CN115920861B - Adsorbent, preparation method and application thereof - Google Patents
Adsorbent, preparation method and application thereof Download PDFInfo
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- CN115920861B CN115920861B CN202211663925.5A CN202211663925A CN115920861B CN 115920861 B CN115920861 B CN 115920861B CN 202211663925 A CN202211663925 A CN 202211663925A CN 115920861 B CN115920861 B CN 115920861B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 44
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005576 amination reaction Methods 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 23
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 21
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 21
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 230000002757 inflammatory effect Effects 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 35
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000008081 blood perfusion Effects 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 208000036796 hyperbilirubinemia Diseases 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 206010019663 Hepatic failure Diseases 0.000 claims description 4
- 208000027119 bilirubin metabolic disease Diseases 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 208000007903 liver failure Diseases 0.000 claims description 4
- 231100000835 liver failure Toxicity 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000010558 suspension polymerization method Methods 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 abstract description 52
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 210000004185 liver Anatomy 0.000 abstract description 8
- 230000010412 perfusion Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 210000004369 blood Anatomy 0.000 abstract description 3
- 239000008280 blood Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000013076 target substance Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 102000004889 Interleukin-6 Human genes 0.000 description 4
- 108090001005 Interleukin-6 Proteins 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229940100601 interleukin-6 Drugs 0.000 description 4
- 102000004127 Cytokines Human genes 0.000 description 3
- 108090000695 Cytokines Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010023126 Jaundice Diseases 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- External Artificial Organs (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorbent, a preparation method and application thereof, and relates to the technical field of adsorbents. According to the invention, divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether are used as monomers for polymerization, and as the three monomers contain hydrophobic and hydrophilic materials, the prepared resin has amphipathy, the hydrophobicity can improve the adsorption performance on bilirubin and inflammatory factors as target substances, the hydrophilicity can improve the blood compatibility, the safety of the resin is improved, and the plasma is fully contacted with the resin, so that the adsorption performance is improved. In addition, the amination is performed by using an amination reagent, and since bilirubin has a carboxyl group, an amine group is introduced into the resin, and the absorption selectivity of bilirubin can be improved by ion absorption. The adsorbent can adsorb bilirubin and inflammatory factors simultaneously, and one perfusion device can replace two perfusion devices in combined artificial liver treatment, so that the operation cost and risk are reduced, and the adsorbent has very good market application value.
Description
Technical Field
The invention relates to the technical field of adsorbents, in particular to an adsorbent, a preparation method and application thereof.
Background
The liver is one of the important organs of human body, and has the functions of synthesis, detoxification, metabolism, secretion, bioconversion, immune defense and the like. When severely damaged by various factors (such as viruses, alcohol, drugs, etc.), a large number of hepatic cells are necrotized, which in turn causes liver failure. DPMAS (double plasma molecular adsorption system) is a combined artificial liver treatment mode, and adopts the combination of neutral macroporous resin and exchange resin. The combined application of the two adsorbents can reduce jaundice symptoms and remove harmful substances such as inflammatory mediators, so that a relatively good external environment is provided for liver cell regeneration, and recovery of the liver is promoted.
The existing artificial liver technology can achieve the aim of adsorbing bilirubin and cell inflammatory factors by using two adsorbents, and generally adopts two perfusion devices connected in series, so that the cost and the risk are high.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an adsorbent, a preparation method and application thereof, and aims to adsorb bilirubin and cell inflammatory factors simultaneously.
The invention is realized in the following way:
In a first aspect, the present invention provides an adsorbent which is a copolymer formed by polymerizing divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether as monomers, and the copolymer is aminated by an aminating agent.
In a preferred embodiment of the invention, the mass ratio of divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether is 80-120:30-50:60-80;
Preferably, the amination reagent is selected from at least one of trimethylamine hydrochloride and triethylamine hydrochloride.
In a second aspect, the present invention also provides a method for preparing an adsorbent, comprising: the copolymer is polymerized by using divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether as monomers, and is aminated by using an amination reagent.
In a preferred embodiment of the present invention, the copolymer is prepared using a suspension polymerization process;
Preferably, it comprises: mixing and dissolving divinylbenzene, ethylene glycol dimethacrylate, allyl alcohol glycidyl ether, an organic solvent and an initiator to obtain an oil phase, mixing the oil phase and the water phase for polymerization reaction, and then carrying out solid-liquid separation to obtain polymer microspheres;
preferably, the polymerization temperature is 70-90 ℃ and the reaction time is 8-12 h; more preferably, the oil phase is added into the water phase during the reaction, and the reaction is carried out by heating to the reaction temperature after stirring uniformly.
In a preferred embodiment of the present invention, the organic solvent is selected from at least one of n-pentanol, methylcyclohexane and chlorobenzene; the ratio of the dosage of the organic solvent to the total mass of the monomers is 1.2-2.0:1; more preferably, the organic solvent comprises n-amyl alcohol and an auxiliary solvent, the auxiliary solvent is selected from at least one of methylcyclohexane and chlorobenzene, and the mass ratio of n-amyl alcohol in the organic solvent is 60-70%.
In a preferred embodiment of the present invention, the initiator is selected from at least one of benzoyl peroxide and azobisisobutyronitrile;
preferably, the ratio of the amount of initiator to the total mass of monomers is from 0.8 to 1:100.
In a preferred embodiment of the invention, the aqueous phase is prepared by a process comprising: mixing inorganic salt, a dispersing agent and water, wherein the mass ratio of the oil phase to the water phase is controlled to be 1:2-4 during the reaction;
Preferably, the inorganic salt is selected from at least one of sodium chloride, potassium chloride, sodium sulfate and calcium chloride;
preferably, the dispersing agent is selected from at least one of polyvinyl alcohol, gelatin and carboxymethyl cellulose;
Preferably, the concentration of inorganic salts in the aqueous phase is 2-8wt% and the concentration of dispersing agent is 0.3-1.0wt%.
In a preferred embodiment of the present invention, the amination of a copolymer with an amination reagent comprises: mixing the obtained polymer with an amination reagent for reaction, controlling the reaction temperature to be 70-90 ℃ and the reaction time to be 12-20 h;
preferably, after the reaction with the amination reagent is completed, the resulting polymer is sequentially subjected to acid washing, alkali washing and ethanol leaching, and then sieved to obtain a resin having a particle size of between 40 mesh and 60 mesh.
In a third aspect, the invention also provides the use of the adsorbent of any of the embodiments described above in the preparation of a dual blood perfusion adsorbent material.
In a fourth aspect, the invention also provides the use of the adsorbent of any of the embodiments described above for the preparation of a blood perfusion for the treatment of hyperbilirubinemia, inflammatory factor storm or liver failure.
The invention has the following beneficial effects: according to the invention, divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether are used as monomers for polymerization, and as the three monomers contain hydrophobic and hydrophilic materials, the prepared resin has amphipathy, the hydrophobicity can improve the adsorption performance on bilirubin and inflammatory factors as target substances, the hydrophilicity can improve the blood compatibility, the safety of the resin is improved, and the plasma is fully contacted with the resin, so that the adsorption performance is improved. In addition, the amination is performed by using an amination reagent, and since bilirubin has a carboxyl group, an amine group is introduced into the resin, and the absorption selectivity of bilirubin can be improved by ion absorption.
Therefore, the adsorbent prepared by the invention can adsorb bilirubin and cell inflammatory factors simultaneously, and can replace bilirubin adsorbent for treating bilirubinemia and inflammatory factor adsorbent for treating inflammatory factor storm simultaneously; in particular, in the combined artificial liver treatment, bilirubin and inflammatory factors are required to be adsorbed simultaneously, the two perfusion devices are used in series in the traditional scheme, and only one perfusion device is required for preparing the resin in the invention, so that the operation cost and risk are reduced, and the resin has very good market application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Bilirubin is one of bile pigments, the main pigment in human bile. Bilirubin is a major metabolite of iron porphyrin compounds in the body, is toxic, and can cause irreversible damage to the brain and nervous system. Bilirubin is an important criterion for clinically judging jaundice and is also an important index of liver function. Inflammatory cytokines refer to cytokines in the inflammatory response that activate neutrophils and lymphocytes in humans against infection, but excessive levels in the body may lead to immune overreactions. Blood perfusion is one of the effective methods for treating hyperbilirubinemia and inflammatory factor storm, and liver is an indispensable organ in bilirubin metabolism, and bilirubin metabolism is blocked in liver failure and may be accompanied with inflammatory reaction.
Because two types of adsorbents are needed to achieve the aim of adsorbing bilirubin and cell inflammatory factors, two perfusion devices are needed to be connected in series for blood perfusion.
The preparation method provided by the embodiment of the invention is to prepare macroporous adsorption resin by using divinylbenzene, glycol dimethacrylate and allyl alcohol glycidyl ether as monomers and adopting a suspension polymerization method, and adding an amination reagent into the resin to aminate to obtain macroporous adsorption anion exchange resin. Specifically, the method comprises the following steps:
S1, copolymerization
The copolymer is obtained by polymerizing divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether as monomers, and the polymerization mode is not limited. The divinylbenzene has hydrophobicity, the allyl alcohol glycidyl ether has hydrophilicity, the prepared resin has amphipathy, the hydrophobicity can improve the adsorption performance on bilirubin and inflammatory factors which are target substances, the hydrophilicity can improve the blood compatibility, the resin safety is improved, and the plasma is fully contacted with the resin so as to improve the adsorption performance.
In some embodiments, the copolymers may be prepared using suspension polymerization methods that include, during actual operation: and mixing and dissolving divinylbenzene, ethylene glycol dimethacrylate, allyl alcohol glycidyl ether, an organic solvent and an initiator to obtain an oil phase, mixing the oil phase and the water phase for polymerization reaction, and then carrying out solid-liquid separation to obtain the porous polymer microsphere.
In order to further improve the adsorption performance of the material, the mass ratio of divinylbenzene to ethylene glycol dimethacrylate to allyl alcohol glycidyl ether is 80-120:30-50:60-80, for example, the mass ratio can be 80:30:60, 100:40:70, 120:50:80 and the like, and can also be any value between the adjacent values.
In some embodiments, the organic solvent is selected from at least one of n-pentanol, methylcyclohexane, and chlorobenzene, and the ratio of the amount of organic solvent to the total mass of monomers is 1.2-2.0:1. The pore structure and specific surface area of the adsorbent can be regulated and controlled by selecting the type of the organic solvent and controlling the dosage, and the adsorption effect on the target object can be improved due to the proper pore structure and high specific surface area. Specifically, the ratio of the amount of the organic solvent to the total mass of the monomers may be 1.2:1, 1.5:1, 1.7:1, 1.9:1, 2.0:1, etc., or may be any value between the above adjacent values.
In a preferred embodiment, the organic solvent comprises n-pentanol and an auxiliary solvent, the auxiliary solvent is selected from at least one of methylcyclohexane and chlorobenzene, and the mass ratio of n-pentanol in the organic solvent is 60-70% (e.g. 60%, 65%, 70%, etc.). The n-amyl alcohol is suitable as the main component of the organic solvent, which is favorable for ensuring the pore structure of the final material to be more proper and improving the adsorption effect.
In some embodiments, the initiator is selected from at least one of benzoyl peroxide and azobisisobutyronitrile, all of which are suitable for the reaction in embodiments of the present invention. The ratio of the initiator to the total mass of the monomers is 0.8-1:100, such as 0.8:100, 0.9:100, 1:100, etc., and can be any value between the adjacent values.
In some embodiments, the aqueous phase is prepared by a process comprising: the inorganic salt is prepared by mixing inorganic salt, dispersing agent and water, wherein the inorganic salt is at least one of sodium chloride, potassium chloride, sodium sulfate and calcium chloride, the dispersing agent is at least one of polyvinyl alcohol, gelatin and carboxymethyl cellulose, and the inorganic salt and the dispersing agent are selected from the above types and are suitable for the polymerization method provided by the embodiment of the invention. The amounts of inorganic salt, dispersant and water are controlled: the mass fraction of inorganic salt in the water phase is 2-8wt% (such as 2wt%, 5wt%, 8wt%, etc.), and the mass fraction of dispersant is 0.3-1.0wt% (such as 0.3wt%, 0.5wt%, 0.8wt%, 1.0wt%, etc.).
In some embodiments, when the oil phase and the water phase are mixed for reaction, the mass ratio of the oil phase to the water phase is controlled to be 1:2-4, the polymerization temperature is 70-90 ℃, and the reaction time is 8-12 h, so that the reaction is fully carried out. In the actual operation process, the oil phase is added into the water phase during the reaction, the temperature is raised to the reaction temperature after the uniform stirring, the reaction is carried out, and the solid-liquid separation mode after the reaction is finished can be filtration.
Specifically, the mass ratio of the oil phase to the water phase can be 1:2, 1:3, 1:4, etc., the polymerization reaction temperature can be 70 ℃, 80 ℃, 90 ℃ and the like, and the reaction time can be 8 hours, 10 hours, 12 hours, and the like.
S2, amination
The copolymer is aminated by an amination reagent, and the bilirubin adsorption selectivity can be improved by introducing an amine group through ion adsorption.
In some embodiments, the amination reagent is selected from at least one of trimethylamine hydrochloride and triethylamine hydrochloride, and can be one or more. Bilirubin has carboxyl, and four-level amino is introduced into resin to raise bilirubin adsorption selectivity through ion adsorption.
In some embodiments, the process of aminating the copolymer with an amination reagent comprises: mixing the obtained polymer with an amination reagent for reaction, controlling the reaction temperature to be 70-90 ℃ and the reaction time to be 12-20 h so as to fully carry out the reaction. The mass ratio of the consumption of the amination reagent to the copolymer is 20-50:100.
Specifically, the reaction temperature may be 70 ℃, 80 ℃, 90 ℃, etc., and the reaction time may be 12 hours, 15 hours, 18 hours, 20 hours, etc.
In some embodiments, after completion of the reaction with the amination reagent, the resulting polymer is sequentially subjected to acid washing, alkali washing and ethanol leaching, and then sieved to obtain a resin having a particle size of between 40 mesh and 60 mesh. Surface impurities are removed through acid washing and alkali washing, and residual monomers and solvents are effectively removed by an ethanol leaching method.
Specifically, the acid washing, alkali washing and ethanol leaching are all existing purification processes, and specific parameters are not limited. For example, the acid washing can be performed by using 5% (wt) hydrochloric acid aqueous solution, and the washing can be performed multiple times; the alkaline washing can be washing by using sodium hydroxide solution with the concentration of 5% (wt) or multiple times; the ethanol extraction is to extract residual organic matters in the resin by adopting a Soxhlet extractor and heating ethanol, and the extraction is carried out for 4-6 times, each time for about 5 hours.
The embodiment of the invention also provides an adsorbent, which is a copolymer formed by polymerizing divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether serving as monomers, and the copolymer is aminated by an amination reagent, so that the adsorbent can be prepared by the preparation method, and can be used for simultaneously adsorbing bilirubin and inflammatory cytokines.
The adsorbent provided by the embodiment of the invention is used for blood perfusion and treating hyperbilirubinemia or inflammatory factor storm, is particularly suitable for combined artificial liver treatment, can be used for blood perfusion by adopting one perfusion device, and reduces the operation cost and risk.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of an adsorbent, which comprises the following steps:
Aqueous phase: polyvinyl alcohol, sodium chloride and water were mixed to obtain 1500mL of a water phase in which the mass fraction of polyvinyl alcohol was 0.5wt% and the mass fraction of sodium chloride was 4wt%.
An oil phase: 100g of divinylbenzene, 30g of ethylene glycol dimethacrylate, 80g of allyl alcohol glycidyl ether, 100g of chlorobenzene, 200g of n-amyl alcohol and 2g of benzoyl peroxide were weighed and dissolved as an oil phase by stirring.
Polymerization reaction: the oil phase was added to the aqueous phase and stirred at 150 rpm. And (3) uniformly mixing the oil phase and the water phase, heating to 80 ℃ for reaction, reacting for 8 hours, and filtering after the reaction is finished to obtain the polymer microsphere.
Amination: 150g of polymer microspheres, 50g of trimethylamine hydrochloride and 500g of water are uniformly mixed and stirred for reaction for 15 hours at the temperature of 80 ℃ at 150 rpm. And respectively carrying out acid washing, alkali washing and ethanol leaching on the polymer obtained by the reaction, and then sieving to obtain the resin with 40-60 meshes.
Example 2
The embodiment provides a preparation method of an adsorbent, which comprises the following steps:
Aqueous phase: polyvinyl alcohol, sodium chloride and water were mixed to obtain 1500mL of a water phase in which the mass fraction of polyvinyl alcohol was 0.5wt% and the mass fraction of sodium chloride was 4wt%.
An oil phase: 80g of divinylbenzene, 50g of ethylene glycol dimethacrylate, 80g of allyl alcohol glycidyl ether, 120g of methylcyclohexane, 250g of n-amyl alcohol and 2g of benzoyl peroxide were weighed out and dissolved as an oil phase by stirring.
Polymerization reaction: the oil phase was added to the aqueous phase and stirred at 150 rpm. And (3) uniformly mixing the oil phase and the water phase, heating to 80 ℃ for reaction, reacting for 10 hours, and filtering after the reaction is finished to obtain the polymer microsphere.
Amination: 150g of polymer microspheres, 50g of trimethylamine hydrochloride and 500g of water are uniformly mixed and reacted for 15 hours under the conditions of stirring at 150rpm and the temperature of 80 ℃. And respectively carrying out acid washing, alkali washing and ethanol leaching on the polymer obtained by the reaction, and then sieving to obtain the resin with 40-60 meshes.
Example 3
The embodiment provides a preparation method of an adsorbent, which comprises the following steps:
Aqueous phase: polyvinyl alcohol, sodium chloride and water were mixed to obtain 1500mL of a water phase in which the mass fraction of polyvinyl alcohol was 0.5wt% and the mass fraction of sodium chloride was 4wt%.
An oil phase: 120g of divinylbenzene, 30g of ethylene glycol dimethacrylate, 60g of allyl alcohol glycidyl ether, 50g of chlorobenzene, 70g of methylcyclohexane, 250g of n-amyl alcohol and 2g of benzoyl peroxide were weighed out and dissolved as an oil phase by stirring.
Polymerization reaction: the oil phase was added to the aqueous phase and stirred at 150 rpm. And (3) uniformly mixing the oil phase and the water phase, heating to 80 ℃ for reaction, reacting for 10 hours, and filtering after the reaction is finished to obtain the polymer microsphere.
Amination: 150g of polymer microspheres, 50g of trimethylamine hydrochloride and 500g of water are uniformly mixed and stirred for 15 hours at the temperature of 80 ℃ under the condition of 150 rpm. And respectively carrying out acid washing, alkali washing and ethanol leaching on the polymer obtained by the reaction, and then sieving to obtain the resin with 40-60 meshes.
Comparative example 1
The only difference from example 3 is that: no divinylbenzene was added to the oil phase and replaced with an equivalent amount of ethylene glycol dimethacrylate.
Comparative example 2
The only difference from example 3 is that: the mass of divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether is 40g, 20g and 150g in sequence.
Comparative example 3
The only difference from example 3 is that: n-pentanol was not added and replaced with an equal amount of n-hexanol.
Comparative example 4
The only difference from example 3 is that: n-pentanol was not added and replaced with an equal amount of n-octanol.
Comparative example 5
The only difference from example 3 is that: n-pentanol was not added and replaced with an equivalent amount of isooctanol.
Comparative example 6
The only difference from example 3 is that: instead of methylcyclohexane, methylcyclohexane was replaced with an equivalent amount of dibutyl phthalate.
Test example 1
The adsorption properties of the adsorbents were obtained by testing examples and comparative examples, and the results are shown in table 1.
The testing method comprises the following steps: 1mL of the wet adsorbent is measured, placed in a 50mL conical flask, washed twice with pure water and filtered out, 10g of plasma with interleukin-6 (IL-6) content of about 500pg/mL and bilirubin content of about 500 mu mol/L is added, and the mixture is placed at 37+/-1 ℃ to be oscillated and adsorbed in a constant-temperature water bath oscillator at a speed of 150rpm for 2 hours, and the interleukin-6 and bilirubin content of the plasma before and after adsorption is tested. The adsorption rate was calculated and the result was as follows:
table 1 results of adsorption performance test of adsorbents prepared in examples and comparative examples
| Project | Interleukin-6 adsorption rate | Bilirubin adsorption rate |
| Example 1 | 59.40％ | 83.32％ |
| Example 2 | 73.91％ | 77.51％ |
| Example 3 | 76.97％ | 80.09％ |
| Comparative example 1 | 0.63％ | 26.32％ |
| Comparative example 2 | 8.11％ | 56.76％ |
| Comparative example 3 | 36.28％ | 35.05％ |
| Comparative example 4 | 16.23％ | 24.93％ |
| Comparative example 5 | 28.32％ | 48.63％ |
| Comparative example 6 | 42.18％ | 52.13％ |
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. The adsorbent is characterized in that the adsorbent is a copolymer formed by polymerizing divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether serving as monomers, and the copolymer is aminated by an amination reagent;
the mass ratio of divinylbenzene to ethylene glycol dimethacrylate to allyl alcohol glycidyl ether is 80-120:30-50:60-80;
The amination reagent is selected from at least one of trimethylamine hydrochloride and triethylamine hydrochloride;
The polymerization is carried out in an organic solvent, wherein the organic solvent is at least one selected from n-amyl alcohol, methylcyclohexane and chlorobenzene; the ratio of the dosage of the organic solvent to the total mass of the monomers is 1.2-2.0:1.
2. A method of preparing the adsorbent of claim 1, comprising: polymerizing divinylbenzene, ethylene glycol dimethacrylate and allyl alcohol glycidyl ether serving as monomers to obtain a copolymer, and aminating the copolymer by using the amination reagent;
the mass ratio of divinylbenzene to ethylene glycol dimethacrylate to allyl alcohol glycidyl ether is 80-120:30-50:60-80;
The amination reagent is selected from at least one of trimethylamine hydrochloride and triethylamine hydrochloride;
The polymerization is carried out in an organic solvent, wherein the organic solvent is at least one selected from n-amyl alcohol, methylcyclohexane and chlorobenzene; the ratio of the dosage of the organic solvent to the total mass of the monomers is 1.2-2.0:1.
3. The method of preparing according to claim 2, wherein the copolymer is prepared by a suspension polymerization method, and the process of preparing the copolymer comprises: and mixing and dissolving divinylbenzene, ethylene glycol dimethacrylate, allyl alcohol glycidyl ether, an organic solvent and an initiator to obtain an oil phase, mixing the oil phase with a water phase for polymerization reaction, and then carrying out solid-liquid separation to obtain the polymer microsphere.
4. The process according to claim 3, wherein the polymerization temperature is 70℃to 90℃and the reaction time is 8 hours to 12 hours.
5. A method according to claim 3, wherein the oil phase is added to the water phase, and the reaction is carried out by heating the mixture to the reaction temperature after stirring the mixture uniformly.
6. A production method according to claim 3, wherein the organic solvent comprises n-pentanol and an auxiliary solvent, the auxiliary solvent is selected from at least one of methylcyclohexane and chlorobenzene, and the mass ratio of n-pentanol in the organic solvent is 60-70%.
7. The method according to claim 3, wherein the initiator is at least one selected from the group consisting of benzoyl peroxide and azobisisobutyronitrile.
8. The process according to claim 7, wherein the ratio of the amount of the initiator to the total mass of the monomers is 0.8 to 1:100.
9. A method of preparing according to claim 3, wherein the preparation of the aqueous phase comprises: and mixing inorganic salt, a dispersing agent and water, and controlling the mass ratio of the oil phase to the water phase to be 1:2-4 during the reaction.
10. The method according to claim 9, wherein the inorganic salt is at least one selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate and calcium chloride.
11. The method according to claim 9, wherein the dispersant is at least one selected from the group consisting of polyvinyl alcohol, gelatin and carboxymethyl cellulose.
12. The preparation method according to claim 9, wherein the concentration of the inorganic salt in the aqueous phase is 2 to 8wt% and the concentration of the dispersant is 0.3 to 1.0wt%.
13. The method of claim 2, wherein aminating the copolymer with the amination reagent comprises: mixing the obtained polymer with the amination reagent for reaction, controlling the reaction temperature to be 70-90 ℃ and the reaction time to be 12-20 h.
14. The method according to claim 13, wherein after the completion of the reaction with the amination reagent, the resulting polymer is sequentially subjected to acid washing, alkali washing and ethanol leaching, and then sieved to obtain a resin having a particle size of between 40 mesh and 60 mesh.
15. Use of the adsorbent of claim 1 or the adsorbent prepared by the method of any one of claims 2-14 in the preparation of a dual blood perfusion adsorbent material.
16. Use of the adsorbent of claim 1 or the adsorbent prepared by the method of any one of claims 2-14 in the preparation of a blood perfusion for the treatment of hyperbilirubinemia, inflammatory factor storm or liver failure.
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| DE102009037015A1 (en) * | 2009-08-07 | 2011-02-17 | Michael Hajek | Apparatus and method for eliminating biologically harmful substances from body fluids |
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| RU2641924C1 (en) * | 2016-12-21 | 2018-01-23 | федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технический университет имени Н.Э. Баумана (национальный исследовательский университет)" (МГТУ им. Н.Э. Баумана) | Sorption material, method of its production and method of its application |
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