CN105859922B - A kind of preparation method of resin lithium - Google Patents
A kind of preparation method of resin lithium Download PDFInfo
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- CN105859922B CN105859922B CN201610282233.4A CN201610282233A CN105859922B CN 105859922 B CN105859922 B CN 105859922B CN 201610282233 A CN201610282233 A CN 201610282233A CN 105859922 B CN105859922 B CN 105859922B
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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Abstract
The invention discloses a kind of preparation methods of resin lithium, include the following steps：1) solvent organic amine and deacetylation reagent are added in the resin into repetitive unit containing N methyl N benzyl acetamides, under microwave irradiation, resin amine is made；Wherein, the deacetylation reagent is tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, ammonium bromide or ammonium chloride；2) step 1) is obtained resin amine to be dissolved in organic solvent, resin lithium salts is obtained by the reaction with highly basic containing lithium；Wherein, the resin is with one of lower structure：
Description
Technical field
The present invention relates to a kind of preparation methods of resin lithium.
Background technology
Resin lithium can be applied to various organic and inorganics as the super base (super-base) of amine-lithium key and react, for example take
Carbanion is converted into for the hydrogen on carbon either nitrogen or nitrogen anion becomes the strong base reagent with strong nucleation.It is existing to be made
Highly basic lithium mainly with butyl lithium, isobutyl group lithium, tert-butyl lithium, lithium amide, lithium hydride and diisopropyl ethyl ammonia lithium and this
The shortcomings that a little reagents, is to be used only once and decompose and be unable to Reusability, but resin lithium salts is as with multiple type lithium ions
Exchanger resin is reusable multiple and does not change its basic structure, and moreover resin lithium salts is also directly applicable to various
In terms of the lithium battery material in field, used LiSF and LiPF at this stage6It will one by one be eliminated in the several years, it is main former
Because lithium battery solution used in being is with some complexity occurred during the corresponding cooperation than row, completeness, practicability and reliable
Property with it is certain the problem of, but resin lithium salts is greatly increased because itself is with the netted lithium ion region of multiple amine-lithium key-shaped adult fish
The surface area and reactivity of its lithium ion, also resin lithium can be directly adhered to metal or nonmetallic with certain viscosity
Surface carries out ion exchange, and existing external multiple countries are stepping up to develop the lithium battery material of Pasting, and the present invention is as state
First autonomous opinion research and development resin type lithium salts, practical application and value will be greatly improved in the precedent of border.
Invention content
The present invention provides a kind of preparation methods of new type resin lithium, and this method reaction step is simple, and yield is high, almost without
Pollution, can Reusability, non-hazardous reaction condition, product is easily purified, and is suitable for domestic mass production.
To solve the above-mentioned problems, the technical solution adopted in the present invention is such, a kind of preparation method of resin lithium,
It is characterized by comprising the following steps：
1) solvent organic amine and deacetylated is added in the resin into repetitive unit containing N- methyl-iV-benzyl acetamides
Change reaction reagent, under microwave irradiation, resin amine is made；The wherein described deacetylation reagent is tetrabutyl ammonium fluoride,
Tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, ammonium bromide or ammonium chloride；
2) it obtains resin amine to step 1) and adds in organic solvent, resin lithium is obtained by the reaction with highly basic containing lithium；
Wherein, the resin is with one of lower structure：
The reaction equation of resins synthesis shown in formula (1) correspondingly resin lithium is as shown in formula I：
The reaction equation of resins synthesis shown in formula (2) correspondingly resin lithium is as shown in formula II：
The reaction equation of resins synthesis shown in formula (3) correspondingly resin lithium is as shown in formula III：
The reaction equation of resins synthesis shown in formula (4) correspondingly resin lithium is as shown in formula IV：
The specific reaction process of step 1) is that resin and solvent organic amine and deacetylation reagent are added to sealing
Among glass tube, under the microwave irradiation of 250-300W, 50-80 DEG C is warming up to, reacts 5-60min, gained reaction solution passes through
It after filter, is washed successively through acid solution, aqueous slkali and water, is dried to obtain resin amine.
The dosage of the deacetylation reagent and the mass ratio of resin are 0.8~1.5：1, preferably 0.8~1.3：
1, more preferable 1~1.1：1.
It is methyl amine that the organic amine, which is selected from, base amine, and propyl amine, methanediamine, base diamines or propyl diamine, have
The dosage of machine amine and the mass ratio of resin are 4~6：1, preferably 5~5.5：1,
Preferably, the reaction temperature control in step 1) is 70 DEG C~80 DEG C.
The specific reaction process of step 2) is adds in organic solvent into resin amine, after being cooled to -78~-50 DEG C, Xiang Qi
Highly basic containing lithium, rate of addition 4-5ml/min is slowly added dropwise, entire be added dropwise maintains the temperature at -78~-50 DEG C in the process, drip
Bi Hou, after temperature is kept as the reaction was continued under conditions of -78~-50 DEG C 2-4h, after filtered, washing resin lithium.
Highly basic containing lithium described in step 2) is butyl lithium, isobutyl group lithium, tert-butyl lithium, lithium amide, lithium hydride, diisopropyl
Base ammonia lithium or lithium metal.
Organic solvent described in step 2) is ether or tetrahydrofuran, and the dosage of organic solvent and the mass ratio of resin are
20~50：1, preferably 30~40：1.
Preferably, the reaction temperature control in step 2) is -78~-75 DEG C.
Advantageous effect：The resin containing N- methyl-iV-benzyl acetamides is relatively warm in present invention selection repetitive unit
With under conditions of, formylated is gone to obtain resin amine, the resin amine of the gained synthetic resin lithium under condition of ultralow temperature, be conducive to amine-
The stability and reactivity of lithium salts, so as to greatly increase the activity of the resin lithium of its synthesis；In addition, this method reaction step is simple
Single, yield is high, almost pollution-free, can Reusability, non-hazardous reaction condition, product is easily purified, is suitable for domestic a large amount of raw
Productionization.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment
It is only used for explaining the present invention, be not intended to limit the scope of the present invention..
Embodiment 1
1) resins of the 10g as shown in following formula (1), 10g ammonium bromides are weighed, 40g ethylenediamines are added among sealed glass tube,
Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCl
Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 500mL again again, dry to collect admittedly
Body obtains 5.3g resin amine.
2) 250mL tetrahydrofurans are added in the 5.3g resins amine obtained by step 1), be then added in there-necked flask, temperature drop
Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min is slowly added dropwise after to -78 DEG C, process is entirely added dropwise, keeps temperature
It is -78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is waiting to have reacted
Bi Hou, fast direct take over filter, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the filter collected
Go out object, as resin lithium, 4.2g, yield are disregarded altogether.
The reaction equation of resins synthesis shown in formula (1) correspondingly resin lithium is as shown in formula I：
Embodiment 2
1) resins of the 10g as shown in following formula (2), 15g ammonium bromides are weighed, 50g ethylenediamines are added among sealed glass tube,
Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCl
Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 400mL again again, dry to collect admittedly
Body obtains 5.1g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.1g resin amine obtained by step 1), are then added in there-necked flask, temperature
Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min is slowly added dropwise after being down to -78 DEG C, process is entirely added dropwise, keeps temperature
It is -78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is waiting to have reacted
Bi Hou, fast direct take over filter, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the filter collected
Go out object, as resin lithium salts, 4.0g, yield are disregarded altogether.
The reaction equation of resins synthesis shown in formula (2) correspondingly resin lithium is as shown in formula II：
Embodiment 3
1) resins of the 10g as shown in following formula (3), 9g ammonium bromides are weighed, 60g ethylenediamines are added among sealed glass tube,
Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCl
Solution is washed, and is washed with 450mL 1M NaOH solutions, is finally washed with water 500mL again again, dry to collect admittedly
Body obtains 5.5g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.1g resin amine obtained by step 1), are then added in there-necked flask, temperature
Tert-butyl lithium 5.8mL, rate of addition 1.76mL/min is slowly added dropwise after being down to -78 DEG C, process is entirely added dropwise, keeps temperature
It is -78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is waiting to have reacted
Bi Hou, fast direct take over filter, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the filter collected
Go out object, as resin amine, 4.1g, yield are disregarded altogether.
The reaction equation of resins synthesis shown in formula (3) correspondingly resin lithium is as shown in formula III：
Embodiment 4
1) resins of the 10g as shown in following formula (4), 12g ammonium bromides are weighed, 40g ethylenediamines are added among sealed glass tube,
Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCl
Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 400mL again again, dry to collect admittedly
Body obtains 5.0g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.0g resin amine obtained by step 1), are then added in there-necked flask, temperature
Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min is slowly added dropwise after being down to -78 DEG C, process is entirely added dropwise, keeps temperature
It is -78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is waiting to have reacted
Bi Hou, fast direct take over filter, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the filter collected
Go out object, as resin lithium, 4.4g, yield are disregarded altogether.
The reaction equation of resins synthesis shown in formula (4) correspondingly resin lithium is as shown in formula IV：
If the resin of formula (1) (2) (3) and (4) is existing in above example, buy in South Korea KUKDO
Chemical or South Korea KANGNAM Chem.
Application Example 1
It weighs the bis- fluorine sulfonamide of 15.77g and is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weigh 22g and implement 1
Prepared resin lithium is dissolved in tetrahydrofuran 20mL formation resin lithium solution and is added in there-necked flask, its temperature is down to -78 DEG C
Later, be slowly added dropwise double fluorine sulfonamide solutions, time for adding 1h thereto, entire drip reacting temperature be maintained at -78 DEG C~-
75 DEG C, -78 DEG C~-75 DEG C the reaction was continued 2h, treat after completion of the reaction, to treat after completion of the reaction, entirely to post-process after being added dropwise
Journey uses after -78 DEG C~-75 DEG C carry out and solvent for use is cooled to -78 DEG C~-75 DEG C, and specific process is：
Fast direct connects filtering reacting liquid, and much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；It is collected into filter
Liquid is after vacuum distillation removes solvent, and after 1h is stirred at room temperature in addition ether 200mL, the solid being obtained by filtration is washed through 50mL ether
After washing three times, double fluorine sulfonamide lithium salts 12.8g are obtained, yield is disregarded.
Application Example 2
It weighs the bis- fluorine sulfonamide of 13.7g and is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weigh 20g embodiments 2
Prepared resin lithium is dissolved in tetrahydrofuran 20mL formation resin lithium solution and adds in into there-necked flask, and double fluorine are slowly added dropwise thereto
Sulfonamide solution, time for adding 1h, entire drip reacting temperature are maintained at -78~-75 DEG C, after being added dropwise, -78~-
The reaction was continued at 75 DEG C 2h, treats after completion of the reaction, to treat after completion of the reaction, entire last handling process is at -78 DEG C~-75 DEG C
Progress and solvent for use use after being cooled to -78 DEG C~-75 DEG C, and specific process is：Fast direct connects filtering reacting liquid, filters out
Object is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；Filtrate is collected into after vacuum distillation removes solvent,
After 1h is stirred at room temperature in addition 200mL ether, the solid being obtained by filtration obtains double fluorine sulfonamide lithiums after the washing three times of 50mL ether
Salt 11.3g, yield are disregarded.
Application Example 3
It weighs the bis- fluorine sulfonamide of 12.45g and is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weigh 13.6g implementations
Resin lithium prepared by 3 is dissolved in tetrahydrofuran 20mL formation resin lithium solution and is added in there-necked flask, its temperature is down to -78 DEG C
Later, double fluorine sulfonamide solutions, time for adding 1h are slowly added dropwise thereto, entire drip reacting temperature is maintained at -78~-75
DEG C, -78~-75 DEG C of the reaction was continued 2h, band after completion of the reaction, are treated after completion of the reaction after being added dropwise, entire last handling process -
Progress and solvent for use use after being cooled to -78 DEG C~-75 DEG C in the case of 78 DEG C~-75 DEG C, and specific process is：Fast direct
Filtering reacting liquid is connect, much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；Filtrate is collected into through subtracting
After solvent is distilled off in pressure, after 1h is stirred at room temperature in addition 200mL ether, the solid being obtained by filtration washs three times through 50mL ether
Afterwards, it is collected into mother liquor and obtains the bis- fluorine sulfonamide lithium salts of 10.5g, yield (in terms of double fluorine sulfonamide) 82% through vacuum distillation.
Application Example 4
It weighs the bis- fluorine sulfonamide of 12.45g and is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weigh 13.6g implementations
Resin lithium prepared by 4 is dissolved in tetrahydrofuran 20mL formation resin lithium solution and is added in there-necked flask, its temperature is down to -78 DEG C
Later, double fluorine sulfonamide solutions, time for adding 1h are slowly added dropwise thereto, entire drip reacting temperature is maintained at -78~-75
DEG C, -78~-75 DEG C of the reaction was continued 2h, band after completion of the reaction, are treated after completion of the reaction after being added dropwise, entire last handling process -
Progress and solvent for use use after being cooled to -78 DEG C~-75 DEG C in the case of 78 DEG C~-75 DEG C, and specific process is：Fast direct
Filtering reacting liquid is connect, much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；Filtrate is collected into through subtracting
After solvent is distilled off in pressure, after 1h is stirred at room temperature in addition 200mL ether, the solid being obtained by filtration washs three times through 50mL ether
Afterwards, it is collected into mother liquor and obtains the bis- fluorine sulfonamide lithium salts of 10.6g through vacuum distillation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (9)
1. a kind of preparation method of resin lithium, which is characterized in that include the following steps：
1) solvent organic amine and deacetylated anti-is added in the resin into repetitive unit containing N- methyl-iV-benzyl acetamides
Reagent is answered, under microwave irradiation, resin amine is made；Wherein, the deacetylation reagent be tetrabutyl ammonium fluoride, four fourths
Ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, ammonium bromide or ammonium chloride；
2) it obtains adding in organic solvent in resin amine to step 1), resin lithium is obtained by the reaction with highly basic containing lithium；
Wherein, the resin is with one of lower structure：
A kind of 2. preparation method of resin lithium according to claim 1, which is characterized in that the specific reaction process of step 1)
Among resin and solvent organic amine and deacetylation reagent are added to sealed glass tube, shone in the microwave of 250-300W
Penetrate down, be warming up to 50-80 DEG C, react 5-60min, gained reaction solution after filtering, successively through acid solution, aqueous slkali and water into
Row washing, is dried to obtain resin amine.
A kind of 3. preparation method of resin lithium according to claim 1 or 2, which is characterized in that deacetylation reagent
Dosage and resin mass ratio be 0.8~1.5：1.
A kind of 4. preparation method of resin lithium according to claim 1 or 2, which is characterized in that the organic amine in step 1)
Selected from for methyl amine, propyl amine, methanediamine or propyl diamine, the dosage of organic amine and the mass ratio of resin are 5~6：1.
A kind of 5. preparation method of resin lithium according to claim 2, which is characterized in that the reaction temperature control in step 1)
It is made as 70 DEG C~80 DEG C.
A kind of 6. preparation method of resin lithium according to claim 1, which is characterized in that the specific reaction process of step 2)
To add in organic solvent into resin amine, after being cooled to -78~-50 DEG C, highly basic containing lithium is slowly added dropwise thereto, rate of addition is
4~5ml/min, entire be added dropwise maintain the temperature at -78~-50 DEG C, after being added dropwise in the process, are -78~-50 keeping temperature
It is filtered after the reaction was continued 2-4h under conditions of DEG C, after washing resin lithium.
7. the preparation method of a kind of resin lithium according to claim 1 or 6, which is characterized in that described in step 2)
Highly basic containing lithium is butyl lithium, isobutyl group lithium, tert-butyl lithium, lithium amide, lithium hydride, diisopropyl ammonia lithium or lithium metal.
8. the preparation method of a kind of resin lithium according to claim 1 or 6, which is characterized in that described in step 2)
Organic solvent is ether or tetrahydrofuran, and the dosage of organic solvent and the mass ratio of resin are 20~50：1.
A kind of 9. preparation method of resin lithium according to claim 1 or 6, which is characterized in that the reaction temperature in step 2)
Degree control is -78~-50 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025457A (en) * | 1997-09-12 | 2000-02-15 | Shikoku Chemicals Corporation | Molten-salt type polyelectrolyte |
| CN101562243A (en) * | 2009-05-20 | 2009-10-21 | 沈阳航空工业学院 | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm |
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2016
- 2016-04-29 CN CN201610282233.4A patent/CN105859922B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025457A (en) * | 1997-09-12 | 2000-02-15 | Shikoku Chemicals Corporation | Molten-salt type polyelectrolyte |
| CN101562243A (en) * | 2009-05-20 | 2009-10-21 | 沈阳航空工业学院 | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm |
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Inventor after: Wang Kai Inventor after: Jin Guofan Inventor after: Zhang Yan Inventor after: Zhang Hui Inventor after: Li Liubin Inventor after: Jin Feng Inventor before: Jin Guofan Inventor before: Jin Feng Inventor before: Wang Kai Inventor before: Zhang Yan Inventor before: Zhang Hui Inventor before: Li Liubin |