CN113105639A - 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 water-retaining agent for improving soil, and discloses a humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material, compared with a single polyacrylic acid water-retaining agent, the composite water-retaining agent has better water retention property and salt tolerance, the carboxyl group of polyacrylic acid has enough affinity to water, the copolymerization with humic acid can affect the internal network structure of the material, improve the water absorption rate of the water-retaining agent, meanwhile, humic acid also has various hydrophilic groups, so that the ion concentration of the electrolyte solution in the water-retaining agent is always higher than the external concentration, thereby forming osmotic pressure, increasing the water absorption capacity of the composite water-retaining agent, in a solution containing sodium chloride ions, the surface of humic acid contains part of non-dissociative hydrophilic functional groups, so that the water absorption capacity of the composite water-retaining agent in a salt solution is increased, and the water retention performance of the composite water-retaining agent obtained by grafting is further improved.
Description
Technical Field
The invention relates to the technical field of water-retaining agents for improving soil, and particularly relates to a humic acid-polyethylene glycol grafted polyacrylic acid composite material and a preparation method thereof.
Background
At present, the sustainable development of agriculture and forestry is regarded as a national strategy in all countries in the world, but due to drought, water resource shortage and soil desertification, the sustainable development of agriculture and forestry is seriously challenged, as is well known, soil is a 'hotbed' for plant growth, is the basis of a green space system, nutrients capable of providing energy for embryo growth are stored in endosperm of seeds, the normal growth of plants depends on balancing the water metabolism of plants, the key factor for plant survival is water in the soil, clay soil is compact in structure, poor in ventilation, loose in sandy soil structure and good in ventilation, but insufficient in water retention, influences the growth of plants in the middle and later periods, although deep ploughing can improve the porosity and water conductivity of the soil, the water retention capacity of the soil under drought conditions is relatively weak, and in the aspects of water and soil conservation, drought resistance and water conservation, the water-retaining agent plays a vital role in promoting the sustainable development of agriculture and forestry, and the addition of the water-retaining agent in sandy soil can improve the porosity and porosity of the soil, improve the water accumulation capacity, and promote the plant root system, seed germination and plant survival capacity.
The main component of the water retention agent is super absorbent resin which is a slightly crosslinked hydrophilic polymer, the action mechanism is that the polymer absorbs natural water through a network structure of hydrophilic groups, swells after absorbing water and then slowly releases water into soil, and the water retention agent can be mainly divided into three types: synthetic type (such as polyacrylate, polyacrylamide and polyacrylonitrile), semi-synthetic type (such as starch-polyacrylonitrile, starch-polyacrylamide and starch-polyacrylic acid) and natural raw materials (such as cellulose type and humic acid type), wherein, the semi-synthetic water-retaining agent has both the degradability of the natural raw materials and the high efficiency of the synthetic water-retaining agent, acrylic acid is an unsaturated organic acid, contains double bond and carboxyl structure inside, has excellent polymerization and esterification capabilities, is a good intermediate, the acrylic water-retaining agent is a high-efficiency water-retaining agent, but the production cost is high, so that the price becomes an important obstacle for popularization and use, and simultaneously, the water-retaining performance in saline-alkali soil is sharply reduced under the influence of the antagonism of various ions in the soil, humic acid is a material of the natural water-retaining agent, in the soil remediation process, can improve the effect between the soil, promote the dispersion between the soil granule, increase the gas permeability and the moisture retention of soil, for plant roots, seed germination and plant survive and create good condition, moreover, humic acid can also play fluffy effect to the arable layer soil, prevent the salt along with the ascending action in capillary hole along with moisture, reduce soil salt content, reduce the accumulative action of salt, alleviate the injury to plant seedling, promote plant seedling to moisture, nutrient substance's absorption, increase the survival rate of seedling, through the mode of free radical solution polymerization, with humic acid and acrylic acid graft copolymerization, the cross-linking thing of formation is a water retaining agent that has excellent performance.
Technical problem to be solved
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, and solves the problems of low water retention performance and poor salt tolerance of a single humic acid water retention agent.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the carbon nanotube-polyethylene glycol grafted chitosan membrane composite material comprises the following steps:
(1) dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5-5, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 30-60 ℃ for 1-3h, adding triethylamine according to the mass ratio of 100:2-3 of polyethylene glycol and triethylamine, continuing to react, after the reaction is finished, separating out diethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium hydrogen persulfate and acrylic acid to perform grafting reaction, after the reaction is finished, adding sodium chloride to perform precipitation, 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, stirring uniformly, performing modification reaction at 20-50 ℃, reacting for 8-16h, extracting with hydrochloric acid after the reaction is finished, adding sodium carbonate into extract liquor to neutralize to neutrality, concentrating, precipitating with 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 for synthetic reaction to obtain phthalimided polyethylene glycol grafted polyacrylic acid;
(5) dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol, refluxing in nitrogen atmosphere, carrying out ammonolysis reaction, after the ethanol is evaporated, dripping ether to generate precipitate, dissolving the 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 20-40 ℃, reacting for 1-3h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent.
Preferably, in the step (2), the mass ratio of the acryloyl chloride modified polyethylene glycol to the potassium persulfate to the sodium persulfate to the acrylic acid is 100:5-10:1-2: 10-20.
Preferably, the reaction temperature of the grafting reaction in the step (2) is 50-80 ℃, and the reaction time is 4-8 t.
Preferably, in the step (3), the polyacrylic acid is grafted by polyethylene glycol, and the mass ratio of the p-toluenesulfonyl chloride to the triethylamine is 100:8-16: 80-120.
Preferably, the mass ratio of the tosylated polyethylene glycol grafted polyacrylic acid to the potassium phthalimide 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 10-16 h.
Preferably, the phthalimide polyethylene glycol grafts polyacrylic acid with N in the step (5)2H4The mass ratio of the components is 100: 8-25.
Preferably, the ammonolysis reaction in the step (5) has a reaction temperature of 170-200 ℃ and a reaction time of 4-8 h.
Preferably, in the step (6), the mass ratio of the humic acid to the thionyl chloride to the amino-terminated polyethylene glycol grafted polyacrylic acid to the 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 2-6 h.
(III) advantageous 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 takes polyethylene glycol as a raw material, generates esterification reaction with acryloyl chloride, takes triethylamine as an acid-binding agent, improves esterification efficiency to obtain acryloyl chloride modified polyethylene glycol, then takes the acryloyl chloride modified polyethylene glycol as a raw material, generates reverse microemulsion copolymerization reaction with acrylic acid in an oxidation reduction initiation system of potassium persulfate-sodium hydrogen persulfate to obtain polyethylene glycol grafted polyacrylic acid, then uses triethylamine as an acid-binding agent, performs hydroxyl esterification reaction at the remaining end of the polyethylene glycol grafted polyacrylic acid, introduces tosyl to obtain tosylated polyethylene glycol grafted polyacrylic acid, then reacts with phthalimide potassium according to a drape Ruire primary amine synthesis reaction to generate phthaloylimide grafted polyethylene glycol grafted polyacrylic acid, and then carrying out ammonolysis reaction with hydrazine hydrate in an ethanol solution to obtain amino-terminated polyethylene glycol grafted polyacrylic acid, then carrying out acyl chloride reaction on humic acid and thionyl chloride, carrying out amidation reaction on the generated intermediate product and amino of the amino-terminated polyethylene glycol grafted polyacrylic acid to generate an amide group, and obtaining the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
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, the carboxyl group of polyacrylic acid has enough affinity to water, and when the polyacrylic acid is copolymerized with humic acid to form the composite water-retaining agent, the composite water-retaining agent can influence the net structure in the material, the formed novel space net structure can increase the hydrophilicity of the composite material and improve the water absorption rate of the water-retaining agent, meanwhile, the humic acid also has various hydrophilic groups, in the composite water-retaining agent, the hydrophilicity of the water-retaining agent can be increased, the net structure of the material can be changed, so that when the composite water-retaining agent swells in water, the groups on a molecular chain are dissociated to release partial electrolyte, and the ion concentration of an electrolyte solution in the water-retaining agent is always greater than the external concentration, thereby form osmotic pressure, the water absorbing capacity of compound water retaining agent has been increased, in the solution that contains the sodium chloride ion, the inside and outside ion concentration of water retaining agent reduces, osmotic pressure weakens, cause the water absorbing capacity of water retaining agent to reduce, but in the numerous hydrophilic group on humic acid surface, contain the hydrophilic functional group of part non-dissociation type, this part receives ionic solution solubility influence relatively less, thereby the water absorbing capacity of compound water retaining agent in the salt solution has been increased, in the compound water retaining agent that obtains through the mode of grafting, humic acid can evenly distributed in water retaining agent composite material, effectual and polyacrylic acid form synergistic action, the water retaining property of compound water retaining agent has further been increased, simultaneously, the polyethylene glycol of grafting is a hydrophilicity long chain, increase the hydrophilicity of compound water retaining agent.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a 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, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 30-60 ℃ for 1-3h, adding triethylamine according to the mass ratio of 100:2-3 of polyethylene glycol and triethylamine, continuing to react, after the reaction is finished, separating out diethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:5-10:1-2:10-20 to the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at the temperature of 50-80 ℃, wherein the reaction time is 4-8t, after the reaction is finished, adding sodium chloride for precipitation, 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 100:8-16:80-120 of the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out modification reaction at 20-50 ℃, wherein the reaction time is 8-16h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into extract liquor to neutralize to neutrality, then concentrating, precipitating by using 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 100:20-35:10-30, and carrying out synthetic reaction at the temperature of 170-200 ℃ for 10-16h to obtain the phthalimidated 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 in a nitrogen atmosphere, carrying out ammonolysis reaction at the temperature of 170-200 ℃, wherein the reaction time is 4-8h, dropping ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 20-40 ℃, reacting for 1-3h, removing unreacted thionyl chloride under reduced pressure after the reaction is finished, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 30-60 ℃, reacting 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 to triethylamine is 100:800-1200:60-100:10-30, and drying to obtain the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
Example 1
(1) Dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 30 ℃ for 1h, then adding triethylamine according to the mass ratio of 100:2 of polyethylene glycol to triethylamine, continuing the reaction, after the reaction is finished, separating out ethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:5:1:10 to the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 50 ℃, wherein the reaction time is 4t, after the reaction is finished, adding sodium chloride for precipitation, 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 of the polyethylene glycol grafted polyacrylic acid, uniformly stirring, performing modification reaction at 20 ℃, wherein the reaction time is 8h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into extract liquor to neutralize to neutrality, then 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 100:20:10, and carrying out synthetic reaction at 170 ℃ for 10 hours to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 170 ℃, wherein the reaction time is 4h, dripping diethyl ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 20 ℃, reacting for 1h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 30 ℃, reacting for 2h, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, wherein the mass ratio of humic acid, thionyl chloride, 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, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 40 ℃ for 1.5h, adding triethylamine according to the mass ratio of 100:2.2 of polyethylene glycol to triethylamine, continuously reacting, after the reaction is finished, separating out diethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:6:1.2:12 to the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 55 ℃, wherein the reaction time is 5t, after the reaction is finished, adding sodium chloride for precipitation, 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 of the polyethylene glycol grafted polyacrylic acid, uniformly stirring, performing modification reaction at 30 ℃, wherein the reaction time is 10 hours, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into extract liquor to neutralize to be neutral, then 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 100:25:15, and carrying out synthetic reaction at 180 ℃ for 12h to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 180 ℃, reacting for 5h, dropping ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 ℃, reacting for 1.5h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 40 ℃, reacting for 3h, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, wherein the mass ratio of humic acid, thionyl chloride, 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, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 50 ℃ for 2h, adding triethylamine according to the mass ratio of 100:2.8 of polyethylene glycol to triethylamine, continuously reacting, after the reaction is finished, separating out diethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:8:1.6:16 to the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 70 ℃, wherein the reaction time is 6t, after the reaction is finished, adding sodium chloride for precipitation, 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 the polyethylene glycol grafted polyacrylic acid to the polyethylene glycol grafted polyacrylic acid of 100:12:100, uniformly stirring, performing modification reaction at 40 ℃, wherein the reaction time is 12h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into an extract liquor to neutralize to neutrality, then 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 100:30:20, and carrying out synthetic reaction at 190 ℃ for 12h to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 190 ℃, reacting for 6h, dropping ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 30 ℃, reacting for 2h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 50 ℃, reacting for 4h, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, wherein the mass ratio of humic acid, thionyl chloride, 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 acryloyl chloride in dichloromethane according to the mass ratio of 100:5, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 60 ℃ for 3 hours, then adding triethylamine according to the mass ratio of 100:3 of polyethylene glycol to triethylamine, continuing the reaction, after the reaction is finished, separating out ethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:10:2:20 of the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 80 ℃, wherein the reaction time is 8t, after the reaction is finished, adding sodium chloride for precipitation, 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 of the polyethylene glycol grafted polyacrylic acid, uniformly stirring, carrying out modification reaction at 50 ℃, wherein the reaction time is 16h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into extract liquor to neutralize to neutrality, then concentrating, precipitating by using 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 100:35:30, and carrying out synthetic reaction at 200 ℃ for 16h to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 200 ℃, wherein the reaction time is 8h, dripping diethyl ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 40 ℃ for 3h, after the reaction is finished, decompressing and removing unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 60 ℃ for 6h, after the reaction is finished, decompressing and removing unreacted dichloromethane and triethylamine, wherein the mass ratio of humic acid, thionyl chloride, 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, uniformly stirring, introducing nitrogen, performing esterification reaction at 24 ℃ for 0.8h, adding triethylamine according to the mass ratio of 100:1.5 of polyethylene glycol to triethylamine, continuously reacting, after the reaction is finished, separating out diethyl ether, and performing suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:4:0.8:8 of the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 40 ℃, wherein the reaction time is 3.2t, after the reaction is finished, adding sodium chloride for precipitation, 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 100:6:60 of the polyethylene glycol grafted polyacrylic acid to the polyethylene glycol grafted polyacrylic acid, stirring uniformly, carrying out modification reaction at 16 ℃, wherein the reaction time is 6h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate to an extract liquor to neutralize to neutrality, then 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 synthetic reaction at 150 ℃ for 8 hours to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 150 ℃, wherein the reaction time is 3.2h, dripping ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 16 ℃ for 0.8h, carrying out reduced pressure to remove unreacted thionyl chloride after the reaction is finished, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 24 ℃ for 1.5h, carrying out reduced pressure to remove unreacted dichloromethane and triethylamine after the reaction is finished, wherein the mass ratio of humic acid, thionyl chloride, amino-terminated polyethylene glycol grafted polyacrylic acid to 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, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 72 ℃ for 3.6h, then adding triethylamine according to the mass ratio of 100:3.6 of polyethylene glycol to triethylamine, continuing to react, after the reaction is finished, separating out diethyl ether, and carrying out suction filtration to obtain acryloyl chloride modified polyethylene glycol;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid according to the mass ratio of 100:12:2.4:25 to the acryloyl chloride modified polyethylene glycol, carrying out grafting reaction at 96 ℃, wherein the reaction time is 10t, after the reaction is finished, adding sodium chloride for precipitation, 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 to the polyethylene glycol grafted polyacrylic acid, uniformly stirring, performing modification reaction at 6 ℃, wherein the reaction time is 20h, after the reaction is finished, extracting by using hydrochloric acid, adding sodium carbonate into extract liquor to neutralize to neutrality, then 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 100:42:36, and carrying out synthetic reaction at 240 ℃ for 19h to obtain phthalimided 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 in nitrogen atmosphere, carrying out ammonolysis reaction at 190 ℃, wherein the reaction time is 10h, dripping diethyl ether after the ethanol is evaporated, generating a precipitate, dissolving the 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 stirring condition, carrying out acyl chloride reaction at 48 ℃, reacting for 3.6h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction at 72 ℃, reacting for 7h, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, wherein the mass ratio of humic acid, thionyl chloride, 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 (3) 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 saturation, and calculating the water absorption rate to represent the water retention performance of the composite water-retaining agent.
| Examples | Mass before treatment (g) | Processed 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 in 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 rate to represent the water-retaining property of the composite water-retaining agent.
| Examples | Mass before treatment (g) | Processed 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 (10)
1. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material is characterized in that: the preparation method of the carbon nano tube-polyethylene glycol grafted chitosan membrane composite material comprises the following steps:
(1) dissolving polyethylene glycol and acryloyl chloride in dichloromethane according to the mass ratio of 100:3.5-5, uniformly stirring, introducing nitrogen, carrying out esterification reaction at 30-60 ℃ for 1-3h, adding triethylamine according to the mass ratio of 100:2-3 of polyethylene glycol and triethylamine, continuing to react, and obtaining acryloyl chloride modified polyethylene glycol after the reaction is finished;
(2) dissolving acryloyl chloride modified polyethylene glycol in deionized water, then adding potassium persulfate, sodium persulfate and acrylic acid to perform grafting reaction, after the reaction is finished, adding sodium chloride to perform precipitation, 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, stirring uniformly, carrying out modification reaction at 20-50 ℃, reacting for 8-16h, extracting with hydrochloric acid after the reaction is finished, adding sodium carbonate into extract liquor to neutralize to neutrality, concentrating, and precipitating with diethyl ether to obtain tosylated polyethylene glycol grafted polyacrylic acid;
(4) dissolving tosylated polyethylene glycol grafted polyacrylic acid and phthalimide potassium salt in N, N-dimethylformamide for synthetic reaction to obtain phthalimided polyethylene glycol grafted polyacrylic acid;
(5) dispersing phthalimide polyethylene glycol grafted polyacrylic acid and hydrazine hydrate in ethanol, refluxing in nitrogen atmosphere, carrying out ammonolysis reaction, after the ethanol is evaporated, dripping ether to generate precipitate, dissolving the solid in dichloromethane, and carrying out suction filtration 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 20-40 ℃, reacting for 1-3h, decompressing after the reaction is finished to remove unreacted thionyl chloride, then adding amino-terminated polyethylene glycol grafted polyacrylic acid, dichloromethane and triethylamine, carrying out amidation reaction, decompressing after the reaction is finished to remove unreacted dichloromethane and triethylamine, and obtaining the humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material.
2. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: in the step (2), the mass ratio of the acryloyl chloride modified polyethylene glycol to the potassium persulfate to the sodium persulfate to the acrylic acid is 100:5-10:1-2: 10-20.
3. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: the reaction temperature of the grafting reaction in the step (2) is 50-80 ℃, and the reaction time is 4-8 t.
4. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: in the step (3), polyacrylic acid is grafted by polyethylene glycol, and the mass ratio of the p-toluenesulfonyl chloride to the triethylamine is 100:8-16: 80-120.
5. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: in the step (4), the mass ratio of the tosylated polyethylene glycol grafted polyacrylic acid to the phthalimide potassium salt is 100:20-35: 10-30.
6. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: the reaction temperature of the synthesis reaction in the step (4) is 170-200 ℃, and the reaction time is 10-16 h.
7. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: in the step (5), the phthalimide polyethylene glycol is grafted with polyacrylic acid and N2H4BetweenThe mass ratio of (A) to (B) is 100: 8-25.
8. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: the reaction temperature of the ammonolysis reaction in the step (5) is 170-200 ℃, and the reaction time is 4-8 h.
9. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: in the step (6), the mass ratio of the humic acid to the thionyl chloride to the amino-terminated polyethylene glycol grafted polyacrylic acid to the triethylamine is 100:800-1200:60-100: 10-30.
10. The humic acid-polyethylene glycol grafted polyacrylic acid composite water-retaining agent material as claimed in claim 1, is characterized in that: the reaction temperature of the amide reaction in the step (6) is 30-60 ℃, and the reaction time is 2-6 h.
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