CN114806496A - High-performance mildew-proof antibacterial soybean meal adhesive and preparation method thereof - Google Patents
High-performance mildew-proof antibacterial soybean meal adhesive and preparation method thereof Download PDFInfo
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- CN114806496A CN114806496A CN202210570650.4A CN202210570650A CN114806496A CN 114806496 A CN114806496 A CN 114806496A CN 202210570650 A CN202210570650 A CN 202210570650A CN 114806496 A CN114806496 A CN 114806496A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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Abstract
The invention belongs to the technical field of biomass adhesives, and particularly relates to a high-performance mildew-proof antibacterial soybean meal adhesive and a preparation method thereof. The adhesive is prepared by taking soybean meal as a main body of the adhesive, adding assistants such as modified nanocellulose and tannic acid, adjusting the pH of an adhesive system to 9.5 by using an alkaline liquid, and uniformly stirring. The method has the advantages that the nanocellulose modified by the phenylboronic acid surface is used to cooperate with the tannic acid to enhance the adhesive for the soybean meal, and the phenylboronic acid group can react with polysaccharide and soybean protein in the soybean meal under the alkaline condition, so that the strength of the adhesive is improved; in addition, the introduced phenylboronic acid, the tannic acid and the like have certain inhibition effects on fungi and bacteria, and the storage period of the adhesive can be prolonged; the prepared plywood does not release formaldehyde, and the problem of formaldehyde pollution in indoor air caused by the artificial board is thoroughly solved; in addition, the invention does not use chemical cross-linking agent, thus conforming to the principles of environmental protection and sustainable development.
Description
Technical Field
The invention belongs to the technical field of biomass adhesives, and particularly relates to a high-performance mildew-proof antibacterial soybean meal adhesive and a preparation method thereof.
Background
The aldehyde resin adhesive has a leading position in the artificial board industry in China, but has the problems of serious formaldehyde pollution, dependence on raw material fossil resources and the like. The soybean meal adhesive has a series of advantages of environmental protection, abundant sources, renewable utilization and the like, and is a biomass adhesive which is most widely researched and applied in the wood industry. The soybean meal adhesive is popularized and applied in artificial board enterprises in China, but the using amount of the soybean meal adhesive is less than 0.1 percent of the total amount of the wood adhesive, and the key reason is that the soybean meal adhesive has poor water-resistant bonding strength and is easy to deteriorate and go moldy. Many foreign researchers have proved that the water-resistant bonding strength and stability of the soybean meal adhesive can be improved by increasing the crosslinking density of the soybean protein in the soybean meal. However, crosslinking modification can cause the adhesive layer to be hard and brittle after the adhesive is cured, and the adhesive still has the problem of easy mildewing and deterioration.
The polysaccharide component with the content of about 35 percent in the soybean meal has high hydrophilicity and low chemical activity, and the negative influence on the water-resistant cementing property of the adhesive cannot be ignored. Therefore, if the polysaccharide component in the bean pulp can be fully utilized, and the problems of poor toughness and easy deterioration of the cured adhesive layer are effectively solved, the key point for improving the performance of the artificial board bonded by the bean pulp adhesive and realizing the large-scale application of the bean pulp in the artificial board is to improve the performance of the artificial board bonded by the bean pulp adhesive.
Disclosure of Invention
The invention provides a high-performance mildew-proof antibacterial soybean meal adhesive, and a preparation method and application thereof, aiming at overcoming the defects of the prior art.
The technical solution for realizing the above purpose of the present invention is:
a preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive comprises the following steps:
step 1: preparing a modified nano-cellulose solution as a cross-linking agent;
step 2: dispersing bean pulp in a modified nano cellulose solution and stirring to obtain a first mixed solution;
and step 3: dispersing tannic acid in the first mixed solution, and stirring to obtain a second mixed solution;
and 4, step 4: and adjusting the pH value of the second mixed solution to a preset value by using alkaline liquid, and stirring and dispersing uniformly to obtain the soybean meal adhesive.
Further, the step 1 specifically includes:
step 1.1: dispersing the Tempo oxidized nano-cellulose in a phosphate buffer solution to prepare a suspension with a preset percent of solid content;
step 1.2: 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and hydroxysuccinimide (NHS) were added to the suspension of step 1.1 in N 2 Stirring at 25 ℃ in the environment to obtain a third mixed solution;
step 1.3: and adding 3-aminophenylboronic acid into the third mixed solution, continuously stirring at room temperature to obtain a fourth mixed solution, and dialyzing the fourth mixed solution to obtain the phenylboronic acid group functionalized modified nano-cellulose solution.
Further, the predetermined percentage of the solid content in step 1.1 is 0.5%, the stirring time in step 1.2 is 30 minutes, and the stirring time at room temperature in step 1.3 is 12 hours.
Further, the mass ratio of the 3-aminophenylboronic acid to the Tempo-oxidized nanocellulose is (2-4): (1-3).
Further, the mass ratio of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) to hydroxysuccinimide (NHS) is (15-16): (1-3).
Further, the stirring time in the step 2 is 10 minutes, the stirring time in the step 3 is 5 minutes, and the stirring time in the step 4 is 10 minutes.
Further, the soybean meal is low-temperature defatted soybean meal, the protein content of the soybean meal is about 46%, the soybean polysaccharide content of the soybean meal is about 35%, and the particle sizes of the soybean meal are 150-180 meshes.
Further, the alkaline liquid in the step 4 is an aqueous solution of NaOH.
Further, in the step 4, the pH of the second mixed solution is adjusted to 9.5.
The high-performance mildew-proof antibacterial soybean meal adhesive is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the nano-cellulose with the phenylboronic acid surface modified and the tannic acid are adopted to enhance the adhesive for the soybean meal, and the phenylboronic acid group can react with polysaccharide and soybean protein in the soybean meal under an alkaline condition, so that the strength of the adhesive is improved; in addition, the introduced phenylboronic acid, the tannic acid and the like have certain inhibition effects on fungi and bacteria, and the storage period of the adhesive can be prolonged.
(2) According to the invention, the polysaccharide and the soybean protein in the soybean meal both participate in the crosslinking reaction of the adhesive system, so that the consumption of the polysaccharide and the soybean protein also plays a positive role in mildew prevention and antibiosis.
(3) The plywood prepared by the invention has no formaldehyde release, and thoroughly solves the problem of formaldehyde pollution in indoor air caused by artificial boards.
(4) In the invention, no chemical cross-linking agent is used, and the used soybean meal, nano-cellulose and tannin are sustainable regeneration materials, thereby conforming to the principles of environmental protection and sustainable development.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The invention relates to a preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive, which comprises the following steps:
step 1: preparing a modified nano-cellulose solution as a cross-linking agent;
step 2: dispersing the soybean meal in a modified nano cellulose solution and stirring to obtain a first mixed solution;
and step 3: dispersing tannic acid in the first mixed solution, and stirring to obtain a second mixed solution;
and 4, step 4: and adjusting the pH value of the second mixed solution to a preset value by using alkaline liquid, and stirring and dispersing uniformly to obtain the soybean meal adhesive.
Preferably, the step 1 specifically includes:
step 1.1: dispersing the Tempo oxidized nano-cellulose in a phosphate buffer solution to prepare a suspension with a preset percent of solid content;
step 1.2: 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and hydroxysuccinimide (NHS) were added to the suspension of step 1.1 in N 2 Stirring at 25 ℃ in the environment to obtain a third mixed solution;
step 1.3: and adding 3-aminophenylboronic acid into the third mixed solution, continuously stirring at room temperature to obtain a fourth mixed solution, and dialyzing the fourth mixed solution to obtain the phenylboronic acid group functionalized modified nano-cellulose solution.
Preferably, the predetermined percentage of solids content in step 1.1 is 0.5%, the stirring time in step 1.2 is 30 minutes, and the stirring time at room temperature in step 1.3 is 12 hours.
Preferably, the mass ratio of the 3-aminophenylboronic acid to the Tempo-oxidized nanocellulose is (2-4): (1-3).
Preferably, the mass ratio of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) to hydroxysuccinimide (NHS) is (15-16): (1-3).
Preferably, the stirring time in the step 2 is 10 minutes, the stirring time in the step 3 is 5 minutes, and the stirring time in the step 4 is 10 minutes.
Preferably, the pH of the second mixed solution is adjusted to 9.5 in the step 4.
Wherein the soybean meal is low-temperature defatted soybean meal, the protein content of the soybean meal is about 46%, the soybean polysaccharide content of the soybean meal is about 35%, and the particle sizes of the soybean meal are 150-180 meshes; the Tempo oxidized nano-cellulose is a commercial product and can be purchased from Tianjin xylem Biotechnology limited company; tannic acid is a commercially available product available from Tianjin Xiansi Biotechnology Ltd; the alkaline liquid is NaOH aqueous solution.
Specific examples and comparative examples are given below.
Example one
A preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive comprises the following steps:
(1) dispersing 15g of soybean meal in the modified nano-cellulose solution, and mechanically stirring for 10 minutes;
(2) adding 2.00g of tannic acid into the solution in the step (1), and stirring for 5 minutes;
(3) and then adjusting the pH value of the adhesive to 9.5 by using alkaline liquid, stirring for 10 minutes, and uniformly dispersing.
The performance and quality indexes of the obtained adhesive are shown in table 1.
Example two
A preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive comprises the following steps:
(1) dispersing 15g of soybean meal in the modified nano-cellulose solution, and mechanically stirring for 10 minutes;
(2) adding 2.75g of tannic acid into the solution in the step (1), and stirring for 5 minutes;
(3) and then adjusting the pH value of the adhesive to 9.5 by using alkaline liquid, stirring for 10 minutes, and uniformly dispersing.
The performance and quality indexes of the obtained adhesive are shown in table 1.
EXAMPLE III
A preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive comprises the following steps:
(1) dispersing 15g of soybean meal in the modified nano-cellulose solution, and mechanically stirring for 10 minutes;
(2) and (3) adding 2.75g of tannic acid into the solution in the step (1), stirring for 15 minutes, and uniformly dispersing.
The performance and quality indexes of the obtained adhesive are shown in table 1.
Comparative example 1
(1) Uniformly dispersing 15g of soybean meal in 38g of water, and mechanically stirring for 10 minutes to uniformly disperse the soybean meal.
The performance and quality indexes of the obtained adhesive are shown in table 1.
Comparative example No. two
(1) Uniformly dispersing 15g of soybean meal in 38g of water, and mechanically stirring for 10 minutes;
(2) and (3) adding 2.75g of tannic acid into the solution in the step (1), stirring for 15 minutes, and uniformly dispersing.
The performance and quality indexes of the obtained adhesive are shown in table 1.
Comparative example No. three
(1) Dispersing 15g of soybean meal in an untreated nano-cellulose solution, and mechanically stirring for 10 minutes;
(2) and (3) adding 2.75g of tannic acid into the solution in the step (1), stirring for 15 minutes, and uniformly dispersing.
The performance and quality indexes of the obtained adhesive are shown in table 1.
The modified soybean meals prepared in examples 1 to 3 of the present invention and comparative examples 1 to 3 were tested as follows.
Specifically, three-layer plywood was prepared from the adhesives obtained in the above examples and comparative examples, and the water-resistant bonding strength was tested.
The size of the poplar veneer is 400 multiplied by 1.6mm 3 The glue application amount is 400g/m 2 And (3) gluing the two sides of the core plate, and hot-pressing for 6 minutes at the unit pressure of 1MPa and the temperature of 120 ℃. The performance of the produced plywood product is detected according to the detection method of GB/T17657-1999 test method for physical and chemical properties of artificial boards and veneered artificial boards, and the detection result is shown in Table 1.
TABLE 1 test result table of samples
The experimental result shows that the formaldehyde release amount of the plywood manufactured by the formaldehyde-free biomass adhesive is very low (the formaldehyde is released by wood body), the bonding strength of the plywood can reach 0.92MPa (more than or equal to 0.7MPa of poplar) according to the detection of national standard II plywood, and is obviously improved compared with a control group, mainly because in a weak alkaline environment, the phenylboronic acid groups on the surface of the modified nano-cellulose, functional groups in a bean pulp matrix (such as glycol on a soybean polysaccharide chain, amino on a soybean protein chain and the like) and pyrocatechol and pyrogallol on tannic acid generate stronger chemical bonding effect.
Experiments prove that the three-layer plywood manufactured by the product of the invention has no formaldehyde release problem, the bonding strength is 0.92MPa, and the standard of national standard II-type plywood is met; in addition, the product of the invention has certain mildew resistance and has obvious bacteriostatic action on escherichia coli and staphylococcus aureus.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of a high-performance mildew-proof antibacterial soybean meal adhesive is characterized by comprising the following steps:
step 1: preparing a modified nano-cellulose solution as a cross-linking agent;
step 2: dispersing the soybean meal in a modified nano cellulose solution and stirring to obtain a first mixed solution;
and step 3: dispersing tannic acid in the first mixed solution, and stirring to obtain a second mixed solution;
and 4, step 4: and adjusting the pH value of the second mixed solution to a preset value by using alkaline liquid, and stirring and dispersing uniformly to obtain the soybean meal adhesive.
2. The preparation method of the high-performance mildewproof antibacterial soybean meal adhesive according to claim 1, wherein the step 1 specifically comprises the following steps:
step 1.1: dispersing the Tempo oxidized nano-cellulose in a phosphate buffer solution to prepare a suspension with a preset percent of solid content;
step 1.2: 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and hydroxysuccinimide (NHS) were added to the suspension of step 1.1 in N 2 Stirring at 25 ℃ in the environment to obtain a third mixed solution;
step 1.3: and adding 3-aminophenylboronic acid into the third mixed solution, continuously stirring at room temperature to obtain a fourth mixed solution, and dialyzing the fourth mixed solution to obtain the phenylboronic acid group functionalized modified nano-cellulose solution.
3. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to claim 2, which is characterized in that,
the preset percentage of the solid content in the step 1.1 is 0.5%, the stirring time in the step 1.2 is 30 minutes, and the continuous stirring time at room temperature in the step 1.3 is 12 hours.
4. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to claim 2, which is characterized in that,
the mass ratio of the 3-aminophenylboronic acid to the Tempo oxidized nano cellulose is (2-4): (1-3).
5. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to claim 2, which is characterized in that,
the mass ratio of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) to hydroxysuccinimide (NHS) is (15-16): (1-3).
6. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to any one of claims 2 to 5,
the stirring time in the step 2 is 10 minutes, the stirring time in the step 3 is 5 minutes, and the stirring time in the step 4 is 10 minutes.
7. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to any one of claims 2 to 5,
the soybean meal is low-temperature defatted soybean meal, the protein content of the soybean meal is about 46%, the soybean polysaccharide content of the soybean meal is about 35%, and the particle sizes of the soybean meal are 150-180 meshes.
8. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to any one of claims 2 to 5,
and the alkaline liquid in the step 4 is NaOH aqueous solution.
9. The preparation method of the high-performance mildewproof and antibacterial soybean meal adhesive according to any one of claims 2 to 5,
in the step 4, the pH value of the second mixed solution is adjusted to 9.5.
10. The high-performance mildew-proof antibacterial soybean meal adhesive is characterized by being prepared by the preparation method of claims 1-9.
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| CN115491174A (en) * | 2022-09-27 | 2022-12-20 | 湖州市南浔区绿色家居产业研究院 | Soybean meal adhesive and preparation method thereof |
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Cited By (2)
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| CN115491174A (en) * | 2022-09-27 | 2022-12-20 | 湖州市南浔区绿色家居产业研究院 | Soybean meal adhesive and preparation method thereof |
| CN115491174B (en) * | 2022-09-27 | 2024-03-19 | 湖州市南浔区绿色家居产业研究院 | Bean pulp adhesive and preparation method thereof |
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