阅读说明：本技术 一种四官能缩水甘油胺型环氧树脂的合成方法 (Synthesis method of tetrafunctional glycidyl amine type epoxy resin ) 是由 李大钱 朱新宝 程振朔 王子怡 黄健 于 2021-09-14 设计创作，主要内容包括：本发明涉及一种四官能缩水甘油胺型环氧树脂的合成方法,包括：1)开环反应,以4,4‘-二氨基二苯甲烷、环氧氯丙烷合成氯醇醚中间体；水作为极性催化剂；2)闭环反应,加入碱金属氢氧化物进行脱氯化氢反应,闭环生成目标产物；3)水洗、精制,将有机相用水萃取,洗涤除去过量的碱金属氢氧化物、反应产生的氯化物,通过负压蒸馏,脱除过量的环氧氯丙烷后得到产品。(The invention relates to a method for synthesizing tetrafunctional glycidyl amine type epoxy resin, which comprises the following steps: 1) ring-opening reaction, synthesizing chlorohydrin ether intermediate with 4, 4' -diaminodiphenylmethane and epichlorohydrin; water as a polar catalyst; 2) performing ring-closure reaction, namely adding alkali metal hydroxide to perform dehydrochlorination reaction, and performing ring closure to generate a target product; 3) washing and refining, extracting the organic phase with water, washing to remove excessive alkali metal hydroxide and chloride generated by reaction, and removing excessive epichlorohydrin through negative pressure distillation to obtain the product.)

1. A method for synthesizing tetrafunctional glycidyl amine type epoxy resin comprises the following steps:

1) ring opening reaction

Synthesizing chlorohydrin ether intermediate by using 4, 4' -diaminodiphenylmethane and epichlorohydrin; water is used as a polar catalyst, and the using amount of the water is 0.2 to 2 times of the weight of the 4, 4' -diaminodiphenylmethane; the mol dosage of the epoxy chloropropane is 6-16 times of that of the 4, 4' -diaminodiphenylmethane, the epoxy chloropropane is added in two parts, in order to avoid large heat release and difficult temperature control when the epoxy chloropropane is added in a large quantity, the addition of the first part accounts for 5-20% of the total amount, and a part of amino groups are firstly reacted;

2) ring closure reaction

Adding alkali metal hydroxide to perform dehydrochlorination reaction, and carrying out ring closure to generate a target product; the alkali metal hydroxide is sodium hydroxide solution with the concentration of 20-50 percent, potassium hydroxide solution or solid alkali metal hydroxide, the molar dosage of the alkali metal hydroxide is 4-6 times of that of 4, 4' -diaminodiphenylmethane, and the reaction temperature is 35-85 ℃;

3) washing and refining

And (3) extracting the organic phase by using water, washing to remove excessive alkali metal hydroxide and chloride generated by reaction, and removing excessive epichlorohydrin by negative pressure distillation to obtain the product.

2. The method for synthesizing a tetrafunctional glycidylamine-type epoxy resin of claim 1, wherein: the step 1) is to mix 4, 4' -diaminodiphenylmethane and H₂Sequentially adding O and epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, and carrying out heat preservation reaction at 60-65 ℃ for 0.5 h; then dropwise adding the rest epoxy chloropropane in 2h, heating to 80-85 ℃, and reacting for 6h under the condition of heat preservation; the step 2) is to drop sodium hydroxide with the concentration of 32 percent at the temperature of 80-85 ℃ within 0.5h, keep the temperature for 0.5h, reduce the temperature to 35-40 ℃, add 1/5 solid sodium hydroxide per 0.5h, add 5 times in totalKeeping the temperature for reaction for 3 hours; adding water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer brine, adding water, shaking uniformly, standing for layering, separating to remove the upper layer water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutrality; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Technical Field

The invention relates to a synthesis method of glycidylamine type tetrafunctional epoxy resin, in particular to a synthesis method of N, N, N ', N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane.

Background

The multifunctional glycidyl amine type epoxy resin has the characteristics of high activity, strong adhesion, large crosslinking density of a cured product, low shrinkage rate, excellent mechanical property, heat resistance, corrosion resistance and the like, and can be used for manufacturing high-temperature-resistant adhesives, heavy-duty anticorrosive coating resins, electrical pouring, high-temperature-resistant composite material base resins and the like. The method can be applied to the high-tech fields of aerospace, steamships, naval vessels, wind power blades, electrical machines, automobiles, high-speed rails and the like.

The molecule contains four epoxy groups, and can react with amino, hydroxyl and acid anhydride to be cured and crosslinked.

The reaction formula is as follows:

the prior synthesis technology has the following disadvantages:

1. polar alcohols are used as catalysts, are soluble in water and are difficult to recover;

2. needs to be extracted and washed by an inert solvent such as toluene (boiling point 110 ℃) and is difficult to separate from epichlorohydrin (boiling point 117 ℃) during recovery;

3. the epichlorohydrin needs to be distilled and recovered twice, and the process is complex.

Disclosure of Invention

The invention aims to provide a method for synthesizing tetra-functional glycidyl amine epoxy resin. The method solves the problems that in the prior art, alcohol substances are needed to be used as catalysts, are dissolved in water and are difficult to recover; the problem that an inert organic solvent is needed to be used for an extraction and water washing process is solved; in the process, the solvent is distilled and recovered only once, thereby optimizing the synthesis process.

A method for synthesizing tetrafunctional glycidyl amine type epoxy resin comprises the following steps:

1. ring opening reaction

Synthesizing chlorohydrin ether intermediate by using 4, 4' -diaminodiphenylmethane and epichlorohydrin, which is characterized in that: the water is used as a polar catalyst, the dosage is 0.2-2 times of the weight of 4,4 '-diaminodiphenylmethane, the molar dosage of epoxy chloropropane is 6-16 times of 4, 4' -diaminodiphenylmethane, the water is added in two parts, the addition of the first part accounts for 5-20% of the total amount, a part of amino groups are reacted first, and the problems of large heat release amount and difficult temperature control when a large amount of epoxy chloropropane is added are avoided.

2) Ring closure reaction

Adding alkali metal hydroxide to perform dehydrochlorination reaction, and carrying out ring closure to generate a target product, wherein the target product is characterized in that: the alkali metal hydroxide is sodium hydroxide solution or potassium hydroxide solution with concentration of 20-50% or solid alkali metal hydroxide, the molar amount of the alkali metal hydroxide is 4-6 times of that of 4, 4' -diaminodiphenylmethane, and the reaction temperature is 35-85 ℃.

2) Washing and refining

And (3) extracting the organic phase by using water, washing to remove excessive alkali metal hydroxide and chloride generated by reaction, and removing excessive epichlorohydrin by negative pressure distillation to obtain the product. The method is characterized in that: the product is directly extracted and washed by water, no solvent is needed to be added, the residual amount of the epoxy chloropropane in the product is reduced by adopting a negative pressure mode, and the recovered epoxy chloropropane can be directly used, thereby being beneficial to the control of the production cost.

The invention has the following positive effects:

1) no alcoholic solvents are used, such as: methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, and the like, which are compatible with water, are difficult to recover;

2) organic solvents used for extraction are not used in the process, such as: benzene, toluene and the like, and the problem that the benzene, the toluene and the epichlorohydrin are difficult to separate during recovery is avoided;

3) the epichlorohydrin is not recovered in the middle process, and only once distillation is carried out in the process.

Detailed Description

The present invention will be described in further detail with reference to the following examples, but the specific embodiments of the present invention are not limited thereto.

Example 1:

40g of 4, 4' -diaminodiphenylmethane, 20g of H₂Sequentially adding O and 20g of epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 165g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dropwise adding 47g of sodium hydroxide solution (with the concentration of 32%) at 80-85 ℃ within 0.5h, keeping the temperature for 0.5h, cooling to 35-40 ℃, adding 5g of solid sodium hydroxide every 0.5h, adding 25g in total, and keeping the temperature for reaction for 3 h; adding 125g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutral; transferring the lower material to the flaskAnd (5) performing pressure distillation to remove epichlorohydrin to obtain the product.

Example 2:

40g of 4, 4' -diaminodiphenylmethane, 10g of H₂Sequentially adding 20g of epoxy chloropropane and O into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 91g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dropwise adding 47g of sodium hydroxide solution (with the concentration of 32%) at 80-85 ℃ within 0.5h, keeping the temperature for 0.5h, cooling to 35-40 ℃, adding 5g of solid sodium hydroxide every 0.5h, adding 25g in total, and keeping the temperature for reaction for 3 h; adding 125g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 3:

40g of 4, 4' -diaminodiphenylmethane, 20g of H₂Sequentially adding O and 30g of epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at 40-45 ℃, dropwise adding 266g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dropwise adding 47g of sodium hydroxide solution (with the concentration of 32%) at 80-85 ℃ within 0.5h, keeping the temperature for 0.5h, cooling to 35-40 ℃, adding 5g of solid sodium hydroxide every 0.5h, adding 25g in total, and keeping the temperature for reaction for 3 h; adding 125g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 4:

40g of 4, 4' -diaminodiphenylmethane, 80gH₂Sequentially adding O and 30g of epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at 40-45 ℃, dropwise adding 192g of epoxy chloropropane within 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dripping 47g sodium hydroxide solution (32%) at 80-85 deg.C for 0.5 hr, maintaining the temperature for 0.5 hr, cooling to 35-40 deg.C, adding 5g solid sodium hydroxide every 0.5 hr, and adding25g, and reacting for 3 hours under the condition of heat preservation; adding 125g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 5:

40g of 4, 4' -diaminodiphenylmethane, 8g of H₂Adding O and 10g of epoxy chloropropane into a four-neck flask in sequence, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 165g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dropwise adding 240g of sodium hydroxide solution (with the concentration of 20%) at the temperature of 80-85 ℃ within 2h, and reacting for 4h under the condition of heat preservation; pouring into a separating funnel, discharging lower layer salt water, adding 50g of water, shaking uniformly, standing for layering, separating to remove upper layer water, and repeatedly washing for 2 times until the pH value of the separated water is neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 6:

mixing 40g of 4, 4' -diaminodiphenylmethane and 40g of H₂Adding O and 35g of epoxy chloropropane into a four-neck flask in sequence, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 165g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; adding 5g of solid sodium hydroxide per 0.5h at 35-40 ℃, totally adding 40g, and reacting for 3h under heat preservation; adding 160g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water reaches neutrality; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 7:

40g of 4, 4' -diaminodiphenylmethane, 60g of H₂Adding O and 15g of epoxy chloropropane into a four-neck flask in sequence, slowly heating to 80-85 ℃, preserving heat, reacting for 2 hours, dripping 133g of epoxy chloropropane in 2 hours, preserving heat, and reacting for 4 hours; dropwise adding 150g of sodium hydroxide solution (with the concentration of 32%) within 2h at the temperature of 60-65 ℃, and reacting for 5h under the condition of heat preservation; pouring into separating funnel, and dischargingAdding 50g of water into the lower layer of brine, shaking up, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water is neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 8:

40g of 4, 4' -diaminodiphenylmethane, 20g of H₂O and 50g of epoxy chloropropane are sequentially added into a four-neck flask, slowly heated to 60-65 ℃ and subjected to heat preservation reaction for 2 hours, 209g of epoxy chloropropane is dropwise added within 2 hours, and subjected to heat preservation reaction for 4 hours; dropwise adding 70g of sodium hydroxide solution (with the concentration of 48%) at the temperature of 50-55 ℃ within 2h, and reacting for 4h under the condition of heat preservation; adding 100g of water to dissolve the generated solid salt, pouring the solid salt into a separating funnel, discharging the lower layer of brine, adding 50g of water, shaking uniformly, standing for layering, separating to remove the upper layer of water, and repeatedly washing for 2 times until the pH value of the separated water is neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 9:

40g of 4, 4' -diaminodiphenylmethane, 20g of H₂Sequentially adding O and 20g of epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 165g of epoxy chloropropane in 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; dropwise adding 112g of potassium hydroxide solution (with the concentration of 50%) within 2h at the temperature of 50-55 ℃, and reacting for 4h under the condition of heat preservation; pouring into a separating funnel, discharging lower layer salt water, adding 50g of water, shaking uniformly, standing for layering, separating to remove upper layer water, and repeatedly washing for 2 times until the pH value of the separated water is neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.

Example 10:

mixing 40g of 4, 4' -diaminodiphenylmethane and 40g of H₂Sequentially adding O and 30g of epoxy chloropropane into a four-neck flask, slowly heating to 60 ℃, reacting for 0.5h at the temperature of 60-65 ℃, dropwise adding 118g of epoxy chloropropane within 2h, heating to 80-85 ℃ after the reaction is finished, and reacting for 6h at the temperature; adding 5g of solid potassium hydroxide per 0.5h at 35-40 ℃, totally adding 45g, and reacting for 3h under heat preservation; adding 50g water to dissolve the generated solid salt, pouring into a separating funnel, discharging the lower layer salt water, adding 50g water, shaking, standing for layeringSeparating to remove the upper water layer, and repeatedly washing for 2 times until the pH value of the separated water is neutral; transferring the lower layer material to a flask for negative pressure distillation, and removing epichlorohydrin to obtain the product.