CN114573864A - Porous adsorption resin and preparation method and application thereof - Google Patents
Porous adsorption resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN114573864A CN114573864A CN202210290487.6A CN202210290487A CN114573864A CN 114573864 A CN114573864 A CN 114573864A CN 202210290487 A CN202210290487 A CN 202210290487A CN 114573864 A CN114573864 A CN 114573864A
- Authority
- CN
- China
- Prior art keywords
- reaction
- porous
- resin
- adsorption resin
- functional
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
- A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
- A23L2/80—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F112/36—Divinylbenzene
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a porous adsorption resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding the oil phase into the water phase, and carrying out suspension polymerization reaction to prepare a porous matrix containing benzene rings in the skeleton; the oil phase comprises a monomer, a pore-foaming agent and an initiator; swelling a porous substrate with dichloroethane, adding a functional reagent 1 and a catalyst to perform a first functional reaction, adding a functional reagent 2 to perform a second functional reaction after the reaction is finished, adding the catalyst to perform a Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying to obtain porous adsorption resin after the reaction is finished; wherein, the functionalization reagent 1 comprises one or more of dichlorobenzyl, biphenyl dichlorobenzyl, p-dichlorobenzyl and dichloromethylanthracene, and the functionalization reagent 2 is melamine or derivatives thereof. The invention does not use chloromethyl ether, obtains the adsorption resin with high specific surface area and highly developed porous structure, improves the hydrophilicity of the resin and improves the fruit juice decoloring effect.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and adsorption materials, and particularly relates to a porous adsorption resin and a preparation method and application thereof.
Background
In recent years, the rapid development of the fruit industry continuously expands the planting area of fruits such as grapes, apples and pears, the fruit processing industry in China also enters a rapid development period, and the fruit processing industry is gradually expanded from the initial apple juice and pear juice to the processing of various fruit juices such as mango juice, strawberry juice and kiwi fruit juice. Along with the intensification of international trade competition, the quality of concentrated juice is more and more emphasized by people, and the color value of an important index for evaluating the quality of the juice is inevitably concerned. The coloring matter is easily browned during the juice processing to affect the sensory quality of the product, and thus, a decoloring treatment must be performed during the juice processing.
In the early days, no matter in the fields of wastewater, fruit juice processing and the like, activated carbon attracts attention due to the advantages of developed specific surface area, strong adsorption capacity, good adsorption effect on pigments and the like, so the activated carbon is also used as the most commonly used decolorizing material and is still used up to now, but the decolorizing effect of the activated carbon in the field of high-quality fruit juice processing does not meet certain specific requirements at present. With the rapid development of membrane technology, the ultrafiltration membrane shows good decolorization performance in the process of concentrating juice, has good repeatability and simple operation, but has poor pollution resistance and difficult cleaning in the use process, and reduces the service life of the membrane, thereby increasing the cost and limiting the application range of the membrane. The adsorption resin has the advantages of high specific surface area, simplicity and convenience in operation, high working efficiency, high selectivity and the like, and pigments, hydrophobic compounds, browning components and the like can be adsorbed on a resin framework through Van der Waals force in the fruit juice decoloring process, so that pigment substances in fruit juice are removed, the color value index of the fruit juice is improved, the quality of the fruit juice is improved, and the problems of poor adsorption selectivity, poor physical and chemical stability, short service life, difficulty in regeneration and the like of adsorbents such as activated carbon, ultrafiltration membranes and the like are solved.
However, most of the prior high specific surface area adsorbent resins used in the fruit juice decolorization industry adopt chloromethyl ether to perform chloromethylation, so that the adsorbent resins can be ensured to have ultrahigh specific surface area and highly developed three-dimensional network structure, thereby showing excellent decolorization effect. However, chloromethyl ether used in chloromethylation has high toxicity and carcinogenicity, and the use of chloromethyl ether is greatly limited with the increase of environmental protection pressure.
Subsequently, in patent CN 111171199B-an adsorbent resin for removing perfluorinated pollutants in water and its preparation and application, researchers developed a method for preparing a porous adsorbent resin with a high specific surface area without undergoing a chloromethylation reaction, in which a functional reagent was added during the preparation of the resin, and the obtained resin had a uniform pore size and a large specific surface area, but due to the addition of the functional reagent, a rigid benzene ring structure was introduced to make the resin have a higher hydrophobicity and have a poor effect in adsorbing hydrophilic pigment molecules. Therefore, improvement in hydrophilicity of the resin is desired.
Disclosure of Invention
The invention aims to provide a porous adsorption resin, a preparation method and application thereof, wherein a functional reagent is added to prepare the adsorption resin with a high specific surface area and a highly developed porous structure on the premise of carrying out chloromethylation reaction without using chloromethyl ether, and meanwhile, the hydrophilicity of the resin is improved, and the decoloration effect on fruit juice is improved.
The invention is realized by the following technical scheme:
a preparation method of porous adsorption resin comprises the following steps:
s1: synthesizing a porous matrix: adding the oil phase into the water phase, and carrying out suspension polymerization reaction to prepare a porous matrix with a skeleton containing benzene rings; the oil phase comprises a monomer, a pore-foaming agent and an initiator;
s2: and (3) functional reaction: swelling a porous substrate with dichloroethane, adding a functional reagent 1 and a catalyst to perform a first functional reaction, adding a functional reagent 2 to perform a second functional reaction after the reaction is finished, adding the catalyst to perform a Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying to obtain porous adsorption resin after the reaction is finished; wherein, the functionalization reagent 1 comprises one or more of dichlorobenzyl, biphenyl dichlorobenzyl, p-dichlorobenzyl and dichloromethylanthracene, and the functionalization reagent 2 is melamine or derivatives thereof.
Preferably, in S1, the monomer includes one or more of styrene, ethylstyrene, methyl acrylate, methyl methacrylate, acrylic acid, acrylonitrile, divinylbenzene, dipropylene benzene, ethylene glycol dimethacrylate and glycerol trimethacrylate, the initiator includes one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide, and the pore-forming agent includes one or more of saturated hydrocarbon, toluene, xylene, tetramethylbenzene and dichloroethane.
Preferably, the mass ratio of the monomer, the initiator and the pore-forming agent is (0.5-1.5) to (150-300) 100.
Preferably, in S1, the suspension polymerization reaction is specifically: reacting for 8-12 hours at 75-95 ℃.
Preferably, in S1, the aqueous phase is prepared by dissolving a dispersant in water, wherein the dispersant is one or more of polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose, lignin and gelatin.
Preferably, in S2, the mass ratio of the porous matrix to the functionalizing agent 1 to the functionalizing agent 2 is 1 (0.3-0.5) to 0.03-0.05.
Preferably, in S2, the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride.
Preferably, the reaction temperature of the first functionalization reaction is 45-60 ℃, and the reaction time is 3-5 hours; the reaction temperature of the second functionalization reaction is 30-35 ℃, and the reaction time is 3-5 hours; the reaction temperature of the Friedel-crafts alkylation reaction is 70-80 ℃, and the reaction time is 6-9 hours.
The porous adsorption resin prepared by the preparation method is adopted.
The porous adsorption resin is applied to decolorization of fruit juice.
Compared with the prior art, the invention has the following beneficial effects:
in the resin synthesis process, a porous matrix is prepared, then a functional reagent 1 is added, and the functional reagent 1 can perform alkylation reaction with a benzene ring on a resin skeleton under the action of a catalyst, so that the resin skeleton is provided with a certain amount of-CH 2The introduction of the Cl group and the functionalizing agent 1 increases the specific surface area of the resin and further enhances the hydrophobic property of the resin; on the basis of the above-mentioned reaction, adding functionalizing agent 2, under the condition of low temp. functionalizing agent 2-NH2The group and the residual-CH in the functionalizing agent 1 introduced into the resin skeleton2Cl groups react, on the one hand-NH in the functionalizing agent 2 which is not completely reacted2The groups can reduce the hydrophobicity of the resin, so that the hydrophilicity of the resin is increased, most pigments in the fruit juice have certain hydrophilicity, the decoloration effect of the fruit juice is favorably improved, and on the other hand, incompletely reacted-NH in the functional reagent 22Hydrogen bonds can be formed between the groups and the pigment molecules, so that the adsorption effect of the resin on the pigment is further improved. Finally, under the action of high temperature and catalyst, residual-CH on the resin framework2The Cl group and the adjacent benzene ring are subjected to substitution reaction again, and the residual suspended double bonds on the resin skeleton are subjected to Friedel-crafts alkylation reaction again, so that the specific surface area of the resin is further improved, and the adsorption capacity of the porous resin is further improved. The resin of the invention has simple synthesis process, and the porous matrix is directly added in the preparation process The adsorption resin with ultrahigh specific surface area and highly developed porous structure can be obtained by functional reaction, and the hydrophilicity of the resin is improved; the resin synthesis process is green and environment-friendly, and carcinogenicity and high-toxicity chloromethyl ether is not used in the resin synthesis process, so that the use of chloromethyl ether is avoided, and the harm to a human body is reduced, and the pollution to the environment is avoided.
Further, the purpose of adding the dispersant is to disperse the oil phase uniformly and to facilitate the formation of balls.
Furthermore, the catalyst has higher catalytic activity and can ensure that the functionalized reagent and the benzene ring react more thoroughly.
The porous adsorption resin prepared by the method has an ultrahigh specific surface area and a highly developed porous structure, and is more favorable for subsequent application.
The porous adsorption resin prepared by the invention has the advantages of large decolorization capacity, good decolorization effect, easy regeneration and the like on fruit juice.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, which are provided to illustrate further features and advantages of the invention, and are not intended to limit the scope of the invention as set forth in the following claims.
The preparation method of the porous adsorption resin for fruit juice decoloration adopts a suspension polymerization mode, and specifically comprises the following steps:
S1: synthesizing a porous matrix: adding the dispersing agent into water, heating, and stirring until the dispersing agent is completely dissolved to prepare a water phase; uniformly mixing a monomer, a pore-foaming agent and an initiator to obtain an oil phase; adding the oil phase into the prepared water phase, standing for complete layering, adjusting the height and the rotating speed of a stirring paddle to control the particle size of the oil phase, uniformly stirring after the particle size is proper, and then heating and preserving heat; and (3) washing away the dispersing agent on the surface of the resin by using hot water after the reaction is finished, extracting a pore-foaming agent in the resin, washing with water, drying, and screening the porous matrix of 60-20 meshes for later use.
S2: and (3) functional reaction: adding the porous substrate prepared in the step S1 into a reaction kettle, swelling with a certain amount of dichloroethane, adding the functional reagent 1 and the catalyst for low-temperature reaction after swelling for a certain time, adding the functional reagent 2 for reaction after the reaction is finished, and finally adding the catalyst for Friedel-crafts alkylation reaction at high temperature. And after the reaction is finished, adding water into the system, recovering dichloroethane through azeotropy of the water and the dichloroethane, washing the resin until the resin is neutral, and discharging to obtain the finished product of the porous adsorption resin.
In the step S1, the mass ratio of water to the dispersing agent is 100 (0.01-0.1), wherein the dispersing agent is one or more of polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose, lignin and gelatin. The purpose of adding the dispersant is to make the oil phase disperse uniformly and more easily form spheres.
In step S1, the mass ratio of the monomer to the initiator to the pore-forming agent is (0.5-1.5) to (150-300). If the addition amounts of the initiator and the pore-forming agent are controlled well, too much initiator is easy to cause implosion, and too little initiator is easy to cause too slow polymerization reaction speed; if the pore-foaming agent is too little, the specific surface area of the resin is too small, and if the pore-foaming agent is too much, the strength of the resin is too low, which is not beneficial to practical application.
In step S1, the monomer includes one or more of styrene, ethylstyrene, methyl acrylate, methyl methacrylate, acrylic acid, acrylonitrile, divinylbenzene, dipropylene benzene, ethylene glycol dimethacrylate and glyceryl trimethacrylate, the initiator includes one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide, and the pore-forming agent includes one or more of saturated hydrocarbon, toluene, xylene, tetramethylbenzene and dichloroethane. The porous adsorption resin with ultra-high specific surface area can be prepared by selecting proper pore-foaming agent in different monomer systems, which is verified in the examples section below.
In step S1, the temperature raising and maintaining is specifically performed for 8-12 hours at 75-95 ℃. At this time and temperature it is ensured that the porous matrix is fully set.
In the step S2, the mass-volume ratio of the porous matrix to dichloroethane is 1 (5-8), which can ensure that the porous matrix is completely swelled in dichloroethane.
In step S2, the mass ratio of the porous matrix to the total catalyst is 1 (0.3-0.5), so that the functionalized reaction and the Friedel-crafts alkylation reaction are ensured to be complete.
In step S2, the mass ratio of the porous matrix to the functionalizing agent 1 to the functionalizing agent 2 is 1 (0.3-0.5) to 0.03-0.05. The amount of the functionalizing agent to be added is also an amount which is determined finally by a plurality of process optimizations, and each index of the resin is optimal within this range.
In step S2, the functionalizing agent 1 includes one or more of dichlorobenzyl, biphenyl dichlorobenzyl, p-dichlorobenzyl and dichloromethylanthracene, and the functionalizing agent 2 is melamine or a derivative thereof.
In step S2, the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride. The two catalysts have higher catalytic activity and can ensure that the functional reagent and the benzene ring react more thoroughly.
In the step S2, the low-temperature reaction temperature is 45-60 ℃, the reaction time is 3-5 hours, the temperature is reduced to below 30 ℃ after the reaction is finished, then the functionalized reagent 2 is added, and the reaction is carried out for 3-5 hours at 30-35 ℃; the high-temperature reaction temperature is 70-80 ℃, and the reaction time is 6-9 hours. The functionalization reagent 1 and the functionalization reagent 2 are ensured to be introduced into the resin framework in a low-temperature range, so that the specific surface area of the resin is increased, and the hydrophilicity of the resin is improved; under the condition of high temperature, the residual double bond on the resin skeleton is Friedel-crafts alkylation reaction and the residual functionalizing agent 1 and functionalizing agent 2 are reacted completely, so that the internal crosslinking degree of the resin is increased, and the specific surface area of the resin is further improved.
The method provided by the invention can be used for preparing the adsorption resin with a simple synthesis process, environmental protection, ultrahigh specific surface area and highly developed porous structure, and has a good decoloration effect on fruit juice.
Example 1
At normal temperature, 500g of water and 0.05g of hydroxyethyl cellulose are added into a 1000ml three-neck flask, and stirred and dissolved at 45 ℃ to prepare a water phase; uniformly mixing 80g of divinylbenzene, 20g of styrene, 150g of tetramethylbenzene and 0.5g of benzoyl peroxide to prepare an oil phase; adding the oil phase into the water phase, standing, adjusting the stirring speed to form uniform liquid drops with a certain size after complete stratification, then keeping constant stirring and slowly heating to 75 ℃ for reaction for 2 hours, reacting at 90 ℃ for 2 hours, reacting at 95 ℃ for 4 hours, stopping the reaction, filtering, washing with hot water for 2-3 times, then extracting and recovering a pore-forming agent with a steam extractor, washing with water, finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out a porous matrix of 60-20 meshes for later use.
And (2) fully swelling 50g of the synthesized porous matrix and 15g of dichlorobenzyl in a 1000ml three-neck flask by using 250ml of dichloroethane, adding 5g of anhydrous ferric chloride, preserving heat at 45 ℃ for 3 hours, after the reaction is finished, reducing the temperature to below 30 ℃, adding 2.0g of melamine, reacting at 30 ℃ for 5 hours, adding 5g of anhydrous ferric chloride after the reaction is finished, heating to 80 ℃ for reacting for 3 hours, cooling to below 75 ℃, adding 5g of anhydrous ferric chloride, and heating to 80 ℃ for continuing the reaction for 3 hours. After the reaction is finished, adding water to boil the balls, recovering dichloroethane, and then washing the resin to be neutral to obtain the brown opaque porous adsorption resin.
Example 2
At normal temperature, 500g of water and 0.5g of gelatin are added into a 1000ml three-neck flask, and stirred and dissolved at 45 ℃ to prepare a water phase; 100g of divinylbenzene, 300g of toluene and 1.5g of benzoyl peroxide are uniformly mixed to prepare an oil phase; adding the oil phase into the water phase, standing, adjusting the stirring speed to form uniform liquid drops with a certain size after complete stratification, then keeping constant stirring and slowly heating to 75 ℃ for reaction for 3 hours, 80 ℃ for reaction for 3 hours, 85 ℃ for reaction for 6 hours, stopping the reaction, filtering, washing with hot water for 2-3 times, then extracting and recovering a pore-forming agent by using a steam extractor, finally drying at 100 ℃ until the moisture is less than or equal to 2%, and screening a porous matrix of 60-20 meshes for later use.
50g of the synthesized porous substrate and 25g of biphenyl dichlorobenzyl are fully swelled by 400ml of dichloroethane in a 1000ml three-necked flask, 10g of anhydrous ferric trichloride is added, the temperature is kept at 60 ℃ for 5 hours, after the reaction is finished, the temperature is reduced to below 30 ℃, 2.5g of melamine is added, the reaction is carried out at 35 ℃ for 3 hours, 7.5g of anhydrous ferric trichloride is added after the reaction is finished, the temperature is increased to 80 ℃ for reaction for 3 hours, the temperature is reduced to below 75 ℃, 7.5g of anhydrous ferric trichloride is added, and the temperature is increased to 80 ℃ for continuous reaction for 6 hours. After the reaction is finished, adding a water boiling ball, recovering dichloroethane, and then washing the resin to be neutral to obtain the dark yellow opaque porous adsorption resin.
Example 3
At normal temperature, 500g of water and 1.5g of sodium carboxymethylcellulose are added into a 1000ml three-neck flask, and are stirred and dissolved at 45 ℃ to prepare a water phase; uniformly mixing 90g of divinylbenzene, 10g of styrene, 150g of toluene, 50g of isododecane and 1.0g of benzoyl peroxide to prepare an oil phase; adding the oil phase into the water phase, standing, adjusting the stirring speed to form uniform liquid drops with a certain size after complete layering, then keeping constant stirring and slowly heating to 80 ℃ for reaction for 2 hours, reacting at 85 ℃ for 8 hours, stopping the reaction, filtering, washing with hot water for 2-3 times, then recovering the mixed pore-forming agent with a steam extractor, detecting the toluene content for reuse in the later period, washing with water, finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out the porous matrix of 60-20 meshes for later use.
50g of the synthesized porous substrate and 15g of dichlorobenzyl are fully swelled by 350ml of dichloroethane in a 1000ml three-necked flask, 10g of anhydrous aluminum trichloride is added, the temperature is kept at 45 ℃ for 5 hours, after the reaction is finished, the temperature is reduced to below 30 ℃, 1.5g of melamine is added, the reaction is carried out at 35 ℃ for 5 hours, 5g of anhydrous aluminum trichloride is added after the reaction is finished, the temperature is increased to 70 ℃ for reaction for 3 hours, 5g of anhydrous aluminum trichloride is added, and the temperature is increased to 80 ℃ for continuous reaction for 6 hours. After the reaction is finished, adding water to boil the ball, recovering dichloroethane, and then washing the resin to be neutral to obtain the yellow opaque porous adsorption resin.
Example 4
At normal temperature, 500g of water and 0.05g of hydroxyethyl cellulose are added into a 1000ml three-neck flask, and stirred and dissolved at 45 ℃ to prepare a water phase; 85g of styrene, 15g of divinylbenzene, 180g of toluene, 70g of n-heptane and 0.5g of benzoyl peroxide are uniformly mixed to prepare an oil phase; adding the oil phase into the water phase, standing, adjusting the stirring speed to form uniform liquid drops with a certain size after complete stratification, then keeping constant stirring and slowly heating to 75 ℃ for reaction for 2 hours, 80 ℃ for reaction for 2 hours, 85 ℃ for reaction for 6 hours, stopping the reaction, filtering, washing with hot water for 2-3 times, then extracting a pore-forming agent by using a methylal extractor, washing with water, finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out a porous matrix of 60-20 meshes for later use.
50g of the synthesized porous matrix and 20g of p-dichlorobenzyl are fully swelled by 400ml of dichloroethane in a 1000ml three-necked bottle, 10g of anhydrous ferric chloride is added, the temperature is kept at 55 ℃ for 5 hours, after the reaction is finished, the temperature is reduced to below 30 ℃, 2.5g of melamine is added, the reaction is carried out at 35 ℃ for 5 hours, after the reaction is finished, 5g of anhydrous ferric chloride is added, the temperature is increased to 80 ℃ for reaction for 3 hours, the temperature is reduced to below 75 ℃, 5g of anhydrous ferric chloride is added, and the temperature is increased to 80 ℃ for continuous reaction for 9 hours. After the reaction is finished, adding water to boil the balls, recovering dichloroethane, and then washing the resin to be neutral to obtain the tan opaque porous adsorption resin.
Comparative experiment 1
The porous substrate is prepared according to the synthesis method in the embodiment 4, 50g of the porous substrate and 20g of p-benzyl dichloride are taken from a 1000ml three-mouth bottle and are fully swelled by 400ml of dichloroethane, 10g of anhydrous ferric chloride is added, the temperature is kept at 55 ℃ for 5 hours, after the reaction is finished, 5g of anhydrous ferric chloride is added, the temperature is raised to 80 ℃ for reaction for 3 hours, the temperature is lowered to below 75 ℃, 5g of anhydrous ferric chloride is added, and the temperature is raised to 80 ℃ for continuous reaction for 9 hours. After the reaction is finished, adding water to boil the balls, recovering dichloroethane, and then washing the resin to be neutral to obtain the tan opaque porous adsorption resin.
Comparative experiment 2
The porous substrate was prepared according to the synthesis method of example 4, 50g of the porous substrate was taken out of a 1000ml three-necked flask and fully swollen with 400ml of dichloroethane, 5g of anhydrous ferric chloride was added, the temperature was raised to 80 ℃ for reaction for 3 hours, the temperature was lowered to 75 ℃ or less, 5g of anhydrous ferric chloride was added, and the temperature was raised to 80 ℃ for further reaction for 9 hours. After the reaction is finished, adding water to boil the balls, recovering dichloroethane, and then washing the resin to be neutral to obtain the brownish red opaque porous adsorption resin.
Table 1 shows the performance indexes of the porous adsorption resin synthesized in the above examples and comparative experiments and the performance indexes of the porous adsorption resin Comparing various performance indexes of the porous adsorption resin for decoloring fruit juice sold on the market, wherein the adsorption capacity of the resin is that a phenol solution (with the concentration of 6.5g/L) is used as an adsorbate, and-OH in phenol can be compared with-NH in melamine2Hydrogen bonds are easy to form between the melamine resin and the melamine resin, which is beneficial to verifying the change of the adsorption capacity of the resin after the melamine is added into the resin. As can be seen from the table, the performance indexes of the porous adsorption resins synthesized in the four embodiments of the invention are all superior to those of the commercially available porous adsorption resins, which proves that the specific surface area of the resin can be improved by adding two functional reagents without chloromethylation reaction. For further comparison, a comparison experiment 1 (only adding the functionalized reagent 1 and not adding the functionalized reagent 2) and a comparison experiment 2 (neither of the two functionalized reagents is added) are designed, and it can be seen from table 1 that in the resin functionalization reaction process, no functionalized reagent is added, the specific surface area of the resin is small, the pore diameter is large, and the adsorption capacity is low; only adding the functionalized reagent 1 and not adding the functionalized reagent 2 reduces the average pore diameter of the resin, increases the specific surface area and the adsorption capacity, but has poorer performances compared with the commercially available adsorption resin; and the addition of the functionalization reagent 2 on the basis of the addition of the functionalization reagent 1 greatly improves the specific surface area and the adsorption capacity of the resin and is superior to the commercial resin. This also means that the two functionalizing agents added during the resin synthesis process have better use effects in practical applications. The decolorization effect of the above examples and comparative experimental resins will be verified by specific application experiments.
TABLE 1 detection results of various indexes of porous adsorption resin
Application of the Experimental examples
Preparing fruit juice: concentrated apple juice (provided by Suiyang Chunhua juice factory) is added into a beaker filled with 500ml of ultrapure water, the BRIX of the juice is adjusted to 12-14 BRIX by using a handheld BRIX meter, and the light transmittance is measured to be 28.5% by using an ultraviolet wind-solar photometer.
Decolorization experiment: the porous adsorption resin prepared in the above examples and comparative experiments and a commercially available porous adsorption resin for decoloring certain fruit juice are sampled and soaked in ethanol for 1-2 hours to remove impurities remaining in the resin, then 5g of the porous adsorption resin is weighed and put into a 250ml conical flask, 100ml of the prepared fruit juice solution is taken by a pipette and added into the conical flask filled with the porous adsorption resin, the mixture is oscillated on a constant temperature oscillator for 1 hour, and the light transmittance (decoloring rate) of the stock solution and the fruit juice sample in the conical flask are measured by an ultraviolet spectrophotometer.
Application experiments prove that the fruit juice decolorization rates of the examples 1-4, the commercial resin and the comparative experiments 1-2 are 94.6%, 97.5%, 92.3%, 95.1%, 91.1%, 87.6% and 82.2% in sequence. The experimental results show that the porous adsorption resin synthesized by the four embodiments of the invention can achieve more than 90% of the decolorization effect on fruit juice. Meanwhile, compared with two comparative experiments, the decolorizing effect of the porous adsorption resin prepared in each embodiment is also higher than that of the porous adsorption resin in the comparative experiments, mainly the functional reagent 1 is added, and under the action of the catalyst, the functional reagent 1 can be subjected to alkylation reaction with a benzene ring on a styrene-divinylbenzene resin skeleton, so that the resin skeleton is provided with a certain amount of-CH 2Cl group, and the moiety-CH2The Cl group reacts with a functional reagent 2 (melamine) under low temperature, and-NH in melamine molecules2The group makes the resin have certain hydrophilicity, most pigments in the fruit juice also have certain hydrophilicity, the addition of the melamine increases the adsorption capacity to the pigments, and simultaneously, the-NH is added2The group and the pigment molecule are easy to form hydrogen bond, and the group also has certain promotion effect on adsorbing the pigment in the fruit juice. Finally, under the action of high temperature and catalyst, residual-CH on the resin skeleton2The Cl group and the adjacent benzene ring are subjected to substitution reaction again, and the residual suspended double bond on the resin skeleton is subjected to Friedel-crafts alkylation reaction again, so that the specific surface area of the resin is further improved, and furtherThe adsorption capacity of the porous resin is increased. In conclusion, the functionalizing agents 1 and 2 are added in the functionalizing reaction, so that the specific surface area of the resin can be increased, the porous structure in the resin can be increased, the hydrophilicity of the resin can be improved, and the good decolorizing effect on the fruit juice can be further shown.
The application experiments prove that the porous adsorption resin prepared by the method has simple synthesis process, avoids using a chloromethyl ether process with carcinogenicity and high toxicity, has an ultrahigh specific surface area and a highly developed pore structure, and also shows good decolorization effect in the decolorization process of fruit juice. Therefore, the porous adsorption resin prepared by the invention has good application prospects in the fields of fruit juice and medical decoloration.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the porous adsorption resin is characterized by comprising the following steps:
s1: porous matrix synthesis: adding the oil phase into the water phase, and carrying out suspension polymerization reaction to prepare a porous matrix with a skeleton containing benzene rings; the oil phase comprises a monomer, a pore-foaming agent and an initiator;
s2: and (3) functional reaction: swelling a porous substrate with dichloroethane, adding a functional reagent 1 and a catalyst to perform a first functional reaction, adding a functional reagent 2 to perform a second functional reaction after the reaction is finished, adding the catalyst to perform a Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying to obtain porous adsorption resin after the reaction is finished; wherein, the functionalization reagent 1 comprises one or more of dichlorobenzyl, biphenyl dichlorobenzyl, p-dichlorobenzyl and dichloromethylanthracene, and the functionalization reagent 2 is melamine or derivatives thereof.
2. The method for preparing porous adsorption resin according to claim 1, wherein in S1, the monomer comprises one or more of styrene, ethylstyrene, methyl acrylate, methyl methacrylate, acrylic acid, acrylonitrile, divinylbenzene, dipropylenebenzene, ethylene glycol dimethacrylate and glyceryl trimethacrylate, the initiator comprises one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide, and the pore-forming agent comprises one or more of saturated hydrocarbon, toluene, xylene, tetramethylbenzene and dichloroethane.
3. The method for preparing the porous adsorption resin according to claim 1, wherein the mass ratio of the monomer to the initiator to the pore-forming agent is 100 (0.5-1.5) to (150-300).
4. The method for preparing the porous adsorbent resin according to claim 1, wherein in S1, the suspension polymerization reaction specifically comprises: reacting for 8-12 hours at 75-95 ℃.
5. The method for preparing the porous adsorption resin according to claim 1, wherein in S1, the aqueous phase is prepared by dissolving a dispersant into water, and the dispersant is one or more selected from polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose, lignin and gelatin.
6. The method for preparing the porous adsorption resin of claim 1, wherein in S2, the mass ratio of the porous matrix to the functionalizing agent 1 to the functionalizing agent 2 is 1 (0.3-0.5) to 0.03-0.05.
7. The method for preparing the porous adsorption resin according to claim 1, wherein in S2, the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride.
8. The preparation method of the porous adsorption resin according to claim 1, wherein the reaction temperature of the first functionalization reaction is 45-60 ℃ and the reaction time is 3-5 hours; the reaction temperature of the second functionalization reaction is 30-35 ℃, and the reaction time is 3-5 hours; the reaction temperature of the Friedel-crafts alkylation reaction is 70-80 ℃, and the reaction time is 6-9 hours.
9. The porous adsorbent resin prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the porous adsorbent resin of claim 9 for decolorizing fruit juices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210290487.6A CN114573864B (en) | 2022-03-23 | 2022-03-23 | Porous adsorption resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210290487.6A CN114573864B (en) | 2022-03-23 | 2022-03-23 | Porous adsorption resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114573864A true CN114573864A (en) | 2022-06-03 |
| CN114573864B CN114573864B (en) | 2023-08-04 |
Family
ID=81783100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210290487.6A Active CN114573864B (en) | 2022-03-23 | 2022-03-23 | Porous adsorption resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114573864B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850600A (en) * | 2022-12-12 | 2023-03-28 | 国网江苏省电力有限公司双创中心 | Oil-resistant porous adsorption resin and preparation method thereof |
| CN116287077A (en) * | 2023-03-13 | 2023-06-23 | 山东至善硒生物科技有限公司 | Selenium polypeptide extraction method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110288191A1 (en) * | 2008-06-11 | 2011-11-24 | Ling Wang | Macroporous absorbent resin for extracting cephalosporin c and method of preparation |
| CN106215881A (en) * | 2016-09-07 | 2016-12-14 | 济南大学 | A kind of preparation method of cyanurotriamide modified porous magnetic dextran microspheres |
| CN111171199A (en) * | 2020-01-15 | 2020-05-19 | 高陵蓝晓科技新材料有限公司 | Adsorption resin for removing perfluorinated pollutants in water body and preparation and application thereof |
-
2022
- 2022-03-23 CN CN202210290487.6A patent/CN114573864B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110288191A1 (en) * | 2008-06-11 | 2011-11-24 | Ling Wang | Macroporous absorbent resin for extracting cephalosporin c and method of preparation |
| CN106215881A (en) * | 2016-09-07 | 2016-12-14 | 济南大学 | A kind of preparation method of cyanurotriamide modified porous magnetic dextran microspheres |
| CN111171199A (en) * | 2020-01-15 | 2020-05-19 | 高陵蓝晓科技新材料有限公司 | Adsorption resin for removing perfluorinated pollutants in water body and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张冲等: "三聚氰胺功能化多孔有机聚合物的合成及其对甲基橙的吸附性能", 《色谱》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850600A (en) * | 2022-12-12 | 2023-03-28 | 国网江苏省电力有限公司双创中心 | Oil-resistant porous adsorption resin and preparation method thereof |
| CN116287077A (en) * | 2023-03-13 | 2023-06-23 | 山东至善硒生物科技有限公司 | Selenium polypeptide extraction method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114573864B (en) | 2023-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114573864B (en) | Porous adsorption resin and preparation method and application thereof | |
| CN111171199B (en) | Adsorption resin for removing perfluorinated pollutants in water body and preparation and application thereof | |
| CN109400771B (en) | Preparation method and application of super-crosslinked porous polyion liquid material | |
| CN104262521B (en) | The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier | |
| CN111530432B (en) | Preparation method of adsorbing material for blood perfusion | |
| CN112321756B (en) | Preparation method of highly sulfonated polystyrene resin | |
| CN110117379B (en) | Adsorbing material for removing LDL (low density lipoprotein) in blood perfusion and preparation method thereof | |
| CN113698524A (en) | Macroporous adsorption resin and synthetic method thereof | |
| CN109833854A (en) | A kind of macroporous absorbent resin and preparation method thereof | |
| CN109320650B (en) | Preparation method of macroporous weakly-alkaline acrylic anion exchange resin | |
| JPH02503634A (en) | A method for decolorizing an aqueous sugar solution using an adsorbent resin and a method for desorbing a colored body from the adsorbent resin | |
| WO2003051808A1 (en) | Weak acid strong base amphoteric adsorptive resins and the process of separation and purification of citric acid | |
| CN110170313A (en) | A kind of method that irradiation grafting prepares lignin adsorbent | |
| CN103316643B (en) | A kind of modified adsorption resin and preparation method thereof | |
| CN109180850A (en) | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin | |
| CN1238111C (en) | High exchange capacity resin catalyst and its preparation method | |
| CN117797789A (en) | Special adsorption resin for straw extraction and preparation method thereof | |
| US5972121A (en) | Decolorization of sugar syrups using functionalized adsorbents | |
| CN105056905B (en) | A kind of preparation method of vanadic anhydride adsorbent | |
| CN113045794A (en) | Macroporous adsorption resin for extracting chlorogenic acid from eucommia leaves and synthetic method thereof | |
| AU2021282481B2 (en) | A method for preparing betaine-modified cellulose ester capable of adsorbing dyes, and application of the cellulose ester | |
| CN112742356B (en) | Adsorption resin for treating waste water and gas and preparation method thereof | |
| CN110743514B (en) | Preparation method of dye adsorbent PVA/ZSM-5 gel beads | |
| CN110536970B (en) | Treatment of sugar solutions | |
| CN119591787A (en) | Preparation method of molecular imprinting polymer for separating asiaticoside |
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 | ||
| CB02 | Change of applicant information |
Address after: 710076 room 10911, floor 9, unit 1, building 2, city gate D, hi tech Zone, Xi'an, Shaanxi Applicant after: Xi'an Lanshen New Material Technology Co.,Ltd. Address before: 710076 room 10911, floor 9, unit 1, building 2, city gate D, hi tech Zone, Xi'an, Shaanxi Applicant before: Xi'an Lanshen New Material Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |