and the reaction time is 1 to 3 hours.
Step two: and (3) mixing the glyoxal aqueous solution with urea, adjusting the pH value to 7.5-8.0, heating and preserving heat for reaction, adding the HPEIU-1800 synthesized in the step one, and continuing heating and preserving heat for reaction to obtain a target product.
In one embodiment of the invention, the aqueous glyoxal solution has a mass concentration of 40%.
In one embodiment of the invention, the molar ratio of the glyoxal to the urea added in the second step is 1 (1.6-1.8).
The addition amount of the glyoxal in the second step is arbitrary, and the amount of each substance can be designed according to the total glue amount. But the molar ratio of the glyoxal to the sum of the urea in the first step and the urea in the second step is 1 (1.4-1.6).
In one embodiment of the present invention, in the second step, the pH value can be adjusted by using an alkaline solution, wherein the alkaline solution is at least one selected from sodium hydroxide and potassium hydroxide aqueous solution, and the mass concentration of the compound in water is 30% to 40%.
In one embodiment of the invention, the temperature of the two times of heating and heat preservation is 55-65 ℃ for 1-1.5 hours.
The embodiment of the invention also relates to application of the branched polymer-urea-glyoxal copolycondensation resin prepared by the method in wood adhesives. The resin can be directly used as a wood adhesive, and the prepared plywood has good dry strength and wet strength.
The branched polyethyleneimine polymers in the following examples and comparative examples were obtained from Shandong Shouguang gold chemical Co., Ltd. Unless otherwise specified,% represents mass%.
Example 1
(1) Under the condition of normal temperature, preparing a branched polyethyleneimine polymer with the average molecular weight of 1800 and urea (U1) according to the molar ratio of 1:6, adding the materials into a reaction container, continuously stirring and heating to 95-100 ℃ under auxiliary devices such as condensation, reflux, stirring and the like, and carrying out heat preservation reaction for 1 hour to obtain a graft modified branched polyethyleneimine polymerization product. And discharging, cooling and reserving, and recording as HPEIU-1800.
(2) Weighing 100G of 40% glyoxal aqueous solution (G) and 25.86G of urea (U2) (molar ratio G: U2 is 1:1.6) at normal temperature, adding the weighed materials into a reaction vessel, adjusting the pH value to 7.5-8.0 by using 40% sodium hydroxide aqueous solution, heating the urea-glyoxal reaction system to 60 ℃ under the conditions of water bath heating, stirring and refluxing, keeping the temperature for reaction for 1 hour, adjusting the pH value of the reaction system to 7.5-8.0 again, adding the HPEIU-1800 polymerization product synthesized in the step (1), adjusting the molar ratio of the glyoxal to the total urea in the system to 1:1.4, and keeping the temperature for reaction for 1 hour under continuous stirring. And then discharging and cooling to obtain the branched polymer-urea-glyoxal copolycondensation resin.
Example 2
(1) Under the condition of normal temperature, preparing a branched polyethyleneimine polymer with the average molecular weight of 1800 and urea (U1) according to the molar ratio of 1:8, then adding the materials into a reaction container, continuously stirring and heating to 95-100 ℃ under auxiliary devices such as condensation, reflux, stirring and the like, carrying out heat preservation reaction for 1h to obtain a graft modified branched polyethyleneimine polymerization product, discharging, cooling and reserving for use, and marking as HPEIU-1800.
(2) Weighing 100G of 40% glyoxal aqueous solution (G) and 24.37G of urea (U2) (molar ratio G: U2 is 1:1.7) at normal temperature, adding the weighed materials into a reaction vessel, adjusting the pH value to 7.5-8.0 by using 40% sodium hydroxide aqueous solution, heating the urea-glyoxal reaction system to 60 ℃ under the conditions of water bath heating, stirring and refluxing, keeping the temperature for reaction for 1 hour, adjusting the pH value of the reaction system to 7.5-8.0 again, adding the HPEIU-1800 polymerization product synthesized in the step (1), adjusting the molar ratio of the glyoxal to the total urea in the system to 1:1.5, and keeping the temperature for reaction for 1 hour under continuous stirring. And then discharging and cooling to obtain the branched polymer-urea-glyoxal copolycondensation resin.
Example 3
(1) Under the condition of normal temperature, preparing a branched polyethyleneimine polymer with the average molecular weight of 1800 and urea (U1) according to the molar ratio of 1:10, then adding the materials into a reaction container, continuously stirring and heating to 95-100 ℃ under auxiliary devices such as condensation, reflux, stirring and the like, carrying out heat preservation reaction for 1h to obtain a graft modified branched polyethyleneimine polymerization product, discharging, cooling and reserving for use, and marking as HPEIU-1800.
(2) Weighing 100G of 40% glyoxal aqueous solution (G) and 22.99G of urea (U2) (molar ratio G: U2 is 1:1.8) at normal temperature, adding the weighed materials into a reaction vessel, adjusting the pH value to 7.5-8.0 by using 40% sodium hydroxide aqueous solution, heating the urea-glyoxal reaction system to 60 ℃ under the conditions of water bath heating, stirring and refluxing, keeping the temperature for reaction for 1 hour, adjusting the pH value of the reaction system to 7.5-8.0 again, adding the HPEIU-1800 polymerization product synthesized in the step (1), adjusting the molar ratio of the glyoxal to the total urea in the system to 1:1.6, and keeping the temperature for reaction for 1 hour under continuous stirring. And then discharging and cooling to obtain the branched polymer-urea-glyoxal copolycondensation resin.
Based on the above examples 1 to 3, urea-glyoxal resin was synthesized according to the following process conditions with reference to the prior art for comparison, and a plywood adhesion test was simultaneously performed.
Comparative example 1
The urea-glyoxal resin synthesis process comprises the following steps: preparing a 40% glyoxal solution (G) and urea (U) according to a molar mass ratio of 1.4 (the molar ratio G: U is 1.4:1), adding all the glyoxal solution and 70% of urea into a reaction container at normal temperature, adjusting the pH value of the system to 7.5-8.0 by using a 40% sodium hydroxide aqueous solution, heating to 90 ℃ in a water bath, adding the rest 30% of urea, reacting for 2 hours in a heat preservation manner, discharging and cooling to obtain a target product. Is marked as GU resin.
Comparative example 2
Preparing a branched polyethyleneimine polymer (HPEI) with the average molecular weight of 600-800 and urea (U) according to the molar ratio of 1:8, adding the materials into a reaction container, continuously stirring and heating to 100 ℃ under auxiliary devices such as condensation, reflux and stirring, preserving heat for reaction for 3 hours to obtain a graft modified branched polyethyleneimine polymer product (HPEIU), and cooling to room temperature. Then weighing a certain amount of 40% glyoxal solution (G) and adding the glyoxal solution (G) into the reaction container (the molar ratio G: HPEIU is 1.4:1), adjusting the pH value of the system to 8.0-8.5 by using a 40% sodium hydroxide aqueous solution, heating to 80-85 ℃, refluxing, stirring, keeping the temperature for reaction for 2 hours, discharging and cooling to obtain the target product. Is recorded as GHPEIU resin.
Description of the drawings: the proportion of the HPEI to the U is 1:8, the proportion is preferably selected on the basis of a large number of experiments, if the molar ratio is reduced, the use amount of urea is increased, and the problem that the synthesized product is unstable is also existed, namely the product is easy to precipitate after cooling, and the effect of using the resin as an adhesive is worse; if the molar ratio is increased, the amount of urea used is reduced, but when the urea is mixed with glyoxal, gelation is likely to occur, and the synthesis is difficult to continue. When the method is used, the adjustable range of the proportion of the HPEI to the U is wider, and the requirements of different occasions can be met.
The molecular weight distribution characteristics of the products at different stages during the reaction of example 1 are shown in fig. 1, fig. 2 and fig. 4. Wherein FIG. 1 is a graph of the molecular weight distribution of branched polyethyleneimine (HPEI); FIG. 2 is a graph showing the molecular weight distribution of a graft-modified branched polyethyleneimine polymerization product (HPEIU-1800); FIG. 3 is a graph of the molecular weight distribution of the reaction product of urea and glyoxal in comparative example 1; FIG. 4 is a graph of the molecular weight distribution of the branched polymer-urea-glyoxal resin of example 1. The test of the molecular weight is characterized by an electrospray ionization mass spectrometer (ESI-MS), and the test is obtained by taking water as a solvent and adopting a positive ion mode for testing.
According to the change of the molecular weight distribution and the change of the corresponding molecular weight value in the figure, the calculation is carried out according to the reaction product, the urea is successfully grafted to the terminal amino group of the HPEI polymer, the conversion is successfully realized between different amino groups, and after the copolycondensation reaction is carried out with a urea-glyoxal system, the molecular weight distribution of the product in the figure 4 shows that the unique product distribution characteristic is formed. The calculation results show that the structural formula of the final product is as follows:
FIG. 5 shows the FT-IR test results for the branched polymer-urea-glyoxal copolycondensation resin of example 1. The infrared analysis mainly looks at the change of functional groups, and the functional groups of different products have certain coincidence and are mainly used as an auxiliary analysis means. It can be seen from the line changes corresponding to different systems in the figure that effective crosslinking reaction is formed among the HPEI polymer, urea (U) and glyoxal (G), because some new characteristic absorption peaks appear in the HPEI-U-G system besides part of the functional groups of the substances, which indicates that polymerization products with different connection modes are formed, meaning that the reaction raw materials are crosslinked with each other to form a new target system.
Test example
The preparation process parameters of the three-layer plywood are as follows:
veneer raw materials: fast growing poplar with thickness of 1.5mm and water content of 8-9%;
sizing amount: 220/m2(double-sided);
hot pressing technological parameters: the hot pressing temperature is 160 ℃, the hot pressing time is 3min, and the theoretical pressure is 1.2 MPa.
In order to meet the requirement of the plywood preparation on the viscosity of the adhesive, the cassava starch with the glue solution mass ratio of 5% is added for viscosity adjustment when the adhesive is used.
The resulting three-ply panels were tested for dry and wet bond strength according to the procedures described in the latest GB/T9846-2015 standard. The wet strength test piece treatment method comprises the following steps: and (3) soaking the prepared sample in cold water at normal temperature for 24 hours, taking out the sample, and wiping off the water on the surface of the test piece for testing. The test results are shown in table 1.
Table 1 plywood bond strength test results
As can be seen from table 1, compared with GU resin, the plywood prepared from the branched polymer-urea-glyoxal resin synthesized in the present invention has significantly changed and improved dry strength and cold water soaking resistance wet strength. Although the water resistance of the resin has certain difference under different proportioning conditions, the water resistance is higher than the requirement of 0.7MPa in the standard. Compared with the HPEIUG resin synthesized under the condition of 80-85 ℃ in the comparative example 2, the resin has obvious advantage in the aspect of water resistance. Although the examples are substantially identical to the functional groups contained in the HPEIUG resin, different effects will result due to variations in the components and distribution of the structural components forming the resin system. The process conditions and the implementation steps of the invention have more obvious effects and outstanding advantages.
In the three embodiments, the addition amount of the HPEI in the three systems is changed due to the change of the proportion of the HPEI to the U, so that the water resistance strength of the three systems is different, and the actual requirements of different occasions can be met. Namely, the introduction amount of the HPEI is adjusted to meet the water resistance requirements of different levels, thereby being beneficial to controlling the cost of the resin and matching the performance.
Comparative example 3
In step (1), a branched polyethyleneimine polymer having an average molecular weight of 1800 and urea (U) were prepared at a molar ratio of 1:4, and the other steps were the same as in example 1. Due to the excessive addition of the HPEI, gelation reaction can be quickly generated in the step (2), and a stable adhesive cannot be synthesized.
Comparative example 4
In step (1), a branched polyethyleneimine polymer having an average molecular weight of 1800 and urea (U) were prepared at a molar ratio of 1:12, and the other steps were the same as in example 1. Due to the excessive addition of urea, the synthesized polymer product of the HPEIU-1800 in the step (1) is unstable, and delamination and precipitation can occur within 1 day, so that the subsequent reaction can not be carried out.
Comparative example 5
In the step (1), a branched polyethyleneimine polymer with the average molecular weight of 600-800 is adopted, and the other steps are the same as those in the example 1. The wet bonding strength of the obtained adhesive is poor and is about 0.3 MPa.
Comparative example 6
In step (1), a branched polyethyleneimine polymer having an average molecular weight of 10000 was used, and the other steps were the same as in example 1. The reaction is not well controlled due to the excessive molecular weight of the branched polyethyleneimine polymer. And the increase of the average molecular weight also rapidly increases the cost of the adhesive.
From comparative examples 3 and 4, it can be seen that the molar ratio of HPEI to U is not arbitrarily set, and that either too high or too low results in a stable adhesive. Comparative examples 5 and 6 also show that stable adhesives could not be obtained if the average molecular weight of the HPEI was outside the scope of the present invention.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The branched polymer-urea-glyoxal copolycondensation resin is characterized in that the resin is obtained by carrying out copolycondensation reaction on branched polyethyleneimine, urea and glyoxal.
2. The process for the preparation of the branched polymer-urea-glyoxal copolycondensation resin according to claim 1, comprising the following steps:
the method comprises the following steps: making branched polyethyleneimine and urea undergo the process of grafting reaction to obtain graft-modified branched polyethyleneimine polymerization product, and recording said product as HPEIU-1800;
step two: and (3) mixing the glyoxal aqueous solution with urea, adjusting the pH value to 7.5-8.0, heating and preserving heat for reaction, adding the HPEIU-1800 synthesized in the step one, and continuing heating and preserving heat for reaction to obtain a target product.
3. The method of claim 2, wherein in step one, the branched polyethyleneimine has an average molecular weight of 1800.
4. The method according to claim 2, wherein in the first step, the molar ratio of the branched polyethyleneimine to the urea is 1 (6-10).
5. The method according to claim 2, wherein in the first step, the reaction temperature is 95-100 ℃ and the reaction time is 1-3 hours.
6. The method according to claim 2, wherein the concentration of the aqueous glyoxal solution in step two is 40% by mass.
7. The method according to claim 2, wherein the molar ratio of the glyoxal in the second step to the urea added in the second step is 1 (1.6-1.8), and the molar ratio of the glyoxal in the second step to the sum of the urea in the first step and the urea in the second step is 1 (1.4-1.6).
8. The method according to claim 2, wherein in the second step, the pH value is adjusted by using an alkaline solution, and the alkaline solution is at least one selected from sodium hydroxide and potassium hydroxide aqueous solution.
9. The method according to claim 2, wherein in the second step, the temperature of the two times of heating and heat preservation is 55-65 ℃ for 1-1.5 hours.
10. Use of the resin prepared by the method of any one of claims 2 to 9 in wood adhesives.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005344084A (en) * | 2004-06-07 | 2005-12-15 | Toyo Plywood Kk | Water-based adhesive composition and method for producing the same |
| CN1944564A (en) * | 2006-10-26 | 2007-04-11 | 时君友 | High performance environment friendly urea-formaldehyde resin adhesive and its preparing method and use |
| JP2009249476A (en) * | 2008-04-04 | 2009-10-29 | Eidai Co Ltd | Blending method of adhesive and manufacturing method of woody decorative sheet using adhesive blended by using blending method |
| WO2010130411A1 (en) * | 2009-05-12 | 2010-11-18 | Dynea Oy | Resin with reduced formaldehyde emission |
| US20130240114A1 (en) * | 2012-03-13 | 2013-09-19 | Georgia-Pacific Chemicals Llc | Adhesive compositions having a reduced cure time and methods for making and using same |
| US20140262019A1 (en) * | 2013-03-14 | 2014-09-18 | Georgia-Pacific Chemicals Llc | Urea mixtures and methods for making and using same |
| CN104311767A (en) * | 2014-10-10 | 2015-01-28 | 湖北省宏源药业科技股份有限公司 | Modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN107722209A (en) * | 2017-10-31 | 2018-02-23 | 西南林业大学 | A kind of environmentally friendly condensation copolymerization resin wood adhesive of formaldehydeless release and preparation method and application |
| CN109467697A (en) * | 2018-11-05 | 2019-03-15 | 西南林业大学 | A kind of branched polyamide-glyoxal resin adhesive and preparation method and application |
| CN112646511A (en) * | 2020-12-04 | 2021-04-13 | 西南林业大学 | Functional curing agent and preparation method thereof |
-
2021
- 2021-07-20 CN CN202110817968.3A patent/CN113336908B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005344084A (en) * | 2004-06-07 | 2005-12-15 | Toyo Plywood Kk | Water-based adhesive composition and method for producing the same |
| CN1944564A (en) * | 2006-10-26 | 2007-04-11 | 时君友 | High performance environment friendly urea-formaldehyde resin adhesive and its preparing method and use |
| JP2009249476A (en) * | 2008-04-04 | 2009-10-29 | Eidai Co Ltd | Blending method of adhesive and manufacturing method of woody decorative sheet using adhesive blended by using blending method |
| WO2010130411A1 (en) * | 2009-05-12 | 2010-11-18 | Dynea Oy | Resin with reduced formaldehyde emission |
| US20130240114A1 (en) * | 2012-03-13 | 2013-09-19 | Georgia-Pacific Chemicals Llc | Adhesive compositions having a reduced cure time and methods for making and using same |
| US20140262019A1 (en) * | 2013-03-14 | 2014-09-18 | Georgia-Pacific Chemicals Llc | Urea mixtures and methods for making and using same |
| CN104311767A (en) * | 2014-10-10 | 2015-01-28 | 湖北省宏源药业科技股份有限公司 | Modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN107722209A (en) * | 2017-10-31 | 2018-02-23 | 西南林业大学 | A kind of environmentally friendly condensation copolymerization resin wood adhesive of formaldehydeless release and preparation method and application |
| CN109467697A (en) * | 2018-11-05 | 2019-03-15 | 西南林业大学 | A kind of branched polyamide-glyoxal resin adhesive and preparation method and application |
| CN112646511A (en) * | 2020-12-04 | 2021-04-13 | 西南林业大学 | Functional curing agent and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| DARIA A. PERMINOVA，等: "Influence of glyoxal on curing of urea-formaldehyde resins", 《INTERNATIONAL JOURNAL OF ADHESION AND ADHESIVES》 * |
| HUI WANG，等: "Enhanced performance of urea–glyoxal polymer with oxidized cassava starch as wood adhesive", 《IRANIAN POLYMER JOURNAL》 * |
| HUI WANG，等: "Preparation and performance of a novel wood adhesive based on hyper‑branched polyethyleneimine, urea and glyoxal", 《IRANIAN POLYMER JOURNAL》 * |
| SHUDUAN DENG，等: "Performance, Reaction Mechanism, and Characterization of Glyoxal–Monomethylol Urea (G–MMU) Resin", 《IND. ENG. CHEM. RES.》 * |
| 刘国伟，等: "聚乙烯亚胺-尿素-乙二醛树脂的合成及性能评价", 《林业工程学报》 * |
| 王凤，等: "聚乙烯亚胺改性尿素-乙二醛聚合物树脂性能研究", 《西北林业学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160520A (en) * | 2022-08-03 | 2022-10-11 | 西南林业大学 | Reticular hyperbranched amino copolycondensation resin and preparation method and application thereof |
| CN115160520B (en) * | 2022-08-03 | 2023-07-04 | 西南林业大学 | Net-shaped hyperbranched amino copolycondensation resin and preparation method and application thereof |
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