CN115010842A - Fluorine-containing strong-basicity anion resin catalyst, preparation method and preparation method of hydroxyethyl (meth) acrylate - Google Patents
Fluorine-containing strong-basicity anion resin catalyst, preparation method and preparation method of hydroxyethyl (meth) acrylate Download PDFInfo
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- CN115010842A CN115010842A CN202210558631.XA CN202210558631A CN115010842A CN 115010842 A CN115010842 A CN 115010842A CN 202210558631 A CN202210558631 A CN 202210558631A CN 115010842 A CN115010842 A CN 115010842A
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- fluorine
- catalyst
- resin catalyst
- fixed bed
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920005989 resin Polymers 0.000 title claims abstract description 94
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 80
- 239000011737 fluorine Substances 0.000 title claims abstract description 80
- 150000001450 anions Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 22
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 238000002156 mixing Methods 0.000 claims description 58
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 51
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 125000000129 anionic group Chemical group 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000008188 pellet Substances 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000005576 amination reaction Methods 0.000 claims description 11
- 238000007265 chloromethylation reaction Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 229940061627 chloromethyl methyl ether Drugs 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 9
- -1 hydroxyethyl (methyl) acrylate Chemical compound 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
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- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims 1
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- 239000002994 raw material Substances 0.000 description 34
- 238000001914 filtration Methods 0.000 description 30
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- 238000010790 dilution Methods 0.000 description 21
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- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 18
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- 238000003860 storage Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- FYDNFZPPZJDFRY-UHFFFAOYSA-K chromium(3+);2-methylprop-2-enoate Chemical compound [Cr+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O FYDNFZPPZJDFRY-UHFFFAOYSA-K 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 239000002815 homogeneous catalyst Substances 0.000 description 3
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- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241001671213 Staphylea Species 0.000 description 1
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- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 description 1
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- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
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- PQQAOTNUALRVTE-UHFFFAOYSA-L iron(2+);diformate Chemical compound [Fe+2].[O-]C=O.[O-]C=O PQQAOTNUALRVTE-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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 halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
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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
- 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
- B01J31/08—Ion-exchange resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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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
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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
- 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
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Abstract
The invention aims to provide a fluorine-containing strong-base anion resin catalyst, a preparation method thereof and a method for preparing hydroxyethyl (meth) acrylate by adopting the catalyst.
Description
Technical Field
The invention belongs to the field of organic compound preparation, and particularly relates to a fluorine-containing strong-basicity anion resin catalyst, a preparation method and application thereof, and a preparation method of hydroxyethyl (meth) acrylate.
Background
Hydroxyethyl (meth) acrylate, abbreviated to HE (M) A. The use of hydroxyethyl (meth) acrylate in thermosetting coatings is of particular importance. On one hand, hydroxy ethyl (meth) acrylate can be used for preparing hydroxyl-containing acrylic resin by homopolymerization or copolymerization with other vinyl monomers, and the resin can form a two-component thermosetting coating together with polyfunctional group crosslinking components which can react with hydroxyl groups such as HDI tripolymer and melamine formaldehyde; on the other hand, hydroxyethyl (meth) acrylate can be prepared into a prepolymer terminated with unsaturated double bonds by reacting hydroxyl with isocyanate, epoxy resin and the like, and can be cured under external conditions such as ultraviolet, which is the principle of UV curing resins and coatings. Both are very important applications of hydroxyethyl (meth) acrylate and are currently in the paint industry.
The hydroxy (meth) acrylate can be obtained by direct esterification of (meth) acrylic acid and ethylene oxide, or by transesterification of methyl (meth) acrylate with ethylene glycol. At present, the industrial production method of hydroxyethyl (meth) acrylate mainly adopts (meth) acrylic acid and ethylene oxide to react and synthesize under the condition of homogeneous catalyst, but the process method has the defects that the catalyst is difficult to recover and reuse, and simultaneously, the process waste water amount is large and the environment is polluted.
CN201810058378.5 provides a method for preparing hydroxyethyl (meth) acrylate, reacting (meth) acrylic acid with ethylene oxide in a tubular reactor in the presence of a catalyst and a polymerization inhibitor at a certain temperature to prepare a crude product of hydroxyethyl (meth) acrylate, wherein the catalyst comprises hexamethylenetetramine and imidazole, the polymerization inhibitor comprises phenothiazine and p-hydroxyanisole, and homogeneous catalysts hexamethylenetetramine and imidazole are used in the reaction process, so that the recovery and the reuse are difficult, and environmental pollution is easily caused;
CN201410334216.1 provides a preparation method of hydroxyethyl (meth) acrylate, which adopts a combined process of a three-section tubular reactor and a tower reactor: firstly, mixing a catalyst, a polymerization inhibitor and (methyl) acrylic acid until solids are dissolved, then mixing with part of propylene oxide and then entering a first tubular reactor for reaction, mixing a reaction liquid flowing out of the first tubular reactor with a certain amount of ethylene oxide and entering a second tubular reactor for reaction, mixing a reaction liquid flowing out of the second tubular reactor with a certain amount of ethylene oxide and entering a third tubular reactor, ageing a reaction liquid flowing out of the third tubular reactor through a section of adiabatic tower reactor, and extracting to obtain a product liquid. The used catalyst is one or more of amine compound, iron compound and chromium compound, which are homogeneous catalysts, are difficult to recycle and are easy to cause environmental pollution;
CN201310194477.3 provides a method for synthesizing hydroxyethyl methacrylate, which comprises the steps of adding methacrylic acid into a reaction kettle, adding a magnetic zeolite molecular sieve, stirring uniformly, adding ethylene oxide, heating the reaction kettle at a certain temperature, reacting for 2-3 h, and distilling to obtain the hydroxyethyl methacrylate.
CN201110224818.8 provides a method for synthesizing hydroxyethyl methacrylate, which comprises the steps of adding iron oxide serving as a catalyst, p-hydroxyanisole serving as a polymerization inhibitor and methacrylic acid serving as a raw material into a four-neck flask, heating to 80-85 ℃, performing nitrogen replacement, introducing ethylene oxide gas after the iron oxide is completely dissolved in the methacrylic acid, introducing the ethylene oxide gas for 3.5-4.5 hours, and continuing to react for 0.5-1.5 hours to obtain crude hydroxyethyl methacrylate reaction liquid.
CN201810058913.7 provides a continuous production method of hydroxyethyl methacrylate, mixed liquid of raw material methacrylic acid, catalyst ferric chloride and polymerization inhibitor ZJ-705 enters a tubular reactor, ethylene oxide is introduced, and ring-opening reaction is carried out at 60-80 ℃ and 0.25-1.0 MPaG to prepare crude hydroxyethyl methacrylate reaction liquid, the catalyst used in the method is ferric chloride, a pipeline filter is easy to block, and the crude hydroxyethyl methacrylate reaction liquid is difficult to recycle.
CN201811365889.8 provides a preparation method of hydroxyethyl methacrylate, wherein a catalyst and a polymerization inhibitor A are dissolved in methacrylic acid to form a feed liquid A, and ethylene oxide is dissolved in a dispersant to form a feed liquid B; the microchannel reaction device is divided into a high-temperature control section and a low-temperature control section according to different controlled temperatures, a feed liquid A and a feed liquid B are continuously fed into the microchannel reaction device, the feed liquid A and the feed liquid B sequentially flow through the high-temperature control section and the low-temperature control section, so that the feed liquid A and the feed liquid B perform ring-opening reaction while flowing in the microchannel reaction device, and the adopted catalysts are iron catalysts and chromium catalysts, namely one or a mixture of more than two of ferric methacrylate, ferric acrylate, ferric hydroxide, ferric sulfate, ferric nitrate, ferric acetate, chromium methacrylate, chromium trioxide, chromium picolinate and chromium formate, so that a pipeline filter is easily blocked and is difficult to recycle.
CN201210012409.6 provides a preparation process of hydroxyethyl methacrylate, which adopts a ring-opening addition process to prepare, wherein the catalyst is selected from chromium compounds such as chromium methacrylate, chromium chloride, chromium phthaleinacetonate, chromium acetate, sodium methyl dichromate, chromium methacrylate, and the like, iron-based catalysts such as iron compounds such as iron chloride, iron powder, iron formate, iron methacrylate, and the like, and chromium-based catalysts, and the catalyst is easy to block a pipeline filter and difficult to recycle.
CN201811244356.4 provides a method for producing hydroxyethyl methacrylate by an ester exchange method, which takes methyl methacrylate and ethylene glycol as raw materials, takes p-toluenesulfonic acid as a catalyst and phenothiazine as a polymerization inhibitor to react at the temperature of 100-120 ℃ to prepare a target product.
CN201310756127.1 provides a preparation method of a perfluorinated quaternary ammonium type strongly basic anion exchange resin, which adopts chloromethylated polystyrene to react with perfluorinated tertiary amine and trimethylamine simultaneously to prepare the strongly basic anion exchange resin. The invention adopts perfluoro tertiary amine and trimethylamine as aminating agents simultaneously, introduces fluorine element, enhances the bonding force of a bond between alkylbenzylamine and alkyl N-C, ensures that amino is not easy to fall off, and ensures that resin can be used at higher temperature, but the fluorine element has higher electronegativity, reduces the catalytic activity of quaternary ammonium salt groups, and limits the wide application of the fluorine element in the field of catalysts.
Based on the defects of the traditional catalyst for the direct ring-opening reaction of (methyl) acrylic acid and ethylene oxide, the continuous production process adopting a novel reaction form and a novel catalyst type needs to be developed to replace the prior art, so that the continuous and stable production of the hydroxyethyl (methyl) acrylate is realized, the environment is protected, the safety is improved, the operation is reduced, and the labor is saved.
Disclosure of Invention
The invention aims to provide a catalyst for direct ring-opening reaction of (methyl) acrylic acid and ethylene oxide and a preparation method thereof.
The invention also aims to provide a preparation method of hydroxyethyl (meth) acrylate, which combines the segmented fixed bed reactor and the catalyst dilution scheme of the invention, and can realize the advantages of continuous production operation of hydroxyethyl (meth) acrylate, high product selectivity, low environmental pollution, low production cost, low labor intensity and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a fluorine-containing strong-base anion resin catalyst, which has at least one of the following structural formulas:
wherein m and n are respectively and independently 5-20, preferably 7-16; in the catalyst, styrene and perfluoroolefin units are randomly copolymerized.
In the present invention, the fluorine-containing strongly basic anionic resin catalyst preferably has the following structure
In the invention, the number average molecular weight of the fluorine-containing strong basic anion resin catalyst is 2600-4000, preferably 2800-3500;
in the invention, the fluorine content in the fluorine-containing strong-base anion resin catalyst is 10-60 wt%, and preferably 15-30%
In the invention, the content of nitrogen element in the fluorine-containing strong-base anion resin catalyst is 1-6 wt%, preferably 3-5 wt%.
The invention also provides a preparation method of the fluorine-containing strong-basicity anion resin catalyst, which comprises the following steps:
(1) carrying out polymerization reaction on styrene, divinylbenzene and perfluoroolefin to prepare copolymer white balls;
(2) adding a chloromethylation reagent, preferably chloromethyl methyl ether, into the copolymer white ball obtained in the step (1) to carry out chloromethylation reaction, and preparing a chloromethylation white ball;
(3) adding an amination reagent, preferably a methanol solution of trimethylamine, into the chloromethylated white spheres obtained in the step (2) to carry out amination reaction to obtain the fluorine-containing strongly basic anion resin catalyst.
In the step (1), the polymerization reaction is carried out at the temperature of 70-120 ℃, preferably 80-110 ℃, for 2-15 hours, preferably 7-10 hours, under the pressure of 1-6 MPaG, preferably 2-5 MPaG, and the pressure is released to normal pressure after the reaction is finished.
The molar ratio of the styrene to the divinylbenzene is 4-7: 1, preferably 5-6: 1.
The mol ratio of the perfluoroolefin to the divinylbenzene is 5-8: 1, preferably 6-7: 1.
The perfluoroolefin is at least one of tetrafluoroethylene and/or hexafluoropropylene, and preferably tetrafluoroethylene.
Preferably, the polymerization reaction also comprises post-treatment processes such as oil droplet preparation and the like after completion.
In the step (2), the chloromethylation reaction is carried out at the temperature of 20-50 ℃, preferably 30-60 ℃ for 3-15 h, preferably 5-10 h.
The mass ratio of the chloromethyl methyl ether to the copolymerized white ball is 0.5-3: 1, and preferably 1-2: 1.
Preferably, the chloromethylation reaction also comprises a post-treatment process such as methanol washing and the like after completion.
In the step (3), the amination reaction is carried out at the temperature of 20-70 ℃, preferably 30-60 ℃ for 5-20 h, preferably 8-15 h.
The mass ratio of the trimethylamine methanol solution to the chloromethylated white spheres is 1-4: 1, and preferably 2-3: 1.
Preferably, after the amination reaction to obtain the amine spheres, the post-treatment process of adding acid to adjust the pH value and the like is also included.
Preferably, the polymerization reaction of step (1) and/or the amination reaction of step (3) is carried out in a nitrogen atmosphere.
The invention also aims to provide a method for preparing hydroxyethyl (meth) acrylate by using the fluorine-containing strong-base anion resin catalyst.
According to the invention, the sectional type reactor is adopted to reasonably and effectively control the feeding airspeed, and the sectional type fixed bed tubular reactor is adopted, preferably the fixed bed tubular reactor with more than three sections, more preferably the fixed bed tubular reactor with the upper section, the middle section and the lower section, so that the content of the byproduct DEGMA can be effectively controlled; if the residence time is prolonged, the selectivity of byproduct DEGMA is improved, and the selectivity of the product is influenced.
According to the invention, the concentration of different sections of catalysts in the sectional type fixed bed tubular reactor is controlled, so that the reaction (heat) at each position in the fixed bed tubular reactor is uniformly distributed, and the selectivity increase of byproduct DEGMA caused by overhigh local temperature is avoided.
In the invention, blank resin pellets are respectively adopted in the sectional tubular fixed bed reactor to dilute the catalysts in different sections, and the mixing proportion of the diluted catalyst filled in the uppermost section is blank resin pellets: the fluorine-containing strong-base anion resin catalyst is 1-4: 1 (volume ratio), preferably 2.5-3: 1 (volume ratio); the mixing ratio of the diluted catalyst filled in the middle section is blank resin pellets: a fluorine-containing strongly basic anionic resin catalyst in a volume ratio of 1-4: 1, preferably 2-2.5: 1; the mixing ratio of the diluted catalyst filled in the lowest section is blank resin pellets: the fluorine-containing strong-base anionic resin catalyst is 1 to 4:1 (volume ratio), preferably 1.5 to 2:1 (volume ratio).
The catalyst concentration of the middle-lower section of the sectional tubular fixed bed reactor is preferably higher than that of the upper section, materials are fed from top to bottom, the concentration of raw materials is gradually reduced from top to bottom, and in order to increase the reaction rate, the catalyst concentration of the lower section reactor is increased to increase the reaction rate so as to improve the conversion rate of the raw materials and the product yield.
In the sectional tubular fixed bed reactor of the present invention, the ratio (volume ratio) of the catalyst packed in the uppermost stage to the catalyst packed in the lowermost stage in the sectional tubular fixed bed reactor is 0.2 to 2:1, and the ratio of the catalyst packed in the intermediate stage to the catalyst packed in the lowermost stage is (0.1n +0.2) to 1:1, where n is 2, 3, 4, 5, 6, 7, 8, etc., and n represents the number of the reaction stage from the uppermost stage to the lower stage.
Preferably, the volume ratio of the catalyst filled in the uppermost section to the catalyst filled in the middle section and the catalyst filled in the lowermost section in the sectional tubular fixed bed reactor is (0.3-1): 0.5-1): 1, preferably (0.4-0.7): 0.5-0.9): 1 (volume ratio).
In the invention, in order to better realize the uniform distribution of the reaction heat of the sectional fixed bed tubular reactor, heat exchange is carried out by using heat exchange media, and the heat exchange media used in different sections are selected from one or more of heat transfer oil Kono T66, heat transfer oil Kono T55, heat transfer oil WD-55 and dimethyl silicon oil with different temperatures.
Preferably, the temperature of the heat exchange medium used in the uppermost stage jacket of the fixed bed tubular reactor is 30 to 80 ℃, the temperature of the heat exchange medium used in the lowermost stage jacket is 40 to 90 ℃, and the temperature of the heat exchange medium used in the middle stage jacket is (29+ n) to (79+ n) ° c, where n is 2, 3, 4, 5, 6, 7, 8, etc., and n represents the number of reaction stages from the uppermost stage to the bottom.
In the invention, the polymerization inhibitor is at least one of ZJ-701, ZJ-705, Wanli 5105, Wanli 5115 and Wanli 5125, preferably ZJ-701;
in the invention, the mass ratio of the polymerization inhibitor to the (meth) acrylic acid is 0.0001-0.005: 1, preferably 0.0005 to 0.001: 1, more preferably 0.0006 to 0.0008: 1.
In the present invention, the molar ratio of (meth) acrylic acid to ethylene oxide is 0.1 to 3:1, preferably 1.0 to 2:1, more preferably 1.01 to 1.2: 1;
in the invention, the volume airspeed of the feeding of the mixed material in the fixed bed tubular reactor is 0.2-3 h -1 Preferably 0.6 to 2.0 hours -1 (ii) a And/or the temperature of a reaction hot spot in the fixed bed tubular reactor is 50-90 ℃, preferably 60-80 ℃; the reaction pressure is 0.2 to 1.0MPaG, preferably 0.4 to 0.7 MPaG.
In the invention, compressed nitrogen is required to be continuously introduced in the reaction process, and the compressed nitrogen can maintain the pressure of a reaction system; preferably, the maximum pressure of compressed nitrogen required to supplement the system pressure is 0.1 to 1.0MPaG, more preferably 0.4 to 0.7 MPaG.
The technical scheme of the invention has the beneficial effects that:
1. the fluorine-containing strong-basicity anion resin catalyst is adopted, the catalyst activity is high, the service life of the catalyst is long, the reaction condition is mild, the selectivity of (methyl) hydroxyethyl ester prepared by continuous production is up to more than 98 percent, and the conversion rate of (methyl) acrylic acid is up to more than 99.9 percent.
2. A sectional type fixed bed reactor is adopted, an upper, middle and lower three-section type fixed bed tubular reactor is preferably selected, continuous production is realized, the production cost is low, and the labor intensity is low;
3. the concentration of the catalyst in different sections is controlled, so that the reaction heat generated in the reaction process can be more uniformly and timely removed in the whole reactor bed, and the conditions that the selectivity of the byproduct DEGMA is higher and the product selectivity is lower due to overhigh local temperature of the bed are avoided.
4. The production process has no wastewater, is environment-friendly, and can be used for large-scale continuous production of the hydroxyethyl (meth) acrylate.
Drawings
FIG. 1 is a GPC chart of a fluorine-containing strongly basic anionic resin catalyst prepared in example 1;
FIG. 2 is a GPC chart of a fluorine-containing strongly basic anionic resin catalyst prepared in example 2;
FIG. 3 is a GPC chart of the fluorine containing strongly basic anionic resin catalyst prepared in example 3;
FIG. 4 is a GPC chart of a fluorine containing strongly basic anionic resin catalyst prepared in example 4;
FIG. 5 is a schematic view of the process for the hydroxyethyl (meth) acrylate reaction of the present invention; the device comprises a raw material mixing tank 1, a feed pump 2, a segmented fixed bed reactor 3, a reaction liquid tank 4, a first pipeline 5, a second pipeline 6, a third pipeline 7, a fourth pipeline 8, a fifth pipeline 9, a sixth pipeline 10, a seventh pipeline 11, an eighth pipeline 12, a ninth pipeline 13, a tenth pipeline 14, an eleventh pipeline 15, a twelfth pipeline 16 and a thirteenth pipeline 17.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
First, the main raw material sources in the example:
1. methacrylic acid, wanhua chemical group, ltd, technical grade;
2. acrylic acid, Vanhua chemical group, Inc., technical grade;
3. ethylene oxide, Vanhua chemical group, Inc., technical grade;
4. tetrafluoroethylene, Dalian specialty gas Co., Ltd, technical grade;
5. hexafluoropropylene, Dalian specialty gases Ltd, technical grade;
6. t-butyl hydroperoxide, Vanhua chemical group, Inc., technical grade;
7. styrene, Tianjin Staphylea chemical Co., Ltd, technical grade;
8. divinylbenzene, Jiangsu Zhengdan chemical industry Co., Ltd, technical grade;
9. gelatin, water-balancing macro-finance adhesive limited, technical grade;
10. methylene blue, shanghai alatin Biotechnology, ltd, analytically pure;
11. n-hexane, industrial grade, by Kyobo chemical Co., Ltd.;
12. chloromethyl methyl ether, Wuhan Chu JiangHaoyu chemical engineering development Co., Ltd, industrial grade;
13. trimethylamine methanol solution (33 wt%), yofeng chemical ltd, changzhou, industrial grade.
Secondly, the product analysis method in the embodiment:
the content of chlorine element in the catalyst is determined by a potentiometric titrator, and the equipment manufacturer and the model are as follows: METROHM 905 TITRANDO;
measuring a BET value of the catalyst by a physical adsorption instrument, wherein the BET value comprises the following components in part by weight: MICROMERICS (USA) ASAP 2020;
the nitrogen content of the catalyst is measured by an element analyzer, and the device manufacturer and the type are as follows: euro Vector (italy) EA 3000;
the molecular weight of the catalyst is measured by a gel chromatograph (GPC), and the manufacturer and the model of the device are as follows: shimadzu (Japan) LC-20 AD; a detector: uv absorption detector/refractive index detector, light source: SPD-20A D2 lamp, wavelength: 550nm, flow rate: 0.015 mL/min;
an X-ray fluorescence spectrometer (XRF) is used for measuring the fluorine content of the catalyst, and the manufacturer and the model of the device are as follows: PANALYTICAL (Netherlands) Axios mAX; and (3) testing conditions: the voltage of the Rh target-SST light pipe is 44kV, the current is 25mA, the power is 4.0kw, the vacuum/He atmosphere is realized, the vacuum degree is 4pa, and the precision of the goniometer is 0.0025 degrees;
the gas chromatography analysis uses a correction factor method, and the manufacturer and model of the instrument are as follows: the island body 1020-plus. The analysis method is as follows: type of column: DB-5(30 × 0.25), carrier gas velocity: 1mL/min, sample size: 0.2 microliter.
As shown in FIG. 5, in the above, middle and lower three-stage fixed bed tubular reactor as an example, blank resin pellets and fluorine-containing strongly basic anionic resin catalyst are uniformly mixed at a certain dilution ratio and then loaded into the upper, middle and lower stages of the stage fixed bed tubular reactor 3, and (meth) acrylic acid and ethylene oxide are added into the raw material mixing tank 1 at a certain ratio, and then polymerization inhibitor ZJ-701 is added thereto, and finally compressed nitrogen is supplemented into the raw material mixing tank 1 through the first pipe 5 to a certain pressure and uniformly mixed, compressed nitrogen is supplemented into the reaction liquid storage tank and the stage fixed bed reactor through the twelfth pipe 16 to a reaction pressure, and oil baths of different temperatures are pumped into the upper, middle and lower stages of the jacket of the tubular reactor through the fourth pipe 8 and the sixth pipe 10 and the eighth pipe 12, respectively, and flow out through the fifth pipe 9 and the seventh pipe 11 and the ninth pipe 13, the raw material mixed liquor in the raw material mixing tank 1 is pumped into the sectional type fixed bed reactor 3 through the second pipeline 6 and the feeding pump 2 to react, the intermediate liquid obtained by the reaction flows into the reaction liquid tank 4 through the tenth pipeline 14, the feeding airspeed is kept unchanged in the feeding process, the pressure of the whole reaction system is controlled to be stable by adjusting a back pressure valve on the eleventh pipeline 15, and the intermediate product obtained by the reaction is discharged through the thirteenth pipeline 17.
Example 1:
the preparation of the fluorine-containing strong-base anion resin catalyst comprises the following steps:
1) tetrafluoroethylene (60kg), styrene (52kg) and divinylbenzene (13kg) were added to 1m 3 Mixing the materials in a material mixing kettle uniformly, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and a proper amount of methylene blue solution of 0.3kg into a reaction kettle, heating to 95 ℃, then dropwise adding an oil phase for reacting for 8.5h, cooling to 25 ℃, filtering to obtain beads, cleaning with 320kg of n-hexane, filtering and drying to obtain copolymer white balls;
2) mixing 150kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to a mass ratio of 1.5:1, heating to 40 ℃, dropwise adding 30kg of anhydrous aluminum chloride for reacting for 7.5h, cooling to 25 ℃, filtering to obtain a bead body, washing with 400kg of ethanol, filtering and drying to obtain a chloromethylated white ball;
3) mixing 150kg of anhydrous methanol and the chloromethylated white spheres obtained in the step 2) according to a mass ratio of 2:1, heating to 45 ℃, dropwise adding 40kg of a 33 wt% trimethylamine methanol solution, reacting for 8.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated salt solution, adding hydrochloric acid to adjust the pH value to 4, washing with 300kg of pure water, and filtering to obtain amine spheres, namely the fluorine-containing strong basic anion resin catalyst;
the strongly basic, fluorine-containing anionic resin catalyst prepared in example 1 (GPC chart shown in FIG. 1) was tested to have a fluorine content of 24.6 wt%, a nitrogen content of 4.5 wt%, and a molecular weight of about 2959 (Mn); in the catalyst, styrene and perfluoroolefin units are randomly copolymerized.
Example 2:
the preparation method of the fluorine-containing strong-base anion resin catalyst comprises the following steps:
1) tetrafluoroethylene (70kg), styrene (62.4kg) and divinyl (13kg) benzene were charged to 1m 3 Mixing the materials in a blending kettle uniformly, and adding 3.12kg of tert-butyl hydroperoxide to prepare an oil phase; adding 250kg of pure water, 1.2kg of gelatin and 0.4kg of proper amount of methylene blue solution into a reaction kettle, heating to 100, adding the mixture into the reaction kettle, reacting for 9.5 hours, cooling to 25 ℃, filtering to obtain beads, cleaning with 400kg, filtering and drying to obtain copolymer white balls;
2) mixing 200kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to a mass ratio of 2:1, heating to 45, dropwise adding 39kg of anhydrous aluminum chloride, reacting for 7.5 hours, cooling to 25 ℃, filtering to obtain a bead body, washing with 500kg of ethanol, filtering and drying to obtain a chloromethylated white ball;
3) mixing 200kg of anhydrous methanol and the chloromethylated white spheres obtained in the step 2) according to a mass ratio of 2:1, heating to 50 ℃, dropwise adding 50kg of a 33 wt% trimethylamine methanol solution to react for 9.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated salt solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, and filtering to obtain amine spheres, namely the fluorine-containing strong basic anion resin catalyst;
the fluorine-containing strongly basic anionic resin catalyst prepared in example 2 (GPC chart shown in FIG. 2) had a structural formula in which m was 9, n was 10, fluorine content was 26.0 wt%, nitrogen content was 4.3 wt%, and molecular weight was 3074 (Mn);
example 3:
the preparation method of the fluorine-containing strong-base anion resin catalyst comprises the following steps:
1) tetrafluoroethylene (60kg), styrene (52kg) and divinylbenzene (13kg) were charged to 1m 3 Mixing the materials in a blending kettle uniformly, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and 0.3kg of a proper amount of methylene blue solution into a reaction kettle, heating to 105 ℃, dropwise adding an oil phase to react for 9.5h, cooling to 25 ℃, filtering to obtain beads, cleaning with 320kg of n-hexane, filtering and drying to obtain copolymer white balls;
2) mixing 250kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to a mass ratio of 2.5:1, heating to 45 ℃, dropwise adding 34kg of anhydrous aluminum chloride for reacting for 8.5h, cooling to 25 ℃, filtering to obtain beads, washing with 450kg of ethanol, filtering and drying to obtain a chloromethylated white ball;
3) mixing 250kg of anhydrous methanol and the chloromethylated white spheres obtained in the step 2) according to a mass ratio of 2:1, heating to 55 ℃, dropwise adding 40kg of a 33 wt% trimethylamine methanol solution, reacting for 9.5 hours, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated salt solution, adding hydrochloric acid to adjust the pH value to 4, washing with 500kg of pure water, and filtering to obtain amine spheres, namely the fluorine-containing strong basic anion resin catalyst;
the strongly basic anion resin catalyst containing fluorine (GPC chart shown in FIG. 3) prepared in example 3, wherein m is 10, n is 10, fluorine content is 25.5 wt%, nitrogen content is 4.1 wt%, and molecular weight is 3271 (Mn);
example 4:
the preparation method of the fluorine-containing strong-base anion resin catalyst comprises the following steps:
1) hexafluoroethylene (90kg), styrene (52kg) and divinylbenzene (13kg) were added to 1m 3 Mixing the materials in a material mixing kettle uniformly, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 240kg of pure water, 1.1kg of gelatin and a proper amount of methylene blue solution of 0.35kg into a reaction kettle, heating to 105 ℃, dropwise adding an oil phase to react for 9.5h, cooling to 25 ℃, filtering to obtain beads, cleaning with 380kg of n-hexane, filtering and drying to obtain copolymer white balls;
2) mixing 250kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to a mass ratio of 2.5:1, heating to 45 ℃, dropwise adding 34kg of anhydrous aluminum chloride for reacting for 8.5h, cooling to 25 ℃, filtering to obtain beads, washing with 450kg of ethanol, filtering and drying to obtain a chloromethylated white ball;
3) mixing 250kg of anhydrous methanol and the chloromethylated white spheres obtained in the step 2) according to a mass ratio of 2:1, heating to 55 ℃, dropwise adding 40kg of a 33 wt% trimethylamine methanol solution, reacting for 9.5 hours, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated salt solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, and filtering to obtain amine spheres, namely the fluorine-containing strong basic anion resin catalyst;
the fluorine-containing strongly basic anionic resin catalyst prepared in example 4 (GPC chart shown in FIG. 4) had a structural formula in which m was 11, n was 7, fluorine content was 24.1 wt%, nitrogen content was 4.6 wt%, and molecular weight was 3556 (Mn);
examples 5 to 10
The green resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were mixed in a ratio of 2.5:1 (volume ratio), mixing the blank resin pellets with the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 in a dilution ratio of 2:1 (volume ratio), loading the mixture into the middle section of a sectional fixed bed tubular reactor 3, mixing the blank resin pellets with the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 in a dilution ratio of 1.5:1 (volume ratio), loading the mixture into the lower section of the sectional fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid in a certain ratio into a raw material mixing tank 1, adding a polymerization inhibitor ZJ-701 into the raw material mixing tank 1, wherein the mass ratio of the ZJ-701 to the methacrylic acid is 0.0006:1, and finally supplementing compressed nitrogen to 0.45MPaG through a first pipeline 5 and mixing the mixture uniformly, supplementing compressed nitrogen to the reaction liquid storage tank and the sectional type fixed bed reactor to 0.45MPaG through a twelfth pipeline 16, pumping the raw material liquid in the raw material mixing tank 1 into the sectional type fixed bed reactor 3 through the feeding pump 2 for reaction, and keeping the feeding airspeed at 0.6h in the feeding process -1 Unchanged and passing through the fourth 8 and sixth 10 and eighth 12 conduitsThe bath temperature is adjusted to control the hot spot temperature of the upper section, the middle section and the lower section of the reactor to be maintained at 65 ℃, the proportion of methacrylic acid and ethylene oxide in the raw material mixed liquid is changed, and the specific reaction process conditions and the reaction results of the embodiments 5-9 are shown in table 1.
TABLE 1
| Example No. 2 | 5 | 6 | 7 | 8 | 9 | 10 |
| Ethylene oxide to methacrylic acid (molar ratio) | 1.01 | 1.04 | 1.08 | 1.12 | 1.16 | 1.2 |
| Dilution ratio of upper stage catalyst | 2.5:1 | 2.5:1 | 2.5:1 | 2.5:1 | 2.5:1 | 2.5:1 |
| Upper stage reaction hot spot temperature/. degree.C | 65 | 65 | 65 | 65 | 65 | 65 |
| The temperature/DEG C of the upper oil bath is controlled | 45 | 45 | 45 | 45 | 45 | 45 |
| Temperature difference/deg.C of upper section | 20 | 20 | 20 | 20 | 20 | 20 |
| Middle stage catalyst dilution ratio | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 |
| Mid-section reaction hot spot temperature/. degree.C | 65 | 65 | 65 | 65 | 65 | 65 |
| The middle section oil bath controls the temperature/° C | 50 | 50 | 50 | 50 | 50 | 50 |
| Temperature difference/deg.C of intermediate section | 15 | 15 | 15 | 15 | 15 | 15 |
| Lower stage catalyst dilution ratio | 1.5:1 | 1.5:1 | 1.5:1 | 1.5:1 | 1.5:1 | 1.5:1 |
| Lower segment reaction hot spot temperature/° c | 65 | 65 | 65 | 65 | 65 | 65 |
| The lower segment of the oil bath controls the temperature/° C | 60 | 60 | 60 | 60 | 60 | 60 |
| Lower temperature difference/deg.C | 5 | 5 | 5 | 5 | 5 | 5 |
| Selectivity/% of byproduct DEGMA | 1.11 | 1.2 | 1.22 | 1.26 | 1.31 | 1.39 |
| Conversion of methacrylic acid/%) | 99.91 | 99.92 | 99.92 | 99.93 | 99.91 | 99.91 |
| Selectivity/% of hydroxyethyl methacrylate | 98.58 | 98.47 | 98.55 | 98.41 | 98.29 | 98.23 |
Example 6 stable operation 2000h, methacrylic acid conversion stabilized at 99.9% and above, hydroxyethyl methacrylate selectivity maintained at 98.0% above, byproduct DEGMA selectivity maintained below 1.5%;
examples 11 to 13
Blank resin pellets and the fluorine-containing strongly basic anion resin catalyst prepared in example 1 were uniformly mixed at a dilution ratio of 2:1 (volume ratio) and then loaded into the middle section of a sectional fixed bed tubular reactor 3, blank resin pellets and the fluorine-containing strongly basic anion resin catalyst prepared in example 1 were uniformly mixed at a dilution ratio of 1.5:1 (volume ratio) and then loaded into the lower section of the sectional fixed bed tubular reactor 3, ethylene oxide and methacrylic acid were loaded into a raw material mixing tank 1 at a molar ratio of 1.04:1, and then a polymerization inhibitor ZJ-701 was added thereto, wherein the mass ratio of ZJ-701 to methacrylic acid was 0.0007: 1, finally supplementing compressed nitrogen to 0.50MPaG and uniformly mixing the compressed nitrogen to the raw material mixing tank 1 through the first pipeline 5, supplementing compressed nitrogen to 0.50MPaG to the reaction liquid storage tank and the sectional type fixed bed reactor through the twelfth pipeline 16, pumping the raw material liquid in the raw material mixing tank 1 into the sectional type fixed bed reactor 3 through the feeding pump 2 for reaction, and keeping the feeding airspeed at 0.6h in the feeding process -1 The temperature of hot spots at the upper, middle and lower sections of the reactor is controlled to be maintained at 65 ℃ by adjusting the temperature of the oil bath in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, the blank resin pellets and the fluorine-containing strong base anion resin catalyst are uniformly mixed and then are loaded into the upper section of the sectional fixed bed tubular reactor 3, and the specific reaction process conditions and the reaction results of the embodiments 11 to 13 are shown in table 2.
TABLE 2
| Example No. 2 | 11 | 12 | 13 |
| Ethylene oxide to methacrylic acid (molar ratio) | 1.04 | 1.04 | 1.04 |
| Dilution ratio of upper stage catalyst | 2.55:1 | 2.75:1 | 3.0:1 |
| Upper stage reaction hot spot temperature/. degree.C | 65 | 65 | 65 |
| The temperature/DEG C of the upper oil bath is controlled | 45 | 46 | 47 |
| Upper temperature difference/° c | 20 | 19 | 18 |
| Dilution ratio of catalyst in middle stage | 2:1 | 2:1 | 2:1 |
| Mid-section reaction hot spot temperature/. degree.C | 65 | 65 | 65 |
| The middle section oil bath controls the temperature/° C | 50 | 50 | 50 |
| Temperature difference/deg.C of |
15 | 15 | 15 |
| Lower stage catalyst dilution ratio | 1.5:1 | 1.5:1 | 1.5:1 |
| Lower segment reaction hot spot temperature/° c | 65 | 65 | 65 |
| The lower segment of the oil bath controls the temperature/° C | 60 | 60 | 60 |
| Lower temperature difference/ |
5 | 5 | 5 |
| Selectivity/% of byproduct DEGMA | 1.18 | 1.24 | 1.23 |
| Conversion of methacrylic acid/%) | 99.93 | 99.92 | 99.92 |
| Selectivity/% of hydroxyethyl methacrylate | 98.48 | 98.57 | 98.61 |
Examples 14 to 16
The green resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were mixed in a ratio of 2.5:1 (volume ratio), uniformly mixing the mixture, putting the mixture into the upper section of a sectional type fixed bed tubular reactor 3, uniformly mixing blank resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 according to the dilution ratio of 1.5:1 (volume ratio), putting the mixture into the lower section of the sectional type fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into a raw material mixing tank 1 according to the molar ratio of 1.08:1, adding a polymerization inhibitor ZJ-701 into the tank, wherein the mass ratio of ZJ-701 to methacrylic acid is 0.0007: 1, finally supplementing compressed nitrogen to the raw material mixing tank 1 to 0.55MPaG through a first pipeline 5, uniformly mixing, and supplementing and compressing to a reaction liquid storage tank and a sectional type fixed bed reactor through a twelfth pipeline 16Nitrogen is added to 0.55MPaG, then the raw material liquid in the raw material mixing tank 1 is pumped into the sectional type fixed bed reactor 3 through the feed pump 2 for reaction, and the feeding airspeed is kept at 0.6h in the feeding process -1 The temperature of hot spots at the upper, middle and lower sections of the reactor is controlled to be maintained at 65 ℃ by adjusting the temperature of the oil bath in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, the blank resin pellets and the fluorine-containing strong base anion resin catalyst are uniformly mixed and then are loaded into the middle section of the sectional fixed bed tubular reactor 3, and the specific reaction process conditions and the reaction results of the embodiments 14 to 16 are shown in table 3.
TABLE 3
| Example No. 2 | 14 | 15 | 16 |
| Ethylene oxide to methacrylic acid (molar ratio) | 1.08 | 1.08 | 1.08 |
| Dilution ratio of upper stage catalyst | 2.5:1 | 2.5:1 | 2.5:1 |
| Upper stage reaction hot spot temperature/. degree.C | 65 | 65 | 65 |
| The temperature of the upper oil bath is controlled to be lower than that of the lower oil bath | 45 | 45 | 45 |
| Temperature difference/deg.C of upper section | 20 | 20 | 20 |
| Middle stage catalyst dilution ratio | 2:1 | 2.25:1 | 2.5:1 |
| Mid-section reaction hot spot temperature/. degree.C | 65 | 65 | 65 |
| The middle section oil bath controls the temperature/° C | 50 | 51 | 52 |
| Temperature difference/deg.C of |
15 | 14 | 13 |
| Lower stage catalyst dilution ratio | 1.5:1 | 1.5:1 | 1.5:1 |
| Lower segment reaction hot spot temperature/° c | 65 | 65 | 65 |
| The lower segment of the oil bath controls the temperature/° C | 60 | 60 | 60 |
| Lower temperature difference/ |
5 | 5 | 5 |
| Selectivity/% of byproduct DEGMA | 1.16 | 1.26 | 1.32 |
| Conversion of methacrylic acid/%) | 99.92 | 99.93 | 99.91 |
| Selectivity/% of hydroxyethyl methacrylate | 98.47 | 98.56 | 98.64 |
Examples 17 to 19
The green resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were mixed in a ratio of 2.5:1 (volume)Ratio) was uniformly mixed, and the mixture was charged into the upper stage of a sectional fixed bed tubular reactor 3, and the blank resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were uniformly mixed at a dilution ratio of 2:1 (volume ratio) and charged into the middle stage of the sectional fixed bed tubular reactor 3, and ethylene oxide and methacrylic acid were charged into a raw material mixing tank 1 at a molar ratio of 1.08:1, and a polymerization inhibitor ZJ-705 was further charged thereinto in a mass ratio of ZJ-705 to methacrylic acid of 0.0008:1, finally supplementing compressed nitrogen to 0.65MPaG and uniformly mixing the compressed nitrogen to the raw material mixing tank 1 through the first pipeline 5, supplementing compressed nitrogen to 0.65MPaG to the reaction liquid storage tank and the sectional type fixed bed reactor through the twelfth pipeline 16, pumping the raw material liquid in the raw material mixing tank 1 into the sectional type fixed bed reactor 3 through the feeding pump 2 for reaction, and keeping the feeding airspeed at 0.6h in the feeding process -1 The temperature of hot spots in the upper, middle and lower sections of the reactor is controlled to be maintained at 65 ℃ by adjusting the temperature of the oil bath in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, the blank resin pellets and the fluorine-containing strong base anion resin catalyst are uniformly mixed and then are loaded into the lower section of the sectional fixed bed tubular reactor 3, and the specific reaction process conditions and the reaction results of the embodiments 17 to 19 are shown in table 4.
TABLE 4
Examples 20 to 25
The green resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were mixed in a ratio of 2.5:1 (volume ratio) was uniformly mixed and charged into the upper stage of a fixed bed reactor 3 of sectional type, and the pellets of the green resin and the fluorine-containing strongly basic anion resin catalyst prepared in example 1 were uniformly mixed in a dilution ratio of 2:1 (volume ratio) and charged into a fixed bed of sectional typeIn the middle section of the tubular reactor 3, the blank resin pellets and the fluorine-containing strongly basic anionic resin catalyst prepared in example 1 were uniformly mixed in a dilution ratio of 1.5:1 (by volume) and then charged into the lower section of the segmented fixed bed tubular reactor 3, ethylene oxide and methacrylic acid were charged into the raw material mixing tank 1 in a molar ratio of 1.05:1, and then a polymerization inhibitor 5125 was added thereto, wherein the mass ratio of 5125 to methacrylic acid was 0.0008:1, finally supplementing compressed nitrogen to 0.70MPaG and uniformly mixing the compressed nitrogen to the raw material mixing tank 1 through the first pipeline 5, supplementing compressed nitrogen to 0.70MPaG to the reaction liquid storage tank and the sectional type fixed bed reactor through the twelfth pipeline 16, pumping the raw material liquid in the raw material mixing tank 1 into the sectional type fixed bed reactor 3 through the feeding pump 2 for reaction, and keeping the feeding airspeed at 2h in the feeding process -1 The hot spot temperatures of the upper, middle and lower sections in the reactor are controlled by adjusting the oil bath temperatures in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, and the specific reaction process conditions and reaction results of the examples 20 to 24 are shown in table 5.
TABLE 5
As can be seen from the data in tables 1, 2, 3, 4 and 5, by adjusting the raw material ratio and changing the dilution ratio of the upper and lower catalysts of the fixed bed tubular reactor, under the superior reaction process conditions, the conversion rate of methacrylic acid can reach 99.9%, the selectivity of hydroxyethyl methacrylate can reach 98.64%, and the selectivity of byproduct DEGMA is only 1.49%.
Comparative example 1
Different from example 5, the reaction verification was performed by using a non-segmented fixed bed reactor, the jacket oil bath temperature was 36 ℃, the control hot spot temperature was 65 ℃, the catalyst dilution ratio of the whole reactor was 2:1 (volume ratio), the conversion of methacrylic acid was 97.9%, the selectivity for byproduct DEGMA was 5.5%, and the selectivity for hydroxyethyl methacrylate was 93.3%.
Comparative example 2
0.7L of a reactant solution (containing 860g (10mol) of a reactant methacrylic acid, 43g of a fluorine-containing strongly basic anion resin catalyst prepared in example 1, and 0.69g of a polymerization inhibitor ZJ-701) was charged into a 1.8L stainless steel reaction vessel; after nitrogen is adopted to pressurize to 0.45MPaG, the stirring speed is kept at 500rpm, the temperature programming is started, the heating rate is 2 ℃/min, 457.6g (10.4mol) of ethylene oxide is started to be added when the temperature of the reaction raw material mixture rises to 65 ℃, the temperature is kept for about 8 hours after the addition, the reaction liquid is cooled to the room temperature, gas is discharged, and the selectivity of a byproduct DEGMA is 4.9% and the selectivity of hydroxyethyl methacrylate is 94.2% after sampling analysis. The intermittent kettle type reactor can be used for ring-opening addition reaction, but the product selectivity is low, the selectivity of byproduct DEGMA is high, and meanwhile, manual operation is more.
Comparative example 3
The difference from the example 6 lies in: the method adopts an outsourced fluorine-free D201 strong-base anion resin catalyst, maintains the temperature of an upper-section reaction hot spot, the temperature of a middle-section reaction hot spot and the temperature of a lower-section reaction hot spot to be 65 ℃, after the operation is carried out for 155 hours, the conversion rate of methacrylic acid is obviously reduced, the initial 99.9 percent is reduced to 59 percent, and the quaternary ammonium salt active component on the main catalyst falls off, and in contrast, the self-made fluorine-containing strong-base anion resin catalyst is adopted, the quaternary ammonium salt active component is not easy to fall off due to the attraction of fluorine atoms to quaternary ammonium salt groups, the service life of the catalyst reaches 2000 hours or more, and the activity of the catalyst is stable in the operation process.
Comparative example 4
Preparing a fluorine-containing strong-basicity anion resin catalyst, wherein in the step 1), the molar ratio of perfluoroolefin to divinylbenzene is not within the range of 5-8: 1, and the steps are as follows:
1) tetrafluoroethylene (10kg), styrene (52kg) and divinyl (13kg) benzene were charged to 1m 3 Mixing in a blending kettle, adding 2.6kg of 0.5 wt% of tert-butyl hydroperoxide (based on styrene) to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and 0.3kg of methylene blue solution into a reaction kettle, heating to 95 ℃, dropwise adding an oil phase to react for 8.5h, cooling to 25 ℃, filtering to obtain beads, cleaning with 320kg of n-hexane, filtering and drying to obtain copolymer white balls;
2) mixing 150kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to a mass ratio of 1.5:1, heating to 40 ℃, dropwise adding anhydrous aluminum chloride for reacting for 7.5h, cooling to 25 ℃, filtering to obtain a bead body, washing with 400kg of ethanol, filtering and drying to obtain a chloromethylated white ball;
3) mixing 150kg of anhydrous methanol and the chloromethylated white spheres obtained in the step 2) according to a mass ratio of 2:1, heating to 45 ℃, dropwise adding 40kg of trimethylamine methanol solution for reacting for 8.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, cleaning and filtering to obtain amine spheres, namely the fluorine-containing strong basic anion resin catalyst;
in the obtained structural formula, the value of m is about 12, the value of n is about 2, the fluorine content is 6.9 wt%, the nitrogen content is 6.2 wt%, and the molecular weight is about 2738 (Mn); the catalyst is used for carrying out a life test, other process conditions are the same as those in example 6, after the catalyst is operated for 270 hours, the methacrylic acid conversion rate is obviously reduced and is reduced to 62% from the initial 99.9%, the preparation process of the comparative example changes the proportion of perfluoroolefin and divinylbenzene, the n value, the molecular weight, the fluorine content and the nitrogen content in the structural formula of the obtained fluorine-containing strong-basicity anion resin are all out of the range of the invention, and the service life of the catalyst is obviously reduced.
Comparative example 5:
different from example 5, the reaction of the catalyst in the preparation method of example 1 in a perfluorinated quaternary ammonium type strong base anion exchange resin in patent CN201310756127.1 proves that the conversion rate of methacrylic acid is 88.3%, the selectivity of byproduct DEGMA is 7.2%, and the selectivity of hydroxyethyl methacrylate is 89.7%, thus, although the catalyst in the preparation method of a perfluorinated quaternary ammonium type strong base anion exchange resin in patent CN201310756127.1 can catalyze the ring opening addition reaction, the activity of the catalyst is poor, the conversion rate of methacrylic acid is obviously reduced, the selectivity of byproduct DEGMA is increased, and the catalytic activity is reduced due to introduction of fluorine into the quaternary ammonium group under the same conditions.
Claims (14)
1. A preparation method of fluorine-containing strong-base anion resin catalyst is characterized by comprising the following steps:
(1) carrying out polymerization reaction on styrene, divinylbenzene and perfluoroolefin to prepare copolymer white balls;
(2) adding a chloromethylation reagent into the copolymer white ball obtained in the step (1) to carry out chloromethylation reaction to prepare a chloromethylated white ball;
(3) and (3) adding an amination reagent into the chloromethylated white spheres obtained in the step (2) to perform amination reaction to obtain the fluorine-containing strong-base anion resin catalyst, wherein the molar ratio of the perfluoroolefin to the divinylbenzene is 5-8: 1.
2. The method for producing a fluorine-containing strongly basic anion resin catalyst according to claim 1, characterized in that: the chloromethylation reaction reagent in the step (2) is chloromethyl methyl ether, and the amination reaction reagent in the step (3) is methanol solution of trimethylamine.
3. The method for preparing the fluorine-containing strongly basic anion resin catalyst according to claim 1 or 2, wherein in the step (1), the polymerization reaction is carried out at a reaction temperature of 70 to 120 ℃ for 2 to 15 hours under a reaction pressure of 1 to 6MPaG, preferably at a reaction temperature of 80 to 110 ℃ for 7 to 10 hours under a reaction pressure of 2 to 5 MPaG; and/or the molar ratio of the styrene to the divinylbenzene is 4-7: 1, preferably 5-6: 1; and/or the perfluoroolefin is at least one of tetrafluoroethylene and hexafluoropropylene, and the molar ratio of the perfluoroolefin to divinylbenzene is 6-7: 1.
4. A method for producing a fluorine-containing strongly basic anionic resin catalyst according to any one of claims 1 to 3, characterized in that: in the step (2), the reaction temperature of the chloromethylation reaction is 20-50 ℃, the reaction time is 3-15 h, preferably the reaction temperature is 30-60 ℃, and the reaction time is 5-10 h; and/or the mass ratio of the chloromethylation reaction reagent to the copolymerized white balls is 0.5-3: 1, preferably 1-2: 1.
5. The method for producing a fluorine-containing strongly basic anionic resin catalyst according to any one of claims 1 to 4, characterized by comprising: in the step (3), the amination reaction is carried out at the reaction temperature of 20-70 ℃ for 5-20 hours, preferably at the reaction temperature of 30-60 ℃ for 8-15 hours; and/or the mass ratio of the amination reagent to the chloromethylated white ball is 1-4: 1, and the mass ratio of the amination reagent to the chloromethylated white ball is preferably 2-3: 1.
6. The fluorine-containing strongly basic anionic resin catalyst obtained by the production process according to any one of claims 1 to 5, which is used for catalyzing a ring-opening addition reaction of (meth) acrylic acid and ethylene oxide.
7. Use of the fluorine-containing strongly basic anionic resin catalyst obtained by the production process according to any one of claims 1 to 5 and/or the fluorine-containing strongly basic anionic resin catalyst according to claim 6 for catalyzing the ring-opening addition reaction of (meth) acrylic acid and ethylene oxide.
8. A method for preparing hydroxyethyl (meth) acrylate is characterized in that: the method comprises the following steps: adding (methyl) acrylic acid, ethylene oxide and a polymerization inhibitor into a sectional fixed bed tubular reactor filled with a fluorine-containing strong-base anion resin catalyst according to a certain proportion, wherein the sectional fixed bed tubular reactor is preferably a fixed bed tubular reactor with more than three sections, and reacting to generate the hydroxyethyl (methyl) acrylate, wherein the fluorine-containing strong-base anion resin catalyst is the catalyst obtained by the preparation method of any one of claims 1 to 5 or the fluorine-containing strong-base anion resin catalyst of claim 6.
9. The method of claim 8, wherein the segmented tubular fixed bed reactor is used to dilute the catalyst in different segments with blank resin beads, the reactor is selected from three segments of fixed bed tubular reactors, the upper segment is filled with diluted catalyst, and the mixing ratio of the blank resin beads is: the volume ratio of the fluorine-containing strong-base anion resin catalyst is 1-4: 1, preferably 2.5-3.5: 1; the mixing proportion of the diluted catalyst filled in the middle section is blank resin pellets: the volume ratio of the fluorine-containing strong-base anion resin catalyst is 1.5-2.5: 1, preferably 2-3: 1; the mixing ratio of the diluted catalyst filled in the lower section is blank resin pellets: the volume ratio of the fluorine-containing strong-base anion resin catalyst is 1-4: 1, preferably 1-1.5: 1.
10. The process of any of claims 8-9, wherein the volume ratio of the catalyst packed in the uppermost stage to the catalyst packed in the intermediate stage and the catalyst packed in the lowermost stage in the segmented tubular fixed bed reactor is (0.3-1): 0.5-1): 1, preferably (0.4-0.7) to (0.5-0.9): 1.
11. the method according to any one of claims 8 to 10, wherein the polymerization inhibitor is at least one of ZJ-701, ZJ-705, 5105, 5115 and 5125, and/or the mass ratio of the polymerization inhibitor to (meth) acrylic acid is 0.0001 to 0.005: 1, preferably 0.0005 to 0.001: 1, more preferably 0.0006 to 0.0008:1, and/or the molar ratio of (meth) acrylic acid to ethylene oxide is 0.1 to 4:1, preferably 1.0 to 3:1, more preferably 1.05 to 2: 1.
12. The process according to any one of claims 8 to 11, wherein the volumetric space velocity of the feed of the mixed material in the fixed bed tubular reactor is between 0.2 and 3h -1 Preferably 0.6 to 2.0 hours -1 (ii) a And/or the temperature of a reaction hot spot in the fixed bed tubular reactor is 50-90 ℃, preferably 60-80 ℃; the reaction pressure is 0.2 to 1.0MPaG, preferably 0.4 to 0.7 MPaG.
13. The method according to any one of claims 8 to 12, wherein the segmented fixed bed tubular reactor exchanges heat using a heat exchange medium, and the heat exchange medium used in different segments is selected from one or more of simethicone and diathermic oil with different temperatures; the temperature of the heat exchange medium adopted at the uppermost section is 30-80 ℃, and preferably 45-65 ℃; the temperature of the heat exchange medium adopted at the uppermost section of the middle section is 40-90 ℃, and preferably 50-70 ℃; the temperature of the heat exchange medium adopted at the lowest section is 50-100 ℃, and is preferably 55-75 ℃.
14. The method according to any one of claims 8 to 13, wherein compressed nitrogen is continuously introduced during the reaction; preferably, the maximum pressure of compressed nitrogen required to supplement the system pressure is 0.1 to 1.0MPaG, more preferably 0.4 to 0.7 MPaG.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116102421A (en) * | 2023-02-10 | 2023-05-12 | 山东兴鲁承宏新材料科技有限公司 | Continuous production process of high-yield acrylic acid alkyl ester |
| CN116102421B (en) * | 2023-02-10 | 2024-03-26 | 山东兴鲁承宏新材料科技有限公司 | Continuous production process of high-yield alkyl acrylate |
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