阅读说明：本技术 一种胶木箱用胶合板的制备方法 (Preparation method of plywood for bakelite box ) 是由 胡铁林 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种胶木箱用胶合板的制备方法,将三块薄木板用胶粘剂胶合制得,该胶粘剂包括如下重量份原料：改性树脂20-30份、改性石墨烯3-5份、苄基二甲胺3-5份、硫酸化蓖麻油1-3份、十二烷基磺酸钠1-3份、邻苯基苯酚1-3份、水10-15份；改性树脂分子链上含有大量的吩噻嗪结构,两个苯环中间夹了一个六元环,使得硫原子的孤对电子在三个环上离域,使得吩噻嗪的氮氢键容易断裂,分子中的硫原子可以被氧化形成亚砜、砜类化合物,使得胶粘剂具有很好的耐热氧效果,在胶合板使用过程中不会出现胶合板开胶,保证了胶木箱正常使用,改性树脂分子侧链含有聚酰亚胺分子链,与改性石墨烯配合能够增强胶粘剂的断裂韧性,使得胶粘剂的胶粘效果更好。(The invention discloses a preparation method of plywood for a plywood case, which is prepared by gluing three thin wood boards by using an adhesive, wherein the adhesive comprises the following raw materials in parts by weight: 20-30 parts of modified resin, 3-5 parts of modified graphene, 3-5 parts of benzyl dimethylamine, 1-3 parts of sulfated castor oil, 1-3 parts of sodium dodecyl sulfate, 1-3 parts of o-phenylphenol and 10-15 parts of water; contain a large amount of phenothiazine structures on the modified resin molecular chain, a six-membered ring has been pressed from both sides in the middle of two benzene rings, make the lone pair electron of sulfur atom delocalize on three ring, make the nitrogen hydrogen bond of phenothiazine fracture easily, sulfur atom in the molecule can be by oxidation formation sulfoxide, sulfone class compound, make the adhesive have fine thermal-oxygen resistant effect, plywood split can not appear in the plywood use, guaranteed bakelite box normal use, modified resin molecule side chain contains the polyimide molecular chain, can strengthen the fracture toughness of adhesive with the cooperation of modified graphene, make the adhesive effect of adhesive better.)

1. A preparation method of plywood for a bakelite box is characterized by comprising the following steps: gluing three thin wood boards by using an adhesive;

the adhesive comprises the following raw materials in parts by weight: 20-30 parts of modified resin, 3-5 parts of modified graphene, 3-5 parts of benzyl dimethylamine, 1-3 parts of sulfated castor oil, 1-3 parts of sodium dodecyl sulfate, 1-3 parts of o-phenylphenol and 10-15 parts of water;

the adhesive is prepared by the following steps:

step S1: mixing modified resin, sulfated castor oil, sodium dodecyl sulfate and water to obtain a mixture;

step S2: and (3) carrying out ultrasonic treatment on the mixture and the modified graphene, adding benzyl dimethylamine, and stirring to obtain the adhesive.

2. The method for preparing plywood for a plywood case according to claim 1, wherein the method comprises the following steps: the modified resin is prepared by the following steps:

step A1: adding p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide into a reaction kettle, introducing nitrogen to replace oxygen, reacting to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting to obtain an intermediate 2, adding the intermediate 2, sulfur and iodine into the reaction kettle, reacting until no hydrogen sulfide gas is generated, obtaining an intermediate 3, adding the intermediate 3, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction to obtain an intermediate 4;

step A2: adding epoxy resin E-51 and the intermediate 4 into a reaction kettle, stirring, adding potassium persulfate, heating for reaction to obtain an intermediate 5, adding 4,4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and N-methylpyrrolidone into the reaction kettle, stirring, adding benzophenone tetracarboxylic dianhydride, and reacting to obtain an intermediate 6;

step A3: adding 2-phenyl-1, 3-propylene glycol, potassium carbonate, dimethyl sulfate and acetone into a reaction kettle, adding potassium hydroxide and tetrahydrofuran into the reaction kettle after reflux reaction, heating and adding propylene alcohol after stirring, carrying out reflux reaction to obtain an intermediate 7, adding the intermediate 7, an intermediate 6, 4-dimethylaminopyridine and tetrahydrofuran into the reaction kettle, adding a hydrochloric acid solution after reaction, carrying out reflux reaction to obtain an intermediate 8, adding the intermediate 8, toluene diisocyanate and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, and carrying out reflux reaction to obtain an intermediate 9;

step A4: and adding the intermediate 5, the intermediate 9 and tetrahydrofuran into a reaction kettle, reacting, adding dibutyl tin dilaurate, and continuing to react to obtain the modified resin.

3. The method for preparing plywood for a plywood case according to claim 2, wherein the method comprises the following steps: the dosage ratio of the p-chlorotoluene, the p-methylaniline, the potassium carbonate, the polyethylene glycol 2000 and the copper oxide in the step A1 is 0.1mol:0.1mol:7.5g:3g:0.8g, the dosage ratio of the intermediate 1, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.01mol:0.01mol:0.03g:40mL, the dosage mass ratio of the intermediate 2, the sulfur and the iodine is 20.5:8:0.12, and the dosage ratio of the intermediate 3, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 6g:11g:100mL:5 mL.

4. The method for preparing plywood for a plywood case according to claim 2, wherein the method comprises the following steps: the amount ratio of the epoxy resin E-51, the intermediate 4 and the potassium persulfate described in the step A2 is 0.02mol:0.01mol:0.03g, and the amount ratio of the 4,4' -diaminodiphenyl ether, the 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, the N-methylpyrrolidone and the benzophenone tetracarboxylic dianhydride is 0.01mol:0.02mol:50mL:0.03 mol.

5. The method for preparing plywood for a plywood case according to claim 2, wherein the method comprises the following steps: the dosage ratio of the 2-phenyl-1, 3-propylene glycol, the potassium carbonate, the dimethyl sulfate, the acetone, the potassium hydroxide, the tetrahydrofuran and the allyl alcohol in the step A3 is 0.01mol:0.01mol:0.02mol:0.08g:30mL:0.01mol, the dosage ratio of the intermediate 7, the intermediate 6, the 4-dimethylaminopyridine, the tetrahydrofuran and the hydrochloric acid solution is 0.01mol:0.1mol:3g:50mL:20mL, and the dosage ratio of the intermediate 8, the toluene diisocyanate and the tetrahydrofuran is 0.01mol:01mol:50 mL.

6. The method for preparing plywood for a plywood case according to claim 2, wherein the method comprises the following steps: the mass ratio of the intermediate 5, the intermediate 9, tetrahydrofuran and dibutyl tin dilaurate in the step A4 is 3:5: 0.15.

Technical Field

The invention relates to the technical field of preparation of bakelite boxes, in particular to a preparation method of plywood for the bakelite boxes.

Background

The plywood is a three-layer or multi-layer plate material formed by rotary cutting wood sections into veneers or slicing battens into veneers and gluing the veneers by using an adhesive, usually odd-layer veneers are used, the fiber directions of adjacent veneers are mutually vertical to glue, the plywood is one of common materials for furniture and is an artificial board, a group of veneers are usually formed by mutually vertical assembly gluing according to the wood grain directions of adjacent layers, usually, a surface board and an inner layer board of the plywood are symmetrically arranged on two sides of a central layer or a board core, and a board blank formed by vertically and horizontally staggered gluing the veneers according to the wood grain directions is pressed under the condition of heating or not heating, wherein the number of layers is usually an odd number, a small number of layers also has an even number, the physical and mechanical properties in the vertical and horizontal directions have small differences, and the common three-ply boards, five ply boards and the like are used. The plywood can improve the utilization rate of wood, is a main way for saving wood, and can also be used as functional materials for airplanes, ships, trains, automobiles, buildings, packing boxes and the like;

the existing plywood adhesive is low in adhesive strength, the plywood is subjected to the action of external force in the using process, the plywood is subjected to glue failure, meanwhile, part of the plywood can be used in a high-temperature environment, and the adhesive is oxidized under the long-time hot oxygen condition, so that the adhesive strength of the plywood is greatly reduced, and the plywood cannot be normally used in a layered mode;

based on the above technical problem, a solution is proposed.

Disclosure of Invention

The invention aims to provide a preparation method of plywood for a bakelite box, which is prepared by gluing three veneers with an adhesive and solves the defects that the existing adhesive has low adhesive strength, is easy to generate mildewing phenomenon and greatly reduces the service life in a hot oxygen environment.

The technical problems to be solved by the invention are as follows:

the purpose of the invention can be realized by the following technical scheme:

a method for preparing plywood for a bakelite box comprises the steps of gluing three thin wood boards by using an adhesive;

the adhesive comprises the following raw materials in parts by weight: 20-30 parts of modified resin, 3-5 parts of modified graphene, 3-5 parts of benzyl dimethylamine, 1-3 parts of sulfated castor oil, 1-3 parts of sodium dodecyl sulfate, 1-3 parts of o-phenylphenol and 10-15 parts of water;

the adhesive is prepared by the following steps:

step S1: adding the modified resin, sulfated castor oil, sodium dodecyl sulfate and water into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 1000-1200r/min to prepare a mixture;

step S2: and carrying out ultrasonic treatment on the mixture and the modified graphene for 30-40min under the condition that the frequency is 8-10kHz, adding benzyldimethylamine, and stirring for 3-5h under the condition that the rotating speed is 1500-2000r/min to prepare the adhesive.

Further, the modified resin is prepared by the following steps:

step A1: adding p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide into a reaction kettle, introducing nitrogen to replace oxygen, reacting for 8-10h at the conditions of the rotation speed of 150-, to prepare an intermediate 4;

the reaction process is as follows:

step A2: adding epoxy resin E-51 and an intermediate 4 into a reaction kettle, stirring and adding potassium persulfate under the conditions that the rotation speed is 120-90 ℃ and the temperature is 80-90 ℃, heating to 170-190 ℃, reacting for 5-8h to obtain an intermediate 5, adding 4,4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and N-methylpyrrolidone into the reaction kettle, stirring for 20-40min under the condition that the rotation speed is 150-200r/min, adding benzophenone tetracarboxylic dianhydride, and reacting for 10-15h under the condition that the temperature is 3-8 ℃ to obtain an intermediate 6;

the reaction process is as follows:

step A3: adding 2-phenyl-1, 3-propanediol, potassium carbonate, dimethyl sulfate and acetone into a reaction kettle, refluxing for 3-5h at 90-100 ℃, adding potassium hydroxide and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, stirring for 1-1.5h at the rotation speed of 150-, preparing an intermediate 8, adding the intermediate 8, toluene diisocyanate and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, and carrying out reflux reaction for 3-5h at the temperature of 80-90 ℃ to prepare an intermediate 9;

the reaction process is as follows:

step A4: adding the intermediate 5, the intermediate 9 and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, reacting for 1-1.5h under the conditions that the rotating speed is 120-115 ℃ and the temperature is 110-115 ℃, adding dibutyltin dilaurate, and continuing to react for 1-1.5h to obtain the modified resin.

Further, the dosage ratio of p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide in the step A1 is 0.1mol:0.1mol:7.5g:3g:0.8g, the dosage ratio of the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride is 0.01mol:0.01mol:0.03g:40mL, the dosage mass ratio of the intermediate 2, sulfur and iodine is 20.5:8:0.12, and the dosage ratio of the intermediate 3, potassium carbonate, deionized water and tetraethylammonium bromide is 6g:11g:100mL:5 mL.

Further, the amount ratio of the epoxy resin E-51, the intermediate 4 and the potassium persulfate described in the step A2 is 0.02mol:0.01mol:0.03g, and the amount ratio of the 4,4' -diaminodiphenyl ether, the 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, the N-methylpyrrolidone and the benzophenone tetracarboxylic dianhydride is 0.01mol:0.02mol:50mL:0.03 mol.

Further, the dosage ratio of the 2-phenyl-1, 3-propanediol, the potassium carbonate, the dimethyl sulfate, the acetone, the potassium hydroxide, the tetrahydrofuran and the allyl alcohol in the step A3 is 0.01mol:0.01mol:0.02mol:0.08g:30mL:0.01mol, the dosage ratio of the intermediate 7, the intermediate 6, the 4-dimethylaminopyridine, the tetrahydrofuran and the hydrochloric acid solution is 0.01mol:0.1mol:3g:50mL:20mL, the mass fraction of the hydrochloric acid solution is 15%, and the dosage ratio of the intermediate 8, the toluene diisocyanate and the tetrahydrofuran is 0.01mol:01mol:50 mL.

Further, the intermediate 5, the intermediate 9, tetrahydrofuran and dibutyl tin dilaurate in the step a4 are used in a mass ratio of 3:5: 0.15.

Further, the modified graphene is prepared by the following steps:

adding graphene oxide and N-methyl pyrrolidone into a reaction kettle, carrying out ultrasonic treatment for 30-40min under the conditions of the frequency of 5-8kHz and the temperature of 0-3 ℃, adding 4,4' -diaminodiphenyl ether, heating to the temperature of 25-30 ℃, stirring for reaction for 20-30min, heating to the temperature of 40-50 ℃, continuing stirring for 20-30min, heating to the temperature of 70-80 ℃, continuing stirring for 20-30min, filtering and drying to obtain the modified graphene.

Furthermore, the dosage ratio of the graphene oxide, the N-methylpyrrolidone and the 4,4' -diaminodiphenyl ether is 0.1g, 100mL and 0.2 g.

The invention has the beneficial effects that:

the invention prepares plywood by gluing three thin wood boards by an adhesive, the adhesive is prepared by blending modified resin, modified graphene, benzyl dimethylamine, sulfated castor oil, sodium dodecyl sulfate and water, the modified resin takes p-chlorotoluene and p-methylaniline as raw materials to react to prepare an intermediate 1, the intermediate 1 is treated by nitrogen-bromosuccinimide to prepare an intermediate 2, the intermediate 2 is reacted with sulfur to prepare an intermediate 3, the intermediate 3 is further treated to prepare an intermediate 4, epoxy resin E-51 and the intermediate 4 are subjected to chain extension reaction to prepare an intermediate 5, 4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and benzophenone tetracarboxylic dianhydride are subjected to polycondensation to prepare an intermediate 6, and 2-phenyl-1, 3-propylene glycol is subjected to hydroxyl protection by dimethyl sulfate and then reacts with allyl alcohol to prepare an intermediate 7, an intermediate 6 and the intermediate 7 are reacted and then protected to prepare an intermediate 8, the intermediate 8 and toluene diisocyanate are reacted to enable one isocyanate in the toluene diisocyanate to react based on the alcoholic hydroxyl group on the intermediate 8 to prepare an intermediate 9, the intermediate 5 and the intermediate 9 are reacted to enable the isocyanate group on the intermediate 9 and the alcoholic hydroxyl group on the intermediate 5 to react to prepare modified resin, the modified graphene takes graphene oxide as a raw material and is functionalized by 4,4' -diaminodiphenyl ether to prepare the modified graphene, the adhesive can well bond veneer boards, the molecular chain of the modified resin contains a large number of phenothiazine structures, and a six-membered ring is sandwiched between two benzene rings, make the lone pair electron of sulfur atom delocalize on three ring, make the easy fracture of nitrogen hydrogen bond of phenothiazine, sulfur atom in the molecule can be by oxidation formation sulfoxide, sulfone class compound, make the adhesive have fine thermal-resistant oxygen effect, plywood split can not appear in the plywood use, the bakelite case normal use has been guaranteed, modified resin molecule side chain contains the polyimide molecular chain, can strengthen the fracture toughness of adhesive with the cooperation of modified graphene, make the adhesive effect of adhesive better, the addition of o-phenylphenol makes the difficult phenomenon of going mildy that appears in plywood veneer department.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A method for preparing plywood for a bakelite box comprises the steps of gluing three thin wood boards by using an adhesive;

the adhesive comprises the following raw materials in parts by weight: 20 parts of modified resin, 3 parts of modified graphene, 3 parts of benzyl dimethylamine, 1 part of sulfated castor oil, 1 part of sodium dodecyl sulfate, 1 part of o-phenylphenol and 10 parts of water;

the adhesive is prepared by the following steps:

step S1: adding the modified resin, sulfated castor oil, sodium dodecyl sulfate and water into a stirring kettle, and stirring for 1h at the rotating speed of 1000r/min to obtain a mixture;

step S2: and carrying out ultrasonic treatment on the mixture and the modified graphene for 30min under the condition that the frequency is 8kHz, adding benzyldimethylamine, and stirring for 3h under the condition that the rotating speed is 1500r/min to prepare the adhesive.

The modified resin is prepared by the following steps:

step A1: adding p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide into a reaction kettle, introducing nitrogen to replace oxygen, reacting for 8 hours at the rotation speed of 150r/min and the temperature of 190 ℃ to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 2, adding the intermediate 2, sulfur and iodine into the reaction kettle, reacting at the rotation speed of 120r/min and the temperature of 180 ℃ until no hydrogen sulfide gas is generated to obtain an intermediate 3, adding the intermediate 3, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 2 hours to obtain an intermediate 4;

step A2: adding epoxy resin E-51 and an intermediate 4 into a reaction kettle, stirring and adding potassium persulfate under the conditions of the rotation speed of 120r/min and the temperature of 80 ℃, heating to the temperature of 170 ℃, reacting for 5 hours to obtain an intermediate 5, adding 4,4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and N-methylpyrrolidone into the reaction kettle, stirring for 20 minutes under the condition of the rotation speed of 150r/min, adding benzophenone tetracarboxylic dianhydride, and reacting for 10 hours under the condition of the temperature of 3 ℃ to obtain an intermediate 6;

step A3: adding 2-phenyl-1, 3-propylene glycol, potassium carbonate, dimethyl sulfate and acetone into a reaction kettle, refluxing for 3h at 90 ℃, adding potassium hydroxide and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, stirring for 1h at 50 ℃ at a rotation speed of 150r/min, heating to 110 ℃, adding propylene alcohol, refluxing for 6h to obtain an intermediate 7, adding the intermediate 7, the intermediate 6, 4-dimethylaminopyridine and tetrahydrofuran into the reaction kettle, reacting for 8h at 70 ℃, adding a hydrochloric acid solution, refluxing for 5h at 115 ℃ to obtain an intermediate 9, adding the intermediate 9, toluene diisocyanate and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, and reacting at 80 ℃, carrying out reflux reaction for 3h to obtain an intermediate 10;

step A4: and adding the intermediate 5, the intermediate 10 and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, reacting for 1h at the rotation speed of 120r/min and the temperature of 110 ℃, adding dibutyltin dilaurate, and continuing to react for 1h to obtain the modified resin.

The modified graphene is prepared by the following steps:

adding graphene oxide and N-methyl pyrrolidone into a reaction kettle, carrying out ultrasonic treatment for 30min under the conditions that the frequency is 5kHz and the temperature is 0 ℃, adding 4,4' -diaminodiphenyl ether, heating to 25 ℃, stirring for reaction for 20min, heating to 40 ℃, continuing to stir for 20min, heating to 70 ℃, continuing to stir for 20min, filtering and drying to obtain the modified graphene.

Example 2

A method for preparing plywood for a bakelite box comprises the steps of gluing three thin wood boards by using an adhesive;

the adhesive comprises the following raw materials in parts by weight: 25 parts of modified resin, 4 parts of modified graphene, 4 parts of benzyl dimethylamine, 2 parts of sulfated castor oil, 2 parts of sodium dodecyl sulfate, 2 parts of o-phenylphenol and 13 parts of water;

the adhesive is prepared by the following steps:

step S1: adding the modified resin, sulfated castor oil, sodium dodecyl sulfate and water into a stirring kettle, and stirring for 1.3h under the condition that the rotating speed is 1200r/min to prepare a mixture;

step S2: and carrying out ultrasonic treatment on the mixture and the modified graphene for 35min under the condition that the frequency is 9kHz, adding benzyl dimethylamine, and stirring for 4h under the condition that the rotating speed is 1800r/min to prepare the adhesive.

The modified resin is prepared by the following steps:

step A1: adding p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide into a reaction kettle, introducing nitrogen to replace oxygen, reacting for 9 hours at the rotation speed of 180r/min and the temperature of 195 ℃ to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 9 hours at the temperature of 85 ℃ to obtain an intermediate 2, adding the intermediate 2, sulfur and iodine into the reaction kettle, reacting at the rotation speed of 150r/min and the temperature of 190 ℃ until no hydrogen sulfide gas is generated to obtain an intermediate 3, adding the intermediate 3, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 2.5 hours to obtain an intermediate 4;

step A2: adding epoxy resin E-51 and an intermediate 4 into a reaction kettle, stirring and adding potassium persulfate under the conditions of the rotation speed of 150r/min and the temperature of 85 ℃, heating to the temperature of 180 ℃, reacting for 6 hours to obtain an intermediate 5, adding 4,4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and N-methylpyrrolidone into the reaction kettle, stirring for 30 minutes under the condition of the rotation speed of 180r/min, adding benzophenone tetracarboxylic dianhydride, and reacting for 13 hours under the condition of the temperature of 5 ℃ to obtain an intermediate 6;

step A3: adding 2-phenyl-1, 3-propylene glycol, potassium carbonate, dimethyl sulfate and acetone into a reaction kettle, refluxing for 4h at the temperature of 95 ℃, adding potassium hydroxide and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, stirring for 1.3h at the rotation speed of 180r/min and the temperature of 55 ℃, heating to the temperature of 115 ℃, adding propylene alcohol, refluxing for 7h to prepare an intermediate 7, adding the intermediate 7, the intermediate 6, 4-dimethylaminopyridine and tetrahydrofuran into the reaction kettle, reacting for 9h at the temperature of 75 ℃, adding a hydrochloric acid solution, refluxing for 6h at the temperature of 118 ℃ to prepare an intermediate 9, adding the intermediate 9, toluene diisocyanate and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, reacting at the temperature of 85 ℃, carrying out reflux reaction for 4h to obtain an intermediate 10;

step A4: and adding the intermediate 5, the intermediate 10 and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, reacting for 1.3h at the rotation speed of 150r/min and the temperature of 113 ℃, adding dibutyltin dilaurate, and continuing to react for 1.3h to obtain the modified resin.

The modified graphene is prepared by the following steps:

adding graphene oxide and N-methyl pyrrolidone into a reaction kettle, carrying out ultrasonic treatment for 35min under the conditions that the frequency is 7kHz and the temperature is 2 ℃, adding 4,4' -diaminodiphenyl ether, heating to 28 ℃, stirring for reaction for 25min, heating to 45 ℃, continuing to stir for 25min, heating to 75 ℃, continuing to stir for 25min, filtering and drying to obtain the modified graphene.

Example 3

A method for preparing plywood for a bakelite box comprises the steps of gluing three thin wood boards by using an adhesive;

the adhesive comprises the following raw materials in parts by weight: 30 parts of modified resin, 5 parts of modified graphene, 5 parts of benzyl dimethylamine, 3 parts of sulfated castor oil, 3 parts of sodium dodecyl sulfate, 3 parts of o-phenylphenol and 15 parts of water;

the adhesive is prepared by the following steps:

step S1: adding the modified resin, sulfated castor oil, sodium dodecyl sulfate and water into a stirring kettle, and stirring for 1.5h under the condition that the rotating speed is 1200r/min to prepare a mixture;

step S2: and carrying out ultrasonic treatment on the mixture and the modified graphene for 40min under the condition of 10kHz frequency, adding benzyldimethylamine, and stirring for 5h under the condition of 2000r/min of rotation speed to prepare the adhesive.

The modified resin is prepared by the following steps:

step A1: adding p-chlorotoluene, p-methylaniline, potassium carbonate, polyethylene glycol 2000 and copper oxide into a reaction kettle, introducing nitrogen to replace oxygen, reacting for 10 hours at the rotation speed of 200r/min and the temperature of 200 ℃ to obtain an intermediate 1, adding the intermediate 1, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 2, adding the intermediate 2, sulfur and iodine into the reaction kettle, reacting at the rotation speed of 150r/min and the temperature of 200 ℃ until no hydrogen sulfide gas is generated to obtain an intermediate 3, adding the intermediate 3, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, and performing reflux reaction for 3 hours to obtain an intermediate 4;

step A2: adding epoxy resin E-51 and an intermediate 4 into a reaction kettle, stirring and adding potassium persulfate under the conditions of the rotation speed of 150r/min and the temperature of 90 ℃, heating to the temperature of 190 ℃, reacting for 8 hours to obtain an intermediate 5, adding 4,4' -diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane and N-methylpyrrolidone into the reaction kettle, stirring for 40 minutes under the condition of the rotation speed of 200r/min, adding benzophenone tetracarboxylic dianhydride, and reacting for 15 hours under the condition of the temperature of 8 ℃ to obtain an intermediate 6;

step A3: adding 2-phenyl-1, 3-propylene glycol, potassium carbonate, dimethyl sulfate and acetone into a reaction kettle, refluxing for 5h at 100 ℃, adding potassium hydroxide and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, stirring for 1.5h at a rotation speed of 200r/min and a temperature of 60 ℃, heating to 120 ℃, adding propylene alcohol, refluxing for 8h to obtain an intermediate 7, adding the intermediate 7, the intermediate 6, 4-dimethylaminopyridine and tetrahydrofuran into the reaction kettle, reacting for 10h at a temperature of 80 ℃, adding a hydrochloric acid solution, refluxing for 8h at a temperature of 120 ℃ to obtain an intermediate 9, adding the intermediate 9, toluene diisocyanate and tetrahydrofuran into the reaction kettle, introducing nitrogen for protection, reacting at a temperature of 90 ℃, carrying out reflux reaction for 5 hours to obtain an intermediate 10;

step A4: and adding the intermediate 5, the intermediate 10 and tetrahydrofuran into a reaction kettle, introducing nitrogen for protection, reacting for 1.5h at the rotation speed of 150r/min and the temperature of 115 ℃, adding dibutyltin dilaurate, and continuing to react for 1.5h to obtain the modified resin.

The modified graphene is prepared by the following steps:

adding graphene oxide and N-methyl pyrrolidone into a reaction kettle, carrying out ultrasonic treatment for 40min under the conditions that the frequency is 8kHz and the temperature is 3 ℃, adding 4,4' -diaminodiphenyl ether, heating to 30 ℃, stirring for reaction for 30min, heating to 50 ℃, continuing stirring for 30min, heating to 80 ℃, continuing stirring for 30min, filtering and drying to obtain the modified graphene.

Comparative example 1

This comparative example compared with example 1, the modified resin was replaced with epoxy resin E-51, and the procedure was the same.

Comparative example 2

Compared with example 1, the comparative example does not add modified graphene, and the rest steps are the same.

Comparative example 3

The comparative example is the adhesive disclosed in Chinese patent CN 109401670A.

The adhesives prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for adhesive strength in accordance with the standard of GB/T14074-2006,

the mold-proofing effect of the adhesive was examined in accordance with the standards referred to in JIS Z2801-2000.

The adhesive prepared in examples 1-3 and comparative examples 1-3 was then glued to a thin wood board, and the board was placed in an environment of 200 ℃ for 24, 48, 72, and 96 hours, and the adhesive strength was measured, with the results shown in the following table;

the table shows that the adhesive prepared in the examples 1-3 has good adhesive strength and good mildew-proof effect, and the adhesive still maintains high adhesive strength after thermal oxidation aging, which indicates that the plywood prepared by the invention has long service life.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.