CN113861429A - Modified polyvinylamine surface-modified fiber material and preparation method thereof - Google Patents
Modified polyvinylamine surface-modified fiber material and preparation method thereof Download PDFInfo
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- CN113861429A CN113861429A CN202111257426.1A CN202111257426A CN113861429A CN 113861429 A CN113861429 A CN 113861429A CN 202111257426 A CN202111257426 A CN 202111257426A CN 113861429 A CN113861429 A CN 113861429A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention discloses a fiber material with a modified polyvinylamine surface modification and a preparation method thereof, belonging to the field of fiber materials. The invention comprises the following raw materials: 0.5-2 parts of cellulose, 15-30 parts of hydrochloric acid solution (3mol/L), 15-30 parts of sodium hydroxide solution (3mol/L), 25-40 parts of etherification reagent, 0.5-2 parts of polyvinylamine, 2-8 parts of carboxyl betaine, 7-10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14-20 parts of N-hydroxysuccinimide, 2-3 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water, and the corresponding fiber material is prepared by surface modification of modified polyvinylamine. The fiber material has simple manufacturing process and wide application in various types of wastewater treatment; meanwhile, the raw material composition does not contain harmful substances, and the method is safe and environment-friendly.
Description
Technical Field
The invention belongs to the field of fiber materials, and particularly relates to a modified polyvinylamine surface-modified fiber material and a preparation method thereof.
Background
The cellulose is a natural high molecular compound with the most abundant deposits in the world, and the production raw materials are derived from wood, cotton linter, wheat straw, reed, hemp, mulberry bark, paper mulberry bark, bagasse and the like, and are inexhaustible natural renewable resources which are the most valuable for human beings. The problem of how to fully utilize cellulose and its derivatives is particularly important. The quality of the printing and dyeing wastewater varies with the type of the adopted fiber and the processing technology, and the components of pollutants are greatly different and huge. The printing and dyeing wastewater has the problems of large discharge amount, complex components, infrequent change, difficult treatment, heavy economic load treatment and the like.
The treatment of the problems in the market at present generally comprises three methods, namely a chemical method, a physical method and a biological method, so that the aim of sewage treatment can be fulfilled. However, many of these methods are complex in process and some of them are expensive. Some effects are not obvious and the reuse rate after sewage treatment is not high.
Disclosure of Invention
The invention aims to provide a fiber material with a modified polyvinylamine surface modification and a preparation method thereof, so as to solve the problems in the background technology. The invention prepares the fiber material surface-modified by using the modified polyvinylamine, and well reduces the COD of the dyeing wastewatercrThe value and the removal rate of the chroma are also high.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a fiber material surface-modified by utilizing modified polyvinylamine comprises the following steps:
(1) dispersing cellulose in an acid solution for pretreatment, and then drying and crushing to obtain pretreated cellulose;
(2) mixing the obtained pretreated cellulose with a sodium hydroxide solution, ethanol and water, uniformly mixing, standing, adding an etherification reagent for etherification, separating, collecting solids, washing and drying to obtain a product A;
(3) dispersing polyvinylamine, carboxyl betaine and a condensing agent in water, uniformly mixing for reaction, dialyzing, separating and freeze-drying after the reaction is finished to obtain a product B;
(4) respectively dissolving the product A and the product B in water to obtain a solution A and a solution B; and adding a dispersing agent and a condensing agent into the solution A, uniformly mixing, adding the solution B for condensation reaction, centrifuging after the condensation reaction is finished, collecting solids, washing and drying to obtain the fiber material.
In one embodiment of the present invention, in the step (1), the acid solution includes hydrochloric acid, sulfuric acid, and phosphoric acid. Further selecting 2-5mol/L hydrochloric acid solution; specifically, a 3mol/L hydrochloric acid solution can be selected.
In one embodiment of the present invention, in the step (1), 0.5 to 2 parts by weight of cellulose is dispersed in 15 to 30 parts by weight of the acid solution.
In one embodiment of the present invention, in the step (1), the pretreatment time is 2 to 3 hours; the temperature is 80-100 ℃. The pretreatment was carried out at 500-.
In one embodiment of the invention, in the step (2), the concentration of the sodium hydroxide solution is 2-5 mol/L; specifically, 3mol/L can be selected.
In one embodiment of the present invention, in the step (2), the weight part ratio of the sodium hydroxide solution to the cellulose in the step (1) is 15-30 parts: 0.5-2 parts.
In one embodiment of the present invention, in the step (2), the weight part ratio of ethanol to the cellulose in the step (1) is 80 parts: 0.5-2 parts.
In one embodiment of the present invention, in the step (2), the weight part ratio of the water to the cellulose in the step (1) is 100 parts: 0.5-2 parts.
In one embodiment of the present invention, in the step (2), the standing time is 1 to 2 hours.
In one embodiment of the present invention, in the step (2), the weight part ratio of the etherification reagent to the cellulose in the step (1) is 25 to 40 parts: 0.5-2 parts.
In one embodiment of the present invention, the etherification reagent is one or more of chloroacetic acid and sodium chloroacetate.
In one embodiment of the present invention, in the step (2), the time of the etherification treatment is 3 to 4 hours; the temperature is 60-80 ℃. The etherification treatment was carried out at 500 and 1000 rpm.
In one embodiment of the present invention, in the step (3), the weight part ratio of the polyvinylamine to the cellulose in the step (1) is 0.5 to 2 parts: 0.5-2 parts.
In one embodiment of the present invention, in the step (3), the weight part ratio of the polyvinylamine to the carboxyl betaine is 0.5 to 2 parts: 2-8 parts.
In one embodiment of the present invention, the carboxy-type betaine is one or more selected from the group consisting of α -alkyl betaine, N-long-chain acylalkylene betaine, and N-long-chain thiocarboxylic betaine.
In one embodiment of the present invention, in the step (3), the condensing agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide.
In one embodiment of the present invention, in the step (3), the weight part ratio of the condensing agent to the polyvinylamine is 20 to 30 parts: 0.5-2 parts.
In one embodiment of the present invention, in the condensing agent in step (3), the weight ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to N-hydroxysuccinimide in the condensing agent is 7-10 parts: 14-20 parts.
In one embodiment of the present invention, in the step (3), the weight part ratio of the polyvinylamine to the water is 0.5 to 2 parts: 100 parts.
In one embodiment of the present invention, in the step (3), the reaction time is 3 to 4 hours; the temperature was room temperature. At 500-.
In one embodiment of the present invention, in the step (3), the dialysis is performed by separating for 4-5 days using a dialysis bag, and then collecting the liquid in the bag for freeze-drying.
In one embodiment of the present invention, in the step (4), the weight part ratio of the dispersing agent to the cellulose in the step (1) is 2 to 3 parts: 0.5-2 parts.
In one embodiment of the present invention, the dispersant is one or more of sodium methylene dinaphthalenesulfonate and sodium methylene dinaphthalenesulfonate.
In one embodiment of the present invention, in the step (4), the weight part ratio of the condensing agent to the polyvinylamine in the step (3) is 20 to 30 parts: 0.5-2 parts.
In one embodiment of the present invention, in the condensing agent in step (4), the weight ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to N-hydroxysuccinimide is 7-10 parts: 14-20 parts.
In one embodiment of the present invention, in the step (4), the time for the condensation reaction is 4 to 5 hours. The temperature was room temperature. The condensation reaction is carried out at 500-1000 rpm.
In one embodiment of the invention, the fiber material is prepared from the following raw materials in parts by weight: 0.5-2 parts of cellulose, 15-30 parts of hydrochloric acid solution (3mol/L), 15-30 parts of sodium hydroxide solution (3mol/L), 25-40 parts of etherification reagent, 0.5-2 parts of polyvinylamine, 2-8 parts of carboxyl betaine, 7-10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14-20 parts of N-hydroxysuccinimide, 2-3 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
In one embodiment of the present invention, in the process of preparing the fiber material, the following raw materials can be specifically selected according to the ratio of important parts: 0.5 part of cellulose, 15 parts of hydrochloric acid solution (3mol/L), 15 parts of sodium hydroxide solution (3mol/L), 25 parts of etherification reagent, 0.5 part of polyvinylamine, 2 parts of carboxyl betaine, 7 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14 parts of N-hydroxysuccinimide, 2 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
In one embodiment of the present invention, in the process of preparing the fiber material, the following raw materials can be specifically selected according to the ratio of important parts: 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L), 20 parts of sodium hydroxide solution (3mol/L), 30 parts of etherification reagent, 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
In one embodiment of the present invention, in the process of preparing the fiber material, the following raw materials can be specifically selected according to the ratio of important parts: 1.5 parts of cellulose, 25 parts of hydrochloric acid solution (3mol/L), 25 parts of sodium hydroxide solution (3mol/L), 35 parts of etherification reagent, 1.5 parts of polyvinylamine, 6 parts of carboxyl betaine, 9 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 18 parts of N-hydroxysuccinimide, 3 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
In one embodiment of the present invention, in the process of preparing the fiber material, the following raw materials can be specifically selected according to the ratio of important parts: 2 parts of cellulose, 30 parts of hydrochloric acid solution (3mol/L), 30 parts of sodium hydroxide solution (3mol/L), 40 parts of etherification reagent, 2 parts of polyvinylamine, 8 parts of carboxyl betaine, 10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 20 parts of N-hydroxysuccinimide, 3 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention provides a fiber material for treating wastewater based on the method.
The invention also provides application of the fiber material in wastewater treatment.
The invention also provides the application of the fiber material in degrading dyeing wastewater CODcrApplication in value.
The invention also provides application of the fiber material in removing the chromaticity of dyeing wastewater.
In one embodiment of the invention, the addition amount of the fiber material is 2-10g/L when the wastewater is treated; specifically, 4g/L can be selected.
Compared with the prior art, the invention has the beneficial effects that:
the fiber material can solve the problem of COD (chemical oxygen demand) of dyeing wastewatercrHigh value, high chroma and the like, and various excellent performances of the prepared modified polyvinylamine surface modified fiber material are enhanced compared with the prior art.
The raw materials adopted by the invention are cellulose and betaine which are natural grade raw materials, and the betaine can be extracted from roots, stems, leaves and fruits of natural plants, so that the environment is not polluted, and the effect of fully and reasonably utilizing environmental resources is achieved.
According to the invention, the etherification reagent is used for increasing the surface carboxyl content of the cellulose, and then the polyvinylamine is adopted to be matched with the betaine modified cellulose, so that the modified polyvinylamine surface modification method has wide application in the aspect of wastewater treatment, has good decoloration and turbidity removal performances, and further improves the performance of the modified polyvinylamine surface modified fiber material in wastewater treatment.
The invention is the common use of composite materials, can improve the performance of a single material, enhances the performance of the original single material and has better effect. The preparation process is simple to operate, has high practicability and can provide good economic benefit; the raw materials are safe and harmless, and the environment is friendly.
Drawings
FIG. 1 is a chromaticity comparison chart of an untreated dyeing wastewater (a) and a water sample treated by the processes of comparative example 1(b) and example 2 (c).
Detailed Description
The molecular weight of the polyvinylamine related to the invention is 300 ten thousand; cellulose has a molecular weight of 162.06.
The invention discloses a fiber material with a modified polyvinylamine surface modification, which comprises the following components in parts by weight: 0.5-2 parts of cellulose, 15-30 parts of hydrochloric acid solution (3mol/L), 15-30 parts of sodium hydroxide solution (3mol/L), 25-40 parts of etherification reagent, 0.5-2 parts of polyvinylamine, 2-8 parts of carboxyl betaine, 7-10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14-20 parts of N-hydroxysuccinimide, 2-3 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention also provides a preparation method of the fiber material surface-modified by utilizing the modified polyvinylamine, which comprises the following specific steps:
step 1, adding 0.5-2 parts of cellulose and 15-30 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2-3 hours at 80-100 ℃ and 1000 r/min at 500-;
step 2, adding 15-30 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the mixture into the cellulose pretreated in the step 1 after the sodium hydroxide solution, the absolute ethyl alcohol and the deionized water are completely mixed, soaking the cellulose for 1-2 hours, then adding 25-40 parts of etherification reagent, washing, drying and crushing the cellulose when the cellulose is treated for 3-4 hours at the temperature of 60-80 ℃ to obtain a product A;
step 3, adding 0.5-2 parts of polyvinylamine, 2-8 parts of carboxyl betaine, 7-10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14-20 parts of N-hydroxysuccinimide, 100 parts of deionized water into a reaction kettle, stirring for 3-4 hours at 500 revolutions per minute, filling the obtained solution into a dialysis bag for dialysis separation for 4-5 days, collecting the liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2-3 parts of a dispersing agent, 7-10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 14-20 parts of N-hydroxysuccinimide into the solution A, and continuing to add the solution B after the solution A is completely dissolved, wherein the solution B continues to be added after the solution A is completely dissolved, and the solution A continues to be dissolved for 4-5 hours at the time of 500-; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Example 1
The invention discloses a fiber material with a modified polyvinylamine surface modification, which comprises the following components in parts by weight: 0.5 part of cellulose (equivalent to 0.5g), 15 parts of hydrochloric acid solution (3mol/L), 15 parts of sodium hydroxide solution (3mol/L), 25 parts of etherification reagent, 0.5 part of polyvinylamine, 2 parts of carboxyl betaine, 7 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14 parts of N-hydroxysuccinimide, 2 parts of dispersant methylene dinaphthalene sodium sulfonate, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention also provides a preparation method of the fiber material surface-modified by utilizing the modified polyvinylamine, which comprises the following specific steps:
step 1, adding 0.5 part of cellulose and 15 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 15 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the cellulose pretreated in the step 1 after completely mixing, soaking for 1 hour, then adding 25 parts of etherifying reagent, treating at 70 ℃ for 3 hours at 600 revolutions per minute, washing, drying and crushing to obtain a product A;
step 3, adding 0.5 part of polyvinylamine, 2 parts of carboxyl betaine, 7 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours, filling the obtained solution into a dialysis bag for dialysis separation for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 7 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 14 parts of N-hydroxysuccinimide and 600 revolutions per minute into the solution A, continuously adding the solution B after the solution A is completely dissolved, and stirring at room temperature for 4 hours at 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Example 2
The invention discloses a fiber material with a modified polyvinylamine surface modification, which comprises the following components in parts by weight: 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L), 20 parts of sodium hydroxide solution (3mol/L), 30 parts of etherification reagent, 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention also provides a preparation method of the fiber material surface-modified by utilizing the modified polyvinylamine, which comprises the following specific steps:
step 1, adding 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L) and 80/600 rpm into a reaction kettle, filtering after 2 hours of treatment, and drying and crushing the treated cellulose;
step 2, adding 20 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the mixture into the cellulose pretreated in the step 1 after the mixture is completely mixed, soaking the mixture for 1 hour, then adding 30 parts of etherifying reagent, washing, drying and crushing the mixture at the temperature of 70 ℃ for 3 hours to obtain a product A;
step 3, adding 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours at 600 rpm, filling the obtained solution into a dialysis bag, dialyzing and separating for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 16 parts of N-hydroxysuccinimide into the solution A, stirring at room temperature for 4 hours after the dispersing agent is completely dissolved, and continuing to add the solution B for 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Example 3
The invention discloses a fiber material with a modified polyvinylamine surface modification, which comprises the following components in parts by weight: 1.5 parts of cellulose, 25 parts of hydrochloric acid solution (3mol/L), 25 parts of sodium hydroxide solution (3mol/L), 35 parts of etherification reagent, 1.5 parts of polyvinylamine, 6 parts of carboxyl betaine, 9 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 18 parts of N-hydroxysuccinimide, 3 parts of dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention also provides a preparation method of the fiber material surface-modified by utilizing the modified polyvinylamine, which comprises the following specific steps:
step 1, adding 1.5 parts of cellulose and 25 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 25 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the cellulose pretreated in the step 1 after completely mixing, soaking for 1 hour, then adding 35 parts of etherifying reagent, 600 revolutions per minute, treating for 3 hours at 70 ℃, washing, drying and crushing to obtain a product A;
step 3, adding 1.5 parts of polyvinylamine, 6 parts of carboxyl betaine, 9 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 18 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours, filling the obtained solution into a dialysis bag for dialysis separation for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 3 parts of dispersing agent, 9 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 18 parts of N-hydroxysuccinimide and 600 revolutions per minute into the solution A, continuously adding the solution B after completely dissolving, and stirring at room temperature for 4 hours at 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Example 4
The invention discloses a fiber material with a modified polyvinylamine surface modification, which comprises the following components in parts by weight: 2 parts of cellulose, 30 parts of hydrochloric acid solution (3mol/L), 30 parts of sodium hydroxide solution (3mol/L), 40 parts of etherification reagent, 2 parts of polyvinylamine, 8 parts of carboxyl betaine, 10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 20 parts of N-hydroxysuccinimide, 3 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
The invention also provides a preparation method of the fiber material surface-modified by utilizing the modified polyvinylamine, which comprises the following specific steps:
step 1, adding 2 parts of cellulose and 30 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 30 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the cellulose pretreated in the step 1 after completely mixing, soaking for 1 hour, then adding 40 parts of etherifying reagent, washing, drying and crushing to obtain a product A when treating for 3 hours at 600 revolutions per minute and 70 ℃;
step 3, adding 2 parts of polyvinylamine, 8 parts of carboxyl betaine, 10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 20 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours at 600 rpm, filling the obtained solution into a dialysis bag, dialyzing and separating for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 3 parts of dispersing agent, 10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 20 parts of N-hydroxysuccinimide and 600 revolutions per minute into the solution A, continuously adding the solution B after completely dissolving, and stirring at room temperature for 4 hours at 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Comparative example 1
Referring to example 2, the hydrochloric acid solution in step (1) was omitted:
a fiber material with a modified polyvinylamine surface modification comprises the following components in parts by weight: 1 part of cellulose, 20 parts of sodium hydroxide solution (3mol/L), 30 parts of etherification reagent, 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
A preparation method of a fiber material with a modified polyvinylamine surface modification comprises the following specific steps:
step 1, adding 1 part of cellulose, 20 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding 30 parts of etherification reagent after complete mixing, processing at 600 revolutions per minute and 70 ℃ for 3 hours, and washing, drying and crushing to obtain a product A;
step 2, adding 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours at 600 rpm, filling the obtained solution into a dialysis bag, dialyzing and separating for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 3, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 16 parts of N-hydroxysuccinimide into the solution A, stirring at room temperature for 4 hours after the dispersing agent is completely dissolved, and continuing to add the solution B for 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Comparative example 2
Referring to example 2, the sodium hydroxide solution in step (1) was omitted:
a fiber material with a modified polyvinylamine surface modification comprises the following components in parts by weight: 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L), 30 parts of etherification reagent, 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
A preparation method of a fiber material with a modified polyvinylamine surface modification comprises the following specific steps:
step 1, adding 1 part of cellulose and 20 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the cellulose pretreated in the step 1 after complete mixing, soaking for 1 hour, then adding 30 parts of etherifying reagent, performing 600 revolutions per minute at 70 ℃, washing, drying and crushing for 3 hours to obtain a product A;
step 3, adding 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours at 600 rpm, filling the obtained solution into a dialysis bag, dialyzing and separating for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 16 parts of N-hydroxysuccinimide into the solution A, stirring at room temperature for 4 hours after the dispersing agent is completely dissolved, and continuing to add the solution B for 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Comparative example 3
Referring to example 2, the etherification reagent in step (2) was omitted:
a fiber material with a modified polyvinylamine surface modification comprises the following components in parts by weight: 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L), 20 parts of sodium hydroxide solution (3mol/L), 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of a dispersing agent, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
A preparation method of a fiber material with a modified polyvinylamine surface modification comprises the following specific steps:
step 1, adding 1 part of cellulose and 20 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 20 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, completely mixing, adding the cellulose pretreated in the step 1, soaking for 1 hour at 600 revolutions per minute at 70 ℃, washing, drying and crushing for 3 hours to obtain a product A;
step 3, adding 1 part of polyvinylamine, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours at 600 rpm, filling the obtained solution into a dialysis bag, dialyzing and separating for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 16 parts of N-hydroxysuccinimide into the solution A, stirring at room temperature for 4 hours after the dispersing agent is completely dissolved, and continuing to add the solution B for 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
Comparative example 4
Referring to example 2, the polyvinylamine in step (3) was omitted:
a fiber material with a modified polyvinylamine surface modification comprises the following components in parts by weight: 1 part of cellulose, 20 parts of hydrochloric acid solution (3mol/L), 20 parts of sodium hydroxide solution (3mol/L), 30 parts of etherification reagent, 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide, 2 parts of dispersant, 80 parts of absolute ethyl alcohol and 100 parts of deionized water.
A preparation method of a fiber material with a modified polyvinylamine surface modification comprises the following specific steps:
step 1, adding 1 part of cellulose and 20 parts of hydrochloric acid solution (3mol/L) into a reaction kettle, treating for 2 hours at 80 ℃ at 600 rpm, filtering, drying and crushing the treated cellulose;
step 2, adding 20 parts of sodium hydroxide solution (3mol/L), 80 parts of absolute ethyl alcohol and 100 parts of deionized water into a reaction kettle, adding the mixture into the cellulose pretreated in the step 1 after the mixture is completely mixed, soaking the mixture for 1 hour, then adding 30 parts of etherifying reagent, washing, drying and crushing the mixture at the temperature of 70 ℃ for 3 hours to obtain a product A;
step 3, adding 4 parts of carboxyl betaine, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 16 parts of N-hydroxysuccinimide and 100 parts of deionized water into a reaction kettle, stirring at room temperature for 3 hours, filling the obtained solution into a dialysis bag for dialysis and separation for 4 days, collecting liquid in the bag, and freeze-drying to obtain a product B;
step 4, respectively dissolving the product A and the product B in 100 parts of deionized water to obtain a solution A and a solution B, adding 2 parts of dispersing agent, 8 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 16 parts of N-hydroxysuccinimide into the solution A, stirring at room temperature for 4 hours after the dispersing agent is completely dissolved, and continuing to add the solution B for 1000 revolutions per minute; and after the reaction is finished, centrifuging, collecting solids, washing and drying to obtain a finished fiber material product.
And (3) testing results:
250mL of dyeing wastewater with the same specification was treated with 1.0g of the modified polyvinylamine surface-modified fiber materials obtained by the treatment methods of examples 1, 2, 3, and 4 and comparative examples 1, 2, 3, and 4, respectively, and the dyeing wastewater was tested after the treatment. The test results are shown in table 1.
The test method comprises the following steps: the dyeing wastewater was analyzed using a multi-parameter water quality analyzer model 5B-3B (V8) from Lianhua environmental protection technologies, Inc., Lanzhou. CODcrThe method is an important index for indicating organic pollution of the water body, can reflect the pollution degree of the water body, and indicates that the water body is more seriously polluted by organic matters when the chemical oxygen demand is larger. The instrument adopts a spectrophotometry method, during testing, a water sample to be tested and a reagent are added into a digestion colorimetric tube, the digestion colorimetric tube is placed into a digestion device for digestion at a constant temperature of 165 ℃ for 15 minutes, and after the digestion is cooled to room temperature, COD is usedcrThe rapid determinator determines and directly reads out COD in the water samplecrThe value is obtained.
TABLE 1 wastewater treatment capacities of fiber materials obtained in examples 1 to 4 and comparative examples 1 to 4
| Serial number | CODcrValue of | Efficiency of treatment |
| Waste water (untreated) | 2033 | - |
| Example 1 | 177 | 91.3％ |
| Example 2 | 11 | 99.5％ |
| Example 3 | 137 | 93.3％ |
| Example 4 | 149 | 92.7％ |
| Comparative example 1 | 893 | 56.1％ |
| Comparative example 2 | 915 | 55.0％ |
| Comparative example 3 | 978 | 51.9％ |
| Comparative example 4 | 1686 | 17.1％ |
Wherein the treatment efficiency is (COD before treatment)crvalue-COD after treatmentcrvalue)/COD before treatmentcrThe value is obtained.
As can be seen, comparative example 1, in which no hydrochloric acid solution was added, removed COD in watercrThe capacity is poor. Comparative example 2 removal of COD from Water without adding sodium hydroxide solutioncrThe capacity is poor. Comparative example 3 removal of COD from Water without addition of Ether reagentcrThe capacity is poor. Comparative example 4 removal of COD in Water without addition of PolyvinylaminecrThe capacity is poor.
The untreated dyeing wastewater and the water samples treated by the processes of the comparative example 1 and the example 2 have the corresponding colorimetric ratio shown in FIG. 1. The untreated dyeing wastewater is in a relatively dark ink color (fig. 1a), and the chroma is reduced but still has a relatively remarkable color (fig. 1b) after being treated by the process of the comparative example 1, namely, the dyeing and removing effects are still to be improved. The wastewater treated by the process of the embodiment 2 of the invention is basically colorless, clear and transparent (figure 1c), and has excellent decolorizing effect.
Example 5
Referring to example 1, the polyvinylamine was replaced with polyethyleneimine and polyacrylamide, respectively, in equal amounts, and the others were unchanged, to obtain the corresponding fiber materials.
The obtained fiber materials were measured for their ability to treat dyeing wastewater, and the results are shown in Table 2.
TABLE 2 Performance results of fiber materials obtained with different amino reagents
| Amino reagents | CODcrValue of |
| Polyvinylamine (example 1) | 177 |
| Polyethylene imine | 225 |
| Polyacrylamide | 213 |
Example 6
Referring to example 2, the amounts of carboxylic acid betaines were replaced with the amounts shown in table 3, respectively, and the other amounts were unchanged to obtain corresponding fiber materials.
The obtained fiber materials were measured for their ability to treat dyeing wastewater, and the results are shown in Table 3.
TABLE 3 Performance results for fiber materials obtained with different polyvinylamine to carboxylic acid betaine mass ratios
| Mass ratio of polyvinylamine to carboxylic acid betaine | CODcrValue of |
| 1:4 (example 2) | 11 |
| 1：1 | 34 |
| 1：2 | 28 |
| 1：3 | 23 |
| 1：5 | 11 |
| 1：6 | 11 |
| 1：7 | 11 |
The various embodiments listed above can be combined with each other without contradiction, and a person skilled in the art can combine the above explanations of the embodiments as a basis for combining technical features in different embodiments.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a modified polyvinylamine surface modified fiber material comprises the following steps:
(1) dispersing cellulose in an acid solution for pretreatment, and then drying and crushing to obtain pretreated cellulose;
(2) mixing the obtained pretreated cellulose with a sodium hydroxide solution, ethanol and water, uniformly mixing, standing, adding an etherification reagent for etherification, separating, collecting solids, washing and drying to obtain a product A;
(3) dispersing polyvinylamine, carboxyl betaine and a condensing agent in water, uniformly mixing for reaction, dialyzing, separating and freeze-drying after the reaction is finished to obtain a product B;
(4) respectively dissolving the product A and the product B in water to obtain a solution A and a solution B; and adding a dispersing agent and a condensing agent into the solution A, uniformly mixing, adding the solution B for condensation reaction, centrifuging after the condensation reaction is finished, collecting solids, washing and drying to obtain the fiber material.
2. The method according to claim 1, wherein in the step (2), the etherification reagent is one or more of chloroacetic acid and sodium chloroacetate.
3. The method according to claim 1, wherein in the step (2), the weight part ratio of the etherification reagent to the cellulose in the step (1) is 25-40 parts: 0.5-2 parts.
4. The method according to claim 1, wherein in the step (3), the weight part ratio of the polyvinylamine to the cellulose in the step (1) is 0.5-2 parts: 0.5-2 parts.
5. The method as claimed in claim 1, wherein in the step (3), the weight part ratio of the polyvinylamine to the carboxyl betaine is 0.5-2 parts: 2-8 parts.
6. The method according to any one of claims 1 to 5, wherein the dispersant is one or more of sodium methylene bis naphthalene sulfonate and sodium methylene bis methyl naphthalene sulfonate.
7. A fibrous material produced by the process of any one of claims 1 to 6.
8. Use of the fibrous material of claim 7 in wastewater treatment.
9. The fiber material of claim 7 is used for degrading dyeing wastewater CODcrApplication in value.
10. Use of the fiber material of claim 7 for removing the color shade of dyeing wastewater.
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