1. The green environment-friendly adhesive is characterized in that: the feed comprises the following raw materials in parts by weight: 20-30 parts of bisphenol A epoxy resin, 5-10 parts of soybean dregs, 10-15 parts of hydrophobic starch, 1-3 parts of sodium dodecyl benzene sulfonate, 5-10 parts of modified organic silicon resin and 2-5 parts of curing agent;

the adhesive is prepared by the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 15-20min under the condition that the rotation speed is 300-500r/min, adding a sodium hydroxide solution, continuously stirring for 1-1.5h, adding the epoxy resin saturated solution, and continuously stirring for 20-30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20-30min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the curing agent into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 8-10MHz to prepare the adhesive.

2. The green environmental-friendly adhesive according to claim 1, wherein: the mass ratio of the soybean dregs to the deionized water in the step S1 is 1-1.2:3, the mass fraction of the sodium hydroxide solution is 20-25% of the volume of the deionized water, the mass fraction of the sodium hydroxide solution is 10-15%, the mass ratio of the hydrophobic starch in the step S2 to the deionized water is 1-1.5:5, and the curing agent in the step S3 is one of diaminodiphenylmethane, m-xylylenediamine and m-phenylenediamine.

3. The green environmental-friendly adhesive according to claim 1, wherein: the hydrophobic starch is prepared by the following steps:

step A1: adding starch and hydrochloric acid solution into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 150-200r/min, heating to 40-50 ℃, continuing stirring for 8-10h, adjusting the pH value of reaction liquid to 7, standing for 3-5min, washing for 2-3 times by using deionized water, filtering to remove filtrate, and drying a filter cake to obtain porous starch;

step A2: adding the porous starch prepared in the step A1, sodium hydroxide and deionized water into a reaction kettle, stirring for 20-30min under the condition that the rotating speed is 200-300r/min, adding a potassium permanganate aqueous solution, continuously stirring for 30-50min, filtering to remove filtrate, and drying a filter cake to obtain oxidized starch;

step A3: adding phenyl chlorosilane into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 150-90 ℃ for 1-1.5h to react for 1-1.5h to obtain an intermediate 1, adding the intermediate 1, tin powder and a hydrochloric acid solution into the reaction kettle, reacting for 2-3h under the conditions that the rotating speed is 150-200r/min and the temperature is 90-95 ℃, cooling to room temperature, and adjusting the pH value of a reaction solution to 9-10 to obtain an intermediate 2;

step A4: adding the intermediate 2 prepared in the step A3 into a reaction kettle, introducing nitrogen for protection, adding ethanol under the conditions of the rotation speed of 120-150r/min and the temperature of 65-70 ℃, performing reflux reaction for 2-3h to prepare an intermediate 3, adding the intermediate 3, deionized water and ethanol into the reaction kettle, introducing nitrogen for protection, stirring for 5-10min under the conditions of the rotation speed of 300-500r/min and the temperature of 70-80 ℃, adding the oxidized starch prepared in the step A2 and 1-hydroxybenzotriazole, performing reaction for 8-10h, filtering to remove filtrate, dispersing the filter cake in toluene, adding dodecanoic acid, performing reaction for 2-3h under the conditions of the rotation speed of 200-300r/min, filtering to remove the filtrate, drying the filter cake, hydrophobic starch is prepared.

4. The green environmental adhesive according to claim 3, wherein: the using amount ratio of the starch to the hydrochloric acid solution in the step A1 is 1g:2mL, the mass fraction of the hydrochloric acid solution is 10-15%, the using amount ratio of the porous starch, the sodium hydroxide and the potassium permanganate solution in the step A2 is 10g:1g:10mL, the mass fraction of the potassium permanganate solution is 1%, the using amount ratio of the phenylchlorosilane to the mixed acid in the step A3 is 1:2, the mixed acid is formed by mixing 68-70% by mass of nitric acid and 70-75% by mass of sulfuric acid in a volume ratio of 1.2:1, the using amount ratio of the intermediate 1, tin powder and the hydrochloric acid solution is 5mL:8g:10mL, the mass fraction of the hydrochloric acid solution is 10-15%, the molar ratio of the intermediate 2 to ethanol in the step A4 is 1:3, and the using amount ratio of the intermediate 3, the porous starch and the 1-hydroxybenzotriazole is 1:2:0.5, the molar ratio of the used dodecanoic acid to the intermediate 3 was 1: 1.

5. The green environmental-friendly adhesive according to claim 1, wherein: the modified organic silicon resin is prepared by the following steps:

step B1: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-;

step B2: dissolving 2, 6-di-tert-butylphenol in N, N-dimethylformamide, adding p-methoxybenzyl ether, stirring uniformly at the rotation speed of 100-120r/min, adding sodium hydride, reacting for 2-3h at the temperature of 25-30 ℃ to obtain an intermediate 4, adding the intermediate 4, lithium diisopropylamide and diphenol monomethyl ether into a reaction kettle, introducing nitrogen for protection, adding N, N-dimethylformamide, refluxing for 1-1.5h at the temperature of 160-180 ℃, adding acrylic acid, and reacting for 2-3h at the temperature of 110-120 ℃ to obtain an intermediate 5;

step B3: and (3) adding the organic silicon resin prepared in the step B1 into a reaction kettle, stirring and adding the intermediate 5 and 1-hydroxybenzotriazole prepared in the step B2 under the condition that the rotation speed is 150-200r/min, reacting for 8-10h, adding 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and a dichloromethane saturated aqueous solution, reacting for 3-5h under the condition that the temperature is 25-30 ℃, and distilling to remove the dichloromethane saturated aqueous solution under the condition that the temperature is 110-120 ℃ to prepare the modified organic silicon resin.

6. The green environmental-friendly adhesive according to claim 5, wherein: the mass ratio of the gamma-aminopropyltriethoxysilane to the dimethyl dimethoxysilane in the step B1 is 1:1, the mass of the hydrochloric acid aqueous solution is 1-2 times of the mass of the gamma-aminopropyltriethoxysilane and the dimethyl dimethoxysilane, the mass fraction of the hydrochloric acid aqueous solution is 10-15%, the mass molar ratio of the p-methoxybenzyl ether to the 2, 6-di-tert-butylphenol in the step B2 is 1:1, the mass of sodium hydride is 10-20% of the mass of the 2, 6-di-tert-butylphenol, the mass of lithium diisopropylamide is 30-40% of the mass of the intermediate 4, the mass of p-diphenol monomethyl ether is 0.1-0.3% of the mass of the intermediate 4, the mass molar ratio of the acrylic acid to the intermediate 4 is 1:1, and the mass ratio of the organic silicon resin to the intermediate 5 in the step B3 is 5:1-1.5, the dosage of the 1-hydroxybenzotriazole is 30-40% of the intermediate 5 by mass, and the dosage of the dichloro-5, 6-dicyan-p-benzoquinone is 5-10% of the total mass of reactants.

7. The preparation method of the green environment-friendly adhesive according to claim 1, characterized in that: the method specifically comprises the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 15-20min under the condition that the rotation speed is 300-500r/min, adding a sodium hydroxide solution, continuously stirring for 1-1.5h, adding the epoxy resin saturated solution, and continuously stirring for 20-30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20-30min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the curing agent into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 8-10MHz to prepare the adhesive.

Background

The adhesive is also called adhesive, abbreviated as glue, and is a non-metal medium material which enables an object to be tightly connected with another object into a whole, the adhesive only occupies a very thin layer of volume between two adhered surfaces, but after the adhesive is used for cementing construction, the obtained cementing piece can meet various requirements of actual needs in the aspects of mechanical property and physical and chemical property, and can effectively bond the materials together.

The surface of the existing adhesive is soaked by water in the use process, water rapidly enters the inside of the adhesive to enable the adhesive to generate bubbles, so that the adhesion effect cannot be achieved, and the adhesive is oxidized after being used for a long time, falls off and loses effect.

Disclosure of Invention

The invention aims to provide a green environment-friendly adhesive and a preparation method thereof.

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

the surface of the existing adhesive is soaked by water in the use process, water rapidly enters the inside of the adhesive to enable the adhesive to generate bubbles, so that the adhesion effect cannot be achieved, and the adhesive is oxidized after being used for a long time, falls off and loses effect.

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

a green environment-friendly adhesive comprises the following raw materials in parts by weight: 20-30 parts of bisphenol A epoxy resin, 5-10 parts of soybean dregs, 10-15 parts of hydrophobic starch, 1-3 parts of sodium dodecyl benzene sulfonate, 5-10 parts of modified organic silicon resin and 2-5 parts of curing agent;

the adhesive is prepared by the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 15-20min under the condition that the rotation speed is 300-500r/min, adding a sodium hydroxide solution, continuously stirring for 1-1.5h, adding the epoxy resin saturated solution, and continuously stirring for 20-30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20-30min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the curing agent into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 8-10MHz to prepare the adhesive.

Further, the mass ratio of the soybean dregs to the deionized water in the step S1 is 1-1.2:3, the mass fraction of the sodium hydroxide solution is 20-25% of the volume of the deionized water, the mass fraction of the sodium hydroxide solution is 10-15%, the mass ratio of the hydrophobic starch in the step S2 to the deionized water is 1-1.5:5, and the curing agent in the step S3 is one of diaminodiphenylmethane, m-xylylenediamine and m-phenylenediamine.

Further, the hydrophobic starch is prepared by the following steps:

step A1: adding starch and hydrochloric acid solution into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 150-200r/min, heating to 40-50 ℃, continuing stirring for 8-10h, adjusting the pH value of reaction liquid to 7, standing for 3-5min, washing for 2-3 times by using deionized water, filtering to remove filtrate, and drying a filter cake to obtain porous starch;

step A2: adding the porous starch prepared in the step A1, sodium hydroxide and deionized water into a reaction kettle, stirring for 20-30min under the condition that the rotating speed is 200-300r/min, adding a potassium permanganate aqueous solution, continuously stirring for 30-50min, filtering to remove filtrate, and drying a filter cake to obtain oxidized starch;

step A3: adding phenyl chlorosilane into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 150-90 ℃ for 1-1.5h to react for 1-1.5h to obtain an intermediate 1, adding the intermediate 1, tin powder and a hydrochloric acid solution into the reaction kettle, reacting for 2-3h under the conditions that the rotating speed is 150-200r/min and the temperature is 90-95 ℃, cooling to room temperature, and adjusting the pH value of a reaction solution to 9-10 to obtain an intermediate 2;

the reaction process is as follows:

step A4: adding the intermediate 2 prepared in the step A3 into a reaction kettle, introducing nitrogen for protection, adding ethanol under the conditions of the rotation speed of 120-150r/min and the temperature of 65-70 ℃, performing reflux reaction for 2-3h to prepare an intermediate 3, adding the intermediate 3, deionized water and ethanol into the reaction kettle, introducing nitrogen for protection, stirring for 5-10min under the conditions of the rotation speed of 300-500r/min and the temperature of 70-80 ℃, adding the oxidized starch prepared in the step A2 and 1-hydroxybenzotriazole, performing reaction for 8-10h, filtering to remove filtrate, dispersing the filter cake in toluene, adding dodecanoic acid, performing reaction for 2-3h under the conditions of the rotation speed of 200-300r/min, filtering to remove the filtrate, drying the filter cake, hydrophobic starch is prepared.

The reaction process is as follows:

further, the dosage ratio of the starch and the hydrochloric acid solution in the step A1 is 1g:2mL, the mass fraction of the hydrochloric acid solution is 10-15%, the dosage ratio of the porous starch, the sodium hydroxide and the potassium permanganate solution in the step A2 is 10g:1g:10mL, the mass fraction of the potassium permanganate solution is 1%, the dosage volume ratio of the phenylchlorosilane to the mixed acid in the step A3 is 1:2, the mixed acid is prepared by mixing nitric acid with the mass fraction of 68-70% and sulfuric acid with the mass fraction of 70-75% in a volume ratio of 1.2:1, the dosage ratio of the intermediate 1, tin powder and the hydrochloric acid solution is 5mL:8g:10mL, the mass fraction of the hydrochloric acid solution is 10-15%, the molar ratio of the intermediate 2 to ethanol in the step A4 is 1:3, the mass ratio of the intermediate 3, the porous starch and 1-hydroxybenzotriazole is 1:2:0.5, the molar ratio of the used dodecanoic acid to the intermediate 3 was 1: 1.

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

step B1: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-;

step B2: dissolving 2, 6-di-tert-butylphenol in N, N-dimethylformamide, adding p-methoxybenzyl ether, stirring uniformly at the rotation speed of 100-120r/min, adding sodium hydride, reacting for 2-3h at the temperature of 25-30 ℃ to obtain an intermediate 4, adding the intermediate 4, lithium diisopropylamide and diphenol monomethyl ether into a reaction kettle, introducing nitrogen for protection, adding N, N-dimethylformamide, refluxing for 1-1.5h at the temperature of 160-180 ℃, adding acrylic acid, and reacting for 2-3h at the temperature of 110-120 ℃ to obtain an intermediate 5;

the reaction process is as follows:

step B3: and (3) adding the organic silicon resin prepared in the step B1 into a reaction kettle, stirring and adding the intermediate 5 and 1-hydroxybenzotriazole prepared in the step B2 under the condition that the rotation speed is 150-200r/min, reacting for 8-10h, adding 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and a dichloromethane saturated aqueous solution, reacting for 3-5h under the condition that the temperature is 25-30 ℃, and distilling to remove the dichloromethane saturated aqueous solution under the condition that the temperature is 110-120 ℃ to prepare the modified organic silicon resin.

Further, the mass ratio of the gamma-aminopropyltriethoxysilane to the dimethyldimethoxysilane in the step B1 is 1:1, the mass of the hydrochloric acid aqueous solution is 1-2 times of the mass of the gamma-aminopropyltriethoxysilane and the dimethyldimethoxysilane, the mass fraction of the hydrochloric acid aqueous solution is 10-15%, the molar ratio of the p-methoxybenzyl ether to the 2, 6-di-tert-butylphenol in the step B2 is 1:1, the mass of sodium hydride is 10-20% of the mass of the 2, 6-di-tert-butylphenol, the mass of lithium diisopropylamide is 30-40% of the mass of the intermediate 4, the molar ratio of the p-diphenol monomethyl ether to the intermediate 4 is 0.1-0.3% of the mass of the intermediate 4 is 1:1, and the mass ratio of the organosilicon resin to the intermediate 5 in the step B3 is 5:1-1.5, the dosage of the 1-hydroxybenzotriazole is 30-40% of the intermediate 5 by mass, and the dosage of the dichloro-5, 6-dicyan-p-benzoquinone is 5-10% of the total mass of reactants.

A preparation method of a green environment-friendly adhesive specifically comprises the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 15-20min under the condition that the rotation speed is 300-500r/min, adding a sodium hydroxide solution, continuously stirring for 1-1.5h, adding the epoxy resin saturated solution, and continuously stirring for 20-30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20-30min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the curing agent into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1-1.5h under the condition that the frequency is 8-10MHz to prepare the adhesive.

The invention has the beneficial effects that: the invention prepares a hydrophobic starch in the process of preparing an adhesive, the hydrophobic starch takes starch as a raw material, the starch is treated by hydrochloric acid to prepare porous starch, the porous starch is oxidized by potassium permanganate to convert hydroxyl on starch molecules into carboxyl, the prepared oxidized starch is obtained by reacting phenylchlorosilane with mixed acid to connect nitro on a benzene ring of the phenylchlorosilane to prepare an intermediate 1, the intermediate 1 is further reacted to convert the nitro into amino to prepare an intermediate 2, the intermediate 2 is reacted with ethanol to generate siloxane to prepare an intermediate 3, the amino on the intermediate 3 is condensed with the carboxyl of the oxidized starch under the action of 1-hydroxybenzotriazole to fix the molecules of the intermediate 3 on the oxidized starch, and the siloxane is hydrolyzed to generate silanol, hydroxyl groups between adjacent silanols are condensed to form a silanol film on the surface of oxidized starch, dodecanoic acid is added, carboxyl on the dodecanoic acid and the rest of alcoholic hydroxyl groups are subjected to esterification reaction, so that a large number of long-chain alkyl groups are connected to the surface of the oxidized starch, the long-chain alkyl groups have good hydrophobicity, the hydrophobic effect of the starch is further improved, the water resistance of the adhesive is further improved, a modified organic silicon resin is prepared, the modified organic silicon resin takes gamma-aminopropyl triethoxysilane and dimethyl dimethoxysilane as raw materials to prepare an organic silicon resin, the side chain of the organic silicon resin contains amino, 2, 6-di-tert-butyl phenol is protected by p-methoxybenzyl ether and then reacts with acrylic acid to prepare an intermediate 5, and the intermediate 5 and the organic silicon resin are subjected to the action of 1-hydroxybenzotriazole, and (3) carrying out reaction to condense carboxyl of the intermediate 5 with amino of the organic silicon resin, and then deprotecting phenolic hydroxyl to prepare modified organic silicon resin, wherein the two sides of the phenolic hydroxyl on the modified organic silicon resin are connected with tert-butyl groups, so that the phenolic hydroxyl is subjected to steric hindrance, hydrogen atoms are easy to fall off from molecules and are combined with peroxide free radicals, alkyl oxygen free radicals and hydroxyl free radicals to lose activity, the adhesive is prevented from aging, and the service life of the adhesive is prolonged.

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 green environment-friendly adhesive comprises the following raw materials in parts by weight: 20 parts of bisphenol A epoxy resin, 10 parts of hydrophobic starch, 1 part of sodium dodecyl benzene sulfonate, 8 parts of deionized water, 5 parts of modified organic silicon resin and 2 parts of diaminodiphenylmethane;

the adhesive is prepared by the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 15min under the condition that the rotating speed is 300r/min, adding a sodium hydroxide solution, continuously stirring for 1h, adding the epoxy resin saturated solution, and continuously stirring for 20min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 10min under the condition that the rotating speed is 500r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the diaminodiphenylmethane into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1h under the condition that the frequency is 8MHz to prepare the adhesive.

The hydrophobic starch is prepared by the following steps:

step A1: adding starch and hydrochloric acid solution into a reaction kettle, stirring for 5min at the rotation speed of 150r/min, heating to 40 ℃, continuing stirring for 8h, adjusting the pH value of the reaction solution to 7, standing for 3min, washing for 2 times by deionized water, filtering to remove filtrate, and drying a filter cake to obtain porous starch;

step A2: adding the porous starch prepared in the step A1, sodium hydroxide and deionized water into a reaction kettle, stirring for 20min at the rotation speed of 200r/min, adding a potassium permanganate aqueous solution, continuously stirring for 30min, filtering to remove filtrate, and drying a filter cake to prepare oxidized starch;

step A3: adding phenyl chlorosilane into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 120r/min and the temperature is 50 ℃, reacting for 1h to obtain an intermediate 1, adding the intermediate 1, tin powder and a hydrochloric acid solution into the reaction kettle, reacting for 2h under the conditions that the rotating speed is 150r/min and the temperature is 90 ℃, cooling to room temperature, and adjusting the pH value of a reaction solution to be 9 to obtain an intermediate 2;

step A4: adding the intermediate 2 prepared in the step A3 into a reaction kettle, introducing nitrogen for protection, adding ethanol at the rotation speed of 120r/min and the temperature of 65 ℃, performing reflux reaction for 2 hours to prepare an intermediate 3, adding the intermediate 3 and deionized water into the reaction kettle, introducing nitrogen for protection, stirring for 5 minutes at the rotation speed of 300r/min and the temperature of 70 ℃, adding the oxidized starch prepared in the step A2 and 1-hydroxybenzotriazole, reacting for 8 hours, filtering to remove filtrate, dispersing a filter cake into toluene, adding dodecanoic acid, reacting for 2 hours at the rotation speed of 200r/min, filtering to remove the filtrate, and drying the filter cake to prepare the hydrophobic starch.

The modified organic silicon resin is prepared by the following steps:

step B1: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10min under the conditions that the rotation speed is 150r/min and the temperature is 60 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5h, after dropwise adding, heating to the temperature of 75 ℃, continuously stirring for 3h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 140 ℃ to remove distillate to prepare the organic silicon resin;

step B2: dissolving 2, 6-di-tert-butylphenol in N, N-dimethylformamide, adding p-methoxybenzyl ether, stirring uniformly at the rotation speed of 100r/min, adding sodium hydride, reacting for 2 hours at the temperature of 25 ℃ to obtain an intermediate 4, adding the intermediate 4, lithium diisopropylamide and p-diphenol monomethyl ether into a reaction kettle, introducing nitrogen for protection, adding N, N-dimethylformamide, refluxing for 1 hour at the temperature of 160 ℃, adding acrylic acid, and reacting for 2 hours at the temperature of 110 ℃ to obtain an intermediate 5;

step B3: and B1, adding the organic silicon resin prepared in the step B1 into a reaction kettle, stirring and adding the intermediate 5 and 1-hydroxybenzotriazole prepared in the step B2 under the condition that the rotating speed is 150r/min, reacting for 8 hours, adding 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and a dichloromethane saturated aqueous solution, reacting for 3 hours at the temperature of 25 ℃, and distilling to remove the dichloromethane saturated aqueous solution under the temperature of 110 ℃ to prepare the modified organic silicon resin.

Example 2

A green environment-friendly adhesive comprises the following raw materials in parts by weight: 25 parts of bisphenol A type epoxy resin, 13 parts of hydrophobic starch, 2 parts of sodium dodecyl benzene sulfonate, 9 parts of deionized water, 8 parts of modified organic silicon resin and 3 parts of m-xylylenediamine;

the adhesive is prepared by the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 20min under the condition that the rotating speed is 300r/min, adding a sodium hydroxide solution, continuously stirring for 1h, adding the epoxy resin saturated solution, and continuously stirring for 30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 15min under the condition that the rotating speed is 500r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 20min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and m-xylylenediamine into the second glue solution prepared in the step S2, and carrying out ultrasonic treatment for 1h under the condition that the frequency is 10MHz to prepare the adhesive.

The hydrophobic starch is prepared by the following steps:

step A1: adding starch and hydrochloric acid solution into a reaction kettle, stirring for 5min at the rotation speed of 200r/min, heating to 50 ℃, continuing stirring for 8h, adjusting the pH value of the reaction solution to 7, standing for 5min, washing for 2 times by using deionized water, filtering to remove filtrate, and drying a filter cake to obtain porous starch;

step A2: adding the porous starch prepared in the step A1, sodium hydroxide and deionized water into a reaction kettle, stirring for 20min at the rotation speed of 300r/min, adding a potassium permanganate aqueous solution, continuously stirring for 50min, filtering to remove filtrate, and drying a filter cake to prepare oxidized starch;

step A3: adding phenyl chlorosilane into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 120r/min and the temperature is 60 ℃, reacting for 1h to obtain an intermediate 1, adding the intermediate 1, tin powder and a hydrochloric acid solution into the reaction kettle, reacting for 3h under the conditions that the rotating speed is 200r/min and the temperature is 90 ℃, cooling to room temperature, and adjusting the pH value of a reaction solution to be 9 to obtain an intermediate 2;

step A4: adding the intermediate 2 prepared in the step A3 into a reaction kettle, introducing nitrogen for protection, adding ethanol at the rotation speed of 150r/min and the temperature of 65 ℃, performing reflux reaction for 3 hours to prepare an intermediate 3, adding the intermediate 3 and deionized water into the reaction kettle, introducing nitrogen for protection, stirring for 5 minutes at the rotation speed of 300r/min and the temperature of 80 ℃, adding the oxidized starch prepared in the step A2 and 1-hydroxybenzotriazole, reacting for 10 hours, filtering to remove filtrate, dispersing a filter cake into toluene, adding dodecanoic acid, reacting for 2-3 hours at the rotation speed of 200r/min, filtering to remove filtrate, and drying the filter cake to prepare the hydrophobic starch.

The modified organic silicon resin is prepared by the following steps:

step B1: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 15min under the conditions that the rotation speed is 200r/min and the temperature is 60 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5h, after dropwise adding, heating to 80 ℃, continuously stirring for 3h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 150 ℃ to remove distillate to prepare the organic silicon resin;

step B2: dissolving 2, 6-di-tert-butylphenol in N, N-dimethylformamide, adding p-methoxybenzyl ether, stirring uniformly at the rotation speed of 100r/min, adding sodium hydride, reacting for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4, adding the intermediate 4, lithium diisopropylamide and p-diphenol monomethyl ether into a reaction kettle, introducing nitrogen for protection, adding N, N-dimethylformamide, refluxing for 1 hour at the temperature of 180 ℃, adding acrylic acid, and reacting for 2 hours at the temperature of 120 ℃ to obtain an intermediate 5;

step B3: and B1, adding the organic silicon resin prepared in the step B1 into a reaction kettle, stirring and adding the intermediate 5 and 1-hydroxybenzotriazole prepared in the step B2 under the condition that the rotating speed is 200r/min, reacting for 8 hours, adding 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and a dichloromethane saturated aqueous solution, reacting for 3 hours at the temperature of 30 ℃, and distilling to remove the dichloromethane saturated aqueous solution under the temperature of 120 ℃ to prepare the modified organic silicon resin.

Example 3

A green environment-friendly adhesive comprises the following raw materials in parts by weight: 30 parts of bisphenol A epoxy resin, 15 parts of hydrophobic starch, 3 parts of sodium dodecyl benzene sulfonate, 10 parts of deionized water, 10 parts of modified organic silicon resin and 5 parts of m-phenylenediamine;

the adhesive is prepared by the following steps:

step S1: dissolving bisphenol A epoxy resin in toluene to prepare an epoxy resin saturated solution, adding soybean dregs and deionized water into a reaction kettle, stirring for 20min under the condition that the rotating speed is 500r/min, adding a sodium hydroxide solution, continuously stirring for 1.5h, adding the epoxy resin saturated solution, and continuously stirring for 30min to prepare a first glue solution;

step S2: adding hydrophobic starch, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring for 15min under the condition that the rotating speed is 800r/min, adding the first glue solution prepared in the step S1, and continuously stirring for 30min to prepare a second glue solution;

step S3: and (4) adding the modified organic silicon resin and the m-phenylenediamine into the second glue solution prepared in the step (S2), and carrying out ultrasonic treatment for 1.5h under the condition that the frequency is 10MHz to prepare the adhesive.

The hydrophobic starch is prepared by the following steps:

step A1: adding starch and hydrochloric acid solution into a reaction kettle, stirring for 10min at the rotation speed of 200r/min, heating to 50 ℃, continuing stirring for 8-10h, adjusting the pH value of the reaction solution to 7, standing for 5min, washing for 3 times by using deionized water, filtering to remove filtrate, and drying a filter cake to obtain porous starch;

step A2: adding the porous starch prepared in the step A1, sodium hydroxide and deionized water into a reaction kettle, stirring for 30min at the rotation speed of 300r/min, adding a potassium permanganate aqueous solution, continuously stirring for 50min, filtering to remove filtrate, and drying a filter cake to prepare oxidized starch;

step A3: adding phenyl chlorosilane into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 150r/min and the temperature is 60 ℃, reacting for 1.5h to obtain an intermediate 1, adding the intermediate 1, tin powder and a hydrochloric acid solution into the reaction kettle, reacting for 3h under the conditions that the rotating speed is 200r/min and the temperature is 95 ℃, cooling to room temperature, and adjusting the pH value of a reaction solution to 10 to obtain an intermediate 2;

step A4: adding the intermediate 2 prepared in the step A3 into a reaction kettle, introducing nitrogen for protection, adding ethanol at the rotation speed of 150r/min and the temperature of 70 ℃, performing reflux reaction for 3 hours to prepare an intermediate 3, adding the intermediate 3 and deionized water into the reaction kettle, introducing nitrogen for protection, stirring for 10 minutes at the rotation speed of 500r/min and the temperature of 80 ℃, adding the oxidized starch prepared in the step A2 and 1-hydroxybenzotriazole, reacting for 10 hours, filtering to remove filtrate, dispersing a filter cake into toluene, adding dodecanoic acid, reacting for 3 hours at the rotation speed of 300r/min, filtering to remove the filtrate, and drying the filter cake to prepare the hydrophobic starch.

The modified organic silicon resin is prepared by the following steps:

step B1: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid aqueous solution for 1h, heating to 80 ℃ after dropwise adding, continuously stirring for 5h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 150 ℃ to remove distillate to obtain the organic silicon resin;

step B2: dissolving 2, 6-di-tert-butylphenol in N, N-dimethylformamide, adding p-methoxybenzyl ether, stirring uniformly at the rotation speed of 120r/min, adding sodium hydride, reacting for 3h at the temperature of 30 ℃ to obtain an intermediate 4, adding the intermediate 4, lithium diisopropylamide and p-diphenol monomethyl ether into a reaction kettle, introducing nitrogen for protection, adding N, N-dimethylformamide, refluxing for 1.5h at the temperature of 180 ℃, adding acrylic acid, and reacting for 3h at the temperature of 120 ℃ to obtain an intermediate 5;

step B3: and B1, adding the organic silicon resin prepared in the step B1 into a reaction kettle, stirring and adding the intermediate 5 and 1-hydroxybenzotriazole prepared in the step B2 under the condition that the rotating speed is 200r/min, reacting for 10 hours, adding 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and a dichloromethane saturated aqueous solution, reacting for 5 hours at the temperature of 30 ℃, and distilling to remove the dichloromethane saturated aqueous solution under the temperature of 120 ℃ to prepare the modified organic silicon resin.

Comparative example

The comparative example is a common adhesive in the market.

The performance of the adhesives prepared in examples 1 to 3 and the comparative example was tested, and the test results are shown in table 1 below;

water resistance: cutting the wood board into the specifications of 500mm multiplied by 20mm, bonding and curing the wood board by using the adhesives prepared in the examples 1-3 and the comparative example respectively, putting the wood board into distilled water with the temperature of 60 ℃, soaking for 10, 15 and 20 hours, and detecting the shear strength (MPa);

aging resistance: cutting the wood board into the specifications of 500mm multiplied by 20mm, bonding and curing the wood board by using the adhesives prepared in the examples 1-3 and the comparative example respectively, then carrying out heat aging at 150 ℃ for 300, 500 and 1000 hours, and detecting the shear strength (MPa);

TABLE 1

	Example 1	Example 2	Example 3	Comparative example
					Normal condition	9.2	8.9	9.1	9.2
Soaking for 10h	9.2	9.0	9.1	9.0
					Soaking for 15h	9.2	9.0	9.0	8.6
Soaking for 20h	9.1	9.0	9.0	8.3
					Aging for 300h	9.2	9.1	9.1	8.5
Aging for 500h	9.0	8.9	9.0	7.8
					Aging for 1000h	9.1	9.1	9.0	7.3

From the above table 1, it can be seen that the adhesives prepared in examples 1 to 3 have no significant change in shear strength after being soaked in water for 20 hours compared with the shear strength under normal conditions, and have no significant change in shear strength after being thermally aged for 1000 hours compared with the shear strength under normal conditions at 150 ℃, while the adhesives prepared in comparative examples have a reduced shear strength after being soaked in water for 15 hours, and have a reduced shear strength after being thermally aged for 300 hours at 150 ℃, so that the invention has good water resistance and aging resistance.

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.