WO2006025374A1

WO2006025374A1 - Process for producing particle-containing ethylene oxide copolymer resin and method of packaging

Info

Publication number: WO2006025374A1
Application number: PCT/JP2005/015750
Authority: WO
Inventors: Alain Vallee; Paul-Andre Lavoie; Michiyuki Kono; Manabu Kikuta; Tetsuya Higashizaki; Hiroyuki Ebisu; Masaki Tezuka; Takao Yokohashi
Original assignee: Avestor Limited Partnership
Priority date: 2004-09-03
Filing date: 2005-08-30
Publication date: 2006-03-09
Also published as: JP2007186533A

Abstract

A process for producing a particle-containing ethylene oxide copolymer resin suffering no decrease in molecular weight of the resin upon mechanical shearing, etc. The production process comprises: a step in which particles comprising an electrochemically active substance are mixed with and dispersed in an ethylene oxide copolymer resin solution comprising a solvent and an ethylene oxide copolymer resin made from 80-95 wt.% ethylene oxide and 5-20 wt.% oxirane compound copolymerizable therewith to prepare a particle-containing ethylene oxide copolymer resin solution; a step in which the solvent is removed from this particle-containing ethylene oxide copolymer resin solution to obtain a flowable particle-containing ethylene oxide copolymer resin; a step in which this flowable particle-containing ethylene oxide copolymer resin is formed into pellets or particles; and a step in which the pellets or particles of the particle-containing ethylene oxide copolymer resin are dried.

Description

Specification

Manufacturing method and packaging method of powder-containing ethylene oxide copolymer resin

TECHNICAL FIELD [0001] The present invention relates to a method for producing a powder-containing ethylene oxide copolymer resin and a packaging method. More specifically, the present invention relates to a powder suitable for use as an extrusion molding raw material. The present invention relates to a production method and a packaging method of a powder-containing ethylene oxide copolymer resin dispersed in a resin copolymer resin.

Background art

[0002] In the processing of thermoplastic resin used in the production of molded articles, films and the like, extrusion molding using an extruder is often performed. In this extrusion molding, it is common to use a pelletized preliminary resin, melt it, mix an additive such as a plasticizer, and supply it to the extruder.

[0003] However, the ethylene oxide copolymer resin is partially decomposed by heat or mechanical shear to cause a decrease in molecular weight. For this reason, there has been a problem in that, when a powder having an oxidizing property such as a vanadium oxide compound is melt-mixed in a kneader and dispersed in a resin and then extruded, the molecular weight of the resin is reduced. .

[0004] As a method for dispersing the powder in the resin, for example, JP 2002-284887A discloses extruding an ethylene butyl alcohol copolymer resin (EVOH) having a water content of 0.5% by weight or more. A method is disclosed in which an aqueous dispersion solution of inorganic fine particles is blended and melt kneaded into EVOH in a water-containing and molten state in this extruder.

However, in this method, in order to disperse the inorganic fine particles uniformly in the resin in the extruder, it is necessary to control the water content of the resin introduced into the extruder and the addition amount of the inorganic fine particles to be kneaded. Equipment and operation methods become complicated. In addition, since the water content of the resin coming out of the extruder is as high as 5 to 40% by weight, when this method is applied to the ethylene oxide copolymer resin used in the present invention, the resin remains sticky. Therefore, pelletization (granulation), which is a post-extrusion process, becomes difficult. In addition, since the melting point of the ethylene oxide copolymer resin is relatively low, it is difficult to apply heat in the drying process, which requires a long time for the drying process. Not right.

Patent Document 1: Japanese Patent Laid-Open No. 2002-284887

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention has been made in view of the above-mentioned problems, and is a method for producing a powder-containing ethylene oxide copolymer resin that can be used for extrusion molding and the like, and has a mechanical share. It is an object of the present invention to provide a production method in which the reduction in the molecular weight of the resin does not substantially decrease. Another object of the present invention is to provide a packaging method for maintaining the performance of the obtained powder-containing ethylene oxide copolymer resin for a long period of time.

Means for solving the problem

[0007] The production method of the present invention is a method for producing a powder-containing ethylene oxide copolymer resin, in which a powder is mixed and dispersed in an ethylene oxide copolymer resin. Ethylene oxide copolymer resin comprising 80 to 95% by weight of ethylene oxide and 5 to 20% by weight of an oxysilane compound copolymerizable with this ethylene oxide, and an ethylene oxide copolymer resin solution having solvent power And a step of preparing a powder-containing ethylene oxide copolymer resin solution by mixing and dispersing a powder containing an electrochemically active substance, and the powder-containing ethylene oxide system. Copolymer resin solution power A step of obtaining a powder-containing ethylene oxide copolymer resin having fluidity by removing the solvent, and a powder-containing ethylene oxide copolymer resin having the fluidity. And pelletizing or granulating And drying the pelletized or granulated powder-containing ethylene oxide copolymer resin.

[0008] As described above, organic powder or inorganic powder can be used as the powder.

[0009] As the electrochemically active substance, one or more selected from the group power consisting of transition metal oxide compounds, phosphate compounds, force bonbons, graphite and carbon one graphite are used. be able to.

[0010] Butylene oxide can be used as an oxysilane compound copolymerizable with ethylene oxide. [0011] In the step of mixing and dispersing the powder in the ethylene oxide copolymer resin solution

It is preferable to prevent the molecular weight from being lowered due to mechanical deterioration of the resin by mixing at a low viscosity.

[0012] The step of removing the solvent from the powder-containing ethylene oxide copolymer resin solution to obtain a powder-containing ethylene oxide copolymer resin resin having fluidity is performed by using a powder-containing ethylene oxide resin solution. It is preferable that the first step of pre-concentrating the copolymer resin solution and the second step of further removing the solvent by stirring at a low temperature using a stirrer having a take-out function are preferable.

[0013] In the step of pelletizing or granulating the powder-containing ethylene oxide copolymer resin, pelletized or granulated resin is pre-cooled and then cooled with a refrigerant while being pelletized. Preferably, it includes a step of wrinkling or granulating.

[0014] It is preferable that the step of drying the powder-containing ethylene oxide copolymer resin includes a step of drying while introducing an inert gas under reduced pressure.

[0015] The powder-containing ethylene oxide copolymer resin of the present invention is packaged by absorbing and absorbing the powder-containing ethylene oxide copolymer resin obtained by any one of the above-described production methods. In order to prevent the deterioration of performance due to oxygen, the packaging container is filled under an inert gas atmosphere.

The invention's effect

[0016] According to the production method of the present invention, it is possible to obtain a powder-containing ethylene oxide copolymer resin having stable physical properties that are free from molecular weight reduction due to thermal degradation or mechanical degradation.

[0017] Further, according to the packaging method of the present invention, since the obtained coffin is not exposed to moisture or oxygen during storage, a decrease in molecular weight is suppressed, and the initial performance is maintained for a long time. The BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, the method for producing a powder-containing ethylene oxide copolymer resin according to the present invention will be described in detail, but the following examples do not limit the scope of the present invention. The present invention can be implemented with appropriate modifications within a range not impairing.

[0019] 1. Mixing and dispersing step of powder-containing ethylene oxide copolymer resin

In the production method of the present invention, first, ethylene oxide copolymer resin and solvent power are also obtained. The powder is added to the thylene oxide copolymer resin solution and mixed and dispersed at a low viscosity. As a result, it is possible to obtain a resin having uniformly dispersed powder having no decrease in molecular weight. Specifically, the viscosity is preferably 1, OOOPa's or less at a temperature of 60 ° C.

[0020] The ethylene oxide copolymer resin used in the present invention is composed of 80 to 95% by weight of ethylene oxide and 5 to 20% by weight of an oxysilane compound copolymerizable with this ethylene oxide (total of both). And 100% by weight). The molecular weight varies depending on the use of the resin and is not particularly limited, but is usually about 50,000 to 200,000 in weight average molecular weight.

[0021] Examples of the oxysilane compound copolymerizable with ethylene oxide include propylene oxide, butylene oxide, methyl daricidyl ether, ethyl daricidyl ether, propyl glycidyl ether, butyl daricidyl ether, and allyl glycidyl ether. Of these, one or more of these can be used. Of these, butylene oxide is particularly preferred.

[0022] Next, it is preferable that the powder contains an electrochemically active substance that is either an organic substance, an inorganic substance, or a mixture of both. Examples of the electrochemically active substance include transition metal oxide compounds, phosphate compounds, carbon, graphite, and carbon graphite mixtures, and may be a mixture of two or more of these. . Examples of transition metal oxide compounds include acid-vanadium compounds, acid-manganese compounds, and titanium oxide compounds. An example of the phosphate compound is iron phosphate.

[0023] As a preferred example of the powder, it is composed of an acid-vanadium compound and a forceful powder used as needed, and the blending ratio of both is an acid vanadium compound: carbon powder = 100- 90: 0 to: L0 include those (weight ^_0/0, the sum of both 100 weight ^_0/0). Examples of vanadium oxide compounds include VO, VO, and Li VO (X: 1. 0 to 1.4

2 5 3 8 3 8

) And their lithiated compounds.

[0024] The average particle size of the powder is not particularly limited, but is usually in the range of 1 to 10 µm.

[0025] The amount of the powder added is preferably in the range of 1 to L0 times, more preferably in the range of 1 to 4 times the weight of the resin.

[0026] Depending on the use of the powder-containing resin, an antioxidant, an antiseptic, a light resistance improver, etc. may be added. Let's add some additional ingredients.

[0027] Examples of the solvent used for diluting and dissolving the resin include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; solvents of ethylene glycol dialkyl ethers such as dimethoxyethane and ethylene glycol dimethyl ether. A cyclic ether solvent such as tetrahydrofuran and dioxane, a solvent of alcohols such as methanol and ethanol; a polar solvent such as acetonitrile, N, N-dimethylformamide and acetone; or water. Of these, toluene and xylene are preferable in terms of cost.

[0028] The amount of the solvent is more preferably 10 to 40% by weight, more preferably 5 to 70% by weight of the resin solids in the solution.

[0029] The apparatus used for mixing and dispersion is not particularly limited, but a reactor equipped with a stirring blade (helical ribbon blade, super blend blade, max blend blade, full zone blade, etc.), a proshaker mixer, a combination mix, etc. Is a preferred example. Since the usage conditions differ depending on the equipment used, set the conditions according to the equipment.

[0030] The temperature of the solution during mixing is preferably 40 to 100 ° C, more preferably 60 to 80 ° C.

[0031] 2. Solvent removal step of powder-containing ethylene oxide copolymer resin solution

The solvent removal step in the present production method is performed by volatilizing and removing the solvent used as a solvent, such as a powder-containing ethylene oxide copolymer resin solution, to provide a fluid-containing powder-containing ethylene oxide copolymer. This is a process for obtaining fat, and the degree of solvent removal is such that the fat is completely free of solvent, and it is not necessary if the solvent falls below a predetermined concentration.

[0032] The solvent removal step passed through a first stage (preliminary concentration) in which the solvent used as the solvent was partially volatilized from the powder-containing ethylene oxide copolymer resin solution at a low temperature and the first stage. Remove the powdered ethylene oxide copolymer resin solution and transfer it to a stirrer equipped with a function.

It is preferable to have a two-stage force with the second stage to remove the solvent at a low temperature to a predetermined concentration. As a result, it is possible to take out the powder-containing ethylene oxide copolymer resin in a desired form as much as possible to prevent deterioration of the molecular weight due to thermal and mechanical deterioration of the powder-containing ethylene oxide copolymer resin. Become. Therefore, if the subsequent pelletization process is taken into consideration, the productivity is very good and the method is economically excellent. . These two-stage solvent removal steps will be described more specifically below.

[0033] (1) First stage

The solvent removal step in the first step is a step of concentration until the amount of solvent (solvent concentration) in the solution is preferably 25 to 60% by weight, more preferably 30 to 50% by weight. When the solvent concentration is less than 25% by weight, the viscosity of the resin solution increases rapidly, requiring a high-powered stirrer and making it difficult to remove the evaporation tank.

[0034] The apparatus used for solvent removal is not particularly limited, but a stirring type evaporation tank capable of reducing pressure is preferable. As the stirring blade, for example, a helical ribbon blade, a super blend blade, a max blend blade, or a full zone blade can be used. You can also use a professional share mixer or combination mix. Use conditions are set according to the device.

[0035] The solvent removal temperature is preferably 40 to 110 ° C, particularly preferably 60 to 90 ° C. When the temperature is lower than 40 ° C, the viscosity at the end of concentration increases. When the temperature exceeds 110 ° C, the molecular weight decreases.

[0036] (2) Second stage

In the second stage of solvent removal step, the solvent concentration is preferably 5 to 30% by weight, more preferably 10 to 25% by weight. If the solvent concentration is less than 5% by weight, it cannot be stirred even with a high-powered stirrer, and the removal of the molecular weight is caused by the mechanical shear that may be impossible to remove. Furthermore, since the fluidity of the fat is lost, it is difficult to arbitrarily change the shape at the time of taking out.

[0037] The device used in the second stage is a solvent removal device having a take-out function, and the take-out function is a mechanism such as a screw that feeds the contents of the device or a mechanism in which the upper part or side part is largely opened. Specific examples include (a) a device equipped with a feed mechanism, a twin screw extruder (KRC), a self-cleaning reactor (SCR), a single screw extruder, and (b) itself. A vacuum drum dryer, a vacuum belt dryer, (c) an open part on the top and Z or side, and a pro-share mixer etc. can be taken out from the open part. Depending on the device used, various shapes such as a block shape (a block shape), a rod shape or a string shape (a strand shape), and a plate shape (a sheet shape) can be used. Use conditions are set according to the device.

[0038] The solvent removal temperature at this stage is preferably 40 to 110 ° C, more preferably 50 to 90 ° C. [0039] 3. Pelletization (granulation) step of powder-containing ethylene oxide copolymer resin The powder-containing ethylene oxide copolymer plate taken out in a shape corresponding to the apparatus through the above steps Make fat as pellets (granular) as the final product. The method is preferably a method in which a lump is once formed into a sheet or string with an extruder or the like, and then the mold is cooled and solidified to process the force into a pellet (granular). It can also be directly pelletized (granular) from the product.

[0040] In order to form a sheet or string into force and pelletize (granulate), a polymer pump or gear pump is attached to the take-out port (wax discharge port) of the solvent removal device described above, and A method of extruding the body-containing ethylene oxide copolymer resin from the solvent removal apparatus and extruding it with a connected extruder, or a method using a T die or a roll instead of the extruder is preferably used.

[0041] Examples of the extruder include a single screw extruder, a twin screw extruder, a self-cleaning reactor (

Forces such as SCR) In order to extrude into a sheet or plate with a certain thickness, it is preferable to attach the extruder with a T-die or nozzle.

[0042] In order to prevent the mechanical deterioration of the extruded molded product, it is preferable to use a device with high speed and high speed to prevent mechanical deterioration. Molding runner crusher, pelletizer 1 (strand cut type, hot cut type, sheet cut type, etc.).

[0043] It is preferable to use a drop former to extrude into pellets or fine particles.

[0044] The temperature when using the extruder is preferably 40 to 110 ° C, more preferably 50 to 80 ° C, and the degree of vacuum is preferably 1 to 25 kPa, more preferably 5 to 15 kPa.

[0045] When pelletizing (granulating), in order to prevent the fusion of the resin to the apparatus, the resin is cooled and solidified with a refrigerant in advance, and is put together with the refrigerant into a pulverizer, and cut or cut. It is preferable to grind. At this time, the refrigerant is introduced by adjusting so that the resin temperature at the outlet is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, and further preferably 0 ° C. or lower. Examples of the refrigerant include liquid nitrogen, carbon dioxide, nitrogen gas and the like. In addition, it is preferable to use pellets in an inert gas atmosphere to prevent oxidation.

[0046] 4. Solvent removal of powder-containing ethylene oxide copolymer rosin 'drying step After the pelletization (granulation) step, the solvent and water remaining in the pellet-like (granular) powder-containing ethylene oxide copolymer resin are removed by placing them under reduced pressure. The device to be used is not particularly limited in shape and material as long as it is a device equipped with a container that can be depressurized and sealed, but it can be depressurized from the upper part of the container and can introduce an inert gas from the lower part. Can be preferably used. The temperature control function is not particularly required, but it may be equipped. Examples of equipment include professional share mixers, nauter mixers, vacuum dryers, and vacuum shelf dryers.

[0047] For example, when solvent removal and drying are performed using a Proshare mixer, the pressure is preferably maintained while keeping the temperature in the range of 0 to 30 ° C so that the resin does not melt or deteriorate. The pressure is reduced to a range of 1 to 10 kPa, more preferably 3 to 6 kPa, to remove residual solvent 'moisture. At this time, an inert gas is introduced from the bottom of the container as necessary.

[0048] Examples of the inert gas include nitrogen gas, helium gas, and argon gas, and the introduced gas is heated to a suitable temperature as necessary.

[0049] 5. Packaging method for powder-containing ethylene oxide copolymer resin

In order to prevent this, the powder-containing ethylene oxide copolymer resin that has been pelletized (granulated) as described above is subject to moisture absorption and performance degradation when exposed to moisture and oxygen after drying. In addition, it is preferable to introduce an inert gas using a depressurized mixing tank and replace moisture or moist air before filling the container. As the inert gas, nitrogen gas, helium gas, argon gas or the like is used as described above. If necessary, the replacement rate can be increased by reducing the pressure in the mixing tank. In addition, it is preferable to flow an inert gas such as dry air or nitrogen through a filling line from the mixing tank to the packaging container.

[0050] As a product packaging container, a gas-permeable and moisture-permeable bag having a low material strength is preferred in order to prevent air from entering. For example, an aluminum laminated bag having an inner surface coated with a resin is preferably used. . The bag is preferably flushed with an inert gas such as nitrogen immediately before filling to expel the pre-filled air. If necessary, after filling the product, introduce an inert gas into the bag using a nozzle, etc., and then seal the opening of the bag.

[0051] Through the above steps, a powder-containing ethylene oxide copolymer resin having stable physical properties and free from molecular weight reduction due to thermal and mechanical deterioration can be obtained. Example

[0052] Examples of the present invention are shown below, but the present invention is not limited thereto.

[0053] The molecular weights (weight average molecular weights) of the copolymers in the following synthesis examples and examples were measured by gel permeation chromatography (GPC) analysis. The measurement conditions are as follows.

[0054] Column: Guard column PWXL + G5000PWXL

+ G4000PWXL + G3000PWXL

+ G2500PWXL (above, manufactured by Tosoh Corporation)

Column size: 7.8mm X 30cm

Column temperature: 40 ° C

Eluent: acetonitrile Ζθ.08Μ-sodium acetate solution = 50-50 (dissolution ratio)

: 1. Om mm

Detector: Differential refraction detector

Reference material: Polyethylene oxide manufactured by Tosoh Corporation, molecular weight 2,000-900, 000

[0055] [Synthesis Example 1]

A 100-liter pressurized reaction vessel equipped with a stirring blade is charged with 35 kg of dehydrated toluene and 5 g of sodium methylate as a catalyst, heated to 90 ° C, and adjusted to a pressure of 200 kPa or less and a temperature of 120 ° C or less. did. Copolymer solution 1 was obtained by charging 15 kg of ethylene oxide and 1,2-butylene oxide as raw materials for the resin in a ratio of 90:10 (weight ratio) and reacting them. When the molecular weight of the copolymer was examined, it was 113,000.

[0056] [Example 1]

50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200 liter combination mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. . Subsequently, 35 kg of lithiated oxyvanadium / carbon powder mixture (US Avestor LLC, lithiated oxyvanadium Z carbon powder = 95: 5 (weight ratio, the same applies below)) was added and stirred for 30 minutes. After preparing a uniform dispersion, toluene was distilled off under reduced pressure until the toluene content was 40% by weight to obtain a concentrated solution. The resulting concentrated solution is transferred to a process air mixer, and toluene is further reduced in pressure until the toluene content reaches 15% by weight. Distilled off. The obtained concentrate was taken out in the form of a lump directly at the upper part of the apparatus. The taken out mass was cooled to 10 ° C or less with carbon dioxide gas, pulverized into granules with a molding runner pulverizer, transferred to a Nauter mixer, and dried under reduced pressure at a temperature of 25 ° C and a pressure of 4 kPa. The dried granular material was transferred to an aluminum laminated bag (inner polyethylene polyethylene coating, the same applies hereinafter) under a nitrogen atmosphere and sealed by heat sealing.

[0057] Table 1 shows the molecular weight immediately after concentration of the concentrate (before pelletization or granulation, the same applies hereinafter), immediately after heat sealing of the granular material, and after storage for 1 month.

[Example 2]

50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200-liter reactor equipped with a Max Blend blade, and 100 kg of toluene was added to adjust the liquid temperature to 80 ° C. Subsequently, 45 kg of lithium oxalate / vanadium / carbon powder mixture (manufactured by US Avestor LLC) was added, and the mixture was stirred for 60 minutes to prepare a uniform dispersion solution. Toluene was distilled off to obtain a concentrated solution. This concentrated solution is transferred to the reactor of the self-cleaning reactor (SCR), and the melt with a toluene content of 20% by weight is taken out and introduced into a vacuum drum drier to form residual flakes. I got a thing. The obtained flake shaped product was cut into pellets with a pelletizer while being cooled with nitrogen gas. The obtained pellets were transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 30 ° C and a pressure of 6 kPa. The dried pellets were transferred to an aluminum laminate bag under a nitrogen atmosphere and sealed by heat sealing.

[0059] Table 1 shows the molecular weight immediately after concentration of the concentrate, immediately after heat sealing of the pellet, and after storage for 1 month.

[0060] [Example 3]

50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 350 liter reactor equipped with a helical blend blade, and 150 kg of toluene was added to adjust the liquid temperature to 55 ° C. Next, 22.5 kg of lithium oxalate / vanadium / carbon powder mixture (manufactured by US Avestor LLC) was added, stirred for 15 minutes to prepare a uniform dispersion, and the toluene content was reduced to 65% by weight under reduced pressure. Toluene was distilled off until a concentrated solution was obtained. This concentrated solution is transferred from the coating nozzle cover onto the belt of the vacuum belt cooler and dried under reduced pressure. Thus, a sheet-like molded product having a toluene content of 5% by weight was obtained. The obtained sheet-shaped product was cut into pellets with a pelletizer while being cooled with nitrogen gas. The obtained pellet was transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 30 ° C and a pressure of 6 kPa. The dried pellets were transferred to an aluminum laminate bag under a nitrogen atmosphere and sealed by heat sealing.

[0061] Table 1 shows the molecular weight immediately after concentration of the concentrate, immediately after heat sealing of the pellet, and after storage for 1 month.

[0062] [Example 4]

50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 350 liter reactor equipped with a helical blend blade, and 150 kg of toluene was added to adjust the liquid temperature to 55 ° C. Next, 22.5 kg of lithium oxalate / vanadium / carbon powder mixture (manufactured by US Avestor LLC) was added, stirred for 15 minutes to prepare a uniform dispersion, and the toluene content was reduced to 60% by vacuum. Toluene was distilled off until a concentrated solution was obtained. This concentrated solution was continuously introduced into a single-screw extruder equipped with a decompression line, and extruded from a nozzle while distilling off toluene under reduced pressure to obtain a strand-shaped product having a toluene content of 10%. The obtained strand-shaped molded product was cut with a pelletizer (strand cut type) while cooling to 5 ° C. with carbon dioxide gas to obtain pellets. The obtained pellets were dried in the same manner as in Example 1, then transferred to an aluminum laminate bag in a glove box in which argon gas was sealed, and sealed by heat sealing.

[0063] Table 1 shows the molecular weights immediately after concentration of the concentrate, immediately after heat sealing of the pellets, and after storage for 1 month.

[0064] [Example 5]

1 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 10 liter reactor equipped with a helical blend blade, and 1 kg of xylene was added to adjust the liquid temperature to 60 ° C. Next, 3.5 kg of lithium lithium oxide vanadium / carbon powder mixture (manufactured by US Avestor LLC) was added, and the mixture was stirred for 60 minutes under a nitrogen atmosphere to prepare a uniform dispersion solution. Toluene was distilled off until the amount reached 15% by weight, and further stirring was stopped to concentrate the toluene content to 2%. The concentrate was removed directly in bulk from the reactor top force. The extracted lump is cooled to 10 ° C or less with carbon dioxide gas and pulverized for molding runners. After being pulverized into granules by a machine, it was introduced into a pelletizer (hot cut type) to obtain pellets. The obtained pellets were transferred to a Nauter mixer and dried under reduced pressure at a temperature of 25 ° C. and a pressure of 8 kPa while introducing nitrogen gas. Transfer the dried granular material to an aluminum laminate bag in a nitriding atmosphere.

And sealed by heat sealing.

[0065] Table 1 shows the molecular weights immediately after concentration of the concentrate, immediately after heat sealing of the pellets, and after storage for 1 month.

[0066] [Comparative Example 1]

10 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200-liter combined mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. . Subsequently, 4 Okg of lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added, stirred for 60 minutes, and then concentrated to 15% by toluene under reduced pressure. Stirring became impossible, making it difficult to remove from the bottom of the combination mix.

[0067] [Comparative Example 2]

50 kg of the copolymer solution 1 obtained in Synthesis Example 1 was charged into a 200-liter combination mix equipped with a stirring blade and a dispersion blade, and 100 kg of toluene was added to adjust the liquid temperature to 60 ° C. . Subsequently, 5 kg of lithiated vanadium oxide / carbon powder mixture (manufactured by US Avestor LLC) was added and stirred for 30 minutes to prepare a uniform dispersion, and then toluene was reduced until the toluene content was reduced to 40% by weight. Was distilled off to obtain a concentrated solution. Further, the concentrated solution was transferred to a Proshare mixer, and toluene was further distilled off under reduced pressure while stirring until the toluene content became 3% by weight. The obtained concentrate was directly taken out as a lump from the upper part of the apparatus at a temperature of 60 ° C. The following operations were performed in the same manner as in Example 1.

[0068] Table 1 shows the molecular weights immediately after concentration of the concentrate, immediately after heat sealing of the pellets, and after storage for 1 month.

[0069] [Comparative Example 3]

In Example 1, pulverization was performed in a molding runner pulverizer in an environment with an air temperature of 27 ° C and a relative humidity of 82%. After 20 minutes from the start of pulverization, the lump was melted and fused inside the pulverizer, and pulverization could not be continued. [0070] [Comparative Example 4]

In Example 2, pellets having a toluene content of 5% by weight obtained by cutting were transferred to a vacuum shelf dryer and dried under reduced pressure at a temperature of 35 ° C. and a pressure of 30 kPa. The toluene content after drying for 5 hours was 2% by weight and was not dried. Subsequently, the pellet was transferred to a polyethylene bag in an air environment having an air temperature of 27 ° C. and a relative humidity of 82%, and sealed by heat sealing.

[0071] Table 1 shows the molecular weight immediately after the concentration of the concentrate, the molecular weight immediately after the heat sealing of the pellet, and after storage for 1 month.

[0072] [Comparative Example 5]

In Example 2, the resin solution was concentrated in the same manner except that the pressure reduction degree of the reactor of the self-cleaning reactor was changed to 50 kPa and the temperature was changed to 80 ° C. Since the composition taken out from the vacuum drum dryer had a solvent concentration of 35% by weight and had fluidity and could not be solidified, a sheet could not be formed.

[0073] [Table 1]

Industrial applicability

The powder-containing ethylene oxide copolymer resin obtained by the production method of the present invention is: For example, it can be suitably used as a positive electrode material for a lithium secondary battery.

Claims

The scope of the claims

[1] A method for producing a powder-containing ethylene oxide copolymer resin, in which a powder is mixed and dispersed in an ethylene oxide copolymer resin,

And Echirenokishido 80-95 weight ^_0/0, Echirenokishido copolymer榭脂and solvent power also E Chirenokishido system copolycondensates consisting of the Echirenokishido copolymerizable with Okishira emission compound 5-20 wt% A step of preparing a powder-containing ethylene oxide copolymer resin solution by mixing and dispersing a powder containing an electrochemically active substance in the combined resin solution;

A step of obtaining a powder-containing ethylene oxide-based copolymer resin having fluidity by removing the powder-containing ethylene oxide-based resin resin solution solvent;

Pelletizing or granulating the powder-containing ethylene oxide copolymer resin having the fluidity; and

Drying the pelletized or granulated powder-containing ethylene oxide copolymer resin; and

A process for producing a powder-containing ethylene oxide copolymer resin characterized by comprising:

[2] The method for producing a powder-containing ethylene oxide copolymer resin according to claim 1, wherein an organic powder is used as the powder.

[3] The method for producing a powder-containing ethylene oxide copolymer resin according to claim 1, wherein an inorganic powder is used as the powder.

[4] The electrochemically active substance is one or more selected from the group force consisting of transition metal oxide compounds, phosphate compounds, carbon, graphite, and carbon-graphite. The method for producing a powder-containing ethylenide-based copolymer resin according to any one of claims 1 to 3, wherein:

5. The powder-containing ethylene oxide copolymer resin according to any one of claims 1 to 4, wherein the oxysilane compound copolymerizable with the ethylene oxide is butylene oxide. Manufacturing method.

[6] In the step of mixing and dispersing the powder in the ethylene oxide copolymer resin solution, mixing at a low viscosity prevents a decrease in molecular weight due to mechanical deterioration of the resin. The method for producing a powder-containing ethylene oxide-based copolymer resin according to any one of claims 1 to 5, wherein:

[7] The step of removing the solvent from the powder-containing ethylene oxide copolymer resin solution to obtain a powder-containing ethylene oxide copolymer resin resin having fluidity is a powder-containing ethylene oxide resin solution. The first stage of pre-concentrating the copolymer resin solution and the second stage of further removing the solvent by stirring at a low temperature using a stirrer equipped with a take-out function. 7. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of 1 to 6.

[8] Process for pelletizing or granulating the powdered ethylene oxide copolymer resin Force pellets or granulated resin is pre-cooled and then cooled with a refrigerant while being pelletized. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of claims 1 to 7, further comprising a step of granulating the powder.

[9] The step of drying the powder-containing ethylene oxide copolymer resin includes a step of drying while introducing an inert gas under reduced pressure. The method for producing a powder-containing ethylene oxide copolymer resin according to any one of 1 to 3 above.

[10] In order to prevent the powder-containing ethylene oxide copolymer resin obtained by the production method according to any one of claims 1 to 9 from moisture absorption and performance deterioration due to oxygen, an inert gas is used. A packaging method for a powder-containing ethylene oxide copolymer resin, wherein the packaging container is filled in an atmosphere.