Terpene-based macroporous adsorption resin and preparation method thereof

Abstract

The invention discloses a terpene-based macroporous adsorption resin and a preparation method thereof. The name of the terpene-based macroporous resin is terpene maleate di(beta-acryloyloxyethyl)ester-methacrylic macroporous adsorption resin. The preparation method of the resin comprises the steps that: a natural perfume alpha-pinene is subjected to isomerization, and is subjected to diene addition with maleic anhydride, such that terpene maleic anhydride is obtained; the terpene maleic anhydride is subjected to an esterification reaction with ethylene glycol, such that terpene maleate di(beta-hydroxy ethyl)ester is prepared; the ester is subjected to an esterification reaction with acrylic acid, such that terpene maleate di(beta-acryloyloxyethyl)ester is obtained; the terpene maleate di(beta-acryloyloxyethyl)ester is adopted as a cross-linking agent, and is subjected to free radical suspension polymerization with a functional monomer methacrylic acid, such that the terpene maleate di(beta-acryloyloxyethyl)ester-methacrylic macroporous adsorption resin is prepared. The terpene-based macroporous adsorption resin is characterized by no toxicity, -COOH group, high specific surface area and large pore amount. The terpene-based macroporous adsorption resin can be used in extraction and separation of natural Chinese herbal medicines.

Description

technical field

[0001] The invention relates to a macroporous adsorption resin and a preparation method thereof, in particular to a terpene-based macroporous adsorption resin and a preparation method thereof. Background technique

[0002] At present, solvent extraction, supercritical liquid extraction or recrystallization methods are commonly used to extract the active ingredients of Chinese herbal medicines such as alkaloids, flavonoids, and saponins. The disadvantages of these methods are that the process flow is long, the extraction rate is not high or the equipment is complicated. Therefore, Chemists have invented macroporous adsorption resins to extract and separate Chinese herbal medicines, which not only have high active ingredients and are easy to operate, but also isolate products with high purity. At present, the most widely used macroporous adsorption resin is polystyrene-type polymer, which uses polystyrene as the skeleton and adopts methods such as copolymerizat...

Examples

Embodiment 1

[0077] 1. Preparation of Terpene Maleic Anhydride

[0078] Put 100mL α-pinene, 200mL ethyl acetate solvent, 0.84g phosphomolybdic acid and 60.5g maleic anhydride in a 500mL three-neck round bottom flask, install a thermometer, reflux condenser and stirrer, and react in a water bath at 80°C for 4h. Cool to room temperature, add 50mL of cyclohexane, wash with saturated aqueous sodium chloride until neutral light yellow liquid, remove polymaleic acid and catalyst, then rectify at -0.1Mpa under reduced pressure, collect 170-180 °C fraction to obtain 46.5 g of terpene maleic anhydride.

[0079] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0080] Get 20g of terpene maleic anhydride prepared by step 1, place in a 250mL three-necked round-bottomed flask, add 1.6g of p-toluenesulfonic acid catalyst and 15mL of ethylene glycol, install a thermometer, water separator, stirrer and reflux Condensate the tube, start the agitator, heat, control the reaction temperature at 120-140...

Embodiment 2

[0089] 1. Preparation of Terpene Maleic Anhydride

[0090] Terpene maleic anhydride was prepared according to step 1 in Example 1.

[0091] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0092] Get 50g terpene maleic anhydride prepared by step 1, place in a three-necked round-bottomed flask of 500mL, add 1.5g p-toluenesulfonic acid catalyst and 47.5mL ethylene glycol, install thermometer, water separator, stirrer and Reflux the condenser, start the agitator, heat, control the reaction temperature at 120-140°C, heat the reaction for 4 hours, stop the reaction, cool to room temperature, wash the product repeatedly with deionized water, remove the catalyst and unreacted ethylene glycol, and then Evaporate and remove water with a rotary evaporator, and measure the acid value of the product to be 13.7mgKOH g -1 ;

[0093] 3. Preparation of terpene maleate bis(β-acryloyloxyethyl)ester

[0094] Get 40g of terpene maleate di(β-hydroxyethyl) prepared by step 2 in a 250mL th...

Embodiment 3

[0101] 1. Preparation of Terpene Maleic Anhydride

[0102] Terpene maleic anhydride was prepared according to step 1 in Example 1.

[0103] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0104] Get 100g of terpene maleic anhydride prepared by step 1, place in a 500mL three-necked round-bottomed flask, add 6g of p-toluenesulfonic acid catalyst and 95mL of ethylene glycol, install a thermometer, water separator, stirrer and reflux condensing tube, start the stirrer, heat, control the reaction temperature at 120-140°C, heat the reaction for 4h, stop the reaction, cool to room temperature, wash the product repeatedly with deionized water, remove the catalyst and unreacted ethylene glycol, and then use a rotary The evaporator evaporates and removes water, and the acid value of the product measured is 14.2mgKOH g -1 ;

[0105] 3. Preparation of terpene maleate bis(β-acryloyloxyethyl)ester

[0106] Get 80g of terpene maleate di(β-hydroxyethyl) prepared by step 2 in a 500m...

technical field

[0001] The invention relates to a macroporous adsorption resin and a preparation method thereof, in particular to a terpene-based macroporous adsorption resin and a preparation method thereof. Background technique

[0002] At present, solvent extraction, supercritical liquid extraction or recrystallization methods are commonly used to extract the active ingredients of Chinese herbal medicines such as alkaloids, flavonoids, and saponins. The disadvantages of these methods are that the process flow is long, the extraction rate is not high or the equipment is complicated. Therefore, Chemists have invented macroporous adsorption resins to extract and separate Chinese herbal medicines, which not only have high active ingredients and are easy to operate, but also isolate products with high purity. At present, the most widely used macroporous adsorption resin is polystyrene-type polymer, which uses polystyrene as the skeleton and adopts methods such as copolymerizat...

Examples

Embodiment 1

[0077] 1. Preparation of Terpene Maleic Anhydride

[0078] Put 100mL α-pinene, 200mL ethyl acetate solvent, 0.84g phosphomolybdic acid and 60.5g maleic anhydride in a 500mL three-neck round bottom flask, install a thermometer, reflux condenser and stirrer, and react in a water bath at 80°C for 4h. Cool to room temperature, add 50mL of cyclohexane, wash with saturated aqueous sodium chloride until neutral light yellow liquid, remove polymaleic acid and catalyst, then rectify at -0.1Mpa under reduced pressure, collect 170-180 °C fraction to obtain 46.5 g of terpene maleic anhydride.

[0079] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0080] Get 20g of terpene maleic anhydride prepared by step 1, place in a 250mL three-necked round-bottomed flask, add 1.6g of p-toluenesulfonic acid catalyst and 15mL of ethylene glycol, install a thermometer, water separator, stirrer and reflux Condensate the tube, start the agitator, heat, control the reaction temperature at 120-140...

Embodiment 2

[0089] 1. Preparation of Terpene Maleic Anhydride

[0090] Terpene maleic anhydride was prepared according to step 1 in Example 1.

[0091] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0092] Get 50g terpene maleic anhydride prepared by step 1, place in a three-necked round-bottomed flask of 500mL, add 1.5g p-toluenesulfonic acid catalyst and 47.5mL ethylene glycol, install thermometer, water separator, stirrer and Reflux the condenser, start the agitator, heat, control the reaction temperature at 120-140°C, heat the reaction for 4 hours, stop the reaction, cool to room temperature, wash the product repeatedly with deionized water, remove the catalyst and unreacted ethylene glycol, and then Evaporate and remove water with a rotary evaporator, and measure the acid value of the product to be 13.7mgKOH g -1 ;

[0093] 3. Preparation of terpene maleate bis(β-acryloyloxyethyl)ester

[0094] Get 40g of terpene maleate di(β-hydroxyethyl) prepared by step 2 in a 250mL th...

Embodiment 3

[0101] 1. Preparation of Terpene Maleic Anhydride

[0102] Terpene maleic anhydride was prepared according to step 1 in Example 1.

[0103] 2. Preparation of terpene di(β-hydroxyethyl) maleate

[0104] Get 100g of terpene maleic anhydride prepared by step 1, place in a 500mL three-necked round-bottomed flask, add 6g of p-toluenesulfonic acid catalyst and 95mL of ethylene glycol, install a thermometer, water separator, stirrer and reflux condensing tube, start the stirrer, heat, control the reaction temperature at 120-140°C, heat the reaction for 4h, stop the reaction, cool to room temperature, wash the product repeatedly with deionized water, remove the catalyst and unreacted ethylene glycol, and then use a rotary The evaporator evaporates and removes water, and the acid value of the product measured is 14.2mgKOH g -1 ;

[0105] 3. Preparation of terpene maleate bis(β-acryloyloxyethyl)ester

[0106] Get 80g of terpene maleate di(β-hydroxyethyl) prepared by step 2 in a 500m...

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