CN113372875B - Bio-based adhesive and preparation method and application thereof - Google Patents
Bio-based adhesive and preparation method and application thereof Download PDFInfo
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- CN113372875B CN113372875B CN202110621134.5A CN202110621134A CN113372875B CN 113372875 B CN113372875 B CN 113372875B CN 202110621134 A CN202110621134 A CN 202110621134A CN 113372875 B CN113372875 B CN 113372875B
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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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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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Abstract
The invention discloses a bio-based adhesive and a preparation method and application thereof, belonging to the technical field of adhesives. The invention provides a specific bio-based core-shell flame-retardant particle, which is prepared by adding a flame retardant into a mixed solution containing a silane coupling agent and an acid-binding agent, and mixing and modifying to obtain a product A; and then mixing the tannic acid with the product A, and modifying to obtain the bio-based core-shell flame-retardant particles. The invention utilizes the bio-based core-shell flame-retardant particles to be compounded with a compound modifier, soy protein, a cross-linking agent and water in a specific proportion to obtain the bio-based adhesive. The bio-based adhesive obtained by the invention has the advantages of low production cost, no toxicity, no pollution, excellent bonding strength, water resistance and flame retardant property, can be used for producing and preparing artificial boards, and has important significance for the preparation and application of artificial boards.
Description
Technical Field
The invention relates to a bio-based adhesive and a preparation method and application thereof, belonging to the technical field of adhesives.
Background
The adhesive is an indispensable chemical product for national economic development, is widely applied to various fields, and is particularly important in the wood processing industry. At present, the adhesives used in the wood and artificial board industry of China still mainly comprise three-aldehyde adhesives (namely urea-formaldehyde resin adhesive, phenolic resin adhesive and melamine resin adhesive), and the usage amount accounts for 60-70% or more of the total adhesive consumption of the artificial board industry. However, the "trialdehyde glue" releases volatile chemical substances such as formaldehyde, phenol and the like in the processes of preparation, use and processing and use (furniture, wood floor, indoor wood decorative material and the like) of the artificial board prepared by the "trialdehyde glue", thereby endangering the environment and the human health. In addition, because the wood material has flammability, hidden danger of fire hazard can be accelerated and expanded when a fire hazard occurs.
In recent years, with the increasing awareness of environmental protection, biomass materials are more and more apt to be used as raw materials to prepare nontoxic, harmless, green and environment-friendly adhesives in the wood adhesive industry. The soybean protein isolate is used as a soybean processing byproduct, has rich sources, low price, easy obtainment and high reactivity, and is an ideal substitute for preparing the environment-friendly wood adhesive. However, due to the characteristics of the structure and the performance of the soybean protein isolate, the prepared adhesive has low bonding strength, poor heat and water resistance and no corrosion resistance, thereby seriously limiting the popularization and the application of the soybean protein isolate adhesive in artificial boards. In addition, due to the special structure of the wood, the flame retardant for preparing the flame-retardant artificial board not only needs to have good flame retardant property, but also needs to have certain water resistance, loss resistance and the like, and also needs to have proper pH value, so that the structure and the performance of the flame retardant artificial board cannot be damaged. Generally, most of the existing flame-retardant artificial boards are produced by using a flame retardant treatment solution to soak a single board and then using an adhesive to bond the single board. The environment-friendly bio-based adhesive with the flame retardant function is researched and prepared by combining flame retardance and gluing, and has important significance for the preparation and application of artificial boards.
Disclosure of Invention
The invention aims to solve the technical problems and provides a bio-based adhesive and a preparation method thereof, and the bio-based adhesive has the advantages of low production cost, no toxicity, no pollution, good bonding strength, water resistance and flame retardant property, and can be used for producing and preparing artificial boards.
The technical scheme of the invention is realized as follows:
firstly, providing a bio-based core-shell flame-retardant particle, wherein the bio-based core-shell flame-retardant particle is prepared by the following method:
adding a flame retardant into a mixed solution containing a silane coupling agent and an acid-binding agent, and mixing and modifying to obtain a product A; and then mixing the tannic acid with the product A, and modifying to obtain the bio-based core-shell flame-retardant particles.
The bio-based core-shell flame-retardant particle is also applied to preparation of biology and adhesives.
The bio-based adhesive comprises the following components in parts by weight: 80-100 parts of water, 10-30 parts of soybean protein, 0.3-2.0 parts of composite modifier, 5-15 parts of cross-linking agent, 0.2-2.0 parts of bio-based core-shell flame-retardant particles and 0.1-0.3 part of functional auxiliary agent;
the composite modifier comprises borax and at least one of sodium bisulfite, sodium sulfite and sodium persulfate.
In one embodiment of the invention, the composite modifier comprises, by mass, 0.3 to 1 part of borax and 0.2 to 1 part of sodium sulfite.
In one embodiment of the present invention, the composite modifier is preferably 0.5 to 1.5 parts by weight; the preferred proportion of the bio-based core-shell flame-retardant particles is 0.5-1.5.
In one embodiment of the present invention, the silane coupling agent is a silane coupling agent containing an amino group.
In one embodiment of the present invention, the acid-binding agent comprises one or more of triethylamine, pyridine, and potassium carbonate.
In one embodiment of the invention, the flame retardant is a flame retardant containing a phenylphosphoryl chloride structure, and is selected from at least one of phenylphosphoryl chloride, phenylphosphoryl dichloride, diphenoxyphosphoryl chloride, diphenylphosphinic chloride and bis (2,6-xylyl) phosphoryl chloride.
In one embodiment of the present invention, the functional auxiliary comprises at least one of an antifoaming agent, a bactericide, and a pH adjuster.
In one embodiment of the present invention, the defoamer may be selected from: silicone defoaming agents, polyether defoaming agents; the bactericide can be selected from: isothiazolinone derivatives, benzimidazolyl esters; the pH regulator can be selected from: sodium hydroxide, hydrochloric acid.
In one embodiment of the present invention, the crosslinking agent is at least one of compounds having a glycidyl ether structure.
Further, the cross-linking agent is selected from at least one of ethylene glycol glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether and glycerol glycidyl ether, or at least one of derivatives obtained by reacting at least one of ethylene glycol glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether and glycerol glycidyl ether with at least one of diethylenetriamine and triethylenetetramine.
In one embodiment of the invention, the bio-based core-shell flame-retardant particles are specifically obtained by the following steps:
(1) Firstly, under the condition of ice-water bath, dissolving a silane coupling agent and an acid-binding agent in diethyl ether, then slowly adding diethyl ether solution containing a flame retardant, continuously stirring for 30-120min, heating to room temperature, continuously reacting for 2-5h to obtain a crude product, and purifying to obtain a product A;
(2) And (2) dissolving Tannic Acid (TA) in water, adjusting the pH value to 8-10, slowly adding the product A obtained in the step (1), reacting for 0.5-6h, and purifying the crude product to obtain the bio-based core-shell flame-retardant particles.
The invention also provides a method for preparing the bio-based adhesive, which comprises the following steps:
1) Dispersing the composite modifier, the bio-based core-shell flame-retardant particles and the soybean protein in water according to the mass part ratio, uniformly mixing and modifying to obtain a soybean protein base modified solution;
2) Adding a cross-linking agent and a functional auxiliary agent into the soybean protein basic modified liquid obtained in the step 1) according to the mass ratio, and uniformly mixing and modifying to obtain the bio-based adhesive.
In one embodiment of the present invention, the temperature of the mixing modification in the step 1) is 40 to 65 ℃. The reaction time is 10-60min.
In one embodiment of the present invention, the mixing modification temperature in the step 2) is 20 to 30 ℃.
In one embodiment of the invention, the preparation method of the bio-based adhesive specifically comprises the following processes:
1) Heating water to 40-65 ℃, then sequentially adding the composite modifier, the bio-based core-shell flame-retardant particles and the soybean protein according to the weight part ratio, and continuously stirring for 10-60min to obtain a soybean protein base modified solution;
2) And cooling the soybean protein base modified liquid to room temperature, adding the cross-linking agent and the functional auxiliary agent in parts by weight, and uniformly stirring to obtain the soybean protein adhesive.
The invention also provides a method for gluing by using the bio-based adhesive.
The invention also provides the application of the bio-based adhesive in wood veneers, shaving boards, blockboards and fiber boards.
The beneficial effects of the invention are embodied in the following aspects:
1. the invention adopts the composite modifier, wherein the borax can play a role in hydrolyzing protein and destroying salt bonds and hydrophobic bonds between molecules, the sodium sulfite can destroy disulfide bonds between protein molecular chains, and the bio-based adhesive which has proper viscosity and is beneficial to sizing can be obtained by adjusting the proportion of the two denaturants.
2. The added bio-based core-shell flame-retardant particles are synthesized from bio-based tannin and a coupling agent modified flame retardant, and are halogen-free, non-toxic, environment-friendly and good in flame retardant property. Meanwhile, borax in the composite modifier also has certain flame retardant property. The resulting bio-based adhesive is thus a flame retardant system consisting of N-P-B. In addition, the obtained modified flame-retardant particles have good hydrophobic property, can effectively prevent the erosion of water to the cured bio-based adhesive, and are beneficial to the wet strength of the bio-based adhesive.
3. The bio-based adhesive prepared by the invention combines the adhesive bonding and flame retardance in the preparation process of the artificial board, greatly shortens the preparation time and reduces the cost.
Drawings
Fig. 1 is an FT-IR spectrum of Tannic Acid (TA), product a (BPOD (Si)), and bio-based core-shell flame retardant particles (TBD (Si)) referred to in example 1.
Fig. 2 is an SEM image of the bio-based core-shell flame retardant particles (TBD (Si)) obtained in example 1.
Detailed Description
Although the present invention has been described in detail, the present invention is not limited thereto, and those skilled in the art can modify the principle of the present invention, and thus, various modifications made in accordance with the principle of the present invention should be understood to fall within the scope of the present invention.
Example 1 preparation of Bio-based core-Shell flame retardant particles
The preparation method of the bio-based core-shell flame retardant particles prepared by using the phenyl phosphoryl chloride flame retardant comprises the following steps:
(1) First, 3-aminopropyltriethoxysilane (0.5 mol) and triethylamine (0.5 mol) were dissolved in diethyl ether (500 mL) in an ice-water bath, and then a solution of phenylphosphoryl chloride (0.5 mol) in diethyl ether was slowly added with continuous stirring for 60min. Heating to room temperature, continuing to react for 4 hours to obtain a crude product, and purifying to obtain a product A;
(2) And (2) dissolving Tannic Acid (TA) in water (0.5 mol/L), adjusting the pH value to 9.0, then slowly adding the tannin A into the solution A obtained in the step (1), reacting for 6 hours, and purifying a crude product to obtain the halogen-free bio-based core-shell flame retardant particles.
The preparation method of the bio-based core-shell flame retardant particles prepared by using the diphenoxyphosphoryl chloride, the diphenylphosphinic chloride and the bis (2,6-xylyl) phosphoryl chloride flame retardant is different from the preparation method of the bio-based core-shell flame retardant particles prepared by using the phenylphosphoryl chloride flame retardant in that the phenylphosphoryl chloride is replaced by the diphenoxyphosphoryl chloride, the diphenylphosphinic chloride and the bis (2,6-xylyl) phosphoryl chloride, and the rest is unchanged.
The preparation method of the bio-based core-shell flame retardant particles prepared by using the phenylphosphoryl dichloride flame retardant comprises the following steps:
(1) Firstly, 3-aminopropyltriethoxysilane (1 mol) and triethylamine (1 mol) are dissolved in diethyl ether (500 mL) under the condition of ice-water bath, and then the diethyl ether solution of phenylphosphoryl dichloride (0.5 mol) is slowly added and the stirring is continued for 60min. Heating to room temperature, continuing to react for 4 hours to obtain a crude product, and purifying to obtain a product A without halogen;
(2) And (2) dissolving Tannic Acid (TA) in water (0.5 mol/L), adjusting the pH value to 9.0, then slowly adding the tannin A into the solution A obtained in the step (1), reacting for 6 hours, and purifying a crude product to obtain the halogen-free bio-based core-shell flame retardant particles.
The morphology and structure of the bio-based core-shell flame-retardant particles prepared by using the phenylphosphoryl dichloride flame retardant are characterized in that:
it can be found from the FT-IR spectrum of FIG. 1 that it is observed in the TA spectrum at 3600-3100cm -1 A wide-OH stretching vibration peak at 1700cm -1 A stretching vibration peak of C = O appears. FT-IR spectrum for BPOD (Si) at 3100-3300cm -1 The weak broad peak appeared corresponding to the stretching vibration of secondary amine, at 2800-3000cm -1 The absorption peak of (2) corresponds to the C-H stretching vibration and is 1260cm -1 A characteristic absorption peak of P = O appears. Further analysis of the FT-IR spectrum of TBD (Si) was observed at 1800-3000cm -1 ，1700cm -1 And 1260cm -1 Characteristic absorption peaks of (A) correspond to C-H stretching vibration, C = O stretching vibration and P = O group, respectively, and are at 1091cm -1 The stretching vibration peak of Si-O-C was observed. The results show that the silylated BPOD (Si) molecules are successfully introduced to obtain TBD (Si) hybrids via the multifunctional reaction platform provided by TA. The size of the TBD (Si) hybrid particles is 50-200nm as can be confirmed by the SEM image of FIG. 2.
Example 2 preparation of a Soy protein adhesive
(1) Heating 85 parts of water (850 g) to 50 ℃, then sequentially adding 1 part of composite modifier (borax: sodium sulfite 3:7), 0.5 part of bio-based core-shell flame-retardant particles (modified by phenyl phosphoryl chloride) and 15 parts of soybean protein, and continuously stirring for 30min to obtain a soybean protein basic modified solution;
(2) And (3) cooling the soybean protein basic modified liquid to room temperature, adding 5 parts of cross-linking agent glycerol triglycidyl ether and 0.2 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
EXAMPLE 3 preparation of Soy protein adhesive
(1) Heating 80 parts of water (800 g) to 40 ℃, then sequentially adding 0.8 part of composite modifier (borax: sodium bisulfite 8:5), 1 part of bio-based core-shell flame retardant particles (modified by diphenoxy phosphoryl chloride) and 20 parts of soybean protein, and continuously stirring for 40min to obtain a soybean protein basic modified solution;
(2) And (3) cooling the soybean protein basic modified liquid to room temperature, adding 8 parts of cross-linking agent 1,4-butanediol glycidyl ether and 0.3 part of functional auxiliary agent (polyether defoaming agent: benzimidazole ester bactericide 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Example 4 preparation of a Soy protein adhesive
(1) Heating 90 parts of water (900 g) to 55 ℃, then sequentially adding 0.6 part of composite modifier (borax: sodium sulfite is 1: 0.5), 1.2 parts of bio-based core-shell flame-retardant particles (modified by diphenylphosphinic chloride) and 25 parts of soybean protein, and continuously stirring for 45min to obtain soybean protein basic modified liquid;
(2) And (3) cooling the soybean protein basic modified liquid to room temperature, adding 10 parts of cross-linking agent 1,6-hexanediol glycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide 1:1), and uniformly stirring to obtain the soybean protein adhesive.
EXAMPLE 5 preparation of Soy protein adhesive
(1) Heating 95 parts of water (950 g) to 60 ℃, then sequentially adding 1.5 parts of composite modifier (borax: sodium persulfate 8:3), 1 part of bio-based core-shell flame retardant particles (modified by bis (2,6-xylyl) phosphoryl chloride) and 25 parts of soybean protein, and continuously stirring for 50min to obtain soybean protein base modified liquid;
(2) And cooling the soybean protein basic modified liquid to room temperature, adding 8 parts of a reaction product of 1,4-butanediol glycidyl ether serving as a cross-linking agent and diethylenetriamine and 0.2 part of a functional auxiliary agent (an organic silicon defoaming agent: 1:1 serving as a benzimidazole ester bactericide), and uniformly stirring to obtain the soybean protein adhesive.
EXAMPLE 6 preparation of Soy protein adhesive
(1) Heating 100 parts of water (1000 g) to 60 ℃, then sequentially adding 1.5 parts of composite modifier (borax: sodium sulfite 5:3), 1.5 parts of bio-based core-shell flame-retardant particles (modified by phenylphosphoryl dichloride) and 30 parts of soybean protein, and continuously stirring for 60min to obtain soybean protein basic modified liquid;
(2) And cooling the soybean protein basic modified liquid to room temperature, adding 12 parts of cross-linking agent glycerol triglycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Comparative example 1
Compared with the example 6, the soybean protein adhesive is a pure soybean protein adhesive without any modification, and comprises the following specific steps: heating 100 parts of water (1000 g) to 60 ℃, adding 30 parts of soybean protein, continuously stirring for 60min, then cooling to room temperature, adding a functional auxiliary agent (an organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Comparative example 2
Compared with the embodiment 6, the method does not add the composite modifier and comprises the following specific steps:
(1) Heating 100 parts of water (1000 g) to 60 ℃, then sequentially adding 1.5 parts of bio-based core-shell flame-retardant particles (modified by phenylphosphoryl dichloride) and 30 parts of soybean protein, and continuously stirring for 30min to obtain a soybean protein basic modified solution;
(2) And (2) cooling the soybean protein basic modified liquid to room temperature, adding 12 parts of cross-linking agent glycerol triglycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Comparative example 3
Compared with the embodiment 6, the method does not add the cross-linking agent and comprises the following specific steps:
(1) Heating 100 parts of water (1000 g) to 60 ℃, then sequentially adding 1.5 parts of composite modifier (borax: sodium sulfite 5:3), 1.5 parts of bio-based core-shell flame-retardant particles (modified by phenylphosphoryl dichloride) and 30 parts of soybean protein, and continuously stirring for 30min to obtain soybean protein basic modified liquid;
(2) And cooling the soybean protein basic modified liquid to room temperature, adding 12 parts of cross-linking agent glycerol triglycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Comparative example 4
Compared with the embodiment 6, the concrete steps without adding the bio-based core-shell flame retardant particles are as follows:
(1) Heating 100 parts of water (1000 g) to 60 ℃, then sequentially adding 1.5 parts of composite modifier (borax: sodium sulfite is 5:3) and 30 parts of soybean protein, and continuously stirring for 30min to obtain soybean protein basic modified liquid;
(2) And cooling the soybean protein basic modified liquid to room temperature, adding 12 parts of cross-linking agent glycerol triglycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Comparative example 5
Compared with the embodiment 6, the added flame retardant is phenyl phosphoryl dichloride, and the specific steps are as follows:
(1) Heating 100 parts of water (1000 g) to 60 ℃, then sequentially adding 1.5 parts of composite modifier (borax: sodium sulfite 5:3), 1.5 parts of phenyl phosphoryl dichloride and 30 parts of soybean protein, and continuously stirring for 60min to obtain a soybean protein basic modified solution;
(2) And cooling the soybean protein basic modified liquid to room temperature, adding 12 parts of cross-linking agent glycerol triglycidyl ether and 0.3 part of functional auxiliary agent (organic silicon defoamer: benzimidazole ester bactericide is 1:1), and uniformly stirring to obtain the soybean protein adhesive.
Performance test results of bio-based adhesive
The viscosity and Limiting Oxygen Index (LOI) of the bio-based adhesives prepared in examples 2-6 and comparative examples 1-5 were respectively tested, and the bonding strength of the plywood prepared from the bio-based adhesives under dry and wet conditions was tested according to the national Standard GB/T17657-2013 physicochemical property test method for Artificial Board and decorative Artificial Board. The results are shown in Table 1:
TABLE 1 Performance results for adhesives obtained in examples 2-6 and comparative examples 1-5
According to the test of national standard GB/T17657-2013 physical and chemical property test method for artificial boards and veneered artificial boards, the examples 2-6 can obtain the bio-based adhesive with excellent bonding strength and water resistance, and also have good flame retardant property. In example 6, the resulting bio-based adhesive had a viscosity of 16010 mPs, a dry adhesive strength of 3.11MPa, a wet adhesive strength of 1.36MPa, and a limiting oxygen index of 27.6%. This is because: 1) By adding the composite modifier, the borax can play a role in hydrolyzing protein and destroying salt bonds and hydrophobic bonds between molecules, the sodium sulfite can destroy disulfide bonds between protein molecular chains, and the bio-based adhesive can have proper viscosity and is convenient for sizing by adjusting the proportion between the two denaturants; 2) By adding the cross-linking agent, a three-dimensional cross-linking network can be constructed in a soybean protein system, the cohesive strength of the adhesive and the mechanical riveting strength between the adhesive and a plate are improved, the corrosion of water can be prevented, and the bonding strength and the water resistance of the obtained adhesive are effectively improved; 3) Under the synergistic effect of borax and the bio-based core-shell flame-retardant particles, an N-P-B flame-retardant system can be constructed in the bio-based adhesive, so that the flame-retardant property is improved. Compared with the comparative example 2, the viscosity of the adhesive obtained by the method is obviously increased to 32560mP & s because the compound modifier is not added in the comparative example 2, and the coating and dispersing performance of the adhesive in the using process can be influenced by the higher viscosity. In addition, compared with example 6, the limiting oxygen index of the adhesive of comparative example 2 is reduced to 24.6%, because borax in the composite modifier has a good flame retardant effect, and the borax cannot form a synergistic flame retardant effect with the bio-based core-shell flame retardant particles due to the fact that the composite modifier is not added in comparative example 2. Comparative example 3 no crosslinking agent was added, so that a crosslinked network could not be formed in the soybean protein system to improve the adhesive strength, and the corrosion of the adhesive by moisture could not be resisted, thereby exhibiting low dry and wet adhesive strengths. In comparative example 4, no bio-based core-shell flame retardant particles were added, so the limiting oxygen index was only 23.2%, which is much lower than the limiting oxygen index of 27.6% for the adhesive obtained in example 5. Comparative example 5 can obtain the same adhesive strength, water resistance and flame retardant property as example 5, but since the flame retardant added in comparative example 5 is phenylphosphoryl dichloride, which contains halogen, it has toxic and side effects and seriously pollutes the environment.
Therefore, the bio-based adhesive obtained by the invention has good sizing performance, can obtain excellent bonding strength and water resistance when used for preparing plywood, and can obtain good flame retardant property. Therefore, the invention can be applied to the fields of wood veneers, shaving boards, core-board boards and fiber boards by preparing the bio-based adhesive which integrates bonding and flame retardance.
Example 7 explore the effect of bio-based core-shell flame retardant particle addition on adhesive performance
Referring to example 6, the addition amounts of the bio-based core-shell flame retardant particles were respectively replaced with 0.2 parts, 1.5 parts, and 2 parts, and other conditions were not changed, to obtain the corresponding cement products.
The performance index of the obtained adhesive was tested, and the results are shown in table 2:
TABLE 2 Performance results of adhesives obtained with different bio-based core-shell flame retardant particle additions
| Adding amount (parts) of bio-based core-shell flame retardant particles | 0.2 | 1.5 | 2 |
| Viscosity (mP. S) | 15890 | 16010 | 16120 |
| Limiting oxygen index LOI (%) | 23.4 | 27.6 | 28.4 |
| Dry bond Strength (MPa) | 2.83 | 3.11 | 2.78 |
| Wet adhesion Strength (MPa) | 1.15 | 1.36 | 1.11 |
Example 8 investigation of the Effect of Complex modifier addition on Adhesives Performance
Referring to example 6, the addition amounts of the composite modifier were respectively replaced by 0.3, 1.5 and 2 parts, and the other conditions were not changed, to obtain the corresponding cement products.
The performance index of the adhesive was tested, and the results are shown in table 3:
TABLE 3 Performance results for adhesives obtained with different amounts of composite modifier added
| Addition amount of composite modifier | 0.3 | 1.5 | 2 |
| Viscosity (mP. S) | 25890 | 16010 | 10050 |
| Limiting oxygen index LOI (%) | 26.8 | 27.6 | 27.9 |
| Dry bond Strength (MPa) | 3.04 | 3.11 | 2.88 |
| Wet adhesion Strength (MPa) | 1.26 | 1.36 | 1.11 |
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalents, improvements, and the like that may be made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A bio-based core-shell flame-retardant particle for preparing a biological adhesive is characterized in that the bio-based core-shell flame-retardant particle is prepared by adding a flame retardant into a mixed solution containing a silane coupling agent and an acid-binding agent, and mixing and modifying to obtain a product A; then, mixing tannic acid with the product A, and modifying to obtain the bio-based core-shell flame-retardant particles;
the flame retardant is a flame retardant containing a phenyl phosphoryl chloride structure and is selected from at least one of phenyl phosphoryl chloride, phenyl phosphoryl dichloride, diphenoxy phosphoryl chloride, diphenyl phosphoryl chloride and bis (2,6-xylyl) phosphoryl chloride.
2. The use of bio-based core-shell flame retardant particles of claim 1 in the preparation of a bioadhesive.
3. The bio-based adhesive is characterized by comprising the following components in parts by weight: 80-100 parts of water, 10-30 parts of soybean protein, 0.3-2.0 parts of composite modifier, 5-15 parts of cross-linking agent, 0.5-2.0 parts of bio-based core-shell flame-retardant particles according to claim 1, and 0.1-0.3 part of functional auxiliary agent;
the composite modifier comprises borax and at least one of sodium bisulfite, sodium sulfite and sodium persulfate;
the cross-linking agent is selected from: at least one of ethylene glycol glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, glycerol glycidyl ether, or selected from: at least one of the derivatives obtained by the reaction of at least one of ethylene glycol glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether and glycerol glycidyl ether with at least one of diethylenetriamine and triethylene tetramine.
4. The bio-based adhesive as claimed in claim 3, wherein the composite modifier comprises 0.3-1 part of borax and 0.2-1 part of sodium sulfite according to the mass part ratio.
5. A method for preparing the bio-based adhesive according to any one of claims 3 to 4, wherein the method comprises the following steps:
(1) Dispersing the composite modifier, the bio-based core-shell flame-retardant particles and the soybean protein in water according to the mass part ratio, and uniformly mixing and modifying to obtain a soybean protein base modified liquid;
(2) And (2) adding a cross-linking agent and a functional auxiliary agent into the soybean protein basic modified liquid obtained in the step (1) according to the mass part ratio, and uniformly mixing and modifying to obtain the bio-based adhesive.
6. A method of gluing using a bio-based adhesive according to any one of claims 3 to 4.
7. Use of the bio-based adhesive of any one of claims 3-4 in wood veneer, particle board, core board, fiber board.
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