CN112011000A - Method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction - Google Patents
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- 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
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The invention discloses a method for carrying out secondary reinforcement on chloromethylated resin by using a crosslinking reaction, which utilizes formaldehyde and hydrochloric acid as a chlorinating agent to carry out methylation reaction, and simultaneously utilizes dichloroethane to carry out secondary crosslinking reaction on the resin containing chloromethyl, thereby greatly reducing the production cost, ensuring safer production, leading the macroporous resin after methylation and secondary crosslinking to have tighter structure and higher strength, leading the specific surface area to reach 1000 square meters per gram, having better adsorption performance and being mainly used as an adsorbent in a blood perfusion device; when the adsorbent is applied to bilirubin adsorption, the adsorption amount is higher than 0.8 mu mol/ml.
Description
Technical Field
The invention relates to the technical field of adsorption resin of a blood perfusion apparatus, in particular to a method for performing secondary reinforcement on chloromethylation resin by using a crosslinking reaction.
Background
A large number of researches show that the hemoperfusion apparatus can effectively treat hyperbilirubinemia, the most used adsorbent is activated carbon, but the adsorption selectivity is poor, and the particles are easy to fall off to cause blood vessel blockage, after the coating treatment, although the problem of particle falling off is basically solved, the cost of the activated carbon is high, the economic burden of patients is increased, in recent years, many researchers are dedicated to research and development of high-molecular adsorbents, the materials have wide applicability and low cost in the hemoperfusion apparatus, and an adsorption structure can be designed in a targeted manner, and the hourly A-type macroporous resin, the hourly B-hourly-6 type resin and the chitosan series which are commonly used at present are adopted.
The macroporous resin is a macromolecular adsorption resin which does not contain exchange groups and has a macroporous structure, has a good macroporous network structure and a larger specific surface area, can selectively adsorb medium molecular substances with the relative molecular weight of 500-5000D, such as bilirubin, aromatic amino acid and the like, and is suitable for removing uremia, burn toxicity, epidemic hemorrhagic fever, menstrual sickness and the like, and has the bioactivity of psychotoxicity, blood toxicity, immune cells and the like.
The analysis of the existing macroporous adsorption resin preparation method shows that the existing macroporous resin production process needs to use high-toxicity chloromethyl ether and other raw materials and needs to be completed in multiple steps, the chloromethyl ether used in the production is a high-toxicity substance and has certain threat to production safety, and the macroporous resin produced by the prior art has the defects of not compact structure, low strength and incapability of meeting the gradually improved use requirements on specific surface area and adsorption performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for performing secondary reinforcement on chloromethylated resin by using a crosslinking reaction, wherein safe raw materials are adopted in the production process, the production safety is improved, the obtained macroporous resin has a more compact structure, a high specific surface area, higher adsorption performance and lower cost, and is particularly suitable for reinforcing the resin of good-friend chloromethyl obtained by performing chloromethyl reaction on formaldehyde, hydrochloric acid and a benzene ring.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for carrying out secondary reinforcement on chloromethyl resin by using crosslinking reaction comprises the following steps:
step 1: synthesizing white balls, namely slowly adding the prepared oil phase into the water phase, heating and stirring, keeping the temperature to form resin particles, extracting a pore-forming agent, and washing and drying the resin particles;
step 2: methylating formaldehyde with hydrochloric acid, adding hydrochloric acid into formaldehyde to prepare a clear solution, putting the resin particles prepared in the step S1 into the clear solution for swelling, and adding a catalyst of anhydrous zinc chloride for methylation after swelling;
and step 3: and (2) secondary crosslinking, namely adding methylal into the resin mother liquor in the chlorination process for washing for 5 times, then adding water for washing until the washing liquid is neutral, drying the resin particles, adding the dried resin particles into dichloroethane for swelling, adding equivalent anhydrous ferric chloride into the swelled mixture twice for stirring, heating to 40-50 ℃, keeping the temperature for 5 hours for secondary crosslinking reaction, and adding water for washing after the crosslinking reaction is finished to obtain the adsorption resin.
The step 1 comprises the steps of water phase preparation, oil phase preparation, mixing and stirring, washing, pore-forming agent extraction, drying and drying in sequence to obtain the resin white ball.
The water phase preparation comprises the step of adding polyvinyl alcohol and sodium chloride with the weight percentage ratio of 1:6 into warm water with the temperature of 50-60 ℃ and stirring, the step of oil phase preparation comprises the step of mixing and stirring divinylbenzene, liquid paraffin, toluene and BPO, the weight percentage ratio of the divinylbenzene, the liquid paraffin and the toluene is 1.5-2.5:1:2-3, and the BPO accounts for 0.5-1% of the mass of the oil phase.
The mixing and stirring comprises the steps of slowly adding the prepared oil phase into a water phase, stirring at a constant speed, heating the mixture in the stirring process, raising the temperature of the mixture from 55 ℃ to 75 ℃ at a heating rate of 5 ℃/10 minutes, keeping the temperature for 2 hours to shape the resin, raising the temperature of the mixture from 75 ℃ to 85 ℃ at a heating rate of 5 ℃/10 minutes after shaping, keeping the temperature for 4 hours, continuing raising the temperature from 85 ℃ to 95 ℃ at a heating rate of 5 ℃/10 minutes, keeping the temperature for 6 hours, taking out resin particles, washing polyvinyl alcohol on the surface of the resin with warm water, extracting a pore-forming agent with acetone in a Soxhlet extractor for 8 hours, and washing and drying the resin particles with water after extraction.
Step 2 comprises solution preparation, swelling and chlorination, wherein the solution preparation comprises mixing hydrochloric acid and formaldehyde in a weight to volume ratio of 1:5 (g: ml) into a clear solution.
The swelling comprises the steps of adding resin into a clear solution for 3 hours, wherein the mass part ratio of the added resin to hydrochloric acid in the clear solution is 1:2-2.5, the temperature in the swelling process is 4-6 ℃, adding catalyst anhydrous zinc chloride for the first time after swelling for 3 hours, adding catalyst anhydrous zinc chloride again after 25-35 minutes, stirring for 25-35 minutes, heating the mixture to 45 ℃, and carrying out heat preservation reaction for 6 hours to complete chlorination.
The weight of the catalyst anhydrous zinc chloride added twice in the methylation process is equal, and the weight part ratio of the anhydrous zinc chloride added each time to the resin in the mixture is 7-8: 100.
And 3, resin washing and secondary crosslinking, wherein the resin washing comprises the steps of pumping resin mother liquor after reaction, adding methylal into a reaction container for washing for 30 minutes for 5 times, then washing with clear water until the washing liquid is neutral, drying resin particles after washing is finished, and controlling the water content of the resin particles to be 5-10%.
Adding dichloroethane to a reaction container in which resin particles are added for swelling at the swelling temperature of 5 ℃, adding anhydrous ferric chloride serving as a catalyst twice after swelling for 3 hours, adding the anhydrous ferric chloride at the interval of 30 minutes, adding the anhydrous ferric chloride, mixing and stirring for 30 minutes, heating to 80 ℃ for reaction, reacting for 6 hours, wherein the weight-to-volume ratio of the added resin particles to the dichloroethane is 1:10 (g: ml), the mass part ratio of the added anhydrous ferric chloride to the resin particles is 7-8:100, and washing to obtain the resin particles after the reaction is finished.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the invention utilizes formaldehyde and hydrochloric acid as chlorinating agents to carry out chloromethylation reaction, and utilizes dichloroethane to carry out secondary crosslinking on resin subjected to the chloromethylation reaction, thereby greatly reducing the production cost, and the adopted raw materials are safe raw materials, the production is safer, the macroporous resin subjected to the secondary crosslinking reaction has tighter structure, higher strength, larger specific surface area which can reach 1000 square meters per gram, better adsorption performance, and is mainly used as the adsorbent in the blood perfusion device.
Detailed Description
The technical solutions of the present invention are described below clearly and completely with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
A method for carrying out secondary reinforcement on chloromethyl resin by using crosslinking reaction comprises the following steps:
(1) white ball synthesis: 1000ml of water are placed in a 2000ml three-necked flask and the temperature is raised to 55 ℃ and 5g of polyvinyl alcohol and 30g of sodium chloride are added and stirred for half an hour as the aqueous phase. 100g of divinylbenzene 80% pure, 50g of liquid paraffin, 150g of toluene, 0.5% of BPO as an oil phase were added to the beaker. Slowly adding the oil phase into the water phase, stirring at a controlled rotation speed until the oil phase has a proper particle size, and stirring at a constant speed. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 minutes. After the resin is shaped for 2 hours, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10 minutes, the temperature is kept for 4 hours, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10 minutes, the resin is taken out after the temperature is kept for 6 hours, the polyvinyl alcohol on the surface of the resin is washed away by warm water, a Soxhlet extractor is used for extracting the pore-forming agent by acetone for 8 hours, and the pore-forming agent is washed and dried by water.
(2) Methylation of formaldehyde and hydrochloric acid: adding 200g of hydrochloric acid into 1000ml of formaldehyde to prepare a clear solution, putting 100g of resin into a 2000ml three-necked bottle, adding the prepared clear solution, and swelling for 3 hours, wherein the temperature in the kettle is controlled not to exceed 4 ℃ in the swelling process. Compared with the prior art, the invention utilizes the mixing of nontoxic formaldehyde and hydrochloric acid to replace the prior raw materials for methylation, can effectively improve the production safety, reduce the production cost and improve the specific surface area of resin particles.
(3) Secondary crosslinking: and (4) extracting the chlorinated resin mother liquor, and washing the resin until the eluate is neutral. Controlling the drying moisture of the resin to be 5% -10%, adding the resin into a reaction container, adding 1000ml of dichloroethane for swelling for 3 hours, wherein the temperature in the reaction container is 5 ℃ in the swelling process, adding 7g of anhydrous ferric trichloride after swelling is finished, adding 7g of anhydrous ferric trichloride again after 30 minutes, stirring for 30 minutes, finally heating to 80 ℃ for reacting for 6 hours, and flushing after the reaction is finished to obtain the resin.
Example 2
(1) White ball synthesis: 1000ml of water are placed in a 2000ml three-necked flask and the temperature is raised to 55 ℃ and 5g of polyvinyl alcohol and 30g of sodium chloride are added and stirred for half an hour as the aqueous phase. 75g of divinylbenzene 80% pure, 50g of liquid paraffin, 100g of toluene, 1% of BPO as oil phase were added to the beaker. Slowly adding the oil phase into the water phase, stirring at a controlled rotation speed until the oil phase has a proper particle size, and stirring at a constant speed. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 minutes. After the resin is shaped for 2 hours, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10 minutes, the temperature is kept for 4 hours, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10 minutes, the resin is taken out after the temperature is kept for 6 hours, the polyvinyl alcohol on the surface of the resin is washed away by warm water, a Soxhlet extractor is used for extracting the pore-forming agent by acetone for 8 hours, and the pore-forming agent is washed and dried by water.
(2) Methylation of formaldehyde and hydrochloric acid: adding 200g of hydrochloric acid into 1000ml of formaldehyde to prepare a clear solution, putting 120g of resin into a 2000ml three-necked bottle, adding the prepared clear solution, and swelling for 3 hours, wherein the temperature in the kettle is controlled not to exceed 4 ℃ in the swelling process. Compared with the prior art, the invention utilizes the mixing of nontoxic formaldehyde and hydrochloric acid to replace the prior methylation, thereby effectively improving the production safety, reducing the production cost and improving the specific surface area of resin particles.
(3) Secondary crosslinking: and (4) extracting the chlorinated resin mother liquor, and washing the resin until the eluate is neutral. Controlling the drying moisture of the resin to be 5% -10%, adding the resin into a reaction container, adding 1000ml of dichloroethane for swelling for 3 hours, wherein the temperature in the reaction container is 5 ℃ in the swelling process, adding 7.5g of anhydrous ferric trichloride after swelling is finished, adding 7.5g of anhydrous ferric trichloride again after 30 minutes, stirring for 30 minutes, finally heating to 80 ℃ for reacting for 6 hours, and flushing after the reaction is finished to obtain the resin.
Example 3
(1) White ball synthesis: 1000ml of water are placed in a 2000ml three-necked flask and the temperature is raised to 55 ℃ and 5g of polyvinyl alcohol and 30g of sodium chloride are added and stirred for half an hour as the aqueous phase. 125g of divinylbenzene 80% pure, 50g of liquid paraffin, 100g of toluene, 1% of BPO as oil phase were added to the beaker. Slowly adding the oil phase into the water phase, stirring at a controlled rotation speed until the oil phase has a proper particle size, and stirring at a constant speed. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 minutes. After the resin is shaped for 2 hours, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10 minutes, the temperature is kept for 4 hours, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10 minutes, the resin is taken out after the temperature is kept for 6 hours, the polyvinyl alcohol on the surface of the resin is washed away by warm water, a Soxhlet extractor is used for extracting the pore-forming agent by acetone for 8 hours, and the pore-forming agent is washed and dried by water.
(2) Methylation of formaldehyde and hydrochloric acid: 220g of hydrochloric acid is added into 1000ml of formaldehyde to prepare a clear solution, 100g of resin is put into a 2000ml three-necked bottle, the prepared clear solution is added at the same time, swelling is carried out for 3 hours, and the temperature in the kettle is controlled not to exceed 4 ℃ in the swelling process. Compared with the prior art, the invention utilizes the mixing of nontoxic formaldehyde and hydrochloric acid to replace the prior raw materials for methylation, can effectively improve the production safety, reduce the production cost and improve the specific surface area of resin particles.
(3) Secondary crosslinking: and (4) extracting the chlorinated resin mother liquor, and washing the resin until the eluate is neutral. Controlling the drying moisture of the resin to be 5-10%, adding the resin into a reaction container, adding 1000ml of dichloroethane for swelling for 3 hours, wherein the temperature in the reaction container is 5 ℃ in the swelling process, adding 8g of anhydrous ferric trichloride after the swelling is finished, adding 8g of anhydrous ferric trichloride again after 30 minutes, stirring for 30 minutes, finally heating to 80 ℃ for reacting for 6 hours, and flushing after the reaction is finished to obtain the adsorption resin.
In a word, the invention utilizes formaldehyde and hydrochloric acid as chlorinating agent to carry out methylation reaction, and utilizes dichloroethane to carry out secondary crosslinking reaction, thereby greatly reducing the production cost, and the adopted raw materials are safe raw materials, the production is safer, the macroporous resin after chlorination and ammonification has tighter structure, higher strength, larger specific surface area which can reach 1000 square meters per gram, and better adsorption performance, and is mainly used as the adsorbent in the blood perfusion device.
Claims (9)
1. A method for carrying out secondary reinforcement on chloromethylated resin by utilizing crosslinking reaction is characterized by comprising the following steps: the method comprises the following steps:
step 1: synthesizing white balls, namely slowly adding the prepared oil phase into the water phase, heating and stirring, keeping the temperature to form resin particles, extracting a pore-forming agent, and washing and drying the resin particles;
step 2: methylating formaldehyde with hydrochloric acid, adding hydrochloric acid into formaldehyde to prepare a clear solution, putting the resin particles prepared in the step S1 into the clear solution for swelling, and adding a catalyst of anhydrous zinc chloride for methylation after swelling;
and step 3: and (2) secondary crosslinking, namely adding methylal into the resin mother liquor in the chlorination process for washing for 5 times, then adding water for washing until the washing liquid is neutral, drying the resin particles, adding the dried resin particles into dichloroethane for swelling, adding equivalent anhydrous ferric chloride into the swelled mixture twice for stirring, heating to 40-50 ℃, keeping the temperature for 5 hours for secondary crosslinking reaction, and adding water for washing after the crosslinking reaction is finished to obtain the adsorption resin.
2. The method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction according to claim 1, wherein: the step 1 comprises the steps of water phase preparation, oil phase preparation, mixing and stirring, washing, pore-forming agent extraction, drying and drying in sequence to obtain the resin white ball.
3. The method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction according to claim 2, wherein: the water phase preparation comprises the step of adding polyvinyl alcohol and sodium chloride with the weight percentage ratio of 1:6 into warm water with the temperature of 50-60 ℃ and stirring, the step of oil phase preparation comprises the step of mixing and stirring divinylbenzene, liquid paraffin, toluene and BPO, the weight percentage ratio of the divinylbenzene, the liquid paraffin and the toluene is 1.5-2.5:1:2-3, and the BPO accounts for 0.5-1% of the mass of the oil phase.
4. The method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction according to claim 2, wherein: the mixing and stirring comprises the steps of slowly adding the prepared oil phase into a water phase, stirring at a constant speed, heating the mixture in the stirring process, raising the temperature of the mixture from 55 ℃ to 75 ℃ at a heating rate of 5 ℃/10 minutes, keeping the temperature for 2 hours to shape the resin, raising the temperature of the mixture from 75 ℃ to 85 ℃ at a heating rate of 5 ℃/10 minutes after shaping, keeping the temperature for 4 hours, continuing raising the temperature from 85 ℃ to 95 ℃ at a heating rate of 5 ℃/10 minutes, keeping the temperature for 6 hours, taking out resin particles, washing polyvinyl alcohol on the surface of the resin with warm water, extracting a pore-forming agent with acetone in a Soxhlet extractor for 8 hours, and washing and drying the resin particles with water after extraction.
5. The method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction according to claim 1, wherein: step 2 comprises solution preparation, swelling and chlorination, wherein the solution preparation comprises mixing hydrochloric acid and formaldehyde in a weight to volume ratio of 1:5 (g: ml) into a clear solution.
6. The method of claim 5, wherein the chloromethylated resin is twice-reinforced by cross-linking reaction, which comprises the following steps: the swelling comprises the steps of adding resin into a clear solution for 3 hours, wherein the mass part ratio of the added resin to hydrochloric acid in the clear solution is 1:2-2.5, the temperature in the swelling process is 4-6 ℃, adding catalyst anhydrous zinc chloride for the first time after swelling for 3 hours, adding catalyst anhydrous zinc chloride again after 25-35 minutes, stirring for 25-35 minutes, heating the mixture to 45 ℃, and carrying out heat preservation reaction for 6 hours to complete chlorination.
7. The method of claim 6, wherein the chloromethylated resin is twice-reinforced by cross-linking reaction, which comprises the following steps: the weight of the catalyst anhydrous zinc chloride added twice in the methylation process is equal, and the weight part ratio of the anhydrous zinc chloride added each time to the resin in the mixture is 7-8: 100.
8. The method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction according to claim 1, wherein: and 3, resin washing and secondary crosslinking, wherein the resin washing comprises the steps of pumping resin mother liquor after reaction, adding methylal into a reaction container for washing for 30 minutes for 5 times, then washing with clear water until the washing liquid is neutral, drying resin particles after washing is finished, and controlling the water content of the resin particles to be 5-10%.
9. The method for performing secondary reinforcement on chloromethylated resin by using cross-linking reaction according to claim 8, wherein: adding dichloroethane to a reaction container in which resin particles are added for swelling at the swelling temperature of 5 ℃, adding anhydrous ferric chloride serving as a catalyst twice after swelling for 3 hours, adding the anhydrous ferric chloride at the interval of 30 minutes, adding the anhydrous ferric chloride, mixing and stirring for 30 minutes, heating to 80 ℃ for reaction, reacting for 6 hours, wherein the weight-to-volume ratio of the added resin particles to the dichloroethane is 1:10 (g: ml), the mass part ratio of the added anhydrous ferric chloride to the resin particles is 7-8:100, and washing to obtain the resin particles after the reaction is finished.
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Cited By (4)
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| CN114405491A (en) * | 2022-01-21 | 2022-04-29 | 昌果生物医药科技河北有限公司 | Preparation method and application of macroporous resin for VOCS adsorption |
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| CN114471485A (en) * | 2022-01-27 | 2022-05-13 | 昌果生物医药科技河北有限公司 | Preparation method and application of macroporous resin for adsorbing exogenous toxins in blood |
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