CN113444119A - Synthesis of carbonate-modified siloxane-based additives - Google Patents
Synthesis of carbonate-modified siloxane-based additives Download PDFInfo
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- CN113444119A CN113444119A CN202010226856.6A CN202010226856A CN113444119A CN 113444119 A CN113444119 A CN 113444119A CN 202010226856 A CN202010226856 A CN 202010226856A CN 113444119 A CN113444119 A CN 113444119A
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- modified siloxane
- carbonate
- reactant
- mixed solution
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 238000005194 fractionation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 5
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical group C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 5
- 239000001632 sodium acetate Substances 0.000 claims abstract description 5
- QNWOFLWXQGHSRH-UHFFFAOYSA-N trimethyl-[methyl(trimethylsilyloxy)silyl]oxysilane Chemical group C[Si](C)(C)O[SiH](C)O[Si](C)(C)C QNWOFLWXQGHSRH-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- UBYRBSCRCKTBDD-UHFFFAOYSA-N 4-prop-2-enyl-1,3-dioxolan-2-one Chemical compound C=CCC1COC(=O)O1 UBYRBSCRCKTBDD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/089—Treatments not covered by a preceding group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
Abstract
The synthesis of carbonate modified siloxane additive belongs to the field of siloxane additive synthesis, and comprises the following steps: dissolving 4-vinyl-1, 3-dioxolane-2-one in an organic solvent, and then adding 0.4-0.6 wt% of tris (triphenylphosphine) rhodium chloride and 0.1-0.12 wt% of sodium acetate to obtain a mixed solution; dropwise adding the reactant into the mixed solution at 50-53 ℃, stirring while adding, reacting at 70-80 ℃ for 3-5h after dropwise adding, and performing vacuum fractionation; when the reactant is pentamethyl disiloxane, the distillate of 123 ℃/12Pa is collected, and the product is
When the reactant is bis-trimethylsiloxy methylsilane, collecting 125 ℃/12Pa distillate and obtaining the product
The preparation method is simple and has high yield.
Description
Technical Field
The invention belongs to the technical field of siloxane synthesis, relates to synthesis of a carbonate modified siloxane additive, and particularly relates to synthesis of a carbonate modified siloxane additive
And
the method of (1).
Background
The carbonate modified siloxane series is an additive for wide-temperature electrolyte of lithium ion battery, mainly comprising
And the derivatives thereof can play a role in forming a protective layer on the surface of the anode and eliminating harmful impurities such as HF, PF5 and the like in the electrolyte, and are beneficial to improving the low-temperature charge and discharge performance and the high-temperature cycle stability of the battery, and researches show that the materials are beneficial to keeping the main low-temperature and normal-temperature physical properties of the electrolyte stable when the addition amount is less than 1 percent. Based on the above, research on the synthesis of the carbonate modified siloxane additive is of great significance in the field of battery electrolytes.
Disclosure of Invention
The invention provides a synthesis method of a carbonate modified siloxane additive for solving the problems, the prepared carbonate modified siloxane additive has few byproducts and high yield, and the carbonate modified siloxane additive can be applied to lithium ion battery electrolyte and can obviously improve the performance and prolong the service life of a lithium ion battery.
The invention adopts the specific technical scheme that: the key point of the synthesis of the carbonate modified siloxane additive is that the carbonate modified siloxane additive comprises
(1) dissolving the raw materials by using an organic solvent, and then adding 0.4-0.6 wt% of tris (triphenylphosphine) rhodium chloride and 0.1-0.12 wt% of sodium acetate into the raw materials to obtain a mixed solution; the raw material is 4-vinyl-1, 3-dioxolane-2-ketone;
(2) dropwise adding the reactant into the mixed solution obtained in the step (1) at 50-53 ℃, stirring while adding, reacting at 70-80 ℃ for 3-5h after dropwise adding, and performing vacuum fractionation to obtain a product;
when the reactant is pentamethyl disiloxane, the distillate of 123 ℃/12Pa is collected, and the product is
When the reactant is bis-trimethylsiloxy methylsilane, collecting 125 ℃/12Pa distillate and obtaining the product
Further, the molar ratio of the raw materials to the reactants is (1-1.2): 1.
Further, the organic solvent is toluene, 1, 2-dichloromethane or chloroform.
The invention has the beneficial effects that: the preparation method is simple, few in byproducts and high in yield, and can be applied to industrialization.
Drawings
FIG. 1 is a graph prepared according to example 1 of the present invention
1H NMR spectrum of (1).
FIG. 2 is a graph prepared according to example 1 of the present invention
13C NMR spectrum of (1).
FIG. 3 is a graph of a sample prepared in example 2 of the present invention
1H NMR spectrum of (1).
FIG. 4 is a graph of a sample prepared in example 2 of the present invention
13C NMR spectrum of (1).
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Dissolving 12.55g of 4-vinyl-1, 3-dioxolane-2-one in 30ml of toluene, and then adding 0.063g of tris (triphenylphosphine) rhodium chloride and 0.015g of sodium acetate to obtain a mixed solution;
(2) at 50 ℃, 14.73g of pentamethyl disiloxane is dropwise added into the mixed solution obtained in the step (1) while stirring, after the dropwise addition, the reaction is carried out for 4h at 75 ℃, vacuum fractionation is carried out, distillate at 123 ℃/12Pa is collected, and 18.60g of product is obtained
The yield thereof was found to be 70.95%.
Example 2
(1) Dissolving 13.69g of 4- (2-propenyl) -1, 3-dioxolan-2-one in 40ml of chloroform, and then adding 0.082g of tris (triphenylphosphine) rhodium chloride and 0.016g of sodium acetate to obtain a mixed solution;
(2) at 53 ℃, 22.25g of bistrimethylsilyltrimethylsilane is dropwise added into the mixed solution in the step (1) while stirring, the reaction is carried out for 3h at 80 ℃ after the dropwise addition, the vacuum fractionation is carried out, distillate at 125 ℃/12Pa is collected, and 24.26g of product is obtained
The yield thereof was found to be 72.14%.
Comparative example 1
(1) Dissolving 12.55g of 4-vinyl-1, 3-dioxolane-2-one in 30ml of toluene, and then adding 0.063g of hydrochloroplatinic acid to obtain a mixed solution;
(2) at 50 ℃, 14.73g of pentamethyl disiloxane is dropwise added into the mixed solution obtained in the step (1) while stirring, after the dropwise addition is finished, the mixed solution reacts at 75 ℃ for 4 hours, vacuum fractionation is carried out, distillate at 123 ℃/12Pa is collected, and 13.66g of product is obtained
The yield thereof was found to be 52.12%.
Comparative example 2
(1) Dissolving 13.69g of 4- (2-propenyl) -1, 3-dioxolan-2-one in 40ml of chloroform, and adding 0.082g of hydrochloric platinic acid to obtain a mixed solution;
(2) at 53 ℃, 22.25g of bistrimethylsilyltrimethylsilane is dropwise added into the mixed solution in the step (1) while stirring, the reaction is carried out for 3h at 80 ℃ after the dropwise addition, the vacuum fractionation is carried out, 125 ℃/12Pa distillate is collected, and 17.16g of product is obtained
The yield thereof was found to be 51.04%.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (3)
1. The synthesis of carbonate modified siloxane additives is characterized in that the carbonate modified siloxane additives comprise
(1) dissolving the raw materials by using an organic solvent, and then adding 0.4-0.6 wt% of tris (triphenylphosphine) rhodium chloride and 0.1-0.12 wt% of sodium acetate into the raw materials to obtain a mixed solution; the raw material is 4-vinyl-1, 3-dioxolane-2-ketone;
(2) dropwise adding the reactant into the mixed solution obtained in the step (1) at 50-53 ℃, stirring while adding, reacting at 70-80 ℃ for 3-5h after dropwise adding, and performing vacuum fractionation to obtain a product;
when the reactant is pentamethyl disiloxane, the distillate of 123 ℃/12Pa is collected, and the product is
When the reactant is bis-trimethylsiloxy methylsilane, collecting 125 ℃/12Pa distillate and obtaining the product
2. The synthesis of carbonate-modified siloxane-based additives according to claim 1, wherein the molar ratio of starting materials to reactants is (1-1.2): 1.
3. The synthesis of carbonate-modified siloxane-based additives according to claim 1, wherein the organic solvent is toluene, 1, 2-dichloromethane or chloroform.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010226856.6A CN113444119B (en) | 2020-03-27 | 2020-03-27 | Synthesis of carbonate modified siloxane additives |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010226856.6A CN113444119B (en) | 2020-03-27 | 2020-03-27 | Synthesis of carbonate modified siloxane additives |
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| CN113444119A true CN113444119A (en) | 2021-09-28 |
| CN113444119B CN113444119B (en) | 2024-05-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854024A (en) * | 2022-05-26 | 2022-08-05 | 东华大学 | Modified carbamate silicone oil emulsion, preparation method thereof and method for preparing polyacrylonitrile carbon fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912242A (en) * | 1989-05-15 | 1990-03-27 | Dow Corning Corporation | Process for preparing silicon esters |
| CN1800191A (en) * | 2004-10-15 | 2006-07-12 | 信越化学工业株式会社 | Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution, secondary battery and capacitor |
| CN101033235A (en) * | 2006-12-21 | 2007-09-12 | 杭州师范学院 | Silicon-hydrogen additive reaction method |
-
2020
- 2020-03-27 CN CN202010226856.6A patent/CN113444119B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912242A (en) * | 1989-05-15 | 1990-03-27 | Dow Corning Corporation | Process for preparing silicon esters |
| CN1800191A (en) * | 2004-10-15 | 2006-07-12 | 信越化学工业株式会社 | Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution, secondary battery and capacitor |
| CN101033235A (en) * | 2006-12-21 | 2007-09-12 | 杭州师范学院 | Silicon-hydrogen additive reaction method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854024A (en) * | 2022-05-26 | 2022-08-05 | 东华大学 | Modified carbamate silicone oil emulsion, preparation method thereof and method for preparing polyacrylonitrile carbon fiber |
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| CN113444119B (en) | 2024-05-03 |
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