CN107759735B - Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof - Google Patents
Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof Download PDFInfo
- Publication number
- CN107759735B CN107759735B CN201610700935.XA CN201610700935A CN107759735B CN 107759735 B CN107759735 B CN 107759735B CN 201610700935 A CN201610700935 A CN 201610700935A CN 107759735 B CN107759735 B CN 107759735B
- Authority
- CN
- China
- Prior art keywords
- water
- hemicellulose
- insoluble
- insoluble hemicellulose
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
Abstract
The invention belongs to the technical field of organic functional materials, and discloses water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof. The method is (1) preparation of water-insoluble hemicellulose; (2) putting water-insoluble hemicellulose into a dilute alkali solution, and heating and dissolving to obtain an alkali solution of the hemicellulose; (3) and (3) under the protection of inert gas, adding a catalyst and an acrylamide monomer into the alkali solution of the hemicellulose obtained in the step (2), carrying out polymerization reaction, cooling, precipitating, washing and drying to obtain the water-insoluble hemicellulose grafted polyacrylamide. The invention has higher grafting rate and grafting efficiency, and reduces the production cost; the invention does not need higher reaction temperature; the prepared product has good water solubility, and can further synthesize a novel environment functional hydrogel material.
Description
Technical Field
The invention belongs to the technical field of organic functional materials, relates to modification of water-insoluble hemicellulose, and particularly relates to water-insoluble hemicellulose grafted polyacrylamide as well as a preparation method and application thereof.
Background
With the increasing development of the oil crisis, how to prepare the organic multifunctional material by modification to realize high-value utilization of the hemicellulose as a polysaccharide resource with wide source and regeneration is more and more concerned by scientists.
Cellulose is a hybrid polysaccharide connecting cellulose and lignin in plant cell walls, is one of three main groups of plant fiber raw materials, has the content which is second to cellulose in nature and accounts for 20-35% of the content of lignocellulose, hemicellulose can be divided into 4 main groups according to the difference of structures of main composition polysaccharides, and comprises xylan, mannan, β -glucan and xyloglucan which are mixed and connected, wherein, the xylan hemicellulose is the most important type in the hemicellulose, the main chain of the xylan hemicellulose is formed by connecting D-xylopyranose with β - (1 → 4) glycosidic bond, and the branched glycosyl groups comprise D-glucuronic acid and 4-O-methyl glucuronic acid, L-arabinose and other oligosaccharides (D-xylose, D-glucose and D-/L-galactose).
Corncobs are the largest agricultural waste in the world, mainly comprising cellulose, hemicellulose and lignin. Corncobs contain a large amount of xylan-based hemicellulose. Corncob hemicellulose is classified into two types, water-soluble hemicellulose (ws-AGX) and water-insoluble hemicellulose (ws-AGX), according to the degree of substitution of the main chain. For water insoluble hemicellulose, 95% of the xylan backbone is unsubstituted, the hemicellulose is mainly in a linear structure, whereas for water soluble hemicellulose about 15% of the xylan backbone is substituted. Although the corncob contains a large amount of water-insoluble hemicellulose, the high-value utilization of the water-insoluble hemicellulose in the corncob has not been realized industrially. Therefore, it is necessary to find a technique to increase the application of water-insoluble hemicellulose.
Disclosure of Invention
The invention aims to provide a preparation method of water-insoluble hemicellulose grafted polyacrylamide, aiming at improving the utilization rate of the water-insoluble hemicellulose and improving the high quality of the water-insoluble hemicellulose.
Another object of the present invention is to provide a water-insoluble half-fiber grafted polyacrylamide prepared by the above method.
Still another object of the present invention is to provide the use of the above water-insoluble half fiber grafted polyacrylamide. The water-insoluble half-fiber grafted polyacrylamide is used for preparing a hydrogel material and is applied to the fields of sewage treatment, drug sustained release and super absorbent materials.
The purpose of the invention is realized by the following scheme:
a preparation method of water-insoluble hemicellulose grafted polyacrylamide is characterized in that potassium persulfate and sodium thiosulfate are used as redox initiators, and under the protection of nitrogen, modification reaction is carried out on water-insoluble hemicellulose, so that a hemicellulose grafted copolymer with good water solubility is prepared, and the preparation method specifically comprises the following steps:
(1) preparation of water-insoluble hemicellulose
(2) Putting water-insoluble hemicellulose into a dilute alkali solution, and heating and dissolving to obtain an alkali solution of the hemicellulose;
(3) and (3) under the protection of inert gas, adding a catalyst and an acrylamide monomer into the alkali solution of the hemicellulose obtained in the step (2), carrying out polymerization reaction, cooling, precipitating, washing and drying to obtain the water-insoluble hemicellulose grafted polyacrylamide.
The catalyst in the step (3) is a mixture of potassium persulfate and sodium thiosulfate;
the molar ratio of the potassium persulfate to the sodium thiosulfate is 1: 1.
The temperature of the polymerization reaction in the step (3) is 10-40 ℃, and the time of the polymerization reaction is 200-280 min.
In the step (2), the heating and dissolving temperature is 50-90 ℃, and the heating and dissolving time is 10-50 min.
In the step (2), the dilute alkali is potassium hydroxide or sodium hydroxide, and the concentration of the dilute alkali solution is 2-4 wt%.
The content of the water-insoluble hemicellulose in the step (2) is 3-7% of the total mass of the water-insoluble hemicellulose and the dilute alkali water solution.
In the step (3), the dosage of the catalyst is 1% -9% of the mass of the water-insoluble hemicellulose, and the dosage of the acrylamide is 1-12 times of the mass of the water-insoluble hemicellulose.
The precipitate in the step (3) is tetrahydrofuran, absolute ethyl alcohol, methanol or acetone, and is preferably acetone; the washing detergent is acetone, methanol or absolute ethyl alcohol, and acetone is preferred.
And (4) drying in the step (3) is vacuum drying, wherein the vacuum drying temperature is 45-60 ℃, and the time is 6-48 h.
In the step (3), the catalyst is added in the form of an aqueous solution of the catalyst, the acrylamide is added in the form of an aqueous solution of the acrylamide, the mass-to-volume ratio of the catalyst to the water in the aqueous solution of the catalyst is (20-35) mg, (5-8) m L, and the mass-to-volume ratio of the acrylamide to the water in the aqueous solution of the acrylamide is (1-5) mg, (10-15) m L.
The water-insoluble hemicellulose in the step (1) is extracted by taking corncobs as raw materials.
The water-insoluble hemicellulose structure is:
the specific preparation steps of the water-insoluble hemicellulose are as follows:
(a) cleaning corncobs, air-drying, crushing, sieving and drying to obtain corncob powder;
(b) extracting the corncob powder by adopting a mixed solvent of benzene and ethanol, and air-drying to obtain degreased corncob powder;
(c) dispersing the degreased corncob powder into a strong alkali solution 1, performing ultrasonic treatment, and filtering to obtain a filtrate 1 and filter residues; adding the filter residue into a strong base solution 2, extracting at normal temperature, and filtering to obtain a filtrate 2;
(d) and combining the filtrate 1 and the filtrate 2, uniformly mixing, neutralizing until the pH value is 5-6, completely precipitating, centrifuging, washing and drying to obtain the water-insoluble hemicellulose. The water-insoluble hemicellulose is in a light yellow powder form.
The sieving mesh number in the step (a) is 200-400 meshes, and the drying condition is that the drying is carried out for 24-28 h at 50-70 ℃.
The volume ratio of benzene to ethanol in the mixed solvent of benzene and ethanol in the step (b) is 2: 1; the extraction condition is extraction for 5-7 h at 50-70 ℃.
In the step (c), the strong alkali solution 1 and the strong alkali solution 2 are the same or different, preferably KOH or NaOH solutions, and the concentrations of the strong alkali solution 1 and the strong alkali solution 2 are 4.0-6.0 wt%.
The solid-liquid ratio of the degreased corncob powder to the strong alkali solution 1 in the step (c) is 1g to 20m L, the ultrasonic treatment condition is that ultrasonic treatment is carried out for 8-12 min at 40-60 ℃, the ultrasonic power is 180-200W, and the frequency is 20-30 kHz.
And (c) the solid-to-liquid ratio of the filter residue to the strong alkali solution 2 in the step (c) is 1g to 20m L, and the normal-temperature extraction time is 2-4 h.
The centrifugal rotating speed is 4500-5000 r/min; the washing is to wash by adopting an ethanol solution with the volume fraction of 75%; the drying is freeze drying, and the freeze drying time is 20-24 hours; the temperature of the freeze drying is-49 to-53 ℃.
The reaction principle equation of the preparation method of the water-insoluble hemicellulose grafted polyacrylamide is as follows:
R-OH represents water-insoluble hemicellulose.
The water-insoluble half-fiber grafted polyacrylamide is used for preparing a hydrogel material and is applied to the fields of sewage treatment, drug sustained release and super absorbent materials.
The water-insoluble hemicellulose grafted polyacrylamide is used for sustained release of drugs, in particular for preparing drugs of a polysaccharide-based colon targeted drug delivery system;
the water-insoluble hemicellulose-grafted polyacrylamide is used for preparing water-insoluble hemicellulose-grafted polyacrylic acid.
The invention has the following beneficial effects:
1. the chemical modification of the water-insoluble hemicellulose is carried out in a homogeneous medium, so that the grafting rate and the grafting efficiency are higher, and the production cost is reduced;
2. potassium persulfate and sodium thiosulfate are used as redox initiators, and a high reaction temperature is not needed;
3. the water-insoluble hemicellulose after chemical modification has good water solubility, and can further synthesize a novel environment functional hydrogel material.
Detailed Description
The present invention is further illustrated below with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of water-insoluble hemicellulose grafted polyacrylamide comprises the following steps:
(1) cleaning corncobs, air-drying, crushing, sieving with a 300-mesh sieve, and drying at 60 deg.C (24h) to obtain corncob powder; extracting the corncob powder with a mixed solvent of benzene and ethanol (volume ratio of benzene to ethanol is 2:1) at 70 deg.C for 6h, and air drying to obtain defatted corncob powder;
(2) adding 30g of degreased corncob powder into 600m L5 wt% NaOH solution, performing ultrasonic treatment for 10min (the ultrasonic power is 200W and the frequency is 20kHz) at 50 ℃, filtering to obtain a filtrate 1 and a filter residue, extracting the filter residue for 3h at normal temperature by using 5.0 wt% KOH aqueous solution (the solid-to-liquid ratio is 1g:20m L), filtering to obtain a filtrate 2, mixing the filtrate 1 and the filtrate 2, neutralizing by using acetic acid until the pH value is 5.5, centrifuging, washing by using 75% ethanol solution in volume fraction, and performing freeze drying for 24h (the freeze drying temperature is-50 ℃) to obtain purified water-insoluble hemicellulose;
(3) dissolving 0.5g of water-insoluble hemicellulose into 10m of NaOH solution with the mass concentration of L being 2%, stirring and dissolving for 10min at 50 ℃ to form a homogeneous solution, and obtaining an alkali solution of the hemicellulose;
(4) under the protection of nitrogen, a mixed solution of potassium persulfate and sodium thiosulfate (20mg of K)2S2O8/Na2S2O3(K2S2O8With Na2S2O3The method comprises the following steps of (1: 1) dissolving in 5m L of deionized water), adding the mixture into a hemicellulose alkali solution, uniformly stirring for 30min, slowly adding an acrylamide aqueous solution (2g acrylamide/15 ml of deionized water), keeping the temperature at 30 ℃ for reaction for 4h, after the reaction is finished, precipitating and washing the mixture by using acetone, and performing vacuum drying (the temperature is 50 ℃ and the time is 8h) to obtain the water-insoluble hemicellulose grafted polyacrylamide graft copolymer, wherein the grafting rate of the product is 172%, and the grafting efficiency is 41.5%.
Example 2
A preparation method of water-insoluble hemicellulose grafted polyacrylamide comprises the following steps:
(1) cleaning corncobs, air-drying, crushing, sieving with a 300-mesh sieve, and drying at 60 deg.C (24h) to obtain corncob powder; extracting the corncob powder with a mixed solvent of benzene and ethanol (volume ratio of benzene to ethanol is 2:1) at 70 deg.C for 6h, and air drying to obtain defatted corncob powder;
(2) adding 30g of degreased corncob powder into 600m L5 wt% NaOH solution, performing ultrasonic treatment for 10min (the ultrasonic power is 200W and the frequency is 20kHz) at 50 ℃, filtering to obtain a filtrate 1 and a filter residue, extracting the filter residue for 3h at normal temperature by using 5.0 wt% KOH aqueous solution (the solid-to-liquid ratio is 1g:20m L), filtering to obtain a filtrate 2, mixing the filtrate 1 and the filtrate 2, neutralizing by using acetic acid until the pH value is 5.5, centrifuging, washing by using 75% ethanol solution in volume fraction, and performing freeze drying for 24h (the freeze drying temperature is-50 ℃) to obtain purified water-insoluble hemicellulose;
(3) dissolving 0.5g of water-insoluble hemicellulose into 10m of NaOH solution with the mass concentration of L being 2%, stirring and dissolving for 10min at 50 ℃ to form a homogeneous solution, and obtaining an alkali solution of the hemicellulose;
(4) under the protection of nitrogen, a mixed solution of potassium persulfate and sodium thiosulfate (25mg of K)2S2O8/Na2S2O3(K2S2O8With Na2S2O3The method comprises the following steps of (1: 1) dissolving in 5m L of deionized water), adding the mixture into an alkali solution of hemicellulose, uniformly stirring for 30min, slowly adding an aqueous solution of acrylamide (2g of acrylamide/15 ml of deionized water), carrying out heat preservation reaction for 4h at 30 ℃, after the reaction is finished, precipitating and washing with acetone, and carrying out vacuum drying (the temperature is 50 ℃ and the time is 8h) to obtain the graft copolymer of the hemicellulose grafted polyacrylamide, wherein the grafting rate is 236% and the grafting efficiency is 64.2%.
Example 3
A preparation method of water-insoluble hemicellulose grafted polyacrylamide comprises the following steps:
(1) cleaning corncobs, air-drying, crushing, sieving with a 300-mesh sieve, and drying at 60 deg.C (24h) to obtain corncob powder; extracting the corncob powder with a mixed solvent of benzene and ethanol (volume ratio of benzene to ethanol is 2:1) at 70 deg.C for 6h, and air drying to obtain defatted corncob powder;
(2) adding 30g of degreased corncob powder into 600m L5 wt% NaOH solution, performing ultrasonic treatment for 10min (the ultrasonic power is 200W and the frequency is 20kHz) at 50 ℃, filtering to obtain a filtrate 1 and a filter residue, extracting the filter residue for 3h at normal temperature by using 5.0 wt% KOH aqueous solution (the solid-to-liquid ratio is 1g:20m L), filtering to obtain a filtrate 2, mixing the filtrate 1 and the filtrate 2, neutralizing by using acetic acid until the pH value is 5.5, centrifuging, washing by using 75% ethanol solution in volume fraction, and performing freeze drying for 24h (the freeze drying temperature is-50 ℃) to obtain purified water-insoluble hemicellulose;
(3) dissolving 0.5g of water-insoluble hemicellulose into 10m of NaOH solution with the mass concentration of L being 2%, stirring and dissolving for 10min at 50 ℃ to form a homogeneous solution, and obtaining an alkali solution of the hemicellulose;
(4) under the protection of nitrogen, a mixed solution of potassium persulfate and sodium thiosulfate (35mg of K)2S2O8/Na2S2O3(K2S2O8With Na2S2O3The method comprises the following steps of (1: 1) dissolving in 5m L of deionized water), adding into an alkali solution of hemicellulose, uniformly stirring (30min), slowly adding an aqueous solution of acrylamide (2g of acrylamide/15 ml of deionized water), keeping the temperature at 30 ℃ for reaction for 4h, after the reaction is finished, precipitating and washing with acetone, and performing vacuum drying (the temperature is 50 ℃ and the time is 8h) to obtain the graft copolymer of the hemicellulose grafted polyacrylamide, wherein the grafting rate is 204% and the grafting efficiency is 55.4%.
Example 4
A preparation method of water-insoluble hemicellulose grafted polyacrylamide comprises the following steps:
(1) cleaning corncobs, air-drying, crushing, sieving with a 300-mesh sieve, and drying at 60 deg.C (24h) to obtain corncob powder; extracting the corncob powder with a mixed solvent of benzene and ethanol (volume ratio of benzene to ethanol is 2:1) at 70 deg.C for 6h, and air drying to obtain defatted corncob powder;
(2) adding 30g of degreased corncob powder into 600m L5 wt% NaOH solution, performing ultrasonic treatment for 10min (the ultrasonic power is 200W and the frequency is 20kHz) at 50 ℃, filtering to obtain a filtrate 1 and a filter residue, extracting the filter residue for 3h at normal temperature by using a KOH aqueous solution (the solid-to-liquid ratio is 1g:20m L) with the concentration of 5.0 wt%, filtering to obtain a filtrate 2, mixing the filtrate 1 and the filtrate 2, neutralizing by using acetic acid until the pH value is 5.5, centrifuging, washing by using an ethanol solution with the volume fraction of 75%, and performing freeze drying for 24h (-50 ℃) to obtain purified water-insoluble hemicellulose;
(3) dissolving 0.5g of water-insoluble hemicellulose into 10m of NaOH solution with the mass concentration of L being 2%, stirring and dissolving for 10min at 50 ℃ to form a homogeneous solution, and obtaining an alkali solution of the hemicellulose;
and step 3: under the protection of nitrogen, a mixed solution of potassium persulfate and sodium thiosulfate (25mg of K)2S2O8/Na2S2O3(K2S2O8With Na2S2O3The method comprises the following steps of (1: 1) dissolving in 5m L of deionized water), adding into an alkali solution of hemicellulose, uniformly stirring (30min), slowly adding an aqueous solution of acrylamide (1g of acrylamide/15 ml of deionized water), keeping the temperature at 30 ℃ for reaction for 4h, after the reaction is finished, precipitating and washing with acetone, and performing vacuum drying (the temperature is 50 ℃ and the time is 8h) to obtain the graft copolymer of the hemicellulose grafted polyacrylamide, wherein the grafting rate is 156% and the grafting efficiency is 53.4%.
Example 5
A preparation method of water-insoluble hemicellulose grafted polyacrylamide comprises the following steps:
(1) cleaning corncobs, air-drying, crushing, sieving with a 300-mesh sieve, and drying at 60 deg.C (24h) to obtain corncob powder; extracting the corncob powder with a mixed solvent of benzene and ethanol (volume ratio of benzene to ethanol is 2:1) at 70 deg.C for 6h, and air drying to obtain defatted corncob powder;
(2) adding 30g of degreased corncob powder into 600m L5 wt% NaOH solution, performing ultrasonic treatment for 10min (the ultrasonic power is 200W and the frequency is 20kHz) at 50 ℃, filtering to obtain a filtrate 1 and a filter residue, extracting the filter residue for 3h at normal temperature by using a KOH aqueous solution (the solid-to-liquid ratio is 1g:20m L) with the concentration of 5.0 wt%, filtering to obtain a filtrate 2, mixing the filtrate 1 and the filtrate 2, neutralizing by using acetic acid until the pH value is 5.5, centrifuging, washing by using an ethanol solution with the volume fraction of 75%, and performing freeze drying for 24h (-50 ℃) to obtain purified water-insoluble hemicellulose;
(3) dissolving 0.5g of water-insoluble hemicellulose into 10m of NaOH solution with the mass concentration of L being 2%, stirring and dissolving for 10min at 50 ℃ to form a homogeneous solution, and obtaining an alkali solution of the hemicellulose;
(4) under the protection of nitrogen, a mixed solution of potassium persulfate and sodium thiosulfate (25mg of K)2S2O8/Na2S2O3(K2S2O8With Na2S2O3The method comprises the following steps of (1: 1) dissolving in 5m L of deionized water), adding into an alkali solution of hemicellulose, uniformly stirring (30min), slowly adding an aqueous solution of acrylamide (5g of acrylamide/15 ml of deionized water), keeping the temperature at 30 ℃ for reaction for 4h, after the reaction is finished, precipitating and washing with acetone, and performing vacuum drying (the temperature is 50 ℃ and the time is 8h) to obtain the graft copolymer of the hemicellulose grafted polyacrylamide, wherein the grafting rate is 216% and the grafting efficiency is 38.7%.
The embodiments of the present invention are described above, and the present invention is not limited to the embodiments described above, and those skilled in the art can change the technical contents described above. However, the technical spirit of the present invention is not to be departed from the technical solution of the present invention, and the above examples are simply modified, equivalent changes and modifications, and still fall within the technical scope of the present invention.
Claims (10)
1. A preparation method of water-insoluble hemicellulose grafted polyacrylamide is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of water-insoluble hemicellulose
(2) Putting water-insoluble hemicellulose into a dilute alkali solution, and heating and dissolving to obtain an alkali solution of the hemicellulose;
(3) adding a catalyst and an acrylamide monomer into the alkali solution of the hemicellulose obtained in the step (2) under the protection of inert gas, carrying out polymerization reaction, cooling, precipitating, washing and drying to obtain water-insoluble hemicellulose grafted polyacrylamide;
the temperature of the polymerization reaction in the step (3) is 10-40 ℃; the amount of the catalyst is 5% or 7% of the mass of the water-insoluble hemicellulose; the amount of the acrylamide is 10 or 4 times of the mass of the water-insoluble hemicellulose.
2. The method for preparing water-insoluble hemicellulose grafted polyacrylamide according to claim 1, wherein: the catalyst in the step (3) is a mixture of potassium persulfate and sodium thiosulfate; the concentration of the dilute alkali solution in the step (2) is 2 to 4 weight percent;
the content of the water-insoluble hemicellulose in the step (2) is 3-7% of the total mass of the water-insoluble hemicellulose and the dilute alkali solution.
3. The method for preparing water-insoluble hemicellulose grafted polyacrylamide according to claim 1, wherein: the polymerization reaction time in the step (3) is 200-280 min;
in the step (2), the heating and dissolving temperature is 50-90 ℃, and the heating and dissolving time is 10-50 min.
4. The method for preparing water-insoluble hemicellulose grafted polyacrylamide according to claim 1, wherein: in the step (2), the dilute alkali is potassium hydroxide or sodium hydroxide; the solvent used for precipitation in the step (3) is tetrahydrofuran, absolute ethyl alcohol, methanol or acetone; the washing detergent is acetone, methanol or absolute ethyl alcohol.
5. The method for preparing water-insoluble hemicellulose grafted polyacrylamide according to claim 1, wherein: the drying in the step (3) is vacuum drying, the temperature of the vacuum drying is 45-60 ℃, and the time is 6-48 hours;
in the step (3), the catalyst is added in the form of an aqueous solution of the catalyst, and the acrylamide is added in the form of an aqueous solution of acrylamide;
the mass volume ratio of the catalyst to water in the aqueous solution of the catalyst is (20-35) mg, (5-8) m L, and the mass volume ratio of acrylamide to water in the aqueous solution of the acrylamide is (1-5) mg, (10-15) m L.
6. The method for preparing water-insoluble hemicellulose grafted polyacrylamide according to claim 1, wherein: the water-insoluble hemicellulose in the step (1) is extracted by taking corncobs as raw materials;
the specific preparation steps of the water-insoluble hemicellulose are as follows:
(a) cleaning corncobs, air-drying, crushing, sieving and drying to obtain corncob powder;
(b) extracting the corncob powder by adopting a mixed solvent of benzene and ethanol, and air-drying to obtain degreased corncob powder;
(c) dispersing the degreased corncob powder into a strong alkali solution 1, performing ultrasonic treatment, and filtering to obtain a filtrate 1 and filter residues; adding the filter residue into a strong base solution 2, extracting at normal temperature, and filtering to obtain a filtrate 2;
(d) and combining the filtrate 1 and the filtrate 2, uniformly mixing, neutralizing until the pH value is 5-6, completely precipitating, centrifuging, washing and drying to obtain the water-insoluble hemicellulose.
7. The method for producing a water-insoluble hemicellulose-grafted polyacrylamide according to claim 6, characterized in that: the sieving mesh number in the step (a) is 200-400 meshes, and the drying condition is that the drying is carried out for 24-28 h at 50-70 ℃;
the volume ratio of benzene to ethanol in the mixed solvent of benzene and ethanol in the step (b) is 2: 1; the extraction condition is extraction at 50-70 ℃ for 5-7 h;
in the step (c), the strong alkali solution 1 and the strong alkali solution 2 are the same or different and are KOH or NaOH solutions, and the concentrations of the strong alkali solution 1 and the strong alkali solution 2 are 4.0-6.0 wt%;
the solid-to-liquid ratio of the degreased corncob powder to the strong base solution 1 in the step (c) is 1g:20m L, wherein the ultrasonic treatment condition is ultrasonic treatment for 8-12 min at 40-60 ℃, the ultrasonic power is 180-200W, and the frequency is 20-30 kHz;
the solid-liquid ratio of the filter residue to the strong alkali solution 2 in the step (c) is 1g to 20m L, and the normal-temperature extraction time is 2-4 h;
the centrifugal rotating speed in the step (d) is 4500-5000 r/min; the washing is to wash by adopting an ethanol solution with the volume fraction of 75%; the drying is freeze drying.
8. A water-insoluble hemicellulose-grafted polyacrylamide obtained by the preparation method according to any one of claims 1 to 7.
9. Use of the water insoluble hemicellulose grafted polyacrylamide according to claim 8, characterized in that: the water-insoluble half-fiber grafted polyacrylamide is used for preparing a hydrogel material and is applied to the fields of sewage treatment, drug sustained release and super absorbent materials.
10. Use of the water insoluble hemicellulose grafted polyacrylamide according to claim 8, characterized in that: the water-insoluble hemicellulose grafted polyacrylamide is used for preparing a polysaccharide-based colon-targeted drug delivery system;
the water-insoluble hemicellulose-grafted polyacrylamide is used for preparing water-insoluble hemicellulose-grafted polyacrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610700935.XA CN107759735B (en) | 2016-08-22 | 2016-08-22 | Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610700935.XA CN107759735B (en) | 2016-08-22 | 2016-08-22 | Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107759735A CN107759735A (en) | 2018-03-06 |
| CN107759735B true CN107759735B (en) | 2020-07-28 |
Family
ID=61264284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610700935.XA Active CN107759735B (en) | 2016-08-22 | 2016-08-22 | Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107759735B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715765B (en) * | 2018-06-19 | 2020-09-08 | 南京工业大学 | Method for preparing hemicellulose-based water-retaining agent by using hemicellulose emulsion through microchannel reaction device |
| CN110240673B (en) * | 2019-06-19 | 2022-03-22 | 天津科技大学 | Poplar steam blasting liquid hemicellulose-based hydrogel and preparation method thereof |
| CN112619322A (en) * | 2021-01-15 | 2021-04-09 | 王忠良 | Air filtering membrane replacing melt-blown fabric and preparation method thereof |
| CN113371884A (en) * | 2021-07-07 | 2021-09-10 | 广州华景建设有限公司 | Rainwater recycling process suitable for garden landscape |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519476A (en) * | 2009-03-30 | 2009-09-02 | 中国科学技术大学 | Method for preparing high-hydroscopicity resin in homogeneous aqueous medium by using straw as raw material |
| CN102250293A (en) * | 2011-05-25 | 2011-11-23 | 重庆工商大学 | Preparation method and application of acrylamide modified grafted corn cob |
| CN103709328A (en) * | 2013-10-28 | 2014-04-09 | 北京林业大学 | Preparation method of hemicelluloses-based organic-inorganic compound hydrogel |
| CN105131185A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Pineapple waste hemicellulose based pH sensitive type porous hydrogel as well as preparation method and application thereof |
-
2016
- 2016-08-22 CN CN201610700935.XA patent/CN107759735B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519476A (en) * | 2009-03-30 | 2009-09-02 | 中国科学技术大学 | Method for preparing high-hydroscopicity resin in homogeneous aqueous medium by using straw as raw material |
| CN102250293A (en) * | 2011-05-25 | 2011-11-23 | 重庆工商大学 | Preparation method and application of acrylamide modified grafted corn cob |
| CN103709328A (en) * | 2013-10-28 | 2014-04-09 | 北京林业大学 | Preparation method of hemicelluloses-based organic-inorganic compound hydrogel |
| CN105131185A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Pineapple waste hemicellulose based pH sensitive type porous hydrogel as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Synthesis and characterization of temperature sensitive hemicellulose-based hydrogels;J.Y. Yang等;《Carbohydrate Polymers》;20110607;第1113-1117页 * |
| 刘柏辰等.磁性半纤维素接枝聚丙烯酰胺水凝胶的制备及其性能研究.《现代化工》.2013,第33卷89-93. * |
| 玉米芯半纤维素的分离及其水凝胶的制备;方驹;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20121216;1.5.2,2.2.1 * |
| 磁性半纤维素接枝聚丙烯酰胺水凝胶的制备及其性能研究;刘柏辰等;《现代化工》;20130630;第33卷;第89-93页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107759735A (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | A review on peach gum polysaccharide: Hydrolysis, structure, properties and applications | |
| CN107759735B (en) | Water-insoluble hemicellulose grafted polyacrylamide and preparation and application thereof | |
| CN102439047B (en) | Process for the preparation of agarose polymer from seaweed extractive | |
| CN103145918B (en) | Preparation method of cellulose-g-resin acid grafted copolymer | |
| CN106243282B (en) | Modification of chitosan/nano-cellulose composite aerogel and its preparation method and application | |
| CN102964524B (en) | Method for extruding in-situ grafting modified cellulose through twin screws with ionic liquid serving as solvent | |
| CN103613709B (en) | With yam starch xanthate for the resin dedicated method of Material synthesis Adsorption of Heavy Metal Ions | |
| CN103588886A (en) | Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
| JP2018039973A (en) | Method for producing pentosan polysulfate | |
| CN111410185B (en) | Method for preparing carbon microspheres by hydrothermal carbonization in high-concentration salt solution | |
| Huang et al. | Ultrafast improvement of cellulose accessibility via non-dissolving pretreatment with LiBrĚ3H2O under room temperature | |
| CN103435717A (en) | Chitosan oligosaccharide | |
| CN102391378B (en) | Method for preparing cellulose acetate from wheat straws | |
| CN102417564B (en) | Water-retaining agent and preparation method thereof by papermaking sludge | |
| CN102942691B (en) | Synthetic method of hemicellulose graft polypropylene oxide | |
| CN101182686A (en) | Decrystallizing method of cellulose in ion liquid | |
| CN110615855B (en) | Method for preparing water-soluble oligomeric derivative by dissolving and degrading biological polysaccharide | |
| CN101418049A (en) | A kind of hyaluronic preparation method | |
| CN112175111B (en) | Method for efficiently separating wood fiber material to obtain high-purity components | |
| CN102617752A (en) | Production process of low molecular weight pectin | |
| CN115010827A (en) | Eutectic solvent, preparation method thereof and method for extracting plant fibers by using eutectic solvent | |
| CN109319899A (en) | A kind of preparation method of environment friendly biological base flocculant | |
| CN114874343A (en) | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof | |
| CN1431227A (en) | Granule content of glucomannan glycering ester of konjak as well as its preparing method and usage | |
| CN113150324B (en) | TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |