CN111303321B - Synthesis method of adsorption resin with ultrahigh specific surface area - Google Patents
Synthesis method of adsorption resin with ultrahigh specific surface area Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an adsorption resin with an ultrahigh specific surface area, and belongs to the field of resin synthesis. According to the invention, lactic acid and a pore-foaming agent are compounded in a divinylbenzene self-polymerization process, so that the average pore size of divinylbenzene self-polymerization is effectively controlled, residual dangling double bonds on resin are soaked under the action of a catalyst, and a positive carbon ion with strong electron withdrawing capability is formed and has nucleophilic attack effect with an adjacent benzene ring, so that bridging is formed, pore channels are increased, and the specific surface area is increased.
Description
Technical Field
The invention belongs to the field of resin synthesis, and particularly relates to a synthesis method of an adsorption resin with an ultrahigh specific surface area.
Background
The prior adsorbent resin with high specific surface area is mainly ultra-high cross-linked adsorbent resin, and since the 70 s of the last century, the ultra-high cross-linked adsorbent resin has the advantages of controllable pore structure, higher specific surface area, easy regeneration and the like, so that the application range of the ultra-high cross-linked adsorbent resin is wider. The pore diameter of the general macroporous absorption resin is concentrated in a mesoporous region (2-50 nm), while the pore diameter of the ultrahigh cross-linked resin is mainly concentrated in a microporous region (less than 2 nm), and the nanometer micropores provide more space sites, so that the absorption capacity of the resin to organic pollutants is larger.
The synthesis process of superhigh cross-linking adsorption resin includes the main steps of suspension copolymerization of styrene and divinylbenzene to polymerize white ball, chloromethylation to obtain the resin containing-CH 2 And performing Friedel-crafts post-crosslinking reaction on Cl-containing chlorine spheres to obtain the ultrahigh crosslinking adsorption resin. For example, chinese patent application No. 201410013169.0, filed on 2014, 1, 13, discloses a method for synthesizing an ultra-high crosslinked polystyrene adsorbent resin, comprising the following steps: (1) free radical polymerization to obtain a polymerized ball; (2) performing chloromethylation reaction to obtain chlorine spheres; (3) And performing post-crosslinking reaction to obtain the ultrahigh crosslinked polystyrene adsorbent resin. The method has the advantages that the synthesis steps are simple, the specific surface area of the synthesized ultrahigh crosslinked polystyrene adsorption resin is larger, the structure is more uniform, and the mechanical strength is higher; however, the specific surface area of the synthesized ultra-high crosslinked polystyrene adsorbent resin is not specifically described in the patent application.
For another example, a chinese patent application No. 201310723964.4, filed as 2014, 2, 24, discloses an ultra-high cross-linked macroporous adsorbent resin suitable for patulin removal, which uses a styrene monomer as a functional monomer, a polyvinyl monomer as a cross-linking agent, suspension polymerization is performed in the presence of a pore-forming agent to obtain low cross-linked macroporous polystyrene white spheres, the obtained white spheres and chloromethyl ether react under the catalysis of lewis acid to obtain chloromethylated macroporous polystyrene resin, and the obtained chloromethylated macroporous polystyrene resin is subjected to Friedel-Crafts alkylation reaction in the presence of a swelling agent by using lewis acid as a catalyst to obtain the ultra-high cross-linked macroporous adsorbent resin. By adopting a novel cross-linking agent and pore-foaming agent system, the obtained resin has the advantages of high specific surface area and uniform pore diameter.
However, by analyzing the pore size distribution of such resins, it was found that the pore size was mainly concentrated below 2nm, and still some were larger than the mesopores and macropores. The ultrahigh cross-linked resin is obtained by self cross-linking reaction of chloromethylated polystyrene resin, the high specific surface area of the resin mainly comes from a large number of microporous structures formed in the post cross-linking process, but partial mesopores and macropores cannot form micropores through reaction.
In recent years, a crosslinking method after double bond suspension is gradually developed, and a new way is provided for synthesizing ultrahigh crosslinking resin. The cross-linking method after suspending double bonds uses high-content divinylbenzene for polymerization, and the prepared divinylbenzene resin has the specific surface area up to 800-900 m according to different using amounts of pore-foaming agents 2 (iv) g. However, not all the double bonds in the divinylbenzene monomer will react during the polymerization process, and the resin obtained at this time still has a lot of residual double bonds (second double bonds) which do not participate in the polymerization, and these part of double bonds are called as dangling double bonds, and through the friedel-crafts cross-linking reaction, the dangling double bonds can react with the adjacent benzene ring and generate cross-linking bridges to form new pore channels, thereby increasing the pore volume and specific surface area of the resin.
The method forms most of pore channels in the first polymerization step, so that compared with the self-crosslinking reaction of chloromethyl resin, the pore structure of the resin is easier to control, and the resin with high specific surface area and more micropores can be synthesized. However, after the first step of divinylbenzene polymerization, the obtained resin has a large average pore size (about 6 to 8 nm), and simultaneously, partial double bonds cannot be fully utilized, and the subsequent crosslinking reaction hardly increases resin micropores, so that the specific surface area of the synthesized resin is still not high.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of low specific surface area of cross-linked resin in the prior art, the invention provides a synthetic method of adsorption resin with ultrahigh specific surface area. According to the invention, in the divinylbenzene self-polymerization process, the lactic acid is added into the oil phase, and the lactic acid and the pore-forming agent are compounded, so that the average pore diameter of divinylbenzene self-polymerization is effectively controlled, and the pores formed by the resin are more uniform, thereby being beneficial to infiltrating residual suspended double bonds on the resin in subsequent reactions to form positive carbon ions with strong electron-withdrawing capability, and the positive carbon ions have nucleophilic attack effect with adjacent benzene rings to form bridging, increase pore channels and improve the specific surface area.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for synthesizing an adsorption resin with an ultrahigh specific surface area, which comprises the following steps:
s10, preparing a water phase
Adding a dispersing agent and salt into water, stirring and heating, and uniformly mixing to obtain a water phase;
s20, preparing an oil phase
Adding lactic acid into divinylbenzene, adding a pore-foaming agent and an initiator, and stirring and uniformly mixing to obtain an oil phase;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring and heating for polymerization reaction to obtain polymer resin;
s40, post-crosslinking reaction
Adding a swelling agent into the polymer resin obtained in the step S30 for swelling, adding a catalyst after swelling, and heating for post-crosslinking reaction to obtain crosslinked resin;
s50, chloromethylation reaction
Adding a chloromethylating agent into the crosslinked resin obtained in the step S40 for swelling, adding a catalyst after swelling, and heating for chloromethylation reaction to obtain chloromethylated resin;
s60, secondary post-crosslinking reaction
And (5) adding a swelling agent into the chloromethylated resin obtained in the step (S50) for swelling, adding a catalyst after swelling, heating for carrying out secondary post-crosslinking reaction, and obtaining the adsorption resin with the ultrahigh specific surface area.
Preferably, in step S20, the mass of the added lactic acid is 10% to 20% of the mass of divinylbenzene.
Preferably, in step S20, the added pore-foaming agent is one or more of toluene, xylene, isobutanol, liquid paraffin and 200# solvent oil; the initiator is one or two of benzoyl peroxide or azodiisobutyronitrile.
Preferably, the swelling time for swelling the polymeric resin in step S40 is T1, and the swelling time for swelling the chloromethylated resin in step S60 is T2, T2> T1.
Preferably, the temperature increase manner of the post-crosslinking reaction of step S40 is different from the temperature increase manner of the secondary post-crosslinking reaction of step S60;
wherein, in step S40, the swollen polymer resin is heated to 60-62 ℃ firstly, and then heated to 80-82 ℃ for post-crosslinking reaction; in step S60, the swelled chloromethylated resin is directly heated to 80-82 ℃ to perform secondary post-crosslinking reaction.
Preferably, in step S10, the dispersant is one or more of gelatin, polyvinyl alcohol and hydroxyethyl cellulose, and the salt is one or both of sodium dihydrogen phosphate and sodium chloride.
Preferably, in step S50, the chloromethylated resin obtained by the reaction is dried until the water content is less than 0.2%.
Preferably, in step S20, the pore-forming agent includes one or more of toluene accounting for 50% to 200% of divinylbenzene, xylene accounting for 50% to 180%, isobutanol accounting for 80% to 160%, liquid paraffin accounting for 60% to 120%, and 200# solvent oil accounting for 80% to 160%; the initiator comprises one or two of benzoyl peroxide accounting for 0.5-2.5% of the mass of the divinylbenzene or azodiisobutyronitrile accounting for 0.2-1.5%.
Preferably, the swelling time T2 for swelling the chloromethylated resin in step S60 is 6 to 8h.
Preferably, in step S40, the post-crosslinking reaction is performed by: adding a swelling agent into the polymer resin obtained in the step S30 for swelling, adding a catalyst after swelling, stirring at normal temperature for 1-2 h, heating to 60-62 ℃, keeping the temperature for 2-3 h, heating to 80-82 ℃, keeping the temperature for 10-12 h, and performing post-crosslinking reaction to obtain crosslinked resin;
in step S60, the secondary post-crosslinking reaction comprises: and (3) adding a swelling agent into the chloromethylated resin obtained in the step (S50) for swelling, adding a catalyst after swelling, stirring at normal temperature for 1-2 h, heating to 80-82 ℃, keeping the temperature for 8-10 h, and carrying out secondary post-crosslinking reaction to obtain the adsorption resin with the ultrahigh specific surface area.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the synthesis method of the adsorption resin with the ultrahigh specific surface area, lactic acid and one or more of pore-foaming agents toluene, xylene, isobutanol, liquid paraffin and 200# solvent oil are compounded in the divinylbenzene self-polymerization process, so that the pore-foaming agents in an oil phase are dispersed more uniformly and finely, the average pore diameter of divinylbenzene self-polymerization is effectively controlled to be about 4-5 nm, and pores formed by the resin are more uniform;
(2) According to the synthesis method of the adsorption resin with the ultrahigh specific surface area, residual suspended double bonds on the resin are soaked through post-crosslinking reaction, chloromethylation reaction and secondary post-crosslinking reaction to form positive carbon ions with strong electron-withdrawing capability, and nucleophilic attack is performed on adjacent benzene rings to form bridging, increase pore channels and improve the specific surface area;
(3) According to the synthesis method of the adsorption resin with the ultrahigh specific surface area, disclosed by the invention, the swelling time of the resin in the second post-crosslinking reaction is longer than that in the first post-crosslinking reaction, namely T2 is more than T1, and T2 is within the range of 6-8 h, so that a pore channel in the resin is filled with a solvent and is fully swelled, and the higher post-crosslinking degree and the higher crosslinking bridge rigidity are ensured;
(4) According to the synthesis method of the adsorption resin with the ultrahigh specific surface area, the synthesized resin has a higher specific surface area, and the pore passages of the resin are mainly concentrated in the micropore area, so that the adsorption capacity of the resin on micromolecular organic matters and volatile gases is extremely large, and the application range of the resin is expanded.
Drawings
FIG. 1 is a schematic flow chart of a method for synthesizing an adsorption resin with an ultra-high specific surface area according to the present invention.
Detailed Description
The invention is further described with reference to specific examples.
As shown in FIG. 1, the method for synthesizing the adsorption resin with ultra-high specific surface area comprises the following steps:
s10, preparing a water phase
Adding a dispersing agent and a salt into water (specifically deionized water), wherein the dispersing agent is one or more of gelatin, polyvinyl alcohol and hydroxyethyl cellulose, and the salt is one or two of sodium dihydrogen phosphate and sodium chloride.
Adding one or more of gelatin which accounts for 0.2-1% of the mass of water, polyvinyl alcohol which accounts for 0.1-0.8%, sodium dihydrogen phosphate which accounts for 0.1-0.4%, sodium chloride which accounts for 5-15% and hydroxyethyl cellulose which accounts for 0.1-0.5% of the mass of water into the water, stirring and heating to 80 ℃, preserving heat for half an hour, uniformly mixing to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding lactic acid into divinylbenzene (preferably divinylbenzene with the purity of 80 percent or higher), adding a pore-foaming agent and an initiator, and stirring and uniformly mixing to obtain an oil phase for later use; wherein the pore-foaming agent is one or more of toluene, xylene, isobutanol, liquid paraffin and 200# solvent oil; the initiator is one or two of benzoyl peroxide or azodiisobutyronitrile.
Specifically, the mass of the added lactic acid is 10-20% of the mass of the divinylbenzene; the added pore-foaming agent comprises one or more of toluene accounting for 50-200% of the mass of divinylbenzene, xylene accounting for 50-180%, isobutanol accounting for 80-160%, liquid paraffin accounting for 60-120%, and 200# solvent oil accounting for 80-160%; the initiator comprises one or two of benzoyl peroxide accounting for 0.5-2.5 percent of the mass of the divinylbenzene or azodiisobutyronitrile accounting for 0.2-1.5 percent of the mass of the divinylbenzene.
S30, polymerization reaction
And (2) adding the oil phase obtained in the step (S20) into the water phase obtained in the step (S10) for stirring, wherein the stirring speed is 100-800 rpm, heating to 70-72 ℃, keeping the temperature for 1-2 h, heating to 75-77 ℃, keeping the temperature for 1-2 h, heating to 80-82 ℃, stirring for 4-5 h, finally heating to 88-90 ℃, and keeping stirring for 4-5 h for polymerization reaction to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin by hot water at the temperature of about 80-82 ℃, acetone or methanol and deionized water, and putting the polymer resin into an oven at the temperature of 70-72 ℃ for drying for later use;
it should be noted that, due to the addition of lactic acid, the porogen is more uniformly dispersed in the oil phase, so that the obtained polymeric resin has smaller and more uniform pore channels.
S40, post-crosslinking reaction
Adding a swelling agent into the polymer resin obtained in the step S30, stirring and swelling, wherein the swelling time T1 is 3-5 h, the swelling agent is one or two of nitrobenzene or dichloroethane, and the mass of the swelling agent is 4-6 times that of the polymer resin; then adding one or more of anhydrous aluminum trichloride, anhydrous ferric chloride and anhydrous zinc chloride which account for 20-40% of the mass of the polymer resin as a catalyst, stirring at normal temperature for 1-2 h, heating to 60 ℃ and keeping the temperature for 2h, and then heating to 80 ℃ and keeping the temperature for 10-12 h for post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and drying the crosslinked resin in a 50 ℃ drying oven for later use;
s50 chloromethylation reaction
Adding a chloromethylating agent into the crosslinked resin obtained in the step S40, and stirring and swelling for 2 hours, wherein the chloromethylating agent is chloromethyl ether, and the mass of the chloromethylating agent is 3-4 times of the mass of the crosslinked resin; then adding anhydrous ferric chloride catalyst, heating to 43 +/-2 ℃, stirring and preserving heat for 8-12 h to carry out chloromethylation reaction, thus obtaining chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, washing the chloromethylated resin with acetone or methanol and deionized water, and putting the washed chloromethylated resin into a 50 ℃ drying oven for standby application, wherein in the step S50, the chloromethylated resin is dried until the water content of the resin is less than 0.2%;
it should be noted that if the water content of the resin is high, the resin is easily broken in the subsequent secondary post-crosslinking reaction, and the chlorine content of the resin is difficult to decrease, and the secondary post-crosslinking reaction is difficult to complete.
S60, secondary post-crosslinking reaction
Adding a swelling agent into the chloromethylated resin obtained in the step S50, stirring and swelling, wherein the swelling time T2 is 6-8 h, the swelling agent is one or two of nitrobenzene or dichloroethane, and the mass of the swelling agent is 4-6 times that of the chloromethylated resin; after swelling, adding one or two of anhydrous aluminum trichloride and anhydrous zinc chloride which account for 20-30% of the mass of the chloromethylated resin as catalysts, stirring at normal temperature for 1-2 h, directly heating to 80 ℃, and preserving heat for 8-10 h to perform secondary post-crosslinking reaction. After the reaction is finished, taking out the resin, and washing the resin by acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area.
It should be noted that the swelling time in step S40 is T1, the swelling time in step S60 is T2, T2> T1, and T2 is preferably 6 to 8 hours, because the polymer chains are always in a fully swollen solvated state during the post-crosslinking process, and when the swelling effect of the resin is better, the pores inside the resin are filled with the solvent and are fully swollen, and the higher the post-crosslinking degree is, the greater the rigidity of the crosslinking bridge is.
The temperature increase method of the post-crosslinking reaction in step S40 is different from the temperature increase method of the secondary post-crosslinking reaction in step S60, and is different from the method of the post-crosslinking reaction in step S60 in that the reaction intensity and the specific surface area of the resin are different from each other, and the resin balls are prevented from being broken.
Example 1
The synthesis method of the adsorption resin with the ultrahigh specific surface area comprises the following steps:
s10, preparing a water phase
Adding 500g of deionized water into a three-neck flask, then adding 4g of gelatin, 2g of polyvinyl alcohol, 1g of disodium hydrogen phosphate and 50g of sodium chloride, stirring, heating to 80 ℃, preserving heat for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 100g of divinylbenzene with the purity of 80 percent into a beaker, then adding 10g of lactic acid, 50g of toluene, 100g of xylene and 2g of benzoyl peroxide, and uniformly stirring to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 500rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin with hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ oven for drying for later use;
s40, post-crosslinking reaction
Weighing 80g of the dried polymer resin obtained in the step S30, putting the weighed resin into a three-neck flask, adding 320g of nitrobenzene to swell for T1=3h, then adding 20g of anhydrous ferric chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 10h, and performing post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and putting the crosslinked resin into a 50 ℃ oven for drying for later use;
s50 chloromethylation reaction
And (2) weighing 80g of the dried crosslinked resin obtained in the step (S40), putting the weighed resin into a three-neck flask, adding 350g of chloromethyl ether, stirring and swelling for 2 hours, then adding 20g of anhydrous ferric chloride, heating to 44 ℃, stirring and keeping the temperature for 8 hours to perform chloromethylation reaction, and thus obtaining chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ drying oven for drying for later use, wherein the water content of the dried resin is less than 0.2%;
s60, secondary post-crosslinking reaction
Weighing 80g of the dried chloromethylated resin obtained in the step S50, adding the dried chloromethylated resin into a three-neck flask, adding 400g of nitrobenzene, stirring and swelling for T2=6h, adding 20g of anhydrous aluminum trichloride after swelling, stirring for 1h at normal temperature, heating to 80 ℃, keeping the temperature for 8h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and cleaning the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area. The resin synthesized in this example was tested to have a specific surface area of 1657m 2 /g。
Example 2
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, preparing a water phase
Adding 1000g of deionized water into a three-neck flask, then adding 10g of gelatin, 5g of polyvinyl alcohol, 4g of disodium hydrogen phosphate and 100g of sodium chloride, stirring, heating to 80 ℃, preserving heat for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 200g of 82% divinylbenzene into a beaker, then adding 12g of lactic acid, 100g of toluene, 300g of isobutanol and 2g of azodiisobutyronitrile, and stirring and uniformly mixing to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 800rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin by using hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ drying oven for drying for later use;
s40, post-crosslinking reaction
Weighing 100g of the dried polymer resin obtained in the step S30, putting the dried polymer resin into a three-neck flask, adding 600g of nitrobenzene to swell T1=5h, adding 30g of anhydrous zinc chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 12h, and performing post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and putting the crosslinked resin into a 50 ℃ oven for drying for later use;
s50 chloromethylation reaction
And (3) weighing 100g of the dried crosslinked resin obtained in the step (S40), putting the dried crosslinked resin into a three-neck flask, adding 400g of chloromethyl ether, stirring and swelling for 2h, adding 40g of anhydrous ferric trichloride, heating to 45 ℃, stirring and preserving heat for 8h to perform chloromethylation reaction, and obtaining the chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ oven for drying for later use;
s60, secondary post-crosslinking reaction
Weighing 100g of the dried chloromethylated resin obtained in the step S50, adding the dried chloromethylated resin into a three-neck flask, adding 400g of dichloroethane for swelling T2=8h, adding 30g of anhydrous zinc chloride after swelling, stirring at normal temperature for 1h, heating to 80 ℃, preserving heat for 10h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and washing the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area. The resin synthesized in the example was tested to have a specific surface area of 1748m 2 /g。
Example 3
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, preparing a water phase
Adding 1000g of deionized water into a three-neck flask, then adding 8g of polyvinyl alcohol, 150g of sodium chloride and 10g of hydroxyethyl cellulose, stirring, heating to 80 ℃, keeping the temperature for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 200g of 80% divinylbenzene into a beaker, then adding 20g of lactic acid, 100g of toluene, 240g of liquid paraffin and 3g of benzoyl peroxide, and uniformly stirring to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 700rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin with hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ oven for drying for later use;
s40, post-crosslinking reaction
Weighing 100g of the dried polymer resin obtained in the step S30, putting the dried polymer resin into a three-neck flask, adding 500g of dichloroethane to swell T1=5h, then adding 30g of anhydrous ferric chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 12h, and carrying out post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and putting the crosslinked resin into a 50 ℃ oven for drying for later use;
s50 chloromethylation reaction
And (2) weighing 100g of the dried crosslinked resin obtained in the step (S40), putting the weighed resin into a three-neck flask, adding 300g of chloromethyl ether, stirring and swelling for 2h, adding 30g of anhydrous ferric trichloride, heating to 44 ℃, stirring and preserving heat for 12h to perform chloromethylation reaction, and obtaining chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ oven for drying for later use;
s60, secondary post-crosslinking reaction
Weighing 100g of the dried chloromethylated resin obtained in the step S50, adding the dried chloromethylated resin into a three-neck flask, adding 600g of dichloroethane for swelling T2=8h, adding 30g of anhydrous aluminum trichloride after swelling, stirring at normal temperature for 1h, heating to 80 ℃, preserving heat for 10h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and washing the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area. The resin synthesized in this example was tested to have a specific surface area of 1620m 2 /g。
Example 4
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, preparing a water phase
Adding 10kg of deionized water into a 50L reactor, then adding 100g of gelatin, 40g of polyvinyl alcohol and 1kg of sodium chloride, stirring, heating to 80 ℃, preserving heat for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 2kg of 80% divinylbenzene into a 10L reactor, then adding 100g of lactic acid, 1kg of toluene, 3kg of isobutanol and 20g of azodiisobutyronitrile, and stirring and uniformly mixing to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 500rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin by using hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ drying oven for drying for later use;
s40, post-crosslinking reaction
Weighing 1kg of the dried polymer resin obtained in the step S30, putting the dried polymer resin into a 20L reactor, adding 6kg of nitrobenzene to swell T1=5h, then adding 300g of anhydrous zinc chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 12h, and carrying out post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and drying the crosslinked resin in a 50 ℃ drying oven for later use;
s50 chloromethylation reaction
And (3) weighing 1kg of the dried crosslinked resin obtained in the step (S40) and putting the weighed dried crosslinked resin into a 20L reactor, adding 4kg of chloromethyl ether, stirring and swelling for 2h, adding 300g of anhydrous ferric trichloride, heating to 45 ℃, stirring and preserving heat for 8h to perform chloromethylation reaction, and obtaining the chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ drying oven for drying for later use;
s60, secondary post-crosslinking reaction
Weighing 1kg of the dried chloromethylated resin obtained in the step S50, adding the dried chloromethylated resin into a three-neck flask, adding 5kg of dichloroethane for swelling T2=8h, adding 200g of anhydrous zinc chloride after swelling, stirring at normal temperature for 1h, heating to 80 ℃, preserving heat for 10h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and cleaning the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area. The resin synthesized in the example was tested to have a specific surface area of 1720m 2 /g。
Comparative example 1
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, preparing a water phase
Adding 500g of deionized water into a three-neck flask, then adding 4g of gelatin, 2g of polyvinyl alcohol, 1g of disodium hydrogen phosphate and 50g of sodium chloride, stirring, heating to 80 ℃, preserving heat for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 100g of divinylbenzene with the purity of 80 percent into a beaker, then adding 50g of toluene, 100g of xylene and 2g of benzoyl peroxide, and stirring and uniformly mixing to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 500rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin by using hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ drying oven for drying for later use;
s40, post-crosslinking reaction
Weighing 80g of the dried polymeric resin obtained in the step S30, putting the dried polymeric resin into a three-neck flask, adding 320g of nitrobenzene to swell T1=3h, then adding 20g of anhydrous ferric chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 10h, and carrying out post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and putting the crosslinked resin into a 50 ℃ oven for drying for later use;
s50 chloromethylation reaction
And (3) weighing 80g of the dried crosslinked resin obtained in the step (S40), putting the weighed dried crosslinked resin into a three-neck flask, adding 350g of chloromethyl ether, stirring and swelling for 2h, then adding 20g of anhydrous ferric trichloride, heating to 44 ℃, stirring and preserving heat for 8h to perform chloromethylation reaction, and obtaining chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ drying oven for drying for later use, wherein the water content of the dried resin is less than 0.2%;
s60, secondary post-crosslinking reaction
Weighing 80g of the dried chloromethylated resin obtained in the step S50, adding the dried chloromethylated resin into a three-neck flask, adding 400g of nitrobenzene, stirring and swelling for T2=6h, adding 20g of anhydrous aluminum trichloride after swelling, stirring for 1h at normal temperature, heating to 80 ℃, keeping the temperature for 8h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and cleaning the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area.
The resin synthesized by the comparative example has the specific surface area of 1430m 2 (ii)/g, lower than the specific surface area of the resin of example 1. Therefore, in the divinylbenzene self-polymerization process, the lactic acid is added into the oil phase, and the lactic acid and the pore-forming agent are effectively compounded, so that the average pore diameter of the divinylbenzene self-polymerization can be controlled, the pores formed by the resin are more uniform, and the specific surface area of the resin obtained by the secondary post-crosslinking reaction is larger.
Comparative example 2
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, preparing a water phase
Adding 500g of deionized water into a three-neck flask, then adding 4g of gelatin, 2g of polyvinyl alcohol, 1g of disodium hydrogen phosphate and 50g of sodium chloride, stirring, heating to 80 ℃, preserving heat for half an hour to obtain a water phase, and cooling the water phase to normal temperature for later use;
s20, preparing an oil phase
Adding 100g of divinylbenzene with the purity of 80 percent into a beaker, then adding 10g of lactic acid, 50g of toluene, 100g of xylene and 2g of benzoyl peroxide, and uniformly stirring to obtain an oil phase for later use;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring at the stirring speed of 500rpm, heating to 70 ℃, preserving heat for 1h, heating to 75 ℃, preserving heat for 1h, heating to 80 ℃, and stirring for 4h; finally, the temperature is raised to 88 ℃, and the stirring is continuously kept for 4 hours for polymerization reaction, so as to obtain the polymer resin. After the reaction is finished, taking out the polymer resin, sequentially washing the polymer resin with hot water at 80 ℃, acetone or methanol and deionized water, and putting the polymer resin into a 70 ℃ oven for drying for later use;
s40, post-crosslinking reaction
Weighing 80g of the dried polymeric resin obtained in the step S30, putting the dried polymeric resin into a three-neck flask, adding 320g of nitrobenzene to swell T1=3h, then adding 20g of anhydrous ferric chloride, stirring at normal temperature for 1h, heating to 60 ℃, keeping the temperature for 2h, heating to 80 ℃, keeping the temperature for 10h, and carrying out post-crosslinking reaction to obtain the crosslinked resin. After the reaction is finished, taking out the crosslinked resin, cleaning the crosslinked resin by using acetone or methanol and deionized water, and drying the crosslinked resin in a 50 ℃ drying oven for later use;
s50 chloromethylation reaction
And (2) weighing 80g of the dried crosslinked resin obtained in the step (S40), putting the weighed resin into a three-neck flask, adding 350g of chloromethyl ether, stirring and swelling for 2 hours, then adding 20g of anhydrous ferric chloride, heating to 44 ℃, stirring and keeping the temperature for 8 hours to perform chloromethylation reaction, and thus obtaining chloromethylated resin. After the reaction is finished, taking out the chloromethylated resin, cleaning the chloromethylated resin by using acetone or methanol and deionized water, and putting the chloromethylated resin into a 50 ℃ drying oven for drying for later use, wherein the water content of the dried resin is less than 0.2%;
s60, secondary post-crosslinking reaction
And (2) weighing 80g of the dried chloromethylated resin obtained in the step S50, adding the weighed resin into a three-neck flask, adding 400g of nitrobenzene, stirring and swelling for T2=2h, adding 20g of anhydrous aluminum trichloride after swelling, stirring for 1h at normal temperature, heating to 80 ℃, keeping the temperature for 8h, and carrying out secondary post-crosslinking reaction. And after the reaction is finished, taking out the resin, and cleaning the resin by using acetone or methanol and deionized water to obtain the adsorption resin with the ultrahigh specific surface area.
The specific surface area of the resin synthesized by the comparative example is 1480m 2 (ii)/g, lower than the specific surface area of the resin of example 1. It can be seen that when the swelling time T1=3h in step S30, the swelling time T2=2h and T2 in step S60 are equal to each other<T1, the swelling effect of the resin cannot be ensured, more space in the pore canal cannot be left for secondary post-crosslinking, and the specific surface area of the resin is increased.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (8)
1. A synthetic method of an adsorption resin with an ultrahigh specific surface area is characterized by comprising the following steps:
s10, preparing a water phase
Adding a dispersing agent and salt into water, stirring and heating, and uniformly mixing to obtain a water phase;
s20, preparing an oil phase
Adding lactic acid into divinylbenzene, wherein the mass of the added lactic acid is 10-20% of that of the divinylbenzene, adding a pore-foaming agent and an initiator, and stirring and uniformly mixing to obtain an oil phase;
s30, polymerization reaction
Adding the oil phase obtained in the step S20 into the water phase obtained in the step S10, stirring and heating for polymerization reaction to obtain polymer resin;
s40, post-crosslinking reaction
Adding a swelling agent into the polymer resin obtained in the step S30 for swelling, wherein the swelling time of the polymer resin for swelling is T1, adding a catalyst after swelling, and heating for post-crosslinking reaction to obtain crosslinked resin;
s50, chloromethylation reaction
Adding a chloromethylating agent into the crosslinked resin obtained in the step S40 for swelling, adding a catalyst after swelling, and heating for chloromethylation reaction to obtain chloromethylated resin;
s60, secondary post-crosslinking reaction
And (5) adding a swelling agent into the chloromethylated resin obtained in the step (S50) for swelling, wherein the swelling time of the chloromethylated resin for swelling is T2, T2 is greater than T1, adding a catalyst after swelling, heating for carrying out secondary post-crosslinking reaction, and thus obtaining the adsorption resin with the ultrahigh specific surface area.
2. The method for synthesizing the adsorption resin with ultra-high specific surface area as claimed in claim 1, wherein: in the step S20, the added pore-foaming agent is one or more of toluene, xylene, isobutanol, liquid paraffin and 200# solvent oil; the initiator is one or two of benzoyl peroxide or azodiisobutyronitrile.
3. The method for synthesizing the adsorption resin with ultra-high specific surface area as claimed in claim 1, wherein: the temperature rise mode of the post-crosslinking reaction in the step S40 is different from the temperature rise mode of the secondary post-crosslinking reaction in the step S60;
in step S40, the temperature of the swelled polymer resin is raised to 60-62 ℃, and then raised to 80-82 ℃ for post-crosslinking reaction; in step S60, the swelled chloromethylated resin is directly heated to 80-82 ℃ for secondary post-crosslinking reaction.
4. The method for synthesizing the adsorption resin with the ultrahigh specific surface area as claimed in claim 1, wherein the method comprises the following steps: in step S10, the dispersant is one or more of gelatin, polyvinyl alcohol, and hydroxyethyl cellulose, and the salt is one or two of sodium dihydrogen phosphate and sodium chloride.
5. The method for synthesizing the adsorption resin with ultra-high specific surface area as claimed in claim 1, wherein: in step S50, the chloromethylated resin obtained by the reaction is dried until the water content is less than 0.2%.
6. The method for synthesizing the adsorption resin with ultra-high specific surface area as claimed in claim 1, wherein: in step S20, the pore-foaming agent comprises one or more of toluene accounting for 50-200% of the mass of divinylbenzene, xylene accounting for 50-180%, isobutanol accounting for 80-160%, liquid paraffin accounting for 60-120%, and 200# solvent oil accounting for 80-160%; the initiator comprises one or two of benzoyl peroxide accounting for 0.5-2.5% of the mass of the divinylbenzene or azodiisobutyronitrile accounting for 0.2-1.5%.
7. The method for synthesizing the adsorption resin with ultra-high specific surface area as claimed in claim 1, wherein: the swelling time T2 for swelling the chloromethylated resin in the step S60 is 6-8 h.
8. The method for synthesizing the adsorption resin with the ultrahigh specific surface area as claimed in claim 3, wherein the method comprises the following steps:
in step S40, the post-crosslinking reaction comprises: adding a swelling agent into the polymer resin obtained in the step S30 for swelling, adding a catalyst after swelling, stirring at normal temperature for 1-2 h, heating to 60-62 ℃, keeping the temperature for 2-3 h, heating to 80-82 ℃, keeping the temperature for 10-12 h, and performing post-crosslinking reaction to obtain crosslinked resin;
in step S60, the secondary post-crosslinking reaction comprises: and (2) adding a swelling agent into the chloromethylated resin obtained in the step (S50) for swelling, adding a catalyst after swelling, stirring at normal temperature for 1-2 h, heating to 80-82 ℃, keeping the temperature for 8-10 h, and performing secondary post-crosslinking reaction to obtain the adsorption resin with the ultrahigh specific surface area.
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