CN115029103B - Preparation method and application of mildew-proof water-resistant soybean protein adhesive - Google Patents
Preparation method and application of mildew-proof water-resistant soybean protein adhesive Download PDFInfo
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- CN115029103B CN115029103B CN202210806804.5A CN202210806804A CN115029103B CN 115029103 B CN115029103 B CN 115029103B CN 202210806804 A CN202210806804 A CN 202210806804A CN 115029103 B CN115029103 B CN 115029103B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
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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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Abstract
The invention relates to the technical field of adhesives, in particular to a mildew-proof water-resistant soybean protein adhesive, and a preparation method and application thereof. The adhesive comprises the following raw materials in parts by mass: 3 to 6 parts of vegetable protein, 7 to 15 parts of water, 0.2 to 0.8 part of modifier and 0.3 to 0.5 part of reinforcing auxiliary agent; the plant protein comprises soybean protein powder, and the modifier is one or more selected from benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride and N, N, N-trimethyl-1-tetradecyl ammonium bromide. The mildew-proof water-resistant protein-based adhesive prepared by the invention does not contain harmful volatile matters such as formaldehyde, phenol and the like, has the advantages of renewable raw material sources, environment friendliness and reproducibility, and has excellent bonding strength, water resistance and mildew resistance, low content of crosslinking auxiliary agent added into the adhesive and low production cost.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a mildew-proof water-resistant soybean protein adhesive, and a preparation method and application thereof.
Background
The wood-based board industry uses large amounts of adhesives, and the yield of wood adhesives is about 75% of the total yield of adhesives. Currently, formaldehyde adhesives (urea formaldehyde, phenolic aldehyde and melamine formaldehyde adhesives) still occupy an important role in the wood industry, and occupy more than 80% of the total glue amount in the wood industry, mainly due to some specific advantages of the formaldehyde adhesives, including higher bonding strength and water resistance, proper viscosity, good durability and the like. However, the aldehyde adhesives and products thereof release harmful substances such as free formaldehyde during the production and use processes, which are harmful to human health. Meanwhile, as petroleum fossil fuel energy is over-developed and utilized, global reserves are drastically reduced, prices are continuously rising, and the environment is increasingly deteriorated. Therefore, development of an environment-friendly wood adhesive using a green renewable biomass base as a raw material has important significance for environmental protection and resource recycling.
In recent years, researchers at home and abroad use various biomass materials as raw materials to prepare environment-friendly adhesives such as starch, cotton seeds, tannins, lignin, soybean meal and the like. The soybean meal is a byproduct obtained after soybean oil is extracted and processed, and is paid attention to because of the unique advantages of low cost, good processing performance, good biodegradability, reproducibility and the like, for example, the invention CN201510103517.8 discloses a water-resistant bio-based formaldehyde-free adhesive for wood, which is prepared by synthesizing soybean meal, biological enzyme, reinforcing agent and filler. However, the soybean protein adhesive prepared by the method has the problem of easy mildew, and seriously influences the storage of the adhesive and the application of the adhesive in the wood industry. As another example, CN201510088407.9 discloses an aldehyde-free vegetable protein-based wood adhesive prepared by using defatted soy protein powder, sodium hydroxide and sodium sulfite as modifiers, and a polyvinyl alcohol solution of sodium silicate and epoxy resin as a cross-linking agent, and then adding maleic anhydride curing agent and organic montmorillonite. The soybean protein adhesive prepared by the method has complex process and higher cost, and is limited to be commercially popularized and applied. The soybean protein-based adhesive has the advantages of abundant sources of raw materials, low cost, wide application and the like, but still has the problems of low mechanical strength and poor water resistance. In addition, the soybean protein is used as a natural nutrient substance, is easily corroded by fungi and mould, so that the soybean protein is degraded, the adhesive structure is damaged, the adhesive strength is low, the durability is poor, the storage stability of the soybean protein adhesive is obviously reduced, and the processing and application of the wood industry are seriously influenced. In addition, microorganisms generated by soy protein adhesives float to living space and may cause respiratory diseases such as asthma, allergy, etc. Some researchers have introduced preservatives into soy protein adhesives to improve mildew resistance, such as tebuconazole, 1, 2-benzisothiazolin-3-one, chlorophenol, o-phenylphenol, 1, 2-benzisothiazolin-3-one, copper sulfate, etc., however, harmful components in the preservatives are harmful to human health and easily bring heavy metal pollution to the environment. Poor compatibility between the preservative and the protein can also negatively impact the adhesive properties of the protein adhesive. In summary, although many researchers at home and abroad provide many modification methods for the problems of adhesive strength, water resistance and the like of the soybean protein adhesive, the preparation method has the defects of complex preparation process, higher cost, insignificant modification effect, poor mildew-proof effect and the like, thereby limiting the industrial production of the soybean protein adhesive and the application of the soybean protein adhesive in the production of environment-friendly artificial boards.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a mildew-proof water-resistant soybean protein (wood) adhesive. The adhesive provided by the invention solves the problems of low adhesive strength, poor water resistance, easy mildew and the like of the soybean protein adhesive. The plywood prepared by the adhesive meets and is superior to the requirements of class II plywood in national standard GB/T9846-2015, has higher bonding strength and excellent water resistance and mildew resistance, is nontoxic, does not contain harmful volatile substances such as formaldehyde, and reduces the harm of aldehyde adhesives to human bodies.
In a first aspect, the mildew-proof water-resistant soybean protein adhesive provided by the invention comprises the following raw materials in parts by mass: 3 to 6 parts of vegetable protein, 7 to 15 parts of water, 0.2 to 0.8 part of modifier and 0.3 to 0.5 part of reinforcing auxiliary agent; the plant protein comprises soybean protein powder, and the modifier is one or more selected from benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride and N, N, N-trimethyl-1-tetradecyl ammonium bromide. According to the invention, renewable biomass resources are used as glue making raw materials, amphipathic micelle molecules rich in active groups are used as physical cross-linking agents and chemical reinforcing auxiliary agents, and a physical-chemical double-cross-linking strategy is adopted to cooperatively prepare the high-performance adhesive. Under the action of external force, hydrophobic association nodes of the micelle structure can slide, an energy dissipation mechanism is endowed to the composite material, the mechanical property of the material is obviously improved, and meanwhile, a large number of quaternary ammonium salt cations rich in micelle molecules have stronger antibacterial property, so that the mildew-proof antibacterial property of the adhesive can be further improved. The environment-friendly adhesive prepared by the method has the advantages of renewable raw material sources, environment friendliness, no volatilization of volatile harmful substances such as formaldehyde and the like in the preparation and use processes, good cementing performance, excellent water resistance, mold resistance and the like.
Preferably, the mildew-proof water-resistant soybean protein adhesive comprises the following raw materials in parts by mass: 3 to 5 parts of soybean protein powder, 7 to 12 parts of water, 0.2 to 0.8 part of modifier and 0.3 to 0.5 part of reinforcing auxiliary agent; the raw materials by mass part are preferably as follows: 3 to 4 parts of soybean protein powder, 7 to 10 parts of water, 0.4 to 0.6 part of modifier and 0.3 to 0.4 part of reinforcing auxiliary agent. The raw material types and the dosage of the adhesive are favorable for further improving the comprehensive performance of the adhesive, and the mildew resistance and the water resistance of the plywood prepared by the adhesive are further improved within the preferable dosage range, and particularly the dry and wet bonding strength is obviously improved.
Preferably, the modifier is benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride or N, N, N-trimethyl-1-tetradecyl ammonium bromide.
Preferably, the modifier is benzalkonium bromide. More preferably, the modifier is a solution with a mass fraction of 2-10%. According to the invention, when the modifying agent adopts the benzalkonium bromide aqueous solution with the concentration, the comprehensive performance, especially the gluing performance and the mildew-proof performance are better.
Further preferably, the reinforcing aid is selected from one or more of 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, cyclohexanediol diglycidyl ether, ethylene glycol diglycidyl ether, n-butyl-2, 3-epoxypropyl ether, glycerol triglycidyl ether, preferably 1, 6-hexanediol diglycidyl ether. The reinforcing auxiliary agent can play a role of a cross-linking agent, and particularly has a synergistic effect on mildew resistance, water resistance and bonding strength by using 0.3-0.4 part of 1, 6-hexanediol diglycidyl ether and benzalkonium bromide.
Further preferably, the soybean protein powder is defatted soybean powder, soybean concentrated protein powder or soybean isolated protein; preferably, the protein content of the soybean protein powder is more than or equal to 42%, and the particle size of the soybean powder is more than 200 meshes, preferably 200-250 meshes.
In a second aspect, the preparation method of the mildew-proof water-resistant soybean protein adhesive provided by the invention comprises the steps of sequentially mixing and stirring soybean protein powder, water, a modifier and an enhancing auxiliary agent; preferably comprising the steps of:
1) Mixing soybean protein powder with water, and stirring to obtain mixed protein liquid;
2) Pretreatment: mixing the mixed protein liquid with a modifier and stirring;
3) Adding the reinforcing auxiliary agent into the pretreated protein liquid, and stirring.
The preparation method of the adhesive provided by the invention has the advantages of simple process, mild conditions, environment friendliness, readily available and renewable raw materials and relatively low cost, and is suitable for wide application in the artificial board industry.
Preferably, the method comprises the following steps:
1) Mixing soybean protein powder with water, and stirring for 5-15 min under the condition of the rotating speed of 800-1500 r/min to obtain mixed protein liquid;
2) Pretreatment of mixed protein liquid: mixing the mixed protein liquid with a modifier, and stirring for 5-15 min under the condition that the rotating speed is 800 r/min;
3) Adding the reinforcing auxiliary agent twice with the input ratio of 1-2:1-2, the interval between the two inputs being 5-15 min, and then continuing stirring for 5-15 min.
According to the invention, the reaction effect of each raw material can be improved by adopting the feeding sequence, the feeding times and the stirring conditions, so that the adhesive strength, the water resistance and the mildew resistance of the mildew-proof water-resistant soybean protein adhesive are further improved.
In the present invention, the water may be tap water or distilled water.
Further preferably, the preparation method of the mildew-proof water-resistant soybean protein adhesive comprises the following steps:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle, and then the mixture is stirred for 10min at room temperature under the condition of 1000r/min of rotating speed, so as to obtain mixed protein liquid;
2) Pretreatment of mixed protein liquid: adding a modifier into the uniformly mixed protein liquid, maintaining the temperature and stirring for 10min under the condition that the rotating speed of a stirring paddle is 800 r/min;
3) Adding the reinforcing auxiliary agent twice, wherein the input ratio is 1:1, the interval between the two inputs is 10min, and then keeping the temperature and continuously stirring for 10min. The preferred parameters are adopted in the invention to achieve better effect.
It is further preferred that the preparation processes of steps 1) to 3) are all carried out at room temperature. The preparation method of the invention does not need to be implemented under the high temperature condition, and is beneficial to industrial production.
In a third aspect, the invention provides application of the mildew-proof water-resistant soybean protein adhesive in preparation of environment-friendly artificial boards. The invention also provides a preparation method of the adhesive for preparing the common plywood, and the obtained board has higher bonding strength, good water resistance and mildew resistance, and solves the problem of formaldehyde release in the production and use processes of the current artificial board. The preparation method of the adhesive provided by the invention is simple in process, environment-friendly, easy to obtain and renewable in raw materials, and suitable for being applied to wood industrialization.
Further preferably, the method comprises the following steps: the mildew-proof water-resistant soybean protein adhesive is adopted, and a eucalyptus veneer with the thickness of 200mm multiplied by 1.6mm is used as a base material, wherein the water content of the base material is 8-12%, and the single-sided sizing amount is 200g/m 2 Sizing, namely assembling the three layers of veneers in a criss-cross manner, and hot-pressing according to the speed of 1.5mm/min under the conditions that the hot-pressing temperature is 120 ℃ and the pressure is 1.0 MPa.
The invention has the advantages that:
(1) The invention provides a preparation method of an environment-friendly renewable mildew-proof water-resistant soybean protein adhesive, which solves the problems of low bonding strength, poor water resistance, easy mildew and the like of the traditional protein adhesive. The soybean protein adhesive prepared by the modified method has the advantages of simple process flow, low cost, remarkable effect improvement and the like, and is suitable for industrial production.
(2) Compared with other modification methods, the invention introduces the modifier, especially the benzalkonium bromide molecular micelle and the flexible crosslinking agent into the adhesive system, and remarkably improves the crosslinking density of the adhesive by a physical-chemical double crosslinking strategy, thereby not only improving the comprehensive properties of the adhesive system in terms of water resistance, mechanics and the like, but also further endowing the benzalkonium bromide molecular micelle with strong antibacterial activity on the basis of the double crosslinking modification, further endowing the soybean protein adhesive with extremely strong mildew-proof property, and greatly prolonging the storage life of the soybean protein adhesive after 60 days of storage in a high-temperature and high-humidity environment, thereby being better used as the adhesive for wood industry.
(3) The wet bonding strength of the plywood prepared by the adhesive provided by the invention reaches 1.22MPa, the related requirements of the national class II plywood are met, the prepared plywood can be stored for 28 days under the conditions of high temperature and high humidity without mildew, and the prepared artificial board is an environment-friendly ecological plywood.
(4) The invention takes the byproduct soybean meal produced by soybean oil as the raw material for producing the adhesive in the wood industry, the source is renewable, the recycling of waste resources is realized, the resource circulation is realized, the damage to the environment is reduced, and the resource utilization efficiency is improved. The soybean protein adhesive disclosed by the invention can reduce excessive development and utilization of non-renewable resources, can solve the problem of harm to human bodies caused by volatilization and release of harmful substances such as formaldehyde and phenol in the production and preparation process of wood products, reduces pollution and damage of chemical products to natural environment, and has the advantages of renewable raw material sources and environment friendliness.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the bonding strength of the adhesives of comparative examples 1-3 and examples 1-8 provided by the present invention;
FIG. 2 is a schematic view of the mildew resistance of the adhesives of comparative examples 1-3 and examples 1-3 provided by the present invention;
FIG. 3 is a schematic view showing the mildew resistance of the adhesives of examples 5-8 provided by the present invention;
FIG. 4 is a schematic view of mildew resistance of plywood prepared from the adhesives of comparative examples 1-3 and examples 1-3 provided by the invention;
FIG. 5 is a schematic view of the mildew resistance of commercial plywood, fiberboard, particle board, and oriented strand board provided by the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, which are used for illustrating the present invention but are not intended to limit the scope of the present invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the following examples and comparative examples of the present invention, 2% -8% of the modifier used was dodecyldimethylbenzyl ammonium bromide solution, and the soybean protein powder used was a soybean protein powder having a protein content of 53% and a soybean flour particle size of 200 mesh.
Example 1
The mildew-proof water-resistant soybean protein adhesive for wood and the preparation method thereof provided by the embodiment are characterized in that the mass of the soybean protein adhesive is prepared in the following manner:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium bromide (modifier): 0.2 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soybean protein adhesive in the embodiment is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred at a rotating speed of 1000r/min for 10min at room temperature to obtain a mixed protein solution;
2) Pretreatment of mixed protein liquid: and adding 0.2 part of modifier into the uniformly mixed protein liquid, and keeping the rotating speed of a stirring paddle at 800r/min for 10min.
3) Adding 0.3 part of auxiliary agent twice, wherein the input ratio is 1:1, the interval between the two inputs is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 2
The mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment are characterized in that the mass of the soybean protein adhesive is prepared in the following manner:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium bromide (modifier): 0.4 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soybean protein adhesive in the embodiment is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred at a rotating speed of 1000r/min for 10min at room temperature to obtain a mixed protein solution;
2) Pretreatment of mixed protein liquid: 0.4 part of modifier is added into the evenly mixed protein liquid, and the rotation speed of a stirring paddle is kept at 800r/min for 10min.
3) Adding 0.3 part of auxiliary agent twice, wherein the input ratio is 1:1, the interval between the two inputs is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 3
The mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment are characterized in that the mass of the soybean protein adhesive is prepared in the following manner:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soybean protein adhesive in the embodiment is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred at a rotating speed of 1000r/min for 10min at room temperature to obtain a mixed protein solution;
2) Pretreatment of mixed protein liquid: 0.4 part of modifier is added into the evenly mixed protein liquid, and the rotation speed of a stirring paddle is kept at 800r/min for 10min.
3) Adding 0.3 part of auxiliary agent twice, wherein the input ratio is 1:1, the interval between the two inputs is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 4
The mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment are characterized in that the mass of the soybean protein adhesive is prepared in the following manner:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium bromide (modifier): 0.8 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soybean protein adhesive is as follows.
Comparative example 1
The mass of the soy protein adhesive in this comparative example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
The specific preparation method of the comparative example protein adhesive is as follows: a stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred uniformly for 10min at room temperature under the stirring condition that the rotating speed is 1000r/min, so as to obtain mixed protein liquid;
comparative example 2
The mass of the soy protein adhesive in this comparative example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
1, 6-hexanediol diglycidyl ether: 0.3 part
The specific preparation method of the comparative example protein adhesive is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred uniformly for 10min at room temperature under the stirring condition that the rotating speed is 1000r/min, so as to obtain mixed protein liquid;
2) Adding 0.3 part of auxiliary agent twice with the input ratio of 1:1, keeping the interval between the two inputs for 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive
Comparative example 3
The mass of the soy protein adhesive in this comparative example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium bromide (modifier): 0.4 part
The specific preparation method of the protein adhesive in the comparative example is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred uniformly for 10min at room temperature under the stirring condition that the rotating speed is 1000r/min, so as to obtain mixed protein liquid;
2) Pretreatment of mixed protein liquid: and adding 0.4 part of modifier into the uniformly mixed protein liquid, and keeping the rotating speed of a stirring paddle at 800r/min for 10min to obtain the comparative soybean protein adhesive.
Example 5
The mass of the soy protein adhesive in this example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
Tributylbenzyl ammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the protein adhesive in the embodiment is as follows:
1) A stirring paddle device is built, soybean protein powder and water are uniformly mixed in a reaction kettle according to a mass ratio of 3:7, and then the mixture is stirred uniformly for 10min at room temperature under the stirring condition that the rotating speed is 1000r/min, so as to obtain mixed protein liquid;
2) Pretreatment of mixed protein liquid: 0.6 part of tributyl benzyl ammonium bromide serving as a modifier is added into the protein liquid which is uniformly mixed and stirred, and the rotating speed of a stirring paddle is kept at 800r/min for 10min.
3) Adding 0.3 part of auxiliary agent twice, wherein the input ratio is 1:1, the interval between the two inputs is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 6
The mass of the soy protein adhesive in this comparative example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
Dodecyl trimethyl ammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
Example the preparation of the protein adhesive was the same as in example 5.
Example 7
The mass of the soy protein adhesive in this example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
Benzalkonium chloride (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The preparation method of the protein adhesive in this example is the same as that in example 5.
Example 8
The mass of the soy protein adhesive in this example was formulated as follows:
water: 7 parts of
Soy protein powder: 3 parts of
N, N, N-trimethyl-1-tetradecyl ammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The preparation method of the protein adhesive in this example is the same as that in example 5.
Experimental example 1
The soybean protein adhesive synthesized according to the above examples and comparative examples was used to prepare a conventional three-ply plywood, and the preparation process was as follows:
a eucalyptus veneer with the thickness of 200mm multiplied by 1.6mm is selected as a base material (the water content is kept at 8-12 percent), and the single-sided sizing amount is 200g/m 2 Sizing, namely assembling the three layers of veneers in a crisscross manner, hot-pressing at the hot-pressing temperature of 120 ℃ and the pressure of 1.0MPa according to the pressure of 1.5mm/min, and obtaining the plywood by a press.
Adhesive performance test:
and testing the performance indexes such as the dry bonding strength, the wet bonding strength and the like of the prepared common plywood according to the requirements in the GB/T17657-2013 artificial board and the decorative artificial board physical and chemical performance test method.
And (3) testing mildew-proof performance of the adhesive and the plywood:
the adhesive samples synthesized in examples and comparative examples were placed in an incubator at 30 ℃ and 90% relative humidity with a digital camera for daily mildew process.
Referring to FIG. 1, it can be seen that the adhesive of examples 1-4 has a dry-wet bonding strength of not less than 0.7MPa and meets the strength requirements of class II plywood standards in GB/T9846-2015. Wherein, compared with the adhesive prepared in the example 3, the adhesive in the comparative example 1 has the advantages that the dry and wet bonding strength is respectively improved from 1.30MPa and 0MPa to 2.22MPa and 1.25MPa, and the wet bonding strength modification effect is quite remarkable. And the release amount of formaldehyde is extremely low in the soybean protein adhesives prepared in the examples and the comparative examples.
Referring to fig. 2, it can be seen that the adhesives prepared in comparative example 3 and examples 1-3 are not mildewed when stored for 60 days under high temperature and high humidity conditions, and the mildew prevention performance of the soy protein adhesives can be remarkably improved by the modification method provided by the invention as shown in the beginning of mildewing of comparative example 1 and comparative example 2 on 1 st and 13 th days respectively. In addition, referring to fig. 3, as can be seen from comparative examples 4-7, the micelle reinforcing modification method provided by the invention is based on that the prepared adhesive has better mildew resistance, but still has slightly poorer mildew resistance than the embodiment, and the invention provides a new simple, convenient and strong-universality strategy for preparing a series of formaldehyde-free, environment-friendly, renewable and mildew-proof protein adhesives, and the comprehensive modification effect of the embodiment of the invention is better. The method of example 3 enables an adhesive to be obtained which has excellent overall properties (adhesion and mold resistance).
Referring to fig. 4, it can be seen that the plywood prepared by the adhesives of comparative example 3 and examples 1 to 3 did not mold significantly after 28 days of storage under high temperature and high humidity conditions, while the plywood prepared by the adhesives of comparative example 1 and comparative example 2 began to mold on days 7 and 14, respectively, and referring to fig. 5, the commercial plywood, the fiberboard, the particle board and the oriented strand board all mold on day 14, and the mildew resistance of the plywood prepared by the adhesives of the present invention was significantly improved.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (11)
1. The mildew-proof water-resistant soybean protein adhesive is characterized by comprising the following raw materials in parts by mass: 3-6 parts of soybean protein powder, 7-15 parts of water, 0.2-0.8 part of modifier and 0.3-0.5 part of reinforcing auxiliary agent; the modifier is one or more selected from benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride and N, N, N-trimethyl-1-tetradecyl ammonium bromide, and the reinforcing auxiliary agent is 1, 6-hexanediol diglycidyl ether; the preparation method of the mildew-proof water-resistant soybean protein adhesive comprises the step of sequentially mixing and stirring soybean protein powder, water, a modifier and an enhancement auxiliary agent.
2. The mildew-proof water-resistant soybean protein adhesive according to claim 1, which is characterized by comprising the following raw materials in parts by mass: 3-5 parts of soybean protein powder, 7-12 parts of water, 0.2-0.8 part of modifier and 0.3-0.5 part of reinforcing auxiliary agent.
3. The mildew-proof water-resistant soybean protein adhesive according to claim 2, which is characterized by comprising the following raw materials in parts by mass: 3-4 parts of soybean protein powder, 7-10 parts of water, 0.4-0.6 part of modifier and 0.3-0.4 part of reinforcing auxiliary agent.
4. The mildew-resistant and water-resistant soy protein adhesive of claim 1 wherein the modifier is benzalkonium bromide.
5. The mildew-proof water-resistant soybean protein adhesive according to any one of claims 1 to 4, wherein the soybean protein powder is defatted soybean powder, soybean concentrated protein powder or soybean protein isolate, the protein content of the soybean protein powder is more than or equal to 42%, and the particle size of the soybean powder is more than 200 meshes.
6. The mildew-proof and water-resistant soybean protein adhesive according to claim 5, wherein the soybean powder particle size of the soybean protein powder is 200-250 meshes.
7. The method for preparing the mildew-proof water-resistant soybean protein adhesive according to any one of claims 1 to 6, which is characterized by comprising the steps of sequentially mixing and stirring soybean protein powder, water, a modifier and an enhancing auxiliary agent.
8. The method for preparing the mildew-proof and water-resistant soybean protein adhesive according to claim 7, which is characterized by comprising the following steps:
1) Mixing soybean protein powder with water, and stirring to obtain mixed protein liquid;
2) Pretreatment: mixing the mixed protein liquid with a modifier and stirring;
3) Adding the reinforcing auxiliary agent into the pretreated protein liquid, and stirring.
9. The method for preparing the mildew-proof and water-resistant soybean protein adhesive according to claim 8, which is characterized by comprising the following steps:
1) Mixing the soybean protein powder with water, and stirring for 5-15 min under the condition that the rotating speed is 800-1500 r/min to obtain mixed protein liquid;
2) Pretreatment of mixed protein liquid: mixing the mixed protein liquid with a modifier, and stirring for 5-15 min under the condition that the rotating speed is 800 r/min;
3) And adding the reinforcing auxiliary agent twice, wherein the input ratio is 1-2:1-2, the interval between the two inputs is 5-15 min, and then continuing stirring for 5-15 min.
10. The method for preparing the mildew-proof and water-resistant soybean protein adhesive according to claim 9, wherein the preparation processes of the steps 1) to 3) are all carried out at room temperature.
11. The application of the mildew-proof water-resistant soybean protein adhesive according to any one of claims 1-6 in preparing environment-friendly artificial boards.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520035A (en) * | 2016-11-24 | 2017-03-22 | 广州昱辰元创节能环保科技有限公司 | Plastic adhesive |
| CN108715729A (en) * | 2018-06-26 | 2018-10-30 | 段小宁 | Fire-retardant, antibiotic property aqueous polyurethane coating and adhesive preparation method |
| CN109020304A (en) * | 2018-07-05 | 2018-12-18 | 苏蒙 | A kind of construction material and preparation method thereof containing diatomite |
| CN109161030A (en) * | 2018-08-15 | 2019-01-08 | 中国林业科学研究院木材工业研究所 | A kind of vegetable protein and preparation method thereof of amino graft modification |
| CN113913152A (en) * | 2021-10-08 | 2022-01-11 | 华南农业大学 | Spirulina protein adhesive and preparation method and application thereof |
-
2022
- 2022-07-08 CN CN202210806804.5A patent/CN115029103B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520035A (en) * | 2016-11-24 | 2017-03-22 | 广州昱辰元创节能环保科技有限公司 | Plastic adhesive |
| CN108715729A (en) * | 2018-06-26 | 2018-10-30 | 段小宁 | Fire-retardant, antibiotic property aqueous polyurethane coating and adhesive preparation method |
| CN109020304A (en) * | 2018-07-05 | 2018-12-18 | 苏蒙 | A kind of construction material and preparation method thereof containing diatomite |
| CN109161030A (en) * | 2018-08-15 | 2019-01-08 | 中国林业科学研究院木材工业研究所 | A kind of vegetable protein and preparation method thereof of amino graft modification |
| CN113913152A (en) * | 2021-10-08 | 2022-01-11 | 华南农业大学 | Spirulina protein adhesive and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Shicun Jin等."Phytic acid-assisted fabrication for soybean meal/nanofiber composite adhesive via bioinspired chelation reinforcement strategy".《Journal of Hazardous Materials》.2020,第399卷123064. * |
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