CN113105639B - Humic acid-polyethylene glycol grafted polyacrylic acid composite material and preparation method thereof - Google Patents
Humic acid-polyethylene glycol grafted polyacrylic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of soil improvement of water-retaining agents, and discloses a humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material, which has better water retention performance and salt tolerance compared with a single polyacrylic acid water-retaining agent, carboxyl groups of polyacrylic acid have enough affinity to moisture, and when the humic acid is copolymerized with humic acid, the humic acid can influence a network structure in the material, so that the water absorption rate of the water-retaining agent is improved, and meanwhile, the humic acid also has various hydrophilic groups, so that the ion concentration of electrolyte solution in the water-retaining agent is always greater than the external concentration, thereby forming osmotic pressure, increasing the water absorption capacity of the composite water-retaining agent.
Description
Technical Field
The invention relates to the technical field of soil improvement by a water-retaining agent, in particular to a humic acid-polyethylene glycol grafted polyacrylic acid composite material and a preparation method thereof.
Background
At present, sustainable development of agriculture and forestry is regarded as a national strategy in all countries of the world, but due to drought, water resource shortage and soil desertification, the sustainable development of agriculture and forestry is severely challenged, soil is a 'warm bed' for plant growth, which is well known as a basis of a green space system, endosperm of seeds is stored with nutrients which can provide energy for embryo growth, normal growth of plants depends on balancing water metabolism of plants, a key factor for plant survival is water in soil, and clay soil is compact in structure, poor in ventilation, loose in sandy soil structure and good in ventilation, but insufficient in water retention, influences middle and later growth of plants, although deep ploughing can improve porosity of soil and water conductivity, water retention capacity of soil is relatively weak under drought conditions, and a water retention agent plays a vital role in promoting sustainable development of agriculture and forestry in terms of water retention, drought resistance and water conservation, and addition of water retention agent in sandy soil can improve not only porosity and porosity of soil, but also can improve soil and root system accumulation capacity and promote plant germination capacity.
The main component of the water-retaining agent is super absorbent resin, is a slightly crosslinked hydrophilic polymer, and has the action mechanism that the polymer absorbs natural water through a network structure of hydrophilic groups, swells after absorbing the water, and then slowly releases the water into soil, wherein the water-retaining agent mainly can be divided into three types: the water retention agent is prepared from natural raw materials (such as cellulose type and humic acid type), wherein the semisynthetic water retention agent has degradability of the natural raw materials and high efficiency of the synthetic water retention agent, acrylic acid is an unsaturated organic acid, contains double bonds and carboxyl structures, has excellent polymerization and esterification capacity, is a good intermediate, and is a high-efficiency water retention agent, but has high production cost, so that the price becomes an important obstacle for popularization and use of the water retention agent, and is influenced by antagonism of various ions in soil.
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a humic acid-polyethylene glycol grafted polyacrylic acid composite material and a preparation method thereof, which solve the problems of low water retention performance and poor salt tolerance of a single humic acid water-retaining agent.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material comprises the following steps of:
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5-5, stirring uniformly, filling nitrogen, esterifying at 30-60 ℃ for 1-3 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2-3, continuing to react, precipitating by using diethyl ether after the reaction is finished, and filtering to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium bisulfate and acrylic acid for grafting reaction, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally performing suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine, uniformly stirring, carrying out modification reaction at 20-50 ℃ for 8-16h, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide, and carrying out a synthetic reaction to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimidized polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol, refluxing under nitrogen atmosphere, performing ammonolysis reaction, dripping diethyl ether after ethanol is evaporated, generating precipitate, dissolving solid in dichloromethane, suction filtering, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 20-40 ℃ for 1-3h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Preferably, in the step (2), the mass ratio of the acrylic chloride modified polyethylene glycol, the potassium persulfate, the sodium persulfate and the acrylic acid is 100:5-10:1-2:10-20.
Preferably, the grafting reaction in the step (2) is carried out at a reaction temperature of 50-80 ℃ for a reaction time of 4-8t.
Preferably, in the step (3), polyacrylic acid is grafted with polyethylene glycol, and the mass ratio of the tosyl chloride to the triethylamine is 100:8-16:80-120.
Preferably, the mass ratio of the tosylated polyethylene glycol grafted polyacrylic acid to the phthalimide potassium salt in the step (4) is 100:20-35:10-30.
Preferably, the reaction temperature of the synthesis reaction in the step (4) is 170-200 ℃ and the reaction time is 10-16h.
Preferably, in the step (5), the phthalimidized polyethylene glycol grafted polyacrylic acid and N 2 H 4 The mass ratio of the two components is 100:8-25.
Preferably, the reaction temperature of the ammonolysis reaction in the step (5) is 170-200 ℃ and the reaction time is 4-8h.
Preferably, in the step (6), the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:800-1200:60-100:10-30.
Preferably, the reaction temperature of the amide reaction in the step (6) is 30-60 ℃ and the reaction time is 2-6h.
(III) beneficial technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material is prepared from polyethylene glycol serving as a raw material through esterification reaction with acrylic chloride, and triethylamine serving as an acid binding agent, so that esterification efficiency is improved, acrylic chloride modified polyethylene glycol is obtained, then acrylic chloride modified polyethylene glycol serving as a raw material is subjected to inverse microemulsion copolymerization reaction with acrylic acid in a redox initiation system of potassium persulfate-sodium persulfate, polyethylene glycol grafted polyacrylic acid is obtained, and then triethylamine serving as the acid binding agent is used, hydroxyl at the residual end of the polyethylene glycol grafted polyacrylic acid is subjected to esterification reaction, tosyl is introduced, tosylated polyethylene glycol grafted polyacrylic acid is obtained, and then the tosylated polyethylene glycol grafted polyacrylic acid is reacted with phthalimide potassium according to a primary amine synthesis reaction of Gebuhelter, so that phthalimide grafted polyacrylic acid is generated, then amino-terminated polyethylene glycol grafted polyacrylic acid is obtained through ammonolysis reaction with hydrazine hydrate in an ethanol solution, and then the humic acid is subjected to acyl chloride reaction with the generated intermediate product, and then amino-terminated polyethylene glycol grafted polyacrylic acid is subjected to amidation reaction, so that an amido group is generated, and the water-retaining property of the water-retaining agent composite material is better than that the water-retaining agent material can be prepared in a water retention method.
Compared with a single polyacrylic acid water-retaining agent, the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material has better water retention performance and salt tolerance, carboxyl groups of polyacrylic acid have enough affinity to water, when the polyacrylic acid is copolymerized with humic acid to form the composite water-retaining agent, the network structure inside the material can be influenced, the formed novel space network structure can increase the hydrophilicity of the composite material, the water absorption rate of the water-retaining agent is improved, meanwhile, humic acid also has various hydrophilic groups, the hydrophilicity of the water-retaining agent can be increased in the composite water-retaining agent, the network structure of the material can be changed, the groups on molecular chains of the composite water-retaining agent are dissociated when the composite water-retaining agent swells with water, the ionic concentration of electrolyte solution in the water-retaining agent is always higher than the external concentration, so that osmotic pressure is formed, the water absorption capacity of the composite water-retaining agent is increased, the ionic concentration of the water-retaining agent is reduced, the water absorption capacity of the composite water-retaining agent is reduced, but the hydrophilic groups on the surface of the hydrophilic group are not dissociated, the ionic groups are contained in the composite water-retaining agent, the ionic water-retaining agent is uniformly distributed in the composite water-retaining agent, the water-retaining agent is further improved, and the water-retaining agent has the water-retaining effect of the water-retaining agent is increased, and the water-retaining agent has the water-retaining effect of the water-retaining agent is more evenly distributed in the water-retaining agent.
Detailed Description
In order to achieve the above object, the present invention provides the following specific embodiments and examples: the preparation method of the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material comprises the following steps:
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5-5, stirring uniformly, filling nitrogen, esterifying at 30-60 ℃ for 1-3 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2-3, continuing to react, precipitating by using diethyl ether after the reaction is finished, and filtering to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving the acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen sulfate and acrylic acid according to the mass ratio of 100:5-10:1-2:10-20, performing grafting reaction at 50-80 ℃ for 4-8t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally performing suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:8-16:80-120 between the polyethylene glycol grafted polyacrylic acid and the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 20-50 ℃ for 8-16 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to neutrality, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:20-35:10-30, and carrying out a synthetic reaction at 170-200 ℃ for 10-16 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:8-25, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 170-200 ℃ for 4-8h, dripping diethyl ether after ethanol evaporation is completed, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 20-40 ℃ for 1-3h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 30-60 ℃ for 2-6h, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid, thionyl chloride, amino-terminated polyethylene glycol grafted polyacrylic acid and triethylamine is 100:800-1200:60-100:10-30, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite material.
Example 1
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5, stirring uniformly, filling nitrogen, esterifying at 30 ℃ for 1h, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2, continuing the reaction, precipitating by using diethyl ether after the reaction is finished, and performing suction filtration to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen persulfate and acrylic acid according to the mass ratio of 100:5:1:10 with the acrylic chloride modified polyethylene glycol, carrying out grafting reaction at 50 ℃ for 4t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally carrying out suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:8:80 with the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 20 ℃ for 8 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:20:10, and carrying out a synthetic reaction at 170 ℃ for 10 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:8, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 170 ℃ for 4 hours, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 20 ℃ for 1h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 30 ℃ for 2h, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:800:60:10, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Example 2
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:4, stirring uniformly, filling nitrogen, esterifying at 40 ℃ for 1.5 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2.2, continuing the reaction, separating out by using diethyl ether after the reaction is finished, and filtering to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium bisulfate and acrylic acid according to the mass ratio of 100:6:1.2:12 with the acrylic chloride modified polyethylene glycol, carrying out grafting reaction at 55 ℃ for 5t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally carrying out suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:10:90 with the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 30 ℃ for 10 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:25:15, and carrying out a synthetic reaction at 180 ℃ for 12 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:10, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 180 ℃ for 5 hours, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under the condition of stirring, carrying out acyl chloride reaction at 25 ℃ for 1.5h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, methylene dichloride and triethylamine, carrying out amidation reaction at 40 ℃ for 3h, and removing unreacted methylene dichloride and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:900:70:15, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Example 3
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:4.5, stirring uniformly, filling nitrogen, esterifying at 50 ℃ for 2 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2.8, continuing the reaction, separating out by using diethyl ether after the reaction is finished, and filtering to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen sulfate and acrylic acid according to the mass ratio of 100:8:1.6:16 with the acrylic chloride modified polyethylene glycol, carrying out grafting reaction at 70 ℃ for 6t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally carrying out suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:12:100 with the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 40 ℃ for 12 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:30:20, and carrying out a synthetic reaction at 190 ℃ for 12 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:20, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 190 ℃ for 6 hours, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 30 ℃ for 2 hours, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 50 ℃ for 4 hours, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:1000:80:20, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Example 4
(1) Dissolving polyethylene glycol and acrylic chloride in methylene dichloride according to the mass ratio of 100:5, stirring uniformly, filling nitrogen, esterifying at 60 ℃ for 3 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:3, continuing the reaction, separating out by using diethyl ether after the reaction is finished, and performing suction filtration to obtain acrylic chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen persulfate and acrylic acid according to the mass ratio of 100:10:2:20 with the acrylic chloride modified polyethylene glycol, carrying out grafting reaction at 80 ℃ for 8t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally carrying out suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:16:120 between the polyethylene glycol grafted polyacrylic acid and the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 50 ℃ for 16 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:35:30, and carrying out a synthetic reaction at 200 ℃ for 16 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:25, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 200 ℃ for 8 hours, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 40 ℃ for 3h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 60 ℃ for 6h, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:1200:100:30, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Comparative example 1
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3, stirring uniformly, filling nitrogen, esterifying at 24 ℃ for 0.8h, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:1.5, continuing the reaction, precipitating by using diethyl ether after the reaction is finished, and filtering to obtain acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium bisulfate and acrylic acid according to the mass ratio of 100:4:0.8:8, performing grafting reaction at 40 ℃ for 3.2t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally performing suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:6:60 between the polyethylene glycol grafted polyacrylic acid and the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out modification reaction at 16 ℃ for 6 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into the extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying the obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:15:8, and carrying out a synthetic reaction at 150 ℃ for 8 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:6, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 150 ℃ for 3.2h, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 16 ℃ for 0.8h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 24 ℃ for 1.5h, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid, thionyl chloride, amino-terminated polyethylene glycol grafted polyacrylic acid and triethylamine is 100:600:50:8, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Comparative example 2
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:6, stirring uniformly, filling nitrogen, esterifying at 72 ℃ for 3.6 hours, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:3.6, continuing the reaction, precipitating by using diethyl ether after the reaction is finished, and filtering to obtain the acryloyl chloride modified polyethylene glycol;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen sulfate and acrylic acid according to the mass ratio of 100:12:2.4:25 with the acrylic chloride modified polyethylene glycol, carrying out grafting reaction at 96 ℃ for 10t, adding sodium chloride for precipitation after the reaction is finished, washing a solid product with ethanol, and finally carrying out suction filtration and drying to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine according to the mass ratio of 100:20:145 between the polyethylene glycol grafted polyacrylic acid and the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out a modification reaction at 6 ℃ for 20 hours, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into an extract to neutralize to be neutral, concentrating, precipitating by using diethyl ether, and drying an obtained solid product to obtain the tosylated polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide according to the mass ratio of 100:42:36, and carrying out a synthetic reaction at 240 ℃ for 19 hours to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol according to the mass ratio of 100:30, refluxing under nitrogen atmosphere, carrying out ammonolysis reaction at 190 ℃ for 10 hours, dripping diethyl ether after ethanol evaporation is finished, generating precipitate, dissolving solid in dichloromethane, carrying out suction filtration, and drying to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 48 ℃ for 3.6h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction at 72 ℃ for 7h, removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished, wherein the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine is 100:1450:120:36, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
And placing 0.5g of the composite water-retaining agent in 500mL of deionized water, standing, measuring the mass of the composite water-retaining agent after natural swelling is saturated, and calculating the water absorption to represent the water retention performance of the composite water-retaining agent.
| Examples | Mass before treatment (g) | Post-treatment mass (g) | Water retention rate (g/g) |
| Example 1 | 0.5 | 91.42 | 181.84 |
| Example 2 | 0.5 | 116.64 | 232.28 |
| Example 3 | 0.5 | 138.25 | 275.50 |
| Example 4 | 0.5 | 98.68 | 196.36 |
| Comparative example 1 | 0.5 | 58.24 | 115.48 |
| Comparative example 2 | 0.5 | 62.54 | 124.08 |
And (3) placing 0.5g of the composite water-retaining agent into 500mL of NaCl solution with the concentration of 0.9%, standing, measuring the mass of the composite water-retaining agent after natural swelling and saturation, and calculating the water absorption to represent the water retention performance of the composite water-retaining agent.
| Examples | Mass before treatment (g) | Post-treatment mass (g) | Water retention rate (g/g) |
| Example 1 | 0.5 | 30.68 | 60.36 |
| Example 2 | 0.5 | 55.25 | 109.5 |
| Example 3 | 0.5 | 46.64 | 92.28 |
| Example 4 | 0.5 | 28.42 | 55.84 |
| Comparative example 1 | 0.5 | 16.84 | 32.68 |
| Comparative example 2 | 0.5 | 14.24 | 27.48 |
Claims (1)
1. A humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material is characterized in that: the preparation method of the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material comprises the following steps:
(1) Dissolving polyethylene glycol and acrylic chloride in dichloromethane according to the mass ratio of 100:3.5-5, stirring uniformly, charging nitrogen, esterifying at 30-60 ℃ for 1-3h, adding triethylamine according to the mass ratio of polyethylene glycol to triethylamine of 100:2-3, continuing to react, and obtaining acrylic chloride modified polyethylene glycol after the reaction is finished;
(2) Dissolving acrylic chloride modified polyethylene glycol in deionized water, adding potassium persulfate, sodium hydrogen sulfate and acrylic acid for grafting reaction, adding sodium chloride for precipitation after the reaction is finished, and washing a solid product with ethanol to obtain polyethylene glycol grafted polyacrylic acid;
(3) Dissolving polyethylene glycol grafted polyacrylic acid in dichloromethane, adding p-toluenesulfonyl chloride and triethylamine, uniformly stirring, carrying out modification reaction at 20-50 ℃ for 8-16h, extracting by using hydrochloric acid after the reaction is finished, adding sodium carbonate into the extract to neutralize to be neutral, concentrating, and precipitating by using diethyl ether to obtain toluenesulfonyl polyethylene glycol grafted polyacrylic acid;
(4) Dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide, and carrying out a synthetic reaction to obtain the phthalimide polyethylene glycol grafted polyacrylic acid;
(5) Dispersing phthalimidized polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol, refluxing under nitrogen atmosphere, performing ammonolysis reaction, dripping diethyl ether after ethanol is evaporated, generating precipitate, dissolving solid in dichloromethane, and performing suction filtration to obtain amino-terminated polyethylene glycol grafted polyacrylic acid;
(6) Adding humic acid into a reaction bottle, adding thionyl chloride under stirring, performing acyl chloride reaction at 20-40 ℃ for 1-3h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, performing amidation reaction, and removing unreacted dichloromethane and triethylamine under reduced pressure after the reaction is finished to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material; in the step (3), polyacrylic acid is grafted by polyethylene glycol, and the mass ratio between the tosyl chloride and the triethylamine is 100:8-16:80-120;
the mass ratio of the tosylated polyethylene glycol grafted polyacrylic acid to the phthalimide potassium salt dissolved in the N, N-dimethylformamide in the step (4) is 100:20-35:10-30;
the mass ratio of humic acid to thionyl chloride to amino-terminated polyethylene glycol grafted polyacrylic acid to triethylamine in the step (6) is 100:800-1200:60-100:10-30;
in the step (2), the mass ratio of the acrylic chloride modified polyethylene glycol to the potassium persulfate to the sodium persulfate to the acrylic acid is 100:5-10:1-2:10-20; the mass ratio of the phthalimidized polyethylene glycol grafted polyacrylic acid to the hydrazine hydrate in the step (5) is 100:8-25;
the reaction temperature of the grafting reaction in the step (2) is 50-80 ℃ and the reaction time is 4-8t;
the reaction temperature of the synthesis reaction in the step (4) is 170-200 ℃ and the reaction time is 10-16h;
the reaction temperature of the ammonolysis reaction in the step (5) is 170-200 ℃ and the reaction time is 4-8h;
the reaction temperature of the amide reaction in the step (6) is 30-60 ℃ and the reaction time is 2-6h.
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