CN110003848B - Preparation method of aldehyde-free modified soy protein adhesive - Google Patents
Preparation method of aldehyde-free modified soy protein adhesive Download PDFInfo
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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
- 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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Abstract
The application discloses a preparation method of an aldehyde-free modified soy protein adhesive, which comprises the following steps: (1) mixing defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride and water, stirring and reacting at 45-52 ℃ for 9-12 hr, and naturally cooling to room temperature; (2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 1-3 hours at 65-72 ℃, and naturally cooling to room temperature; the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and the P123 type PEO-PPO-PEO block copolymer is 40-50: 4-5: 0.5-1.0: 0.2-0.3: 100: 1-2: 2-3: 7-9; has the advantage of improving the water-resistant bonding strength.
Description
Technical Field
The invention relates to a preparation method of an aldehyde-free modified soy protein adhesive.
Background
As one of the raw materials for developing the wood industry, adhesives have been used for a long time. Until 600 years ago, people use natural adhesives to bond living goods. In the 80 s of the 20 th century, along with social progress and high-speed development of science and technology, the use of the adhesive also permeates all aspects of national life, and plays a role in promoting the rapid development of economy. In the late twentieth century, "trioxai glue" mainly composed of a polymer material and a composite material slowly entered the lives of people. The raw materials of the trialdehyde glue are from petroleum, and the trialdehyde glue has abundant petroleum resources and excellent performance in China, so that the trialdehyde glue plays an important role in industrial production. However, these materials contain many organic substances and pose a threat to human health and even have carcinogenic effects. In the face of increasingly strict environmental protection conditions in the market, people's demands for adhesives tend to low-toxicity and nontoxic green environmental-protection adhesives.
The soybean protein adhesive is a vegetable protein adhesive prepared by adding a modifier or an auxiliary agent into natural raw materials such as soybean flour or soybean meal. The method solves the formaldehyde hazard from the source, the soybean in China has wide planting area, easy cultivation and low cost, and the soybean protein adhesive is more and more popular internationally due to the economic characteristics of 'green, environmental protection and circulation' nowadays.
However, the water-resistant bonding strength of the soybean protein glue can not meet the requirement of industrial application, and the popularization of the soybean glue is greatly hindered.
Disclosure of Invention
The invention aims to provide a preparation method of an aldehyde-free modified soy protein adhesive, which has the advantage of improving the waterproof bonding strength.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride and water, stirring and reacting at 45-52 ℃ for 9-12 hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 1-3 hours at 65-72 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and the P123 type PEO-PPO-PEO block copolymer is 40-50: 4-5: 0.5-1.0: 0.2-0.3: 100: 1-2: 2-3: 7-9.
By adopting the technical scheme, the molecular structure of the protein is firstly destroyed by utilizing urea, the hydrophobic groups in the molecules are exposed, so that the solubility of the protein in water is reduced, the molecular structure of the protein is changed from curling to stretching, part of reactive active sites in the exposed molecules are exposed, the bonding force between the protein and other molecules is increased to cause reaction, and hydrophobicity is generated; then, the nicotinamide and zinc carbonate are used for filling the interior of the protein to improve the action area, improve the wettability and enhance the bonding strength, and the modified protein has proper crystallinity and obtains proper porosity; meanwhile, hydrophobic groups are exposed outside by utilizing the modification of the P123 type PEO-PPO-PEO block copolymer, the flexibility of the chain is improved (the problem that the molecular chain is difficult to move due to the improvement of crystallinity is solved), and the bonding strength is further improved while the hydrophobicity is enhanced. Within the scope of the present application, the water-resistant bond strength can be increased, since other reactions also occur in the system, such as the solubilization of PEO-PPO-PEO block copolymers of the P123 type.
Preferably, the method comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 1.5:2.5: 8.
Preferably, the method comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 70 deg.C for 2hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and the P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 2-3: 0.1-0.2: 1.5:2.5: 8.
By adopting the technical scheme, the stable reaction system keeps proper crystallinity, and the fluctuation of adhesive strength is reduced.
Preferably, the method comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8.
Preferably, the method comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8;
(3) mixing alkylphenol polyglycol ether, citric acid, gingerol, ethanol and water in the mass ratio of 1:0.5: 4, stirring uniformly, spray drying to obtain particles, and adding the particles into the reaction system in the step (2), wherein the mass ratio of the particles to the reaction system in the step (2) is 0.02: 1.
The technical effects of the invention are mainly reflected in the following aspects: the components have good compatibility, the adhesive strength and the water resistance are greatly improved, and the stability is good; has better durable antibacterial property.
Detailed Description
The room temperature refers to the indoor temperature, and is generally 15-35 ℃.
Example 1 a: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 1.5:2.5: 8.
Example 1 b: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 45 deg.C for reaction for 12hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 3 hours at 65 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 40: 4: 0.5: 0.2: 100: 1: 2: 7.
Example 1 c: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 52 deg.C for reaction for 9hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 1hr at 72 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 50: 5: 1.0: 0.3:100: 2: 3: 9.
Example 2 a: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8.
Example 2 b: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 70 deg.C for 2hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 2: 0.1: 1.5:2.5: 8.
Example 2 c: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 70 deg.C for 2hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 3: 0.2: 1.5:2.5: 8.
Example 3 a: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8;
(3) mixing alkylphenol polyglycol ether, citric acid, gingerol, ethanol and water in the mass ratio of 1:0.5: 4, stirring uniformly, spray drying to obtain particles, and adding the particles into the reaction system in the step (2), wherein the mass ratio of the particles to the reaction system in the step (2) is 0.02: 1.
Comparative example 1 d: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps: mixing defatted soybean protein powder, urea and water, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature; the mass ratio of the defatted soybean protein powder, the urea and the water is 44:4.5: 100.
Comparative example 1 e: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps: mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature; the mass ratio of the defatted soybean protein powder, the urea, the monocalcium phosphate, the sodium chloride and the water is 44:4.5:0.6:0.24: 100.
Comparative example 1 f: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea and water, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed calcium carbonate and sodium dodecyl benzene sulfonate into the reaction system in the step (1), stirring and reacting for 2 hours at the temperature of 70 ℃, and naturally cooling to room temperature;
the mass ratio of the degreased soybean protein powder, the urea, the water, the calcium carbonate and the sodium dodecyl benzene sulfonate is 44:4.5: 100: 1.5: 8.
Comparative example 1 g: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44: 3: 0.4: 0.1: 100: 1.5:2.5: 8.
Comparative example 1 h: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44: 7: 1.5: 0.5: 100: 1.5:2.5: 8.
Comparative example 1 i: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 0.5: 1: 5.
Comparative example 1 j: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride and water, stirring at 50 deg.C for reaction for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 3: 5: 11.
Comparative example 2 d: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 70 deg.C for 2hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 1: 0.02: 1.5:2.5: 8.
Comparative example 2 e: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 70 deg.C for 2hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100: 5:0.5: 1.5:2.5: 8.
Comparative example 3 b: a preparation method of the aldehyde-free modified soy protein adhesive comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8;
(3) adding the Japanese retinispora extract into the reaction system in the step (2), wherein the mass ratio of the Japanese retinispora extract to the reaction system in the step (2) is 0.02%: 1.
determination of adhesive Strength
The adhesive just prepared was taken and placed in an environment of 25 ℃/40% RH, and the adhesive strength before and after soaking was tested for 0, 90 and 360 days of placement. Soaking treatment: the glued wood samples were placed in a container, soaked in tap water at room temperature for 24h and then air dried at 25 ℃ for 24 h. The parallel test is carried out for 5 times, and the average value is taken. The test results are shown in table 1.
The specific test method of the adhesive strength comprises the following steps: the upper and lower surfaces of two pieces of wood (each wood sample having a length of 85mm, a width of 65mm, and a thickness of 10mm) were bonded together with a coating area of 65mm × 40 mm. The glued wood is firstly stuck together, then clamped and dried for 24 d. The tensile shear strength (adhesive strength) of the wood sample was measured by a WDW-100 type microcomputer controlled electronic universal tester, and the compression speed was 10 mm/min. The tensile shear strength σ is calculated as follows: sigma is F/S; in the formula: f-shear force, N; s-area of action, m2。
Table 1 shows: (1) compared with comparative examples 1d-1j, the adhesive strength of examples 1a-1c is greatly improved before and after soaking in water after 0, 90 and 360 days of placement in an environment of 25 ℃/40% RH, which shows that the adhesive strength, the stability of the adhesive strength in an environment of 25 ℃/40% RH and the water resistance of examples 1a-1c are better than those of comparative examples 1d-1 j; (2) compared with comparative examples 2d-2e and example 1a, the adhesive strength of examples 2a-2c is greatly improved before and after soaking in water after 0, 90 and 360 days of placement in an environment of 25 ℃/40% RH, which shows that the adhesive strength, the stability of the adhesive strength in an environment of 25 ℃/40% RH and the water resistance of examples 2a-2c are better than those of comparative examples 2d-2e and example 1 a; (3) example 3a the adhesive strength before and after soaking in water after 0, 90 and 360 days of exposure to 25 ℃/40% RH was higher than the adhesive strength of comparative example 3b under the same conditions, indicating that example 3a is more compatible with the protocol of the present application.
TABLE 1 bonding Strength measurement results (Unit: MPa)
Bacteriostasis test
The method comprises the steps of firstly carrying out ultraviolet surface sterilization on vessels and tools used for experiments, respectively transferring 0.5mL of spore suspension of white rot fungi, aspergillus niger and brown rot fungi into sterilized culture dishes by using a liquid transfer machine, cooling the heated and melted culture medium to 45 ℃, and respectively pouring into the culture dishes of the three spore suspensions, wherein each culture dish contains 15mL of the culture medium. Shaking up to mix the bacterial suspension and the culture medium fully. After the culture medium is coagulated, a hole with the diameter of 5mm is punched at the middle position of the culture medium by a puncher, 100 mu l of adhesive is respectively and slowly injected into the hole by a pipette, then the bottom opening of each culture dish is sealed by a rubber-pulling film and is cultured at the temperature of 28 +/-1 ℃, the diameter change of the bacteriostatic circle is observed and determined every few days, and the observation and the test are carried out for 360 days. The measurement was repeated 5 times for 3 test bacteria per adhesive, and the results were averaged and the test results are shown in Table 2.
Table 2 shows: compared with the comparative example 3b, the example 3a has faster bacteriostasis rate and longer bacteriostasis time to white rot fungi, aspergillus niger and brown rot fungi, and has better bacteriostasis effect.
TABLE 2 results of the bacteriostatic test
The above are only typical examples of the present invention, and besides, the present invention may have other embodiments, and all the technical solutions formed by equivalent substitutions or equivalent changes are within the scope of the present invention as claimed.
Claims (2)
1. A preparation method of an aldehyde-free modified soy protein adhesive is characterized by comprising the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and the P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8.
2. The preparation method of the aldehyde-free modified soy protein adhesive as claimed in claim 1, which comprises the following steps:
(1) mixing defatted soybean protein powder, urea, calcium dihydrogen phosphate, sodium chloride, water, ethanol and calcium chloride, stirring at 50 deg.C for 10hr, and naturally cooling to room temperature;
(2) adding the premixed zinc carbonate, nicotinamide and P123 type PEO-PPO-PEO block copolymer into the reaction system in the step (1), stirring and reacting for 2 hours at 70 ℃, and naturally cooling to room temperature;
the mass ratio of the defatted soybean protein powder, urea, monocalcium phosphate, sodium chloride, water, ethanol, calcium chloride, zinc carbonate, nicotinamide and the P123 type PEO-PPO-PEO block copolymer is 44:4.5:0.6:0.24:100:2.5:0.15:1.5:2.5: 8;
(3) mixing alkylphenol polyglycol ether, citric acid, gingerol, ethanol and water according to the mass ratio of 1:1:0.5:0.5:4, uniformly stirring, carrying out spray drying to obtain particles, and adding the particles into the reaction system in the step (2), wherein the mass ratio of the particles to the reaction system in the step (2) is 0.02% to 1.
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| CN102120926A (en) * | 2010-12-29 | 2011-07-13 | 浙江省农业科学院 | Soybean protein adhesive and preparation method thereof |
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| "新型复合纤维蛋白胶的磷酸钙骨水泥的生物安全性研究";丁超;《组织工程与重建外科杂志》;20151231;第11卷(第5期);第301-304页 * |
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