CN115260399B - Acrylonitrile skeleton macroporous resin and preparation method and application thereof - Google Patents
Acrylonitrile skeleton macroporous resin and preparation method and application thereof Download PDFInfo
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- CN115260399B CN115260399B CN202211033036.0A CN202211033036A CN115260399B CN 115260399 B CN115260399 B CN 115260399B CN 202211033036 A CN202211033036 A CN 202211033036A CN 115260399 B CN115260399 B CN 115260399B
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- acrylonitrile
- mass
- skeleton
- macroporous resin
- trimethylolpropane trimethacrylate
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 108010078777 Colistin Proteins 0.000 claims abstract description 31
- 229960001127 colistin sulfate Drugs 0.000 claims abstract description 29
- ZESIAEVDVPWEKB-ORCFLVBFSA-N n-[(2s)-4-amino-1-[[(2s,3r)-1-[[(2s)-4-amino-1-oxo-1-[[(3s,6s,9s,12s,15r,18s,21s)-6,9,18-tris(2-aminoethyl)-3-[(1r)-1-hydroxyethyl]-12,15-bis(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-h Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.CC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O.CCC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O ZESIAEVDVPWEKB-ORCFLVBFSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 16
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 16
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011324 bead Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 229960003943 hypromellose Drugs 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical group CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000855 fermentation Methods 0.000 description 7
- 230000004151 fermentation Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- KNIWPHSUTGNZST-UHFFFAOYSA-N polymyxin E2 Natural products CC(C)CCCCC(=O)NC(CCN)C(=O)NC(C(C)O)C(=O)NC(CCN)C(=O)NC1CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C(CC(C)C)NC(=O)C(CCN)NC1=O KNIWPHSUTGNZST-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 108010093965 Polymyxin B Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229960003346 colistin Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- XDJYMJULXQKGMM-UHFFFAOYSA-N polymyxin E1 Natural products CCC(C)CCCCC(=O)NC(CCN)C(=O)NC(C(C)O)C(=O)NC(CCN)C(=O)NC1CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C(CC(C)C)NC(=O)C(CCN)NC1=O XDJYMJULXQKGMM-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SBKRTALNRRAOJP-BWSIXKJUSA-N N-[(2S)-4-amino-1-[[(2S,3R)-1-[[(2S)-4-amino-1-oxo-1-[[(3S,6S,9S,12S,15R,18R,21S)-6,9,18-tris(2-aminoethyl)-15-benzyl-3-[(1R)-1-hydroxyethyl]-12-(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-hydroxy-1-oxobutan-2-yl]amino]-1-oxobutan-2-yl]-6-methylheptanamide (6S)-N-[(2S)-4-amino-1-[[(2S,3R)-1-[[(2S)-4-amino-1-oxo-1-[[(3S,6S,9S,12S,15R,18R,21S)-6,9,18-tris(2-aminoethyl)-15-benzyl-3-[(1R)-1-hydroxyethyl]-12-(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-hydroxy-1-oxobutan-2-yl]amino]-1-oxobutan-2-yl]-6-methyloctanamide sulfuric acid Polymers OS(O)(=O)=O.CC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@@H](NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](Cc2ccccc2)NC(=O)[C@@H](CCN)NC1=O)[C@@H](C)O.CC[C@H](C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@@H](NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](Cc2ccccc2)NC(=O)[C@@H](CCN)NC1=O)[C@@H](C)O SBKRTALNRRAOJP-BWSIXKJUSA-N 0.000 description 1
- 108010040201 Polymyxins Proteins 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- KNIWPHSUTGNZST-SSWRVQTPSA-N colistin B Chemical compound CC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O KNIWPHSUTGNZST-SSWRVQTPSA-N 0.000 description 1
- -1 colistin cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JORAUNFTUVJTNG-BSTBCYLQSA-N n-[(2s)-4-amino-1-[[(2s,3r)-1-[[(2s)-4-amino-1-oxo-1-[[(3s,6s,9s,12s,15r,18s,21s)-6,9,18-tris(2-aminoethyl)-3-[(1r)-1-hydroxyethyl]-12,15-bis(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-h Chemical compound CC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O.CCC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O JORAUNFTUVJTNG-BSTBCYLQSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000024 polymyxin B Polymers 0.000 description 1
- 229960005266 polymyxin b Drugs 0.000 description 1
- 229960003548 polymyxin b sulfate Drugs 0.000 description 1
- 239000003910 polypeptide antibiotic agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Abstract
The invention discloses an acrylonitrile skeleton macroporous resin, a preparation method and application thereof. The preparation method comprises the following steps: 1) Mixing hydroxypropyl methylcellulose with water to obtain a disperse phase; 2) Mixing acrylonitrile, trimethylolpropane trimethacrylate, an initiator and C3-C8 n-alkyl alcohol to obtain an organic phase; 3) Adding the organic phase into the disperse phase, stirring to form spherical beads, heating to 75-90 ℃ and solidifying; and (5) washing after the reaction is finished to obtain the acrylonitrile skeleton resin matrix. The acrylonitrile skeleton macroporous resin obtained by the invention has good adsorption effect on colistin sulfate.
Description
Technical Field
The invention relates to an acrylonitrile skeleton macroporous resin, a preparation method and application thereof.
Background
Polymyxin B is used as a polypeptide antibiotic, has the advantage of being capable of achieving rapid sterilization without causing bacteria to generate drug resistance, and has the advantage of being incomparable with other antibiotics in clinical application.
The colistin sulfate is white or similar crystal powder as a sulfate existence form of the colistin B, has bitter taste, no odor and hygroscopicity. Polymyxin B sulfate is a water-soluble substance that is easily dissolved in a dispersed phase and is not easily dissolved in common organic solvents such as ether, ketone, ester, chloroform, and the like. The polymyxin sulfate has poor stability, is easily influenced by the outside, and is easily decomposed in the presence of an acid-base environment or an organic solvent at a higher temperature, so that the activity is low.
The separation process of colistin sulfate mainly comprises a solvent extraction method, a membrane separation method, an adsorption method, a foam separation method and an ion exchange method. The adsorption method mainly adopts active carbon as an adsorbent and uses acidic alcohol solution for elution, but the adsorption method has poor selectivity and low yield. At present, the colistin sulfate is mainly extracted by an ion exchange resin method in industry, and colistin cations are adsorbed by macroporous resin, so that the colistin is separated from fermentation liquor filtrate. However, conventional ion exchange resins have poor selectivity for colistin sulfate, resulting in a resin having a low adsorption capacity for colistin sulfate.
Macroporous adsorption resins (also known as macroporous resins) are a class of organic polymeric adsorbents. It has stable physical and chemical properties, is insoluble in acid, alkali and organic solvent, and is not interfered by inorganic salts, strong ions and low molecular compounds. It has better physical property, can be repeatedly used for many times, and is easier to regenerate.
Therefore, there is a need to provide a macroporous resin capable of effectively extracting colistin sulfate, and a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a preparation method of acrylonitrile skeleton macroporous resin, which has good adsorption effect on colistin sulfate, and the adsorption capacity of the prepared acrylonitrile skeleton macroporous resin reaches more than 440 mu/mL. Another object of the present invention is to provide an acrylonitrile skeleton macroporous resin prepared according to the above preparation method. It is a further object of the present invention to provide a use of the acrylonitrile-skeleton macroporous resin.
The invention realizes the aim through the following technical scheme.
In one aspect, the invention provides a preparation method of acrylonitrile skeleton macroporous resin, which comprises the following steps:
1) Mixing hydroxypropyl methylcellulose with water to obtain a disperse phase; wherein the mass ratio of the hypromellose to the water is 0.5-3:100;
2) Mixing acrylonitrile, trimethylolpropane trimethacrylate, an initiator and C3-C8 n-alkyl alcohol to obtain an organic phase; wherein, the weight of the trimethylolpropane trimethacrylate is 8-12% of the sum of the weight of the trimethylolpropane trimethacrylate and the weight of the acrylonitrile; the initiator is lauroyl peroxide or cumene hydroperoxide; the mass of the initiator is 0.5 to 1.5 percent of the sum of the mass of the acrylonitrile and the mass of the trimethylolpropane trimethacrylate; the ratio of the mass of the n-alkyl alcohol of C3-C8 to the sum of the mass of the monomer and the mass of the trimethylolpropane trimethacrylate is 0.5-1.5:1;
3) Adding the organic phase into the disperse phase, stirring to form spherical beads, heating to 75-90 ℃ and solidifying; washing after the reaction is finished to obtain an acrylonitrile skeleton resin matrix; wherein the volume ratio of the disperse phase to the organic phase is 2-3:1. Thus being beneficial to obtaining the acrylonitrile skeleton macroporous resin with higher adsorption capacity to colistin sulfate.
The mass ratio of hypromellose to water may be 0.5 to 3:100, preferably 1 to 3:100, more preferably 1.5 to 2.5:100. During the preparation of the dispersed phase, it may be heated, for example to 45-60 ℃, to promote dissolution of the hypromellose.
In certain embodiments, the initiator is lauroyl peroxide. In other embodiments, the initiator is cumene hydroperoxide.
The volume ratio of the disperse phase to the organic phase may be from 2 to 3:1, preferably from 2 to 2.5:1.
The curing temperature may be 75 to 90 ℃, preferably 80 to 85 ℃. The curing time may be 7 to 10 hours. The purpose of water washing after the reaction is finished is mainly to remove the n-alkyl alcohol of C3-C8.
The invention discovers that macroporous resin obtained by adopting specific monomers, hydroxypropyl methylcellulose, trimethylolpropane trimethacrylate, an initiator and C3-C8 n-alkyl alcohol for combined use has higher adsorption quantity on colistin sulfate.
According to the preparation method of the present invention, preferably, the curing time is 7 to 10 hours. Preferably 8 to 10 hours.
The n-alkyl alcohol having 3 to 8 carbon atoms represents an n-alkyl alcohol having 3 to 8 carbon atoms. The n-alkyl alcohol may be selected from one or more of n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol and n-octanol. According to the preparation method of the present invention, preferably, the n-alkyl alcohol of C3 to C8 is n-butanol. The adsorption quantity of the obtained acrylonitrile skeleton macroporous resin to colistin sulfate is higher.
According to the production method of the present invention, preferably, the trimethylolpropane trimethacrylate is 8.5 to 11% by mass of the sum of the trimethylolpropane trimethacrylate and acrylonitrile. According to a preferred embodiment of the present invention, the trimethylolpropane trimethacrylate is 8.7 to 10% by mass of the sum of the trimethylolpropane trimethacrylate and acrylonitrile. The adsorption quantity of the acrylonitrile skeleton macroporous resin to colistin sulfate is higher.
According to the production method of the present invention, preferably, the mass of the initiator is 0.7 to 1.5% of the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate. According to a preferred embodiment of the invention, the mass of the initiator is 0.9 to 1.1% of the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate. The adsorption quantity of the acrylonitrile skeleton macroporous resin to colistin sulfate is higher.
According to the preparation method of the present invention, preferably, the ratio of the mass of the C3-C8 n-alkyl alcohol to the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate is 0.8-1.4:1. According to a preferred embodiment of the present invention, the ratio of the mass of the C3-C8 n-alkyl alcohol to the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate is 0.9-1.1:1.
The preparation method according to the present invention preferably further comprises the steps of:
4) Adding the obtained acrylonitrile skeleton resin matrix into an alkali metal hydroxide aqueous solution, and reacting for 12-28 h at 90-135 ℃; and after the reaction is finished, washing with water to obtain the acrylonitrile skeleton macroporous resin. The adsorption quantity of the acrylonitrile skeleton macroporous resin to colistin sulfate is higher. The aqueous alkali metal hydroxide solution may be a sodium hydroxide solution or a potassium hydroxide solution, preferably a sodium hydroxide solution. The reaction temperature may be from 90 to 135℃and preferably from 100 to 130 ℃. The reaction time may be 12 to 28 hours, preferably 16 to 24 hours.
According to the production method of the present invention, preferably, the concentration of the alkali metal hydroxide aqueous solution is 23 to 33wt%; the mass ratio of the acrylonitrile skeleton resin matrix to the alkali metal hydroxide aqueous solution is 1:3-6. The solid obtained by the reaction was washed with water to neutrality.
The concentration of the aqueous alkali metal hydroxide solution may be 23 to 33wt%, preferably 27 to 33wt%, more preferably 28 to 32wt%.
The mass ratio of the acrylonitrile skeleton resin matrix to the alkali metal hydroxide aqueous solution may be 1:3 to 8, preferably 1:4 to 7. This can facilitate hydrolysis of the nitrile group to a carboxyl group and adsorption of colistin sulfate.
According to one embodiment of the invention, the preparation method of the acrylonitrile skeleton macroporous resin comprises the following steps:
1) Mixing hydroxypropyl methylcellulose with water to obtain a disperse phase; wherein the mass ratio of the hypromellose to the water is 0.5-3:100;
2) Mixing acrylonitrile, trimethylolpropane trimethacrylate, an initiator and C3-C8 n-alkyl alcohol to obtain an organic phase;
wherein, the weight of the trimethylolpropane trimethacrylate is 8-12% of the sum of the weight of the trimethylolpropane trimethacrylate and the weight of the acrylonitrile; the initiator is lauroyl peroxide or cumene hydroperoxide; the mass of the initiator is 0.5 to 1.5 percent of the sum of the mass of the acrylonitrile and the mass of the trimethylolpropane trimethacrylate; the ratio of the mass of the n-alkyl alcohol with the carbon number of 3-8 to the sum of the mass of the acrylonitrile and the trimethylol propane trimethacrylate is 0.5-1.5:1;
3) Adding the organic phase into the disperse phase, stirring to form spherical beads, heating to 75-90 ℃ and solidifying; washing after the reaction is finished to obtain an acrylonitrile skeleton resin matrix; wherein, the volume ratio of the disperse phase to the organic phase is 2-3:1;
4) Adding the obtained acrylonitrile skeleton resin matrix into sodium hydroxide solution, and reacting for 12-28 h at 90-135 ℃; and after the reaction is finished, washing with water to obtain the acrylonitrile skeleton macroporous resin.
On the other hand, the invention also provides the acrylonitrile skeleton macroporous resin prepared by the preparation method of the acrylonitrile skeleton macroporous resin.
In still another aspect, the invention further provides a use of the acrylonitrile skeleton macroporous resin in extracting colistin sulfate according to the above, wherein the adsorption amount of the acrylonitrile skeleton macroporous resin to the colistin sulfate is more than 440 mu/mL.
The acrylonitrile skeleton macroporous resin prepared by the preparation method has higher adsorption quantity to colistin sulfate and better adsorption effect. The invention adopts specific monomers of acrylonitrile, hydroxypropyl methylcellulose, trimethylolpropane trimethacrylate, initiator and C3-C8 n-alkyl alcohol to react under specific reaction conditions, and the obtained macroporous resin has higher adsorption quantity to colistin sulfate.
Drawings
FIG. 1 is an infrared spectrum of an acrylonitrile-skeleton resin matrix obtained in example 1 and an acrylonitrile-skeleton macroporous resin.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited thereto.
The test method is described as follows:
(1) Adsorption quantity test: 100mL of the prepared acrylonitrile skeleton macroporous resin is filled into a resin column, fermentation stock solution containing colistin sulfate with the pH value of 4.5 is introduced into the resin column at the flow rate of 0.5BV/h for dynamic adsorption, and after excessive adsorption, the total volume and the titer of adsorption tail liquid are measured. The adsorption amount was calculated as follows:
resin adsorption amount= (v1×concentration of colistin sulfate in fermentation stock solution-v2×concentration of colistin sulfate in adsorption tail solution after adsorption)/resin volume.
V1 is the volume of the introduced fermentation stock solution, and the unit is mL; v2 is the volume of solution (i.e., adsorption tail) remaining after adsorption in mL. The unit of colistin sulfate concentration is mu/mL. The unit of resin volume is mL.
(2) Infrared spectrum testing: drying the material, testing without tabletting, and testing wave number range of 4000-400 cm -1 Equipment model: a Tensor type II infrared spectrometer, bruce, germany.
Example 1
According to the formulation of table 1:
1) 4.0g of hypromellose was added to 200mL of deionized water, heated to 50℃and until the hypromellose was completely dissolved, giving a dispersed phase.
2) The acrylonitrile, trimethylolpropane trimethacrylate, lauroyl peroxide and n-butanol were uniformly mixed to obtain an organic phase.
3) Adding the organic phase into the dispersion phase, stirring to form uniform-sized beads, slowly heating to 80 ℃, and curing for 8 hours. After the reaction, the mixture was washed with water to obtain an acrylonitrile-based resin matrix.
4) 20g of an acrylonitrile-skeleton resin matrix was added with 120g of a 32wt% sodium hydroxide solution, and reacted at 130℃with stirring for 24 hours. And after the reaction is finished, washing with water until the reaction solution is nearly neutral, and obtaining the acrylonitrile skeleton macroporous resin.
The obtained acrylonitrile skeleton macroporous resin was subjected to dynamic adsorption test on a fermentation stock solution containing colistin sulfate, and the results are shown in table 2.
Comparative examples 1 to 4
The types and amounts of the raw materials are shown in Table 1, and the rest is the same as in example 1.
The obtained acrylonitrile skeleton macroporous resin was subjected to dynamic adsorption test on a fermentation stock solution containing colistin sulfate, and the results are shown in table 2.
TABLE 1
TABLE 2
| Sequence number | Adsorption capacity (mu/mL) |
| Example 1 | 463.2 |
| Comparative example 1 | 363.8 |
| Comparative example 2 | 397.2 |
| Comparative example 3 | 403.2 |
| Comparative example 4 | 432.7 |
As shown in the table, the invention adopts hydroxypropyl methylcellulose, trimethylolpropane trimethacrylate, n-butyl alcohol and acrylonitrile to react under specific conditions, and the obtained macroporous resin has higher adsorption quantity to colistin sulfate, which can reach more than 440 mu/mL and even 463.2 mu/mL.
The acrylonitrile skeleton resin matrix and the acrylonitrile skeleton macroporous resin obtained in example 1 were subjected to infrared analysis. The results are shown in FIG. 1. In FIG. 1, a represents the infrared curve of the acrylonitrile skeleton resin matrix. b represents the infrared curve of the acrylonitrile skeleton macroporous resin. 2245cm as shown in a of FIG. 1 -1 The part is the stretching vibration peak of the acrylonitrile skeleton resin matrix C.ident.N. 2245cm as shown in b in FIG. 1 -1 The peak at 1735cm disappeared -1 A narrow peak appears at this point, which is the c=o stretching vibration peak of the carboxyl group. This indicates that the nitrile groups have been hydrolyzed to carboxyl groups.
Example 2
1) 3.3g of hypromellose was added to 220mL of deionized water and heated to 50℃until the hypromellose was completely dissolved, giving a dispersed phase.
2) 57.5g of acrylonitrile, 6.38g of trimethylolpropane trimethacrylate, 0.96g of cumene hydroperoxide and 127.76g of n-butanol were uniformly mixed to obtain an organic phase.
3) Adding the organic phase into the dispersion phase, stirring to form uniform-sized beads, slowly heating to 85 ℃, and curing for 8 hours. After the reaction, the mixture was washed with water to obtain an acrylonitrile-based resin matrix.
4) 20g of an acrylonitrile-skeleton resin matrix was added to 100g of a 32wt% sodium hydroxide solution, and reacted at 120℃with stirring for 24 hours. And after the reaction is finished, washing with water until the reaction solution is nearly neutral, and obtaining the acrylonitrile skeleton macroporous resin.
The obtained acrylonitrile skeleton macroporous resin was subjected to dynamic adsorption test on a fermentation stock solution containing colistin sulfate, and the results are shown in table 3.
TABLE 3 Table 3
| Sequence number | Adsorption capacity (mu/mL) |
| Example 2 | 445.7 |
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the acrylonitrile framework macroporous resin is characterized by comprising the following steps of:
1) Mixing hydroxypropyl methylcellulose with water to obtain a disperse phase; wherein the mass ratio of the hypromellose to the water is 0.5-3:100;
2) Mixing acrylonitrile, trimethylolpropane trimethacrylate, an initiator and C3-C8 n-alkyl alcohol to obtain an organic phase; wherein, the weight of the trimethylolpropane trimethacrylate is 8-12% of the sum of the weight of the trimethylolpropane trimethacrylate and the weight of the acrylonitrile; the initiator is lauroyl peroxide or cumene hydroperoxide; the mass of the initiator is 0.5 to 1.5 percent of the sum of the mass of the acrylonitrile and the mass of the trimethylolpropane trimethacrylate; the ratio of the mass of the n-alkyl alcohol with the carbon number of 3-8 to the sum of the mass of the acrylonitrile and the trimethylol propane trimethacrylate is 0.5-1.5:1;
3) Adding the organic phase into the disperse phase, stirring to form spherical beads, heating to 75-90 ℃ and solidifying; washing after the reaction is finished to obtain an acrylonitrile skeleton resin matrix; wherein the volume ratio of the disperse phase to the organic phase is 2-3:1.
2. The method of claim 1, wherein the curing time is 7 to 10 hours.
3. The method according to claim 1, wherein the n-alkyl alcohol having 3 to 8 carbon atoms is n-butanol.
4. The production method according to claim 1, wherein the mass of the trimethylolpropane trimethacrylate is 8.5 to 11% of the sum of the mass of the trimethylolpropane trimethacrylate and the mass of acrylonitrile.
5. The preparation method according to claim 1, wherein the mass of the initiator is 0.7 to 1.5% of the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate.
6. The method according to claim 1, wherein the ratio of the mass of the C3-C8 n-alkyl alcohol to the sum of the mass of acrylonitrile and trimethylolpropane trimethacrylate is 0.8-1.4:1.
7. The method of manufacturing according to claim 1, further comprising the steps of:
4) Adding the obtained acrylonitrile skeleton resin matrix into an alkali metal hydroxide aqueous solution, and reacting for 12-28 h at 90-135 ℃; and after the reaction is finished, washing with water to obtain the acrylonitrile skeleton macroporous resin.
8. The method according to claim 7, wherein the concentration of the aqueous alkali metal hydroxide solution is 23 to 33wt%; the mass ratio of the acrylonitrile skeleton resin matrix to the alkali metal hydroxide aqueous solution is 1:3-8.
9. The acrylonitrile-skeleton macroporous resin produced by the method for producing the acrylonitrile-skeleton macroporous resin according to any one of claims 1 to 8.
10. Use of the acrylonitrile skeleton macroporous resin according to claim 9 in extracting colistin sulfate, wherein the adsorption quantity of the acrylonitrile skeleton macroporous resin to the colistin sulfate reaches more than 440 mu/mL.
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