WO2023243204A1

WO2023243204A1 - Aromatic thioether sulfone polymer, composition, and molded article, and methods for producing same

Info

Publication number: WO2023243204A1
Application number: PCT/JP2023/014953
Authority: WO
Inventors: 智理鶴岡
Original assignee: Dic株式会社
Priority date: 2022-06-14
Filing date: 2023-04-13
Publication date: 2023-12-21
Also published as: JPWO2023243204A1

Abstract

Provided are an aromatic thioether sulfone polymer, an aromatic thioether sulfone polymer composition, and an aromatic thioether sulfone polymer molded article that have a high refractive index, have less coloring, and have high transparency, and methods for producing the same. In detail, this aromatic thioether sulfone polymer is characterized by having a refractive index of 1.65 or more, a brightness of 85 or more, a transmission rate of 70% or more, and an oligomer content of 3.5 parts by mass or less. This method is for producing the aromatic thioether sulfone polymer.

Description

Aromatic thioether sulfone polymers, compositions, molded articles, and methods for producing them

The present invention relates to aromatic thioether sulfone polymers, compositions, molded articles, and methods for producing them.

In recent years, resin materials have been widely used for optical materials such as optical lenses, prism sheets, and parts for organic light emitting diode devices (OLED) due to their excellent processability and productivity. Furthermore, due to the trend toward smaller and lighter optical members, resin materials with a high refractive index are required. Conventional resins generally have a refractive index of 1.30 to 1.70, and there are almost no general-purpose materials with a refractive index exceeding 1.70.

A common approach to increasing the refractive index of resins is to introduce substituents with high molar refraction, small molar volume, and high specific gravity into molecules according to the Lorentz-Lorentz equation. That is, introduction of halogen atoms and sulfur atoms is said to be effective. Since sulfur atoms have high polarizability, stability, and ease of introduction into polymers, sulfur-containing resins for various optical materials have been reported. For example, a compound having a thiourethane skeleton is disclosed as a sulfur-containing resin. However, this compound has low heat resistance and has problems in use under high temperature conditions (Patent Document 1, Patent Document 2, Patent Document 3).

On the other hand, aromatic polythioethers have a high sulfur content in the resin skeleton and a very high density, so they are promising high refractive materials. In particular, aromatic thioether sulfone polymers are highly transparent because they are amorphous resins, and they also have excellent heat resistance due to their high glass transition temperature of about 220°C, making them optical materials that can be used even under high-temperature conditions. It is expected that However, in the conventionally reported production methods of aromatic thioether sulfone polymers, the resulting resins are colored and lack transparency, so their use as optical materials has been avoided (Patent Document 4, Patent Document 5).

Japanese Patent Application Publication No. 09-324023 Japanese Patent Application Publication No. 2006-003624 Japanese Patent Application Publication No. 2009-256692 Japanese Unexamined Patent Publication No. 4-275335 International Publication No. 90/03210 pamphlet

Therefore, the problem to be solved by the present invention is to provide an aromatic thioether sulfone polymer, a composition, a molded article, and a method for producing the same, which has a high refractive index, little coloring, and high transparency. .

In order to solve the above-mentioned problems, the present inventors conducted intensive studies and found that in the presence of a carbamide solvent, a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and It has been found that by polymerizing with an alkali metal hydroxide, it is possible to provide an aromatic thioether sulfone polymer that has a high refractive index, little coloration, and high transparency. It has also been found that an aromatic thioether sulfone polymer with excellent thermal stability can be provided when the oligomer content is within a specific value range.

That is, the present disclosure provides an aromatic thioether sulfone polymer having a refractive index of 1.65 or more, a brightness of 85 or more, a transmittance of 70% or more, and an oligomer content of 3.5 parts by mass or less. Regarding.

The present disclosure also provides a method for polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent. The present invention relates to a method for producing an aromatic thioether sulfone polymer.

Note that in the present disclosure, a polymer having 2 to 40 repeating units (a mixture of dimers to 40-mers) may be referred to as an "oligomer."

According to the present invention, it is possible to provide an aromatic thioether sulfone polymer that has a high refractive index, little coloring, and high transparency, and a method for producing the same.

Hereinafter, an embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to the following description, and can be modified in various ways within the scope of the gist. It can be implemented by

The aromatic thioether sulfone polymer has the following general formula (1) (wherein R ₁ to R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, It represents a phenyl group, a methoxy group, an ethoxy group, and X represents -O-, -SO ₂ -, -SO- or -CO-) as a repeating unit.

Here, in the structural moiety represented by the general formula (1), particularly R ₁ to R ₄ in the formula are preferably hydrogen atoms from the viewpoint of mechanical strength of the aromatic thioethersulfone polymer.

In addition, the aromatic thioether sulfone polymer has not only a structural moiety represented by the general formula (1) but also a substituted phenyl group, a ketone group, an aliphatic group, etc., represented by the general formula (1). It may be contained in an amount of 30 mol% or less of the total amount of structural moieties. Regarding their bonding mode, either a random copolymer or a block copolymer may be used. Further, it may contain a trifunctional structural moiety represented by the following general formula (2). In that case, the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.

Further, the aromatic thioether sulfone polymer has the following general formula (3) (wherein, ring Z is an aromatic hydrocarbon ring, and R ₅ and R ₆ may be any substituent, for example, an alkyl group, a cycloalkyl group, aryl group, aralkyl group, or alkoxy group. Y is -O-, -S-, -SO ₂ -, -SO- or -CO-, k is an integer from 0 to 4, and m is 0 or more. p is an integer of 1 or more). In the following general formula (3), ring Z may be a benzene ring or a naphthalene ring. In that case, the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.

In addition, when copolymerizing the 9,9-bisarylfluorene skeleton moiety, the following formula (4) (wherein, ring Z may be an aromatic hydrocarbon ring, and R ₅ to R ₇ may be any substituent, Examples include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkoxy groups. Y is -O-, -S-, -SO ₂ -, -SO- or -CO-, and k is an integer of 0 to 4. , m is an integer of 0 or more, p is an integer of 1 or more) can also be used. In the following general formula (4), ring Z may be a benzene ring or a naphthalene ring. In that case, the amount is preferably in the range of 0.001 to 10 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total number of moles with other structural parts.

The aromatic thioether sulfone polymer according to this embodiment has an excellent refractive index. Specifically, the refractive index is preferably 1.65 or more, more preferably 1.70 or more. In addition, in the present disclosure, the refractive index is a value measured at room temperature (23° C.) and 589 nm using a test piece of an aromatic thioether sulfone polymer molded to a thickness of 40 μm using a method based on JIS K 7142.

The aromatic thioether sulfone polymer according to this embodiment has excellent transparency. Specifically, the brightness is preferably 85 or more, more preferably 90 or more, and the transmittance is preferably 70% or more, more preferably 80% or more. In addition, in this disclosure, brightness is obtained by reflection measurement using a colorimetric colorimeter using an aromatic thioether sulfone polymer molded to a thickness of 40 μm as a test piece and using a white plate as a background in accordance with JIS Z 8781-4. The ^{transmittance} is the transmittance of the same test piece measured at a wavelength of 450 nm using an ultraviolet-visible spectrophotometer.

The aromatic thioether sulfone polymer according to this embodiment has an oligomer content of 3.5 parts by mass or less per 100 parts by mass. In this range, the amount of gas generated when the polymer is heated and melted can be reduced, resulting in a polymer with excellent thermal stability. Note that the oligomer content of the polymer in the present disclosure can be measured by the method described in the Examples.

Since the aromatic thioether sulfone polymer according to the present embodiment has excellent melt stability, the rate of viscosity change during retention is small. Specifically, the viscosity change rate is preferably 10% or less, more preferably 8% or less. Note that the viscosity change rate in the present disclosure can be measured by the method described in Examples.

The method for producing the aromatic thioether sulfone polymer is not particularly limited, but examples include the method for producing the aromatic thioether sulfone polymer described below.

<Method for producing aromatic thioether sulfone polymer>
The method for producing an aromatic thioether sulfone polymer according to the first embodiment of the present disclosure includes combining a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal sulfide in a water-containing organic carbamide solvent. It is characterized by polymerizing a metal hydrosulfide and an alkali metal hydroxide.

Furthermore, the method for producing an aromatic thioether sulfone polymer according to the second embodiment of the present disclosure includes:
A step of polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent to obtain a crude reaction mixture. (1)
step (2) of washing the crude reaction mixture;
step (3) of solid-liquid separation of the crude reaction mixture to obtain solid phase component (A);
The solid phase component (A) is brought into contact with an organic solvent and then subjected to solid-liquid separation to obtain a solid phase component (B) (4). The details will be explained below.

Process (1)
The water-containing organic carbamide solvent used in this embodiment is a mixture of water and an organic carbamide solvent. The organic carbamide solvent is not particularly limited as long as it is a compound having one or more carbamide groups, and any known organic solvent can be used. Examples include dimethylimidazolidinone (DMI), dimethylpropylene urea (DMPU), hexamethylphosphate triamide (HMPA), and tetramethylurea (TMU). In particular, DMI is preferred from the viewpoints of thermal stability, smoothness of polymerization reaction, economic efficiency, and the like. The water content of the water-containing organic carbamide solvent is preferably 1 mol/kg or more, more preferably 5 mol/kg or more, even more preferably 7 mol/kg or more, and preferably 30 mol/kg or less, based on the organic carbamide solvent. More preferably, it is 20 mol/kg or less. If it is below this range, there is a high possibility that a decomposition reaction will occur, and if it is above this range, there is a high possibility that the polymerization reaction will be significantly delayed or the granulation rate of the produced copolymer will be significantly reduced.

The dihaloaromatic compound used in this embodiment is, for example, a halogenated aromatic compound having two halogen atoms directly bonded to an aromatic ring, and specifically, p-dichlorodiphenylsulfone, o- Dichlordiphenylsulfone, m-dichlordiphenylsulfone, p-dibromodiphenylsulfone, o-dibromodiphenylsulfone, m-dibromodiphenylsulfone, p-diiododiphenylsulfone, o-diiododiphenylsulfone, m-diiododiphenylsulfone , p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromnaphthalene, dichlorodiphenylbenzene, dibromodiphenylbenzene, dichlorobenzophenone, Examples include dihaloaromatic compounds such as bromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlordiphenyl sulfide, dibromodiphenylsulfide, dichlorbiphenyl, dibrombiphenyl, and mixtures thereof, and these compounds can be block copolymerized. It's okay. Among these, preferred are dihalogenated benzenes, and particularly preferred are those containing 80 mol% or more of p-dichlorodiphenylsulfone.

Furthermore, dihaloaromatic compounds having functional groups with active hydrogen such as amino groups, thiol groups, and hydroxyl groups can be mentioned, and specific examples include 2,6-dichloroaniline and 2,5-dichloroaniline. , 2,4-dichloroaniline, 2,3-dichloroaniline and other dihaloanilines; 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2',4-di Examples include dihaloaminodiphenyl ethers such as chlordiphenyl ether, and compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof.

In addition, active hydrogen-containing dihaloaromatic compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing dihaloaromatic compounds are substituted with other inert groups, such as hydrocarbon groups such as alkyl groups. Aromatic compounds can also be used.

Among these various active hydrogen-containing dihaloaromatic compounds, active hydrogen-containing dihaloaromatic compounds are preferred, and dichloroaniline is particularly preferred.

Examples of dihaloaromatic compounds having a nitro group include dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; Halonitro diphenyl ethers; Dihalonitro diphenyl sulfones such as 3,3'-dinitro-4,4'-dichloro diphenyl sulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5-dinitro Mono- or dihalonitropyridines such as pyridine; or various dihalonitronaphthalenes; 9,9-bis(4-chlorophenyl)fluorene, 9,9-bis(4-bromophenyl)fluorene, 9,9-bis( 4-iodophenyl)fluorene, 9,9-bis(4-chloro-3-methylphenyl)fluorene, 9,9-bis(4-bromo-3-methylphenyl)fluorene, 9,9-bis(4-iodo -3-methylphenyl)fluorene, 9,9-bis(4-chloro-3-ethylphenyl)fluorene, 9,9-bis(4-bromo-3-ethylphenyl)fluorene, 9,9-bis(4- iodo-3-ethylphenyl)fluorene, 9,9-bis(4-chloro-3-isopropylphenyl)fluorene, 9,9-bis(4-bromo-3-isopropylphenyl)fluorene, 9,9-bis(4 -iodo-3-isopropylphenyl)fluorene, 9,9-bis(4-chloro-3,5-dimethylphenyl)fluorene, 9,9-bis(4-bromo-3,5-dimethylphenyl)fluorene, 9, Examples include dihalofluorenes such as 9-bis(4-iodo-3,5-dimethylphenyl)fluorene.

Furthermore, in this embodiment, an alkali metal sulfide, or an alkali hydrosulfide and an alkali metal hydroxide (hereinafter sometimes referred to as a sulfidating agent) are used as raw materials.

In this embodiment, the alkali metal sulfide includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. Such alkali metal sulfides can be used as hydrates or aqueous mixtures or as anhydrides. Moreover, an alkali metal sulfide can also be derived by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. Note that a small amount of alkali metal hydroxide may be added in order to react with alkali metal hydrosulfide and alkali metal thiosulfate, which are usually present in a small amount in the alkali metal sulfide.

Further, the alkali metal hydrosulfide includes lithium hydrogen sulfide, sodium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof. Such alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or as anhydrides.

Furthermore, the alkali metal hydrosulfide is used together with an alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc. Each of these may be used alone, or two or more types may be used in combination. It may also be used as Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferred because they are easily available, and sodium hydroxide is particularly preferred.

The amount of the sulfidating agent used in this step is preferably 0.1 mol/kg, more preferably 0.3 mol/kg, preferably 20 mol/kg or less, and 10 mol/kg based on the organic carbamide solvent. The following are more preferable. When it is less than 0.1 mol/kg, the productivity of the polymer decreases, which is disadvantageous from an economical point of view. On the other hand, if it is greater than 20 mol/kg, the viscosity of the system during the reaction will become high, making stirring difficult and potentially reducing the yield.

In this step, the molar ratio of the dihaloaromatic compound to the sulfidating agent is preferably in the range of 0.95 to 1.2 (mol/mol), more preferably 1.00 to 1.10 (mol/mol). ) is within the range. If it is smaller than 0.95 (mol/mol), a decomposition reaction may occur or the resulting aromatic copolymer may have poor thermal stability; if it is larger than 1.2 (mol/mol), polymerization may The reaction may be difficult to proceed and it may be difficult to increase the molecular weight.

The polymerization conditions for the above sulfidating agent and the dihaloaromatic compound in the presence of the above organic carbamide solvent are generally at a temperature of 150 to 330°C, and a pressure that substantially eliminates the polymerization solvent and the dihaloaromatic compound as the polymerization monomer. The pressure should be within a range such that the pressure is maintained in the liquid phase, and is generally selected from the range of 0.1 to 20 MPa, preferably 0.1 to 2 MPa. The reaction time varies depending on temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably in the range of 1 hour to 10 hours. In order to obtain a higher molecular weight aromatic thioether sulfone polymer, it is preferable to use a reaction temperature profile of two or more stages. When carrying out this two-step operation, it is preferable to carry out the first step at a temperature of 90°C or higher because the reaction rate is not too low and is practical, and an aromatic thioether sulfone polymer with a sufficiently high molecular weight can be obtained, and side reactions can occur. It is preferable to carry out the process at a temperature of 180° C. or lower since the speed does not increase. Further, a temperature of 120 to 160°C is particularly preferable. At the end of the first stage, the residual rate of the dihaloaromatic compound in the polymerization reaction system is preferably 1 mol% or more because it is easy to finally obtain a high molecular weight aromatic thioether sulfone polymer, and the residual rate of the dihaloaromatic compound in the polymerization reaction system is preferably 1 mol% or more. The content is preferably 40 mol% or less since side reactions such as the like are less likely to occur. It is preferable that the temperature is then raised and the final stage reaction is carried out at 180 to 300°C for 1 to 50 hours. The above temperature range is preferably a reaction temperature of 180°C or higher because it is easy to obtain an aromatic thioether sulfone polymer with a sufficiently high molecular weight, and side reactions such as depolymerization are difficult to occur, and a high molecular weight product can be stably produced. It is preferable to carry out the reaction at 300° C. or lower because it is easy to obtain.

In this embodiment, there is also a form obtained by reacting the crude reaction product in the presence of a sulfidating agent and an organic carbamide solvent while continuously or intermittently adding a dihalo aromatic compound and an organic carbamide solvent. include.

As described above, by polymerizing a dihaloaromatic compound and a sulfidating agent in an organic carbamide solvent, an aromatic thioether sulfone polymer is obtained as a product, but in addition to that, oligomers are also produced as a secondary product. be born. Substances contained in the crude reaction mixture after the reaction may also include, for example, by-products such as an alkali metal-containing inorganic salt and a terminal SH group-containing compound, and unreacted raw materials.

Process (2)
Step (2) is a step of washing the crude reaction mixture obtained in step (1).

The solvent used for washing the crude reaction mixture in this step is not particularly limited as long as it is compatible with the organic carbamide solvent and the unreacted monomer below the boiling point, but the organic carbamide solvent used in step (1) It is preferable to use a similar solvent from the viewpoint of affinity. Further, preferable solvents other than organic carbamide-based solvents include amide-based, ester-based, and ether-based solvents, and specifically, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide. (DMAc) and the like.

The temperature at which the washing solvent is added is not particularly limited, but is preferably in the range of 10°C or higher, more preferably 20°C or higher, and preferably 200°C or lower, more preferably 150°C or lower. There is no particular restriction on the amount of the solvent used for one washing, but it is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably The content ranges from 100 parts by weight or more, preferably 5000 parts by weight or less, more preferably 1800 parts by weight or less, even more preferably 600 parts by weight or less.

Process (3)
Step (3) is a step of subjecting the crude reaction mixture that has passed through step (2) to solid-liquid separation to obtain a solid phase component (A) containing at least an aromatic thioether sulfone polymer.

The method for solid-liquid separation is not particularly limited, and known devices and methods can be used. For example, an appropriate method can be selected, such as a vacuum distillation method, a centrifugation method, a screw decanter method, a vacuum filtration method, and a pressure filtration method. Moreover, these methods can be combined or repeated. Furthermore, step (2) and step (3) can be repeated.

The degree of separation and removal of the liquid phase component containing the organic carbamide solvent is not particularly limited, but if the proportion of solid content (solid content concentration) in the solid phase component (A) is 100 parts by mass of the solid phase component (A). The amount is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more. Although the upper limit is not limited, it is preferably 100 parts by mass or less, more preferably less than 100 parts by mass, and even more preferably 99 parts by mass or less.

Process (4)
Step (4) is a step of contacting the solid phase component (A) obtained in step (3) with an organic solvent and then performing solid-liquid separation to obtain the solid phase component (B).

The organic solvent that can be used in this step is not particularly limited, and any known organic solvent can be used. For example, formamide, acetamide, N-methylformamide, N,N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphorol. Amides, ureas and lactams such as amides, N-dimethylpropylene urea and 1,3-dimethyl-2-imidazolidinonic acid; Sulfolanes such as sulfolane and dimethylsulfolane; Nitriles such as benzonitrile; Methyl alcohol, ethyl alcohol , n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, benzyl alcohol, and other alcohols with 10 or less carbon atoms; 2-methoxyethyl alcohol , 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, 2-isopropoxyethyl alcohol, etc. Alcohols with 10 or less carbon atoms; alcohols with 10 or less carbon atoms containing a ketone group such as 3-hydroxy-2-butanone; alcohols with 10 or less carbon atoms containing an ester group such as methyl hydroxyisobutyrate; methylphenyl Examples include ketones such as ketones and mixtures thereof, and among these, alcohols and ketones are preferred. Furthermore, a mixture of two or more of the above organic solvents may be used. Furthermore, the organic solvent may contain water.

In this embodiment, as the polar organic solvent, it is preferable to use an organic solvent such as an alcohol or a ketone, since impurities such as residual oligomers can be efficiently removed. Furthermore, it is preferable to use a hydrous alcohol. is more preferable because the salt generated during polymerization can be efficiently removed. When using a hydrous alcohol, the concentration of the alcohol solvent in the aqueous solution is not particularly limited, but the amount of the alcohol solvent is preferably in the range of 1000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of water. The amount is preferably 25 parts by mass or more, more preferably 45 parts by mass or more.

The conditions for bringing the solid phase component (A) into contact with the organic solvent in this step range from preferably 10°C or higher, more preferably 20°C or higher, to preferably 100°C or lower, more preferably 70°C or lower. and the pressure (gauge pressure) is less than 0.1 MPa, preferably in the range of 0.05 MPa or less, and more preferably under atmospheric pressure.

There is no particular restriction on the amount of organic solvent used in this step, but in order to improve the cleaning efficiency, it is preferably 50 parts by mass or more, more preferably 100 parts by mass, based on 100 parts by mass of the aromatic thioethersulfone polymer. The amount ranges from 10000 parts or more, more preferably 2000 parts or more, more preferably 10000 parts or less, even more preferably 2000 parts or less.

After washing, the same method as step (3) can be used to obtain the solid phase component (B) through solid-liquid separation. After that, the filtered aromatic thioethersulfone polymer may be dried as it is and used as an aromatic thioethersulfone polymer powder, or it may be further washed with warm water or hot water, separated into solid and liquid, and dried. It is also possible to prepare a powdery or granular aromatic thioether sulfone polymer by performing this step. Furthermore, the obtained powdery or granular aromatic thioethersulfone polymer can be heat-treated to form a crosslinked aromatic thioethersulfone polymer.

The aromatic thioether sulfone polymer obtained by the above production method has an excellent refractive index. Specifically, the refractive index is preferably 1.65 or more, more preferably 1.7 or more, and preferably 1.8 or less. Note that in the present disclosure, the refractive index is a value measured at room temperature (23° C.) and 589 nm using a test piece of an aromatic thioether sulfone polymer melt-molded to a thickness of 40 μm using a method based on JIS K 7142.

Further, the aromatic thioether sulfone polymer obtained by the above production method has excellent transparency. Specifically, the brightness is preferably in the range of 85 or higher, more preferably 90 or higher, and preferably 99.9 or lower. Further, the transmittance is preferably in the range of 70% or more, more preferably 80% or more, and preferably 99.9% or less. In the present disclosure, brightness is obtained by reflection measurement using a colorimeter with a test piece of an aromatic thioethersulfone polymer melt-molded to a thickness of 40 μm using a white plate as a background in accordance with JIS Z 8781-4. The ^{transmittance} is the transmittance of the same test piece measured at a wavelength of 450 nm using an ultraviolet-visible spectrophotometer.

Furthermore, the aromatic thioether sulfone polymer obtained by the above production method has a low oligomer content. Specifically, the oligomer content per 100 parts by mass is preferably 3.5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.8 parts by mass or less. preferable. Within this range, the amount of gas generated when the polymer is heated and melted can be reduced. Note that the oligomer content of the polymer in the present disclosure can be measured by the method described in the Examples.

Furthermore, the aromatic thioether sulfone polymer obtained by the above production method has excellent melt stability, so the rate of viscosity change during retention is small. Specifically, the viscosity change rate is preferably 10% or less, more preferably 8% or less. Note that the viscosity change rate in the present disclosure can be measured by the method described in Examples.

<Composition, method for producing the composition>
The aromatic thioethersulfone polymer composition according to this embodiment is formed by blending the aromatic thioethersulfone polymer according to this embodiment described above and other substances. Further, the method for producing a composition according to the present embodiment includes a step of blending the aromatic thioether sulfone polymer produced by the above method with another substance and melt-kneading the mixture.

The aromatic thioether sulfone polymer according to this embodiment may contain other substances such as a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive agent, as long as the effects of the present invention are not impaired. It can be used as a composition by containing additives such as flame retardants, lubricants, coupling agents, and fillers. As the filler, known and commonly used materials can be used as long as they do not impair the effects of the present invention. Examples include inorganic fillers. Specifically, fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, natural fiber, etc. It can also be used for glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, glass beads, zeolite, milled fiber, calcium sulfate, etc. Non-fibrous fillers can also be used.

The aromatic thioether sulfone polymer according to the present embodiment may be used as a composition by mixing the following synthetic resins and elastomers as other substances within the range that does not impair the effects of the present invention. can. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, polyarylene, polyarylene sulfide, polyethylene, polypropylene, polytetra Examples include fluorinated ethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, etc. Examples of elastomers include polyolefin rubber, fluororubber, silicone rubber, etc. It will be done.

The method of blending and kneading the above-mentioned components with the aromatic thioethersulfone polymer according to the present embodiment is not particularly limited, but the aromatic thioethersulfone polymer and optional components as needed are blended and melted. The kneading method, more specifically, includes a method of uniformly dry-mixing the mixture using a tumbler or a Henschel mixer as necessary, and then charging the mixture into a twin-screw extruder and melt-kneading it.

The melt-kneading machine is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity, for example, a discharge rate of the resin component in the range of 5 to 500 (kg/hr) and a screw rotation speed of 50 to 500 (rpm). It is preferable to melt and knead while appropriately adjusting the range, and melt and knead under conditions such that the ratio (discharge amount/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). is even more preferable. Further, the addition and mixing of each component to the melt-kneading machine may be performed simultaneously or may be performed separately. For example, when adding additives among the components, it is preferable from the viewpoint of dispersibility to introduce them into the twin-screw kneading extruder from a side feeder. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin input part (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, and 0. More preferably, it is .3 or more. Moreover, it is preferable that this ratio is 0.9 or less, and it is more preferable that it is 0.7 or less.

The aromatic thioethersulfone polymer composition according to the present embodiment obtained by melt-kneading as described above has a morphology in which the aromatic thioethersulfone polymer forms a continuous phase and other essential components and optional components are dispersed. have After the melt-kneading, the aromatic thioethersulfone polymer composition according to the present embodiment can be produced by a known method, for example, by extruding the molten polymer composition into a strand shape, and then forming the composition into pellets, chips, granules, powder, etc. After processing into the form, it is preferable to perform preliminary drying at a temperature range of 100 to 150°C as necessary.

<Molded products and molded product manufacturing methods>
The molded article according to this embodiment is obtained by melt-molding the aromatic thioether sulfone polymer composition according to this embodiment described above. Further, the method for producing a molded article according to the present embodiment includes a step of melt-molding the aromatic thioethersulfone polymer composition obtained by the method for producing an aromatic thioethersulfone polymer composition according to the present embodiment described above. It is characterized by having the following.

The aromatic thioether sulfone polymer composition can be molded by various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, and transfer molding. When molding is performed by injection molding, various molding conditions are not particularly limited, and molding can be performed by a general method.

The use of the aromatic thioether sulfone polymer and polymer composition according to the present embodiment is not particularly limited, and can be used as various products. For example, electrical/electronic parts such as connectors, printed circuit boards, and molded seals, automotive parts such as lamp reflectors and various electrical components, interior materials for various buildings, aircraft, automobiles, etc., OA equipment parts, camera parts, etc. It can be widely used as precision parts such as watch parts. In particular, since it has excellent refractive index and transparency, it is suitable for various optical materials such as plastic lenses such as eyeglass lenses, camera lenses, and prism lenses, hard coating agents, antireflection films, prism lenses, and LED sealing materials.

The present invention will be specifically described below with reference to Examples. These examples are illustrative and not limiting.

(1) Measurement of oligomer content The polymers obtained in each example and comparative example were weighed into a 10.0000 g flask using a precision balance. After extraction with acetone for 1 hour using a Soxhlet extractor, the acetone solution was dried in an oven at 50° C. From the amount of residue, the oligomer content of each sample was calculated from the following formula. The measurement results are shown in Table 1.
(Weighed value of residue after drying) ÷ (Weighed value of polymer used for extraction) x 100

(2) Measurement of refractive index The polymers obtained in each example and comparative example were melt-molded into a 40 μm thick film and used as a test piece. The refractive index at a wavelength of 589 nm was measured using "Prism Coupler" manufactured by Metricon in accordance with JIS K 7142. The measurement results are shown in Table 1.

(3) Measurement of lightness (L ^* value) The polymers obtained in each example and comparative example were melt-molded into a film with a thickness of 40 μm and used as a test piece. The brightness was measured using a colorimeter "ZE 6000" manufactured by Nippon Denshoku Kogyo Co., Ltd. The measurement was performed in accordance with JIS Z 8781-4, and the lightness (L ^* value) was measured by reflection measurement using a white plate as a background. The larger the value, the less the polymer is colored. The measurement results are shown in Table 1.

(4) Measurement of transmittance The polymers obtained in each example and comparative example were melt-molded into a film with a thickness of 40 μm and used as a test piece. Transmittance at 450 nm was measured using a UV-visible spectrophotometer "UV-3150" manufactured by Shimadzu Corporation. The measurement results are shown in Table 1.

(5) Measurement of amount of gas generated 4.0000 g of the polymer obtained in each Example and Comparative Example was weighed into an aluminum petri dish using a precision balance. After leaving the sample in a dryer set at 150° C. for 1 hour, the Petri dish was taken out, allowed to cool to room temperature, and then weighed. Next, the petri dish was left to stand in a dryer set at 370° C. for 1 hour, then taken out, allowed to cool to room temperature, and then weighed. The weight loss of each sample was calculated using the following formula. The measurement results are shown in Table 1.
{(Weighing value after heating at 150°C) - (Weighing value after heating at 370°C)} ÷ (Weighing value after heating at 150°C) x 100

(6) Evaluation of melt viscosity and melt stability The viscosity change rate of the polymers obtained in each example and comparative example was evaluated using a Shimadzu flow tester "CFT-500D" at a temperature of 300°C and a load of 1.96 MPa. , was calculated from the following equation from the value measured using an orifice with a ratio of orifice length to orifice diameter of 10/1. The viscosity change rate is an absolute value. The measurement results are shown in Table 1.
Viscosity change rate (%) = | (Melt viscosity Pa・s measured after holding for 30 minutes/Melt viscosity Pa・s measured after holding for 6 minutes) | × 100

(7) DSC Measurement The glass transition point (Tg) of the polymers obtained in each Example and Comparative Example was measured using a differential scanning calorimeter ("DSC8500" manufactured by Perkin Elmer).

・Example 1-Step (1)
In a 1L autoclave made of titanium, 4,4-dichlorodiphenylsulfone (0.52 mol, 147.88 g), sodium acetate (0.50 mol, 41.02 g), dimethylimidazolidinone (hereinafter referred to as DMI) (3.82 mol, 436 .54g), deionized water (2.22mol, 39.96g), sodium sulfide (47.6%, 0.50mol, 59.34g), sodium hydroxide (48.8%, 0.50mol, 41.08g) ), heated to 200°C, and heated under seal at 200°C for 3 hours.

・Example 1-Step (2)
After the polymerization was completed, the crude reaction mixture slurry was collected in a container and DMI (300 mL) was added. This slurry was filtered using a 200 mesh wire gauze to obtain a solid phase component. DMI (300 mL) was further added to the obtained solid phase component, and the mixture was heated and stirred at 120° C. for 30 minutes. Thereafter, the slurry was cooled to 60°C.

・Example 1-Step (3)
The cooled slurry was filtered through a 200 mesh wire gauze to remove liquid phase components.

・Example 1-Step (4)
After cooling the obtained solid phase component to room temperature, an aqueous methanol solution was added, decantation was performed, and the liquid phase component was removed by filtration. The solid phase component was further washed with warm water (70° C.), decanted, and filtered to remove the liquid phase component. This process was repeated three times. The obtained solid phase component was dried at 120° C. for 2 hours under normal pressure, and then further dried under reduced pressure at 150° C. for 5 hours to obtain a polymer (1). Table 1 shows the properties of the obtained polymer (1).

・Comparative example 1
Polymer (2) was obtained in the same manner as in steps (1) and (2) of Example 1, except that NMP was used instead of DMI. Table 1 shows the properties of the obtained polymer.

・Comparative example 2
In a 1 L autoclave, 4,4-dichlorodiphenylsulfone (0.54 mol, 154.70 g), sodium carbonate (0.53 mol, 56.60 g), sodium acetate (0.53 mol, 43.70 g), sodium hydroxide (0 .53 mol, 62.82 g), sodium sulfide (47.6%, 0.53 mol, 62.82 g), NMP (2.13 mol, 221.70 g), deionized water (0.13 mol, 2.27 g). The mixture was heated to 200°C, and kept at 200°C for 3 hours under sealed conditions. Next, a mixed solvent of 160 mL of NMP and 26.7 mL of deionized water was added, and the mixture was stirred until the temperature reached 150°C. The reaction mixture was removed from the reaction vessel as a solid particulate material and the liquid was filtered with suction. The obtained solid phase component was washed with deionized water (90°C, 600 mL) and filtered. This step was repeated twice with a final wash with deionized water at room temperature.
40 g of the polymer purified and recovered as described above, 400 g of deionized water, and 4.0 g of zinc acetate were added to a 1 L autoclave, heated to 185° C., and stirred for 1 hour. Thereafter, it was cooled to room temperature (23°C). The resulting slurry was washed with hot water (90° C., 400 mL) while stirring. Next, the slurry was dried under reduced pressure at a temperature of 160°C to obtain a polymer (3). Table 1 shows the properties of the obtained polymer.

・Comparative example 3
In a 1 L autoclave, sodium hydrogen sulfide (47.6%, 0.50 mol, 58.87 g), sodium hydroxide (48.8%, 0.45 mol, 36.89 g), and anhydrous sodium acetate (0.25 mol, 20. 51 g), sodium carbonate (0.06 mol, 6.36 g), and NMP (4.00 mol, 396.72 g) were added, and the mixture was heated at 130° C. for 3 hours under sealed conditions. This system was cooled to 70°C, 4,4-dichlorodiphenylsulfone (0.51 mol, 146.45 g) was added together with NMP (0.50 mol, 49.59 g), and after heating at 260°C for 2 hours, 1°C The mixture was cooled to 120°C at a rate of 1/min. This system was extracted into NMP (1.5 mol, 148.77 g) and filtered through a 200 mesh wire gauze at 70°C to remove liquid phase components. The obtained solid phase component was washed five times with 250 mL of 70°C warm water, and finally 5 mL of acetic acid was added to obtain a polymer (4). Table 1 shows the properties of the obtained polymer.

From Table 1, it is recognized that the aromatic thioether sulfone polymers of Examples have a low oligomer content and are excellent in brightness and transmittance. Furthermore, the amount of gas generated and the rate of change in viscosity were small, indicating excellent thermal stability.

Claims

An aromatic thioether sulfone polymer having a refractive index of 1.65 or more, a brightness of 85 or more, a transmittance of 70% or more, and an oligomer content of 3.5 parts by mass or less. (However, the brightness and transmittance are the values measured on a film-like test piece with a thickness of 40 μm.In addition, the brightness is the value measured by reflection using a white plate as a background in accordance with JIS Z 8781-4. Transmittance is the value measured at a wavelength of 450 nm.)
The aromatic thioether sulfone polymer according to claim 1, which has a viscosity change rate of 0 to 10%. (However, the viscosity change rate was calculated from the following formula from the value measured by a flow tester using an orifice with a temperature of 300°C, a load of 1.96 MPa, and a ratio of orifice length to orifice diameter of 10/1. (It must be something.)
Viscosity change rate [%] = | (melt viscosity measured after holding for 30 minutes [Pa・s]/melt viscosity measured after holding for 6 minutes [Pa・s]) | × 100
An aromatic thioethersulfone polymer composition comprising the aromatic thioethersulfone polymer according to claim 1 or 2 and another substance.
A molded article obtained by melt-molding the aromatic thioethersulfone polymer composition according to claim 3.
An aromatic product characterized by polymerizing a dihaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent. A method for producing a group thioether sulfone polymer.
A crude reaction mixture is obtained by polymerizing an alkali metal sulfide and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a water-containing organic carbamide solvent. Process (1),
step (2) of washing the crude reaction mixture;
step (3) of solid-liquid separation of the crude reaction mixture to obtain solid phase component (A);
a step (4) of contacting the solid phase component (A) with an organic solvent and then performing solid-liquid separation to obtain the solid phase component (B), and
The molar ratio of the dihaloaromatic compound in step (1) and (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide is 0.95 to 1.2. The method for producing an aromatic thioether sulfone polymer according to claim 5.
The method for producing an aromatic thioether sulfone polymer according to claim 5 or 6, wherein the obtained polymer has a refractive index of 1.65 or more, a brightness of 85 or more, and a transmittance of 70% or more. (However, the brightness and transmittance are the values measured on a film-like test piece with a thickness of 40 μm.In addition, the brightness is the value measured by reflection using a white plate as a background in accordance with JIS Z 8781-4. Transmittance is the value measured at a wavelength of 450 nm.)
The method for producing an aromatic thioether sulfone polymer according to claim 7, further comprising an oligomer content of 3.5 parts by mass or less.
The method for producing an aromatic thioether sulfone polymer according to claim 5 or 6, wherein the viscosity change rate of the obtained polymer is 0 to 10%. (However, the viscosity change rate was calculated from the following formula from the value measured by a flow tester using an orifice with a temperature of 300°C, a load of 1.96 MPa, and a ratio of orifice length to orifice diameter of 10/1. (It must be something.)
Viscosity change rate [%] = | (melt viscosity measured after holding for 30 minutes [Pa・s]/melt viscosity measured after holding for 6 minutes [Pa・s]) | × 100
A method for producing an aromatic thioethersulfone polymer composition, comprising the step of blending the aromatic thioethersulfone polymer produced by the method according to claim 5 or 6 with another substance and melt-kneading the mixture.
A method for producing a molded article, comprising the step of melt-molding the aromatic thioethersulfone polymer composition produced by the method according to claim 10.