Preparation method and application of maleated rosin-based hydrogel

Abstract

The invention discloses a preparation method and application of maleated rosin-based hydrogel. The method comprises the following steps: (1) reacting maleated rosin with ethylenediamine to synthesize N-aminoethyl maleated rosin imide; and (2) reacting the N-aminoethyl maleated rosin imide with acryloyl chloride to synthesize the N-(N '-acryloyl) aminoethyl maleated rosin imide. And (3) preparation of the maleated rosin-based hydrogel: carrying out crosslinking copolymerization on the N-(N '-acryloyl) aminoethyl maleated rosin imide and dimethylaminopropyl acrylamide to prepare the maleated rosin-based hydrogel. The method is simple in reaction operation, mild in reaction condition and low in cost; the specificity of the reaction is relatively good, and the subsequent separation and purification are relatively simple; finally, the hydrogel product obtained by the method has better water absorption performance, can be used for removing toxic heavy metal cations in an environmental water body, can meet the application requirements of some special occasions, and has stronger practical value and market prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of a maleic rosin-based hydrogel and application thereof. Background Art

[0002] Hydrogel is a kind of polymer with a network structure that can swell in water and retain a large amount of water without dissolving. Due to its good hydrophilicity and biocompatibility, hydrogel is widely used in various fields such as agriculture, forestry and horticulture, industry, animal husbandry, food industry, medical materials, sanitary products and textiles. Hydrogel is also a very promising adsorbent material. Compared with traditional separation technologies such as membrane separation, chemical precipitation, liquid-liquid extraction, etc., hydrogel adsorption materials have the characteristics of high efficiency, easy operation, low energy consumption and no secondary pollution. They are widely used in the enrichment and separation of metal ions in industrial wastewater and environmental sewage. In order to improve the reuse rate of wastewater and reduce the harm caused by heavy metals, it is urgent to find a green, pollution-free and efficient method for treating heavy metal wastewater. As one of the wastewater treatment processes, adsorption has the advantages of simple operation, wide application and long service life. It is considered to be the most practical wastewater treatment process and is widely used in many industrial fields. However, the reproducibility and recovery rate of adsorbents are still the current problems. Therefore, researchers have gradually begun to devote themselves to the research of green, pollution-free, low-cost new natural adsorption materials, and hydrogel adsorbents are also one of the research hotspots in related fields.

[0003] Hydrogels can be divided into natural polymers and synthetic resins according to their raw material sources. Natural polymer compounds are economical in source, have good biocompatibility and biodegradability, and have the characteristics of extremely low toxicity. Therefore, natural polymer compounds have become important raw materials for preparing hydrogels. One of the raw materials of a maleic rosin-based hydrogel prepared by the present invention is a natural forest product resource that is renewable in nature, degradable in the environment, and recyclable in the food chain. Rosin itself has strong biochemical activity, and the hydrogen phenanthrene ring skeleton gives it good structural rigidity and mechanical properties, making it widely used in many fields. And rosin acid can react chemically through the two active groups of carboxyl and conjugated double bonds, and target the preparation of rosin derivatives for various purposes.

[0004] Maleic rosin is a product obtained by addition reaction of rosin and maleic anhydride (maleic anhydride). By introducing maleic rosin into the hydrogel structure, it is expected to obtain a series of maleic rosin-based hydrogel systems with good biocompatibility, good degradability and meeting the requirements of green chemistry, thereby greatly expanding the research scope of natural product hydrogels. Compared with other polymer adsorbents such as chitosan, fiber, resin, etc., the grids of the hydrogel of the present invention contain a large number of water molecules, and have a looser hydrophilic three-dimensional network structure. The mass transfer efficiency of adsorbents such as metal ions on the maleic rosin-based hydrogel adsorbent will be higher. Through the present invention, the advantages of my country's rich rosin resources and unique chemical structure can be brought into play, the development of rosin raw materials and products thereof can be promoted, new ways for high value-added utilization of rosin can be explored, and the foundation for the application of natural product rosin in the field of new technology can be laid. Summary of the invention

[0005] The technical task of the present invention is to provide a preparation method and application of a maleic rosin-based hydrogel in view of the deficiencies of the prior art.

[0006] The technical task of the present invention is achieved in the following manner: a method for preparing a maleic rosin-based hydrogel and its application, which is characterized by comprising the following steps:

[0007] (1) Maleic rosin is added to an appropriate amount of methanol, and then a certain amount of ethylenediamine is added, and stirred to react to obtain N-aminoethyl maleic rosin imide.

[0008] (2) Adding a proper amount of acryloyl chloride dropwise into a dichloromethane solution of N-aminoethyl maleic rosin imide at a certain temperature, stirring the reaction for a proper time, separating and purifying, and obtaining N-(N′-acryloyl)aminoethyl maleic rosin imide monomer.

[0009] (3) N-(N′-acryloyl)aminoethyl maleic rosin imide is added to an appropriate amount of toluene, and then a certain amount of initiator, emulsifier, water and dimethylaminopropyl acrylamide are added. The reaction temperature is set and the reaction is continued for a period of time. After the reaction is completed, the product is washed and dried to obtain a maleic rosin-based hydrogel.

[0010] Preferably, in step (1), the molar ratio of maleic rosin to ethylenediamine is 1:1 to 3. The mass ratio of methanol to maleic rosin is 1:2.5 to 5.5.

[0011] Preferably, in step (2), the temperature for adding acryloyl chloride is -5°C to 15°C. The molar ratio of N-aminoethyl maleic rosin imide to acryloyl chloride is 1:2 to 6. The stirring time is 3 to 6 hours.

[0012] Preferably, in step (3), the mass ratio of N-(N′-acryloyl)aminoethyl maleic rosin imide to dimethylaminopropyl acrylamide is 1:3.3-6.3. The volume ratio of toluene to water is 1:3-4. The initiators are azobisisobutyronitrile and potassium persulfate, and the amount of the initiator is 1%-10% of the total mass of N-(N′-acryloyl)aminoethyl maleic rosin imide and dimethylaminopropyl acrylamide. The emulsifiers are Tween 60 and Span 85. The reaction temperature is 60°C-75°C, and the reaction time is 6-12 hours.

[0013] Preferably, in step (1), the maleic rosin is derived from the modification of rosin from a renewable biomass resource.

[0014] By adopting the above scheme, the present invention has the following advantages:

[0015] The invention uses maleic rosin as a starting raw material, and its precursor comes from the modification of rosin, a renewable biomass resource, which has a wide source and a low price. While bringing economic benefits, it can reduce pollution and realize the comprehensive utilization of rosin, which has both economic and environmental benefits. The method has simple reaction operation, mild reaction conditions and low cost. The reaction has good specificity and subsequent separation and purification is relatively simple. Finally, the hydrogel product obtained by the method has good water absorption performance, can be used to remove toxic heavy metal cations in environmental water, can meet the application requirements of some special occasions, and has strong practical value and market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Chemical reaction principle diagram of maleic rosin-based hydrogel prepared by the present invention

[0017] Figure 2 Infrared spectrum of the maleic rosin-based hydrogel-related products prepared by the present invention DETAILED DESCRIPTION

[0018] The present invention is further illustrated by the following examples. Unless otherwise specified, all of them are conventional methods, and the experimental reagents and materials involved are conventional biochemical reagents and materials unless otherwise specified.

[0019] Example 1

[0020] (1) Add 10 g of maleic rosin to 70 ml of methanol, then add 1.5 g of ethylenediamine, stir to react, and filter to obtain N-aminoethyl maleic rosin imide.

[0021] (2) 5.84 g of acryloyl chloride was added dropwise into a dichloromethane solution of 10 g of N-aminoethylmaleic rosin imide at 0° C., and the mixture was stirred for reaction for 3 hours. The mixture was extracted with saturated brine, the organic phase was collected, and the organic phase was rotary evaporated to obtain N-(N′-acryloyl)aminoethylmaleic rosin imide monomer.

[0022] (3) Take 2.5g of N-(N′-acryloyl)aminoethyl maleic rosin imide, add 30ml of toluene, 15.623g of dimethylaminopropyl acrylamide, then add 200mg of azobisisobutyronitrile and 200mg of potassium persulfate, 0.8ml of Tween 60, 0.2ml of Span 85, and 100ml of pure water. Set the reaction temperature to 60°C, and continue the reaction for 8 hours with mechanical stirring. After the reaction is completed, the product is washed and dried with ethyl acetate to obtain a maleic rosin-based hydrogel.

[0023] Example 2

[0024] (1) Add 10 g of maleic rosin to 70 ml of methanol, then add 3 g of ethylenediamine, stir to react, and filter to obtain N-aminoethyl maleic rosin imide.

[0025] (2) 9.73 g of acryloyl chloride was added dropwise into a dichloromethane solution of 10 g of N-aminoethylmaleic rosin imide at 0° C., and the mixture was stirred for reaction for 5 hours. The mixture was extracted with saturated brine, the organic phase was collected, and the organic phase was rotary evaporated to obtain N-(N′-acryloyl)aminoethylmaleic rosin imide monomer.

[0026] (3) Take 1.5g of N-(N′-acryloyl)aminoethyl maleic rosin imide, add 30ml of toluene, 7.812g of dimethylaminopropyl acrylamide, then add 200mg of azobisisobutyronitrile and 200mg of potassium persulfate, 0.8ml of Tween 60, 0.2ml of Span 85, and 100ml of pure water. Set the reaction temperature to 60°C, and continue the reaction for 8 hours with mechanical stirring. After the reaction is completed, the product is washed and dried with ethyl acetate to obtain a maleic rosin-based hydrogel.

[0027] Example 3

[0028] (1) Add 10 g of maleic rosin to 70 ml of methanol, then add 4.5 g of ethylenediamine, stir to react, and filter to obtain N-aminoethyl maleic rosin imide.

[0029] (2) 11.679 g of acryloyl chloride was added dropwise into a dichloromethane solution of 10 g of N-aminoethylmaleic rosin imide at 0° C., and the mixture was stirred for reaction for 6 hours. The mixture was extracted with saturated brine, the organic phase was collected, and the organic phase was rotary evaporated to obtain N-(N′-acryloyl)aminoethylmaleic rosin imide monomer.

[0030] (3) Take 5g of N-(N′-acryloyl)aminoethyl maleic rosin imide, add 30ml of toluene, 15.623g of dimethylaminopropyl acrylamide, then add 200mg of azobisisobutyronitrile and 200mg of potassium persulfate, 0.8ml of Tween 60, 0.2ml of Span 85, and 100ml of pure water. Set the reaction temperature to 60°C, and continue the reaction for 12 hours with mechanical stirring. After the reaction is completed, the product is washed and dried with ethyl acetate to obtain a maleic rosin-based hydrogel.

[0031] Example 4

[0032] (1) Add 10 g of maleic rosin to 70 ml of methanol, then add 1.5 g of ethylenediamine, stir to react, and filter to obtain N-aminoethyl maleic rosin imide.

[0033] (2) 11.679 g of acryloyl chloride was added dropwise into a dichloromethane solution of 10 g of N-aminoethylmaleic rosin imide at 0° C., and the mixture was stirred for reaction for 6 hours. The mixture was extracted with saturated brine, the organic phase was collected, and the organic phase was rotary evaporated to obtain N-(N′-acryloyl)aminoethylmaleic rosin imide monomer.

[0034] (3) Take 5g of N-(N′-acryloyl)aminoethyl maleic rosin imide, add 30ml of toluene, 15.623g of dimethylaminopropyl acrylamide, then add 200mg of azobisisobutyronitrile and 200mg of potassium persulfate, 0.8ml of Tween 60, 0.2ml of Span 85, and 100ml of pure water. Set the reaction temperature to 60°C, and continue the reaction for 8 hours with mechanical stirring. After the reaction is completed, the product is washed and dried with ethyl acetate to obtain a maleic rosin-based hydrogel.

[0035] Example 5

[0036] This example uses synthesized maleic rosin-based hydrogel as raw material to treat Cu 2+ The initial concentration of simulated sewage is 50 mg / L, and the specific process is as follows:

[0037] Take 0.03 g of the prepared maleic rosin-based hydrogel and add it to 25 mL of Cu 2+ The wastewater was shaken at room temperature for 24 hours. After the treatment, it was filtered with a filter membrane and measured by atomic absorption.

[0038] The experiment showed that maleic rosin-based hydrogel adsorbs Cu 2+ The adsorption amount is 29.348 mg / g.

[0039] Example 6

[0040] This example uses synthesized maleic rosin-based hydrogel as raw material to treat Ni 2+ The initial concentration of simulated sewage is 50 mg / L, and the specific process is as follows:

[0041] Take 0.03 g of the prepared maleic rosin-based hydrogel and add it to 25 mL of Ni 2+ The wastewater was shaken at room temperature for 24 hours. After the treatment, it was filtered with a filter membrane and measured by atomic absorption.

[0042] The experiment showed that maleic rosin-based hydrogel adsorbs Ni 2+ The adsorption amount is 21.828 mg / g.

[0043] Example 7

[0044] This example uses the synthesized maleic rosin-based hydrogel as raw material to treat Pb 2+ The initial concentration of simulated sewage is 50 mg / L, and the specific process is as follows:

[0045] Take 0.03 g of the prepared maleic rosin-based hydrogel and add it to 25 mL of Pb 2+ The wastewater was shaken at room temperature for 24 hours. After the treatment, it was filtered with a filter membrane and measured by atomic absorption.

[0046] The experiment showed that maleic rosin-based hydrogel adsorbs Pb 2+ The adsorption amount is 23.923 mg / g.

Claims

1. A method for preparing a maleic rosin-based hydrogel and its application, characterized in that It includes the following steps: (1) Maleic rosin is added to an appropriate amount of methanol, and then a certain amount of ethylenediamine is added, and stirred to react to obtain N-aminoethyl maleic rosin imide. (2) Adding a proper amount of acryloyl chloride dropwise into a dichloromethane solution of N-aminoethyl maleic rosin imide at a certain temperature, stirring the reaction for a proper time, separating and purifying, and obtaining N-(N′-acryloyl)aminoethyl maleic rosin imide monomer. (3) N-(N′-acryloyl)aminoethyl maleic rosin imide is added to an appropriate amount of toluene, and then a certain amount of initiator, emulsifier, water and dimethylaminopropyl acrylamide are added. The reaction temperature is set and the reaction is continued for a period of time. After the reaction is completed, the product is washed and dried to obtain a maleic rosin-based hydrogel.

2. The method for preparing a maleic rosin-based hydrogel according to claim 1, characterized in that: In step (1), the molar ratio of maleic rosin to ethylenediamine is 1:1 to 3. The mass ratio of methanol to maleic rosin is 1:2.5 to 5.

5.

3. The method for preparing a maleic rosin-based hydrogel according to claim 1, characterized in that: In step (2), the temperature for adding acryloyl chloride is -5°C to 15°C. The molar ratio of N-aminoethyl maleic rosin imide to acryloyl chloride is 1:2 to 6. The stirring time is 3 to 6 hours.

4. The method for preparing a maleic rosin-based hydrogel according to claim 1, characterized in that: In step (3), the mass ratio of N-(N′-acryloyl)aminoethyl maleic rosin imide to dimethylaminopropyl acrylamide is 1:3.3-6.

3. The volume ratio of toluene to water is 1:3-4. The initiators are azobisisobutyronitrile and potassium persulfate, and the amount of the initiator is 1%-10% of the total mass of N-(N′-acryloyl)aminoethyl maleic rosin imide and dimethylaminopropyl acrylamide. The emulsifiers are Tween 60 and Span 85. The reaction temperature is 60°C-75°C, and the reaction time is 6-12 hours.

5. The method for preparing a maleic rosin-based hydrogel according to claim 1, characterized in that: In step (1), the maleic rosin is derived from the modification of rosin from renewable biomass resources.

Images