JP5743538B2 - Polyether copolymer - Google Patents

Description

The present invention relates to a polyether copolymer. More specifically, the present invention relates to a polyether copolymer that can be suitably applied to various uses such as electrochemical field through a step of forming a molten polymer into a sheet, pelletizing, and the like.

The polyether copolymer is a copolymer having a main chain having a plurality of ether bonds composed of monomer units such as alkylene oxide, and exhibits characteristics derived from the polyether structure, and is an industrial resin. It is used as a material and plastic material. General applications that have been used so far include a wide range of applications such as molding materials, adhesives, paints, sealants, and surfactants. In recent years, however, they are particularly related to information technology (IT). The application to the electrochemical field is expected. In these applications, the polyether copolymer is used by melting and molding, or by dispersing and dissolving in a solvent for coating.

Regarding conventional polyether copolymers, as a production method thereof, a monomer mixture containing ethylene oxide and a substituted oxirane compound having a specific structure as essential raw materials is polymerized while stirring with a specific stirring power in a solvent. A method for producing an ethylene oxide copolymer is disclosed (for example, see Patent Document 1). Further, as a processing method for using the polyether copolymer, for example, as a method for pelletizing the polyether copolymer, an ethylene oxide-butylene oxide system having a crystallization temperature in the range of 10 to 60 ° C. The copolymer resin is melted and extruded to a predetermined thickness, and the extruded molten resin is cooled and solidified by bringing it into contact with a metal surface having a temperature equal to or lower than the crystallization temperature of the resin. A method of cutting a resin into pellets is disclosed (for example, see Patent Document 2).

Japanese Patent No. 4289890 (page 1-2) Japanese Patent No. 3837636 (1st page)

By the way, when supplying and using a polyether copolymer, it may be required to carry out a step of pelletizing the molten polymer in the production process from the viewpoint of ease of handling. In particular, in the electrochemical field and the like, it has been studied to use a polyether copolymer as a polymer electrolyte, but in order to use it for such applications, it is preferable to use a pelletized one. For example, it is envisaged that a raw material such as a lithium compound is blended into a pellet-shaped polymer and molded into a sheet or film to be used in the form of a polymer electrolyte sheet or film. In recent years, with the growing interest in environmental issues, the conversion of energy resources from fossil fuels such as oil and coal has been studied, and in order to store and use alternative energy sources, they are repeatedly used. A secondary battery capable of discharging is attracting attention, but the use of a polyether copolymer as a polymer electrolyte used in the secondary battery is expected. Therefore, it is important to make it possible to stably supply a polyether copolymer in a form suitable for electrochemical device applications such as a polymer electrolyte in the technical field.
Still further, the hot cut for cutting the molten resin at the discharge port of the extruder includes the possibility of foreign metal contamination because contact between metals is unavoidable, and is not desirable for electrolyte applications. Therefore, it is preferable to granulate a polymer formed into a strand shape or a sheet shape.

As described above, when the polyether copolymer is industrially supplied, when the polyether copolymer in a molten state is processed into a pellet or the like, for example, it is bent and attached to the apparatus. There was a problem that trouble sometimes occurred. In particular, in electrochemical device applications such as polymer electrolytes, high accuracy and quality are required, so that the degree of processability of the polyether copolymer can be sufficiently suppressed and processed. It is also a question of how the processability of the polyether copolymer can be improved. If it becomes possible to use a polyether copolymer with improved processability, it is preferable from the viewpoint of increasing the efficiency of processing steps such as pelletization and reducing the incidence of defective products.

This invention is made | formed in view of the said present condition, It aims at providing the polyether copolymer excellent in workability and handleability, and suitable for electrochemical device uses, such as a polymer electrolyte.

The inventors of the present invention have made various studies so that the polyether copolymer can be suitably used in various fields such as the electrochemical field. As a result, processability such as pelletization is an important technology in the polyether copolymer. We focused on the fact that it has significant significance. And the mechanical properties of the synthesized polyether copolymer will greatly change its workability, and the optimum range as a polyether copolymer with excellent workability in specific physical properties such as yield stress and breaking stress. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly. The optimum range is an index of how much the processability of the polyether copolymer can be processed with sufficiently reduced defects, which has not been assumed so far. In addition, even when the polyether copolymer is used without being formed into a sheet or pellet, since the viscosity is relatively low compared to a polyether having a higher tensile strength, the synthesis equipment specifications are special. It is excellent in terms of being light and easy to use, having good liquid drainage when transported by piping, filling a shipping container, excellent handleability, and good workability by the user. It is. In particular, in electrochemical device applications such as polymer electrolytes, high accuracy and quality can be obtained when processing and using a polyether copolymer, even if it is used without being formed into a sheet, pelletized or not. It can be achieved.

That is, the present invention is a polyether copolymer characterized in that the yield stress in a tensile test at a temperature of 20 ° C. is 1.0 to 8.0 MPa.
The present invention is described in detail below.

The polyether copolymer of the present invention has a yield stress of 1.0 to 8.0 MPa in a tensile test at a temperature of 20 ° C. In the step of pelletizing the polyether copolymer, when the sheet-like or strand-like polyether copolymer is tensioned and introduced into the granulating apparatus, the yield stress value is the polyether copolymer of the present invention. When the value is lower than the lower limit of the value, the strength against tension is low, so that the sheet or strand may be cut or bent. In addition, those having a high yield stress often have high molecular weight and viscosity, and the polyether copolymer having a yield stress value higher than the upper limit of the value of the polyether copolymer of the present invention is However, it is not preferable because it is difficult to mold. Furthermore, since the polyether copolymer having a yield stress value higher than the upper limit of the value of the polyether copolymer of the present invention is stiff and hard, it is wound with a roll when formed into a sheet. There is a risk that the pelletizer teeth may be chipped and cause foreign matter contamination when pelletizing. On the other hand, a polyether copolymer having a yield stress within the above specific range has an appropriate strength and excellent workability. The yield stress in the tensile test at 20 ° C. is preferably 1.5 to 7.5 MPa, more preferably 2.0 to 7.0 MPa, and still more preferably 3.0 to 5.0 MPa. It is.
The yield stress will be described later by a tensile test using an Instron universal testing machine (product name “1185 type testing machine”, manufactured by Instron) at a temperature of 20 ° C. and a tensile speed of 20 mm / min. It can be measured in the same manner as in the examples. As a test piece used for the test, it is preferable to use a test piece having a length of 5 to 10 cm, a width of 1 to 2 cm, and a thickness of 150 to 200 μm.

The polyether copolymer preferably has a breaking stress in a tensile test at a temperature of 20 ° C. of 4.0 to 20 MPa. A polyether copolymer having a breaking stress value in such a range has higher workability, and can be suitably used depending on the use in which it is formed into a sheet or pelletized. The breaking stress in the tensile test at a temperature of 20 ° C. is preferably 4.5 to 18.0 MPa, more preferably 5.0 to 15.0 MPa, and still more preferably 5.0 to 12.0 MPa. It is.
In addition, the said breaking stress can be measured by performing the same tensile test as the yield stress mentioned above.
As described above, the polyether copolymer of the present invention is excellent in processability and handleability and is suitable for use in electrochemical devices such as polymer electrolytes. It is a polyether copolymer that is particularly suitable for processing by the conversion process.

As described above, the polyether copolymer of the present invention has a yield stress in a specific range in a tensile test at a temperature of 20 ° C., and if it is a polyether copolymer having such characteristics, The structure is not particularly limited, but the following general formula (1);
AxByCz (1)
(In the formula, A represents —CH ₂ CH ₂ O—, B represents —CH ₂ CH (R ¹ ) O—, R ¹ represents —Re—Rf—R ³ , Re represents _{- (CH 2 CH 2 O)} p- and represents, p is the same or different, is .Rf represents an integer of _{0~10, - (CH 2 O)} q- and represents, q are the same or different , 0 or 1. R ³ is the same or different and may have a substituent, an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, or a carbon number having 6 to 16 carbon atoms. Represents an aryl group, an aralkyl group having 7 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms, C represents —CH ₂ CH (R ² ) O—, and R ² represents —Re—Rf—. .R ⁴ representing a R ⁴ are the same or different, an alkenyl group having 2 to 16 carbon atoms, cycloalkenyl of 3 to 16 carbon atoms Group represents a (meth) acryloyl group, x represents the mole fraction of A, y represents B, z represents the mole fraction of C, x is 0.80 to 0.98, and y is 0 0.02 to 0.20, and z is preferably 0 to 0.05).
The polyether copolymer having such a configuration is one of preferred embodiments of the copolymer that can satisfy the above yield stress and breaking stress.

B in the general formula (1) represents —CH ₂ CH (R ¹ ) O—, and R ¹ represents —Re—Rf—R ³ . Said Re _{is, - (CH 2 CH 2 O} ) p- and represents, p is the same or different and each represents an integer of 0. The p is preferably 0 to 5, and more preferably 0 to 3. Particularly preferred is 0. Rf represents — (CH ₂ O) q—, and q is the same or different and represents 0 or 1. R ³ may be the same or different and may have a substituent, an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or 7 carbon atoms. Represents an -16 aralkyl group or an acyloxy group having 2 to 16 carbon atoms. Examples of the substituent in R ³ include an alkoxy group having 1 to 6 carbon atoms and an acyloxy group having 2 to 16 carbon atoms. As the R ³ Of these, which may have a substituent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, 7 carbon atoms 10 aralkyl groups and acyloxy groups having 2 to 10 carbon atoms are preferred, more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms, and a carbon number. A 6-8 aryl group, a C7-9 aralkyl group, and a C2-6 acyloxy group. More preferably, they are an optionally substituted alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and a phenyl group, and particularly preferably an alkyl group having 1 or 2 carbon atoms. is there.
In B, a ring structure may be formed by the carbon atom constituting R ¹ and two carbon atoms other than R ¹ .

Specific examples of preferred form of B include propylene oxide, butylene oxide, 1,2-epoxypentane, 1, and the like as raw material monomers used for introducing B into the polyether copolymer. Examples include 2-epoxyhexane, 1,2-epoxyoctane, cyclohexene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, and ethylene glycol methyl glycidyl ether. Among these, methyl glycidyl ether, propylene oxide, butylene oxide, and 1,2-epoxypentane are more preferable, and propylene oxide and butylene oxide are more preferable.

C in the general formula (1) represents —CH ₂ CH (R ² ) O—, and R ² represents —Re—Rf—R ⁴ . Re and Rf are the same as Re and Rf described above. R ⁴ is the same or different and represents an alkenyl group having 2 to 16 carbon atoms, a cycloalkenyl group having 3 to 16 carbon atoms, or a (meth) acryloyl group. Examples of the substituent in R ⁴ include an alkenyl group having 2 to 16 carbon atoms, a cycloalkenyl group having 3 to 16 carbon atoms, and a group represented by — (OCH ₂ CH ₂ ) r—O—Rg (r is 0 Represents an integer of from 10 to 10. Rg represents an alkenyl group having 2 to 16 carbon atoms. Thus, R ⁴ is a crosslinkable functional group, and among these, R ⁴ includes an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, and a (meth) acryloyl group. Preferable are an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 7 carbon atoms, and a (meth) acryloyl group, and an alkenyl group having 3 to 6 carbon atoms is particularly preferable.
In C, a ring structure may be formed by the carbon atom constituting R ² and ^two carbon atoms other than R ² .

Specific examples of preferred C include epoxy butene, 3,4-epoxy-1-pentene, 1, and the raw material monomer used for introducing C into the polyether copolymer. 2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl-4 -Hexanoate or vinyl glycidyl ether, allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpenyl glycidyl ether, cyclohexenyl methyl glycidyl ether, 4-vinylbenzyl glycidyl ether, 4-allylbenzyl glycidyl ether, allyl glycidyl ether Ether, ethylene glycol allyl glycidyl ether, ethylene glycol vinyl glycidyl ether, diethylene glycol allyl glycidyl ether, diethylene glycol vinyl glycidyl ether, triethylene glycol allyl glycidyl ether, triethylene glycol vinyl glycidyl ether, oligoethylene glycol allyl glycidyl ether, oligoethylene glycol vinyl glycidyl ether Ether. Among these, epoxybutene and allyl glycidyl ether are more preferable, and allyl glycidyl ether is more preferable.

In the above general formula (1), x represents the mole fraction of A, y is B, and z is the mole fraction of C, x is 0.80 to 0.98, and y is 0.02 to 0.0. 20 and z is 0 to 0.05. Among these, x is 0.85-0.97, y is 0.03-0.15, z is preferably 0-0.03, more preferably x Is 0.90 to 0.96, y is 0.04 to 0.10, and z is 0 to 0.02.
In the general formula (1), each of A, B, and C may be one type or two or more types. In the case of two or more types, the combined state may be a block shape, a random shape, or an alternating state. Also, the combined state of A, B, and C may be a block shape, a random shape, or an alternating state. Since the melting point of the obtained polyether copolymer can be adjusted depending on the bonding state, the type of monomer used for producing the polyether copolymer and the single monomer. By appropriately setting the bonding state according to the blending ratio of each monomer in the monomer mixture, the melting point of the polyether copolymer can be in a preferable range as described later.

The polyether copolymer having the structure represented by the general formula (1) is, for example, ethylene oxide used for introducing A in the general formula (1), the general formula (1) described above, as described later. The raw material monomer used for introducing B in the above and the raw material monomer used for introducing C in the general formula (1) described above are represented by x, y, and z in the general formula (1). It can be produced by stirring and polymerizing a monomer mixture containing a mole fraction in a solvent. In the polyether copolymer thus obtained, the terminal structure is a monomer bonded to the terminal portion among the monomers contained in the monomer mixture, or a single monomer. It originates from the residue of the reaction initiator used when polymerizing the body mixture, and examples thereof include an alkali metal salt of a hydroxyl group such as an alkoxy group, a hydroxyl group, and -O ^- Na ⁺ . In addition, the said terminal structure may be further substituted by substitution reaction etc., and this substitution reaction can be performed with the reagent, reaction conditions, etc. which are normally used as substitution reaction.
Furthermore, in addition to the raw material monomers used for introducing A, B and C, the polyether copolymer having the structure represented by the above general formula (1) is used in addition to these raw material monomers. It may be obtained by polymerizing a monomer mixture containing other monomer components. That is, the polyether copolymer having the structure represented by the general formula (1) is a structural site derived from the other monomer components in addition to the structural sites represented by A, B and C. You may have.
However, the ratio of the structural portion represented by the general formula (1) to the entire polyether copolymer having the structure represented by the general formula (1) is 99 to 100% by mass. Is preferred. More preferably, it is 99.5-100 mass%, More preferably, it is 99.9-100 mass%.

The polyether copolymer preferably has a weight average molecular weight of 30,000 to 500,000. When the weight average molecular weight is in such a range, it is possible to contribute to giving an appropriate strength when the polyether copolymer is formed into a strand, a sheet, or a pellet. More preferably, it is 50,000-300,000 as a weight average molecular weight, More preferably, it is 50,000-200,000, Most preferably, it is 80,000-150,000.
In addition, the weight average molecular weight of the said polyether copolymer can be measured by the method similar to the Example mentioned later.

The polyether copolymer preferably has a melting point of 35 to 55 ° C. When the melting point is in such a range, it is possible to contribute to giving an appropriate strength when the polyether copolymer is formed into a sheet and pelletized. More preferably, it is 35-50 degreeC as melting | fusing point, More preferably, it is 40-50 degreeC.
The melting point of the polyether copolymer can be measured by the same method as in the examples described later.

Moreover, it is preferable that the crystallization temperature of the said polyether copolymer is 12-45 degreeC. When the crystallization temperature is within such a range, it is possible to contribute to giving an appropriate strength when the polyether copolymer is formed into a sheet and pelletized. More preferably, it is 13-35 degreeC as crystallization temperature, More preferably, it is 15-30 degreeC.
In addition, the crystallization temperature of the said polyether copolymer can be measured by the method similar to the Example mentioned later.

The polyether copolymer preferably has a shear viscosity of 10 to 50,000 Pa · s when the shear rate is 100 (1 / second) to 500 (1 / second) at 100 ° C. When the viscosity is in such a range, the polyether copolymer can be contributed to imparting an appropriate strength upon stranding or sheeting. More preferably, it is 50-10,000 Pa.s as a viscosity, More preferably, it is 100-5,000 Pa.s.
The viscosity of the polyether copolymer should be measured using a dynamic viscoelasticity measuring device (product name “ARES rheometer”, manufactured by TIA Instruments) or a capillary viscometer (manufactured by ROSAND). Can do.

The method for producing the polyether copolymer is not particularly limited as long as the polyether copolymer having the structure described above is obtained, and can be performed by a commonly used polymerization method. Examples of the production method include, for example, ethylene oxide used for introducing A in the general formula (1) into the obtained polyether copolymer, and a single raw material used for introducing B in the general formula (1). Monomer containing a monomer and a raw material monomer used for introducing C in the above-described general formula (1) in a proportion such that the molar fraction of x, y, z in the general formula (1) And a method of stirring and polymerizing the body mixture in a solvent. The polymerization method is not particularly limited, and examples thereof include a solution polymerization method, a precipitation polymerization method, and a suspension polymerization. Among these, it is preferable to carry out by a solution polymerization method from the viewpoint of productivity of the polyether copolymer.
The monomer mixture contains other components in addition to ethylene oxide and the raw material monomer as long as the obtained polyether copolymer can exhibit the effects of the present invention. May be. When a monomer mixture contains the said other component, it is preferable that content of the other component in 100 mass% of monomer mixtures is 50 mass% or less. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

The method for adding the monomer mixture to the reaction system is not particularly limited, but the monomer mixture may be supplied all at once to the reaction system charged with the solvent, or continuously or intermittently. It is good also as the method of supplying to. Furthermore, when the monomer mixture is continuously or intermittently supplied, the monomer mixture may be prepared and supplied in advance, or the raw material monomers contained in the monomer mixture may be supplied. Each may be supplied independently and added to the reaction system to form a mixture.
Among the production methods described above, a method in which solution polymerization is performed while continuously supplying a monomer mixture in a solvent charged in advance is a preferable form from the viewpoint of productivity and safety.

In the method for producing a polyether copolymer, as a solvent used when performing a polymerization reaction in the presence of a solvent, a solvent usually used for a polymerization reaction can be used. For example, benzene, toluene, xylene, Aromatic hydrocarbon solvents such as ethylbenzene; Aliphatic hydrocarbon solvents such as heptane, octane, n-hexane, n-pentane and 2,2,4-trimethylpentane; Fats such as cyclohexane and methylcyclohexane Organic solvents such as cyclic hydrocarbon solvents; ether solvents such as diethyl ether, dibutyl ether and methyl butyl ether; solvents of ethylene glycol dialkyl ethers such as dimethoxyethane; cyclic ether solvents such as tetrahydrofuran (THF) and dioxane; Is mentioned. Among these, toluene and xylene are preferable.

The amount of the solvent used is not particularly limited and can be appropriately set according to the kind of the monomer mixture used in the reaction, the reaction form, and the like. For example, the charged amount of the monomer mixture is 100 parts by mass. The solvent is preferably used in an amount of 0 to 300 parts by mass. More preferably, it is 10-250 mass parts, More preferably, it is 50-200 mass parts.

The method for producing the polyether copolymer can be performed using a reaction initiator, an antioxidant, a solubilizing agent, or the like that is usually used in the polymerization reaction.
Examples of the reaction initiator include alkaline catalysts such as sodium hydroxide, potassium hydroxide, potassium alcoholate, sodium alcoholate, potassium carbonate and sodium carbonate; metals such as metal potassium and metal sodium; calcined aluminum hydroxide and magnesium, Al-Mg based composite oxide catalysts such as magnesium oxide with added metal ions, calcined hydrotalcite, or catalysts obtained by surface modification thereof; barium oxide, barium hydroxide, layered compound, strontium oxide, strontium hydroxide, And calcium catalysts, cesium compounds, double metal cyanide complexes, acid catalysts such as Lewis acids and Friedel-Crafts catalysts, and the like. The said reaction initiator may be used independently and may use 2 or more types together.

Since the amount of the reaction initiator used affects the molecular weight of the synthesized polyether copolymer, the amount of the above reaction initiator used can be appropriately set according to the molecular weight of the synthesized polyether copolymer. However, for example, it is preferable to use 0.01 to 1.0% by mass of the reaction initiator with respect to 100% by mass of the monomer mixture. By setting it as such a usage-amount, the polyether copolymer with the preferable molecular weight mentioned above can be manufactured. More preferably, the amount of the reaction initiator used is 0.01 to 0.5% by mass, and more preferably 0.02 to 0.1% by mass with respect to 100% by mass of the monomer mixture. It is.

The addition method of the reaction initiator is not particularly limited, and may be charged with a solvent before supplying the monomer mixture into the reaction system, or may be collectively performed after starting the supply of the monomer mixture. It is good also as throwing in or supplying continuously or intermittently.

The reaction temperature during the polymerization reaction for producing the polyether copolymer is preferably 50 to 150 ° C. More preferably, it is 60-120 degreeC, More preferably, it is 70-110 degreeC. The reaction time is preferably 1 to 24 hours. More preferably, it is 2-20 hours, More preferably, it is 3-15 hours.
The atmosphere in the reaction system during the polymerization reaction is preferably an inert gas atmosphere. As the inert gas, nitrogen gas, helium gas, and argon gas are preferable.
The method for producing the polyether copolymer may be a ripening step subsequent to the step for carrying out the polymerization reaction described above, and further, the solvent component is evaporated from the reaction system to purify the polyether copolymer. You may perform the process to collect | recover.

In addition, the method for producing the polyether copolymer includes an antioxidant after the step of performing the polymerization reaction described above, or when the aging step is performed subsequent to the polymerization reaction step, after the aging step. Is preferably added. As described above, after the polymerization reaction of the polyether copolymer is completed, by adding an antioxidant, the thermal stability of the copolymer is improved, and it is used for the stranding, sheeting, and pelletizing steps. In this case, the strength reduction can be improved, and it becomes possible to reduce the work environment management burden in the production of strands, sheets and pellets in general including stranding, sheeting and pelletizing processes. .
Thus, the polyether copolymer containing composition containing the polyether copolymer of this invention and antioxidant is also one of this invention.

The antioxidant is not particularly limited as long as it is normally used as an antioxidant, but a phenol-based antioxidant, a diphenylamine-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant are used. It is preferable.
Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4-butylidenebis- (6-t-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris ( , 5-Ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyloxy- 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate And the like.

Examples of the diphenylamine-based antioxidant include diphenylamine, p, p′-dibutyldiphenylamine, p, p′-ditert-butyldiphenylamine, p, p′-dipentyldiphenylamine, p, p′-dihexyldiphenylamine, p, p'-diheptyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, monooctyldiphenylamine, monononyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine, carbon number 4-9 mixed alkyldiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 4-n-butylaminophenol, 4-buty Ruaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl Phenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N, N, N ′, N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-di [(2-methylphenyl ) Amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) niguanide, di [4- (1 ′, 3′-dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1 Naphthylamine, styrenated diphenylamine, phenothiazine, 10-methylphenothiazine, 2-methylphen Thiazine, 2-trifluoromethyl phenothiazine, Fenozajin and the like.

Examples of the phosphite antioxidant include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,5-ditertiarybutylphenyl) phosphite, and tris (nonyl). Phenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) octylphos Phyto, diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl Sphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4- Dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (mixed alkyl having 12 to 15 carbon atoms) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis ( 4,6-dia Ruphenyl)] isopropylidene diphenyl phosphite, tetratridecyl-4,4′-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-) 5-tert-butyl-4-hydroxyphenyl) butane-triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert Butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 2-butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol monophosphite, tetrakis (2-tert-butyl-4-methylphenyl) biphenylene diphosphonite, tetrakis (2,4-ditert-amylphenyl) biphenylene diphosphonite, tetrakis (2,4-ditert-butyl-5-methylphenyl) ) Biphenylene diphosphonite, tetrakis (2-tert-butyl-4,6-dimethylphenyl) biphenylene diphosphonite and the like.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl ester, dimyristyl ester, myristyl stearyl ester, and distearyl ester of thiodipropionic acid; pentaerythritol tetra (β-dodecyl mercaptopropio) Β-alkyl mercaptopropionic acid esters of polyols such as nate).

Among the above-mentioned antioxidants, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4-butylidenebis- (6-tert-butyl-3-methylphenol), phenothiazine 10-methylphenothiazine, 2-methylphenothiazine, 2-trifluoromethylphenothiazine, and phenozazine are preferable, and 4,4-butylidenebis- (6-t-butyl-3-methylphenol) is more preferable.
As these antioxidants, only 1 type may be used and 2 or more types may be used.

As the usage-amount of the said antioxidant, it is preferable to use 0.01-1.0 mass% of antioxidant with respect to 100 mass% of synthesized polyether copolymers, for example. By setting it as such usage-amount, it becomes possible to fully exhibit the effect by adding the antioxidant mentioned above. More preferably, it is 0.05-0.8 mass% with respect to 100 mass% of synthesized polyether copolymers as the usage-amount of antioxidant, More preferably, it is 0.1-0.7 mass. %.

When the polyether copolymer of the present invention is made into a strand, a sheet or a pellet by a stranding process, a sheeting process or a pelletizing process, it has an appropriate strength, and high workability is obtained. From the above, it is preferable to use it as a strand, a sheet, or a pellet. That is, it is also one aspect of the present invention that the polyether copolymer of the present invention is a strand-forming polymer, a sheet-forming polymer, or a pellet-forming polymer. A preferred application of such a stranded or sheeted polyether copolymer is a polymer electrolyte of a secondary battery that is currently attracting attention, and the polyether copolymer of the present invention. Can also be suitably used as a polymer electrolyte. Thus, it is also one aspect of the present invention that the polyether copolymer of the present invention is a polymer for polymer electrolyte.
The polyether copolymer of the present invention can be used as a polymer electrolyte after being formed into a sheet, but the polymer electrolyte is not limited to a sheeted form, and does not go through a stranding process or a sheeting process. It is also possible to use the polyether copolymer of the present invention that is not formed into a strand or sheet as a polymer electrolyte. It is within the scope of the present invention to use the polyether copolymer of the present invention which is not formed into a strand or sheet as a polymer for polymer electrolyte.

The method for forming the polyether copolymer of the present invention into a strand, a sheet, and a pellet is not particularly limited. First, as a method for forming a strand and a sheet, for example, a synthesized polyether copolymer is used. A method of forming the polymer into a strand or a sheet after removing the volatile component by devolatilization is exemplified.

As a method for forming the polyether copolymer into a sheet, the sheet-formed and synthesized polyether copolymer is melted and extruded at a certain thickness, and the metal surface is maintained at a temperature equal to or lower than the melting point of the copolymer. And a method of solidifying the molten polyether copolymer into a sheet by bringing it into contact.
In the above sheeting method, the temperature of the copolymer when extruding the molten polyether copolymer is too high, so that the efficiency at the time of cooling deteriorates, so the melting point of the polyether copolymer The temperature is preferably higher than 200 ° C. More preferably, it is less than 150 degreeC, More preferably, it is less than 100 degreeC.

In the sheet forming method, the molten polyether copolymer is extruded with a constant thickness, and the thickness of the obtained sheet is preferably 0.1 to 5 mm. Even if the polyether copolymer of the present invention is a thick sheet, the polyether copolymer of the present invention has an appropriate strength and high processability. The effect of the polymer will be exhibited more remarkably. More preferably, it is 0.2-3 mm as thickness of a sheet | seat, More preferably, it is 0.5-2.5 mm.
Moreover, as a method for forming a strand, a method of extruding from a strand die is the most general, but the thickness is preferably 0.1 mm to 20 mm. More preferably, they are 0.5 mm-10 mm, More preferably, they are 1 mm-5 mm.

The method for maintaining the temperature of the metal surface at a temperature not higher than the melting point of the polyether copolymer is not particularly limited as long as the temperature can be maintained. For example, cooling air, water, a refrigerant such as ethylene glycol The method of cooling by is mentioned.

And it can pelletize by introduce | transducing into the pelletizer the polyether copolymer made into the strand form or sheet form as mentioned above, and cut | disconnecting. As the pelletizer, those usually used can be appropriately used.

The polyether copolymer of the present invention has the above-described configuration and has high processability and handleability because it has an appropriate strength, such as a polymer electrolyte through sheeting or pelletization. It is a polyether copolymer that can be suitably used for electrochemical device applications.

EXAMPLES Hereinafter, although an Example is hung up and this invention is demonstrated further in detail, this invention is not limited only to these Examples. Hereinafter, for convenience, “part by weight” may be simply referred to as “part”, “time” may be simply referred to as “h”, and “liter” may be simply referred to as “L”. In addition, “weight” may be written as “wt” (for example, “wt%” is written as “wt%”, and “weight / weight” is written as “wt / wt”).

Pretreatment of the raw materials used in the following Examples and Comparative Examples was performed as follows.
[Dehydration treatment with molecular sieve]
After adding 10 wt% molecular sieve (Union Showa Co., Ltd., product name: molecular sieve (type: 4A 1.6)) to the raw material monomer and solvent to be dried, the atmosphere is replaced with nitrogen and 12 hours at room temperature. It was left above.

Moreover, the following evaluation and measurement were performed about the reaction mixture (S-1 to S-5, C-1, C-2) obtained in Examples 1-5 and Comparative Examples 1-2. These results are shown in Tables 1 and 2. The weight average molecular weight (Mw) of the polymer contained in each reaction mixture is also shown in Table 1 and Table 2.
[Measurement of weight average molecular weight (Mw)]
The obtained reaction mixture (including ethylene oxide copolymer) was dissolved in a predetermined solvent, and then a GPC apparatus (product name; HLC-8220 GPC, manufactured by Tosoh Corporation) was used to prepare a calibration curve using a standard molecular weight sample of polyethylene oxide. , Column: TSKgel SuperAW5000, TSKgel SuperAW4000, TSKgel SuperAW3000, TSKgel SuperAW2500 (all connected by Tosoh Corporation) were used, and the weight average molecular weight (Mw) was measured.

[Thermal analysis: melting point, crystallization temperature, crystallization heat]
Using a differential thermal analyzer, the melting point, crystallization temperature and crystallization heat of the polymer were measured in the following temperature pattern. The ethylene oxide copolymer used as a sample was prepared by drying the obtained reaction mixture at 80 ° C. for 2 hours with a vacuum drier to remove volatile components in the reaction mixture.
Temperature pattern: Analyzing device (Seiko Denshi Kogyo Co., Ltd., product name: Thermal analyzer SSC5200H system) Rapid heating (rapid heating) to 100 ° C to melt the polymer once, then quenching to -150 ° C to crystallize The melting point was determined from the melting behavior of crystals when the polymerized polymer was heated to 100 ° C. at 5 ° C./min. Furthermore, the crystallization temperature was calculated | required from the exothermic peak accompanying the crystallization which appears when cooling from 100 degreeC to -20 degreeC at 5 degrees C / min. The results are described in Tables 1 and 2 below.

<Preparation of measurement membrane>
The coating solution was prepared so that the obtained reaction mixture and acetonitrile might be set to 1: 3 (weight ratio). The prepared coating solution was cast on a Teflon (registered trademark) plate and then dried in a vacuum dryer at 80 ° C. and 5 mmHg for 2 hours to form a film having a thickness of 150 to 200 μm. After drying, the Teflon (registered trademark) plate was transferred to the glove box and left at room temperature for 3 hours. A test piece having a width of 1 cm and a length of 5 cm was prepared by cutting in a glove box.
<Pretreatment of test sample>
The obtained test piece was put in an aluminum laminate bag and left to stand overnight in a thermostatic chamber at 20 ° C. to adjust the temperature.
<Tensile test>
The measurement was performed using an Instron universal testing machine (product name “1185 type testing machine”, manufactured by Instron) under the conditions of a temperature of 20 ° C., a tensile speed of 20 mm / min, and 300 mm / min. Tables 1 and 2 show the film thickness of the measurement film and the test results of the tensile test. Table 1 shows the test results when the test was conducted at a tensile speed of 20 mm / min, and Table 2 shows the test results when the test was conducted at a tensile speed of 300 mm / min.

[Example 1]
A 1 L reactor equipped with a Max Blend blade (Sumitomo Heavy Industries, Ltd.) and an addition port was replaced with nitrogen three times (0.5 MPa), and this reactor was dehydrated with molecular sieves. 286.5 parts of applied toluene (water content: 20 ppm or less) and 0.71 part of t-butoxypotassium (20 wt% tetrahydrofuran solution) as a reaction initiator were sequentially added, and the pressure in the reactor was adjusted to 0. Pressurized with nitrogen until 3 MPa.
While stirring the MaxBlend blade at 130 rpm, the internal temperature of the reactor was raised to 90 ° C. with an oil bath, and then ethylene oxide supply was started at a supply rate of 76.5 parts / h and fixed for 40 minutes. Supplied. Twenty minutes after the start of the supply of ethylene oxide, supply of butylene oxide (water content: 400 ppm or less) subjected to dehydration treatment with molecular sieve was started at a supply rate of 18.9 parts / h, and was supplied quantitatively for 20 minutes. . After 40 minutes from the start of the supply of ethylene oxide, ethylene oxide was further supplied quantitatively at a supply rate of 51 parts / h and butylene oxide was further supplied for 1 hour at a supply rate of 12.6 parts / h. After 1 hour and 40 minutes from the start of the supply of ethylene oxide, ethylene oxide was further supplied quantitatively at a supply rate of 38.25 parts / h for butylene oxide and 9.45 parts / h for butylene oxide, respectively. Three hours after the start of the supply of ethylene oxide, ethylene oxide was quantitatively supplied at a supply rate of 25.5 parts / h for another 2 hours. Five hours after the start of the supply of ethylene oxide, ethylene oxide was quantitatively supplied at a supply rate of 20.4 parts / h for another 2.5 hours (supply amount of ethylene oxide: a total of 258 parts, supply amount of butylene oxide: a total of 28 .5 parts). During the supply, the reaction was carried out at 100 ° C. ± 5 ° C. while monitoring and controlling the internal temperature rise and the internal pressure rise due to polymerization heat.
After completion of the supply, the mixture was further aged by holding at 100 ° C. ± 5 ° C. for 2 hours.
After completion of the aging, 142.7 g of a 1 wt% toluene solution of 4,4-butylidenebis- (6-t-butyl-3-methylphenol) as an antioxidant was mixed, and 4,4-butylidenebis- (6-t-butyl) was mixed. -3-methylphenol) was adjusted to 0.5 wt% with respect to the synthesized polymer. Thereafter, the solvent was distilled off from the reaction mixture by devolatilization under reduced pressure to obtain a reaction mixture (S-1) containing a polymer having a weight average molecular weight Mw of 94,000 and a melting point of 44 ° C.

[Example 2]
A reaction mixture containing a polymer having a weight average molecular weight Mw of 124,000 and a melting point of 44 ° C. (S-2) except that the internal temperature is monitored and controlled at 90 ° C. ± 5 ° C. )

Example 3
Example, except that 0.5 part of t-butoxypotassium (20 wt% tetrahydrofuran solution) was used, the reaction was started after confirming that the internal temperature reached 85 ° C., and monitored and controlled at 95 ° C. ± 5 ° C. Operation similar to 1 was performed and the reaction mixture (S-3) containing the polymer whose weight average molecular weight Mw is 151,000 and melting | fusing point is 45 degreeC was obtained.

Example 4
Example except that 0.4 part of t-butoxypotassium (20 wt% tetrahydrofuran solution) was used, the reaction was started after confirming that the internal temperature reached 80 ° C., and monitored and controlled at 90 ° C. ± 5 ° C. Operation similar to 1 was performed and the reaction mixture (S-4) containing the polymer whose weight average molecular weight Mw is 183,000 and melting | fusing point is 41 degreeC was obtained.

Example 5
A 1 L reactor equipped with a Max Blend blade (Sumitomo Heavy Industries, Ltd.) and an addition port was replaced with nitrogen three times (0.5 MPa), and this reactor was dehydrated with molecular sieves. 286.5 parts of toluene (water content: 20 ppm or less) applied and 0.54 parts of t-butoxypotassium (20 wt% tetrahydrofuran solution) as a reaction initiator were sequentially added, and the pressure in the reactor was adjusted to 0. Pressurized with nitrogen until 3 MPa.
While stirring the MaxBlend blade at 130 rpm, the internal temperature of the reactor was raised to 90 ° C in an oil bath, and then ethylene oxide supply was started at a supply rate of 51 parts / h, and quantified for 2.5 hours. Supplied. 45 minutes after the start of the supply of ethylene oxide, the supply of a comonomer mixture (mixing ratio (wt / wt): butylene oxide / allyl glycidyl ether = 8/3) subjected to a dehydration treatment with a molecular sieve was supplied at a supply rate of 9 parts / h. Start and feed quantitatively for 1 hour 45 minutes. 2.5 hours after the start of the supply of ethylene oxide, ethylene oxide was supplied quantitatively at a supply rate of 25.5 parts / h for butene oxide and 3.15 parts / h for butylene oxide, respectively, for another 5 hours. (Supply amount of ethylene oxide: 255 parts in total, supply amount of comonomer: 31.5 parts in total). During the supply, the reaction was carried out at 100 ° C. ± 5 ° C. while monitoring and controlling the internal temperature rise and the internal pressure rise due to polymerization heat.
After completion of the supply, the mixture was further aged by holding at 100 ° C. ± 5 ° C. for 2 hours.
After completion of the aging, 142.7 g of a 1 wt% toluene solution of 4,4-butylidenebis- (6-t-butyl-3-methylphenol) as an antioxidant was mixed, and 4,4-butylidenebis- (6-t-butyl) was mixed. -3-methylphenol) was adjusted to 0.5 wt% with respect to the synthesized polymer. Thereafter, the solvent was distilled off from the reaction mixture by devolatilization under reduced pressure to obtain a reaction mixture (S-5) containing a polymer having a weight average molecular weight Mw of 104,000 and a melting point of 48 ° C.

[Comparative Example 1]
The amount of ethylene oxide and comonomer used and the supply conditions were changed as follows, and the same operation as in Example 5 was performed except that the antioxidant was not added. The weight average molecular weight Mw was 89,000, and the melting point was 31 ° C. A reaction mixture (C-1) containing a certain polymer was obtained.
[Monomer usage]
-Ethylene oxide: 235 parts-Comonomer mixture: 51.5 parts (mixing ratio (wt / wt): butylene oxide / allyl glycidyl ether = 15/3)
[Supply conditions]
-Supply start-2.5 hours ethylene oxide: 47 parts / h
Comonomer mixture: 10.3 parts / h
2.5 hours to 7.5 hours ethylene oxide: 23.5 parts / h
Comonomer mixture: 5.15 parts / h

[Comparative Example 2]
The above-described test was conducted using polyethylene glycol 20000 (C-2, weight average molecular weight (Mw): 20,000, melting point: 58 ° C.) manufactured by Wako Pure Chemical Industries.

In Tables 1 and 2, R1, R2, x, y, and z are each in the above general formula (1) when the polymer contained in each reaction mixture is expressed using the above general formula (1). R ¹ , R ² , x, y, and z are represented. “Tc” represents the crystallization temperature, and “dH” represents the heat of crystallization. Further, “-” represents that the obtained reaction mixture was hard and brittle and a significant test result could not be obtained by a tensile test.

From the results of Examples and Comparative Examples, the following was found.
The polyether copolymers obtained in Examples 1 to 5 have a yield stress in a tensile test at a temperature of 20 ° C. of 1.0 to 8.0 Mpa, and the polymer is converted into such a polyether copolymer. It can be seen that the polymer can have a suitable Young's modulus, yield elongation and elongation at break, and from this, it is excellent in handleability and workability in synthesis, transportation, filling, sheeting, etc. I found out that I can do it.
In addition, in the said Example, a specific thing is used as a monomer component for synthesize | combining a polyether copolymer, and the polyether copolymer which has a specific structure is used, but temperature 20 degreeC The mechanism by which a polyether copolymer having a yield stress in the tensile test in Fig. 1 is excellent in handleability and workability during synthesis, transportation, filling, and sheeting is the same.
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

Claims (4)

The test piece used for the test has a length of 5 cm, a width of 1 cm, and a thickness of 150 to 200 μm, and a yield stress in a tensile test at a temperature of 20 ° C. and a tensile speed of 20 mm / min or 300 mm / min is 1.0 to 8 .0MPa der is, and,
The breaking stress is 4.0 to 20 MPa,
Weight average molecular weight, polyether copolymers, characterized in 50,000 to 200,000 der Rukoto. The polyether copolymer has the following general formula (1):
AxByCz (1)
(In the formula, A represents —CH ₂ CH ₂ O—, B represents —CH ₂ CH (R ¹ ) O—, R ¹ represents —Re—Rf—R ³ , Re represents _{- (CH 2 CH 2 O)} p- and represents, p is the same or different, is .Rf represents an integer of _{0~10, - (CH 2 O)} q- and represents, q are the same or different , 0 or 1. R ³ is the same or different and may have a substituent, an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, or a carbon number having 6 to 16 carbon atoms. Represents an aryl group, an aralkyl group having 7 to 16 carbon atoms, or an acyloxy group having 2 to 16 carbon atoms, C represents —CH ₂ CH (R ² ) O—, and R ² represents —Re—Rf—. .R ⁴ representing a R ⁴ are the same or different, an alkenyl group having 2 to 16 carbon atoms, cycloalkenyl of 3 to 16 carbon atoms Group represents a (meth) acryloyl group, x represents the mole fraction of A, y represents B, z represents the mole fraction of C, x is 0.80 to 0.98, and y is 0 The polyether copolymer according to claim 1 , wherein the polyether copolymer has a structure represented by: 0.02 to 0.20 and z is 0 to 0.05. The polyether copolymer according to claim 1 or 2 , wherein the polyether copolymer has a melting point of 35 to 55 ° C. The polyether copolymer according to any one of claims 1 to 3 , wherein the polyether copolymer is a polymer for a polymer electrolyte.