CN104448288A - Method for synthesizing polyepichlorohydrin - Google Patents

Abstract

The invention discloses a method for synthesizing polyepichlorohydrin. The method comprises the following steps: catalyzing chloropropane by using a catalyst and additives, thereby obtaining epoxy chloropropane for later use; sequentially adding diethyl aluminum chloride and absolute ether into a three-opening flask with a stirrer, stirring for 10 minutes, cooling to be 0 DEG C, dropwise adding epoxypropane to react for 30-50 minutes, sucking out the volatile matters in time, further adding a methanol solution containing sodium hydroxide, stirring at normal temperature for 50 minutes, and stopping the reaction; moving the reaction mixture into a liquid separation funnel, washing, layering, and washing the obtained coarse product by using 5% hydrochloric acid, 5% sodium bicarbonate and distilled water till being neutral; and reducing the pressure by using a rotational evaporator, thereby obtaining 8.23g of polyepichlorohydrin. The polyepichlorohydrin yield is greater than 84.9%.

Description

A kind of method of synthesizing polyepichlorohydrin

technical field

The invention belongs to the field of polymerization reaction and relates to a synthesis method of polyepichlorohydrin.

Background technique

Polyepichlorohydrin is light yellow to amber viscous liquid or solid. It is formed by the ring-opening polymerization of epichlorohydrin. Polyepichlorohydrin has the advantages of oil resistance, acid resistance, etc., and has outstanding resistance to gas penetration. Its shock absorption and high temperature resistance are also good, and it has good adhesion. The photoresist with excellent performance can be made by treating polyepichlorohydrin with cinnamic acid. Polyepichlorohydrin can be used to make sealing gaskets and oil-resistant hot melt adhesives, seawater-resistant, oil-resistant adhesives, etc., as well as flame-retardant, water-resistant, and oil-resistant polyurethane adhesives and coatings. The ring-opening polymerization products of epoxy compounds are increasingly important as intermediate systems for new polymer materials.

The traditional initiators for synthesizing polyepichloropropylene are mostly 1,4-butanol bistrifluoromethanesulfonate, trifluoroacetic acid, etc.; these synthetic methods have their own advantages, but a large amount of homogeneous compounds are produced during the polymerization reaction. Polymer. Therefore, necessary aftertreatment must be carried out to the polymerized product, which means that the process is more complicated, and the quality of the manufactured product cannot reach the desired performance.

Contents of the invention

In order to solve the large amount of impurities produced by synthesizing polyepichlorohydrin in the prior art, reduce the complicated process and improve the quality of the polycyclic compound.

The synthetic route of the present invention is:

The synthetic process that the present invention relates to polyacrylic acid comprises the following steps:

1. Synthesis of epichlorohydrin:

(1) Put 30g of chloropropane and 6.5g of catalyst (phosphotungstic heteropolyacid/Ti0 ₂ ) into a 100mL four-necked flask, then add 10mL of hydrogen peroxide and 5g of diamine hydrogen phosphate under stirring state, and reflux under chloropropane 6 hours of reaction;

(2) After the reaction is completed, the system is divided into oil and water phase suspensions after standing for 1-2 hours;

(3) The oil layer was separated to obtain 23.36 mL of epichlorohydrin for future use.

2. Synthesis of initiator AlEt ₂ Cl:

(1) earlier in the there-necked flask that stirring bar is housed, add 5g diethyl aluminum chloride successively, the 50ml anhydrous diethyl ether that is dried through molecular sieve, stir 10 minutes at normal temperature;

(2) Cool the stirred solution to 0° C. with ice-brine, and add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1-2 drops/sec and maintaining the temperature at 0-20°C. After reacting for 30 minutes, the volatile matter was extracted in time to obtain viscous initiator AlEt ₂ Cl.

3. Synthesis of polyepichlorohydrin:

(1) Add 20mL of pre-prepared epichlorohydrin to the initiator solution and keep the temperature at 0°C in an ice-water bath for 8 hours;

(2) Add 10ml of methanol solution containing sodium hydroxide again, and stop the reaction after polymerization at 25° C. for 5 hours under the protection of nitrogen;

(3) The reaction mixture was transferred to a 1000 mL separatory funnel, washed with deionized water, and allowed to stand to separate layers. Transfer the organic layer to a 1000ml distillation flask;

(4) Then add 40-50 mL of 5% hydrochloric acid, 55-65 mL of 5% sodium bicarbonate and 100 mL of distilled water to wash the crude product until neutral. Then use a rotary evaporator to depressurize, heat to 70-80° C. to remove solvent and other small molecular substances, and obtain 8.23 g of polyepichlorohydrin with a yield of 84.9%.

Specific implementation plan:

Put 30g of chloropropane and 6.5g of catalyst (phosphotungstopolyacid/Ti0 ₂ ) into a 100mL four-neck flask, then add 10mL of hydrogen peroxide and 5g of diamine hydrogen phosphate under stirring, and react for 6 hours under reflux of chloropropane . After the reaction was completed, the system was separated into oil and water phase suspensions after standing for 1-2 hours; the oil layer was separated by essence to obtain 23.36 mL of epichlorohydrin for later use. Then add 5g of diethylaluminum chloride and 50ml of anhydrous diethyl ether dried over molecular sieves to the three-necked flask equipped with a stirring bar, and stir at room temperature for 10 minutes. Cool the stirred solution to 0°C with ice-salt water, Add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1-2 drops/second and maintaining the temperature at 0-20°C. React for 30-50 minutes, extract volatile matter in time, add 20 mL of pre-prepared epichlorohydrin to the solution, and keep the temperature at 0° C. in an ice-water bath for 8 hours. Add 10 ml of methanol solution containing sodium hydroxide, and polymerize at 25° C. for 5 hours under the protection of nitrogen to terminate the reaction. The reaction mixture was transferred to a 1000 mL separatory funnel, washed with deionized water, and allowed to stand to separate layers. Transfer the organic layer to a 1000ml retort. Then add 40-50 mL of the crude product, 5% hydrochloric acid, 55-65 mL of 5% sodium bicarbonate, and 100 mL of distilled water to wash until neutral. Then use a rotary evaporator to depressurize, heat to 70-80° C. to remove solvent and other small molecular substances, and obtain 8.23 g of polyepichlorohydrin with a yield of 84.9%.

Example 1

Put 30g of chloropropane and 6.5g of catalyst (phosphotungstopolyacid/Ti0 ₂ ) into a 100mL four-neck flask, then add 10mL of hydrogen peroxide and 5g of diamine hydrogen phosphate under stirring, and react for 6 hours under reflux of chloropropane . After the reaction was completed, the system was separated into oil and water phase suspensions after standing for 1 hour; the oil layer was separated by distillation to obtain 23.36 mL of epichlorohydrin for future use. Then add 5g of diethylaluminum chloride and 50ml of anhydrous diethyl ether dried over molecular sieves to the three-necked flask equipped with a stirring bar, and stir at room temperature for 10 minutes. Cool the stirred solution to 0°C with ice-salt water, Add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1 drop/sec and maintaining the temperature at 5 °C. After reacting for 30 minutes, the volatile matter was extracted in time, and then 20 mL of pre-prepared epichlorohydrin was added to the solution, and the temperature was kept at 0° C. in an ice-water bath for 8 hours to react. Add 10 ml of methanol solution containing sodium hydroxide, and polymerize at 25° C. for 5 hours under the protection of nitrogen to terminate the reaction. The reaction mixture was transferred to a 1000 mL separatory funnel, washed with deionized water, and allowed to stand to separate layers. Transfer the organic layer to a 1000ml retort. Then the crude product was sequentially added to 40mL, 5% hydrochloric acid, 55mL 5% sodium bicarbonate, and 100mL distilled water to wash until neutral. Then use a rotary evaporator to depressurize, heat to 70-80° C. to remove small molecular substances such as solvents, and obtain 8.15 g of polyepichlorohydrin with a yield of 82.9%.

Example 2

Put 30g of chloropropane and 6.5g of catalyst (phosphotungstic heteropoly acid salt/Ti02) into a 100mL four-neck flask, then add 10mL of hydrogen peroxide and 5g of diammonium hydrogen phosphate under stirring, and react under reflux of chloropropane for 6 hours. After the reaction was completed, the system was separated into oil and water phase suspensions after standing for 1.5 hours; the oil layer was separated by distillation to obtain 23.36 mL of epichlorohydrin for future use. Then add 5g of diethylaluminum chloride and 50ml of anhydrous diethyl ether dried by molecular sieves to the three-necked flask equipped with a stirring bar, and stir at room temperature for 10 minutes, then cool the stirred solution to 10°C with ice-salt water, Add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1 drop/sec and maintaining the temperature at 0 °C. After reacting for 30 minutes, the volatile matter was extracted in time, and 20 mL of pre-prepared epichlorohydrin was added to the solution, and the reaction was carried out at 0°C in an ice-water bath for 8 hours. Add 10 ml of methanol solution containing sodium hydroxide, and polymerize at 25° C. for 5 hours under the protection of nitrogen to terminate the reaction. The reaction mixture was transferred to a 1000 mL separatory funnel, washed with deionized water, and allowed to stand to separate layers. Transfer the organic layer to a 1000ml retort. Then the crude product was sequentially added to 45mL, 5% hydrochloric acid, 60mL 5% sodium bicarbonate, and 100mL distilled water to wash until neutral. Then use a rotary evaporator to depressurize, heat to 70-80° C. to remove solvent and other small molecular substances, and obtain 8.00 g of polyepichlorohydrin with a yield of 80.5%.

Example 3

Put 30g of chloropropane and 6.5g of catalyst (phosphotungstopolyacid/Ti0 ₂ ) into a 100mL four-neck flask, then add 10mL of hydrogen peroxide and 5g of diamine hydrogen phosphate under stirring, and react for 6 hours under reflux of chloropropane After the reaction is over, the system is divided into oil and water phase suspensions after standing for 1-2 hours; the oil layer is separated by essence to obtain 23.36mL of epichlorohydrin for subsequent use. Then add 5g of diethylaluminum chloride and 50ml of anhydrous diethyl ether dried over molecular sieves to the three-necked flask equipped with a stirring bar, and stir at room temperature for 10 minutes. Cool the stirred solution to 0°C with ice-salt water, Add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1 drop/sec and maintaining the temperature at 20 °C. After reacting for 30 minutes, the volatile matter was extracted in time, and then 20 mL of pre-prepared epichlorohydrin was added to the solution, and the temperature was kept at 0° C. in an ice-water bath for 8 hours to react. Add 10 ml of methanol solution containing sodium hydroxide, and stir at room temperature for 50 minutes to terminate the reaction. The reaction mixture was transferred to a 1000 mL separatory funnel, washed with deionized water, and allowed to stand to separate layers. Transfer the organic layer to a 1000ml retort. Then the crude product was sequentially added to 50 mL, 5% hydrochloric acid, 65 mL 5% sodium bicarbonate, and 100 mL distilled water to wash until neutral. Then use a rotary evaporator to depressurize, heat to 70-80° C. to remove small molecular substances such as solvents, and obtain 8.13 g of polyepichlorohydrin with a yield of 81.6%.

Claims (3)

1. a method for synthesizing polyepichlorohydrin is characterized in that the synthesis of epichlorohydrin: (1) Put 30g of chloropropane and 6.5g of catalyst (phosphotungstic heteropolyacid/Ti0 ₂ ) into a 100mL four-necked flask, then add 10mL of hydrogen peroxide and 5g of diamine hydrogen phosphate under stirring state, and reflux under chloropropane 6 hours of reaction; (2) After the reaction is completed, the system is divided into oil and water phase suspensions after standing for 1-2 hours; (3) The oil layer was separated to obtain 23.36 mL of epichlorohydrin for future use. 2. a kind of method for synthesizing polyepichlorohydrin according to claim 1, is characterized in that: (1) earlier in the there-necked flask that stirring bar is housed, add 5g diethyl aluminum chloride successively, the 50ml anhydrous diethyl ether that is dried through molecular sieve, stir 10 minutes at normal temperature; (2) Cool the stirred solution to 0° C. with ice-brine, and add 10 mL of propylene oxide dropwise. By controlling the dropping rate to 1-2 drops/sec and maintaining the temperature at 0-20°C. After reacting for 30 minutes, the volatile matter was extracted in time to obtain viscous initiator AlEt ₂ Cl. 3. a kind of method for synthesizing polyepichlorohydrin according to claim 1, is characterized in that: (1) Add 20ml of pre-prepared epichlorohydrin to the initiator solution and keep the reaction at 0°C for 8 hours in an ice-water bath; (2) Add 10ml of methanol solution containing sodium hydroxide again, and stop the reaction after polymerization at 25° C. for 5 hours under the protection of nitrogen; (3) The reaction mixture was moved to a 1000mL separatory funnel, washed with deionized water, left to stand for layers, and the organic layer was transferred to a 1000ml distillation flask; (4) Then add 40mL of the crude product, 5% hydrochloric acid, 55mL of 5% sodium bicarbonate, and 100mL of distilled water to wash until neutral; then reduce the pressure with a rotary evaporator, heat to 70-80°C to remove small molecules such as solvents substance to obtain 8.23 mL of polyepichlorohydrin.