CN111892616A - Synthesis method of trimethylene borate - Google Patents
Synthesis method of trimethylene borate Download PDFInfo
- Publication number
- CN111892616A CN111892616A CN201910367804.8A CN201910367804A CN111892616A CN 111892616 A CN111892616 A CN 111892616A CN 201910367804 A CN201910367804 A CN 201910367804A CN 111892616 A CN111892616 A CN 111892616A
- Authority
- CN
- China
- Prior art keywords
- trimethylene borate
- borate
- boric acid
- trimethylene
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- JKYPBYBOZSIRFW-UHFFFAOYSA-N 3-(4-chlorophenyl)oxolane-2,5-dione Chemical compound C1=CC(Cl)=CC=C1C1C(=O)OC(=O)C1 JKYPBYBOZSIRFW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 9
- 229940035437 1,3-propanediol Drugs 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 8
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
A synthesis method of trimethylene borate belongs to the technical field of battery electrolyte additives, and comprises the steps of taking 1, 3-propylene glycol and boric acid as raw materials, adding 1, 3-propylene glycol, boric acid and hydrocarbons under the condition of argon, heating to a reflux temperature, stirring until water is brought out, cooling, drying, removing a solvent by reduced pressure distillation at 60 ℃ to obtain a crude trimethylene borate product, and rectifying to obtain a pure trimethylene borate product. The raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, the reaction conditions are mild and stable, the three wastes are less, the energy consumption is low, and the product yield is high and can reach more than 94%.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte additives, relates to a method for synthesizing trimethylene borate by using trimethylene borate as a battery electrolyte additive, and particularly relates to a method for synthesizing trimethylene borate.
Background
With the wide application of 4G mobile phones, tablet computers, electric vehicles and other devices, the battery is required to support longer-time operation, and higher requirements are provided for the endurance of the lithium ion battery. Therefore, increasing the specific energy density of lithium ion batteries has become one of the problems to be solved urgently. As is known from research, increasing the operating voltage of a lithium ion battery is considered to be one of the most effective methods for increasing the energy density of the lithium ion battery.
Boron-containing compounds are often applied to lithium ion batteries of different anode materials as additives, and in the battery cycle process, a protective film is formed on the surface of an anode by a plurality of boron-containing compounds to stabilize the interface between an electrode and electrolyte, so that the battery performance is improved. The trimethylene borate has a remarkable effect, and can meet the performance requirements of the lithium ion battery under high voltage and high and low temperature conditions. However, in the existing synthesis technology of trimethylene borate, the problems of complex process, difficulty in realizing industrial production, high cost, low product yield and the like exist in the synthesis process, so that the research on the synthesis method of trimethylene borate has great practical significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing trimethylene borate, which is simple, cheap and easily available in raw materials, mild and stable in reaction conditions, and high in yield and purity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the synthesis method of the trimethylene borate comprises the steps of adopting 1, 3-propylene glycol and boric acid as raw materials, adding the 1, 3-propylene glycol, the boric acid and hydrocarbons under the condition of argon, heating to the reflux temperature, stirring until water is brought out, cooling, drying, removing the solvent by vacuum distillation at 60 ℃ to obtain a crude trimethylene borate product, and rectifying to obtain a pure trimethylene borate product.
The molar ratio of boric acid to 1, 3-propanediol is 2: (3-8).
The hydrocarbon is selected from hydrocarbons which form azeotropes with water.
The hydrocarbon is selected from benzene, toluene or dichlorotoluene.
After cooling, the mixture was dried over anhydrous sodium sulfate.
The crude product of the trimethylene borate is rectified under reduced pressure at the temperature of 100-110 ℃ to obtain the pure product of the trimethylene borate.
The invention has the beneficial effects that:
the raw materials used in the invention are cheap and easily available, the synthesis method is simple and easy to operate, the reaction conditions are mild and stable, the three wastes are less, the energy consumption is low, and the product yield is high and can reach more than 94%.
Drawings
FIG. 1 is a 1H map of the present invention for the synthesis of trimethylene borate.
FIG. 2 is a 13C map of the present invention for the synthesis of trimethylene borate.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1000mL of argon gas was introduced into a four-necked flask to displace the gas therein, and 36.00g of 1, 3-propanediol, 15.46g of boric acid and 250mL of benzene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 20g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain a crude product of the trimethylene borate. The crude trimethylene borate was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 28.65g of colorless liquid trimethylene borate (yield 94%).
The colorless liquid obtained above was measured to have a density of 1.153g/mL and a boiling point of 146 deg.C (normal pressure), and its purity was measured to be 99.8%.
Example 2
1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then 23g of 1, 3-propanediol, 12.4g of boric acid and 250mL of toluene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 20g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain a crude product of the trimethylene borate. The crude trimethylene borate was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 23.22g of a colorless liquid trimethylene borate (yield 95.3%).
The colorless liquid obtained above was measured to have a density of 1.154g/mL and a boiling point of 145 deg.C (normal pressure), and its purity was determined to be 99.82%.
Example 3
First, 1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then 30.4g of 1, 3-propanediol, 12.4g of boric acid and 250mL of dichlorotoluene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 20g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain a crude product of the trimethylene borate. The crude trimethylene borate was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 23.4g of a colorless liquid trimethylene borate (yield 96.1%).
The colorless liquid obtained above was measured to have a density of 1.151g/mL and a boiling point of 147 deg.C (normal pressure), and its purity was found to be 99.76%.
Example 4
1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then 38g of 1, 3-propanediol, 12.4g of boric acid and 250mL of toluene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 20g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain a crude product of the trimethylene borate. The crude trimethylene borate thus obtained was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 23.07g of a colorless liquid trimethylene borate (yield 94.7%).
The colorless liquid obtained above was measured to have a density of 1.156g/mL and a boiling point of 148 ℃ at normal pressure, and the purity thereof was found to be 99.83%.
Example 5
First, 1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then, 45.6g of 1, 3-propanediol, 12.4g of boric acid and 300mL of dichlorotoluene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 25g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain the crude product of the trimethylene borate. The crude trimethylene borate was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to obtain 23.68g of colorless liquid trimethylene borate (yield 97.2%).
The colorless liquid obtained above was measured to have a density of 1.155g/mL and a boiling point of 146 deg.C (normal pressure), and its purity was determined to be 99.81%.
Example 6
First, 1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then 53.2g of 1, 3-propanediol, 12.4g of boric acid and 330mL of benzene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 25g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain the crude product of the trimethylene borate. The crude trimethylene borate was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 23.58g of a colorless liquid trimethylene borate (yield 96.8%).
The colorless liquid obtained above was measured to have a density of 1.154g/mL and a boiling point of 147 deg.C (normal pressure), and its purity was determined to be 99.78%.
Example 7
1000mL of argon was introduced into a four-necked flask to displace the inside gas, and then 60.8g of 1, 3-propanediol, 12.4g of boric acid and 350mL of toluene were added thereto, and the mixture was heated to reflux temperature and stirred until water was taken out. After cooling, 25g of anhydrous sodium sulfate is added for drying, and the solvent is removed by reduced pressure distillation at 60 ℃ to obtain the crude product of the trimethylene borate. The crude trimethylene borate thus obtained was subjected to rectification under reduced pressure at 100 ℃ and 110 ℃ to give 23.24g of a colorless liquid trimethylene borate (yield 95.4%).
The colorless liquid obtained above was measured to have a density of 1.157g/mL and a boiling point of 146 deg.C (normal pressure), and its purity was 99.73%.
The product is detected by a gas phase method, and is characterized by 1H-NMR and 13C-NMR to be identified as the trimethylene borate, and the reference is made to figure 1 and figure 2.
Claims (6)
1. The synthesis method of the trimethylene borate adopts 1, 3-propylene glycol and boric acid as raw materials, and is characterized in that under the condition of argon, 1, 3-propylene glycol, boric acid and hydrocarbons are added, the temperature is raised to the reflux temperature, the stirring is carried out until water is removed, the cooling and drying are carried out, the solvent is removed by vacuum distillation at the temperature of 60 ℃ to obtain a crude trimethylene borate product, and the crude trimethylene borate product is obtained by rectification.
2. The method of synthesizing trimethylene borate of claim 1, wherein the molar ratio of boric acid to 1, 3-propanediol is 2: (3-8).
3. The method of synthesizing trimethylene borate of claim 1, wherein the hydrocarbon is selected from the group consisting of hydrocarbons that form azeotropes with water.
4. The method of claim 3, wherein the hydrocarbon is selected from the group consisting of benzene, toluene and dichlorotoluene.
5. The method of synthesizing trimethylene borate according to claim 1, wherein the cooled product is dried over anhydrous sodium sulfate.
6. The method as claimed in claim 1, wherein the crude trimethylene borate is further rectified under reduced pressure at 100-110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367804.8A CN111892616A (en) | 2019-05-05 | 2019-05-05 | Synthesis method of trimethylene borate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367804.8A CN111892616A (en) | 2019-05-05 | 2019-05-05 | Synthesis method of trimethylene borate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111892616A true CN111892616A (en) | 2020-11-06 |
Family
ID=73169170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910367804.8A Withdrawn CN111892616A (en) | 2019-05-05 | 2019-05-05 | Synthesis method of trimethylene borate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111892616A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232103A (en) * | 2022-08-03 | 2022-10-25 | 四平市精细化学品有限公司 | Preparation method of cyclic sulfate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120289733A1 (en) * | 2011-05-11 | 2012-11-15 | Anderson Development Company | Novel borate derivatives and their applications |
-
2019
- 2019-05-05 CN CN201910367804.8A patent/CN111892616A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120289733A1 (en) * | 2011-05-11 | 2012-11-15 | Anderson Development Company | Novel borate derivatives and their applications |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232103A (en) * | 2022-08-03 | 2022-10-25 | 四平市精细化学品有限公司 | Preparation method of cyclic sulfate |
| CN115232103B (en) * | 2022-08-03 | 2023-09-29 | 四平市精细化学品有限公司 | Preparation method of cyclic sulfate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7060846B2 (en) | Pentafluorosulfanyl-substituted thienothiophene monomers and conducting polymers | |
| KR102144626B1 (en) | A method for synthesis of benzene sulfonate derivatives | |
| CN102779649A (en) | Preparation method of thin layer graphene polymer composite material | |
| CN111892616A (en) | Synthesis method of trimethylene borate | |
| CN109912621B (en) | Asymmetric naphthalene nucleus small molecule receptor material and preparation method and application thereof | |
| CN104744674B (en) | Polyoxy nitrogen free radical derivative containing polypyrrole skeleton, its application and by its obtained lithium ion battery | |
| CN109206437B (en) | Organic hole transport material with tetrathienopyrrole as core and preparation and application thereof | |
| CN110105375A (en) | Give-by-to type Uniformpoly thiophene derivative and preparation method thereof to-by-using dithieno pyrroles as molecular center | |
| CN112625062B (en) | Electrolyte additive, electrolyte containing additive and lithium ion battery | |
| Yin et al. | Synthesis and characterization of symmetrical sulfur-fused polycyclic aromatic hydrocarbons with controlled shapes | |
| CN104926861A (en) | Preparation method of tris(trimethylsilyl)phosphate ester | |
| CN109503653B (en) | Synthesis method of tri (trihydrocarbylsilyl) phosphate | |
| CN108711624A (en) | More carbonyl azacyclo- organic compounds of organic positive electrode for lithium battery and preparation method thereof | |
| CN109608362A (en) | Hexafluoropropylene trimer is cracked to form the method and perfluor isobutyronitrile and application of perfluor isobutyronitrile | |
| CN101870707A (en) | Method for synthesizing and purifying tris (trimethylsilyl) borate suitable for serving as electrolyte additive | |
| CN111892620A (en) | Synthesis method of diphenyl difluorosilane | |
| CN109776593B (en) | Preparation method of 1, 3-dimethyl-1, 3-tetraethylenedisiloxane | |
| CN103012047A (en) | Simple synthesis method of benzophenanthrene | |
| CN110511235B (en) | Oxygen group element fused perylene diimide acceptor material and preparation method and application thereof | |
| Cakmak et al. | Synthesis and characterization of conducting and non-conducting polymers of sodium 2, 4, 6-trichlorophenolate by microwave initiation | |
| CN112876658A (en) | Dithienopyrrole-based polymer and preparation method and application thereof | |
| CN110526246A (en) | A kind of synthetic method vulcanizing silicon powder | |
| CN111925389A (en) | Trisilyl-containing propinyl phosphate compound and preparation method and application thereof | |
| CN109712822A (en) | Based on four p-hydroxybenzene manganoporphyrins-phthalic acid ester supercapacitor | |
| CN104250364A (en) | Zwitterionic amino polyfluorene derivative and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201106 |
|
| WW01 | Invention patent application withdrawn after publication |