CN110590996A - Reflux precipitation polymerization preparation method and application of sulfonic group-containing polymer microspheres - Google Patents
Reflux precipitation polymerization preparation method and application of sulfonic group-containing polymer microspheres Download PDFInfo
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- CN110590996A CN110590996A CN201910971699.9A CN201910971699A CN110590996A CN 110590996 A CN110590996 A CN 110590996A CN 201910971699 A CN201910971699 A CN 201910971699A CN 110590996 A CN110590996 A CN 110590996A
- Authority
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- Prior art keywords
- monomer
- acid
- sulfonic acid
- containing sulfonic
- reflux
- Prior art date
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- 239000004005 microsphere Substances 0.000 title claims abstract description 62
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 238000010992 reflux Methods 0.000 title claims abstract description 31
- 238000012673 precipitation polymerization Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005642 Oleic acid Substances 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 11
- 239000003225 biodiesel Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- WGZCUXZFISUUPR-UHFFFAOYSA-N acetonitrile;oxolane Chemical compound CC#N.C1CCOC1 WGZCUXZFISUUPR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- FKCBLVCOSCZFHV-UHFFFAOYSA-N acetonitrile;ethanol Chemical compound CCO.CC#N FKCBLVCOSCZFHV-UHFFFAOYSA-N 0.000 claims description 2
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 2
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 claims description 2
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 239000011973 solid acid Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/51—
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- 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
- C08F212/00—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
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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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
- C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a reflux precipitation polymerization preparation method of sulfonic acid group-containing polymer microspheres, which takes olefin monomers containing sulfonic acid or sulfonate as functional monomers, styrene or acrylic acid (ester) monomers as matrix monomers and diene monomers as crosslinking monomers, and initiates polymerization to prepare the sulfonic acid group-containing polymer microspheres by using a free radical initiator in a single solvent or a mixed solvent under the reflux condition. The invention also provides an application of the polymer microsphere containing sulfonic group, which is applied to catalyzing methanol and oleic acid to synthesize biodiesel. The reflux precipitation polymerization preparation method of the polymer microsphere containing sulfonic group is simple, short in time consumption, low in cost, high in acid density and good in stability; as a solid acid catalyst, the catalyst has the advantages of environmental friendliness, high catalytic activity, recyclability and the like, and can be widely applied to the fields of biodiesel preparation and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of new materials, in particular to a reflux precipitation polymerization preparation method and application of polymer microspheres containing sulfonic groups.
[ background of the invention ]
The acid catalysis method is a common method in the fields of petrochemical industry and the like, and is widely applied to chemical reaction processes such as esterification, etherification, ester exchange, oxidation, hydrolysis, acetalization and the like. The solid acid catalysis has the advantages of mild reaction conditions, less corrosion to reaction equipment, less generated waste, easy separation and recycling, and the like. The existing solid acid catalyst mainly comprises mesoporous silicon-based solid acid, carbon-based solid acid and polymer-based solid acid. The preparation process of the mesoporous silicon is complex, the cost is high, the energy consumption is large, the acid stability is poor, and the hydrophobicity is poor; the preparation of the carbon-based solid acid needs high-temperature carbonization, sulfonation and other processes, and has the problems of high energy consumption, high pollution and the like, and the acid sites of the carbon-based solid acid are easy to fall off and have general stability. The polymer microsphere solid acid has the advantages of easy preparation, easy modification, acid and alkali resistance, hydrophobic property and the like of a polymer, has the advantages of larger microsphere specific surface area, small steric hindrance of surface active sites, easy separation and recovery and the like, and has great potential in the aspect of catalytic preparation of biodiesel and the like.
The reflux precipitation polymerization is an effective method for preparing the monodisperse polymer microsphere, the reaction process is simple, the time consumption is short, the control is easy, a stabilizing agent or a surfactant is not required to be added, and the obtained microsphere has a clean surface and high uniformity. For example, Chinese patent (application No. 201210510948.2) adopts reflux precipitation polymerization to prepare a polymer gel microsphere, the particle size is uniform and controllable, and the polymer gel microsphere has a good application prospect in the field of biotechnology. The patent (application No. 201910056050.4) utilizes reflux precipitation polymerization to prepare the temperature-responsive iron-based nanoenzyme and prepare the nano catalytic microsphere with peroxidase activity, the reaction operation is simple, the obtained particles have small and uniform particle size, large specific surface area and high catalytic activity. In the above patent, the reflux precipitation polymerization monomers are mainly acrylic acid (ester) monomers, acrylamide monomers, etc., and the rule of the influence of the alkene monomers containing functional groups such as sulfonic acid (salt) on the reflux precipitation polymerization process is not clear, which will restrict the wide application of the polymerization technology in the development of functional microspheres. The invention adopts the reflux precipitation polymerization technology to copolymerize alkene monomers containing sulfonic acid (salt) with styrene, acrylic acid (ester) and other monomers to prepare the sulfonic acid group-containing polymer microsphere solid acid, and the synthesis reaction method is simple, the reaction condition is mild, the microsphere has uniform particle size, larger specific surface area and higher acid catalytic activity and can be recycled.
[ summary of the invention ]
Aiming at a series of problems that the existing solid acid catalyst has complex preparation process, high cost, large energy consumption, large steric hindrance of an acid site, easy shedding, poor stability, and the catalytic activity needs to be improved; the invention aims to provide a simple method for preparing polymer microsphere solid acid with high acid density, good stability and large specific surface area.
The invention also aims to provide the application of the polymer microsphere containing sulfonic group in preparing biodiesel, which has high catalytic activity and can be recycled.
In order to realize the technical purpose of the invention, the invention adopts the technical scheme that:
a reflux precipitation polymerization preparation method of polymer microspheres containing sulfonic groups comprises the steps of dissolving a matrix monomer, a crosslinking monomer and an alkene monomer containing sulfonic acid or sulfonate in a solvent, ultrasonically dispersing and dissolving for 2 minutes, and preparing a monomer mixed solution; adding an initiator into the monomer mixed solution, stirring and heating until reflux, wherein the system is white and turbid after the reflux is started, and stopping the reaction after a certain time; and after the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, collecting and recycling supernatant, adding absolute ethyl alcohol, ultrasonically dispersing, centrifugally separating, repeatedly washing for three times, and drying to obtain the polymer microsphere containing sulfonic groups.
It is further noted that the supernatant is recovered by distillation; reduces the pollution of waste liquid and the cost of raw materials. The stirring adopts mechanical stirring, and the rotating speed is 300 r/min; the heating adopts oil bath heating; the drying includes natural drying, freeze drying and vacuum drying.
Preferably, the matrix monomer is at least one of styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate.
Preferably, the crosslinking monomer is at least one of divinylbenzene, N-methylenebisacrylamide, and ethylene glycol dimethacrylate.
Preferably, the sulfonic acid or sulfonate-containing ethylenic monomer is at least one of 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium p-styrenesulfonate, sodium 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt, and potassium 3-sulfopropylmethacrylate salt.
It is further noted that the sulfonic acid group-containing monomer (2-acrylamido-2-methyl-1-propanesulfonic acid) may be copolymerized with other monomers to prepare sulfonic acid group-containing polymeric microspheres; the sulfonate-containing monomer is copolymerized with other monomers to prepare the sulfonate-containing polymer microsphere, and then the polymer microsphere solid acid can be obtained through acidification treatment.
Preferably, the initiator is at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile and dibenzoyl peroxide.
Preferably, the solvent is a single solvent of ethanol, acetonitrile, benzene or toluene or a mixed solvent of acetonitrile-ethanol, acetonitrile-water, acetonitrile-tetrahydrofuran, ethanol-benzene and ethanol-toluene.
Preferably, the dosage of the alkene monomer containing sulfonic acid or sulfonate accounts for 20-120 wt% of the total amount of the matrix monomer and the crosslinking monomer;
it should be further noted that the vinyl monomer containing sulfonic acid or sulfonate should not be too much, otherwise it will affect the formation and particle size uniformity of the polymeric microsphere particles; nor too little, otherwise the resulting polymeric microspheres have too low an acid density to affect acid catalytic activity.
The crosslinking monomer accounts for 10-80 wt% of the total amount of the matrix monomer and the crosslinking monomer;
the ratio of the initiator amount to the total monomer amount is 0.5 wt% to 5 wt%;
the total concentration of the alkene monomer containing sulfonic acid or sulfonate, the matrix monomer and the crosslinking monomer is 0.1 wt% -10 wt%.
Preferably, the polymerization temperature is 60-120 ℃, and the reflux reaction time is 0.5-5 h.
The invention also provides an application of the polymer microsphere containing sulfonic group, and the polymer microsphere containing sulfonic group prepared by reflux precipitation polymerization is applied to catalyzing esterification reaction of oleic acid and methanol to prepare biodiesel.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
(1) according to the invention, the alkene monomer containing sulfonic acid or sulfonate is copolymerized with other monomers, so that the prepared polymer microsphere has high sulfonic acid content, is connected through a covalent bond and has good stability;
(2) the reflux precipitation polymerization adopted by the invention has short time consumption and simple and easily controlled reaction, and the obtained polymeric microspheres containing sulfonic groups have uniform particle size and clean surfaces;
(3) the polymeric microspheres containing sulfonic groups obtained by the invention can be used as a solid acid catalyst, has little corrosion to a reactor, is easy to separate and recycle, and can be recycled;
(4) the product of the invention can be applied to the fields of biodiesel preparation and the like.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a TEM image of the sulfonic acid group-containing polymer microspheres obtained in example 1;
FIG. 2 is a TEM image of the sulfonic acid group-containing polymer microspheres obtained in example 2;
FIG. 3 is an XPS plot of X-ray photoelectron spectroscopy of microspheres of example 3 containing sulfonic acid groups;
FIG. 4 is a FT-IR chart of Fourier transform infrared spectrum of the sulfonic acid group-containing polymer microspheres of example 4;
FIG. 5 is a graph of conversion versus time of catalytic performance of the sulfonic acid group-containing polymeric microspheres of example 5.
[ detailed description ] embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
Example 1
(1) 0.750g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 0.250g of styrene and 0.450g of divinylbenzene were added to 40mL of acetonitrile, and the mixture was dissolved by ultrasonic dispersion for 2 minutes to prepare a monomer mixture solution. 0.0135g of azobisisobutyronitrile is added to the monomer mixture, mechanically stirred (300r/min) and heated to 90 ℃ in an oil bath, after the reflux has started, the system appearsWhite turbid, and reaction was stopped after 3 h. After the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, and collecting supernatant and distilling and collecting acetonitrile; and adding absolute ethyl alcohol into the solid at the lower layer, performing ultrasonic dispersion, performing centrifugal separation, repeatedly washing for three times, and performing vacuum drying to obtain the polymer microsphere containing sulfonic groups. The particle size of the polymer microsphere containing sulfonic group is 1560nm, the particle size distribution index PDI is 0.102, and the specific surface area is 186m2·g-1The acid density was 1.97 mmol. multidot.g-1The TEM photograph is shown in FIG. 1.
(2) The prepared sulfonic group-containing polymer microspheres are used for catalyzing oleic acid and methanol to esterify and synthesize biodiesel, and the method comprises the following specific steps: in a 100mL three-necked flask with a mechanical stirring and reflux condenser, 10g of oleic acid, 11.34g of methanol and 0.4g of microspheres of a sulfonic acid group-containing polymer were added, and ultrasonically dispersed for 5min to form a uniform suspension. Stirring (350r/min), heating to 80 ℃, stopping the reaction after reacting for 8 hours, sampling to determine the acid value, and calculating to obtain the conversion rate of the oleic acid. And (3) centrifugally separating the reaction product, collecting a solid, alternately washing the solid with ethanol and acetone for three times, drying the solid in vacuum at the temperature of 60 ℃ overnight, and performing catalytic reaction by using the solid as a catalyst again according to the steps. The oleic acid conversion (C) of the sulfonic acid group-containing polymer microspheres recycled three times was 91.35%, 87.56% and 85.54%, respectively.
Example 2
(1) 0.500g of sodium vinylsulfonate, 1.000g of methyl methacrylate, and 0.250g of ethylene glycol dimethacrylate were added to 40mL of acetonitrile-tetrahydrofuran (2:1, v), and dispersed and dissolved for 2 minutes by ultrasonic waves to prepare a monomer mixture solution. 0.0210g of azobisisobutyronitrile is added into the monomer mixed solution, the mixture is mechanically stirred (500r/min), the mixture is heated to 60 ℃ by an oil bath, white turbidity appears in the system after the reflux begins, and the reaction is stopped after 5 hours. After the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, and collecting supernatant liquor and distilling and collecting tetrahydrofuran and acetonitrile; dispersing the lower-layer solid in a sulfuric acid solution, and stirring for 24 hours at room temperature; and (3) performing centrifugal separation, adding absolute ethyl alcohol, performing ultrasonic dispersion, performing centrifugal separation again, repeatedly washing for three times in the way, and performing vacuum drying to obtain the polymer microsphere containing sulfonic groups. Testing the sulfonic acid group-containing polymerThe spheres had a particle size of 1420nm, a particle size distribution index PDI of 0.139 and a specific surface area of 129m2·g-1The acid density was 1.84 mmol. multidot.g-1The TEM photograph is shown in FIG. 2.
(2) The same as in (2) of example 1. The oleic acid conversion rates (C) of the sulfonic acid group-containing polymer microspheres in three times of recycling are 85.43%, 84.29% and 83.68%, respectively.
Example 3
0.800g of sodium p-styrenesulfonate, 0.400g of styrene and 0.800g of divinylbenzene were added to 40mL of acetonitrile/ethanol (4:1, v), and dissolved for 2 minutes by ultrasonic dispersion to prepare a monomer mixed solution. 0.0400g of azobisisobutyronitrile is added into the monomer mixed solution, mechanically stirred (300r/min), heated to 85 ℃ by an oil bath, and the system becomes white and turbid after the reflux begins, and stops after the reaction is carried out for 4 hours. After the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, collecting supernatant, and distilling and collecting acetonitrile and ethanol; dispersing the lower-layer solid in a sulfuric acid solution, and stirring for 24 hours at room temperature; and (3) performing centrifugal separation, adding absolute ethyl alcohol, performing ultrasonic dispersion, performing centrifugal separation again, repeatedly washing for three times in the way, and performing vacuum drying to obtain the polymer microsphere containing sulfonic groups. The particle size of the polymer microsphere containing sulfonic group is 503nm, the particle size distribution index PDI is 0.089, and the specific surface area is 259m2·g-1The acid density was 2.16 mmol. multidot.g-1The XPS spectrum is shown in FIG. 3.
(2) The same as in (2) of example 1. The oleic acid conversion rates (C) of the sulfonic acid group-containing polymer microspheres recycled for three times are 93.08%, 91.76% and 90.17%, respectively.
Example 4
0.800g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 0.850g of styrene, and 0.850g of divinylbenzene were added to 40mL of ethanol/benzene (1:3, v), and dissolved by ultrasonic dispersion for 2 minutes to prepare a monomer mixture solution. 0.1000g of dibenzoyl peroxide is added to the monomer mixture, mechanically stirred (300r/min) and heated to 80 ℃ by an oil bath, after the reflux begins, the system becomes white and turbid, and the reaction is stopped after 1 h. After the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, collecting supernatant liquor, and distilling and collecting ethanol and benzene; adding anhydrous water into the lower solidEthanol, ultrasonic dispersion, centrifugal separation, repeated washing for three times, and vacuum drying to obtain the polymer microsphere containing sulfonic group. The particle size of the polymer microsphere containing sulfonic group is 870nm, the particle size distribution index PDI is 0.098, and the specific surface area is 227m2·g-1The acid density was 2.03 mmol/g-1The FT-IR photograph is shown in FIG. 4.
(2) The same as in (2) of example 1. The oleic acid conversion rates (C) of the sulfonic acid group-containing polymer microspheres in three times of recycling are 90.13%, 89.72% and 87.84%, respectively.
Example 5
0.600g of 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt, 0.550g of acrylic acid, and 0.450g of N, N-methylenebisacrylamide were added to 40mL of acetonitrile/water (3:1, v), and dissolved by ultrasonic dispersion for 2 minutes to prepare a monomer mixture solution. 0.0400g of azobisisovaleronitrile is added into the monomer mixed solution, the mixture is mechanically stirred (300r/min), the mixture is heated to 100 ℃ by an oil bath, the system becomes white and turbid after the reflux begins, and the reaction is stopped after 3 hours. After the reaction liquid is cooled to room temperature, pouring out and centrifugally separating, and collecting supernatant and distilling and collecting acetonitrile; dispersing the lower-layer solid in a sulfuric acid solution, and stirring for 24 hours at room temperature; and (3) performing centrifugal separation, adding absolute ethyl alcohol, performing ultrasonic dispersion, performing centrifugal separation again, repeatedly washing for three times in the way, and performing vacuum drying to obtain the polymer microsphere containing sulfonic groups. The particle size of the polymer microsphere containing sulfonic group is 1290nm, the particle size distribution index PDI is 0.138, and the specific surface area is 176m2·g-1The acid density was 1.84 mmol. multidot.g-1The catalytic performance of the sulfonic acid group-containing polymer microspheres is shown in FIG. 5.
(2) The same as in (2) of example 1. The oleic acid conversion rates (C) of the sulfonic acid group-containing polymer microspheres in three times of recycling are 85.43%, 84.73% and 83.16%, respectively.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
(1) according to the invention, the alkene monomer containing sulfonic acid or sulfonate is copolymerized with other monomers, so that the prepared polymer microsphere has high sulfonic acid content, is connected through a covalent bond and has good stability;
(2) the reflux precipitation polymerization adopted by the invention has short time consumption and simple and easily controlled reaction, and the obtained polymeric microspheres containing sulfonic groups have uniform particle size and clean surfaces;
(3) the polymeric microspheres containing sulfonic groups obtained by the invention can be used as a solid acid catalyst, has little corrosion to a reactor, is easy to separate and recycle, and can be recycled;
(4) the product of the invention can be widely applied to the fields of biodiesel preparation and the like.
While embodiments of the invention have been disclosed above, it is not limited to the applications set forth in the specification and the embodiments, which are fully applicable to various fields of endeavor for which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (9)
1. A reflux precipitation polymerization preparation method of polymer microspheres containing sulfonic acid groups is characterized in that a matrix monomer, a crosslinking monomer and an alkene monomer containing sulfonic acid or sulfonate are dissolved in a solvent to prepare a monomer mixed solution; and adding an initiator into the monomer mixed solution, carrying out reflux reaction for a certain time at a certain temperature, and carrying out acidification, separation, washing and drying to obtain the polymer microsphere containing sulfonic groups.
2. The method of claim 1, wherein the matrix monomer is at least one of styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
3. The method of claim 1, wherein the crosslinking monomer is at least one of divinylbenzene, N-methylenebisacrylamide, and ethyleneglycol dimethacrylate.
4. The method of claim 1, wherein the vinyl monomer containing sulfonic acid or sulfonic acid salt is at least one of 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium p-styrenesulfonate, sodium 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and potassium 3-sulfopropylmethacrylate.
5. The method of claim 1, wherein the initiator is at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, and dibenzoyl peroxide.
6. The method of claim 1, wherein the solvent is a single solvent selected from ethanol, acetonitrile, benzene, and toluene, or a mixed solvent selected from acetonitrile-ethanol, acetonitrile-water, acetonitrile-tetrahydrofuran, ethanol-benzene, and ethanol-toluene.
7. The method of claim 1, wherein the polymer microspheres with sulfonic acid groups are prepared by reflux precipitation polymerization,
the dosage of the alkene monomer containing sulfonic acid or sulfonate accounts for 20-120 wt% of the total amount of the matrix monomer and the crosslinking monomer;
the crosslinking monomer accounts for 10-80 wt% of the total amount of the matrix monomer and the crosslinking monomer;
the ratio of the initiator amount to the total monomer amount is 0.5 wt% to 5 wt%;
the total concentration of the alkene monomer containing sulfonic acid or sulfonate, the matrix monomer and the crosslinking monomer is 0.1 wt% -10 wt%.
8. The method for preparing polymer microspheres with sulfonic acid groups by refluxing, precipitation and polymerization as claimed in claim 1, wherein the polymerization temperature is 60-120 ℃ and the refluxing time is 0.5-5 h.
9. The application of the polymer microsphere containing sulfonic group, which is characterized in that the polymer microsphere containing sulfonic group prepared by the reflux precipitation polymerization according to any one of claims 1 to 8 is applied to the preparation of biodiesel by catalyzing the esterification reaction of oleic acid and methanol.
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