CN110669526B - Preparation method of composite water-retaining agent for saline-alkali soil - Google Patents
Preparation method of composite water-retaining agent for saline-alkali soil Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000002689 soil Substances 0.000 title claims abstract description 39
- 239000003513 alkali Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229920001046 Nanocellulose Polymers 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 23
- 206010016807 Fluid retention Diseases 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000003516 soil conditioner Substances 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002681 soil colloid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a preparation method of a composite water-retaining agent for saline-alkali soil, which comprises the following steps: mixing the nano-cellulose crystal and deionized water to prepare a suspension, adding a mixed solution of TEMPO and sodium bromide, stirring and mixing, adding a sodium hydroxide solution to adjust the pH, adding a sodium hypochlorite solution, reacting until the pH of the solution is unchanged, filtering, and drying the solid to prepare a carboxylated nano-cellulose crystal; dispersing the modified nano-crystalline cellulose into deionized water to prepare a dispersion solution, adding a mixed solution of tetrabutyl titanate and ethyl orthosilicate, stirring for reaction, filtering after the reaction is finished, and drying the solid to prepare a modified nano-crystalline cellulose; mixing the modified cellulose crystal with acrylic acid and sodium acrylate, adding a cross-linking agent and ammonium persulfate to react, cooling to room temperature after the reaction is finished, filtering, and drying to obtain the composite water-retaining agent. The method disclosed by the invention is simple to operate and low in cost, and the prepared composite water-retaining agent has good water-retaining and fertilizer-retaining properties and certain biodegradability.
Description
Technical Field
The invention relates to the field of preparation of water-retaining agents, and particularly relates to a preparation method of a composite water-retaining agent for saline-alkali soil.
Background
The water retention agent is also called as super absorbent resin, and the molecular structure of the water retention agent has a large number of hydrophilic groups, such as carboxyl, hydroxyl, amide and the like, and the water retention agent is a swelling high polymer with low crosslinking degree and a three-dimensional network structure. When the water-retaining agent is added into water, the water-retaining agent can rapidly absorb water and swell to hundreds or even thousands of times of the self weight, and the water-retaining agent also has stronger water retention capacity. As a functional polymer water-saving material, the water-retaining agent has a wide application range, and is mainly reflected in the aspects of medicine, building engineering, agricultural science and the like.
Saline-alkali soil is a general term for saline soil and alkaline earth, and refers to soil with salt content of more than 0.1-0.2%, or soil with alkalinity of more than 15-20% due to adsorption of exchangeable resin in the soil by soil colloid, and further soil with harm to normal growth of plants. The reason for salt accumulation in soil mainly includes natural factors and human factors, the natural factors mainly include climate, terrain, soil vegetation, soil moisture change and the like, and the human factors have serious influence on soil salinization, especially secondary salinization phenomenon. In order to promote the sustainable development of the ecological environment, the improvement of the current saline-alkali soil is needed. The water retention agent is used as a water retention material, can effectively improve the water retention capacity of soil, and is often compounded with a soil conditioner and added into the saline-alkali soil to improve the physical and chemical properties of the soil.
Traditional water-retaining agent has very high absorption efficiency in the deionized water, but when having cation in the solution, its absorption efficiency can greatly reduced, and water-retaining agent degradability is relatively poor moreover, applies it into soil, causes secondary pollution to soil easily. Therefore, with the increasing awareness of environmental protection, the research and development of water retention agents mainly focus on the synthesis of water retention agents using natural polymer materials as monomers, such as chitosan, cellulose, alginate, and the like. And along with the increase of the demand of people, the requirements on the water-retaining agent are more strict, and the composite water-retaining agent with high water absorption speed, high salt resistance and strong mechanical property is prepared. At present, a plurality of preparation methods of the water-retaining agent exist, but most of the preparation methods have the defects of high cost, complex process, high requirement on equipment and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the preparation method of the composite water-retaining agent for the saline-alkali soil is provided, the method is simple to operate, the prepared composite water-retaining agent is good in stability, has good water and fertilizer retention performance, does not cause secondary pollution to the soil, and is low in preparation cost, and the composite water-retaining agent can be used for improving the saline-alkali soil, so that the physicochemical property of the saline-alkali soil can be effectively improved, and the water and fertilizer retention capacity of the saline-alkali soil can be improved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension, then adding a mixed solution of TEMPO and sodium bromide into the suspension, stirring and dispersing uniformly, adding a sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a sodium hypochlorite solution, reacting until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing the solid, and drying to prepare carboxylated nano-cellulose crystals;
(2) dispersing the prepared carboxylated nano cellulose crystal in deionized water to prepare a dispersion solution, then adding a mixed ethanol solution of tetrabutyl titanate and ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction, filtering after the reaction is finished, and drying the solid to prepare a modified nano cellulose crystal;
(3) and adding a cross-linking agent and ammonium persulfate into the prepared mixed aqueous solution of the modified nano cellulose crystal, acrylic acid and sodium acrylate, stirring for reaction, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
As a preferable technical scheme, in the step (1), the mass concentration of the nano-cellulose crystals in the suspension is 1-3%.
As a preferable technical scheme, in the step (1), the mass ratio of the nano-crystalline cellulose, TEMPO, sodium bromide and sodium hypochlorite is (1-2): (0.11-0.12): (0.3-0.35): (1.1-1.5).
As a preferable technical solution, in the step (2), the mass ratio of the carboxylated nanocellulose crystal, tetrabutyl titanate and ethyl orthosilicate is 1: (4-7): 10.
as a preferable technical scheme, in the step (2), the time of the hydrolysis reaction is 10-20 h.
As an improved technical scheme, in the step (3), the cross-linking agent is N, N-methylene bisacrylamide.
As a preferred technical scheme, in the step (3), the use amounts of the components are as follows in parts by weight: 1-3 parts of modified nano cellulose crystal, 10-15 parts of acrylic acid, 7-9 parts of sodium acrylate, 1-2 parts of cross-linking agent and 0.03-0.06 part of initiator.
As a preferable technical scheme, in the step (3), the reaction temperature is 60-80 ℃, and the reaction time is 1-4 h.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the water-retaining agent has strong water absorption capacity, is non-toxic and harmless, can effectively improve the water and fertilizer retention performance of soil when being used in the soil, and the sodium polyacrylate is one kind of water-retaining agent, has high water absorption rate and high water absorption speed, but has less durable water retention performance and poorer biodegradability. In order to solve the technical problem, the nano-crystalline cellulose is added into the sodium polyacrylate resin as a modifier, the nano-crystalline cellulose has higher specific surface area, high strength and certain biodegradability, and the surface of the nano-crystalline cellulose has a large amount of hydrophilic groups such as hydroxyl groups and the like, but the nano-crystalline cellulose has poor compatibility with the polyacrylic resin and poor mechanical properties. Based on the method, firstly, the nano-cellulose crystal is subjected to carboxylation treatment, then the nano-cellulose crystal is placed in a mixed solution of a titanium source and a silicon source, hydrolysis reaction is carried out under certain conditions, and silicon dioxide and titanium dioxide generated by hydrolysis are coated on the surface of the nano-cellulose crystal to prepare the modified nano-cellulose crystal.
The composite water-retaining agent prepared by the invention has the advantages of large water absorption multiplying power, excellent water-retaining property, simple preparation method and low cost.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 1%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is 0.11% and 0.3% respectively; wherein the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 1: 0.11: 0.3: 1.1;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 4 parts of tetrabutyl titanate and 10 parts of ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction for 10 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 1 part of N, N-methylene bisacrylamide and 0.03 part of ammonium persulfate into a mixed aqueous solution of 1 part of the modified cellulose crystal, 10 parts of acrylic acid and 7 parts of sodium acrylate in parts by weight, heating to 60 ℃, stirring for reaction for 1 hour, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
Example 2
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 3%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is 0.12% and 0.35% respectively; the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 1: 0.12: 0.35: 1.5;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 7 parts of tetrabutyl titanate and 10 parts of ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction for 20 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 2 parts by weight of N, N-methylene bisacrylamide and 0.06 part by weight of ammonium persulfate into a mixed aqueous solution of 3 parts by weight of the modified cellulose crystal, 15 parts by weight of acrylic acid and 9 parts by weight of sodium acrylate, heating to 80 ℃, stirring for reaction for 4 hours, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
Example 3
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 1.5%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is respectively 0.11% and 0.3%; wherein the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 1: 0.11: 0.3: 1.2;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 5 parts of tetrabutyl titanate and 10 parts of ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction for 12 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 1.2 parts by weight of N, N-methylene bisacrylamide and 0.04 part by weight of ammonium persulfate into a mixed aqueous solution of 1.5 parts by weight of the prepared modified cellulose crystal, 11 parts by weight of acrylic acid and 7.5 parts by weight of sodium acrylate, heating to 65 ℃, stirring for reaction for 2 hours, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
Example 4
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 1%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is 0.12% and 0.35% respectively; wherein the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 2: 0.12: 0.35: 1.3;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 5.5 parts of tetrabutyl titanate and 10 parts of tetraethoxysilane, stirring at normal temperature for hydrolysis reaction for 15 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 1.5 parts of N, N-methylene bisacrylamide and 0.045 part of ammonium persulfate into a mixed aqueous solution of 2 parts of the modified cellulose crystal, 13 parts of acrylic acid and 8 parts of sodium acrylate in parts by weight, heating to 65 ℃, stirring for reaction for 1.5h, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
Example 5
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 2.5%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is respectively 0.11% and 0.3%; wherein the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 2: 0.11: 0.3: 1.4;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 6 parts of tetrabutyl titanate and 10 parts of ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction for 16 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 1 part by weight of N, N-methylene bisacrylamide 1.6 parts and ammonium persulfate 0.05 part into a mixed aqueous solution of the modified cellulose crystal prepared by the step 1 part, acrylic acid 13 parts and sodium acrylate 8 parts, heating to 70 ℃, stirring for reaction for 3 hours, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to prepare the composite water-retaining agent.
Example 6
A preparation method of a composite water-retaining agent for saline-alkali soil comprises the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension with the mass concentration of 2.5%, then adding a mixed aqueous solution of TEMPO and sodium bromide into the suspension, uniformly stirring and dispersing, adding a 0.15mol/L sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a 8% sodium hypochlorite solution to react until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing and drying the solid to prepare carboxylated nano-cellulose crystals, wherein the mass concentration of the TEMPO and the sodium bromide is 0.12% and 0.35% respectively; wherein the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 1: 0.12: 0.35: 1.5;
(2) dispersing 1 part of the prepared carboxylated nano cellulose crystal into 10 parts of deionized water to prepare a dispersion liquid, then adding a mixed ethanol solution of 6.5 parts of tetrabutyl titanate and 10 parts of tetraethoxysilane, stirring at normal temperature for hydrolysis reaction for 18 hours, filtering after the reaction is finished, and drying the solid to prepare the modified nano cellulose crystal;
(3) adding 2.5 parts by weight of the prepared modified cellulose crystal into a mixed aqueous solution of 14 parts by weight of acrylic acid and 8.5 parts by weight of sodium acrylate, adding 1.8 parts by weight of N, N-methylene bisacrylamide and 0.05 part by weight of ammonium persulfate, heating to 75 ℃, stirring for reaction for 3.5 hours, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to obtain the composite water-retaining agent.
Comparative example
The nanocellulose crystal was subjected to the same modification as in example 6 except that the modification was not carried out in the steps (1) to (2) described in example 6, to obtain a water-retaining agent.
The performance of the water-retaining agents prepared in examples 1 to 6 and the comparative example was tested as follows, and the test method and test results were as follows:
1. water absorption performance
Water absorption Performance test in pure Water:
respectively weighing m1The soil conditioner prepared in examples 1 to 6 and comparative example was used as a sample, and the sample was placed in a predetermined volume of deionized water, saturated with water, and then drained through a 100 mesh sieve to remove excess water, and the mass of the sample was measured and recorded as m2According to Q1＝(m2-m1)/m1Calculating the water absorption performance of the sample; in the formula, Q1Is the water absorption rate of the composite additive, m1The mass of the composite additive before water absorption; m is2Is the mass of the composite additive after water absorption.
Water absorption Performance in sodium chloride solution test:
respectively weighing m1The soil improvement agents obtained in examples 1 to 6 and comparative example were used as samples, and the samples were placed in a 0.1% sodium chloride solution and saturated with water, and excess water was drained off through a 100 mesh sieve, and the mass of the samples was measured and recorded as m3According to Q2＝(m3-m1)/m1Calculating the water absorption performance of the sample; in the formula, Q2Is the water absorption rate of the composite additive, m1The mass of the composite additive before water absorption; m is3Is the mass of the composite additive after water absorption.
2. Water retention property
Placing the sample which is saturated by water in deionized water and sodium chloride solution in an oven at the temperature of 150 ℃, weighing after 2h, wherein the water retention property can be measured by the water retention rate, and the R is m2'/m1'. 100% Water Retention, wherein R represents Water Retention, m1' is the mass of the composite additive after water absorption and before dehydration; m is2' is the mass of the composite additive after water absorption and dehydration.
The test results are shown in table 1.
TABLE 1
From the test results, the composite water-retaining agent prepared by directly adding the nano-cellulose crystal into the sodium polyacrylate water-retaining agent for blending has poor water absorption performance and water retention performance. In comparison, the water-retaining agent prepared by firstly performing carboxylation treatment on the nano-cellulose crystal, then performing coating treatment on the surface of the nano-cellulose crystal and then mixing the nano-cellulose crystal with the sodium polyacrylate water-retaining agent has more excellent water absorption performance and water retention performance, mainly because the modified nano-cellulose crystal has better compatibility with the sodium polyacrylate water-retaining agent and the hydrophilic groups on the surface of the nano-cellulose crystal are greatly increased. Compared with a comparative example, the composite water-retaining agent prepared by the invention has more excellent water absorption performance and water retention performance in a sodium chloride solution.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (4)
1. A preparation method of a composite water-retaining agent for saline-alkali soil is characterized by comprising the following steps:
(1) dispersing nano-cellulose crystals in deionized water to prepare a suspension, then adding a mixed solution of TEMPO and sodium bromide into the suspension, stirring and dispersing uniformly, adding a sodium hydroxide solution to adjust the pH of a reaction system to be neutral, slowly adding a sodium hypochlorite solution, reacting until the pH of the solution is unchanged, dropwise adding ethanol to terminate the reaction, filtering the reaction solution, washing the solid, and drying to prepare carboxylated nano-cellulose crystals; the mass ratio of the nano-crystalline cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is (1-2): (0.11-0.12): (0.3-0.35): (1.1-1.5);
(2) dispersing the prepared carboxylated nano cellulose crystal in deionized water to prepare a dispersion solution, then adding a mixed ethanol solution of tetrabutyl titanate and ethyl orthosilicate, stirring at normal temperature for hydrolysis reaction, filtering after the reaction is finished, and drying the solid to prepare a modified nano cellulose crystal; the mass ratio of the carboxylated nano-cellulose crystal to the tetrabutyl titanate to the ethyl orthosilicate is 1: (4-7): 10;
(3) adding a cross-linking agent and ammonium persulfate into the prepared mixed aqueous solution of the modified nano-cellulose crystal, acrylic acid and sodium acrylate, stirring and reacting for 1-4 h at the temperature of 60-80 ℃, cooling to room temperature after the reaction is finished, filtering, washing the solid to be neutral, and drying to prepare the composite water-retaining agent; the dosage of each component is as follows according to the weight portion: 1-3 parts of modified nano cellulose crystal, 10-15 parts of acrylic acid, 7-9 parts of sodium acrylate, 1-2 parts of cross-linking agent and 0.03-0.06 part of initiator.
2. The preparation method of the composite water-retaining agent for saline-alkali soil as claimed in claim 1, wherein in the step (1), the mass concentration of the nano cellulose crystal in the suspension is 1-3%.
3. The preparation method of the composite water-retaining agent for saline-alkali soil as claimed in claim 1, wherein in the step (2), the hydrolysis reaction time is 10-20 h.
4. The preparation method of the composite water-retaining agent for saline-alkali soil as claimed in claim 1, wherein in the step (3), the cross-linking agent is N, N-methylene bisacrylamide.
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