CN102225985B - Preparation method of macroporous sodium carboxymethylcellulose grafted copolymer with rapid swelling absorption property - Google Patents
Preparation method of macroporous sodium carboxymethylcellulose grafted copolymer with rapid swelling absorption property Download PDFInfo
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Abstract
The invention discloses a preparation method of a macroporous sodium carboxymethylcellulose grafted copolymer with a rapid swelling absorption property. The method comprises the following steps: adding N,N'-methylenebisacrylamide as an initiator, an ammonium persulfate and N,N,N',N'-tetramethylenediamine redox initiation system as an initiator, polyoxyethylene-oxypolypropylene as a foam stabilizer and acrylamide in a thick sodium carboxymethylcellulose liquid system; then adding sodium carbonate or sodium bicarbonate and acid so as to generate carbon dioxide gas inside the system, thus a full foaming system is formed so as to rapidly generate polymerization reaction, thereby obtaining the macroporous sodium carboxymethylcellulose grafted copolymer with the rapid swelling absorption property. By the product disclosed by the invention, the purpose of rapid swelling absorption can be achieved, the absorption capacity to organic matters in wastewater is improved, and gel can achieve absorption balance in a short time through mutual perforative super-macroporous structure.
Description
Technical field
The present invention relates to a kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property.
Background technology
Wastewater treatment is as the important step of state treatment environmental pollution, also is the problem of a lot of focus of attentions for a long time.Absorption method with its can some compound of selective enrichment characteristic in field of waste water treatment special status is arranged.Although can realize good adsorbing and removing effect, there are the aftertreatment difficulty in sorbent material commonly used such as gac, straw, diatomite, flyash, wilkinite etc., cause easily the deficiency of secondary pollution, make its industrialization still have certain difficulty.Along with the development of scientific research, the adsorptivity macromolecular material that has in a large number high adsorption capacity, highly selective has emerged in large numbers out.Polymer adsorbing material take natural polymer as raw material is because of advantages such as its wide material sources, nontoxic easy degraded, inexpensive easy recovery, stable performance, simple process, more and more paid attention to and pays close attention in field of waste water treatment.
It is abundant that Mierocrystalline cellulose has reserves, can constantly regenerate, and cost is low, and nontoxic and energy microorganism is decomposed, and can avoid producing the advantages such as environmental pollution.Xylo-Mucine (CMC-Na) is through modification and with a kind of water-soluble cellulose ether of carboxyl by Mierocrystalline cellulose.CMC-Na not only possesses the characteristics of cellulose base water-absorbing material, also has good biodegradability, and in 96h, it can reach degradable, can be classified as environment-friendly material.And because the introducing of electron-donating group carboxyl in the macromole, thereby can form the bridging complex compound with many metal ion crosslinked, can close with polyvalent metal ion generation huge legendary turtle, absorption or ion exchange, it can effectively be removed multivalence toxic heavy metal ion in the waste water as sorbent material, the main form by non covalent bond of its absorption, therefore can realize wash-out regeneration, thereby realize recycling of organic enrichment in the waste water, separation and recovery and sorbing material.
CMC-Na is carried out grafting, copolymerization and modification, can not destroy the performance of CMC-Na, can also give its some new performance.By with the graft copolymerization of different monomers, can be implemented in the application of processing textile waste, paper waste, coating waste-water, daily chemical wastewater, leather waste water etc. aspect.Polyacrylamide is the most representative polymeric flocculant, the CMC-Na grafted polyacrylamide can reduce the expensive of polyacrylamide on the one hand, on the other hand, the grafts Stability Analysis of Structures, be easy to carry out structurally-modified to polyacrylamide, as passing through the cationic product of quaternised modified one-tenth, compare with synthetic organic polymer by the natural macromolecule modification product, have the simple and lower-cost advantage of technique.
And how to prepare the carboxymethyl cellulose prime system superpolymer with high percentage of grafting, to realize it to the high adsorbing and removing rate of various waste water, become the problem that first will be considered.Consider from the angle of cost, efficient, realize that quick adsorption also is the important factor of a kind of sorbing material application performance of examination.In material, introduce the splendid approach that vesicular structure is realization this purpose.The common method for preparing porous material comprises freeze-drying, phase separation method, template, pore-creating agent method.For freeze-drying, must make first carboxymethyl cellulose prime system graft copolymer, again by the lyophilize pore, the material preparation cycle is longer.Template only makes the size and shape of suitable template ability control punch owing to the size and shape in hole is determined by template.But because its specific range scale, template is applicable to prepare the aperture at 2-50nm and above inorganic and organic porous material.Phase separation method generally only is suitable for being prepared with PNIPAM gel or other polyacrylamide derivative gel of temperature-sensing property.And the processes such as the dissolving of pore-creating agent method, washing, immersion and removal pore-creating agent need expend time in, and have prolonged the material preparation cycle; Easy residual on a small quantity not eluted pore-creating agent in the product is so that the perforate of pore structure is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property.Product of the present invention has the oversized hole structure, fluffy, porous, specific surface area is large behind the gel swelling, thereby realizes the purpose of Fast-swelling absorption, improved organic loading capacity in the waste water, and the oversized hole structure that runs through mutually is so that gel can reach adsorption equilibrium within a short period of time.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property, adopt the viscous fluid system of Xylo-Mucine, add therein N, N '-methylene-bisacrylamide (MBA) (Chemical Reagent Co., Ltd., Sinopharm Group) is as linking agent, ammonium persulphate (APS) (Chemical Reagent Co., Ltd., Sinopharm Group) and N, N, N', N'-Tetramethyl Ethylene Diamine (TMEDA) (Chemical Reagent Co., Ltd., Sinopharm Group) redox initiation system is as initiator, polyoxyethylene-propylene oxide (PF127) (Chemical Reagent Co., Ltd., Sinopharm Group) is as suds-stabilizing agent, and acrylamide (AM) monomer (chemical plant, Gansu Province, west, Guangdong); Then the adding by yellow soda ash or sodium bicarbonate and acid makes the inner carbon dioxide that produces of system, forms the fully system of foaming, and polymerization occurs rapidly, thereby prepares the macropore Xylo-Mucine graft copolymer with Fast-swelling absorption property.Polymerization early stage is with carbon dioxide isolation monomer and when gases are heated, they expand waits effect hierarchy of control temperature, so that graft polymerization reaction carries out under the condition of constant or slow intensification, thereby be conducive to the graft polymerization that the skeleton free radical causes, the non-graft copolymerization of control monomer.Polymerization later-stage utilization gas deviate to distribute heat of polymerization, take away moisture so that graftomer is able to purifying and drying, form simultaneously uniform vesicular structure, whole reaction process just can be finished in 5 minutes;
Described polyreaction comprises the steps:
1) the viscous fluid system after the abundant gelatinization is moved in the beaker, under the 45-65 ℃ of bath temperature, add in the beaker and account for the PF127 of acrylamide (AM) monomer mass per-cent 0.1%-0.5% and acrylamide (AM) monomer of 5g, fully stirring mixes; Wherein, PF127 is described polyoxyethylene-propylene oxide;
2) add successively the MBA that accounts for AM monomer mass per-cent 0.01%-0.08% in the viscous fluid toward mixing, the TMEDA of 0.2%-1.2%, the APS of 0.2%-1.2%, the acid of 3%-30%, and stir while adding;
3) rapidly in system, add yellow soda ash or the sodium bicarbonate that accounts for AM monomer mass per-cent 5%-50%, stir while adding, add the rear while and stop stirring at once; This moment, system generated carbonic acid gas because yellow soda ash or sodium bicarbonate and acid act on, and formed the fully system of foaming.Polymerization occurs rapidly, can finish within very short time;
4) after product dewaters with alcohol immersion, place 50-60 ℃ vacuum drying oven to dry.
The viscous fluid system of described Xylo-Mucine is purchased from chemical plant, Gansu Province, west, Guangdong with the CMC-Na(that accounts for acrylamide (AM) monomer mass per-cent 5%-30%, Xylo-Mucine) is raw material, distilled water together with 5-10mL adds in the 250mL there-necked flask that whipping appts is housed, in 50-80 ℃ of water-bath, fully stir gelatinization, form the viscous fluid system.
A kind of in acetic acid, the hydrochloric acid adopted in described acid.
Described yellow soda ash or sodium bicarbonate will grind to form finely powdered in advance.
Beneficial effect of the present invention is: the foam system dispersion copolymerization method that the present invention adopts has that dispersion medium is easily separated, production unit is simple, speed of response is fast, polymkeric substance purity advantages of higher, is a kind of energy-efficient oligosaprobic polymerization technique.In the vacuole, finish graft reaction, can realize the unification of high polymerization rate and high conversion, utilize foam system to disperse graft polymerization to prepare carboxymethyl cellulose prime system graft copolymer, graft reaction and pore are carried out synchronously, have greatly shortened the material preparation cycle.The product C MC-Na-g-PAM of the present invention's preparation has the oversized hole structure, specific surface area is large behind the gel swelling, thereby realize the purpose of Fast-swelling absorption, improved organic loading capacity in the waste water, and the oversized hole structure that runs through mutually is so that gel can reach adsorption equilibrium within a short period of time, and CMC-Na-g-PAM of the present invention has the performance that can reuse, and use value is higher, has also solved the problem that causes secondary pollution.For different performance needs, CMC-Na-g-PAM is carried out modification, can realize that it is in the application in waste water from dyestuff, heavy metal wastewater thereby, leather waste water etc. field.Manufacture craft of the present invention is simple, quick, manufacturing cost is starkly lower than the polymer adsorbing material that synthesizes with other preparation methods, macroporous structure makes it have large specific surface area and adsorption rate fast, and absorption property obviously is better than other polymer adsorbing material, but and have a reusing; When utilizing and then, decreasing ratio still can reach 89.7%.The present invention is being with a wide range of applications aspect textile waste, paper waste, coating waste-water, daily chemical wastewater, leather waste water etc. the wastewater treatment.
Embodiment
Embodiment 1
A kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property of present embodiment, adopt the viscous fluid system of Xylo-Mucine, add therein N, N '-methylene-bisacrylamide (MBA) is as linking agent, ammonium persulphate (APS) and N, N, N', N'-Tetramethyl Ethylene Diamine (TMEDA) redox initiation system is as initiator, and polyoxyethylene-propylene oxide (PF127) is as suds-stabilizing agent, and acrylamide (AM); Then the adding by yellow soda ash and hydrochloric acid makes the inner carbon dioxide that produces of system, forms the fully system of foaming, and polymerization occurs rapidly, thereby prepares the macropore Xylo-Mucine graft copolymer with Fast-swelling absorption property.Polymerization early stage is with carbon dioxide isolation monomer and when gases are heated, they expand waits effect hierarchy of control temperature, so that graft polymerization reaction carries out under the condition of constant or slow intensification, thereby be conducive to the graft polymerization that the skeleton free radical causes, the non-graft copolymerization of control monomer.Polymerization later-stage utilization gas deviate to distribute heat of polymerization, take away moisture so that graftomer is able to purifying and drying, form simultaneously uniform vesicular structure, just can finish in the whole reaction process several minutes.
Concrete preparation method is as follows:
1) at first with the CMC-Na of 1g, the distilled water of 8mL adds in the there-necked flask of the 250mL that whipping appts is housed, in 60 ℃ of water-baths, fully stirs gelatinization, forms the pasty state viscous fluid.
2) CMC-Na after the abundant gelatinization is moved in the beaker, place under 50 ℃ of bath temperatures, add the AM monomer of 0.2mL 10%PF127 and 5g in the beaker, fully stirring mixes.
3) continue in beaker, to add successively 0.05mL 2.5%MBA, the hydrochloric acid of 5.5mL 6mol/L, 0.2mL 20%TMEDA, 0.2mL20%APS constantly is stirred to and mixes.
4) rapidly in system, add 2g yellow soda ash (grinding to form in advance finely powdered), stir while adding, add the rear while and stop stirring at once.System generates carbonic acid gas owing to yellow soda ash and hydrochloric acid effect at this moment, and forms the system that fully foams.Polymerization occurs rapidly, can finish within very short time.
5) after product dewaters with alcohol immersion, place 50-60 ℃ vacuum drying oven to dry.
By the way, can obtain to surpass 98% to the decreasing ratio of dyestuff, loading capacity can be up to 9.72mg/g, and in 20min, can reach the CMC-Na-g-PAM macropore quick adsorption gel of swelling adsorption equilibrium, and the recyclable recycling of product, during the 4th recycling, decreasing ratio still can reach 89.7%.
Embodiment 2
A kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property of present embodiment, adopt the viscous fluid system of Xylo-Mucine, add therein N, N '-methylene-bisacrylamide (MBA) is as linking agent, ammonium persulphate (APS) and N, N, N', N'-Tetramethyl Ethylene Diamine (TMEDA) redox initiation system is as initiator, and polyoxyethylene-propylene oxide (PF127) is as suds-stabilizing agent, and acrylamide (AM) monomer; Then the adding by sodium bicarbonate and acetic acid makes the inner carbon dioxide that produces of system, forms the fully system of foaming, and polymerization occurs rapidly, thereby prepares the macropore Xylo-Mucine graft copolymer with Fast-swelling absorption property.Polymerization early stage is with carbon dioxide isolation monomer and when gases are heated, they expand waits effect hierarchy of control temperature, so that graft polymerization reaction carries out under the condition of constant or slow intensification, thereby be conducive to the graft polymerization that the skeleton free radical causes, the non-graft copolymerization of control monomer.Polymerization later-stage utilization gas deviate to distribute heat of polymerization, take away moisture so that graftomer is able to purifying and drying, form simultaneously uniform vesicular structure, whole reaction process just can be finished in 5 minutes.
Concrete preparation method is as follows:
1) at first with the CMC-Na of 0.25g, the distilled water of 5mL adds in the there-necked flask of the 250mL that whipping appts is housed, in 50 ℃ of water-baths, fully stirs gelatinization, forms the pasty state viscous fluid.
2) CMC-Na after the abundant gelatinization is moved in the beaker, place under 45 ℃ of bath temperatures, add the AM monomer of 0.05mL 10%PF127 and 5g in the beaker, fully stirring mixes.
3) continue in beaker, to add successively 0.02mL 0.5%MBA, the acetic acid of 0.5mL 6mol/L, 0.05mL 20%TMEDA, 0.05mL 20%APS constantly is stirred to and mixes.
4) rapidly in system, add 0.25g sodium bicarbonate (grinding to form in advance finely powdered), stir while adding, add the rear while and stop stirring at once.System generates carbonic acid gas owing to sodium bicarbonate and vinylformic acid effect at this moment, and forms the system that fully foams.Polymerization occurs rapidly, can finish within very short time.
5) after product dewaters with alcohol immersion, place 50-60 ℃ vacuum drying oven to dry.
By the way, can obtain to surpass 98% to the decreasing ratio of dyestuff, loading capacity can be up to 9.72mg/g, and in 20min, can reach the CMC-Na-g-PAM macropore quick adsorption gel of swelling adsorption equilibrium, and the recyclable recycling of product, during the 4th recycling, decreasing ratio still can reach 89.7%.
Embodiment 3
A kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property of present embodiment, adopt the viscous fluid system of Xylo-Mucine, add therein N, N '-methylene-bisacrylamide (MBA) is as linking agent, ammonium persulphate (APS) and N, N, N', N'-Tetramethyl Ethylene Diamine (TMEDA) redox initiation system is as initiator, and polyoxyethylene-propylene oxide (PF127) is as suds-stabilizing agent, and acrylamide (AM); Then the adding by yellow soda ash and hydrochloric acid makes the inner carbon dioxide that produces of system, forms the fully system of foaming, and polymerization occurs rapidly, thereby prepares the macropore Xylo-Mucine graft copolymer with Fast-swelling absorption property.Polymerization early stage is with carbon dioxide isolation monomer and when gases are heated, they expand waits effect hierarchy of control temperature, so that graft polymerization reaction carries out under the condition of constant or slow intensification, thereby be conducive to the graft polymerization that the skeleton free radical causes, the non-graft copolymerization of control monomer.Polymerization later-stage utilization gas deviate to distribute heat of polymerization, take away moisture so that graftomer is able to purifying and drying, form simultaneously uniform vesicular structure, whole reaction process just can be finished in 5 minutes.
Concrete preparation method is as follows:
1) at first with the CMC-Na of 1.5g, the distilled water of 10mL adds in the there-necked flask of the 250mL that whipping appts is housed, in 80 ℃ of water-baths, fully stirs gelatinization, forms the pasty state viscous fluid.
2) CMC-Na after the abundant gelatinization is moved in the beaker, place under 65 ℃ of bath temperatures, add the AM monomer of 0.25mL 10%PF127 and 5g in the beaker, fully stirring mixes.
3) continue in beaker, to add successively 0.16mL 2.5%MBA, the hydrochloric acid of 6.5mL 6mol/L, 0.3mL 20%TMEDA, 0.3mL20%APS constantly is stirred to and mixes.
4) rapidly in system, add 2.5g yellow soda ash (grinding to form in advance finely powdered), stir while adding, add the rear while and stop stirring at once.System generates carbonic acid gas owing to yellow soda ash and hydrochloric acid effect at this moment, and forms the system that fully foams.Polymerization occurs rapidly, can finish within very short time.
5) after product dewaters with alcohol immersion, place 50-60 ℃ vacuum drying oven to dry.
By the way, can obtain to surpass 98% to the decreasing ratio of dyestuff, loading capacity can be up to 9.72mg/g, and in 20min, can reach the CMC-Na-g-PAM macropore quick adsorption gel of swelling adsorption equilibrium, and the recyclable recycling of product, during the 4th recycling, decreasing ratio still can reach 89.7%.
Claims (4)
1. preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property, it is characterized in that: the viscous fluid system that adopts Xylo-Mucine, add therein N, N '-methylene-bisacrylamide is as linking agent, ammonium persulphate and N, N, N', N'-Tetramethyl Ethylene Diamine redox initiation system is as initiator, and polyoxyethylene-propylene oxide is as suds-stabilizing agent, and acrylamide monomer; Then the adding by yellow soda ash or sodium bicarbonate and acid makes the inner carbon dioxide that produces of system, forms abundant foaming system, and polyreaction occurs rapidly, thereby prepares the macropore Xylo-Mucine graft copolymer with Fast-swelling absorption property;
Described polyreaction comprises the steps:
1) the viscous fluid system after the abundant gelatinization is moved in the beaker, under the 45-65 ℃ of bath temperature, in beaker, add PF127 and the 5g acrylamide monomer that accounts for acrylamide monomer mass percent 0.1%-0.5%, fully stir, mix; Wherein, PF127 is described polyoxyethylene-propylene oxide;
2) add successively the MBA that accounts for acrylamide monomer mass percent 0.01%-0.08% in the viscous fluid toward mixing, the TMEDA of 0.2%-1.2%, the APS of 0.2%-1.2%, the acid of 3%-30% stirs while adding;
3) rapidly in system, add yellow soda ash or the sodium bicarbonate that accounts for acrylamide monomer mass percent 5%-50%, stir while adding, add the rear while and stop stirring at once; This moment, system generated carbonic acid gas because yellow soda ash or sodium bicarbonate and acid act on, and formed the fully system of foaming; Polymerization occurs rapidly, can finish within very short time;
4) after product dewaters with alcohol immersion, place 50-60 ℃ vacuum drying oven to dry.
2. a kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property as claimed in claim 1, it is characterized in that: the viscous fluid system of described Xylo-Mucine is take the CMC-Na that accounts for acrylamide monomer mass percent 5%-30% as raw material, distilled water together with 5-10mL adds in the 250mL there-necked flask that whipping appts is housed, in 50-80 ℃ of water-bath, fully stir gelatinization, form the viscous fluid system.
3. a kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property as claimed in claim 1 is characterized in that: a kind of in acetic acid, the hydrochloric acid adopted in described acid.
4. a kind of preparation method with macropore Xylo-Mucine graft copolymer of Fast-swelling absorption property as claimed in claim 1, it is characterized in that: described yellow soda ash or sodium bicarbonate will grind to form finely powdered in advance.
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| CN112316907A (en) * | 2020-09-29 | 2021-02-05 | 陕西科技大学 | Heterogeneous-pore-based covalent organic framework foam material and preparation method and application thereof |
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| CN113461863B (en) * | 2021-07-27 | 2023-12-01 | 天津工业大学 | Polymer water-absorbent resin and preparation method and application thereof |
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