CN112812079A - Synthesis method of hexafluoroisopropyl glycidyl ether - Google Patents
Synthesis method of hexafluoroisopropyl glycidyl ether Download PDFInfo
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- CN112812079A CN112812079A CN202011561433.6A CN202011561433A CN112812079A CN 112812079 A CN112812079 A CN 112812079A CN 202011561433 A CN202011561433 A CN 202011561433A CN 112812079 A CN112812079 A CN 112812079A
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- glycidyl ether
- hexafluoroisopropanol
- hexafluoroisopropyl
- hexafluoroisopropyl glycidyl
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
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- C07D301/00—Preparation of oxiranes
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Abstract
The invention relates to the technical field of fluorine-containing monomers, in particular to a method for synthesizing hexafluoroisopropyl glycidyl ether. The synthesis method of hexafluoroisopropyl glycidyl ether comprises the following steps: (1) adding alkali into hexafluoroisopropanol to react, and distilling the reaction solution under reduced pressure after the reaction is finished until no fraction is generated to obtain hexafluoroisopropanol salt; (2) reacting hexafluoroisopropanol with epoxy chloropropane, and performing suction filtration on a reaction solution after the reaction is finished to obtain a hexafluoroisopropyl glycidyl ether crude product; (3) and purifying the hexafluoroisopropyl glycidyl ether crude product to obtain hexafluoroisopropyl glycidyl ether. The synthesis method of hexafluoroisopropyl glycidyl ether has the advantages of simple synthesis route, high product yield and high purity.
Description
Technical Field
The invention relates to the technical field of fluorine-containing monomers, in particular to a method for synthesizing hexafluoroisopropyl glycidyl ether.
Background
The fluorine-containing glycidyl ether is an important fluorine-containing intermediate, can be used as a functional additive of epoxy resin, and can also be subjected to ring-opening polymerization to form fluorine-containing polyol so as to prepare fluorine-containing polyurethane.
Patent CN102898567A discloses a method for obtaining a fluorine-containing epoxy resin monomer by Micheal addition of fluorine-containing (meth) acrylate and malonate under alkaline conditions and then ester exchange reaction with epoxypropanol. A new fluorine-containing glycidyl ether monomer is synthesized by reacting epichlorohydrin with tetrafluoropropanol in Duch waves and the like (Duch, Scheiwei, Duch and the like; synthesis and characterization of fluorine-containing glycidyl ether; national high polymer materials science and engineering research and research institute in 2006, 2006), so that the coating achieves good anti-pollution and anti-corrosion properties. Chenshiwu et al (Chenshiwu, Likaebei, Xushihong; research on synthesis of fluorocarbon polyether monomer-1, 1,5 trihydrooctafluoropentyl glycidyl ether; energetic material; 1999.7(1):5) synthesized octafluoropentyl glycidyl ether and polymerized into fluorine-containing polyol to prepare polyurethane adhesive. Royal loyalty and the like (royal loyalty, laevo limonite; synthesis and characterization of fluorine-containing glycidyl ether; novel chemical material 2008(08):70-71) adopts dodecafluoroheptanol and epoxy chloropropane to synthesize dodecafluoroheptyl glycidyl ether by a two-step method of etherification and ring closure.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a synthesis method of hexafluoroisopropyl glycidyl ether, which has the advantages of simple synthesis route, high product yield and high purity.
The synthesis method of hexafluoroisopropanol glycidyl ether provided by the invention comprises the steps of preparing hexafluoroisopropanol salt by using hexafluoroisopropanol and alkali as raw materials, and preparing hexafluoroisopropanol glycidyl ether by using hexafluoroisopropanol salt and epoxy chloropropane as raw materials.
Specifically, the synthesis method of hexafluoroisopropyl glycidyl ether comprises the following steps:
(1) adding alkali into hexafluoroisopropanol to react, and distilling the reaction solution under reduced pressure after the reaction is finished until no fraction is generated to obtain hexafluoroisopropanol salt;
(2) reacting hexafluoroisopropanol with epoxy chloropropane, and performing suction filtration on a reaction solution after the reaction is finished to obtain a hexafluoroisopropyl glycidyl ether crude product;
(3) and purifying the hexafluoroisopropyl glycidyl ether crude product to obtain hexafluoroisopropyl glycidyl ether.
Wherein the alkali is NaOH, NaH, KOH, Na2CO3、K2CO3、CH3CH2One of ONa.
When preparing hexafluoroisopropanol salt, preparing hexafluoroisopropanol by adopting an excess method, wherein the molar ratio of hexafluoroisopropanol to alkali is 1.5-10: 1; preferably 2.5-6: 1. The excess hexafluoroisopropanol may be removed by distillation or the like.
In the preparation of hexafluoroisopropyl glycidyl ether, the preparation is carried out by an epichlorohydrin excess method, and the molar ratio of epichlorohydrin to sodium hexafluoroisopropoxide is 1.1-5:1, preferably 1.6-3: 1.
In the step (1), the reaction temperature is 25-100 ℃, preferably 50-70 ℃; the reaction time is 2-8h, preferably 3-5 h.
In the step (2), the reaction temperature is 30-100 ℃, preferably 50-90 ℃; the reaction time is 3 to 12 hours, preferably 6 to 10 hours.
In the step (2), hexafluoroisopropanol or water is added into a reaction system to promote the reaction, and the molar ratio of the hexafluoroisopropanol or water to the sodium hexafluoroisopropanol is 0.1-1.5: 1.
And (3) purifying the hexafluoroisopropyl glycidyl ether crude product by adopting filtering, extracting and distilling operations. The filtration adopts suction filtration, a G5 sand core funnel can be used, and the filter cake is not washed; and extracting the filtrate after suction filtration with water, and then distilling, preferably distilling under reduced pressure, wherein the temperature of a heating source is controlled to be 60-130 ℃, and the operating pressure is 0-80 kPa.
Taking the synthesis of sodium hexafluoroisopropoxide first and then hexafluoroisopropyl glycidyl ether as an example, the synthesis route is as follows:
compared with the prior art, the invention has the following beneficial effects:
according to the invention, hexafluoroisopropanol and alkali are used as raw materials to prepare hexafluoroisopropanol salt, and hexafluoroisopropanol salt and epoxy chloropropane are used as raw materials to prepare hexafluoroisopropyl glycidyl ether, so that the synthesis route is simple, the product yield is high, and the purity is high.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of hexafluoroisopropyl glycidyl ether prepared in example 7 of the present invention;
FIG. 2 is a nuclear magnetic fluorine spectrum of hexafluoroisopropyl glycidyl ether prepared in example 7 of the present invention;
FIG. 3 is an IR spectrum of hexafluoroisopropyl glycidyl ether prepared in example 7 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Preparation of sodium hexafluoroisopropoxide: 320g hexafluoroisopropanol was added to a 250mL round bottom flask, then 37g NaOH was added in portions with stirring, and the reaction was carried out at 50 ℃ for 3 hours. And then carrying out reduced pressure distillation on the reaction liquid, controlling the temperature of a heating source at 80 ℃ and the operation pressure at 0kPa until no fraction is generated, and drying the obtained solid at 70 ℃ for 6h to obtain the sodium hexafluoroisopropoxide with the yield of 98.4%.
Example 2
Preparation of sodium hexafluoroisopropoxide: a250 mL round-bottom flask was charged with 400g hexafluoroisopropanol, then 37g NaOH was added in portions with stirring, and reacted at 40 ℃ for 5 hours. And then carrying out reduced pressure distillation on the reaction liquid, controlling the temperature of a heating source at 100 ℃ and the operating pressure at 40kPa until no fraction is generated, and drying the obtained solid at 70 ℃ for 6h to obtain the sodium hexafluoroisopropoxide with the yield of 99.2%.
Example 3
Preparation of sodium hexafluoroisopropoxide: 175g hexafluoroisopropanol was added to a 250mL round bottom flask, followed by 50g CH in portions with stirring3CH2ONa, reaction at 70 ℃ for 4 h. Then carrying out reduced pressure distillation on the reaction liquid, controlling the temperature of a heating source at 80 ℃ and the operation pressure at 80kPa until no fraction is generated, and drying the obtained solid at 70 ℃ for 6h to obtain hexafluoroisopropylSodium alcoholate, yield 99.7%.
Example 4
Preparation of hexafluoroisopropyl glycidyl ether: adding 17G of epoxy chloropropane and 22G of sodium hexafluoroisopropoxide into a 100mL round-bottom flask, reacting in a 70 ℃ water bath for 8 hours, carrying out suction filtration on a reaction solution by using a G5 sand core funnel to realize liquid-solid separation, using water-soluble substances in a water extraction liquid phase, carrying out reduced pressure distillation on an organic phase after liquid separation, controlling the temperature of a heating source at 100 ℃, and carrying out vacuum pumping by using a water pump, wherein the yield of a target product, namely hexafluoroisopropyl glycidyl ether, is 26%.
Example 5
Preparation of hexafluoroisopropyl glycidyl ether: adding 35G of epoxy chloropropane, 60G of sodium hexafluoroisopropanol and 9G of hexafluoroisopropanol into a 250mL round-bottom flask, reacting in a water bath at 70 ℃, wherein the reaction time is 8h, performing suction filtration on a reaction liquid by using a G5 sand core funnel to realize liquid-solid separation, performing reduced pressure distillation on an organic phase by using water-soluble substances in a water extraction liquid phase after liquid separation, controlling the temperature of a heating source at 120 ℃, and performing vacuum pumping by using a water pump, wherein the yield of a target product, namely hexafluoroisopropyl glycidyl ether, is 45%.
Example 6
Preparation of hexafluoroisopropyl glycidyl ether: adding 35G of epoxy chloropropane, 60G of sodium hexafluoroisopropanol and 9G of hexafluoroisopropanol into a 250mL round-bottom flask, reacting in a water bath at 70 ℃, wherein the reaction time is 8h, carrying out suction filtration on a reaction liquid by using a G5 sand core funnel to realize liquid-solid separation, then carrying out reduced pressure distillation on a liquid phase, controlling the temperature of a heating source at 80 ℃, and carrying out vacuum pumping by using a water pump, wherein the yield of a target product hexafluoroisopropyl glycidyl ether is 38%.
Example 7
Preparation of hexafluoroisopropyl glycidyl ether: adding 23g of epoxy chloropropane, 40g of sodium hexafluoroisopropoxide and 3.8g of deionized water into a 250mL round-bottom flask, reacting in a water bath at 80 ℃, wherein the reaction time is 6h, centrifuging the reaction solution at the rotating speed of 5000r/min for 8min to realize liquid-solid separation, using water-soluble substances in a water extraction liquid phase, carrying out reduced pressure distillation on an organic phase after liquid separation, controlling the temperature of a heating source at 90 ℃, and vacuumizing by using a water pump, wherein the yield of a target product, namely hexafluoroisopropyl glycidyl ether, is 36%.
The nuclear magnetic hydrogen spectrum of the target product hexafluoroisopropyl glycidyl ether is shown in figure 1, the nuclear magnetic fluorine spectrum is shown in figure 2, and the infrared spectrum is shown in figure 3.
In FIG. 1, 1H NMR (400MHz) delta 4.38 to 4.29(1H, H, H-C (CF)3)2-),4.21～4.18(1H,q,-C-O-CH2-),3.64～3.60(1H,m,-C-O-CH2-),3.24～3.20(1H,m,-CH-O-)，2.84～2.82(1H,t,-O-CH2-)，2.60～2.58(1H,q,-O-CH2-)。
In FIG. 2, IR (. nu.max) (cm-1) 3068,3013,2942,2895 (. nu.C-H), 1375 (. sigma.C-H), 1291, 1196, 1104 (. nu.C-F), 1005,899 (C-O).
Claims (9)
1. A method for synthesizing hexafluoroisopropyl glycidyl ether is characterized in that: firstly, hexafluoroisopropanol and alkali are used as raw materials to prepare hexafluoroisopropanol salt, and then hexafluoroisopropanol salt and epoxy chloropropane are used as raw materials to prepare hexafluoroisopropyl glycidyl ether.
2. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 1, characterized in that: the method comprises the following steps:
(1) adding alkali into hexafluoroisopropanol to react, and distilling the reaction solution under reduced pressure after the reaction is finished until no fraction is generated to obtain hexafluoroisopropanol salt;
(2) reacting hexafluoroisopropanol with epoxy chloropropane, and performing suction filtration on a reaction solution after the reaction is finished to obtain a hexafluoroisopropyl glycidyl ether crude product;
(3) and purifying the hexafluoroisopropyl glycidyl ether crude product to obtain hexafluoroisopropyl glycidyl ether.
3. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 1 or 2, characterized in that: the alkali is NaOH, NaH, KOH or Na2CO3、K2CO3、CH3CH2One of ONa.
4. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 1 or 2, characterized in that: the molar ratio of hexafluoroisopropanol to base is 1.5-10: 1.
5. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 1 or 2, characterized in that: the mol ratio of the epichlorohydrin to the sodium hexafluoroisopropoxide is 1.1-5: 1.
6. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 2, characterized in that: in the step (1), the reaction temperature is 25-100 ℃, and the reaction time is 2-8 h.
7. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 2, characterized in that: in the step (2), the reaction temperature is 30-100 ℃, and the reaction time is 3-12 h.
8. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 2, characterized in that: in the step (2), hexafluoroisopropanol or water is added into a reaction system, and the molar ratio of the hexafluoroisopropanol or water to the hexafluoroisopropanol sodium is 0.1-1.5: 1.
9. The method for synthesizing hexafluoroisopropyl glycidyl ether according to claim 2, characterized in that: and (3) purifying the hexafluoroisopropyl glycidyl ether crude product by adopting filtering, extracting and distilling operations.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115043794A (en) * | 2022-06-10 | 2022-09-13 | 杭州宝明新材料科技有限公司 | Preparation method of allyl fluorine-containing glycidyl ether |
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Application publication date: 20210518 |