CN114573864B - Porous adsorption resin and preparation method and application thereof - Google Patents
Porous adsorption resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a porous adsorption resin, a preparation method and application thereof, comprising the following steps: adding the oil phase into the water phase, and carrying out suspension polymerization reaction to prepare a porous matrix with benzene rings in the framework; the oil phase comprises a monomer, a pore-forming agent and an initiator; swelling the porous matrix with dichloroethane, adding a functionalizing agent 1 and a catalyst for a first functionalization reaction, adding a functionalizing agent 2 for a second functionalization reaction after the reaction is finished, adding a catalyst for Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying after the reaction is finished to obtain porous adsorption resin; wherein the functionalization reagent 1 comprises one or more of dichlorobenzene, biphenyl dichlorobenzene, p-dichlorobenzene and dichloromethyl anthracene, and the functionalization reagent 2 is melamine or derivatives thereof. According to the invention, chloromethyl ether is not used, so that the adsorption resin with high specific surface area and highly developed porous structure is obtained, meanwhile, the hydrophilicity of the resin is improved, and the decoloring effect of the juice is improved.
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 fruit industry makes the planting area of fruits such as grapes, apples and pears continuously expand, and the fruit processing industry in China also enters the rapid development period and gradually expands from the original apple juice and pear juice to the processing of various fruit juices such as mango juice, strawberry juice and kiwi juice. With the increase of international trade competition, the quality of concentrated juice is more and more paid attention to, and important index color values for evaluating the quality of the juice are necessarily paid attention to. The pigments are liable to undergo browning during juice processing, thereby affecting the organoleptic quality of the product, and therefore, a decoloring treatment must be performed during juice processing.
In the early stage, the activated carbon has the advantages of developed specific surface area, strong adsorption capacity, good adsorption effect on pigment and the like in the fields of wastewater, juice processing and the like, so the activated carbon is also used as the most commonly used decolorizing material, and the decolorizing effect of the activated carbon in the field of high-quality juice processing is still used until now, but the decolorizing effect of the activated carbon does not meet certain specific requirements. With the rapid development of membrane technology, the ultrafiltration membrane has good decolorizing performance, good repeatability and simple operation in the fruit juice concentration process, but the membrane has poor anti-pollution performance in the use process, is difficult to clean, 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, simple operation, high working efficiency, high selectivity and the like, and pigment, hydrophobic compounds, browning components and the like can be adsorbed on the resin skeleton through Van der Waals force in the fruit juice decoloring process, so that pigment substances in the 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, difficult regeneration and the like of adsorbents such as activated carbon, ultrafiltration membranes and the like are also solved.
However, the high specific surface area adsorption resin used in the fruit juice decolorization industry at present adopts the chloromethyl ether to undergo chloromethylation, so that the adsorption resin can be ensured to have an ultrahigh specific surface area and a highly developed three-dimensional network structure, thereby showing an excellent decolorization effect. However, chloromethyl ether used for 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 CN111171199B, an adsorption resin for removing perfluoro contaminants in a water body, and a method for preparing a porous adsorption resin with a high specific surface area without chloromethylation reaction, which is prepared by adding a functionalizing agent in the process of preparing the resin, has a uniform pore size and a large specific surface area, but has a relatively high hydrophobicity due to the introduction of the functionalizing agent, and has a relatively poor effect in adsorbing hydrophilic pigment molecules due to the introduction of a rigid benzene ring structure. Therefore, there is a need for improvement in hydrophilicity of the resin.
Disclosure of Invention
The invention aims to provide a porous adsorption resin, a preparation method and application thereof, and a functional reagent is added on the premise of not using chloromethyl ether to carry out chloromethylation reaction to prepare the adsorption resin with high specific surface area and highly developed porous structure, and meanwhile, the hydrophilicity of the resin is improved, and the decoloring effect on fruit juice is improved.
The invention is realized by the following technical scheme:
a method for preparing porous adsorption resin, comprising 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 benzene rings in the framework; the oil phase comprises a monomer, a pore-forming agent and an initiator;
s2: and (3) functionalization reaction: swelling the porous matrix with dichloroethane, adding a functionalizing agent 1 and a catalyst for a first functionalization reaction, adding a functionalizing agent 2 for a second functionalization reaction after the reaction is finished, adding a catalyst for Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying after the reaction is finished to obtain porous adsorption resin; wherein the functionalization reagent 1 comprises one or more of dichlorobenzene, biphenyl dichlorobenzene, p-dichlorobenzene and dichloromethyl anthracene, and the functionalization reagent 2 is melamine or derivatives thereof.
Preferably, in S1, the monomer includes one or more of styrene, ethyl styrene, 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 any one or more of saturated hydrocarbon, toluene, xylene, tetramethylbenzene and dichloroethane.
Preferably, the mass ratio of the monomer to the initiator to the porogen is 100 (0.5-1.5) (150-300).
Preferably, in S1, the suspension polymerization reaction is specifically: reacting for 8-12 hours at 75-95 ℃.
Preferably, in S1, the water phase is prepared by dissolving a dispersing agent into water, wherein the dispersing agent 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, the functionalizing agent 1 and the functionalizing agent 2 is 1 (0.3-0.5): 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 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 prepared.
The porous adsorption resin is applied to fruit juice decolorization.
Compared with the prior art, the invention has the following beneficial effects:
in the resin synthesis process, porous matrix is prepared first and then added with workThe functionalizing agent 1, under the action of the catalyst, the functionalizing agent 1 can carry out alkylation reaction with benzene rings on the resin skeleton, so that the resin skeleton is provided with a certain amount of-CH 2 Cl groups are introduced into the resin, so that the specific surface area of the resin is increased, and the hydrophobic property of the resin is further enhanced; adding a functionalizing agent 2 on the basis, and performing-NH (NH) of the functionalizing agent 2 under the low-temperature condition 2 Group and residual-CH in functionalizing agent 1 introduced on resin skeleton 2 Cl groups react, on the one hand, the incompletely reacted-NH in the functionalizing agent 2 2 The groups can reduce the hydrophobicity of the resin, so that the hydrophilicity of the resin is increased, and most pigments in the juice have certain hydrophilicity, which is beneficial to improving the decoloration effect of the juice, and on the other hand, the non-fully reacted-NH in the functionalization reagent 2 2 Hydrogen bond can be formed between the groups and pigment molecules, so that the adsorption effect of the resin on pigment is further improved. Finally, under the action of high temperature and catalyst, residual-CH on the resin skeleton 2 The Cl groups and the adjacent benzene rings are subjected to substitution reaction again, meanwhile, the residual dangling double bonds on the resin skeleton are subjected to Friedel-crafts alkylation reaction again, the specific surface area of the resin is further improved, and the adsorption capacity of the porous resin is further improved. The resin synthesis process is simple, and the porous matrix is directly subjected to functionalization reaction in the preparation process to obtain the adsorption resin with ultrahigh specific surface area and highly developed porous structure, and the hydrophilicity of the resin is improved; the resin synthesis process is environment-friendly, no carcinogenicity and high toxicity chloromethyl ether are used in the resin synthesis process, the use of chloromethyl ether is avoided, the harm to human bodies is reduced, and the environment is not polluted.
Further, the purpose of the dispersant is to make the oil phase disperse uniformly and to make it easier to ball.
Furthermore, the catalyst has higher catalytic activity, and can ensure that the functionalization reagent and the benzene ring react more thoroughly.
The porous adsorption resin prepared by the invention has ultrahigh specific surface area and highly developed porous structure, and is more beneficial to subsequent application.
The porous adsorption resin prepared by the invention has the advantages of large decolorizing capacity, good decolorizing effect, easy regeneration and the like for fruit juice.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The preparation method of the porous adsorption resin for decoloring the fruit juice 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-forming 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 rotating speed of a stirring paddle to control the granularity of the oil phase, stirring at a uniform speed after the granularity is proper, and then carrying out heating and heat preservation operation; washing the dispersant on the surface of the resin with hot water after the reaction is finished, extracting the pore-forming agent in the resin, washing with water, drying, and screening out the porous matrix between 60 and 20 meshes for later use.
S2: and (3) functionalization reaction: adding the porous matrix prepared in the step S1 into a reaction kettle, swelling with a certain amount of dichloroethane, adding the functionalization reagent 1 and the catalyst for low-temperature reaction after swelling for a certain time, adding the functionalization reagent 2 for reaction after the reaction is finished, and finally adding the catalyst for Friedel-crafts alkylation reaction under the high-temperature condition. And adding water into the system after the reaction is finished, recovering dichloroethane by azeotropy of water and dichloroethane, and then washing the resin with water to neutral and discharging to obtain the finished 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 the dispersant is to make the oil phase disperse uniformly and to make it easier to ball.
In the step S1, the mass ratio of the monomer to the initiator to the porogen is 100 (0.5-1.5) (150-300). The addition amount of the initiator and the pore-foaming agent is controlled, the initiator is easy to initiate polymerization when the amount is too large, and the polymerization reaction speed is too slow when the amount is too small; too little resin specific surface area of the pore-forming agent is too small, and too much resin strength is too low, which is unfavorable for practical application.
In the step S1, the monomer comprises one or more of styrene, ethyl styrene, methyl acrylate, methyl methacrylate, acrylic acid, acrylonitrile, divinylbenzene, dipropylene benzene, glycol dimethacrylate and glycerol trimethacrylate, the initiator comprises one or more of benzoyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide, and the pore-forming agent comprises any one or more of saturated hydrocarbon, toluene, xylene, tetramethylbenzene and dichloroethane. The choice of suitable porogens in the different monomer systems allows the preparation of porous adsorbent resins having ultra-high specific surface areas, as demonstrated in the examples section below.
In the step S1, the temperature rise and the heat preservation are specifically carried out for 8 to 12 hours at the temperature of 75 to 95 ℃. The porous matrix is ensured to be completely shaped during the time and at the temperature.
In the step S2, the mass volume ratio of the porous matrix to the dichloroethane is 1 (5-8), so that the porous matrix can be ensured to be completely swelled in the dichloroethane.
In the step S2, the mass ratio of the porous matrix to the total catalyst is 1 (0.3-0.5), so that the functionalization reaction and Friedel-crafts alkylation reaction are ensured to be complete.
In the 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 addition amount of the functionalizing agent is mainly the amount finally determined through multiple process optimization, and various indexes of the resin are optimal in the range.
In the step S2, the functionalizing agent 1 comprises one or more of dichlorobenzene, biphenyl dichlorobenzene, p-dichlorobenzene and dichloromethyl anthracene, and the functionalizing agent 2 is melamine or derivatives thereof.
In the step S2, the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride. The two catalysts have higher catalytic activity, and can ensure that the functionalization 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, and then the functionalization reagent 2 is added for reaction for 3-5 hours at 30-35 ℃; the high-temperature reaction temperature is 70-80 ℃ and the reaction time is 6-9 hours. The introduction of the functionalization reagent 1 and the functionalization reagent 2 on the resin skeleton is ensured in a low-temperature range, the specific surface area of the resin is increased, and meanwhile, the hydrophilicity of the resin is improved; under the high temperature condition, the residual dangling double bonds on the resin skeleton are subjected to Friedel-crafts alkylation reaction, and the residual functionalizing agent 1 and the functionalizing agent 2 are completely reacted, so that the internal crosslinking degree of the resin is increased, and the specific surface area of the resin is further improved.
The method can be used for preparing the adsorption resin with simple synthesis process, environment friendliness, superhigh specific surface area and highly developed porous structure, and has good decolorization effect on fruit juice.
Example 1
500g of water and 0.05g of hydroxyethyl cellulose are added into a 1000ml three-neck flask at normal temperature, and stirred and dissolved at 45 ℃ to prepare an aqueous 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 layering, then keeping constant stirring, slowly heating to 75 ℃ for reaction for 2 hours, reacting for 2 hours at 90 ℃, reacting for 4 hours at 95 ℃, stopping the reaction, filtering, washing with hot water for 2-3 times, extracting and recovering the pore-foaming agent by a steam extractor, washing with water, finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out the porous matrix between 60 and 20 meshes for standby.
After 50g of the synthesized porous matrix and 15g of dichlorobenzene are fully swelled by 250ml of dichloroethane in a 1000ml three-necked flask, 5g of anhydrous ferric trichloride is added, the temperature is kept at 45 ℃ for 3 hours, after the reaction is finished, the temperature is reduced to below 30 ℃, 2.0g of melamine is added, the reaction is carried out at 30 ℃ for 5 hours, after the reaction is finished, 5g of anhydrous ferric trichloride is added, the temperature is raised to 80 ℃ for 3 hours, the temperature is reduced to below 75 ℃, then 5g of anhydrous ferric trichloride is added, and the temperature is raised to 80 ℃ for 3 hours for continuous reaction. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the brown opaque porous adsorption resin.
Example 2
500g of water and 0.5g of gelatin are added into a 1000ml three-neck flask at normal temperature, and stirred and dissolved at 45 ℃ to prepare an aqueous phase; uniformly mixing 100g of divinylbenzene, 300g of toluene and 1.5g 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 layering, then keeping constant stirring and slowly heating to 75 ℃ for reaction for 3 hours, reacting for 3 hours at 80 ℃ and reacting for 6 hours at 85 ℃, stopping the reaction, filtering, washing with hot water for 2-3 times, extracting and recovering the pore-foaming agent by a steam extractor, finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out the porous matrix between 60 and 20 meshes for standby.
After 50g of the synthesized porous matrix and 25g of biphenyl dichlorobenzene 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, the temperature is reduced to below 30 ℃ after the reaction is finished, 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 raised to 80 ℃ for 3 hours, the temperature is reduced to below 75 ℃, 7.5g of anhydrous ferric trichloride is added, and the temperature is raised to 80 ℃ for 6 hours for continuous reaction. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the dark yellow opaque porous adsorption resin.
Example 3
500g of water and 1.5g of sodium carboxymethyl cellulose are added into a 1000ml three-neck flask at normal temperature, stirred and dissolved at 45 ℃ to prepare an aqueous 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, stopping the reaction at 85 ℃ for 8 hours, filtering, washing with hot water for 2-3 times, recovering the mixed pore-foaming agent by a steam extractor, repeatedly using the mixed pore-foaming agent by detecting the toluene content in the later stage, washing with water, and finally drying at 100 ℃ until the water content is less than or equal to 2%, and screening out porous matrixes between 60 meshes and 20 meshes for later use.
After 50g of the above-synthesized porous matrix and 15g of dichlorobenzene were sufficiently swelled with 350ml of dichloroethane in a 1000ml three-necked flask, 10g of anhydrous aluminum trichloride was added, the temperature was kept at 45℃for 5 hours, after the completion of the reaction, the temperature was lowered to below 30℃and 1.5g of melamine was added, the reaction was carried out at 35℃for 5 hours, after the completion of the reaction, 5g of anhydrous aluminum trichloride was added, the temperature was raised to 70℃for 3 hours, then 5g of anhydrous aluminum trichloride was added, and the reaction was continued at 80℃for 6 hours. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the yellow opaque porous adsorption resin.
Example 4
500g of water and 0.05g of hydroxyethyl cellulose are added into a 1000ml three-neck flask at normal temperature, and stirred and dissolved at 45 ℃ to prepare an aqueous phase; uniformly mixing 85g of styrene, 15g of divinylbenzene, 180g of toluene, 70g of n-heptane 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 layering, then keeping constant stirring and slowly heating to 75 ℃ for reaction for 2 hours, reacting for 2 hours at 80 ℃, reacting for 6 hours at 85 ℃, stopping the reaction, filtering, washing with hot water for 2-3 times, extracting the 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 the porous matrix between 60 meshes and 20 meshes for standby.
After 50g of the synthesized porous matrix and 20g of p-dichlorobenzene 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 55 ℃ for 5 hours, the temperature is reduced to below 30 ℃ after the reaction is finished, 2.5g of melamine is added, the reaction is carried out at 35 ℃ for 5 hours, 5g of anhydrous ferric trichloride is added after the reaction is finished, the temperature is raised to 80 ℃ for 3 hours, the temperature is reduced to below 75 ℃, then 5g of anhydrous ferric trichloride is added, and the temperature is raised to 80 ℃ for further reaction for 9 hours. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the tan opaque porous adsorption resin.
Comparative experiment 1
A porous substrate was prepared according to the synthesis method in example 4, 50g of the porous substrate and 20g of p-dichlorobenzene were fully swelled with 400ml of dichloroethane in a 1000ml three-necked flask, 10g of anhydrous ferric trichloride was added, the temperature was kept at 55℃for 5 hours, after the reaction was completed, 5g of anhydrous ferric trichloride was added, the temperature was raised to 80℃for 3 hours, the temperature was lowered to 75℃or below, and then 5g of anhydrous ferric trichloride was added, and the reaction was continued at 80℃for 9 hours. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the tan opaque porous adsorption resin.
Comparative experiment 2
A porous substrate was prepared according to the synthesis method of example 4, 50g of the porous substrate was fully swelled with 400ml of dichloroethane in a 1000ml three-necked flask, 5g of anhydrous ferric chloride was added, the temperature was raised to 80℃for 3 hours, the temperature was lowered to 75℃or below, and then 5g of anhydrous ferric chloride was added, and the reaction was continued at 80℃for 9 hours. And adding water to boil the balls after the reaction is finished, recovering dichloroethane, washing the resin with water to be neutral, and finally obtaining the reddish brown 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 for fruit juice decolorization commercially available at present, wherein the adsorption amount of the resin is that phenol solution (concentration of 6.5 g/L) is used as adsorbate, and the-OH energy in phenol and-NH energy in melamine 2 Hydrogen bond is easy to form between the melamine and the resin, which is favorable for 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 various performance indexes of the porous adsorption resin synthesized in the four embodiments of the invention are better than those of the commercial porous adsorption resin, which also proves that the specific surface area of the resin can be improved by adding two kinds of functionalization reagents without chloromethylation reaction. For further comparison, comparative experiment 1 (only functionalized reagent 1 was added, no functionalized reagent 2 was added) and comparative experiment 2 (both functionalized reagents were not added) were designed, and it can also be seen from Table 1 that no functionalized reagent was added, the specific surface area of the resin during the resin functionalization reactionThe pore diameter is smaller, the adsorption quantity is larger, and the adsorption quantity is also lower; the average pore diameter of the resin is reduced, the specific surface area and the adsorption capacity are both increased, but the performance is poorer than that of the commercial adsorption resin when the functionalization reagent 1 is only added and the functionalization reagent 2 is not added; on the basis of adding the functionalization reagent 1, the functionalization reagent 2 is added, so that the specific surface area and the adsorption quantity of the resin are greatly improved, and the resin is superior to the resin sold in the market. This also means that the addition of two functionalizing agents during the resin synthesis process provides better results in practical applications. The decoloring effect of the resins of the above examples and comparative experiments will be verified by specific application experiments.
TABLE 1 detection results of various indexes of porous adsorption resin
Experimental examples of application
Preparing fruit juice: concentrated apple juice (supplied by the Katsumadai Katsuku juice factory) was added to a beaker containing 500ml of ultrapure water, the sugar degree of the juice was adjusted to 12 to 14BRIX by using a hand-held sugar degree meter, and the light transmittance thereof was measured to be 28.5% by using an ultraviolet wind-light photometer.
Decoloring experiment: the porous adsorption resin prepared in the example and the comparative experiment and the porous adsorption resin for decoloring commercially available fruit juice are sampled and soaked in ethanol for 1-2 hours, residual impurities in the resin are removed, then 5g of the porous adsorption resin are weighed and filled into 250ml conical flasks, 100ml of prepared fruit juice solution is taken by a pipette and added into the conical flasks 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 raw juice and the fruit juice sample in the conical flasks is measured by an ultraviolet wind-light photometer.
The fruit juice decolorization rates of examples 1-4, commercially available resins and comparative examples 1-2 were 94.6%, 97.5%, 92.3%, 95.1%, 91.1%, 87.6% and 82.2% in this order, as verified by application experiments. From experimentsThe result shows that the decolorization effect of the porous adsorption resin synthesized by the four embodiments of the invention on the fruit juice can reach more than 90%. Meanwhile, compared with two comparative experiments, the decoloring effect of the porous adsorption resin prepared in each embodiment is higher than that of the porous adsorption resin in the comparative experiments, and the porous adsorption resin is mainly added with a functionalization reagent 1, and under the action of a catalyst, the functionalization reagent 1 can carry out alkylation reaction with benzene rings on a styrene-divinylbenzene resin skeleton, so that the resin skeleton is provided with a certain amount of-CH 2 Cl groups, and part of-CH 2 The Cl group reacts with the functionalizing agent 2 (melamine) under the condition of low temperature, and the-NH in the melamine molecule 2 The groups lead the resin to have certain hydrophilicity, most pigments in the juice also have certain hydrophilicity, and the addition of the melamine increases the adsorption capacity to the pigments and simultaneously leads the pigment to be-NH 2 The groups and pigment molecules are easy to form hydrogen bonds, and the dye has certain promotion effect on adsorbing pigment in the fruit juice. Finally, under the action of high temperature and catalyst, residual-CH on the resin skeleton 2 The Cl groups and the adjacent benzene rings are subjected to substitution reaction again, and the residual dangling 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. In summary, the functionalization reagent 1 and the functionalization reagent 2 are added in the functionalization 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 a good decoloring effect on juice can be further shown.
The application experiment proves that the porous adsorption resin prepared by the method has simple synthesis process, avoids using the carcinogenic and highly toxic chloromethyl ether process, and the obtained resin has ultrahigh specific surface area and highly developed pore structure and also has good decolorization effect in the process of decolorizing fruit juice. Therefore, the porous adsorption resin prepared by the invention has good application prospect in the field of fruit juice and medicine decolorization.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. The preparation method of the porous adsorption resin is characterized by comprising the following steps of:
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 benzene rings in the framework; the oil phase comprises a monomer, a pore-forming agent and an initiator; wherein the water phase is prepared by dissolving a dispersing agent into water, and the dispersing agent is one or more of polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose, lignin and gelatin; the monomer comprises one or more of styrene, ethyl styrene, divinylbenzene and dipropylene benzene;
s2: and (3) functionalization reaction: swelling the porous matrix with dichloroethane, adding a functionalizing agent 1 and a catalyst for a first functionalization reaction, adding a functionalizing agent 2 for a second functionalization reaction after the reaction is finished, adding a catalyst for Friedel-crafts alkylation reaction after the reaction is finished, and separating and purifying after the reaction is finished to obtain porous adsorption resin; wherein the functionalization reagent 1 comprises one or more of dichlorobenzene, biphenyl dichlorobenzene, p-dichlorobenzene and dichloromethyl anthracene, and the functionalization reagent 2 is melamine; the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride;
in S2, the mass ratio of the porous matrix to the functionalization reagent 1 to the functionalization reagent 2 is 1 (0.3-0.5): 0.03-0.05; 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 Friedel-crafts alkylation reaction is 70-80 ℃ and the reaction time is 6-9 hours.
2. The method for preparing porous adsorption resin according to claim 1, wherein in S1, 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 porogen is 100:150-300.
4. The method for producing a porous adsorption resin according to claim 1, wherein in S1, the suspension polymerization reaction is specifically: reacting for 8-12 hours at 75-95 ℃.
5. The porous adsorption resin prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the porous adsorption resin according to claim 5 for fruit juice decolorization.
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