WO2004076065A1

WO2004076065A1 - Carbon dioxide gas absorber and process for producing the same

Info

Publication number: WO2004076065A1
Application number: PCT/JP2004/002075
Authority: WO
Inventors: Hideharu Iwasaki; Nozomu Sugoh; Kazuya Shimizu; Hiroyuki Kawai
Original assignee: Kuraray Co., Ltd.
Priority date: 2003-02-28
Filing date: 2004-02-23
Publication date: 2004-09-10
Also published as: JPWO2004076065A1; JP4732168B2

Abstract

A highly safe carbon dioxide gas absorber that can easily absorb carbon dioxide gas and can avoid problems such as lowering of electrolyte concentration; and an industrially advantageous process capable of producing such a carbon dioxide gas absorber with reduced cost in high yield. In particular, a carbon dioxide gas absorber comprised mainly of a resin capable of easy carbonylation and a carbonylation catalyst; and a process for producing the same.

Description

Description Carbon dioxide absorber and its manufacturing method

The present invention relates to a carbon dioxide absorber and a method for producing the same. The carbon dioxide gas absorber provided by the present invention is excellent in carbon dioxide gas absorbing ability, and thus is suitably used for a device such as a secondary battery or a storage battery that generates carbon dioxide gas and deteriorates in performance. Background art

Conventionally, in secondary batteries, etc., the internal pressure rises due to the carbon dioxide gas generated during initial charging and high-temperature storage, and the opening of the open valve causes liquid leakage, resulting in reduced hermeticity and, in some cases, rapid deterioration. There was a problem that bursting could occur due to an excessive increase in internal pressure. In order to solve such a problem, various studies have been made on a novel non-aqueous electrolyte which does not generate carbon dioxide gas. For example, Japanese Patent Application Laid-Open No. 2002-237337 discloses lithium use ol Soshirike one preparative _{_{(L i 4 S i O 4}} ) and lithium meta silicate are one preparative (with i ₂ S i 〇 _3), temperature range (one 2 0 ° C in a non-aqueous electrolyte secondary battery A method of rapidly absorbing carbon dioxide gas within a temperature of about 150 ° C.) is disclosed.

In addition, when manufacturing a secondary battery or a capacitor, Japanese Patent Application Laid-Open No. 2000-2000 discloses a method in which a specific voltage is applied at a stage before a case is sealed as a final step. However, there is disclosed a method of removing residual moisture that causes deterioration and a functional group that generates water due to decomposition. However, the method using an electrolyte as an absorbent for carbon dioxide gas is not an effective method because the concentration of the electrolyte in the secondary battery decreases and other problems such as a decrease in the effective capacity voltage occur. hard. In addition, in the method of applying a specific voltage and energizing before the case is sealed to remove residual water and functional groups that generate moisture due to decomposition, water must be added during the work process that should be performed under water-free conditions. This not only reduces battery production efficiency, but also makes judgment for removal difficult and unproductive.

In reality, it is impossible to completely remove the substance that causes deterioration, and carbon dioxide is generated by a trace amount of the causative substance.Although the problem of carbon dioxide generation has been sufficiently solved, There is no such thing at present. Therefore, an object of the present invention is to provide a highly safe carbon dioxide gas absorber that can easily absorb carbon dioxide gas and can avoid problems such as reduction in electrolyte concentration. Another object of the present invention is to provide an industrially advantageous production method capable of producing such a carbon dioxide gas absorber inexpensively and with good yield. Disclosure of the invention

Means for Solving the Problems The present inventors diligently studied and found that the above object can be achieved by a carbon dioxide gas absorber comprising an easily-powered luponylated resin and a calponylation catalyst, and a method for producing the same, and reached the present invention. That is, the present invention is a carbon dioxide gas absorber mainly comprising an easily carbonylable resin and a catalyst for the formation of a carbonyl compound. Further, another invention of the present invention is to disperse and dissolve the catalyzed sulfonylation catalyst in an easily catalyzed rubonylation resin solution in which the easily catalyzed resin is dissolved in an organic solvent, and then remove the organic solvent. That This is a method for producing a carbon dioxide gas absorber characterized by the following. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, “carbonylation” means a reaction that reacts with carbon dioxide to generate a carbonyl group in a molecule. The easily carbonylable resin used in the present invention is not particularly limited as long as it is a resin having a functional group which is easily carbonylated by reacting with carbon dioxide in the presence or absence of a catalyst. However, in view of the easiness of carbonylation and the stability as a resin, those having an epoxy group at the molecular terminal and Z or in the molecular chain are preferable. Examples of such easily-powered resin include epoxidized resins of polygen resins such as cis-polybutadiene, trans-polybutadiene, mixed polybutadiene, cis-polyisoprene, trans-polyisoprene, and mixed polyisoprene; styrene-butadiene Epoxidized resin of block copolymer, epoxidized resin of styrene-soprene block copolymer, epoxidized resin of styrene-butadiene random copolymer, epoxidized resin of styrene-isoprene random copolymer, styrene-butadiene-styrene Epoxidized resin of block copolymer, epoxidized resin of styrene-isoprene-styrene block copolymer, polyoctenylene, polynorpolene, epoxidized resin of ring-opening polymer, polyglycidyl acrylate, poly Examples include glycidyl methacrylate and polyglycidyl vinyl ether. Among these, polyglycidyl pinyl ether, polyglycidyl methacrylate and polyglycidyl acrylate are particularly preferred.

Of these easily-powered luponylated resins, such as polybutadiene In the case of epoxidized resin having unsaturated bonds, the epoxidation rate of carbon-carbon double bond in the resin may be 90% or more from the viewpoint of carbon dioxide absorption efficiency, but other electrochemical reactions Is preferably 98% or more in order not to cause the occurrence of the problem.

In the carbon dioxide gas absorbent of the present invention, the easily-powered luponylated resin preferably has a number-average molecular weight in the range of 100 000 000 000, and 200 000 000 Those in the range are more preferred. When using the carbon dioxide absorber of the present invention, it may be used alone, or may be supported on a carrier or another material. The carbon dioxide gas absorber of the present invention can be formed into a single and free shape, and can have a low solubility in a solvent, particularly when a force-resistant resin having an average molecular weight in the above range is used. Therefore, compared to the case where this is used for secondary batteries, storage batteries, etc., and when mechanical substances and low molecular weight substances are supported on a carrier, there is no fear of causing the adsorbed decomposition of the electrolyte m , High volumetric efficiency and design freedom.

As the carbonylation catalyst used in the present invention, a lithium salt or a quaternary ammonium salt containing octogen is preferable. Examples of the halogen-containing lithium salt include lithium chloride, titanium bromide, lithium iodide, lithium perchlorate, lithium tetrafluoroborate, U-titanium hexafluorophosphate, and the like. However, lithium bromide, lithium tetrafluoroborate and lithium hexafluorophosphate are preferred.

The ammonium groups of the quaternary ammonium salts containing octylogen include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium tetralanthyl. Ammonium, tetrahexylammonium, tetraheptylammonium, trimethylethylammonium, U-methylpropylammonium, trimethylbutylammonium, u-methylbenzylammonium Trimethylmethylammonium, triethylpropylammonium, triethylbutylammonium, triux-butyl benzylammonium, tripropylmethylammonium, tripropylmethylammonium, trimethylpropylammonium Ammonia, tripropylbenzylammonium, triptylmethylammonium, triptylethylammonium, tributylpropylammonium, tributylbenzylammonium, trioctylmethylammonium, trioctyljem Chillammonium, Trioctylpropyrarnmonium Trioctyl pentaammonium, dimethyldiethylammonium, dimethyldipropylammonium, dimethyldibutylammonium, dimethyldioctylammonium, dimethyldibenzylammonium, getylzip Examples include pyrammonium, getyl dibutylammonium, getyldibenzylammonium, methylpyridinium, and cetylpyridinium ammonium groups. Examples of the quaternary ammonium salt containing a halogen include chloride, promide, iodide, tetrafluorophosphate, perchlorate, and pentafluorophosphate of the above-mentioned ammonium group. it can.

The amount of the catalyst used is not particularly limited. However, in consideration of the compatibility with the above-described easily-responylated resin, 100 parts by weight of the easily-carponylated resin is used. 0.001 to 100 parts by weight In consideration of absorption efficiency, operability, and economy, 0.0250 parts by weight, more preferably 0.01 to 20 parts by weight Department. Usually an easily carbonylated resin 0.001 to 0.5 mol per 1 mol of the easily-powered luponylated functional group contained therein, and 0.00002 to 0.3 in consideration of reactivity, economy and the like. Mole, more preferably in the range of 0.005 to 0.2 mole.

The carbon dioxide gas absorber of the present invention is manufactured by dispersing a catalyzed ruponylation catalyst in a readily susceptible luponylated resin solution in which an easily catalyzed ruponylated resin is dissolved in an organic solvent, dissolving the resultant, and then removing the organic solvent. be able to.

The organic solvent is not particularly limited as long as it does not reduce the force-ponylation activity of the force-ponylation catalyst.Examples of the organic solvent include pentane, hexane, cyclohexane, heptane, octane, and cyclohexane. Aliphatic hydrocarbons such as octane and decane; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Jetyl ether, methyl t-butyl ether, tetrahydrofuran, tetrahydropyran, diisopropyl ether, dibutyl ether, etc. Esters of methyl acetate, ethyl acetate, butyl acetate, etc .; powers of dimethyl carbonate, getylcapone, ethylene, polyethylene, propylene, etc. And the like. Above all, it is preferable to use tetrahydrofuran or propylene carbonate in consideration of the solubility of the easily applied luponylated resin, the persistence in the carbon dioxide gas absorber, the operability, and the like.

The amount of the organic solvent used is preferably such that the concentration of the easily luponylated resin is 0.1 to 30% by weight in consideration of the dispersibility of the electroluponylation catalyst. It is preferable to use the compound in such an amount as to give a concentration of 0.5 to 28 weight in consideration of the operability and the cost.

Temperature and force of dissolving carbonylable resin in organic solvent The temperature at which the catalyst is dispersed and dissolved varies depending on the organic solvent used, but is usually in the range of 0 to 200, and in the range of 20 to 150 ° C in consideration of operability. Is preferred. These operations are usually performed in an atmosphere of an inert gas such as nitrogen or argon in consideration of safety and the like.

The organic solvent is removed from the solution obtained by dispersing and dissolving the catalyzed rubonylation catalyst in the easily catalyzed rubonylation resin solution. It is efficient to remove the organic solvent under reduced pressure, and it is also desirable from the viewpoint of preventing alteration and the like. The degree of pressure reduction depends on the organic solvent used. It is more preferable to adjust the temperature to 50 ° C. or lower.

In the present invention, after removing the organic solvent, the obtained carbon dioxide gas absorbent is preferably handled under nitrogen, and if necessary, is stored in water or an organic solvent. The carbon dioxide absorber obtained in this way is molded into pellets, films, fibers, woven fabrics, non-woven fabrics, etc., if necessary, as long as its function is not impaired. Applies to equipment. When the carbon dioxide gas absorber obtained according to the present invention is applied to, for example, a battery, it is practically sufficient if about 10% of the epoxy groups are calponylated, and stored in a film-like space in the space below the battery. When used as a separator component, it functions as a carbon dioxide gas absorber. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Example 1

100 milliliters internal volume equipped with stirrer, thermometer and distillation column Take 2 g of POJ U sidylvinyl ether (number-average molecular weight: 300,000) into a 3 ml flask of (mL), and add 30 g of tetrahydrofuran.

40 g of 1, octylmethylammonium amide U was added to the resulting solution dissolved at 40 ° C., and the mixture was stirred at 30 ° C. and uniformly dispersed (polyoxy group in poly (U) sidyl propyl ether). The pressure in the system was reduced to 7 Torr (0.93 kPa), and

Π The furan was removed by evaporation. Another 40 after the evaporation of the Tetrahi F-mouth franc ceased to be observed. C, dried at 7 Torr for 5 hours to obtain a carbon dioxide absorber.

,) Says its;

Pressure gauge, pressure gauge and gas conductor f

Take 10 g of stainless steel (s US3116) with an internal volume of 10 ml and put 1 g of carbon dioxide gas absorber in the pressure vessel, replace the inside of the system with nitrogen, and then replace with carbon dioxide. Pressurize the system to 3 atmospheres

/ Adjust the inside of the reactor to 30 ° C and keep the pressure inside the reactor at 3 atm.

After 8 hours, the inside of the system was purged with nitrogen, then the carbon dioxide absorber was taken out of the reactor, and a part of it was dissolved in a heavy-mouthed form. ! — As measured by NMR, 26% of the epoxy functional groups of the polydaricidyl vinyl ether were calponylated. This indicates that the carbon dioxide gas absorber obtained in Example 1 absorbed carbon dioxide gas.

Example 2

A carbon dioxide gas absorber was obtained in the same manner as in Example 1 except that polyglycidyl acrylate (number average molecular weight: 420) was used instead of polyglycidyl vinyl ether. The absorption of carbon dioxide in the obtained carbon dioxide absorber was examined in the same manner as in Example 1. As a result, 31% of the epoxy functional groups of the polyglycidyl acrylate were calponylated. As a result, the carbon dioxide absorber obtained in Example 2 absorbed carbon dioxide. I understand.

Example 3

A gas carbonate absorber was obtained in the same manner as in Example 2 except that tetrabutylammonium bromide was used instead of trioctylmethylammonium chloride. When the carbon dioxide absorption of the obtained carbon dioxide absorbent was examined in the same manner as in Example 1, 34% of the epoxy functional groups of the polyglycidyl acrylate were carbonylated. This indicates that the carbon dioxide absorber obtained in Example 3 absorbed carbon dioxide.

Example 4

A carbon dioxide gas absorber was obtained in the same manner as in Example 2 except that tetrabutylammonium tetrafluoroborate was used instead of trioctylmethylammonium chloride. When the absorption of carbon dioxide was measured for the obtained carbon dioxide absorbent in the same manner as in Example 1, it was found that 32% of the epoxy functional groups of polydaricydyl acrylate were calponylated. This indicates that the carbon dioxide absorber obtained in Example 4 absorbed carbon dioxide.

Example 5

A carbon dioxide gas absorber was obtained in the same manner as in Example 2 except that tetrabutylammonium pentafluorophosphate was used in place of trioctylmethylammonium mouth lid. Examination of the absorption of carbon dioxide gas in the same manner as described above revealed that 26% of the epoxy functional groups of the polyglycidyl acrylate had been converted to phenol. This indicates that the carbon dioxide absorber obtained in Example 5 absorbed carbon dioxide.

Example 6 A carbon dioxide gas absorber was obtained in the same manner as in Example 2 except that lithium bromide was used instead of trioctylmethylammonium chloride. The carbon dioxide absorption of the obtained carbon dioxide gas absorber was examined in the same manner as in Example 1. As a result, 41% of the epoxy functional groups of the polyglycidyl acrylate were calponylated. This indicates that the carbon dioxide absorber obtained in Example 6 absorbed carbon dioxide.

Example 7

A carbon dioxide gas absorber was obtained in the same manner as in Example 1 except that lithium tetrafluoroborate was used instead of trioctylmethylammonium chloride. The absorption of carbon dioxide in the obtained carbon dioxide absorber was examined in the same manner as in Example 1. As a result, 33% of the epoxy functional groups of the polyglycidyl vinyl ether were calponylated. This indicates that the carbon dioxide absorber obtained in Example 7 absorbed carbon dioxide.

Example 8

A carbon dioxide gas absorber was obtained in the same manner as in Example 1 except that lithium hexafluorophosphate was used instead of lithium tetrafluoroporate. The absorption of carbon dioxide in the obtained carbon dioxide absorber was examined in the same manner as in Example 1. As a result, it was found that 27% of the epoxy functional groups of the polyglycidyl vinyl ether had been carbonylated. This indicates that the carbon dioxide absorber obtained in Example 8 absorbed carbon dioxide.

Example 9

A carbon dioxide gas absorber was obtained in the same manner as in Example 1 except that polyepoxylated cis polyisoprene (number average molecular weight: 1000) was used instead of polyglycidyl ether. The carbon dioxide absorption of the obtained carbon dioxide gas absorber was examined in the same manner as in Example 1, and it was found that 19% of the epoxy functional groups of isoprene were carbonylated. This indicates that the carbon dioxide absorber obtained in Example 9 absorbed carbon dioxide.

Example 10

Implemented except that polyglycidyl methacrylate (number average molecular weight: 400000) was used in place of polyglycidyl ether and lithium hexafluorophosphate was used in place of trioctylmethylammonium chloride A carbon dioxide gas absorber was obtained in the same manner as in Example 1. The absorption of carbon dioxide in the obtained carbon dioxide absorber was examined in the same manner as in Example 1. As a result, 21% of the epoxy functional groups of the polyepoxidized polyisoprene were carbonylated. This indicates that the carbon dioxide gas absorber obtained in Example 10 absorbed carbon dioxide gas. Industrial applicability

The carbon dioxide gas absorber provided by the present invention is excellent in carbon dioxide gas absorbing ability, so that it is suitably used for a device such as a secondary battery or a storage battery that generates carbon dioxide gas and deteriorates in performance.

Claims

The scope of the claims

1. A carbon dioxide gas absorber mainly composed of easily luponylated resin and a strong luponylation catalyst.

2. The carbon dioxide absorber according to claim 1, wherein the carbonylation catalyst is a lithium salt or a quaternary ammonium salt containing halogen.

3. The carbon dioxide gas absorber according to claim 1 or 2, wherein the number-average molecular weight of the easily applied luponylated resin is in the range of 200 to 2000.

4. The carbon dioxide gas absorber according to any one of claims 1 to 3, wherein the easily-powered luponylated resin is polyglycidyl acrylate, polyglycidyl methacrylate, or polydaricidyl vinyl ether.

5. A carbon dioxide absorber characterized by dispersing and dissolving a catalyzed luponylation catalyst in a readily susceptible luponylated resin solution in which an easily catalyzed luponylated resin is dissolved in an organic solvent, and then removing the organic solvent. Manufacturing method.