CN109517577B - Tough soybean meal protein adhesive and preparation method thereof - Google Patents
Tough soybean meal protein adhesive and preparation method thereof Download PDFInfo
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- CN109517577B CN109517577B CN201811409054.8A CN201811409054A CN109517577B CN 109517577 B CN109517577 B CN 109517577B CN 201811409054 A CN201811409054 A CN 201811409054A CN 109517577 B CN109517577 B CN 109517577B
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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
- 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
- C09J11/04—Non-macromolecular additives inorganic
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a tough soybean meal protein adhesive and a preparation method thereof, wherein the tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight: soybean meal, trypsin, dispersion medium water, sodium periodate, triethylene tetramine, dodecyl glycidyl ether and a curing agent. The tough soybean meal protein adhesive prepared by the method of the invention comprises the following steps: the soybean meal molecules are degraded, modified and recombined to form a prepolymer, so that the protein is fully extended, the molecular active groups are obviously increased, the reaction activity is improved, the solubility and the water retention are improved, the toughness is increased, and the adhesive prepared by adding the curing agent has high water-resistant bonding performance and high stability; the waterproof requirement of the artificial board adhesive can be met, the consumption of the cross-linking agent is reduced, so that the cost of the adhesive is reduced, and the practicability of the protein adhesive is ensured.
Description
Technical Field
The invention relates to the technical field of artificial board adhesives, in particular to a tough soybean meal protein adhesive and a preparation method thereof.
Background
China is deficient in precious wood resources, but has abundant artificial forest resources, artificial boards prepared from artificial forest fast growing wood and agricultural forest processing residues through adhesives are main raw materials for furniture floors and indoor decoration in human living environment, the total yield of the artificial boards in China is 3.2 billion cubic meters in 2016 years, and accounts for about 50% of the total yield in the world. According to the calculation that an artificial board with 9 cubic meters is produced on average per ton of adhesive, the wood adhesive consumption in 2015 in China is about 4000 ten thousand tons (solid content is 50%), wherein the urea-formaldehyde resin and modified products thereof account for more than 90% of the total output of the adhesive and dominate. The urea-formaldehyde resin adhesive is widely used in the wood industry due to the advantages of sufficient raw materials, low price, good water solubility, light color of an adhesive layer and the like. However, the urea-formaldehyde resin also has obvious defects, such as poor aging resistance and water resistance, and the like, and cannot be used for preparing outdoor artificial boards, and the like, and the fatal defects of the urea-formaldehyde resin are that the glued artificial boards have the problem of formaldehyde release, pollute the living environment and damage the body health of people.
The artificial board prepared by adopting the vegetable protein adhesive can solve the problem of free formaldehyde emission of the artificial board, but has the problems of poor water-resistant adhesive bonding performance and unstable production, which are caused by poor protein solubility, large particle size and large molecular weight of raw materials such as bean pulp, cotton pulp and peanut pulp for preparing the protein adhesive, and the modification method of adding the external cross-linking agent cannot modify a matrix, so that the cross-linking structure of the protein adhesive is unevenly distributed, a large number of weak interface layers are formed, the water retention capacity is poor, and although the average strength meets the requirement, the adhesive bonding quality difference of different areas of the artificial board is large, the adhesive bonding strength is unstable and the production efficiency is low.
Disclosure of Invention
Aiming at the defects, the invention aims to provide the tough soybean meal protein adhesive and the preparation method thereof, and the adhesive has the special characteristics of high toughness besides small molecular weight, high activity, high curing speed, strong water retention capacity, high water-resistant bonding performance and high stability, can effectively reduce the internal stress of the prepared artificial board, has high dry strength and water-resistant bonding performance of the prepared board, and can meet the water-resistant requirement of the artificial board adhesive; and the preparation method has low cost and is easy to implement.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight:
35 parts of soybean meal, 0.1-0.3 part of trypsin, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of triethylene tetramine, 0.3-0.8 part of dodecyl glycidyl ether and 0.6-1.0 part of curing agent.
The preferable mode is that the feed is composed of the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of trypsin, 70 parts of dispersion medium water, 2 parts of sodium periodate, 0.2 part of triethylene tetramine, 0.3 part of dodecyl glycidyl ether and 0.6 part of curing agent.
The preferable mode is that the feed is composed of the following raw materials in parts by weight: 35 parts of soybean meal, 0.3 part of trypsin, 70 parts of dispersion medium water, 5 parts of sodium periodate, 0.5 part of triethylene tetramine, 0.8 part of dodecyl glycidyl ether and 1 part of curing agent.
Preferably, the content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes.
Preferably, the trypsin molecular weight reducing agent is a protease.
Preferably, the sodium periodate and the triethylene tetramine are both activators.
Preferably, the dodecyl glycidyl ether is a protein molecule recombination agent.
Preferably, the curing agent is glycerol triglycidyl ether.
Preferably, the dispersion medium water is selected from common tap water or softened water.
A preparation method of the tough soybean meal protein adhesive comprises the following steps:
(1) weighing the components according to the weight ratio in the tough soybean meal protein adhesive to prepare raw materials;
(2) uniformly dispersing soybean meal powder, water and trypsin in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, reacting for 5 hours, adding triethylene tetramine, reacting for 2 hours at 50 ℃, heating to 90 ℃, and reacting for 6 hours;
(4) heating the mixture obtained in the step 3 to 80 ℃, adjusting the pH to =10, adding dodecyl glycidyl ether to react for 3 hours, cooling and discharging to obtain a prepolymer of the tough soybean meal protein adhesive;
(5) and (4) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing.
After the technical scheme is adopted, the invention has the beneficial effects that:
the tough soybean meal protein adhesive and the preparation method thereof are characterized in that the tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight: soybean meal, trypsin, dispersion medium water, sodium periodate, triethylene tetramine, dodecyl glycidyl ether and a curing agent. The adhesive disclosed by the invention has the special characteristics of high toughness besides small molecular weight, high activity, high curing speed, strong water retention capacity, high water-resistant bonding performance and high stability, can effectively reduce the internal stress of the prepared artificial board, has high dry strength and water-resistant bonding performance of the prepared board, and can meet the water-resistant requirement of the artificial board adhesive.
The soybean meal molecules are degraded, modified and recombined to form a prepolymer, so that the protein is fully extended, the molecular active groups are obviously increased, the reaction activity is improved, the solubility and the water retention are improved, and the adhesive prepared by adding the curing agent has high water-resistant adhesive bonding performance and high stability; the waterproof requirement of the artificial board adhesive can be met, the consumption of the cross-linking agent is reduced, so that the cost of the adhesive is reduced, and the practicability of the protein adhesive is ensured.
Trypsin in the raw material enables protein to be unfolded and hydrolyzed into small molecular polypeptide chains, and internal active groups are fully exposed; sodium periodate oxidizes the inert hydroxyl on polypeptide, polysaccharide and fiber to raise reaction activity, and triethylene tetramine can be grafted on the oxidized polypeptide, protein and fiber to provide lots of amino groups. The activating agent can effectively stretch and break the soybean meal molecules, increase the number and types of reactive groups on the soybean meal molecules, improve the reactivity of the soybean meal molecules and reduce the viscosity of the adhesive.
In the raw material, the dodecyl glycidyl ether is a protein molecule recombination agent, so that hydrolyzed small molecular proteins can be recombined to form a prepolymer with a certain molecular weight, the cohesion of the adhesive molecule is increased, and in addition, the dodecyl glycidyl ether is a long-chain structure, so that the flexibility of the adhesive molecule can be improved.
The curing agent in the raw material is glycerol triglycidyl ether, and can effectively react with hydroxyl and amino in the soybean meal molecules to form a cross-linked network structure so as to cure the adhesive.
The invention has the advantages that:
1) according to the invention, the degradation agent and the activating agent are adopted, so that the soybean meal molecules are fully stretched and broken to form soybean meal micromolecules, the number and the types of active groups of a molecular system are increased, and the reaction activity is improved;
2) according to the invention, activated small-molecular soybean meal is connected into the soybean meal protein adhesive prepolymer with a certain molecular weight by adopting the epoxide, so that the problem of low adhesive strength caused by adhesive penetration caused by hydrolysis of the soybean meal into small molecules is solved. In addition, the formed prepolymer of the soybean meal protein adhesive has uniform molecular weight, good permeability, good water solubility and good water-retaining property, the problems of low adhesive dry strength, poor adhesive stability, poor water-retaining property and poor water solubility of the common protein adhesive are solved by the prepared adhesive, the reaction activity is improved, the types and the number of the soybean meal molecules are increased, the reaction capacity with a cross-linking agent is increased, and the using amount of a curing agent is reduced;
3) according to the preparation method, toxic substances are not added, the molecules of the soybean meal are degraded by using protease, the types and the number of reactive groups of the soybean meal are effectively improved by using an activating agent on the basis of degrading small molecules, the molecules of the soybean meal are recombined by using an epoxide to form a prepolymer of the soybean meal raw material, and finally a curing agent is added to cure the soybean meal protein adhesive. High efficiency, no release of harmful substances, high reaction activity of product, good solubility and water retention. The adhesive prepared can effectively improve the performance of the adhesive and promote the application of the protein adhesive;
the test proves that: the bean pulp protein adhesive has the advantages of good water retention, high solubility, high curing speed, easy formation of a cross-linked structure, high cross-linked density, good water resistance and stable performance after curing, and the prepared plywood product has stable and improved quality and obviously reduced weak interface layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The percent in the present invention means mass percent unless otherwise specified; but the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains several grams of solute; the percentage between the liquids refers to the ratio of the volumes at 20 ℃.
The general scheme is as follows:
the tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight:
35 parts of soybean meal, 0.1-0.3 part of trypsin, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of triethylene tetramine, 0.3-0.8 part of dodecyl glycidyl ether and 0.6-1.0 part of curing agent.
The content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes.
The above-mentioned trypsin molecular weight reducing agent.
The sodium periodate and the triethylene tetramine are both activating agents.
The dodecyl glycidyl ether is a protein molecule recombination agent.
The curing agent is glycerol triglycidyl ether.
The dispersion medium water is selected from common tap water or softened water.
The tough soybean meal protein adhesive has the advantages that: the soybean meal molecules are degraded, modified and recombined to form a prepolymer, so that the protein is fully extended, the molecular active groups are obviously increased, the reaction activity is improved, the solubility and the water retention are improved, the toughness is increased, and the adhesive prepared by adding the curing agent has high water-resistant bonding performance and high stability; the waterproof requirement of the artificial board adhesive can be met, the consumption of the cross-linking agent is reduced, so that the cost of the adhesive is reduced, and the practicability of the protein adhesive is ensured.
Example 1
The tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight:
70 kg of softened water;
35 kg of defatted soybean protein powder;
0.1kg of trypsin;
2kg of sodium periodate;
0.2kg of triethylene tetramine;
0.3kg of dodecyl glycidyl ether;
0.6kg of curing agent.
When the tough soybean meal protein adhesive in the embodiment is used: stirring the prepared soybean meal protein adhesive prepolymer and the curing agent for 10 minutes at normal temperature, and uniformly stirring for use.
Example 2
The tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight:
70 kg of softened water;
35 kg of defatted soybean protein powder;
0.3kg of trypsin;
5kg of sodium periodate;
0.5kg of triethylene tetramine;
0.8kg of dodecyl glycidyl ether;
1kg of curing agent.
Example 3
A preparation method of the tough soybean meal protein adhesive comprises the following steps:
(1) weighing the components according to the weight ratio in the tough soybean meal protein adhesive to prepare raw materials;
(2) uniformly dispersing soybean meal powder, water and trypsin in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, reacting for 5 hours, adding triethylene tetramine, reacting for 2 hours at 50 ℃, heating to 90 ℃, and reacting for 6 hours;
(4) heating the mixture obtained in the step 3 to 80 ℃, adjusting the pH to =10, adding dodecyl glycidyl ether to react for 3 hours, cooling and discharging to obtain a prepolymer of the tough soybean meal protein adhesive;
(5) and (4) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing.
The preparation methods provided in this example can be used for both the aldehyde protein adhesives of example 1 and example 2. The preparation method has the advantages of low cost and easy implementation, so that the tough soybean meal protein adhesive can be processed in a large scale and is widely used.
Comparative examples 1 to 3
Compared with examples 1-2, control 1 was a mixture of common soybean meal powder, water and curing agent; the control group 2 is the soybean meal powder which is not degraded and is mixed with activated water and curing agent; the control group 3 is a soybean meal protein adhesive which is degraded and activated to generate a prepolymer but is not added with a curing agent.
Test examples
Three-layer plywood was prepared using the adhesives of examples 1-2 and comparative examples 1-3, respectively, of the present invention.
Poplar veneer: drying to 10% of water content; size 40cm by 0.15 cm.
The preparation method comprises the following normal preparation processes:
sizing: the glue coating amount is 400g/m2。
Pressure, temperature, time: 0.8MPa, 120 ℃ for 6 minutes.
The performance of the transverse spliced product is detected according to the detection method of GB/T17657-1999 test method for physical and chemical properties of artificial boards and facing artificial boards, and the detection result is shown in Table 1.
TABLE 1 plywood bond Strength
The experimental result shows that the water-resistant bonding performance of the prepared plywood can be effectively improved by the bean pulp protein adhesive, the bonding strength is higher than 1.25MPa and the dry strength is higher than 1.50 percent according to the detection of a II plywood, the bonding strength is improved by about 50 percent compared with that of a control group, the standard deviation calculation shows that the stability of the adhesive prepared from activated bean pulp protein is obviously improved, and the reinforcing effect is obvious. The breaking elongation reaches more than 5 percent, and the high-temperature curing speed reaches within 5 minutes.
The above-mentioned preferred embodiments of the present invention are not intended to limit the present invention, and any modification, equivalent to a tough soybean meal protein adhesive and structural improvement of the preparation method thereof, made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of a tough soybean meal protein adhesive is characterized in that,
the tough soybean meal protein adhesive is prepared from the following raw materials in parts by weight: 35 parts of soybean meal, 0.1-0.3 part of trypsin, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of triethylene tetramine, 0.3-0.8 part of dodecyl glycidyl ether and 0.6-1.0 part of curing agent; the content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes; the curing agent is glycerol triglycidyl ether;
the preparation method comprises the following steps:
(1) weighing the components according to the weight ratio in the tough soybean meal protein adhesive to prepare raw materials;
(2) uniformly dispersing soybean meal powder, water and trypsin in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, adding triethylene tetramine after reacting for 5 hours, reacting for 2 hours at 50 ℃, heating to 90 ℃, and reacting for 6 hours;
(4) heating the mixture obtained in the step (3) to 80 ℃, adjusting the pH to =10, adding dodecyl glycidyl ether to react for 3 hours, cooling and discharging to obtain a tough soybean meal protein adhesive prepolymer;
(5) and (3) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing, wherein the curing agent is glycerol triglycidyl ether.
2. The preparation method of the tough soybean meal protein adhesive according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of trypsin, 70 parts of dispersion medium water, 2 parts of sodium periodate, 0.2 part of triethylene tetramine, 0.3 part of dodecyl glycidyl ether and 0.6 part of curing agent.
3. The preparation method of the tough soybean meal protein adhesive according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 35 parts of soybean meal, 0.3 part of trypsin, 70 parts of dispersion medium water, 5 parts of sodium periodate, 0.5 part of triethylene tetramine, 0.8 part of dodecyl glycidyl ether and 1 part of curing agent.
4. The preparation method of the tough soybean meal protein adhesive according to any one of claims 1 to 3, wherein the dispersion medium water is selected from common tap water or softened water.
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| CN102746821A (en) * | 2012-07-25 | 2012-10-24 | 武秀英 | Biological adhesive for plywood and preparation method thereof |
| CN104610909A (en) * | 2015-02-26 | 2015-05-13 | 许丽萍 | Aldehyde-free vegetable protein-based wood adhesive as well as preparation and application methods thereof |
| CN104629678A (en) * | 2015-03-10 | 2015-05-20 | 茌平县廷森木业有限公司 | Water-resistant bio-based formaldehyde-free adhesive for wood and preparation method thereof |
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