CN115029103A - 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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- CN115029103A CN115029103A CN202210806804.5A CN202210806804A CN115029103A CN 115029103 A CN115029103 A CN 115029103A CN 202210806804 A CN202210806804 A CN 202210806804A CN 115029103 A CN115029103 A CN 115029103A
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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, and particularly relates 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: 3-6 parts of vegetable protein, 7-15 parts of water, 0.2-0.8 part of modifier and 0.3-0.5 part of reinforcing additive; the vegetable protein comprises soybean protein powder, and the modifier is selected from one or more of 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, the raw material source of the mildew-proof water-resistant protein-based adhesive is renewable, and the mildew-proof water-resistant protein-based adhesive has the advantages of environmental protection and reproducibility, and has excellent bonding strength, water resistance and mildew resistance, lower content of a crosslinking auxiliary agent added in the adhesive and lower production cost.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a mildew-proof water-resistant soybean protein adhesive and a preparation method and application thereof.
Background
The artificial board industry has a huge amount of adhesives, and the yield of wood adhesives accounts for about 75% of the total yield of the adhesives. Currently, formaldehyde adhesives (urea formaldehyde, phenol formaldehyde and melamine formaldehyde adhesives) still occupy an important position in the wood industry, and account for more than 80% of the total adhesive consumption in the wood industry, mainly due to the fact that the aldehyde adhesives have certain specific advantages including high bonding strength and water resistance, proper viscosity, good durability and the like. However, the aldehyde adhesive and the products thereof release harmful substances such as free formaldehyde and the like during the production and use processes, thereby harming human health. Meanwhile, global reserves are sharply decreased with the excessive exploitation and utilization of petroleum fossil fuel energy, prices are continuously increased, and the environment is increasingly deteriorated. Therefore, the development of the environment-friendly wood adhesive taking the green renewable biomass as the 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, cottonseed, tannin, lignin, soybean meal and the like. The soybean meal is a byproduct after the extraction and processing of the soybean oil, and is attracted by attention due to the unique advantages of low cost, good processing performance, good biodegradability, renewability and the like, for example, the invention CN201510103517.8 discloses that a waterproof bio-based formaldehyde-free adhesive for wood is prepared by synthesizing the soybean meal, biological enzyme, a reinforcing agent and a filler. However, the soybean protein adhesive prepared by the method has the problem of easy mildew, and the storage and the application in the wood industry of the adhesive are seriously influenced. For another example, CN201510088407.9 discloses an aldehyde-free vegetable protein-based wood adhesive prepared by using defatted soybean protein powder, sodium hydroxide and sodium sulfite as modifiers, selecting a polyvinyl alcohol solution of sodium silicate and epoxy resin as a cross-linking agent, and then adding a maleic anhydride curing agent and organic montmorillonite. The method for preparing the soy protein adhesive has complex process and higher cost, and limits the commercial popularization and application of the soy protein adhesive. The soybean protein-based adhesive has the advantages of rich raw material sources, low price, wide application and the like, but still has the problems of low mechanical strength and poor water resistance. In addition, as a natural nutrient substance, the soybean protein is easily corroded by fungi and mould, so that the soybean protein is degraded, the adhesive structure is damaged, the bonding strength is low, the durability is poor, the storage stability of the soybean protein adhesive is obviously reduced, and the processing and the application of the wood industry are seriously influenced. In addition, the microorganisms generated from the soy protein adhesive may cause respiratory diseases such as asthma and allergy by floating to the living space. Some researchers have introduced preservatives into soybean protein adhesives to improve mold resistance, such as tebuconazole, 1, 2-benzisothiazolin-3-one, chlorophenol, o-phenylphenol, 1, 2-benzisothiazol-3-one, and copper sulfate, etc., however, harmful components in the preservatives are harmful to human health and easily cause heavy metal pollution to the environment. Poor compatibility between preservatives and proteins can also negatively impact the adhesive properties of the protein adhesive. In conclusion, although many researchers at home and abroad propose a plurality of modification methods for the problems of the bonding strength, the water resistance and the like of the soybean protein adhesive, the defects of complex preparation process, high cost, insignificant modification effect, poor mildew-proof effect and the like exist, so that the application of the soybean protein adhesive in industrial production and the production of environment-friendly artificial boards is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a mildew-proof water-resistant soy protein (wood) adhesive. The adhesive provided by the invention solves the problems of low bonding 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 various requirements of II-type plywood in national standard GB/T9846-2015, has high bonding strength and excellent water resistance and mildew resistance, is nontoxic, does not contain harmful volatile substances such as formaldehyde and the like, 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: 3-6 parts of vegetable protein, 7-15 parts of water, 0.2-0.8 part of modifier and 0.3-0.5 part of reinforcing additive; the vegetable protein comprises soybean protein powder, and the modifier is selected from one or more of benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride and N, N, N-trimethyl-1-tetradecyl ammonium bromide. The invention takes renewable biomass resources as a glue making raw material, takes amphiphilic micelle molecules rich in active groups as a physical cross-linking agent and a chemical enhancement additive to prepare the high-performance adhesive in a synergistic way through a physical-chemical double cross-linking strategy. 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, meanwhile, a large amount of quaternary ammonium salt cations rich in micelle molecules have strong antibacterial property, and 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 and environmental friendliness, does not volatilize volatile harmful substances such as formaldehyde and the like in the preparation and use processes, and has the characteristics of good bonding property, excellent water resistance, mildew resistance and the like.
Preferably, the mildew-proof water-resistant soybean protein adhesive comprises 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 additive; preferably 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 additive. The raw material types and the dosage of the adhesive are beneficial to 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 optimal dosage range, and particularly the dry and wet bonding strength is obviously improved.
Preferably, the modifier is benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyltrimethyl ammonium bromide, benzalkonium chloride or N, N, N-trimethyl-1-tetradecylammonium bromide.
Preferably, the modifier is benzalkonium bromide. Preferably, the modifier is a solution with the mass fraction of 2-10%. According to research, the invention discovers that when the modifier adopts the benzalkonium bromide aqueous solution with the concentration, the comprehensive performance, particularly the gluing performance and the mildew resistance are better.
Further preferably, the reinforcing aid is one or more selected from 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, cyclohexanediol diglycidyl ether, ethylene glycol diglycidyl ether, n-butyl-2, 3-glycidyl ether and glycerol triglycidyl ether, and preferably 1, 6-hexanediol diglycidyl ether. The reinforcing additive can play a role of a cross-linking agent, and particularly, the 1, 6-hexanediol diglycidyl ether and benzalkonium bromide in the dosage range of 0.3-0.4 part have a synergistic effect on mildew resistance, water resistance and bonding strength.
Further preferably, the soybean protein powder is defatted soybean powder, soybean protein concentrate powder or soybean protein isolate; preferably, the protein content of the soybean protein powder is not less than 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 soy protein adhesive provided by the invention comprises the steps of sequentially mixing and stirring soy protein powder, water, a modifier and an enhancement additive; 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 enhancing 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, environmental protection, easily obtained and renewable raw materials, relatively low cost and suitability for wide application in the industry of artificial boards.
Preferably, the method comprises 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 at the rotating speed of 800 r/min;
3) adding the reinforcing auxiliary agent in two times, wherein the adding ratio is 1-2: 1-2, the interval between the two times of adding is 5-15 min, and then continuously stirring for 5-15 min.
According to the invention, the reaction effect of the raw materials can be improved by adopting the feeding sequence and times and the stirring condition, and 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 selected from tap water or distilled water.
Further preferably, the preparation method of the mildew-proof water-resistant soy protein adhesive comprises the following steps:
1) a stirring paddle device is constructed and equipped, soybean protein powder and water are uniformly mixed in a reaction kettle, and then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min, so as to obtain mixed protein liquid;
2) pretreatment of mixed protein liquid: adding a modifier into the uniformly mixed protein solution, keeping the temperature, and stirring for 10min at the rotating speed of a stirring paddle of 800 r/min;
3) adding the reinforcing additive in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, and then keeping the temperature to continue stirring for 10 min. The effect is better by adopting the optimized parameters.
Further preferably, the preparation processes of steps 1) to 3) are all carried out at room temperature. The preparation method disclosed by the invention is not required to be implemented under a high-temperature condition, and is beneficial to industrial production.
In a third aspect, the invention provides an application of the mildew-proof water-resistant soybean protein adhesive in preparation of an environment-friendly artificial board. The invention also provides a preparation method for preparing the common plywood by using the adhesive, 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, easily available and renewable in raw materials, and suitable for application in wood industrialization.
Further preferably, the method comprises the following steps: the mildew-proof water-resistant soybean protein adhesive is adopted, a eucalyptus veneer with the thickness of 200mm multiplied by 1.6mm is used as a base material, the water content of the base material is 8-12%, and the single-side adhesive application amount is 200g/m 2 Gluing, namely assembling the three layers of veneers in a criss-cross manner, and carrying out hot pressing according to the pressure 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 beneficial effects that:
(1) the invention provides a preparation method of an environment-friendly renewable mildew-proof water-resistant soybean protein adhesive, the protein adhesive prepared by the method solves the problems of low bonding strength, poor water resistance, easy mildew and the like of the traditional protein adhesive, and the adhesive shows good bonding performance and excellent water resistance and mildew resistance. The soybean protein adhesive prepared by the modified method has the advantages of simple process flow, low cost, obvious effect improvement and the like, and is suitable for industrial production.
(2) Different from other modification methods, the invention introduces the modifier, especially benzalkonium bromide molecular micelle and flexible cross-linking agent into the adhesive system, obviously improves the cross-linking density of the adhesive by a physical-chemical double cross-linking strategy, not only improves the water resistance, mechanics and other aspects of the adhesive system, but also greatly prolongs the storage life of the soybean protein adhesive because the benzalkonium bromide molecular micelle has stronger antibacterial activity, further endows the soybean protein adhesive with extremely strong mildew resistance after the double cross-linking modification, does not mildew after being stored for 60 days in a high-temperature and high-humidity environment, and better serves as the adhesive in the 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 national II-type plywood are met, the prepared plywood can be stored under the condition of high temperature and high humidity for 28 days without mildewing, and the prepared artificial board is a green environment-friendly ecological plywood.
(4) According to the invention, the byproduct soybean meal produced in the production of soybean oil is used as a raw material for producing the adhesive in the wood industry, the source of the byproduct soybean meal 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 that harmful substances such as formaldehyde, phenol and the like are volatilized and released to cause harm to human bodies in the production and preparation process of wooden products, reduces pollution and damage of chemical products to the natural environment, and has the advantages of renewable raw material sources and environmental friendliness.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of the bonding strength of adhesives of comparative examples 1-3 and examples 1-8 provided by the invention;
FIG. 2 is a schematic representation of the mildew resistance of the adhesives of comparative examples 1-3 and examples 1-3 provided in accordance with the present invention;
FIG. 3 is a schematic representation of the mold resistance of the adhesives of examples 5-8 provided in the present invention;
FIG. 4 is a schematic representation of the mildew resistance of plywood made with the adhesives of comparative examples 1-3 and examples 1-3, provided by the present invention;
fig. 5 is a schematic view showing the mold resistance of commercial plywood, fiberboard, particle board and oriented strand board provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
In the following examples and comparative examples of the invention, 2-8% of dodecyl dimethyl benzyl ammonium bromide solution is used as modifier, and the used soybean protein powder is soybean protein powder with 53% of protein content and 200 meshes of bean powder particle size.
Example 1
According to the soybean protein adhesive for the mildew-proof water-resistant wood and the preparation method thereof, the soybean protein adhesive is prepared according to the following steps:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium bromide (modifier): 0.2 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soy protein adhesive in the embodiment is as follows:
1) a stirring paddle device is constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, and then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min to obtain mixed protein liquid;
2) pretreatment of mixed protein liquid: 0.2 part of modifier is added into the evenly mixed and stirred protein liquid, and the condition that the rotating speed of a stirring paddle is kept at 800r/min is kept for 10 min.
3) Adding 0.3 part of auxiliary agent in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 2
According to the mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment, the soybean protein adhesive is prepared according to the following steps:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium bromide (modifier): 0.4 portion of
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part of
The specific preparation method of the soy protein adhesive in this embodiment is as follows:
1) a stirring paddle device is built and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, and then the mixture is stirred for 10min at the room temperature at the rotating speed of 1000r/min to obtain mixed protein liquid;
2) pretreatment of mixed protein liquid: 0.4 part of modifier is added into the evenly mixed and stirred protein liquid, and the condition that the rotating speed of a stirring paddle is kept at 800r/min is kept for 10 min.
3) Adding 0.3 part of auxiliary agent in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 3
According to the mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment, the soybean protein adhesive is prepared according to the following steps:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
The specific preparation method of the soy protein adhesive in the embodiment is as follows:
1) a stirring paddle device is constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, and then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min to obtain mixed protein liquid;
2) pretreatment of mixed protein liquid: 0.4 part of modifier is added into the evenly mixed and stirred protein liquid, and the rotating speed of a stirring paddle is kept at 800r/min for 10 min.
3) Adding 0.3 part of auxiliary agent in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 4
According to the mildew-proof water-resistant soybean protein adhesive and the preparation method thereof provided by the embodiment, the soybean protein adhesive is prepared by the following steps of:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium bromide (modifier): 0.8 part of
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part of
The specific preparation method of the soy protein adhesive is as follows.
Comparative example 1
The quality of the soy protein adhesive in the comparative example is prepared in the following way:
water: 7 portions of
Soybean protein powder: 3 portions of
The specific preparation method of the comparative example protein adhesive is as follows: a stirring paddle device is constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min, and the mixture is uniformly stirred to obtain mixed protein liquid;
comparative example 2
The quality of the soy protein adhesive in the comparative example is prepared in the following way:
water: 7 portions of
Soybean protein powder: 3 portions 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 constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min, and the mixture is uniformly stirred to obtain mixed protein liquid;
2) adding 0.3 part of auxiliary agent in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, 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 the comparative example is prepared in the following manner:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium bromide (modifier): 0.4 part of
The specific preparation method of the protein adhesive in the comparative example is as follows:
1) a stirring paddle device is constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min, and the mixture is uniformly stirred 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 soybean protein adhesive in the comparative example.
Example 5
The mass of the soy protein adhesive in the embodiment is prepared in the following manner:
water: 7 portions of
Soybean protein powder: 3 portions of
Tributylbenzyl ammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part of
The specific preparation method of the protein adhesive in the embodiment is as follows:
1) a stirring paddle device is constructed and prepared, the soybean protein powder and water are uniformly mixed in a reaction kettle according to the mass ratio of 3:7, then the mixture is stirred for 10min at the room temperature and the rotating speed of 1000r/min, and the mixture is uniformly stirred to obtain mixed protein liquid;
2) pretreatment of mixed protein liquid: and adding 0.6 part of tributyl benzyl ammonium bromide serving as a modifier into the uniformly mixed and stirred protein solution, and keeping the rotating speed of a stirring paddle at 800r/min for 10 min.
3) Adding 0.3 part of auxiliary agent in two times, wherein the adding ratio is 1:1, the interval between the two times of adding is 10min, and then keeping the temperature and continuously stirring for 10min to obtain the soybean protein adhesive.
Example 6
The quality of the soy protein adhesive in the comparative example is prepared in the following way:
water: 7 portions of
Soybean protein powder: 3 portions of
Dodecyl trimethyl ammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part
EXAMPLES A specific preparation method of the protein adhesive is the same as that of example 5.
Example 7
The mass of the soy protein adhesive in the embodiment is prepared in the following manner:
water: 7 portions of
Soybean protein powder: 3 portions of
Benzalkonium chloride (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 the same as that in the embodiment 5.
Example 8
The quality of the soy protein adhesive in this example was formulated as follows:
water: 7 portions of
Soybean protein powder: 3 portions of
N, N-trimethyl-1-tetradecylammonium bromide (modifier): 0.6 part
1, 6-hexanediol diglycidyl ether (adjuvant): 0.3 part of
The specific preparation method of the protein adhesive in this embodiment is the same as that in embodiment 5.
Experimental example 1
The common three-layer plywood is prepared by the soybean protein adhesive synthesized according to the above examples and comparative examples, and the preparation process is as follows:
selecting 200mm × 200mm × 1.6mm eucalyptus veneer as base material (water content is maintained at 8-12%), and applying glue at 200g/m per side 2 Gluing, namely assembling the three layers of veneers in a criss-cross manner, hot-pressing at the temperature of 120 ℃ and under the pressure of 1.0MPa according to the thickness of 1.5mm/min, and then pressing to obtain the plywood.
Testing the performance of the adhesive:
and testing the performance indexes of the prepared common plywood, such as dry bonding strength, wet bonding strength and the like according to the requirements in the test methods of the physical and chemical properties of the GB/T17657-2013 artificial board and the veneer artificial board.
Testing the mildew resistance of the adhesive and the plywood:
the adhesive samples synthesized in examples and comparative examples and the commercial plywood were placed in an incubator at 30 ℃ and 90% relative humidity, and the mildew process was recorded with a digital camera every day.
Referring to FIG. 1, it can be seen that the dry and wet bonding strengths of the adhesives of examples 1-4 are all greater than or equal to 0.7MPa, and meet the strength requirement of the class II plywood standard in GB/T9846-. Compared with the adhesive prepared in example 3, the dry bonding strength and the wet bonding strength of the adhesive prepared in comparative example 1 are respectively improved from 1.30MPa and 0MPa to 2.22MPa and 1.25MPa, and the wet bonding strength modification effect is very obvious. In addition, the soybean protein adhesives prepared in the examples and comparative examples have extremely low formaldehyde emission.
Referring to fig. 2, it can be seen that the adhesives prepared in comparative example 3 and examples 1-3 do not mildew after being stored for 60 days under high temperature and high humidity conditions, while comparative example 1 and comparative example 2 begin to mildew after day 1 and day 13, respectively, which fully illustrates that the modification method provided by the present invention can significantly improve the mildew resistance of the soy protein adhesive. In addition, referring to fig. 3, it can be seen from comparative examples 4 to 7 that the adhesive prepared by the micelle-enhanced modification method provided by the invention shows better mildew resistance, but is still slightly worse than the mildew resistance of the examples, and the invention provides a simple, convenient and strong-universality new strategy for preparing a series of formaldehyde-free, environment-friendly, renewable and mildew-proof protein adhesives, and the comprehensive modification effect of the examples of the invention is better. The method in the embodiment 3 can obtain the adhesive with good comprehensive performance (bonding performance and mildew resistance).
Referring to fig. 4, it can be seen that the plywood prepared by the adhesives of comparative example 3 and examples 1-3 has no significant mildew after being stored for 28 days under the high-temperature and high-humidity conditions, whereas the plywood prepared by the adhesives of comparative example 1 and comparative example 2 has mildew after being stored for 7 days and 14 days, respectively, and referring to fig. 5, the plywood prepared by the adhesives synthesized by the invention has significantly improved mildew resistance after being stored for 14 days.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
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 vegetable protein, 7-15 parts of water, 0.2-0.8 part of modifier and 0.3-0.5 part of reinforcing additive; the vegetable protein comprises soybean protein powder, and the modifier is selected from one or more of benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyl trimethyl ammonium bromide, benzalkonium chloride and N, N, N-trimethyl-1-tetradecyl ammonium bromide.
2. The mildew-proof water-resistant soybean protein adhesive as claimed in 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 additive; preferably 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 additive.
3. The mold-proof water-resistant soy protein adhesive as claimed in claim 2, wherein the modifier is benzalkonium bromide, tributylbenzyl ammonium bromide, dodecyltrimethyl ammonium bromide, benzalkonium chloride or N, N-trimethyl-1-tetradecyl ammonium bromide; preferably, the modifier is a solution with the mass fraction of 2-10%.
4. The mold-proof water-resistant soy protein adhesive as claimed in claim 13, wherein said modifier is benzalkonium bromide.
5. The mildew-proof water-resistant soy protein adhesive as claimed in any one of claims 1 to 4, wherein the enhancing additive is one or more selected from 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, cyclohexanediol diglycidyl ether, ethylene glycol diglycidyl ether, n-butyl-2, 3-glycidyl ether and glycerol triglycidyl ether, and is preferably 1, 6-hexanediol diglycidyl ether.
6. The mildew-proof water-resistant soybean protein adhesive as claimed in any one of claims 1 to 5, wherein the soybean protein powder is defatted soybean powder, soybean protein concentrate powder or soybean protein isolate, the protein content of the soybean protein powder is not less than 42%, and the particle size of the soybean powder is more than 200 meshes, preferably 200 to 250 meshes.
7. The preparation method of the mold-proof water-resistant soy protein adhesive as claimed in any one of claims 1 to 6, which is characterized by comprising the steps of mixing and stirring the soy protein powder, water, the modifier and the enhancing aid in sequence; 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 enhancing auxiliary agent into the pretreated protein liquid, and stirring.
8. The preparation method of the mildew-proof water-resistant soy protein adhesive as claimed in claim 7, 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 at the rotating speed of 800 r/min;
3) adding the reinforcing auxiliary agent in two times, wherein the adding ratio is 1-2: 1-2, the interval between the two times of adding is 5-15 min, and then continuously stirring for 5-15 min.
9. The preparation method of the mildew-proof water-resistant soy protein adhesive as claimed in claim 8, wherein the preparation processes of steps 1) -3) are all carried out at room temperature.
10. The use of the soybean protein adhesive of any one of claims 1 to 6 for producing an environmentally friendly artificial board.
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