WO2021197057A1 - 通过微反应器合成氧杂环丁烷衍生物的合成方法 - Google Patents
通过微反应器合成氧杂环丁烷衍生物的合成方法 Download PDFInfo
- Publication number
- WO2021197057A1 WO2021197057A1 PCT/CN2021/081185 CN2021081185W WO2021197057A1 WO 2021197057 A1 WO2021197057 A1 WO 2021197057A1 CN 2021081185 W CN2021081185 W CN 2021081185W WO 2021197057 A1 WO2021197057 A1 WO 2021197057A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microreactor
- oxetane
- catalyst
- synthesizing
- reaction
- Prior art date
Links
- 150000002921 oxetanes Chemical class 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000006266 etherification reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 25
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 15
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine salts Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 4
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 125000003566 oxetanyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 description 23
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000011368 organic material Substances 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HLQNHQOKIVRFLM-UHFFFAOYSA-N 3-[1-[1-(oxetan-3-yl)propoxy]propyl]oxetane Chemical compound C1OCC1C(CC)OC(CC)C1COC1 HLQNHQOKIVRFLM-UHFFFAOYSA-N 0.000 description 1
- DWFIEBGQPZWYND-UHFFFAOYSA-N 3-ethyl-3-(phenylmethoxymethyl)oxetane Chemical compound C=1C=CC=CC=1COCC1(CC)COC1 DWFIEBGQPZWYND-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
Definitions
- the present invention relates to the field of organic synthesis, in particular to a method for synthesizing oxetane derivatives through a microreactor.
- etherification reaction with halogenated organic compounds under the action of alkali can obtain a series of oxetane derivatives, which can be used as photocurable cations
- the monomers in the system are used in light-curable inks, coatings, adhesives and other fields.
- Representative products are 3-ethyl-3-[(oxiranyl-2-methoxy)methyl]oxy Etidine, bis[1-ethyl(3-oxetanyl)methyl] ether and 3-benzyloxymethyl-3-ethyloxetane.
- These oxetane products have become one of the raw materials with the most market potential in the field of cationic light curing due to their low viscosity, good dilution, fast crosslinking speed, and excellent film-forming properties.
- the main purpose of the present invention is to provide a synthetic method for synthesizing oxetane derivatives through a microreactor, so as to solve the long reaction time, cumbersome operation and the existing synthetic methods of oxetane derivatives.
- the problem of poor security While realizing continuous production, the selectivity of the etherification reaction is ensured, and the product yield is improved.
- the present invention provides a synthetic method for synthesizing oxetane derivatives through a microreactor.
- the oxetane derivatives have a structure represented by formula (I):
- R is a straight or branched C 2 ⁇ C 12 alkyl group, an alkyl group containing an ethylene oxide structure, an alkyl group containing an oxetane structure, a phenyl group, a tolyl group, a benzyl group, or a bi- Phenyl group, n is 1-4;
- the above-mentioned synthesis method for synthesizing oxetane derivatives by microreactor includes: combining 3-ethyl-3-hydroxymethyloxetane, raw material Ha, catalyst, alkali Transported to the micro-reactor for etherification reaction to obtain an etherification product system, the general formula of the raw material Ha is R-(X) n , X is a halogen; and the etherification product system is separated to obtain an oxetane derivative Things.
- the inner diameter of the reaction channel of the microreactor is 200-10000 ⁇ m.
- the alkali is an alkali metal compound or an aqueous solution of an alkali metal compound
- the alkali metal compound is selected from one or more of the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; preferably, the alkali
- the metal compound is sodium hydroxide; the concentration of the aqueous solution of the alkali metal compound is 10%-20%; the catalyst is selected from one or more of the group consisting of polyethers, cyclic polyethers and quaternary ammonium salts.
- the catalyst is selected from the group consisting of polyethylene glycol, polyethylene glycol alkyl ether, 18-crown-6, 15-crown-5, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride One or more of the group consisting of ammonium, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
- the catalyst is selected from one or more of the group consisting of polyethylene glycol dimethyl ether, 18-crown-6 and tetrabutylammonium bromide.
- the addition amount of the catalyst is 0.1 to 5%.
- the addition amount of the catalyst is 0.5-2%.
- reaction temperature of the etherification reaction is 10-60°C, and the material residence time is 2-5 min.
- the device used in the separation step includes: a two-stage thin film evaporation device or a rectification tower.
- the inner diameter of the reaction channel of the microreactor is 500-8000 ⁇ m.
- the microreactor has the advantages of high heat and mass transfer coefficient, good mixing performance, easy temperature control, and safe and controllable process.
- Using the advantages of the microreactor to prepare oxetane derivatives can greatly improve the mass and heat transfer of the reaction system, reduce the reaction time, increase production efficiency, increase product yield, and realize the continuity and automation of the process, and improve the process safety.
- Limiting the pore diameter of the reaction channel of the microreactor within the above-mentioned range is beneficial to increase the selectivity of the etherification reaction, and thus is beneficial to increase the conversion rate of the oxetane derivative.
- the reaction device required for the above synthesis process is small in size, the production site occupies a small area, the required human resources are small, and the safety is high.
- Fig. 1 shows a schematic structural diagram of an oxetane derivative preparation device according to a typical embodiment of the present invention.
- Micro mixer 11. Organic material storage tank; 12. Alkaline solution storage tank; 20. Micro reactor; 21. Buffer tank; 30. Phase separation tank; 31. Waste water storage tank; 32. Organic phase storage tank; 40. First-level thin-film evaporator; 41. Crude product storage tank; 42. Recovery material storage tank; 50. Second-level thin-film evaporator; 51. Finished product storage tank; 52. Reboil storage tank;
- this application provides a synthetic method for synthesizing oxetane derivatives through a microreactor.
- the oxetane derivatives have the structure shown in formula (I):
- R is a straight or branched C 2 ⁇ C 12 alkyl group, an alkyl group containing an ethylene oxide structure, an alkyl group containing an oxetane structure, a phenyl group, a tolyl group, a benzyl group, or a bi- Phenyl, n is 1-4;
- the synthesis method of the oxetane derivative includes: transporting 3-ethyl-3-hydroxymethyloxetane, raw material Ha, catalyst, and alkali to the microreactor
- the etherification reaction is carried out in the process to obtain an etherification product system.
- the general formula of the raw material Ha is R-(X) n , where X is a halogen; and the etherification product system is separated to obtain an oxetane derivative.
- microreactors Compared with conventional reactors, microreactors have the advantages of high heat and mass transfer coefficient, good mixing performance, easy temperature control, and safe and controllable process.
- Using the advantages of the microreactor to prepare oxetane derivatives can greatly improve the mass and heat transfer of the reaction system, reduce the reaction time, increase production efficiency, increase product yield, and realize the continuity and automation of the process, and improve the process safety.
- the reaction device required for the above synthesis process is small in size, the production site occupies a small area, the required human resources are small, and the safety is high.
- the inner diameter of the reaction channel of the microreactor is 200-10000 ⁇ m. Limiting the pore diameter of the reaction channel of the microreactor within the above range is beneficial to further increase the selectivity of the etherification reaction and further increase the conversion rate of the oxetane derivative.
- the inner diameter of the reaction channel of the microreactor is 200 ⁇ m, 500 ⁇ m, 4000 ⁇ m, 6000 ⁇ m, 8000 ⁇ m, and 10000 ⁇ m. More preferably, the inner diameter of the reaction channel of the microreactor is 500-8000 ⁇ m.
- the base is an alkali metal compound or an aqueous solution of an alkali metal compound.
- Alkali metal compounds can be selected from those commonly used in this field.
- the alkali metal compound includes but is not limited to one or more of the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; more preferably, the alkali metal compound is sodium hydroxide; The concentration of the aqueous solution of the compound is 10-20%.
- the catalyst in the above synthesis method may be of the type commonly used in the art, and the catalyst includes, but is not limited to, one or more of the group consisting of polyethers, cyclic polyethers, and quaternary amine salts.
- the catalyst includes but is not limited to polyethylene glycol, polyethylene glycol alkyl ether, 18-crown-6, 15-crown-5, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutyl
- ammonium chloride, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride are examples of the group consisting of ammonium chloride, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
- the use of the above-mentioned catalysts is beneficial to further increase the reaction rate of the etherification reaction and shorten the reaction period.
- the catalyst includes, but is not limited to, one or more of the group consisting of polyethylene glycol dimethyl ether, 18-crown-6 and tetrabutylammonium bromide.
- the added amount of the catalyst is 0.1 to 5%.
- the amount of the catalyst includes but is not limited to the above range, and limiting it within the above range is beneficial to further increase the reaction rate of the etherification reaction.
- the amount of catalyst added can be 0.1%, 0.5%, 1%, 1.5%, 2%, 3%, 4% by weight based on the weight of 3-ethyl-3-hydroxymethyloxetane. %. More preferably, the addition amount of the catalyst is 0.5-2% based on the weight percentage of the weight of 3-ethyl-3-hydroxymethyloxetane.
- the molar ratio of 3-ethyl-3-hydroxymethyloxetane to the halogen in the raw material Ha is 1: (1.0-1.2).
- the molar ratio of 3-ethyl-3-hydroxymethyloxetane to the halogen in the raw material Ha includes but is not limited to the above range, and limiting it within the above range is beneficial to increase 3-ethyl-3-hydroxymethyl Conversion rate of oxetane.
- the reaction temperature of the etherification reaction is 10-60°C, and the material residence time is 2-5 min.
- the reaction temperature and material residence time of the etherification reaction include but are not limited to the above range, and limiting it to the above range is beneficial to further increase the yield of the etherified product.
- the reaction temperature of the etherification reaction can be 10°C, 20°C, 30°C, 40°C, 50°C, 60°C.
- the above-mentioned separation step can be carried out by using devices commonly used in the art.
- the device used in the separation step includes: a two-stage thin film evaporation device or a rectification tower.
- the microreactor 20, the first-stage thin film evaporator 40, and the second-stage thin film evaporator 50 are adjusted to the set temperature, and the organic raw material feed pump 101 and the raw material feed pump 102 are turned on to make the raw materials enter the micromixer 10 for processing. Mix, stay in the microreactor 20 for a certain period of time, then enter the buffer tank 21, and take the organic phase GC to detect the conversion rate.
- phase separation tank 30 After accumulating a certain amount of material in the buffer tank 21, it enters the phase separation tank 30, stands still to separate the organic phase and the water phase, and the two phases enter the waste water storage tank 31 and the organic phase storage tank 32 respectively.
- Example 2 The difference from Example 1 is that the inner diameter of the reaction channel of the microreactor is 200 ⁇ m.
- Example 2 The difference from Example 1 is that the reaction channel size of the microreactor is 10000 ⁇ m.
- Example 2 The difference from Example 1 is that the addition amount of the catalyst is 1.0%, the catalyst is polyethylene glycol dimethyl ether, and the material residence time is 5 minutes.
- Example 1 The difference from Example 1 is: the addition amount of the catalyst is 1.0%, the catalyst is 18-crown-6, and the material residence time is 4 min.
- Example 1 The difference from Example 1 is: the addition amount of the catalyst is 1.0%, the catalyst is polyethylene glycol, and the material residence time is 4 min.
- Example 1 The difference from Example 1 is: the addition amount of the catalyst is 1.0%, the catalyst is tetradecyl trimethyl ammonium chloride, and the material residence time is 5 min.
- Example 1 The difference from Example 1 is that the reaction temperature of the etherification reaction is 30°C.
- Example 2 The difference from Example 1 is that the reaction channel size of the microreactor is 12000 ⁇ m.
- Example 1 The difference from Example 1 is that the metered amount of 3-ethyl-3-hydroxymethyloxetane (MOX101), caustic soda, and catalyst are mixed and uniformly charged into the organic material storage tank 11, and the epichlorohydrin is charged.
- the inner diameter of the reaction channel of the microreactor is 500 ⁇ m.
- Example 1 The difference from Example 1 is that the metered amount of 3-ethyl-3-hydroxymethyloxetane (MOX101), epichlorohydrin, and the catalyst are mixed and uniformly charged into the organic material storage tank 11, and the alkaline solution is charged. Into the raw material storage tank 12.
- the reaction channel size of the microreactor is 8000 ⁇ m.
- Example 1 The difference from Example 1 is that the reaction temperature of the etherification reaction is 100°C.
- Example 1 The difference from Example 1 is that the reaction temperature of the etherification reaction is 5°C.
- Example 1 The difference from Example 1 is: the addition amount of the catalyst is 0.1%, the catalyst is tetrabutylammonium bromide, and the material residence time is 5 min.
- Example 1 The difference from Example 1 is that the metered 3-ethyl-3-hydroxymethyloxetane (MOX101) and caustic soda are mixed and uniformly charged into the organic material storage tank 11, and the epichlorohydrin and the catalyst are loaded. Into the raw material storage tank 12. The addition amount of the catalyst is 5%, the catalyst is 18-crown-6, and the material residence time is 2 min.
- Example 1 The difference from Example 1 is that the metered 3-ethyl-3-hydroxymethyloxetane (MOX101) and caustic soda are mixed and uniformly charged into the organic material storage tank 11, and the epichlorohydrin and the catalyst are loaded. Into the raw material storage tank 12. The catalyst addition amount is 4%, the catalyst is tetrabutylammonium bromide, and the material residence time is 3min.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Description
Claims (10)
- 根据权利要求1所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述微反应器的反应通道内径为200~10000μm。
- 根据权利要求1所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述碱为碱金属化合物或碱金属化合物的水溶液,碱金属化合物选自氢氧化锂、氢氧化钠、氢氧化钾和氢氧化钙组成的组中的一种或多种;优选地,所述碱金属化合物为氢氧化钠;所述碱金属化合物的水溶液的浓度为10~20%;所述催化剂选自聚醚类、环状聚醚类和季胺盐类组成的组中的一种或多种。
- 根据权利要求1或2所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述催化剂选自聚乙二醇、聚乙二醇烷基醚、18-冠-6、15-冠-5、四乙基溴化铵、四丁基溴化铵、四丁基氯化铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵和十四烷基三甲基氯化铵组成的组中的一种或多种。
- 根据权利要求4所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述催化剂选自聚乙二醇二甲醚、18-冠-6和四丁基溴化铵组成的组中的一种或多种。
- 根据权利要求1至5中任一项所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,以占所述3-乙基-3-羟甲基氧杂环丁烷重量的重量百分含量计,所述催化剂添加量为0.1~5%。
- 根据权利要求6所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,以占所述3-乙基-3-羟甲基氧杂环丁烷重量的重量百分含量计,所述催化剂添加量为0.5~2%。
- 根据权利要求1所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述醚化反应的反应温度为10~60℃,物料停留时间为2~5min。
- 根据权利要求8所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述分离的步骤采用的装置包括:二级薄膜蒸发装置或精馏塔。
- 根据权利要求1所述的通过微反应器合成氧杂环丁烷衍生物的合成方法,其特征在于,所述微反应器的反应通道内径为500~8000μm。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022560041A JP2023520477A (ja) | 2020-04-03 | 2021-03-16 | オキセタン誘導体をマイクロ反応器により合成する合成方法 |
KR1020227037912A KR20220161446A (ko) | 2020-04-03 | 2021-03-16 | 마이크로 반응기를 통해 옥세탄 유도체를 합성하는 합성 방법 |
US17/913,671 US20230116611A1 (en) | 2020-04-03 | 2021-03-16 | Synthesis method for synthesizing oxetane derivative by microreactor |
EP21780711.4A EP4112610A4 (en) | 2020-04-03 | 2021-03-16 | SYNTHESIS PROCESS FOR THE SYNTHESIS OF AN OXETONE DERIVATIVE USING A MICROREACTOR |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010261424 | 2020-04-03 | ||
CN202010261424.9 | 2020-04-03 | ||
CN202110184195.XA CN113493427A (zh) | 2020-04-03 | 2021-02-10 | 通过微反应器合成氧杂环丁烷衍生物的合成方法 |
CN202110184195.X | 2021-02-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021197057A1 true WO2021197057A1 (zh) | 2021-10-07 |
Family
ID=77927690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/081185 WO2021197057A1 (zh) | 2020-04-03 | 2021-03-16 | 通过微反应器合成氧杂环丁烷衍生物的合成方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230116611A1 (zh) |
EP (1) | EP4112610A4 (zh) |
JP (1) | JP2023520477A (zh) |
KR (1) | KR20220161446A (zh) |
TW (1) | TWI807290B (zh) |
WO (1) | WO2021197057A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114262310A (zh) * | 2021-12-27 | 2022-04-01 | 山东广浦生物科技有限公司 | 双(1-2(3-氧杂环丁基)甲基)醚的制备方法 |
CN114957168A (zh) * | 2022-05-17 | 2022-08-30 | 大连天源基化学有限公司 | 一种3,3′-(氧基双亚甲基)双(3-乙基)氧杂环丁烷及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5750590A (en) * | 1995-02-22 | 1998-05-12 | Heraeus Kulzer Gmbh | Polymerizable material |
JP2000086646A (ja) * | 1998-09-11 | 2000-03-28 | Toagosei Co Ltd | ビス(3−アルキルオキセタン−3−イルメチル)エーテルの製造方法 |
JP2002138084A (ja) * | 2000-11-01 | 2002-05-14 | Toagosei Co Ltd | 3−アルキル−3−ヒドロキシメチルオキセタンを原料とするエーテル類の製造方法 |
WO2004106314A1 (ja) * | 2003-05-28 | 2004-12-09 | Ube Industries, Ltd. | オキセタン環含有ビフェニル化合物の製造方法 |
JP2007217471A (ja) * | 2006-02-14 | 2007-08-30 | Fujifilm Corp | カチオン重合性組成物、並びにこれを用いた画像形成方法および記録物 |
CN104876807A (zh) * | 2015-05-19 | 2015-09-02 | 安徽生源化工有限公司 | 羟基苯醚(iii)的合成工艺 |
CN104892549A (zh) * | 2015-04-20 | 2015-09-09 | 南昌大学 | 一种可用于紫外光固化的烯丙基氧杂环丁烷类化合物的合成方法 |
CN110845643A (zh) * | 2018-08-21 | 2020-02-28 | 常州强力电子新材料股份有限公司 | 可能量固化的环氧接枝改性的氯磺化聚乙烯树脂、含有其的可能量固化组合物及应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1021858B (de) * | 1956-12-14 | 1958-01-02 | Bayer Ag | Verfahren zur Herstellung aromatischer Oxacyclobutanderivate |
US5463084A (en) * | 1992-02-18 | 1995-10-31 | Rensselaer Polytechnic Institute | Photocurable silicone oxetanes |
JP3508502B2 (ja) * | 1997-09-30 | 2004-03-22 | 宇部興産株式会社 | オキセタン環を有するビフェニル誘導体 |
EP1719769B1 (en) * | 2004-02-23 | 2011-10-05 | Nippon Steel Chemical Co., Ltd. | Process for producing alicyclic oxetane compound |
WO2010032712A1 (ja) * | 2008-09-20 | 2010-03-25 | 国立大学法人長岡技術科学大学 | マイクロリアクター |
JP5683796B2 (ja) * | 2009-07-13 | 2015-03-11 | 株式会社Kri | 微小構造体の製造方法およびマイクロリアクター |
JP2017133039A (ja) * | 2017-05-10 | 2017-08-03 | Dic株式会社 | 重合体の製造方法 |
-
2021
- 2021-03-16 JP JP2022560041A patent/JP2023520477A/ja active Pending
- 2021-03-16 EP EP21780711.4A patent/EP4112610A4/en active Pending
- 2021-03-16 KR KR1020227037912A patent/KR20220161446A/ko not_active Application Discontinuation
- 2021-03-16 WO PCT/CN2021/081185 patent/WO2021197057A1/zh unknown
- 2021-03-16 US US17/913,671 patent/US20230116611A1/en active Pending
- 2021-04-01 TW TW110112178A patent/TWI807290B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5750590A (en) * | 1995-02-22 | 1998-05-12 | Heraeus Kulzer Gmbh | Polymerizable material |
JP2000086646A (ja) * | 1998-09-11 | 2000-03-28 | Toagosei Co Ltd | ビス(3−アルキルオキセタン−3−イルメチル)エーテルの製造方法 |
JP2002138084A (ja) * | 2000-11-01 | 2002-05-14 | Toagosei Co Ltd | 3−アルキル−3−ヒドロキシメチルオキセタンを原料とするエーテル類の製造方法 |
WO2004106314A1 (ja) * | 2003-05-28 | 2004-12-09 | Ube Industries, Ltd. | オキセタン環含有ビフェニル化合物の製造方法 |
JP2007217471A (ja) * | 2006-02-14 | 2007-08-30 | Fujifilm Corp | カチオン重合性組成物、並びにこれを用いた画像形成方法および記録物 |
CN104892549A (zh) * | 2015-04-20 | 2015-09-09 | 南昌大学 | 一种可用于紫外光固化的烯丙基氧杂环丁烷类化合物的合成方法 |
CN104876807A (zh) * | 2015-05-19 | 2015-09-02 | 安徽生源化工有限公司 | 羟基苯醚(iii)的合成工艺 |
CN110845643A (zh) * | 2018-08-21 | 2020-02-28 | 常州强力电子新材料股份有限公司 | 可能量固化的环氧接枝改性的氯磺化聚乙烯树脂、含有其的可能量固化组合物及应用 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4112610A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114262310A (zh) * | 2021-12-27 | 2022-04-01 | 山东广浦生物科技有限公司 | 双(1-2(3-氧杂环丁基)甲基)醚的制备方法 |
CN114957168A (zh) * | 2022-05-17 | 2022-08-30 | 大连天源基化学有限公司 | 一种3,3′-(氧基双亚甲基)双(3-乙基)氧杂环丁烷及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP4112610A1 (en) | 2023-01-04 |
JP2023520477A (ja) | 2023-05-17 |
EP4112610A4 (en) | 2024-04-10 |
TWI807290B (zh) | 2023-07-01 |
US20230116611A1 (en) | 2023-04-13 |
KR20220161446A (ko) | 2022-12-06 |
TW202138358A (zh) | 2021-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021197057A1 (zh) | 通过微反应器合成氧杂环丁烷衍生物的合成方法 | |
CN110655645B (zh) | 强碱性阴离子交换树脂在制备端羟基聚醚季铵盐中的应用 | |
CN106243344B (zh) | 一种环氧基封端聚醚连续开环生产工艺 | |
CN104230724A (zh) | 一种二乙醇单异丙醇胺的制备方法 | |
NO132579B (zh) | ||
CN110305237B (zh) | 一种链转移剂、其制备方法及应用 | |
CN104592166B (zh) | 一种烯丙基缩水甘油醚的分子筛固载催化合成方法 | |
CN115785028B (zh) | 一种高环氧值腰果酚缩水甘油醚的制备方法 | |
CN108250428B (zh) | 一种梳型多亲水链松香嵌段聚醚磺酸盐及其制备方法 | |
CN106366090A (zh) | α‑松油醇合成1,8‑桉叶素的方法 | |
EP2964619B1 (en) | Process for the preparation of triazine carbamates | |
CN102766156A (zh) | 四甲基二乙烯基二硅氮烷的制备方法 | |
CN105348029A (zh) | 一种对二甲苯环二体的制备方法 | |
CN101525320A (zh) | 3,4-环氧基环己基甲酸-3’,4’-环氧基环己基甲酯的制备方法 | |
CN113493427A (zh) | 通过微反应器合成氧杂环丁烷衍生物的合成方法 | |
CN105585451B (zh) | 一种环戊烯直接水合制备环戊醇的方法 | |
CN110655479A (zh) | 一种微反应器合成bp-4的方法 | |
JP7438391B2 (ja) | マイクロ反応器によってオキセタン化合物を合成する方法 | |
CN104496739A (zh) | 二苯甲烷的绿色催化合成方法 | |
CN102924407A (zh) | 一种一元羧酸缩水甘油酯的精制方法 | |
CN106278914A (zh) | 一种增产胺的合成工艺 | |
CN103288641B (zh) | 一种甲基丙烯酸羟丙酯的合成方法 | |
CN104961617A (zh) | 一种姥鲛烷的合成方法 | |
CN102212044B (zh) | 一种氧杂环丁烷类化合物的合成方法 | |
CN111100053B (zh) | 二硒醚及其制备方法、含硒表面活性剂及其制备方法、用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21780711 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022560041 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2021780711 Country of ref document: EP Effective date: 20220923 |
|
ENP | Entry into the national phase |
Ref document number: 20227037912 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |