JP2016138235A - Composition for polyether polymer-containing molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for a polyether polymer-containing molding material, which is suitable for molding into pellets or the like.SOLUTION: Provided is a composition for a polyether polymer-containing molding material, where the polyether polymer has a weight-average molecular weight of 50,000-150,000 and a crack having a length of 1 cm or more is not generated in a sheet in the following bending test, which sheet is obtained by molding the composition for a polyether polymer-containing molding material. The 180° bending test: the bending test (bending time: 1 second) is performed on a sheet, which is obtained by molding the composition for a polyether polymer-containing molding material in a size of 150 mm×50 mm×2.0 mm by using a mandrel test machine including a mandrel having a diameter of 2 mm and presence or absence of the crack is confirmed.SELECTED DRAWING: None

Description

The present invention relates to a composition for a molding material containing a polyether polymer. More specifically, the present invention relates to a composition for a molding material containing a polyether polymer that can be suitably applied to various uses such as the electrochemical field.

The polyether polymer is a polymer having a main chain having a plurality of ether bonds composed of monomer units such as alkylene oxide, exhibiting characteristics derived from the polyether structure, industrial resin material, It is used as a 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). It is expected to be applied to the electrochemical field. In these applications, the polyether polymer is used by melting and molding, or by dispersing and dissolving in a solvent and coating.

As for conventional polyether polymers, many of the polyether polymer-containing molding material compositions distributed in the market are supplied in powder form. From the viewpoint of ease of handling, polyether polymers are used. In some cases, a pelletizing step may be performed. For this reason, a polyether polymer suitable for pelletization has also been studied, and 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. Is disclosed (for example, see Patent Document 1).

JP 2012-140505 A

As described above, most of the polyether polymer-containing molding material compositions currently distributed are difficult to handle because they are supplied in powder form, and the supply accuracy is not sufficient. Moreover, since the weight average molecular weight is large and the melt viscosity is high, it cannot be said that it is sufficiently suitable for extrusion molding in pelletization or the like.

This invention is made | formed in view of the said present condition, and aims at providing the composition for molding materials containing a polyether polymer suitable for shaping | molding to a pellet etc.

As a result of various studies on the composition for a polyether polymer-containing molding material, the present inventors made a mandrel with a predetermined method using a sheet containing a composition containing a polyether polymer having a specific weight average molecular weight. As a result of performing a bending test using a testing machine, it has been found that those that do not cause cracks of 1 cm or more in length are suitable for molding into pellets, and that the above problems can be solved brilliantly, The present invention has been achieved.

That is, the present invention is a composition for a molding material containing a polyether polymer, and the polyether polymer has a weight average molecular weight of 50,000 to 150,000. Is a polyether polymer-containing composition for molding material in which cracks having a length of 1 cm or more do not occur in a sheet formed from.
[Bending test]
About the sheet | seat which shape | molded the composition for molding materials into the magnitude | size of 150 mm x 50 mm x 2.0 mm, with a mandrel testing machine provided with the mandrel of diameter 2mm, a 180 degree bending test (folding time: 1 second) was performed, Check for cracks.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The polyether polymer-containing molding material composition of the present invention (hereinafter also referred to as a molding material composition) has cracks of 1 cm or more in the sheet formed from the molding material composition in the bending test. It can be confirmed visually. The present inventors have found that the composition for molding material is suitable for molding into a pellet or the like if there is toughness that does not cause a crack of 1 cm or more in length by this method. The molding material composition is preferably a molding material composition that does not cause cracks having a length of 0.5 cm or more in the bending test, and more preferably for molding materials that does not cause cracks having a length of 0.3 cm or more. It is a composition.
When producing pellets from the molding material composition, the molten molding material composition is usually continuously extruded, cooled, sheeted, and pelletized by cutting. In general, a polyether polymer having a high crystallinity tends to increase in crystallinity with time from immediately after the composition for molding material in a molten state is cooled and solidified. In the mechanical strength measurement of the above-mentioned Patent Document 1, since it takes time from the production of the polymer to the measurement, the crystallinity of the polyether polymer is changed at the time of measurement, and the polymer is suitable for pelletization. There was room for improvement as a method of judging whether or not. On the other hand, in the bending test of the present invention, a sheet that is an intermediate for producing pellets can be used, and the toughness of the composition for molding material can be evaluated in the process of producing pellets. It becomes the evaluation method according to. Further, in Patent Document 1, although the determination of the mechanical strength threshold when determining whether or not it is suitable for molding into a pellet or the like is complicated, in the bending test of the present invention, the length of the sheet is 1 cm or more as described above. Since it can be judged by the presence or absence of cracks, it is a simpler evaluation method.

A sheet obtained by molding the composition for molding material of the present invention used for the bending test into a size of 150 mm × 50 mm × 2.0 mm can be produced in the same manner as in the examples described later.
The above bending test was conducted under the model No. Yasuda Seiki Co., Ltd. at a temperature of 25 ° C. It can carry out similarly to the Example mentioned later using the mandrel testing machine provided with the mandrel of diameter 2mm of 514. FIG.

The structure of the polyether polymer of the present invention is not particularly limited as long as it is a polyether polymer having such a characteristic that a crack having a length of 1 cm or more does not occur in the sheet obtained by molding the molding material composition in the bending test. Although not limited, the polyether polymer is preferably a copolymer having structural units derived from ethylene oxide and other monomers. As the polyether polymer of the present invention, 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 0.999, and y is 0 It is more preferable that it has a structure represented by ˜0.20 and z is 0 to 0.15. In the above general formula (1), A is a structural unit derived from ethylene oxide, and B and C are derived from other monomers.
A preferred embodiment of a polymer that does not cause cracking when the above bending test is performed on a sheet obtained by molding a composition for molding material containing a polyether polymer having such a configuration. One.

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 the preferred form of B include propylene oxide, butylene oxide, 1,2-epoxypentane, 1,2 and the like, as exemplified by raw material monomers used for introducing B into the polyether polymer. -Epoxyhexane, 1,2-epoxyoctane, cyclohexene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, 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 the preferred form of C include epoxybutene, 3,4-epoxy-1-pentene, 1,2 and the like as examples of the raw material monomer used for introducing C into the polyether polymer. -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, 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 0.999, and y is 0 to 0.20. Yes, z is 0-0.15. Among these, x is 0.85 to 0.99, y is 0 to 0.15, z is preferably 0 to 0.07, and more preferably, x is 0.90 to 0.98, y is 0.02 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. In addition, since it is possible to adjust the melting point of the obtained polyether polymer depending on what kind of bonding state it is, the type and monomer of the raw material monomer for producing the polyether polymer By appropriately setting the bonding state according to the blending ratio of each monomer in the mixture, the melting point of the polyether polymer can be in a preferable range as described later.

As described later, the polyether polymer having the structure represented by the general formula (1) is, for example, ethylene oxide used for introducing A in the general formula (1), and the general formula (1) described above. The raw material monomer used for introducing B and the raw material monomer used for introducing C in the general formula (1) described above are the moles of x, y, and z in the general formula (1). It can be produced by stirring and polymerizing a monomer mixture containing a fraction in a solvent. In the polyether polymer thus obtained, the terminal structure is a monomer bonded to the terminal portion among the monomers contained in the monomer mixture, or a monomer. It comes from the residue of the reaction initiator used when polymerizing the mixture, and examples thereof include an alkoxy group, a hydroxyl group, and an alkali metal salt of a hydroxyl group such as —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 polymer having the structure represented by the above general formula (1) can be used in addition to the raw material monomers. It may be obtained by polymerizing a monomer mixture containing other monomer components. That is, in the polyether polymer having the structure represented by the general formula (1), in addition to the structural parts represented by A, B and C, the structural part derived from the other monomer component is added. You may have.
However, the ratio of the structural portion represented by the general formula (1) to the entire polyether polymer having the structure represented by the general formula (1) is 99 to 100% by mass. preferable. More preferably, it is 99.5-100 mass%, More preferably, it is 99.9-100 mass%.

The polyether polymer has a weight average molecular weight of 50,000 to 150,000. If the weight average molecular weight of the polyether polymer is 50,000 or more, the toughness is excellent, and therefore, good results are shown in the above bending test, and the sheet breakage when pelletizing the composition for molding material is sufficiently suppressed. can do. Further, if the weight average molecular weight of the polyether polymer is 150,000 or less, it is not necessary to use a high temperature in order to obtain a melt viscosity suitable for extrusion molding when the composition for molding material is pelletized. The deterioration can be sufficiently suppressed, the sheet can be sufficiently cooled, the sheet peelability from the cooling drum can be further improved, and the sheet take-up speed can be sufficiently increased.
More preferably, it is 50,000-140,000 as a weight average molecular weight, More preferably, it is 60,000-130,000.
In addition, the weight average molecular weight of the said polyether polymer can be measured by the method similar to the Example mentioned later.

The polyether polymer 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 providing an appropriate strength when the polyether polymer-containing molding material composition 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.
In addition, melting | fusing point of the said polyether polymer can be measured by the method as described in the Example mentioned later.

Further, the polyether polymer preferably has a crystallization temperature of 12 to 45 ° C. When the crystallization temperature is within such a range, it is possible to contribute to imparting an appropriate strength when the polyether polymer-containing molding material composition 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 polymer can be measured with a differential thermal analyzer.

The polyether polymer 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 composition for a polyether polymer-containing molding material 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 polymer can be measured using a dynamic viscoelasticity measuring device (product name “ARES rheometer”, manufactured by TIA Instruments) or a capillary viscometer (manufactured by Rosand). it can.

The method for producing the polyether polymer is not particularly limited as long as the polyether polymer having the structure described above is obtained, and can be performed by a commonly used polymerization method. Examples of the production method include ethylene oxide used for introducing A in the general formula (1) into the obtained polyether polymer, and a single raw material used for introducing B in the general formula (1) described above. And a monomer containing a raw material monomer used for introducing C in the general formula (1) described above in a proportion that gives a molar fraction of x, y, z in the general formula (1) Examples thereof include a method of stirring and polymerizing the 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 polymer.
The monomer mixture contains other components in addition to ethylene oxide and the raw material monomer as long as the obtained polyether polymer can exhibit the effects of the present invention. Also good. 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 polymer, as a solvent used in the polymerization reaction in the presence of a solvent, a solvent usually used for the polymerization reaction can be used. For example, benzene, toluene, xylene, ethylbenzene Aromatic hydrocarbon solvents such as heptane, octane, n-hexane, n-pentane, 2,2,4-trimethylpentane and the like; alicyclic rings such as cyclohexane and methylcyclohexane Organic solvents such as formula 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; Can be 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 polyether polymer can be produced using a reaction initiator, an antioxidant, a solubilizing agent and the like that are usually used in the polymerization reaction.
Examples of the reaction initiator include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alcoholates such as potassium alcoholate and sodium alcoholate; alkali metal carbonates such as potassium carbonate and sodium carbonate; metal potassium and metal sodium Metals such as aluminum hydroxide / magnesium calcined products, metal ion-added magnesium oxide, calcined hydrotalcite, etc. Al-Mg based composite oxide catalysts or catalysts obtained by surface modification thereof; barium oxide, barium hydroxide, And layered compounds, strontium oxides, strontium hydroxides, calcium compounds, cesium compounds, double metal cyanide complexes, acid catalysts such as Lewis acids and Friedel-Crafts catalysts, and the like. Preferably, alcoholates such as sodium methoxide, sodium ethoxide, and t-butoxypotassium are used. Among the alcoholates, t-butoxy potassium is preferable. The said reaction initiator may be used independently and may use 2 or more types together.

Since the usage amount of the reaction initiator affects the molecular weight of the synthesized polyether polymer, the usage amount of the above reaction initiator can be appropriately set according to the molecular weight of the synthesized polyether polymer. 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 charged monomer mixture. By setting it as such a usage-amount, the polyether polymer 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 polymer 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.
In the method for producing the polyether polymer, a ripening step may be carried out 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 and collect the polyether polymer. You may perform a process (henceforth a devolatilization process).

The devolatilization step is not particularly limited as long as the solvent used in the polymerization reaction of the polymer is distilled off, but it is preferably performed under reduced pressure, and the pressure is preferably 13 to 100,000 Pa. More preferably, it is 133-70,000 Pa, More preferably, it is 1333-40,000 Pa.

When performing the said devolatilization process by heating, it is preferable that the temperature is 40-300 degreeC, More preferably, it is 60-250 degreeC, More preferably, it is 90-200 degreeC. When the said temperature is 40 degreeC or more, the quantity of the remaining solvent can be suppressed more fully, and when it is 300 degrees C or less, it can fully suppress that a polymer thermally decomposes.

The polyether polymer-containing molding material composition of the present invention preferably contains a neutralizing agent. By including the neutralizing agent, the stability of the polymer can be further improved, and more homogeneous pellets can be produced by using such a composition for a polyether polymer-containing molding material.
The neutralizing agent is not particularly limited, but for example, inorganic acids (mineral acids) such as carbonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid; formic acid, acetic acid, oxalic acid, benzoic acid, paratoluenesulfonic acid, Examples include organic acids such as citric acid and lactic acid. Preferably, neutralization with an organic acid such as acetic acid and lactic acid or carbonic acid is effective, and acetic acid and carbonic acid are more preferable.

When a neutralizing agent is added to the polyether polymer-containing molding material composition, it is important to control the amount of excess acid or excess base in the composition to be less than 1 × 10 ⁻⁶ mol / g. Preferably, it is less than 0.5 × 10 ⁻⁶ mol / g, more preferably less than 0.3 × 10 ⁻⁶ mol / g, still more preferably less than 0.2 × 10 ⁻⁶ mol / g.
The excess acid amount or excess base amount is an excess acid amount or excess base amount in the composition. In the composition for a polyether polymer-containing molding material, the amount of acidic substance is larger than the amount of basic substance, and the amount of acidic substance and basic substance are the same. Is expressed in terms of excess acid amount. In addition, in the composition of the present invention, on the basis that the contained amount of each of the acidic substance and the basic substance is equal, the state where the amount of acidic substance is smaller than the amount of basic substance is a state where excess base exists And the degree is expressed by the amount of excess base. When the excess acid amount or the excess base amount of the polyether polymer-containing molding material composition is within the above range, the composition is more tough and exhibits better moldability in pelletization. The amount of free acid or free base contained in the composition of the present invention is easily and preferably calculated from the raw materials used when the composition is produced, but can also be measured, for example, as follows.
0.1 g of the composition is dissolved in 9.9 g of distilled water to prepare a 1% aqueous solution, and the pH is measured with a commercially available pH meter. If the pH at this time is 7 or less, neutralization titration is performed with a 0.1 M aqueous sodium hydroxide solution. While measuring the pH, when the volume of the 0.1 M aqueous sodium hydroxide solution required to reach the inflection point is Vml, the excess acid amount Xmol / g is calculated by the following formula.
X = 0.1 × f × V / 1000 / amount of composition (f; titer of aqueous sodium hydroxide solution)
Similarly, when the pH of a 1% aqueous solution at this time exceeds 7, neutralization titration with 0.1 M hydrochloric acid is performed. While measuring pH, when the volume of 0.1 M required to reach the inflection point was V ′ ml, the excess base amount Ymol / g is calculated by the following formula.
Y = 0.1 × f × V ′ / 1000 / composition amount (f; titer of hydrochloric acid)

The polyether polymer-containing molding material composition preferably contains an antioxidant. By including an antioxidant, the thermal stability of the polymer is further improved, and when the polyether polymer-containing composition is subjected to a stranding, sheeting, and pelletizing step, the strength reduction is further improved. Therefore, it becomes possible to reduce the management burden of the working environment in the overall production of strands, sheets and pellets including stranding, sheeting, pelletizing processes and the like.

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. As said antioxidant, the thing similar to the thing of Unexamined-Japanese-Patent No. 2012-140505 is mentioned.

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

As content of the said antioxidant, it is preferable that it is 0.01-1.0 mass% of antioxidant with respect to 100 mass% of polyether polymers. By setting it as such content, 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 polyether polymers, More preferably, it is 0.1-0.7 mass% as content of antioxidant.

The polyether polymer-containing molding material composition of the present invention may contain moisture, and the processability is improved by appropriately containing water, and the polyether polymer-containing molding material composition is formed into a sheet and pellets. It can be made more excellent in the handleability at the time of conversion. Specifically, the moisture content of the polyether polymer-containing molding material composition is preferably adjusted to 2% by mass or less with respect to 100% by mass of the molding material composition. If the water content is 2% by mass or less, it is possible to sufficiently suppress the occurrence of tack on the surface of the molded body, and the handling becomes excellent. Further, if the water content is 0.5% by mass or more, the fluidity at the time of molding is improved, and the processability is improved.
Moreover, when using the said polyether polymer containing composition for molding materials for the electrolyte layer of a polymer battery, etc., it is preferable that a moisture content is 0.5 mass% or less. If the water content is 0.5% by mass or less, the moisture reacts with the metal ions and the like to generate hydroxide and the like, and an insulating layer is formed at the metal-electrolyte layer interface. Since it can suppress more fully that a voltage continues rising, it can be excellent by the cycling characteristics of a battery. More preferably, it is 0.1 mass% or less, More preferably, it is 0.04 mass% or less.

The present invention is also a molded product obtained by molding the polyether polymer-containing molding material composition of the present invention.
Although it does not restrict | limit especially as said molded article, A strand, a sheet | seat, a pellet, etc. are mentioned. Among these, pellets are preferable.

The present invention is also a method for producing a molded product, wherein the production method is a method for producing a molded product including a step of molding the polyether polymer-containing molding material composition of the present invention into a molded product. is there.

In the production method described above, the method for forming the molding material composition into a strand, sheet or pellet is not particularly limited, but as a method for first forming the strand or sheet, for example, a molding material composition is used. A method of forming a strand or a sheet after removing volatile components by devolatilization is mentioned.

As a method of forming the molding material composition into a sheet, the molding material composition synthesized into a sheet is melted and extruded at a certain thickness, and the melting point of the polyether polymer contained in the molding material composition Examples include a method of solidifying the molten composition for molding material into a sheet by bringing it into contact with a metal surface maintained at the following temperature.
Examples of the metal surface include a cooling metal surface that is provided in a cooling device and can come into contact with a resin. As the cooling device, for example, a drum cooler (for example, a product name “COMPACT CONTI COOLER” manufactured by Tsubako Co., Ltd., a product name “Drum Cooler DC” manufactured by Mitsubishi Chemical Engineering Co., Ltd., a product manufactured by Modern Machinery Co., Ltd.) Name "Laminator" etc.), single belt cooler (eg Sandvik product name "steel belt cooler", Nippon Steel Conveyor Co., Ltd. product name "steel belt single cooler" etc.), double belt cooler (eg Product name “Double Steel Belt Cooler” manufactured by Sandvik, etc.). The metal surface may be a metal plate (plate-like) surface or a non-plate-like metal surface. These cooling metal surfaces are cooled to a desired temperature, for example, by blowing a refrigerant from the back side.
In the above sheeting method, the temperature of the molding composition at the time of extruding the molding composition in a molten state is too high, so that the efficiency at the time of cooling deteriorates. The temperature is preferably higher than 200 ° C. than the melting point of the coalescence. More preferably, it is less than 150 degreeC, More preferably, it is less than 100 degreeC.

In the sheet forming method, the molten molding material composition is extruded with a constant thickness, and the thickness of the sheet to be obtained is preferably 0.1 to 5 mm. Even when the composition for molding material of the present invention is a thick sheet, the composition for molding material of the present invention has a proper strength and high workability. The effect of the composition 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 polymer is not particularly limited as long as the temperature can be maintained. For example, by a coolant such as cooling air, water, or ethylene glycol. The method of cooling is mentioned.

And it can pelletize by introduce | transducing into a pelletizer the polyether polymer made into the strand or the sheet as mentioned above, and cut | disconnecting. As the pelletizer, various conventionally known sheet pelletizers can be appropriately modified and used. Specific examples of the sheet pelletizer include product names PM-350 manufactured by Tanaka Co., Ltd., and product names SGE-220 and SGE-350 manufactured by Horai Co., Ltd.

The production method of the present invention performs the above bending test to form a composition suitable for molding (hereinafter also referred to as a screening process) and a composition suitable for molding selected in the screening process. And a step of forming a molded product (hereinafter also referred to as a molding step).

In the screening step, a crack having a length of 1 cm or more does not occur in the sheet obtained by molding the polyether polymer-containing molding material composition of the present invention into a size of 150 mm × 50 mm × 2.0 mm by the bending test described above. One is selected as a composition suitable for molding. The said sheet | seat can be shape | molded by performing the above-mentioned sheet forming process.
Further, in the production method of the present invention, when a molded product is produced from the molding material composition once through the sorting step, when the molded product is produced for the same molding material composition, the sorting step is performed. Can be omitted. That is, as long as the same molding material composition as the molding material composition that has been subjected to the sorting step at least once is used, even if the sorting step is not performed thereafter, it is included in the manufacturing method that performs the sorting step and the molding step. It is.

In the forming step, the composition suitable for forming selected in the selecting step can be formed into a strand, sheet or pellet by performing the above-described strand forming step, sheet forming step or pelletizing step. Preferably, a pelletizing step is performed.
In general, polyether polymers often have high crystallinity, and when cooled and solidified from a molten state, the crystallinity tends to increase with time immediately after that. In the production method of the present invention, By performing the molding process, the toughness of the molding material composition can be evaluated quickly and easily before the crystallinity changes in the pellet manufacturing process. Can be designed.

The polyether polymer-containing molding material composition of the present invention has moderate toughness when it is made into a strand, sheet or pellet by the stranding process, sheeting process or pelletizing process, and high processability is obtained. Therefore, it is preferable to use it in the form of a strand, a sheet, or a pellet. And, as a preferable use of the composition for a molding material containing polyether polymer containing such a strand or sheet, a polymer electrolyte of a secondary battery and an electrode mixture for a secondary battery which are currently attracting attention The polyether polymer-containing molding material composition of the present invention can also be suitably used as a polymer electrolyte and an electrode mixture for a secondary battery. Thus, the polyether polymer-containing molding material composition of the present invention can be suitably used as a polymer solid electrolyte containing a polyether polymer-containing molding material composition and an electrolyte salt. Moreover, the composition for polyether polymer containing molding materials of this invention can be used suitably also as an electrode compound material for secondary batteries containing the composition for polyether polymer containing molding materials and electrolyte salt.

It is preferable to use a lithium salt as the electrolyte salt. Specific examples include lithium borofluoride, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium difluorosulfonylimide (LiFSI), and lithium tetracyanoborate. (LiTCB). Among these, lithium bistrifluoromethanesulfonylimide (LiTFSI) and lithium difluorosulfonylimide (LiFSI) are preferable.

The polyether copolymer of the present invention can be used as a positive electrode mixture by uniformly mixing an electrode active material and a conductive additive. Such a polyether copolymer of the present invention can be suitably used as a binder for electrodes.
The positive electrode mixture is obtained by mixing the above-described polyether copolymer as a binder with an electrode active material and a conductive additive. Here, the electrode active material generally refers to a host compound having an activity of accepting lithium ions as a guest in order to insert and desorb lithium ions, and is required for a lithium secondary battery. It is an essential component for obtaining power, reaction amount (energy density), reversibility, and ionic conductivity. As a host compound having an activity of accepting lithium ions as a guest, titanium sulfide (TiS ₃ , TiS ₂ ), vanadium oxide (V ₂ O ₅ ), manganese oxide (MnO ₂ ), niobium selenide (NbSe ₃ ), metal element Various composite oxides containing lithium (including LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiFeO ₂ , nickel, manganese, cobalt, a binary positive electrode material containing two elements, nickel, manganese, and cobalt) NMC ternary positive electrode material or solid solution positive electrode material). In addition, an olivine-type positive electrode active material represented by the general formula LiaMbPO ₄ (M is a transition metal element, a = 0 to 2, b = 0.8 to 1.2) can also be suitably used. In the above general formula, M is preferably at least one selected from the group consisting of Fe, Mn, Co, Ni and Cu, and is at least one selected from the group consisting of Fe, Mn, Co and Ni. It is more preferable. Specific examples of such an olivine-type positive electrode active material include LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , LiNiPO _{4, and the} like.
The conductive auxiliary agent that can be used as the positive electrode mixture is not particularly limited as long as it is usually used for the positive electrode of a lithium secondary battery, and examples thereof include acetylene black, ketjen black, and graphite. Can be mentioned. Only 1 type may be used for a conductive support agent and it may use 2 or more types together. The conductive aid used is generally in the form of a solid powder.

The polymer solid electrolyte or the electrode mixture for secondary battery can constitute a battery.
As the form of the battery, a primary rechargeable battery; a rechargeable secondary battery (storage battery); a battery using mechanical charge (mechanical replacement of the negative electrode); a third electrode separate from the positive electrode and the negative electrode (for example, Any form such as a battery using an electrode for removing oxygen and hydrogen generated during charging and discharging may be used. For example, a secondary battery (storage battery) is preferable. A lithium secondary battery is more preferable.

The polyether polymer-containing molding material composition of the present invention has the above-described configuration and has appropriate toughness, and therefore can be suitably used for molding into pellets.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

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 polymer mixture (S-1 to S-8) obtained in manufacture examples 1-6 and comparative manufacture examples 1-2. These results are shown in Tables 1 and 2. Tables 1 and 2 also show the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymers contained in each polymer mixture.
[Measurement of weight average molecular weight (Mw)]
GPC apparatus (manufactured by Tosoh Corporation, product name: HLC-8320 GPC, column: TSKgel G5000PW, TSKgel G4000PW, TSKgel G3000PW, TSKgel G2500PW (all manufactured by Tosoh), eluent: “acetonitrile / 0.08M sodium acetate aqueous solution (volume ratio) : 50/50) "), a calibration curve was prepared using a standard molecular weight sample of polyethylene oxide. Then, the polymerization reaction liquid (including the polymer) obtained after the reaction was dissolved in a predetermined solvent and measured to obtain Mn, Mw, and Mw / Mn. Mn represents the number average molecular weight.

[Thermal analysis: melting point, glass transition temperature]
Using a differential thermal analyzer, the melting point and glass transition temperature of the polymer were measured in the following temperature pattern. The polyether polymer used as a sample was prepared by removing the volatile matter in the polymer mixture by drying the obtained polymer mixture at 80 ° C. for 2 hours using a vacuum dryer.
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 and then cooling to -100 ° C, then 5 The DSC curve when the temperature was raised to 100 ° C. at a rate of ° C./min was measured to determine the melting point and glass transition temperature.

[Production Example 1]
Toluene, isopropanol, and 1M t-butoxypotassium tetrahydrofuran solution are added to the reactor, and the temperature of the reactor is increased by an oil bath. After confirming that the internal temperature has reached 90 ° C., supply of ethylene oxide and butylene oxide is performed. During the supply, ethylene oxide was supplied over 450 minutes and butylene oxide was supplied over 180 minutes at 100 ° C. ± 5 ° C. while monitoring and controlling the increase in internal temperature and internal pressure due to the heat of polymerization. After completion of the supply, the mixture was further aged by maintaining at 100 ° C. for 2 hours. The amount of raw materials charged, reaction time, and properties of the polyether polymer are shown in Table 1.

[Production Examples 2-6 and Comparative Production Examples 1-2]
Except having changed the preparation amount and reaction time of each raw material as shown in Tables 1 and 2, the polyether polymer mixtures of Production Examples 2 to 6 and Comparative Production Examples 1 and 2 were produced according to the same formulation as Production Example 1.

<Examples 1-6, Comparative Examples 1-3>
As shown in Table 3, as a neutralizing agent for 100 parts of the polymer mixture obtained in Production Examples 1 to 6 and Comparative Production Examples 1 and 2, with respect to t-butoxypotassium introduced during the production of the polyether polymer. 0.98 molar equivalent of acetic acid was added and stirred overnight. After stirring overnight, a 2 wt% toluene solution of 4,4-butylidenebis- (6-tert-butyl-3-methylphenol) as an antioxidant was mixed, and 4,4-butylidenebis- (6-tert-butyl-3) was mixed. -Methylphenol) was added at 6000 ppm with respect to the synthesized polymer. Then, the solvent was distilled off from the reaction mixture by devolatilization under reduced pressure to obtain a polyether polymer-containing molding material composition.

About the composition for molding materials containing polyether polymer obtained in Examples 1-6 and Comparative Examples 1-3, the sheet | seat used for a bending test was created with the following method, and the bending test was done. Moreover, about the composition for these molding materials, it pelletized with the following method and evaluated whether it was suitable for the shaping | molding to a pellet. Furthermore, the stability of the polymer was evaluated. The results are shown in Table 4.

[Create sheet]
Equipment used: Desktop test press SA-302, manufactured by Tester Sangyo Co., Ltd.
Temperature condition: 70 ° C
Sheet thickness: 2mm
Work content;
A 0.1 mm-thick Teflon (registered trademark) sheet is laid on a metal press plate, and a polyether polymer-containing molding material composition previously melted is placed thereon. ) A sheet and a metal press plate were placed in order.
The sample was placed in a preheated press and pressed while heating to a predetermined thickness, and then the sample was removed from the press and allowed to stand until it returned to room temperature.
The polymer end was fixed and the Teflon (registered trademark) sheet was slowly peeled off to obtain a polymer sheet.

[Bending test]
The obtained polymer sheet was cut into a size of 150 mm × 50 mm × 2.0 mm, and model No. manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used. It was mounted on a mandrel testing machine equipped with a 514 2 mm diameter mandrel and bent 180 ° at a temperature of 25 ° C. with a bending time of 1 second. The bent part of the folded sheet was visually confirmed, and when a crack was generated, the length of the crack was measured.

[Pelletization]
Equipment used: Horai Co., Ltd. Sheet pelletizer Model SGE-220
Operating conditions: Set size 2.0-4.5 (length) x 3.0 mm (width)
Vertical blade frequency: 15-26 Hz, horizontal blade frequency: 30-40 Hz
Work content;
The polyether polymer-containing molding material compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were fed to a KRC kneader by a gear pump. The jacket temperature was adjusted so that the melt viscosity of the polyether polymer-containing molding material composition was 500 to 2000 Pa · s. The resin discharged from the T die installed in the KRC kneader at a liquid feeding speed of 30 kg / hr is cooled by a drum cooler (Drum Cooler DC manufactured by Mitsubishi Chemical Engineering Co., Ltd.), and has a thickness of 1.5 to 2.0 mm. A sheet was obtained. The obtained cooling sheet was pelletized using a sheet pelletizer (Model SGE-220 manufactured by Horai Co., Ltd.).
The state of sheet formation was evaluated based on the presence or absence of cracks in the sheet and the handleability of the sheet.
The state of the polymer piece after the pelletization treatment was observed, and the pellet shape was evaluated based on the presence / absence of fine chips, cracks and cracks in the polymer piece.
The stability of the polymer was evaluated by measuring the amount of antioxidant in the polymer piece after treatment.

When pelletization was performed using Comparative Example 1, cracks occurred in a part of the sheet during peeling or handling from the cooling roll. The obtained polymer piece was irregularly cracked and chipped, a lot of fine chips were generated, and a homogeneous pellet could not be obtained.

When pelletization was performed using Comparative Examples 2 and 3, the sheet peelability from the cooling drum was poor, and the sheet was stretched and deformed during peeling. In Comparative Example 3, the amount of the antioxidant in the polymer piece was greatly reduced.

* 1 A crack occurred in a part of the sheet.
* 2 The sheet peelability from the cooling drum was poor and the sheet was deformed.
* 3 Irregular cracks and chips occurred, and many fine chips were generated.

Claims (5)

A molding material composition comprising a polyether polymer,
The polyether polymer has a weight average molecular weight of 50,000 to 150,000,
A polyether polymer-containing composition for molding material, wherein a crack having a length of 1 cm or more does not occur in a sheet obtained by molding the composition for molding material in the following bending test.
[Bending test]
About the sheet | seat which shape | molded the composition for molding materials into the magnitude | size of 150 mm x 50 mm x 2.0 mm, with a mandrel testing machine provided with the mandrel of diameter 2mm, a 180 degree bending test (folding time: 1 second) was performed, Check for cracks. 2. The polyether polymer-containing composition for molding material according to claim 1, wherein the polyether polymer is a copolymer having structural units derived from ethylene oxide and other monomers. The polyether polymer-containing molding material composition according to claim 1, wherein the molding material composition contains a neutralizing agent. A molded article obtained by molding the polyether polymer-containing molding material composition according to any one of claims 1 to 3. A method for producing a molded article, comprising:
This manufacturing method includes the process of shape | molding the composition for molding materials containing the polyether polymer in any one of Claims 1-3, and making it into a molded article, The manufacturing method of the molded article characterized by the above-mentioned.