CN109503778B - Preparation method of tobacco stem-based composite hydrogel - Google Patents
Preparation method of tobacco stem-based composite hydrogel Download PDFInfo
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- CN109503778B CN109503778B CN201811430648.7A CN201811430648A CN109503778B CN 109503778 B CN109503778 B CN 109503778B CN 201811430648 A CN201811430648 A CN 201811430648A CN 109503778 B CN109503778 B CN 109503778B
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- acrylic acid
- composite hydrogel
- sodium acrylate
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- tobacco stems
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 241000208125 Nicotiana Species 0.000 title claims abstract description 63
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 41
- 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 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 40
- 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 33
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 30
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 20
- 244000028419 Styrax benzoin Species 0.000 claims description 15
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 15
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 15
- 229960002130 benzoin Drugs 0.000 claims description 15
- 235000019382 gum benzoic Nutrition 0.000 claims description 15
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000002689 soil Substances 0.000 description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 10
- 239000012965 benzophenone Substances 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- -1 diphenyl ethyl Chemical group 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Abstract
The invention discloses a preparation method of tobacco stem-based composite hydrogel, which comprises the following steps: step 1: mixing the pretreated tobacco stems, acrylic acid and sodium acrylate neutralization solution, an initiator and a cross-linking agent, and irradiating the mixed solution for 3-25min by using an ultraviolet lamp at room temperature to obtain composite hydrogel; the power of the ultraviolet lamp is 50-500W, the distance between the ultraviolet lamp and the mixed liquid is 15-50 cm, the neutralization degree of acrylic acid and sodium acrylate neutralization liquid is 75-85%, the mass of the initiator is 0.85-1.25% of that of the acrylic acid and sodium acrylate neutralization liquid, and the mass of the cross-linking agent is 0.05-0.08% of that of the acrylic acid and sodium acrylate neutralization liquid; step 2: soaking the composite hydrogel in methanol or ethanol, standing for 12-24 h, removing unreacted monomers and incompletely reacted oligomers, and drying; wherein the drying temperature is 50-100 ℃, and the drying time is 4-12 h. The method can convert the tobacco stems with lower utilization value into the composite hydrogel with high added value.
Description
Technical Field
The invention relates to the technical field of hydrogel preparation, in particular to tobacco stem-based composite hydrogel and a preparation method thereof.
Background
The tobacco stems are byproducts of the tobacco industry, are important natural renewable resources, have rich yield, and currently, about hundreds of thousands of tons of tobacco stem resources are abandoned every year in China, so that the environment is polluted, the existing resources are seriously wasted, and the research on the comprehensive utilization of the abandoned tobacco stems has important practical significance. The main components of the tobacco stems are cellulose, pectin, total sugar, protein and the like, wherein the cellulose content is the largest, the cellulose contains a large number of hydroxyl groups, the hydroxyl groups are active in chemical property and are easy to be chemically modified to obtain a composite polymer material, and the waste tobacco stems are ideal raw materials for synthesizing the composite polymer material. The traditional method for synthesizing the composite hydrogel, such as a solution polymerization method and a suspension emulsion polymerization method, has long reaction time, high energy consumption, secondary pollution caused by the addition of other reaction solvents and complex post-treatment.
Disclosure of Invention
The invention designs and develops a preparation method of tobacco stem-based composite hydrogel, which adopts an ultraviolet radiation initiation method, takes waste tobacco stems as raw materials, takes acrylic acid and sodium acrylate as monomers, synthesizes the tobacco stem-based composite hydrogel in the presence of a photoinitiator and a cross-linking agent, has short reaction time, less energy consumption, no need of adding other reaction solvents, no secondary pollution and simpler and more convenient treatment.
The technical scheme provided by the invention is as follows:
a preparation method of tobacco stem-based composite hydrogel comprises the following steps:
step 1: mixing the pretreated tobacco stems, acrylic acid and sodium acrylate neutralization solution, an initiator and a cross-linking agent, and irradiating the mixed solution for 3-25min by using an ultraviolet lamp at room temperature to obtain composite hydrogel;
the power of the ultraviolet lamp is 50-500W, the distance between the ultraviolet lamp and the mixed liquid is 15-50 cm, the neutralization degree of acrylic acid and sodium acrylate neutralization liquid is 75-85%, the mass of the initiator is 0.85-1.25% of that of the acrylic acid and sodium acrylate neutralization liquid, and the mass of the cross-linking agent is 0.05-0.08% of that of the acrylic acid and sodium acrylate neutralization liquid;
step 2: soaking the composite hydrogel in methanol or ethanol, standing for 12-24 h, removing unreacted monomers and incompletely reacted oligomers, and drying;
wherein the drying temperature is 50-100 ℃, and the drying time is 4-12 h.
Preferably, the pretreatment of the tobacco stems comprises:
crushing the tobacco stems, sieving the crushed tobacco stems by a 40-mesh sieve, placing the crushed tobacco stems in 10% NaOH solution, stirring the mixture for 2 hours at the temperature of 95 ℃, removing supernatant liquor, and adding NaClO and H into the residual mixed liquor2O2Stirring the mixed solution in ice water bath for 2h, carrying out suction filtration, washing to be neutral, drying to constant weight, crushing, and sieving with a 120-mesh sieve.
Preferably, the preparation of the acrylic acid and sodium acrylate neutralized liquid comprises:
dripping acrylic acid monomer into 20% NaOH solution while stirring to obtain acrylic acid and sodium acrylate neutralized solution;
wherein, the proportion of the acrylic acid monomer and NaOH is controlled to ensure that the neutralization degree of the acrylic acid and sodium acrylate neutralization solution is 75-85%.
Preferably, the initiator is a single photoinitiator or a mixed initiator consisting of a photoinitiator and a thermal initiator.
Preferably, the photoinitiator is one of benzoin and derivatives, benzils, alkylbenzophenones and benzophenones.
Preferably, the thermal initiator is one of an organic peroxide, an azo initiator, and cerium ammonium nitrate.
Preferably, the benzoin and the derivative thereof are one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether, the benzil is one of diphenyl ethyl ketone and α -dimethoxy- α -phenyl ethyl ketone, the alkyl benzophenone is one of α -diethoxy ethyl ketone, α -hydroxyalkyl phenyl ketone and α -amine alkyl phenyl ketone, and the benzophenone is one of benzophenone and 2, 4-dihydroxy benzophenone.
Preferably, the organic peroxide is benzoyl peroxide, methyl ethyl ketone peroxide, and the inorganic peroxide is one of ammonium persulfate, potassium persulfate and sodium persulfate; the azo initiator is azobisisobutyronitrile.
Preferably, the crosslinking agent is N, N-methylene bisacrylamide.
The invention has the following beneficial effects:
(1) the preparation method of the tobacco stem-based composite hydrogel adopts an ultraviolet radiation initiation method, takes waste tobacco stems as raw materials, takes acrylic acid and sodium acrylate as monomers, and synthesizes the tobacco stem-based composite hydrogel in the presence of a photoinitiator and a cross-linking agent.
(2) The invention provides a new way for the recycling of the tobacco stems, and the tobacco stems with lower utilization value can be converted into the composite hydrogel with high added value. The composite hydrogel has high water absorption and water retention performance, and can be used as a water retention agent to be applied to the fields of agriculture, industry and the like.
Drawings
FIG. 1 is a graph showing the change of water absorption capacity with time of TS-PAA-1 according to example 1 of the present invention.
FIG. 2 is a water retention curve of the TS-PAA-1 swollen hydrogel of example 1 of the present invention at 60 ℃.
FIG. 3 is a water retention curve of the TS-PAA-1 swelling hydrogel of example 1 of the present invention under normal temperature conditions.
FIG. 4 is a histogram analysis of the effect of the TS-PAA-1 hydrogel of example 1 on the water holding capacity of soil.
FIG. 5 is a histogram analysis of the effect of the TS-PAA-1 hydrogel of the present invention on the acidity and alkalinity of soil.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
The invention provides a preparation method of tobacco stem-based composite hydrogel, which comprises the following steps:
step 1: pre-treating the tobacco stems,
weighing a certain amount of tobacco stems, crushing and sieving the tobacco stems by a 40-mesh sieve, then placing the tobacco stems in a proper amount of 10% NaOH solution, boiling the mixture for 2 hours under the condition of stirring at 95 ℃, standing the mixture, removing supernatant liquid, adding a mixed solution of NaClO and H2O2 into the residual mixed solution, stirring the mixture for 2 hours in an ice water bath, carrying out suction filtration, washing a filter cake until the pH value is neutral, drying the filter cake to constant weight, crushing the filter cake, and sieving the filter cake by a 120-mesh sieve for.
Step 2: preparing acrylic acid and sodium acrylate neutralization solution,
weighing a certain amount of acrylic acid monomer, dropwise adding the acrylic acid monomer into a proper amount of 20% NaOH solution, stirring while adding to obtain acrylic acid and sodium acrylate neutralization solution for later use, wherein the neutralization degree of the acrylic acid and sodium acrylate neutralization solution is 75% -85% according to different proportions of the monomer and NaOH.
And step 3: mixing the pretreated tobacco stems, acrylic acid and sodium acrylate neutralization solution, an initiator and a cross-linking agent, and irradiating the mixed solution for 3-25min by using an ultraviolet lamp at room temperature to obtain composite hydrogel;
the power of the ultraviolet lamp is 50-500W, the distance between the ultraviolet lamp and the mixed liquid is 15-50 cm, the neutralization degree of acrylic acid and sodium acrylate neutralization liquid is 75-85%, the mass of the initiator is 0.85-1.25% of that of the acrylic acid and sodium acrylate neutralization liquid, and the mass of the cross-linking agent is 0.05-0.08% of that of the acrylic acid and sodium acrylate neutralization liquid;
and 4, step 4: soaking the composite hydrogel in methanol or ethanol, standing for 12-24 h, removing unreacted monomers and incompletely reacted oligomers (the unreacted monomers and the incompletely reacted oligomers can be dissolved in the methanol or ethanol, and the purpose of adding the methanol and the ethanol is to dissolve the substances);
wherein the drying temperature is 50-100 ℃, and the drying time is 4-12 h.
The initiator is a single photoinitiator or a mixed initiator consisting of a photoinitiator and a thermal initiator.
The photoinitiator is one of benzoin and derivatives (one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether), benzils (one of diphenyl ethanone and α -dimethoxy- α -phenyl acetophenone), alkyl benzophenones (one of α -diethoxy acetophenone, α -hydroxyalkyl benzophenone and α -amine alkyl benzophenone) and benzophenones (one of benzophenone and 2, 4-dihydroxy benzophenone).
The thermal initiator is one of organic peroxide (benzoyl peroxide, methyl ethyl ketone peroxide, inorganic peroxide such as one of ammonium persulfate, potassium persulfate and sodium persulfate), azo initiator (azodiisobutyronitrile) and ammonium ceric nitrate.
The cross-linking agent is N, N-methylene bisacrylamide.
Example 1
Weighing 0.18g of pretreated tobacco stems, placing the tobacco stems in a 50m L beaker, uniformly mixing acrylic acid with neutralization degree of 80% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium sulfate according to the mass ratio of 30: 100: 0.06: 1.0: 0.25, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 250W ultraviolet lamp for irradiation for 3min, wherein the distance between the ultraviolet lamp and the mixed solution is 20cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (12h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the composite hydrogel in an oven at 60 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-1.
Example 2
Weighing 0.24g of pretreated tobacco stems, placing the tobacco stems in a 50m L beaker, uniformly mixing acrylic acid with the neutralization degree of 85% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium persulfate according to the mass ratio of 40: 100: 0.08: 0.8: 0.20, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 250W ultraviolet lamp for irradiation for 4min, wherein the distance between the ultraviolet lamp and the mixed solution is 25cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (15h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the composite hydrogel in an oven at 70 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-2.
Example 3
Weighing 0.24g of pretreated tobacco stems, placing the tobacco stems in a beaker of 100m L, uniformly mixing acrylic acid neutralizing liquid with the neutralization degree of 75%, a cross-linking agent N, N-methylene bisacrylamide and a photoinitiator benzoin dimethyl ether according to the mass ratio of 40: 100: 0.05: 0.85, carrying out ultrasonic treatment for 1min, placing the mixed solution under an ultraviolet lamp of 250W for irradiating for 4min, wherein the distance between the ultraviolet lamp and the mixed solution is 25cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking, standing overnight (24h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the pure composite hydrogel in an oven at 80 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-3.
Example 4
Weighing 0.18g of pretreated tobacco stems, placing the tobacco stems in a 50m L beaker, uniformly mixing acrylic acid with neutralization degree of 80% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium sulfate according to the mass ratio of 30: 100: 0.06: 1.0: 0.25, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 50W ultraviolet lamp for irradiating for 25min, wherein the distance between the ultraviolet lamp and the mixed solution is 15cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (12h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the composite hydrogel in an oven at 60 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-4.
Example 5
Weighing 0.18g of pretreated tobacco stems, placing the tobacco stems in a 50m L beaker, uniformly mixing acrylic acid with neutralization degree of 80% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium sulfate according to the mass ratio of 30: 100: 0.06: 1.0: 0.25, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 500W ultraviolet lamp for irradiation for 3min, wherein the distance between the ultraviolet lamp and the mixed solution is 50cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (12h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the composite hydrogel in an oven at 60 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-5.
Example 6
Weighing 0.18g of pretreated tobacco stems, placing the tobacco stems in a 50m L beaker, uniformly mixing acrylic acid with neutralization degree of 80% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium sulfate according to the mass ratio of 30: 100: 0.06: 1.0: 0.25, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 500W ultraviolet lamp for irradiation for 3min, wherein the distance between the ultraviolet lamp and the mixed solution is 25cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (12h), removing unreacted monomers and incompletely reacted oligomers to obtain pure composite hydrogel, and drying the composite hydrogel in an oven at 60 ℃ to constant weight to obtain dry composite hydrogel TS-PAA-6.
Comparative example 1
Weighing 0.00g of pretreated tobacco stems (namely, no tobacco stems) and placing the tobacco stems in a 50m L beaker, adding acrylic acid with the neutralization degree of 80% and sodium acrylate neutralization solution, a cross-linking agent N, N-methylene bisacrylamide, a photoinitiator benzoin dimethyl ether and a thermal initiator ammonium sulfate, removing the tobacco gunn, uniformly mixing the other components according to the mass ratio of 30: 100: 0.06: 1.0: 0.25, carrying out ultrasonic treatment for 1min, placing the mixed solution under a 250W ultraviolet lamp for irradiation for 3min, wherein the distance between the ultraviolet lamp and the mixed solution is 20cm, taking out the composite hydrogel, placing the composite hydrogel in ethanol for soaking overnight (12h), removing unreacted monomers and incompletely reacted oligomers to obtain the composite hydrogel, and drying the composite hydrogel in an oven at 60 ℃ to constant weight to obtain the dry composite hydrogel TS-PAA-7.
Water absorption test:
crushing the tobacco stalk-based composite hydrogel obtained in the above examples 1-6 and the composite hydrogel obtained in the comparative example 1, sieving with a 40-80 mesh sieve, taking 0.05g of composite hydrogel powder, placing the composite hydrogel powder in a 250M L conical flask, adding sufficient distilled water or 0.9 wt% NaCl solution, sealing, placing the conical flask in a constant-temperature shaking water bath kettle, shaking for t min at room temperature, filtering with a 300-mesh nylon bag, standing for 30min, weighing, and recording the hydrogel mass as M before and after water absorption0And MtCalculating the water absorption multiplying power Q when the water absorption time is t according to the formula (1)t(g/g)。
The maximum adsorption capacities of the cabo-based composite hydrogel obtained in examples 1 to 6 and the composite hydrogel obtained in comparative example 1 are shown in table 1.
TABLE 1 maximum adsorption Capacity of Stem-based composite hydrogels obtained in examples 1-6 and composite hydrogel obtained in comparative example 1
As can be seen from Table 1, the composite hydrogel obtained under the conditions of examples 1-6 has a distilled water adsorption rate greater than that of a 0.9 wt% NaCl solution, a distilled water adsorption rate greater than 4000g/g, and a 0.9 wt% NaCl solution adsorption rate of 1751-2082g/g, and the composite hydrogel TS-PAA-2 obtained in example 2 has better water absorption performance, the maximum distilled water absorption rate reaches 4257g/g, and the 0.9 wt% NaCl solution absorption rate reaches 2082 g/g. The composite hydrogel without the tobacco stems is low in water absorption, the multiplying power for absorbing distilled water is 1372g/g, and the multiplying power for absorbing 0.9 wt% NaCl solution is only 453 g/g. Therefore, the composite hydrogels obtained under the conditions of examples 1-6 have higher water absorption performance.
The experimental results were analyzed in detail by taking the hydrogel TS-PAA-1 obtained in example 1 as an example.
As shown in FIG. 1, under the conditions of example 1, the maximum adsorption capacities of the composite hydrogel to distilled water and a 0.9 wt% NaCl solution were 4019g/g and 2034g/g, respectively. The imbibition process of the composite hydrogel is fast first and slow later, the absorption capacities for distilled water and 0.9 wt% NaCl solution are 3379 and 1321g/g respectively when imbibing for 1 minute, and the absorption capacities for distilled water and 0.9 wt% NaCl solution are 3840 and 1920g/g respectively when imbibing for 5 minutes. After 10 minutes, the adsorption rate tended to be flat. The composite hydrogel has high water absorption performance.
Testing the water retention:
putting a certain amount of the cabo-based composite hydrogel obtained in the above examples 1 to 6 into sufficient distilled water, taking out the hydrogel after swelling balance after water absorption and swelling balance, weighing about 80g of the hydrogel after swelling balance, and recording the mass as m0Drying in a drying oven at 40-60 deg.C for a certain time, weighing and recording hydrogel mass, and recording the mass as m when the drying time is t mintCalculating the water retention property W of the composite hydrogel according to the formula (2)R。
The experimental results were analyzed in detail by taking the hydrogel TS-PAA-1 obtained in example 1 as an example.
As shown in FIGS. 2 and 3, for TS-PAA-1 (the hydrogel obtained in example 1), the water retention property decreases the fastest in the first three hours (shown in FIG. 2) under the condition of 60 ℃, the water retention property decreases continuously in 3-17.5 hours, the water retention property decreases slowly after more than 17.5 hours, and the water retention property is about 0.02% after 24 hours. Under the normal temperature condition (shown in figure 3), the water retention property of the hydrogel is fastest reduced in the first 4 days, the water retention property is continuously reduced after 4 days, the reduction speed is slowed, and when 15 days, the water retention property of the hydrogel is 37.9%, and the water retention properties of TS-PAA-2, TS-PAA-3, TS-PAA-4, TS-PAA-5 and TS-PAA-6 are similar and have little difference, so that the hydrogel has good water retention property.
Influence on soil water retention:
taking 100g of dried soil, sieving to obtain soil particles of about 3mm, adding dry gel with the mass fractions of 0.0%, 0.5%, 1.0%, 1.5% and 2.0% respectively, uniformly mixing, adding the mixture into a glass tube (the diameter is 4cm) with the bottom sealed by non-woven fabric, vertically fixing the glass tube filled with the mixed soil on an iron support, dripping distilled water from the upper opening, stopping adding water when first dripping water seeps from the bottom, stopping adding water until water does not seep, weighing, and recording the total mass of glass tube soil columns before and after adding water as W respectively0And W1Calculating the water holdup W of the soil according to the formula (3)H。
The experimental results were analyzed in detail by taking the hydrogel TS-PAA-1 obtained in example 1 as an example.
As shown in fig. 4, the addition of the TS-PAA-1 hydrogel can improve the water retention rate of the soil, and the increase of the water retention rate of the soil increases with the increase of the addition amount of the hydrogel, and when the addition amount of the composite hydrogel is 0.0%, 0.5%, 1.0%, 1.5%, and 2.0%, the water retention rate of the soil increases from 38.49% to 42.69, 51.13, 73.36, and 81.85%, respectively. Therefore, the hydrogel can greatly improve the water retention rate of the soil.
Influence on soil acidity and alkalinity:
the preparation of the soil solution comprises the steps of adding tap water with the same mass into 2000g of dry soil, soaking for 12 hours, stirring at variable intervals, standing, carrying out suction filtration to obtain a soil aqueous solution stock solution, respectively taking a certain amount of the soil aqueous solution stock solution, and adjusting the pH value with 0.1 mol/L HCl and 0.1 mol/L NaOH to obtain the soil aqueous solution with the pH value of 5-9.
And (3) taking 100m of soil aqueous solution with L pH value of 5-9, respectively adding 0.1g of xerogel, sealing, standing for 2h, filtering, taking supernatant, and measuring the pH value.
The experimental results were analyzed in detail by taking the hydrogel TS-PAA-1 obtained in example 1 as an example.
As shown in fig. 5, when the pH of the original soil solution is acidic, the addition of the composite hydrogel increases the pH of the soil solution, and when the pH of the original soil solution is 5.00 and 6.00, the pH of the original soil solution is increased to 5.49 and 6.31 after the addition of the hydrogel; when the pH value of the original soil solution is alkaline, the pH value of the soil solution is reduced by adding the composite hydrogel, and when the pH value of the original soil solution is 8.00 and 9.00, the pH value of the original soil solution is respectively reduced to 7.46 and 7.82 after adding the hydrogel. Therefore, the addition of the TS-PAA-1 composite hydrogel can improve the acid-base performance of the soil.
The preparation method of the tobacco stem-based composite hydrogel adopts an ultraviolet radiation initiation method, takes waste tobacco stems as raw materials, takes acrylic acid and sodium acrylate as monomers, and synthesizes the tobacco stem-based composite hydrogel in the presence of a photoinitiator and a cross-linking agent. The invention provides a new way for the recycling of the tobacco stems, and the tobacco stems with lower utilization value can be converted into the composite hydrogel with high added value. The composite hydrogel has high water absorption and water retention performance, and can be used as a water retention agent to be applied to the fields of agriculture, industry and the like.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (2)
1. The preparation method of the tobacco stem-based composite hydrogel is characterized by comprising the following steps:
step 1: mixing the pretreated tobacco stems, acrylic acid and sodium acrylate neutralization solution, a photoinitiator, a thermal initiator and a cross-linking agent, and irradiating the mixed solution for 3-25min by using an ultraviolet lamp at room temperature to obtain composite hydrogel;
the power of the ultraviolet lamp is 50-500W, the distance between the ultraviolet lamp and the mixed liquid is 15-50 cm, and the neutralization degree of the acrylic acid and sodium acrylate neutralization liquid is 75-85%;
the photoinitiator is benzoin dimethyl ether;
the thermal initiator is ammonium persulfate;
the cross-linking agent is N, N-methylene bisacrylamide; the mass ratio of the tobacco stems, the acrylic acid and the sodium acrylate neutralizing liquid to the cross-linking agent to the photoinitiator to the thermal initiator is 30: 100: 0.06: 1.0: 0.25 or 40: 100: 0.08: 0.8: 0.20;
the pretreatment of the tobacco stems comprises the following steps:
crushing the tobacco stems, sieving the crushed tobacco stems by a 40-mesh sieve, placing the crushed tobacco stems in 10% NaOH solution, stirring the mixture for 2 hours at the temperature of 95 ℃, removing supernatant liquor, and adding NaClO and H into the residual mixed liquor2O2Stirring the mixed solution in an ice-water bath for 2 hours, carrying out suction filtration, washing to be neutral, drying to constant weight, crushing, and sieving with a 120-mesh sieve;
step 2: soaking the composite hydrogel in methanol or ethanol, standing for 12-24 h, removing unreacted monomers and incompletely reacted oligomers, and drying;
wherein the drying temperature is 50-100 ℃, and the drying time is 4-12 h.
2. The preparation method of the tobacco stem-based composite hydrogel according to claim 1, wherein the preparation of the acrylic acid and sodium acrylate neutralization solution comprises the following steps:
dripping acrylic acid monomer into 20% NaOH solution while stirring to obtain acrylic acid and sodium acrylate neutralized solution;
wherein, the proportion of the acrylic acid monomer and NaOH is controlled to ensure that the neutralization degree of the acrylic acid and sodium acrylate neutralization solution is 75-85%.
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