JP2023002372A - Production method of sulfur-containing polymer - Google Patents

Abstract

To provide a production method of a sulfur-containing polymer excellent in transmittance after heating.SOLUTION: A production method of a sulfur-containing polymer having a sulfoxide skeleton in the main chain includes an oxidation step for oxidize a sulfur-containing polymer having a sulfoxide skeleton in the main chain with at least one kind of compound selected from the group consisting of hypochlorous acid, a hypochlorite, and a compound capable of producing hypochlorous acid.SELECTED DRAWING: None

Description

The present invention relates to a method for producing sulfur-containing polymers. More particularly, it relates to a method for producing a sulfur-containing polymer, which includes an oxidation step using a specific compound.

Polycarbonate having an aromatic ring and polymeric materials having a fluorene skeleton are known as high refractive index materials. Materials with a large Abbe's number, that is, with small light dispersion are required as refractive index adjusting materials for improving the light extraction efficiency of LEDs and lens materials for imaging systems. As materials with such a high refractive index and low light dispersion, materials into which sulfur molecules or halogen molecules are introduced, materials containing metal oxide nanoparticles, and the like have been developed.

For example, polyarylene sulfide is known as a sulfur-containing material. For example, a method for producing polyarylene sulfide is known in which diphenyl disulfide and/or thiophenol are polymerized using a vanadium compound as an oxidation polymerization catalyst. (See Patent Document 1, for example).

JP 2015-048442 A

As a result of investigations by the present inventors, it has been found that polyarylene sulfide obtained by oxidation polymerization using a vanadium compound as an oxidation polymerization catalyst has a problem in transmittance after heating. Accordingly, an object of the present invention is to provide a method for producing a sulfur-containing polymer having excellent transmittance after heating.

The present inventors have made detailed studies on a method for oxidizing sulfide groups in polyarylene sulfide to sulfinyl groups, and found that the transmittance of the resulting polymer after heating is improved when a specific compound is used. , conceived of the present invention. That is, the present invention is a method for producing a sulfur-containing polymer having a sulfoxide skeleton in its main chain, which is selected from the group consisting of hypochlorous acid, hypochlorite, and a compound capable of generating hypochlorous acid. A method for producing a sulfur-containing polymer, comprising an oxidation step of oxidizing a sulfur-containing polymer having a sulfide skeleton in its main chain using at least one compound.

Since the method for producing a sulfur-containing polymer of the present invention includes a step of oxidizing a sulfur-containing polymer having a sulfide skeleton in the main chain using a specific compound, The sulfur-containing polymer having such a property has excellent transmittance after heating. As a result, the material using the polymer has excellent transmittance after heating, and is useful as an optical material for lenses and the like.

The present invention will be described in detail below. A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.
In the present specification, "(meth)acrylate" means "acrylate" or "methacrylate", "(meth)acryl" means "acryl" or "methacryl", and "(meth)acryloyl ” means “acryloyl” or “methacryloyl”. Moreover, (meth)acrylate may be called (meth)acrylic acid ester.

1. Method for Producing Sulfur-Containing Polymer The method for producing a sulfur-containing polymer of the present invention is a method for producing a sulfur-containing polymer having a sulfoxide skeleton in its main chain, comprising hypochlorous acid, hypochlorite and hypochlorite. It is characterized by including an oxidation step of oxidizing a sulfur-containing polymer having a sulfide skeleton in its main chain using at least one compound selected from the group consisting of compounds capable of generating chloric acid.

In the following description, the method for producing a sulfur-containing polymer of the present invention is also simply referred to as the production method of the present invention. In the present invention, having a sulfide skeleton in the main chain means having a structure containing at least one sulfide group (-S-) on the main chain of the polymer, and having a sulfoxide skeleton in the main chain. means having a structure containing at least one sulfinyl group (--S(=O)--) on the main chain of the polymer.

The production method of the present invention includes an oxidation step of oxidizing a sulfur-containing polymer having a sulfide skeleton in its main chain. By the oxidation step, at least a part of the sulfide skeleton in the sulfur-containing polymer having a sulfide skeleton in the main chain is oxidized to a sulfoxide skeleton to obtain a sulfur-containing polymer having a sulfoxide skeleton in the main chain. In the present invention, the sulfur-containing polymer having a sulfide skeleton in the main chain and the sulfur-containing polymer having a sulfoxide skeleton in the main chain, which are subjected to the oxidation step, are referred to as a sulfide-containing polymer and a sulfoxide-containing polymer, respectively. There is also

<Sulfide-containing polymer>
The sulfur-containing polymer having a sulfide skeleton in the main chain, that is, the sulfide-containing polymer is preferably, for example, a sulfur-containing polymer having a structural unit (A) represented by the following general formula (1).

(In formula (1), X ¹ represents a divalent aromatic hydrocarbon group which may have a substituent.)
Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a triphenylene group, a biphenylene group, and a phenanthrylene group. Among them, the divalent aromatic hydrocarbon group is preferably a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, or a triphenylene group, and is a phenylene group, in that the light dispersion of the polymer becomes smaller. is more preferable.

The substituent (also referred to as "substituent A") that the divalent aromatic hydrocarbon group may have is preferably a reactive functional group, a halogen atom, or a substituent ("substituent B , aryl, aralkyl, or sulfur-containing substituents, which may have a

Examples of the reactive functional groups include a carboxy group (--COOH), a phosphate group (--OPO(OH) ₃ ), a hydroxyl group (--OH), a sulfo group (--SO ₃ H), a sulfate group (--OSO ₃ H), acidic functional groups such as phosphonic acid group (-PO(OH) ₃ ), phosphinic acid group (-PO(OH)-), mercapto group (-SH); amino group, ammonium group, imino group, amide group , imide group, maleimide group, cyano group, and other basic functional groups; group), a group having a reactive ionic bond (for example, a group having a reactive cyclic ether group such as an epoxy group and an oxetane group); and the like.

Examples of the groups containing these functional groups include groups having the aforementioned acidic functional groups, basic functional groups, or curable functional groups, and hydrocarbon chains or bonding groups. That is, in the present invention, the reactive functional group includes not only the above-described acidic functional group, basic functional group and curable functional group, but also groups containing these functional groups and bonding chains. Examples of the bond chain include divalent hydrocarbon groups such as alkylene groups and arylene groups, bond groups such as ether, ester, carbonyl and amide groups, and combinations thereof. For example, when a carboxy group is preferred as the reactive functional group, it means that the reactive functional group is preferably a carboxy group and/or a group containing a carboxy group.

Preferred forms of the reactive functional group differ from the viewpoint of various physical properties in the sulfoxide-containing polymer obtained by the production method of the present invention.
For example, from the viewpoint of improving the dispersibility of inorganic particles, an acidic functional group, a basic functional group, or a group containing these functional groups is preferable, and a carboxy group, a phosphoric acid group, a phosphonic acid group, a hydroxyl group, or these Groups containing functional groups are more preferred. From the viewpoint of a low coefficient of linear expansion, a carboxy group, a phosphoric acid group, a phosphonic acid group, a hydroxyl group, or a group containing these functional groups is preferred, and a hydroxyl group or a group containing a hydroxyl group is more preferred. From the viewpoint of improving the adhesion to the substrate, a carboxy group, a phosphoric acid group, a phosphonic acid group, or a group containing these functional groups is preferable, and a phosphoric acid group, a phosphonic acid group, or a functional group containing these groups are more preferred. Examples of substrates that can improve adhesion include inorganic substrates such as inorganic particle substrates (coatings), metal oxide particle substrates (coatings), glass substrates, silicone substrates, and copper substrates, and organic particle substrates (coatings). , organic substrates such as polymer film substrates. From the viewpoint of improving heat resistance, mechanical strength, and solvent resistance, a carboxy group, a hydroxyl group, an amino group, a maleimide group, a curable functional group, or a group containing these functional groups is preferable, and a carboxy group, a hydroxyl group, an amino group, , maleimide group, vinyl group, (meth)acryloyl group, allyl group, methallyl group, epoxy group, oxetane group, or groups containing these functional groups are more preferred.

Among them, the reactive functional group is a carboxyl group, a phosphoric acid group, a phosphonic acid group, a hydroxyl group, a curable functional group, or these functional groups in that it can provide a higher refractive index along with excellent physical properties. It is preferably a group containing a carboxy group, a phosphate group, a hydroxyl group, a vinyl group, an epoxy group, or more preferably a group containing these functional groups, a phosphate group, a hydroxyl group, a vinyl group, or these is more preferably a group containing a functional group of In addition to the high refractive index, the reactive functional group is a carboxy group, a phosphoric acid group, or a functional A group containing a group is preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with the bromine atom being preferred.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2 -methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group and the like. Among them, an alkyl group having 1 to 18 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is even more preferable.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, s-butoxy, t-butoxy, pentyloxy, phenoxy, cyclohexyloxy, and benzyloxy groups. Among them, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is preferable, and a methoxy group is more preferable.

Examples of the aryl group include phenyl group, naphthyl group, anthryl group, biphenyl group and triphenyl group. Among them, a phenyl group is preferred. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms.

Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, phenylpentyl group, phenylhexyl group, and phenyloctyl group. The aralkyl group preferably has 7 to 14 carbon atoms, more preferably 7 to 9 carbon atoms.

Examples of the sulfur-containing substituent include thioalkyl groups and thioaryl groups. Among them, a thioalkyl group is preferred. The number of carbon atoms in the sulfur-containing substituent is preferably 1-8, more preferably 1-6, even more preferably 1-4.

The alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing substituent may further have a substituent (substituent B), and the substituent (substituent B) may be an alkyl group, Examples thereof include halogen atoms and hydroxyl groups, and among them, alkyl groups are preferable from the viewpoint of solubility of the polymer, and hydroxyl groups are preferable from the viewpoint of dispersibility of inorganic particles.

Among them, the substituent (substituent A) that the divalent aromatic hydrocarbon group may have in that the refractive index and Abbe number can be further increased, is more preferred, a methyl group and a thioalkyl group are more preferred, and a methyl group is particularly preferred. Further, from the viewpoint of improving the dispersibility of inorganic particles, the substituent that the divalent aromatic hydrocarbon group may have is more preferably a hydroxyl group or a sulfur-containing substituent, such as a hydroxyl group, a thioalkyl group, or a thioaryl group. A group is more preferred, and a hydroxyl group is particularly preferred.

The number of substituents A that the divalent aromatic hydrocarbon group may have is not particularly limited, but is preferably as small as possible in terms of further increasing the refractive index of the polymer. Specifically, It is preferably 1 to 6, more preferably 1 to 3, even more preferably 1.

In the divalent aromatic hydrocarbon group, the position where the substituent A is bonded is not particularly limited. The same applies when the divalent aromatic hydrocarbon group is a phenylene group, and when the substituent A is, for example, an alkyl group, the bonding position is not particularly limited, but the resulting sulfoxide-containing polymer may not react with the solvent. From the viewpoint of solubility and light resistance, it is preferably bonded to the 4-position of the phenylene group.

The structural unit (A) is preferably a structural unit (A-1) represented by the following general formula (1-1) in that the refractive index becomes higher.

(Wherein, R ¹ is the same or different and is an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent which may have a reactive functional group, a halogen atom, or a substituent. a represents the number of R ¹ and is an integer of 0 to 4.)
When there is more than one R ¹ , each may be the same or different.

A reactive functional group, a halogen atom, or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent represented by R ¹ is represented by the general formula It is preferably the same as the substituent that the divalent aromatic hydrocarbon group in (1) may have. Among them, the above R ¹ is more preferably a methyl group or a thioalkyl group, and particularly preferably a methyl group, in that the refractive index can be further increased. In general formula (1-1) above, a represents the number of substituents R ¹ and is an integer of 0-4. a is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, since the refractive index is further increased.

In a preferred embodiment, the sulfide-containing polymer is not further limited as long as it is a sulfur-containing polymer having the structural unit (A). / Or it may further contain a structural unit (C) represented by the following general formula (3).

(In formulas ( ² ) and ( ³ ), X2 and X3 are the same or different and represent a divalent aromatic hydrocarbon group which may have a substituent.)
In the structural unit (B) represented by the general formula ( ² ), X2 represents a divalent aromatic hydrocarbon group which may have a substituent. As the divalent aromatic hydrocarbon group represented by X2, the same groups as the above ^- mentioned ^divalent aromatic hydrocarbon group represented by X1 are preferably exemplified. Examples of the substituent that the divalent aromatic hydrocarbon group represented by X ² may have include the substituent that the divalent aromatic hydrocarbon group represented by X ¹ described above may have, and Similar groups are preferably mentioned. The divalent aromatic hydrocarbon group represented by X2 or a substituent thereof may be the same as or different from the ^divalent aromatic hydrocarbon group represented by X1 or ^a substituent thereof. may

The above structural unit (B) is preferably a structural unit (B-1) represented by the following general formula (2-1) in that it is highly polar due to its solubility and the like.

(Wherein, R ² is the same or different and is an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent which may have a reactive functional group, a halogen atom, or a substituent. and b represents the number of R ² and is an integer from 0 to 4.)
When there is more than one R ² , they may be the same or different.

Reactive functional groups, halogen atoms, or alkyl groups, alkoxy groups, aryl groups, aralkyl groups, or sulfur-containing substituents that may have substituents represented by R ² include the above-described R Groups similar to those represented by ¹ can be mentioned. Among them, the above R ² is more preferably a methyl group or a thioalkyl group, and particularly preferably a methyl group, in that the refractive index can be further increased. In the above general formula (2-1), b represents the number of substituents R ² and is an integer of 0-4. b is preferably 1 to 3, more preferably 1 or 2, even more preferably 1, in that the refractive index is further increased.

In the structural unit (C) represented by general formula ( ³ ) above, X3 represents a divalent aromatic hydrocarbon group which may have a substituent. As the divalent aromatic hydrocarbon group represented by X3 ^, the same groups as the above ^- mentioned divalent aromatic hydrocarbon group represented by X1 are preferably exemplified. The substituent that the divalent aromatic hydrocarbon group represented by X ³ may have includes the substituent that the divalent aromatic hydrocarbon group represented by X ¹ described above may have, and Similar groups are preferably mentioned. The ^divalent aromatic hydrocarbon group represented by X3 or ^a substituent thereof may be the same as the divalent aromatic hydrocarbon group represented by X1 or X2 or a substituent thereof ^, can be different.

The structural unit (C) is preferably a structural unit (C-1) represented by the following general formula (3-1) in terms of high transparency.

(Wherein, R ³ is the same or different and is an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent which may have a reactive functional group, a halogen atom, or a substituent. and c represents the number of R ³ and is an integer of 0 to 4.)
When there is more than one R ³ , they may be the same or different. The alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent which may have a reactive functional group, halogen atom, or substituent represented by R ³ may be the above-described R Groups similar to those represented by ¹ can be mentioned. Among them, the above R ³ is more preferably a methyl group or a thioalkyl group, and particularly preferably a methyl group, in that the refractive index can be further increased. In general formula (3-1) above, c represents the number of substituents R ³ and is an integer of 0-4. c is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in terms of further increasing the refractive index.

The sulfide-containing polymer may be a polymer containing only the structural unit (A), or a copolymer containing the structural unit (A) and the structural unit (B) and/or the structural unit (C). may be The form of the copolymer is not particularly limited, and may be, for example, an alternating copolymer, a block copolymer, or a random copolymer. The sulfide-containing polymer may have one or more of the structural units (A), (B), or (C).

In the sulfide-containing polymer, the content of the structural unit (A) is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, relative to 100 mol% of the total structural units of the polymer. is more preferred, and 95 to 100 mol % is even more preferred. The total content of the structural unit (B) and the structural unit (C) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, relative to 100 mol% of all structural units. , more preferably 0 to 5 mol %.

In the sulfide-containing polymer, the total content of the structural units (A), (B) and (C) is preferably 50 mol% or more with respect to 100 mol% of the total structural units of the polymer, It is more preferably 80 mol % or more, still more preferably 90 mol % or more, even more preferably 95 mol % or more, and particularly preferably 100 mol %.

The sulfide-containing polymer may have a structural unit (D) other than the structural unit (A), the structural unit (B), and the structural unit (C). Examples of the structural unit (D) include structural units having at least the reactive functional group described above.

Examples of monomers into which the structural unit (D) can be introduced include monomers having a polymerizable double bond and the reactive functional group. Examples of the polymerizable double bond include a vinyl group, a (meth)acryloyl group, an allyl group, a methallyl group, etc. Among them, a (meth)acryloyl group is preferable. Examples of the monomer having the polymerizable double bond and the reactive functional group include 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and 3-carboxy(meth)acrylate. Carboxy group-containing (meth)acrylates such as propyl and 4-carboxybutyl (meth)acrylate; phosphoric acid group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate; glycidyl (meth)acrylate, 3, epoxy group-containing (meth)acrylates such as 4-epoxycyclohexylmethyl (meth)acrylate; and vinyl ether group-containing (meth)acrylates such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

The content of the structural unit (D) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, more preferably 0 to 5%, based on 100 mol% of the total structural units of the polymer. More preferably, it is mol %.

The above sulfide-containing polymer preferably has the above-described reactive functional groups at the ends of the main chain and/or side chains. By having the reactive functional group at least at the end of the main chain or the side chain, the sulfoxide-containing polymer obtained after the oxidation reaction can exhibit excellent physical properties due to the reactive functional group. The case of having the reactive functional group in the side chain means not only the case where the side chain of the sulfide-containing polymer has the reactive functional group, but also the structures represented by the general formulas (1) to (3). The case where the substituent in the units (A) to (C) is the above reactive functional group or a group containing the above reactive functional group is also included.

Although the weight average molecular weight (Mw) of the sulfide-containing polymer is not particularly limited, it is preferably from 500 to 10,000,000. When the weight average molecular weight is within the above range, the sulfoxide-containing polymer obtained by the production method of the present invention can be suitably used as an optical material. The weight average molecular weight is more preferably 1,000 or more, still more preferably 3,000 or more, and even more preferably 10,000 or more, while it is more preferably 1,000,000 or less, and 100,000 or less. is more preferred.

The dispersity (weight average molecular weight/number average molecular weight) of the sulfide-containing polymer is preferably 1 or more and 10 or less. When the degree of dispersion is within the above range, the moldability of the sulfoxide-containing polymer obtained by the production method of the present invention is good. The degree of dispersion is more preferably 5 or less, and even more preferably 3 or less, in that the moldability can be further improved.

The weight-average molecular weight and number-average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method, and specifically can be obtained by the method described in the examples below. The dispersity can be determined by dividing the weight average molecular weight by the number average molecular weight.

The sulfide-containing polymer preferably has a glass transition temperature (Tg) of 80 to 250°C. When the glass transition temperature is within the above range, the sulfoxide-containing polymer obtained by the production method of the present invention can be easily molded. From the viewpoint of increasing the heat resistance of the sulfoxide-containing polymer obtained by the production method of the present invention, the glass transition temperature is more preferably 90° C. or higher, further preferably 100° C. or higher. is more preferably 200° C. or less from the viewpoint of facilitating the

The glass transition temperature was measured using a differential scanning calorimeter (DSC) from a DSC curve obtained by heating from room temperature to 250°C (heating rate of 10°C/min) in a nitrogen gas atmosphere. It can be obtained by a method of evaluation based on the intersection of tangent lines at the point of inflection.

<Compound>
In the oxidation step, at least one compound selected from the group consisting of hypochlorous acid, hypochlorite salts, and compounds capable of generating hypochlorous acid is used. At least one compound selected from the group consisting of hypochlorous acid, hypochlorite salts, and compounds capable of generating hypochlorous acid is also collectively referred to as compound (Z).

The hypochlorite is not particularly limited, but alkali metal salts such as potassium hypochlorite and sodium hypochlorite; alkaline earth metal salts such as calcium hypochlorite are preferable.

Examples of the compound capable of generating hypochlorous acid include trichloroisocyanuric acid (TCCA), trichloroisocyanurates such as sodium trichloroisocyanurate, N-chlorosuccinimide, N-chlorophthalimide, alkali metal salts such as sodium hypochlorite, Alkaline earth metal salts such as calcium hypochlorite, alkali metal salts such as chlorous acid and sodium chlorite, alkaline earth metal salts such as calcium chlorite, chlorine dioxide, and chlorine. Among them, trichloroisocyanuric acid (TCCA) is preferred.
The compound (Z) may be used alone or in combination of two or more.
Among the above compounds (Z), hypochlorous acid, hypochlorite, or trichloroisocyanuric acid (TCCA) is more preferred, and trichloroisocyanuric acid (TCCA) is even more preferred.

<Oxidation reaction>
The oxidation reaction in the oxidation step is preferably carried out in a solvent. A solvent used in the oxidation reaction is also referred to as an oxidation reaction solvent.
Examples of the oxidation reaction solvent include chloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3- Chlorinated hydrocarbons such as dichlorobenzene; ethers such as tetrahydrofuran, diethyl ether and cyclopentyl methyl ether; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylformamide; esters such as ethyl acetate and water are preferred, and one or more of these can be used. Among these, ether is more preferred, and tetrahydrofuran is even more preferred.

On the other hand, the oxidation reaction is preferably carried out in the presence of water. The presence of water promotes the oxidation reaction and allows the oxidation reaction to be completed in a short period of time even at low temperatures.
Therefore, the oxidation reaction solvent is preferably a mixed solvent of an organic solvent and water. The content of water is not particularly limited, but the content of water is preferably 1 to 30% by mass with respect to 100% by mass of the oxidation reaction solvent (mixed solvent). It is more preferably 2% by mass or more, still more preferably 5% by mass or more, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

In the oxidation step, the compound (Z) is preferably mixed with the sulfide-containing polymer. In mixing, the above compound (Z) may be used as it is, or may be used after being dissolved or dispersed in a solvent.

For example, when hypochlorous acid or hypochlorite is used as the compound (Z), it is preferable to use an aqueous solution containing these. As the hypochlorous acid (salt) aqueous solution, sodium chloride aqueous solution, hydrochloric acid water, or hypochlorous acid water containing hypochlorous acid as the main component obtained by electrolyzing a mixed solution of hydrochloric acid and sodium chloride. can also be used.

Also, the compound capable of generating hypochlorous acid may be used as it is when mixed with the sulfide-containing polymer, or may be used after being dissolved or dispersed in a solvent.

Before mixing with the compound (Z), the sulfide-containing polymer is preferably dispersed or dissolved in a solvent in advance. That is, it is preferable to mix a solution or a dispersion of the sulfide-containing polymer dissolved in a solvent with the compound (Z). As the solvent, the same solvent as the oxidation reaction solvent used in the oxidation reaction can be used.

It is preferable that the average particle size of the sulfide-containing polymer in the dispersion is 100 μm or less, since a sulfoxide-containing polymer having a uniform degree of oxidation can be easily obtained. The average particle size is more preferably 10 μm or less, and even more preferably 1 μm or less. Although the upper limit is not particularly limited, it is preferably 0.001 μm or more, more preferably 0.01 μm or more. The average particle size is the 50% particle size in the volume-based particle size distribution, and can be measured by a dynamic light scattering method or a static light scattering method.

When water is contained in the oxidation reaction solvent, the sulfide-containing polymer is dispersed or dissolved in the mixed solvent by adding and mixing the sulfide-containing polymer to a mixed solvent of an organic solvent and water. Alternatively, water may be added after adding and mixing the sulfide-containing polymer in an organic solvent to disperse or dissolve it.

The concentration of the sulfide-containing polymer in the solution is not particularly limited, but the content of the sulfide-containing polymer with respect to 100% by mass of the solution is preferably 0.01 to 99.9% by mass, and more preferably. is 0.1 to 80% by mass, more preferably 1 to 50% by mass.
The same applies to the concentration of the sulfide-containing polymer in the dispersion.

The mixing ratio of the compound (Z) to the sulfide-containing polymer is not particularly limited, but is usually 0.01 in terms of the amount (mol) of the compound (Z) per 1 mol of sulfur atoms in the sulfide-containing polymer. It is preferably up to 100 mol, more preferably 0.1 to 10 mol, even more preferably 0.1 to 3 mol.

In addition, the hypochlorous acid generated from the compound (Z) is expressed as the amount (mol) of hypochlorous acid generated from the compound (Z) per 1 mol of sulfur atoms in the sulfide-containing polymer, and is 0.5. It is preferably from 01 to 100 mol, more preferably from 0.1 to 10 mol, even more preferably from 0.1 to 3 mol.

The reaction temperature for the oxidation reaction is not particularly limited as long as it is a temperature at which the desired oxidation reaction proceeds. It is more preferably 5° C. or higher, and more preferably 100° C. or lower, even more preferably 50° C. or lower, in terms of suppressing side reactions. The reaction time of the oxidation reaction is not particularly limited, but is usually 0.1 to 100 hours, preferably 0.5 to 20 hours, more preferably 1 hour or more, and from the viewpoint of excellent productivity. , more preferably 10 hours or less, more preferably 5 hours or less.

When part of the sulfide groups (--S--) in the sulfide-containing polymer are oxidized to sulfonyl groups ( _--SO.sub.2-- ), the reaction may be carried out for a longer time than the reaction time described above. The amount of the compound (Z) used in this case is not particularly limited as long as the desired oxidation reaction of the sulfur atom proceeds. It is preferably up to 100 mol, more preferably 2 to 50 mol, even more preferably 2 to 10 mol.

It is preferable to wash the sulfoxide-containing polymer obtained by the above-described oxidation step because acid and the like may remain therein. The washing method is not particularly limited, and includes washing with water, an acid, a base, or the like. In addition, in order to remove unreacted substances, the polymer may be passed through a filter or washed with a solvent. Although the solvent is not particularly limited, the same solvent as the reaction solvent can be used.

Using the compound (Z) as an oxidizing agent in the oxidation step is also one of the preferred embodiments of the production method of the present invention.
Moreover, in the oxidation step, an oxidizing agent other than the compound (Z) can be used. The oxidizing agent is not particularly limited as long as it is a substance having oxidizing properties. More than one species can be appropriately selected and used.

When an oxidizing agent other than the compound (Z) is used, the amount used is preferably within a range that does not impair the effects of the present invention. For example, the total amount of oxidizing agents other than compound (Z) is preferably 0 to 20% by mass, more preferably 0 to 5% by mass, based on 100% by mass of compound (Z) used in the oxidation step. and more preferably 0 to 1% by mass. Further, when the effect of using an oxidizing agent other than compound (Z) is desired to be exerted, the total amount of oxidizing agents other than compound (Z) should be more than 20% by mass with respect to 100% by mass of compound (Z) used. may

<Polymer terminal control step>
The production method of the present invention preferably further includes a terminal control step of performing a reaction for controlling polymer terminals. The sulfoxide-containing polymer obtained by the oxidation step has, for example, a sulfonyl chloride structure (--S(=O) ₂ --Cl) at its terminal. By chemically denaturing or modifying the terminal structure, the solubility and permeability can be improved, and new functions can be imparted to the terminal.
Controlling the polymer terminal means controlling the terminal of the sulfoxide-containing polymer obtained by the oxidation reaction to an arbitrary structure. A reaction for controlling the terminal of a polymer is sometimes called a terminal control reaction.

The termination control step may be performed on the sulfide-containing polymer, on the sulfoxide-containing polymer, or during the oxidation step. That is, it may be performed before the oxidation step, after the oxidation step, or simultaneously with the oxidation step.

Among them, the polymer terminal control step is preferably carried out after the oxidation step or carried out simultaneously with the oxidation step, and the terminal control reaction in the polymer terminal control step is started after the oxidation reaction in the oxidation step has started. is preferred. That is, it is preferable to start the oxidation reaction first and then carry out the terminal control reaction after the oxidation reaction is completed or after the oxidation reaction has progressed to some extent.
The terminal control reaction is preferably carried out in a solvent. As the solvent, the same solvent as the oxidation reaction solvent can be used.

The terminal control step is preferably a step using a reducing substance.
By using a reducing substance, for example, at least one end of the sulfoxide-containing polymer can be controlled to have a structure having a thiol group. Furthermore, by making the terminal a thiol group, it can be modified with a compound containing an ethylenically unsaturated double bond, and various functional groups can be introduced.

The reducing substance is not particularly limited, but sodium hydride, sodium borohydride, lithium aluminum hydride, butyllithium, diborane, sodium cyanoborohydride, lithium triethylborohydride, tri(sec-butyl) hydride. Lithium borohydride, potassium tri(sec-butyl)borohydride, diisobutylaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, tributyltin hydride, lithium hexamethyldisilazide, lithium diisopropylamide, and other metals or semi-metals Metal hydrides and their complex compounds (art complexes); Metals such as metallic tin and metallic zinc; Compounds containing low-valent metal ions such as divalent ions of iron and divalent ions of tin; Acids such as formic acid and oxalic acid phosphine-based organic compounds such as triphenylphosphine; and inorganic compounds such as hydrazine. These 1 type(s) or 2 or more types can be used. Among these, metals are preferred, and zinc is more preferred. When zinc is used, even if the heavy metal used as a catalyst or the like remains in the process of producing a sulfoxide-containing polymer, for example, in the process of producing a sulfide-containing polymer, the heavy metal can be removed, thereby suppressing coloration. A sulfoxide-containing polymer having a high molecular weight is easily obtained.
Also, when a metal is used as the reducing substance, its form is not particularly limited, but it is preferably in the form of fine particles.

The terminal control reaction using the reducing substance is preferably carried out in the coexistence of an acid. By carrying out in the coexistence of an acid, the terminal control reaction to the thiol of the terminal structure can be promoted. This effect becomes remarkable when a metal, especially zinc, is used as the reducing substance. Examples of the acid include hydrochloric acid (hydrochloric acid), hydrobromic acid, hydroiodic acid, hydrohalic acid such as hydrofluoric acid, inorganic acids such as sulfuric acid, nitric acid; formic acid, acetic acid, propionic acid, lauric acid , stearic acid and benzoic acid; and sulfonic acids such as p-toluenesulfonic acid. Among them, hydrochloric acid is preferred.

The amount of the reducing substance used is not particularly limited, but it is preferable to use the reducing substance in an amount of 0.01 to 1000% by mass based on 100% by mass of the sulfide-containing polymer. It is more preferably 0.1% by mass or more, still more preferably 5% by mass or more, more preferably 100% by mass or less, and still more preferably 50% by mass or less.

The amount of the acid used is not particularly limited, but it is preferable to use the acid in an amount of 0.01 to 5000% by mass based on 100% by mass of the sulfide-containing polymer. More preferably 0.5% by mass or more, still more preferably 10% by mass or more, more preferably 500% by mass or less, still more preferably 100% by mass or less.

A sulfoxide-containing polymer having a thiol group at the polymer terminal can be obtained by a terminal control reaction using a reducing substance. Enthiol reaction is possible. A sulfoxide-containing polymer into which a functional group possessed by the compound is introduced can be obtained by the reaction.

The compound containing the ethylenically unsaturated double bond is not particularly limited, but (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid esters; vinyl acetate, vinyl chloride, vinylidene fluoride and the like Vinyl-based monomers; allyl-based monomers such as allyl acetate, allyl chloride, allyl alcohol, allyl ether, and allyl cyanide; Monomer: Styrenic monomers such as styrene and divinylbenzene are preferred. Among these, 1 type, or 2 or more types can be used. Among them, (meth)acrylic monomers are preferable because of the excellent industrial availability of compounds having various functional groups.

For example, by using (meth)acrylic acid as a compound containing an ethylenically unsaturated double bond, a carboxy group can be introduced at the polymer terminal, and by using a (meth)acrylic acid alkyl ester, a polymer An alkyl group can be introduced at the end of the coalescence, and an ethylenically unsaturated double bond ((meth)acryloyl group) can be introduced at the end of the polymer by using a polyfunctional (meth)acrylic acid alkyl ester. .

It is also preferred that the terminal control step is a step using ammonia, a primary amine or a secondary amine. By using ammonia, primary amine or secondary amine, at least one end of the sulfoxide-containing polymer can be controlled to "-S(=O)2-R". Here, R is NH ₂ when ammonia is used, or an amine residue resulting from dehydrogenation of the amino group in the amine used when amine is used.

In the terminal control step, it is also preferable to coexist with a basic substance. That is, in the terminal control step, the sulfoxide-containing polymer is preferably reacted with ammonia, primary amine or secondary amine in the presence of a basic substance.

The basic substance is not particularly limited. For example, it may be ammonia, a primary amine, a secondary amine, or a basic substance other than these. For example, ammonia, primary amines, or secondary amines in excess of equivalent amounts to modify the ends can also be used as basic substances. However, substances other than ammonia, primary amines, and secondary amines are preferable as the basic substance because they can suppress side reactions. For example, tertiary amines, alkali metal hydroxides, alkali metal carbonates and the like are preferred. Preferred tertiary amines include aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine, and aromatic amines such as pyridine and dimethylaminopyridine. Preferred alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. Preferred alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and cesium hydrogencarbonate.

<Polymerization process>
The production method of the present invention preferably further includes a polymerization step of polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer having a sulfide skeleton in its main chain (sulfide-containing polymer). That is, as the sulfide-containing polymer used in the oxidation step in the production method of the present invention, it is preferable to use a sulfide-containing polymer obtained by polymerizing a monomer component containing a sulfur-containing monomer. Preferably, the polymerization step is usually performed before the oxidation step.

The sulfur-containing monomer is not particularly limited as long as it can be polymerized to give a sulfur-containing polymer having a sulfide skeleton in the main chain, but disulfide compounds and thiol compounds are preferred. More preferred are diaryl disulfide compounds represented by the following general formula (4) and thioaryl compounds represented by the following general formula (5).

(In formulas (4) and (5), A ¹ and A ² are the same or different and represent a monovalent aromatic hydrocarbon group which may have a substituent.)
The monovalent aromatic hydrocarbon group represented by A ¹ and A ² is an aromatic hydrocarbon obtained by making the divalent aromatic hydrocarbon group represented by X ¹ in the general formula (1) monovalent. Examples include hydrogen groups, such as phenyl, naphthyl, anthryl, triphenyl, biphenyl, and phenanthryl groups. Among them, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, or a triphenyl group is preferable, and a phenyl group is more preferable.

The substituents that the monovalent aromatic hydrocarbon group represented by A ¹ and A ² may have and the number thereof are the divalent aromatic hydrocarbon groups represented by X ¹ in the general formula (1) The same applies to the substituents that the hydrocarbon group may have.

The diaryl disulfide compound is preferably a compound represented by the following general formula (4-1). The thioaryl compound is preferably a compound represented by the following general formula (5-1).

(In formulas (4-1) and (5-1), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same or different, hydrogen atom, halogen atom , represents an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent which may have a reactive functional group or a substituent.)
The halogen atom, the reactive functional group, or the alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent, which may have a substituent, is represented by the general formula (1-1) described above. is the same as each group represented by R ¹ in . Further, the substituents that these groups may have include those similar to the substituent B described above, and among them, alkyl groups, halogen atoms, and hydroxyl groups are preferred.

Specific examples of the diphenyl sulfide compounds include 3,3′-dimethyldiphenyl disulfide, 2,2′-dimethyldiphenyl disulfide, 2,2′,3,3′-tetramethyldiphenyl disulfide, 2,2′, 5,5′-tetramethyldiphenyl disulfide, 2,2′,6,6′-tetramethyldiphenyl disulfide, 3,3′,5,5′-tetramethyldiphenyl disulfide, 2,2′,3,3′, 5,5′-hexamethyldiphenyl disulfide, 2,2′,3,3′,6,6′-hexamethyldiphenyl disulfide, 2,2′,3,3′,5,5′,6,6′- Octamethyldiphenyl disulfide, 2,2'-diethyldiphenyl disulfide, 3,3'-diethyldiphenyl disulfide, 2,2',6,6'-tetraethyldiphenyl disulfide, 2,2',3,3'-tetraethyldiphenyl disulfide , 2,2′,5,5′-tetraethyldiphenyl disulfide, 3,3′,5,5′-tetraethyldiphenyl disulfide, 2,2′,3,3′,5,5′-hexaethyldiphenyl disulfide, 2 ,2′,3,3′,6,6′-hexaethyldiphenyl disulfide, 2,2′,3,3′,5,5′,6,6′-octaethyldiphenyl disulfide, 2,2′-di Propyldiphenyl disulfide, 3,3'-dipropyldiphenyl disulfide, 2,2',6,6'-tetrapropyldiphenyl disulfide, 2,2',3,3'-tetrapropyldiphenyl disulfide, 2,2',5 ,5′-tetrapropyldiphenyl disulfide, 3,3′,5,5′-tetrapropyldiphenyl disulfide, 2,2′,3,3′,5,5′-hexapropyldiphenyl disulfide, 2,2′,3 ,3′,6,6′-hexapropyldiphenyl disulfide, 2,2′,3,3′,5,5′,6,6′-octapropyldiphenyl disulfide, 2,2′-diisopropyldiphenyl disulfide, 3, 3'-diisopropyldiphenyl disulfide, 2,2',6,6'-tetraisopropyldiphenyl disulfide, 2,2',3,3'-tetraisopropyldiphenyl disulfide, 2,2',5,5'-tetraisopropyldiphenyl disulfide, 3,3′,5,5′-tetraisopropyldiphenyl disulfide, 2,2′,3,3′,5,5′-hex cycloisopropyldiphenyldisulfide, 2,2',3,3',6,6'-hexaisopropyldiphenyldisulfide, 2,2',3,3',5,5',6,6'-octaisopropyldiphenyldisulfide, etc. is mentioned.

Specific examples of the thiol compounds include 3-methylbenzenethiol, 2-methylbenzenethiol, thiophenol (benzenethiol), 2,3-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2,6- dimethylbenzenethiol, 3,5-dimethylbenzenethiol and the like.

The disulfide compounds can also be prepared by oxidation of thiol compounds. Therefore, in the polymerization step, a thiol compound can be used as a precursor of the disulfide compound. A disulfide compound can be obtained by oxidatively bonding two molecules of a thiol compound. The method for oxidative bonding is not particularly limited, and a known method can be used.

The polymerization is preferably oxidative polymerization. The oxidative polymerization is not particularly limited, and oxidative polymerization using a quinone compound, oxidative polymerization using a catalyst, or the like can be used. In the production method of the present invention, oxidative polymerization using a catalyst is preferable from the viewpoint of requiring a small amount of waste liquid. In both cases of oxidation polymerization using a quinone compound and oxidation polymerization using a catalyst, the sulfoxide obtained by subjecting the obtained sulfide-containing polymer to the above-described production method of the present invention The contained polymer has excellent transmittance after heating.

For example, a diaryl disulfide compound represented by the above general formula (4) or a monomer composition containing a thioaryl compound represented by the above general formula (5) is used as a raw material, and oxidative polymerization is performed using a quinone compound. When done, the resulting sulfide-containing polymers have problems with transmittance after heating. Although the cause is not clear, the sulfide-containing polymer obtained by oxidation polymerization using the quinone compound has disulfide bonds at its terminals, and the disulfide bonds generate radicals when heated, and the polymer This is considered to be the cause of the reaction that causes the coloration of However, by subjecting the above sulfide-containing polymer to the above-described production method of the present invention (above oxidation step), the resulting sulfoxide-containing polymer exhibits excellent transmittance after heating. This is probably because the terminal structure of the polymer changed due to the oxidation step.

Further, when the diaryl disulfide compound represented by the above general formula (4) or the monomer composition containing the thioaryl compound represented by the above general formula (5) is used as a raw material, oxidation polymerization using a catalyst is performed. Although there are differences depending on the composition of the catalyst used, the obtained sulfide-containing polymer has a problem in transmittance after heating. Refining by a method such as reprecipitation is the same. Although the cause is not clear, the sulfide-containing polymer obtained by oxidative polymerization using a catalyst has a disulfide bond at its terminal, and the metal component derived from the catalyst is strongly bound (coordinated) to the disulfide bond. It is considered that this is because it easily contributes to coloring due to heating.

However, by subjecting the above sulfide-containing polymer to the above-described production method of the present invention (above oxidation step), the resulting sulfoxide-containing polymer exhibits excellent transmittance after heating. Although it is not certain, this is not because the terminal structure of the polymer changed due to the oxidation step, and the metal component derived from the catalyst was released from the sulfoxide-containing polymer, or changed to a form that does not easily contribute to coloration due to heating. I can think of it.

Oxidative polymerization using a quinone compound will be described. The quinone compound that can be used in oxidation polymerization using a quinone compound is not particularly limited, but examples include 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ), 2,3,5,6 -tetrachloroparabenzoquinone, 2,3,5,6-tetrabromobenzoquinone, 2,3,5,6-tetrafluoroparabenzoquinone, anthraquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone , 2,3-dibromo-1,4-naphthoquinone, 2,3-dicyano-1,4-naphthoquinone, 3,4,5,6-tetrachloroorthobenzoquinone, 3,4,5,6-tetrabromoorthobenzoquinone , 3,4,5,6-tetrafluorobenzoquinone and the like. Among them, DDQ is preferable because of its high oxidizing power and easy availability. Only one kind of the quinone-based compound may be used, or two or more kinds thereof may be used.

Moreover, when using the said quinone type compound, it is also preferable to use an acid further. When an acid is used in combination with a quinone compound, the oxidizing power of the quinone compound can be maintained. The acid is not particularly limited, and examples include sulfuric acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, and trifluoroacetic acid. , perfluoropropionic acid, perfluorobutyric acid and the like. Among them, 1,1,2,2-tetrafluoroethanesulfonic acid is preferable from the viewpoint of increasing acidity. Only one kind of the acid may be used, or two or more kinds thereof may be used.

When the quinone compound and acid are used in combination, the amount of acid added is preferably 10 to 1000 mol, and preferably 50 to 500 mol, per 100 mol of the total amount of the quinone compound to be added. More preferably, it is 80 to 120 mol. The amount of the quinone compound to be added is preferably 0.1 to 3 mol, more preferably 0.8 to 1.5 mol, more preferably 0.8 to 1.5 mol, per 1 mol of the monomer component used. More preferably 9 to 1.1 mol.

In the polymerization step, the polymerization temperature is not particularly limited as long as it is a temperature at which oxidative polymerization proceeds, but is preferably 0 to 200° C., more preferably 10° C. or higher, in terms of facilitating the progress of oxidative polymerization. 15° C. or higher is more preferable, and 180° C. or lower is more preferable, and 150° C. or lower is even more preferable in that side reactions can be suppressed. The polymerization time is not particularly limited, but is usually 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and further preferably 10 to 24 hours. preferable.

A solvent may be used in the polymerization. Preferred solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3 -dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, cyclopentyl methyl ether and the like.

As the solvent, it is preferable to reduce halogens such as chloroform and chlorobenzene, which are highly harmful to the environment, particularly halogen solvents containing chlorine and bromine. It is preferably 100% by mass or less, more preferably 50% by mass or less, still more preferably 10% by mass or less, and even more preferably 1% by mass or less with respect to the coalescence.

Oxidative polymerization using a catalyst will be described. In the polymerization step, the monomer components are polymerized in the presence of a catalyst. For example, it is more preferable to carry out the polymerization reaction by heating a composition containing the monomer component and the catalyst.
A composition containing a monomer component and a catalyst is also called a raw material composition, and a composition from the start of a polymerization reaction to the end of the polymerization reaction is also called a reaction composition. A composition obtained by a polymerization reaction is also called a polymer composition.

As the catalyst, a catalyst (oxidation polymerization catalyst) having oxidation polymerization activity for the monomer component containing the disulfide compound and/or the thiol compound is preferable. The catalyst is not particularly limited, but includes metal elements such as vanadium (V), zirconium (Zr), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe). Substances are preferred. The form of the metal-containing substance is not particularly limited, and examples thereof include metals containing the metal element, metal compounds, and other forms.

Examples of the metal include a metal (single substance) consisting only of the metal, and an alloy containing the metal as a main component. The metal compound is not particularly limited as long as it contains a metal, and inorganic compounds, organic acid salts, complexes (coordination compounds) and the like can be mentioned. Examples of the inorganic compounds include halides, sulfates, nitrates, phosphates, silicates, carbonates, hydroxides, oxides, sulfides, tellurides, and intermetallic compounds. Among them, halides are preferred. As the halide, fluoride, chloride, bromide and iodide are preferable, and chloride is more preferable. The organic acid salt is not particularly limited as long as it is an organic acid salt containing a metal element, and examples thereof include carboxylates and sulfonates. As the carboxylate, for example, acetate, oxalate and the like are preferable. As the sulfonate, for example, p-toluenesulfonate, trifluoromethanesulfonate, and the like are preferable. The complex is not particularly limited as long as it contains a metal element. Examples include diketone complexes and β-diketoester complexes.

Examples of other forms of the substance containing the metal element include a form in which metal ions such as monovalent ions and trivalent ions of metal are contained as cations in cation exchangers such as zeolite and mica.

Only one kind of the substance containing the metal element may be used, or two or more kinds thereof may be used in combination.
The substance containing the metal element is not particularly limited in its existence form in the raw material composition. For example, it may be dispersed in the raw material composition in the form of particles or the like, or it may exist in a state of being dissolved in a monomer component or a solvent when it is used. Solvents will be described later. The same applies to the existence form of the substance containing the metal element in the reaction composition.

Among the above substances containing metal elements, substances containing vanadium and substances containing iron as metal elements (these are also referred to as vanadium-containing substances and iron-containing substances, respectively) are preferable in terms of their high catalytic activity for oxidative polymerization.

The iron-containing substance preferably contains iron as a main component as a metal element. Specifically, the content of iron is preferably 50 mol% or more, more preferably 80 mol% or more, more preferably 95 mol% with respect to 100 mol% of the total content of the metal elements contained in the iron-containing substance. It is more preferably 98 mol % or more, and particularly preferably 100 mol %.

The vanadium-containing substance preferably contains vanadium as a metal element as a main component, and the preferred content of vanadium relative to the total amount of metal elements is the same as the content of iron in the iron-containing substance.
Specific forms and preferred forms of the vanadium-containing substance and the iron-containing substance conform to the above-described forms of the substance containing the metal element.

As the iron-containing substance, an iron compound having chlorine in the molecule is preferable. A compound containing iron having an oxidation number of 3 or more is preferable. Examples of such iron-containing substances include ferric chloride (Fe(Cl) ₃ ), 5,10,15,20-tetraphenyl-21H,23H-porphine iron (III) chloride, iron trifluoromethanesulfonate (III), among others, are particularly preferred.

As the vanadium-containing substance, a metal containing vanadium and an oxovanadium compound having a V=O bond in the vanadium compound molecule are preferable. Examples of the oxovanadium compound include vanadyl acetylacetonate, oxovanadium salen complex, N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, tetraphenylporphyrin oxovanadium, and the like. The amount of the catalyst is not particularly limited, but the total content of the metal elements contained in the catalyst is preferably in the range of 0.001 to 50 mol% with respect to 100 mol% of the monomer component, and the molecular weight is 30 mol% or less is preferable, 10 mol% or less is more preferable, and 5 mol% or less from the viewpoint of easily obtaining a high sulfur-containing polymer and/or from the viewpoint of facilitating the removal of catalyst residues by a simple refining process. More preferably, it is 0.01 mol % or more, still more preferably 0.1 mol % or more, and particularly preferably 1 mol % or more, from the viewpoint of enhancing the polymerization reactivity.

The polymerization is preferably carried out in the presence of oxygen. Conducting the reaction in the presence of oxygen further promotes the oxidative polymerization reaction. As a specific embodiment, a method of supplying an oxygen-containing gas during the polymerization reaction is preferred. That is, the polymerization is preferably carried out under supply of an oxygen-containing gas. For example, a method of supplying an oxygen-containing gas to the gas phase during the polymerization reaction, a method of bubbling an oxygen-containing gas into the reaction composition during the polymerization reaction, and the like are employed.

It is considered that the hydrogen desorption reaction from the carbon atoms constituting the aromatic rings contained in the monomer component can be promoted by conducting the above polymerization reaction in the presence of oxygen gas. In addition, in the polymerization step, the oxidation number of the metal contained in the catalyst can usually change, but by performing the polymerization reaction in the presence of oxygen gas, the valence of the metal contained in the catalyst can be increased to a high oxidation number. It is considered that the oxidative polymerization can be further promoted because the oxidative polymerization can be maintained. From this point of view, the method of continuously supplying the oxygen-containing gas to the reaction composition during the polymerization reaction is preferred, and the method of bubbling is particularly preferred.

The oxygen-containing gas is preferably a gas containing oxygen molecules (O ₂ ). The oxygen-containing gas may contain gas components other than oxygen molecules (O ₂ ). Gas components other than oxygen molecules (O ₂ ) contained in the oxygen-containing gas are not particularly limited, but are preferably helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe ), rare gases such as radon (Rn); and inert gases such as nitrogen (N ₂ ). Carbon dioxide (CO ₂ ), water vapor, etc. may be contained in addition to the inert gas.

The content of oxygen molecules (O ₂ ) in the oxygen _- containing gas is not particularly limited. It is preferably 0.1 to 100% by volume. More preferably, it is 1% by volume or more, and still more preferably 10% by volume or more. The upper limit is more preferably 60% by volume or less, more preferably 30% by volume or less.

The total content of the oxygen molecules (O ₂ ) and the inert gas in the oxygen-containing gas is not particularly limited, but at normal temperature (25° C.) and 1 atm, the oxygen molecules (O ₂ ) and the inert gas in the oxygen-containing gas It is preferable that the total volume ratio of the gases is 80 to 100% by volume with respect to 100% by volume of the oxygen-containing gas. More preferably, it is 95% by volume or more, and still more preferably 98% by volume or more.

Examples of the oxygen-containing gas include, but are not limited to, oxygen gas, mixed gas of oxygen and nitrogen, and air. It is preferable to use air from the viewpoint of being excellent in economic efficiency.
The water vapor concentration in the oxygen-containing gas is not particularly limited, but is preferably 1000 g/m ³ or less, more preferably 10 g/m ³ or less, still more preferably 1 g/m ³ or less, and most preferably 0.1 g/m ³ or less. Preferred is dry air.

The supply amount of the oxygen-containing gas is not particularly limited, but it should be 0.0001 m ³ /min to 10 m ³ /min as the supply amount per minute (supply rate) per 1 m ³ of the total volume of the reaction composition. is preferred. From the viewpoint of increasing the reaction rate, it is more preferably 0.0005 m ³ /min or more, and still more preferably 0.001 m ³ /min or more. From the viewpoint of easy control of the reaction temperature, the upper limit is more preferably 1 m ³ /min or less, and still more preferably 0.1 m ³ /min or less.

The supply amount of the oxygen-containing gas is not particularly limited, but the supply amount (supply rate) of oxygen (O ₂ ) per minute per 1 m ³ of the total volume of the reaction composition is 0.00002 m ³ /min to 2 m ³ /min is preferred. From the viewpoint of increasing the reaction rate, it is more preferably 0.0001 m ³ /min or more, and still more preferably 0.0002 m ³ /min or more. The upper limit is more preferably 0.2 m ³ /min or less, still more preferably 0.02 m ³ /min or less, from the viewpoint of easy control of the reaction temperature.

It is preferable to use an acid and/or a salt thereof in the polymerization step. By using an acid and/or a salt thereof together with the above catalyst, it becomes easy to control the molecular weight of the polymer obtained by the polymerization reaction to a high range, and it becomes easy to obtain a high-molecular-weight sulfide-containing polymer even in a short time.

Bronsted acid is preferable as the acid. For example, inorganic acids such as phosphoric acid, phosphonic acid, nitric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, persulfuric acid, sulfurous acid; methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, 10-camphorsulfonic acid, trifluoromethanesulfonic acid sulfonic acids such as , 1,1,2,2-tetrafluoroethanesulfonic acid; carboxylic acids such as acetic acid, trifluoroacetic acid, perfluoropropionic acid, perfluorobutyric acid and benzoic acid;

As the acid, an acid having an acid dissociation constant of -19 to 4 is preferable. More preferably, the acid dissociation constant is 3 or less and -8 or more.

The salt of the acid is not particularly limited as long as it is a salt of the acid. Examples include group 1 metal elements of the periodic table such as sodium and potassium; etc. with the above acids are preferred. Among them, for example, sodium persulfate, ammonium persulfate, sodium toluenesulfonate, sodium trifluoromethanesulfonate and the like are preferable. The salt with the acid preferably has a pH of 1 to 6.9, more preferably 2 to 6 at 25° C. when dissolved in pure water.

Examples of acids having an acid dissociation constant of -19 to 4 include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, persulfuric acid, sulfurous acid, hydrochloric acid, hydrobromic acid; methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, sulfonic acids such as 10-camphorsulfonic acid, trifluoromethanesulfonic acid and 1,1,2,2-tetrafluoroethanesulfonic acid; chlorocarboxylic acids such as chloroacetic acid, dichloroacetic acid and trichloroacetic acid; Fluorocarboxylic acids such as fluoroacetic acid, perfluoropropionic acid, perfluorobutyric acid, 4-fluorobenzoic acid, and the like are included. Among them, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, and persulfuric acid are preferred. One of the above acids and/or salts thereof may be used, or two or more thereof may be used.

The amount of the acid and/or its salt used is preferably 0.01 to 100 mol %, more preferably 0.1 to 10 mol %, more preferably 0.1 to 10 mol %, based on 100 mol % of the monomer component. More preferably 5 to 5 mol %.
The amount of the acid and/or its salt used is preferably 0.1 to 1000 mol%, preferably 1 to 100 mol%, with respect to 100 mol% of the total amount of the metal elements contained in the substance containing the metal element. %, more preferably 5 to 50 mol %.

The pH of the entire reaction system to which the acid and/or its salt is added (raw material composition containing the acid and/or its salt) is preferably pH 0.1 to 7, and 1 to 6, from the viewpoint of improving the reaction efficiency. More preferably, 2 to 5 are most preferable. The pH is a value when the reaction system (raw material composition containing an acid and/or its salt) is measured as it is, and is measured using pH test paper and a pH measuring machine.

In the polymerization step, the polymerization temperature is not particularly limited as long as it is a temperature at which polymerization, preferably oxidative polymerization, proceeds. , more preferably 100°C or higher, and more preferably 200°C or lower, and even more preferably 180°C or lower, in order to suppress side reactions. The polymerization time is not particularly limited, but is usually 0.1 to 300 hours, preferably 1 to 200 hours, more preferably 5 to 100 hours, and further preferably 10 to 50 hours. preferable.

The polymerization reaction can be carried out in a molten state of the monomer components, or in a state of dissolving or dispersing the monomer components in a solvent. When the polymerization is carried out in a molten state, it is preferable to set the polymerization temperature to a temperature equal to or higher than the melting point of the monomer component. In that case, it is preferable to heat the raw material composition and carry out the polymerization reaction while maintaining the temperature of the reaction composition at a temperature equal to or higher than the melting point of the monomer component.

Further, when the monomer component is dissolved or dispersed in a solvent, the polymerization may be carried out at a temperature below the boiling point of the solvent, under reflux conditions, or at a temperature above the boiling point. Polymerization may be carried out in a pressurized state while heating to .

The above solvent is not particularly limited, but preferred solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1, 2-dichlorobenzene, 1,3-dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, cyclopentyl methyl ether and the like. The amount of the solvent used is not particularly limited, but it is preferably 1 to 10,000 parts by mass, more preferably 10 to 1,000 parts by mass, based on 100 parts by mass of the raw material monomer component.

In the above polymerization, monomer components may be sequentially added during the polymerization reaction. In the polymerization step, the above-described thiol compound may be oxidatively polymerized to obtain a disulfide compound, and then the resulting disulfide compound may be oxidatively polymerized.

By maintaining the composition (raw material composition) containing the monomer component and the catalyst at the polymerization temperature for the polymerization time, the polymerization reaction of the monomer component occurs to form a sulfur-containing polymer (sulfide-containing polymer). coalescence) is produced, and a polymer composition containing at least the polymer (sulfide-containing polymer) and the catalyst is obtained.

The production method of the present invention is characterized by having the above-described oxidation step, but as described above, preferably includes the above-described polymer terminal control step, and preferably includes the above-described polymerization step. The most preferred embodiment of the production method of the present invention is a production method comprising the polymerization step, the oxidation step, and the polymer terminal control step. For example, it is a manufacturing method comprising the following steps (1) to (3).
(1) Polymerization step: Polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer having a sulfide skeleton in the main chain (sulfide-containing polymer).
(2) Oxidation step: oxidizing a sulfide-containing polymer to obtain a sulfoxide-containing polymer.
(3) Polymer terminal control step: A reaction for controlling the polymer terminal is carried out.

Here, as described above, the polymerization step (1) is preferably performed before the oxidation step (2), and the timing of performing the polymer terminal control step (3) is as described above. Among them, the polymer terminal control step (3) is preferably performed after the oxidation step (2) or performed simultaneously with the oxidation step (2). It is preferred to initiate a terminal control reaction in the process. That is, it is preferable to start the oxidation reaction first and then carry out the terminal control reaction after the oxidation reaction is completed or after the oxidation reaction has progressed to some extent.

<Purification process>
The production method of the present invention preferably has a purification step in addition to the oxidation step, and more preferably has a purification step in addition to the oxidation step, the polymer terminal control step and the polymerization step. When oxidative polymerization using a catalyst is performed in the polymerization step, the metal component contained in the metal compound used as the catalyst tends to cause coloration, depending on the type of metal, and should be removed. However, since the metal component is strongly coordinated with the terminal of the polymer (sulfide-containing polymer), it is difficult to remove it.

Even if the polymer (sulfide-containing polymer) is a polymer containing a metal component (sulfide-containing polymer), by subjecting it to the oxidation step in the present invention, only the sulfur atoms in the main chain skeleton of the polymer can be oxidized. Not only that, but also the terminal structure changes, so the coordinating power of the sulfur atom in the polymer to the metal component is reduced, making it easier to remove.

Therefore, a conventionally known purification method can be used as the purification method. For example, it is preferable to use a reprecipitation method. The reprecipitation method is not particularly limited, but for example, a composition containing a polymer such as a sulfide-containing polymer or a sulfoxide-containing polymer is dropped into methanol acidified with hydrochloric acid to precipitate the polymer, which is then filtered. Examples include a method of obtaining a precipitate and washing the obtained precipitate with water or a lower alcohol such as methanol. It is preferable to remove components derived from the compound (Z) used in the oxidation step by the purification method.

As the purification step, a method using a conventionally known adsorbent such as activated carbon can be used to remove components derived from the compound (Z) used in the oxidation step and impurity components derived from the polymerization step. It is also preferable to use the reprecipitation method and the method using an adsorbent together. The timing of performing the purification step is not particularly limited, and may be performed before the oxidation step, after the oxidation step, or after the polymer terminal control step. That is, the sulfide-containing polymer obtained after the purification step may be subjected to the oxidation step, or the polymer obtained in the oxidation step or the polymer terminal control step (sulfoxide-containing polymer) may be may be performed on a composition comprising:

Among them, the above purification step is performed on the composition containing the polymer obtained after all of the above polymerization step, the oxidation step, and the polymer terminal control step, which is derived from the raw materials used in each step. It is preferable in that a sulfoxide-containing polymer containing few impurities can be obtained. For example, when the production method of the present invention has a polymer terminal control step, the composition containing the polymer (sulfoxide-containing polymer) obtained after performing the oxidation step and the polymer terminal control step is purified. is preferably performed, and when the production method of the present invention does not have a polymer terminal control step, the composition containing the polymer (sulfoxide-containing polymer) obtained after the oxidation step is purified. is preferred.

The production method of the present invention may have other steps in addition to the polymerization step, the oxidation step, the polymer terminal control step and the purification step. Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent replacement step, and a dissolution step. These steps can be performed by a known method.

2. Sulfur-containing polymer obtained by the production method of the present invention The sulfur-containing polymer obtained by the above-described production method of the present invention is a sulfur-containing polymer having a sulfoxide skeleton in its main chain (sulfoxide-containing polymer). Among the sulfur-containing polymers obtained by the production method of the present invention, preferred sulfoxide-containing polymers are described below.

The sulfoxide-containing polymer has excellent transmittance after heating. The transmittance after heating can be determined by the visible light transmittance after heating at 260° C., for example. Specifically, a sample containing a sulfoxide-containing polymer is heated in air at 260° C. for 10 minutes, and the transmittance Ta (%) after heating is measured.

As the sample, a laminate of a colorless and transparent glass substrate and a thin film of a sulfoxide-containing polymer having a thickness of 1 μm formed on one side thereof is used. The above sample can be prepared, for example, by applying a solution of a sulfoxide-containing polymer in a solvent to a colorless and transparent glass substrate and one side thereof, followed by drying. As a preferred specific example, a solution is prepared by dissolving a sulfoxide-containing polymer in hexafluoro-2-propanol to a concentration of 5% by mass, and the resulting solution is applied to a glass substrate ( S1111 manufactured by Matsunami Glass Industry Co., Ltd.) is spin-coated at about 500 rpm for 60 seconds and dried at 100° C. for 10 minutes to form a thin film (thickness: 1 μm).

The visible light transmittance can be measured using a commercially available spectrophotometer. For example, a spectrophotometer (UV-visible/infrared spectrophotometer V-700 series manufactured by JASCO Corp.) can be used. As the visible light transmittance for determining the transmittance after heating, the transmittance at a wavelength of 400 nm is usually employed. Parallel line transmittance is adopted as the transmittance.

In the above sulfoxide-containing polymer, the transmittance (Ta) after heating obtained by the above evaluation method is preferably 81% or more, more preferably 82% or more, and 85% or more. is more preferred.

In the above evaluation method, the sulfoxide-containing polymer preferably has a transmittance (Tb) before heating at 260° C. of 82% or more, more preferably 83% or more, and more preferably 85% or more. It is even more preferable to have
The transmittance (Tb) can be measured by the same method as the transmittance (Ta).
The absolute value of the difference between the transmittance (Ta) and the transmittance (Tb) of the sulfoxide-containing polymer is preferably 5% or less, more preferably 3% or less, and 2% or less. is more preferable, and 1% or less is particularly preferable.

The sulfoxide-containing polymer is preferably a sulfur-containing polymer having at least the structural unit (B) represented by the general formula (2) described in the description of the sulfide-containing polymer, and X ² and X ² The substituents which may have are as described in the description of the sulfide-containing polymer, including these preferred embodiments. Furthermore, the sulfoxide-containing polymer is preferably a sulfur-containing polymer having at least the structural unit (B-1) represented by the general formula (2-1), and R ² and R ² have Substituents, including these preferred embodiments, are as described in the description of the sulfide-containing polymer.

The sulfoxide-containing polymer is not particularly limited as long as it is a sulfur-containing polymer having a sulfoxide skeleton in the main chain, preferably a sulfur-containing polymer having the above structural unit (B), but may contain other structural units. good too. For example, further comprising the structural unit (A) represented by the above general formula (1) and/or the structural unit (C) represented by the above general formula (3) described in the description of the sulfide-containing polymer good too.

In the sulfoxide-containing polymer, the structural unit (A) is preferably a structural unit (A-1) represented by the general formula (1-1), and the structural unit (C) is the general formula (3- The structural unit (C-1) represented by 1) is preferred. substituents X ¹ and X ¹ may have, substituents X ³ and X ³ may have, substituents R ¹ and R ¹ may have, R ³ and R ³ The substituents which may have are as described in the description of the sulfide-containing polymer, including these preferred embodiments.

The sulfoxide-containing polymer may be a polymer containing only the structural unit (B), or may be a copolymer further containing the structural unit (A) and/or the structural unit (C). The form of the copolymer is not particularly limited, and may be, for example, an alternating copolymer, a block copolymer, or a random copolymer. The sulfoxide-containing polymer may have one or more of the structural units (A), (B), or (C).

The content of the structural unit (B) in the sulfoxide-containing polymer is preferably higher than the content of the structural unit (B) in the sulfide-containing polymer subjected to the oxidation step. In the sulfoxide-containing polymer, the content of the structural unit (B) is preferably 10 to 99 mol%, more preferably 30 to 97 mol%, relative to 100 mol% of the total structural units of the polymer. is more preferred, and 60 to 95 mol % is even more preferred. The total content of the structural unit (A) and the structural unit (C) is preferably 1 to 90 mol%, more preferably 3 to 70 mol%, relative to 100 mol% of all structural units. , more preferably 5 to 40 mol %. The content of the structural unit (A) is preferably 1 to 90 mol%, more preferably 3 to 70 mol%, and 5 to 40 mol% with respect to 100 mol% of all structural units. It is even more preferable to have

In the sulfoxide-containing polymer, the total content of the structural units (A), (B) and (C) is preferably 50 mol% or more with respect to 100 mol% of the total structural units of the polymer, It is more preferably 80 mol % or more, still more preferably 90 mol % or more, even more preferably 95 mol % or more, and particularly preferably 100 mol %.

The sulfoxide-containing polymer may have a structural unit (D) other than the structural unit (A), the structural unit (B), and the structural unit (C). Examples of the structural unit (D) include structural units having at least the reactive functional group described above. The monomer into which the structural unit (D) can be introduced is as described in the description of the sulfide-containing polymer. The content of the structural unit (D) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, more preferably 0 to 5%, based on 100 mol% of the total structural units of the polymer. More preferably, it is mol %.

The sulfoxide-containing polymer preferably has the above-described reactive functional group at the main chain end and/or side chain. By having the reactive functional group at least at the end of the main chain or the side chain, the sulfoxide-containing polymer obtained after the oxidation reaction can exhibit excellent physical properties due to the reactive functional group. The case of having the reactive functional group in the side chain means not only the case where the side chain of the sulfoxide-containing polymer has the reactive functional group, but also the structures represented by the general formulas (1) to (3). The case where the substituent in the units (A) to (C) is the above reactive functional group or a group containing the above reactive functional group is also included.

The sulfoxide-containing polymer preferably has a heavy metal content of 0.0001 ppm or more and 1200 ppm or less relative to the sulfur-containing polymer. The sulfoxide-containing polymer has a high refractive index and excellent optical transparency. Moreover, the transmittance after heating is also excellent. The amount of heavy metals is more preferably 500 ppm or less, still more preferably 200 ppm or less, and even more preferably 100 ppm or less relative to the polymer (solid content). In addition, the amount of heavy metals is more preferably 0.001 ppm or more relative to the sulfoxide-containing polymer (solid content) from the viewpoint that molded products using the sulfoxide-containing polymer tend to have excellent toughness. It is more preferably 0.01 ppm or more. The amount of heavy metals can be determined by the ICP emission spectroscopic analysis described above.

In the sulfoxide-containing polymer, the element content ratio (O/S) between the oxygen atom O bonded to the sulfur atom S in the main chain and the sulfur atom S in the main chain is 0.1 to 1.5. preferable. Transparency and a refractive index become it higher that the said element content ratio is the above-mentioned range.
The sulfur atom S in the main chain specifically means, for example, the sulfur atom S of -SO- in the main chain in the structural unit (B) represented by the general formula (2). In the structural unit (A) represented by the above general formula (1), it means the sulfur atom S of -S- in the main chain, and in the structural unit (C) represented by the above general formula (3), It means the sulfur atom S of -SO ₂ - in the main chain. Specifically, the oxygen atom bonded to the sulfur atom S of the main chain is, for example, the oxygen atom O of —SO— in the main chain in the structural unit (B) represented by the general formula (2). In structural unit (C) represented by general formula (3) above, it means oxygen atom O of —SO ₂ — in the main chain.

The element content ratio (O / S) is more preferably 0.3 or more, still more preferably 0.5 or more, in that the transparency can be further increased. It is more preferably 1.3 or less, even more preferably 1.1 or less, in that it can be made even higher. The above element content ratio is evaluated using an X-ray photoelectron spectrometer (XPS), and the peak intensities of the oxygen atom 1s orbital (O1s), the carbon atom 1s orbital (C1s), and the sulfur atom 2p orbital (S2p) are evaluated and measured. can be obtained by

The weight average molecular weight (Mw) of the sulfoxide-containing polymer is preferably from 500 to 10,000,000. When the weight average molecular weight is within the above range, it can be suitably used as an optical material. The weight average molecular weight is more preferably 1,000 or more, still more preferably 3,000 or more, even more preferably 10,000 or more, from the viewpoint of improving mechanical properties, and 1,000,000 or less from the viewpoint of reducing melt viscosity. is more preferably 100,000 or less.

The dispersity (weight average molecular weight/number average molecular weight) of the sulfoxide-containing polymer is preferably 1 or more and 10 or less. Molding|molding becomes it easy that the said dispersion degree is the above-mentioned range. The degree of dispersion is more preferably 5 or less, and even more preferably 3 or less, in that the moldability can be further improved. The weight-average molecular weight and number-average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method, and specifically can be obtained by the method described in the examples below. The dispersity can be determined by dividing the weight average molecular weight by the number average molecular weight.

The sulfoxide-containing polymer preferably has a glass transition temperature (Tg) of 80 to 250°C. When the glass transition temperature is within the above range, molding can be easily performed. The glass transition temperature is more preferably 90° C. or higher, still more preferably 100° C. or higher, from the viewpoint of increasing heat resistance, and is 200° C. or lower from the viewpoint of facilitating molding. is more preferable. The glass transition temperature was measured using a differential scanning calorimeter (DSC) from a DSC curve obtained by heating from room temperature to 250°C (heating rate of 10°C/min) in a nitrogen gas atmosphere. It can be obtained by a method of evaluation based on the intersection of tangent lines at the point of inflection.

The sulfoxide-containing polymer preferably has a refractive index of 1.69 or more. When the refractive index is within the above range, various applications such as optical materials (members), machine parts materials, electrical/electronic parts materials, automobile parts materials, civil engineering and construction materials, molding materials, etc., as well as materials for paints and adhesives. It can be widely and suitably used for. The refractive index is more preferably 1.7 or higher, and even more preferably 1.71 or higher. The refractive index is measured by forming a film with a thickness of 50 nm using the polymer as a measurement sample, using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific), and using Na D line (589 nm). can be obtained by

The sulfoxide-containing polymer preferably has an Abbe number of 10 or more. When the Abbe number is within the above range, the optical material has small light dispersion and is suitable for lenses. The Abbe number is more preferably 15 or more, still more preferably 18 or more, and even more preferably 20 or more. The Abbe number is preferably 60 or less, more preferably 55 or less, from the viewpoint of adjusting the light dispersion. The Abbe number is measured using the polymer in the same manner as in the measurement of the refractive index, and the D line (589.3 nm) and F line (486.1 nm) are measured using the spectroscopic ellipsometer. , C-line (656.3 nm) is measured, and the following calculation formula can be used.
Abbe number (vD) = (nD-1) / (nF-nC)
In the formula, nD, nF, and nC represent the refractive indices at Fraunhofer's D line (589.3 nm), F line (486.1 nm), and C line (658.3 nm), respectively.

The sulfoxide-containing polymer obtained by the production method of the present invention has excellent transmittance after heating. Further, according to a preferred embodiment, the polymer has a sulfoxide skeleton in the main chain, so that it has a high refractive index and optically excellent transparency to visible light. According to the preferable aspect, it becomes excellent also in solubility and workability. In addition, the polymer obtained in the preferred embodiment of the production method of the present invention contains few impurities used in the polymerization process, etc., and the material using the polymer has excellent colorless transparency and is resistant to coloration over time. becomes suppressed.
Therefore, the sulfur-containing polymer (sulfoxide-containing polymer) obtained by the production method of the present invention can be used alone or as a composition in which other components are combined for various purposes such as optical materials. .

3. Composition Containing Sulfoxide-Containing Polymer Obtained by Production Method of the Present Invention A composition containing a sulfoxide-containing polymer obtained by the production method of the present invention will be described. The composition is also referred to as a sulfoxide-containing polymer composition or polymer composition.
The content of the sulfoxide-containing polymer in the sulfoxide-containing polymer composition is preferably 1 to 100% by mass, preferably 10 to 50% by mass, based on 100% by mass of the total solid content of the sulfoxide-containing polymer composition. and more preferably 30 to 70% by mass.

The other component is not particularly limited, and can be appropriately selected from known components according to the purpose and application of the sulfoxide-containing polymer composition.
For example, transparency and refractive index can be controlled by selecting inorganic substances as other components. The sulfoxide-containing polymer and the sulfoxide-containing polymer composition containing an inorganic substance are also embodiments of the sulfoxide-containing polymer obtained by the production method of the present invention.

Examples of the inorganic substances include metals, inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, inorganic hydroxides, and the like. The above inorganic substances may be used alone or in combination of two or more.
Examples of the metals include lithium (Li), sodium (Na), potassium (K), boron (B), magnesium (Mg), calcium (Ca), manganese (Mn), strontium (Sr), barium (Ba ), titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), tin (Sn), silicon (Si ), cesium (Ce), indium (In), and the like.

As the inorganic oxide, a metal oxide containing a metal element is preferable. Examples of the metal oxide include a single metal oxide composed of one metal element, a composite oxide composed of two or more metal elements, and an element different from the single metal oxide or the composite oxide. is a solid solution oxide. The dissimilar element may be a metallic element, or may be a non-metallic element other than oxygen, such as nitrogen or fluorine. Examples of the metal element include the metal elements described above. Examples of the single metal oxide include magnesium oxide, calcium oxide, strontium oxide, barium oxide, titanium oxide, zinc oxide, cerium oxide, silicon oxide, tin oxide, zirconium oxide, aluminum oxide, and indium oxide. . Examples of the composite oxide include perovskite-type composite oxides such as barium titanate, barium strontium titanate, strontium titanate, barium zirconium strontium titanate, barium zirconium titanate, and lead zirconate titanate; spinel, lithium titanate, and the like. spinel-type composite oxides; and composite oxides such as aluminum titanate. Examples of the solid solution oxides include solid solution oxides obtained by dissolving dissimilar metal elements and/or nonmetallic elements other than oxygen, such as nitrogen and fluorine, in the above single metal oxides or composite oxides.

As the inorganic nitride, a metal nitride is preferable, and examples thereof include boron nitride, carbon nitride, and aluminum nitride. As the inorganic carbide, metal carbide is preferable, and examples thereof include silicon carbide, calcium carbide, titanium carbide, boron carbide, and the like. As the inorganic sulfides, metal sulfides are preferable, and examples thereof include copper sulfide, zinc sulfide, and cadmium sulfide. As the inorganic hydroxide, metal hydroxides are preferable, and examples thereof include aluminum hydroxide, magnesium hydroxide, barium hydroxide, and the like.

Among them, the inorganic substance is preferably an inorganic oxide, and more preferably a metal oxide, because it has a wide bandgap (transparent to visible light). Among the above inorganic substances, Ti, Zr, Ce, Zn, Ti, Zr, Ce, Zn, Oxides containing In, Al, Si, and Sn as main components of metal elements are more preferable, and include titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), zinc oxide (ZnO), and indium oxide. (In ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ) and tin oxide (SnO ₂ ) are particularly preferred.

Among the above inorganic substances, zirconium oxide, titanium oxide, and silicon dioxide are more preferred in that they can further improve the transparency of the sulfoxide-containing polymer composition and that the composition can be made to have a low linear expansion. Zirconium oxide and titanium oxide are more preferable from the viewpoint of improving the refractive index of the sulfoxide-containing polymer composition. Further, perovskite-type composite oxides are preferable because they have a high dielectric constant and the sulfoxide-containing polymer composition can be suitably used as a ferroelectric material and a piezoelectric material. Boron nitride, aluminum hydroxide, and aluminum titanate are preferred in that they have high thermal conductivity and can be suitably used as a heat dissipation material for the sulfoxide-containing polymer composition.

Zinc oxide (ZnO), indium oxide (In ₂ O ₃ ) or tin oxide (SnO ₂ ) is used from the viewpoint of imparting antistatic properties or conductivity while suppressing coloring due to the addition of inorganic substances to the sulfoxide-containing polymer composition. In addition, a solid solution oxide in which a dissimilar metal element or an additive element such as fluorine is dissolved is preferable. For example, zinc oxide in which In, Al or Ga is dissolved, indium oxide in which Sn or Ti is dissolved, Sb or F. Solid solution tin oxide or the like is more preferable.

The shape of the inorganic substance is not particularly limited, and may be amorphous, granular, plate-like, fibrous, block-like, etc., but granular is preferred. The inorganic substance may be surface-treated. The surface treatment is not particularly limited as long as it does not affect the effects of the present invention, and includes a method using a silane coupling agent, a method of reacting a compound having a phosphoric acid group, and a compound having a carboxylic acid group. A known method such as a method of reacting can be mentioned.

The average particle size of the inorganic substance is preferably 1 nm or more and 1000 nm or less. When the average particle size of the inorganic substance is within the above range, the light transmittance in the visible light region and the infrared region can be improved. The average particle size of the inorganic substance is more preferably 5 nm or more, still more preferably 10 nm or more, and more preferably 100 nm or less, even more preferably 50 nm or less. The average particle diameter can be determined by observing the inorganic material with a SEM (magnification of 1000 to 100,000 times, preferably 10,000 times) and analyzing the obtained image, and the number of individual particles (primary particles ), and evaluate the 50% particle size based on the number-based particle size distribution. For image analysis, known image analysis software (eg, Mac-View manufactured by Mountec) can be used.

The content of the inorganic substance is not particularly limited, and can be appropriately set according to the purpose and application of the sulfoxide-containing polymer composition. For example, the content of the inorganic substance is preferably 10 parts by mass or more with respect to 100 parts by mass of the sulfoxide-containing polymer in terms of further improving transparency and achieving low linear expansion. It is preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and most preferably 80 parts by mass or more. In addition, from the viewpoint of reducing the melt viscosity when producing a resin molded product, the content of the inorganic substance is preferably 90 parts by mass or less, and 80 parts by mass or less with respect to 100 parts by mass of the sulfoxide-containing polymer. more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

In addition to the sulfoxide-containing polymer and inorganic substance described above, the sulfoxide-containing polymer composition includes, for example, pigments, dyes, antioxidants, ultraviolet absorbers, resins, reactive diluents, light stabilizers, plasticizers, non- Reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, adhesion improvers such as coupling agents, heat stabilizers, antibacterial and antifungal agents, Flame retardant, matting agent, antifoaming agent, leveling agent, wetting/dispersing agent, anti-settling agent, thickener/anti-sagging agent, anti-color splitting agent, emulsifier, anti-slip/scratch agent, anti-skinning agent, drying It may contain components such as agents, antifouling agents, antistatic agents, conductive agents (static aids), and solvents. These components may be used alone or in combination of two or more. These components can be appropriately selected from known ones and used. Moreover, the blending amounts of these components can be appropriately set.

When the sulfoxide-containing polymer composition is used as an optical material, it may contain other components as appropriate depending on the use of the optical material. Specific examples of the other components include ultraviolet absorbers, IR cut agents, reactive diluents, pigments, detergents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, antifoaming agents, and the like. are preferably mentioned.

The sulfoxide-containing polymer composition preferably has a glass transition temperature (Tg) of 80 to 250°C. When the glass transition temperature is within the above range, molding can be easily performed. The glass transition temperature is more preferably 90° C. or higher, still more preferably 100° C. or higher, from the viewpoint of increasing heat resistance, and is 200° C. or lower from the viewpoint of facilitating molding. is more preferable. The glass transition temperature can be obtained by the same method as the method for measuring the glass transition temperature of the polymer described above.

The sulfoxide-containing polymer composition preferably has a refractive index of 1.69 or more. When the refractive index is within the above range, it can be suitably applied as an optical material or the like. The refractive index is more preferably 1.70 or higher, and even more preferably 1.71 or higher. The refractive index can be obtained by the same method as the method for measuring the refractive index of the polymer described above.

The sulfoxide-containing polymer composition preferably has an Abbe number of 10 or more. When the Abbe number is within the above range, the optical material has small light dispersion and is suitable for lenses. The Abbe number is more preferably 15 or more, still more preferably 18 or more, and even more preferably 20 or more. The Abbe number is more preferably 60 or less, and even more preferably 55 or less, from the viewpoint of adjusting the light dispersion. The Abbe number can be obtained by the same method as the method for measuring the Abbe number of the polymer described above.

The sulfoxide-containing polymer composition preferably has a visible light transmittance of 70% or more. When the visible light transmittance is within the above range, it can be suitably used as an optical material. The visible light transmittance is more preferably 80% or more, still more preferably 85% or more, and even more preferably 88% or more. The visible light transmittance is the parallel line transmittance, and can be obtained by the same method as the method for measuring the visible light transmittance of the sulfoxide-containing polymer described above.

The method for producing the sulfoxide-containing polymer composition is not particularly limited, and it can be prepared by mixing the sulfoxide-containing polymer, the inorganic substance, and, if necessary, other components. Examples of the mixing include known means such as bead mills, roll mills, ball mills, jet mills, kneaders and blenders.

Moreover, the sulfoxide-containing polymer and the sulfoxide-containing polymer composition of the present invention are preferably thermoplastic. Molding processing is easy as it is thermoplastic, and it is excellent also in productivity.

The sulfoxide-containing polymer and sulfoxide-containing polymer composition of the present invention can also be suitably used as a molding material. The molding method is not particularly limited, and generally known methods for processing thermoplastic resins, such as injection molding, extrusion molding, T-die method, and inflation method, can be mentioned. Alternatively, it may be molded into a desired shape by a method such as casting or coating. The shape is not particularly limited, and includes various known shapes such as lenses, sheets, and films.

4. Uses The sulfoxide-containing polymer and sulfoxide-containing polymer composition obtained by the production method of the present invention are suitably used for optical materials, optical device members, display device members and the like. Specific examples of such applications include spectacle lenses, imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and vehicle-mounted cameras, lenses such as light beam condensing lenses, light diffusion lenses, and LEDs. Sealing materials, optical adhesives, optical adhesives, optical transmission bonding materials, filters, diffraction gratings, diffractive optical elements, prisms, light guides, watch glass, transparent glass such as cover glass for display devices and cover glass; photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)), photoswitches, LEDs, micro LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, disconnectors, light Optodevice applications such as dividers and optical fiber adhesives; substrates for display elements such as LCD, organic EL, and PDP, substrates for color filters, substrates for touch panels, index matching materials used for touch panels, display protective films, display backlights, etc. , light guide plates, antireflection films, antifogging films, and display device applications such as light extraction improvers such as LEDs and organic ELs.

Among these, imaging lenses, filters, diffraction gratings, diffractive optical elements, prisms, light guides, LEDs, micro LEDs, light emitting elements, color filters, and touch panels are more preferable. In addition, the sulfoxide-containing polymer obtained by the production method of the present invention usually tends to have a wide absorption region in the visible region and the infrared region. Such polymers are also suitable for use as optical materials in the visible and infrared regions.

The sulfoxide-containing polymer and the sulfoxide-containing polymer composition obtained by the production method of the present invention can be used not only for optical applications but also for machine parts materials, electric/electronic parts materials, automobile parts materials, civil engineering and construction materials, molding materials, and the like. In addition, it is used for various purposes such as materials for paints and adhesives. For example, the sulfoxide-containing polymer obtained by the production method of the present invention usually tends to have excellent heat resistance. separators, filters such as gas separation membranes and liquid separation membranes, electrode materials for fuel cells and Li batteries, and battery members such as electrolyte materials. In addition, it can be suitably used as an insulating material, an antenna material, etc., utilizing low dielectric properties.

The sulfoxide-containing polymer and sulfoxide-containing polymer composition obtained by the production method of the present invention can be suitably used as molding materials. Examples of the molding method include molds such as conventionally known injection molding, T-die method, inflation method, imprint molding, and nanoimprint molding, and molding using resin molds. It may be molded into a desired shape by a method such as casting or coating. The shape is not particularly limited, and includes various known shapes such as lenses, sheets, and films.

In addition, the sulfoxide-containing polymer and the sulfoxide-containing polymer composition obtained by the production method of the present invention are suitable for processing by conventionally known etching processes such as plasma etching and conventionally known resist processes utilizing solubility differences. can be used. It can also be suitably used for coating by spin coating, bar coating, squeegee coating, inkjet coating, and the like. The composition containing the sulfoxide-containing polymer obtained by the production method of the present invention is preferably a thermoplastic resin composition from the viewpoint of good processability, and the viscosity is low, so that fine fineness can be obtained during molding. A curable resin composition is preferable in terms of good conformability to molds and resin molds.
As described above, the sulfoxide-containing polymer and sulfoxide-containing polymer composition obtained by the production method of the present invention can be suitably used in a wide range of applications including optical applications.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %". Polymers obtained in Examples and Comparative Examples, sulfide-containing polymers used in Examples, etc. were evaluated according to the following methods.

<Measurement of heavy metal content>
Using an ICP emission spectrometer ICP-8100 (manufactured by Shimadzu Corporation), appropriate plasma conditions (high frequency output 1.4 kW, coolant gas 20.0 L / min, plasma gas 1.40 L / min, carrier gas 0.60 L / min , plasma light source), the heavy metal content (iron content) in the polymer was evaluated based on the calibration curve, and the heavy metal content (ppm) relative to the polymer was determined. As a measurement sample, a sample diluted appropriately with a solvent was used so that the concentration of the polymer was 0.1 to 10% by mass. As a solvent, N-methylpyrrolidone was used for the polymer whose main chain was not oxidized, and dimethylformamide was used for the polymer whose main chain was oxidized with an oxidation rate of 90% or more.

<Weight average molecular weight (Mw)>
A gel permeation chromatography (GPC) method was used to determine the weight average molecular weight of the polymer under the following conditions.
Apparatus 1: SHIMAZU, CBM-20A.
Apparatus 2: Agilent Technologies 1260 Infinity.
Detectors: Refractive Index Detector (RI) (SHIMAZU, SPD-20MA) and UV-visible infrared spectrophotometer (SHIMAZU, SPD-20MA).
Column: TOSOH, TSKgel SuperHM-N.
Column temperature: 40°C.
Flow rate: 0.3 ml/min.
Calibration curve: Polystyrene Standards.
Eluent: chloroform, tetrahydrofuran.

<MALDI (time-of-flight mass spectrometry)>
The obtained polymer was subjected to MALDI measurement under the following conditions.
Apparatus: time-of-flight mass spectrometer (Bruker AutoflexIII)
Sample preparation: Dissolve about 2 mg of a sample to be measured in 1.0 g of tetrahydrofuran, 20 mg of 2,5-dihydroxybenzoic acid as a matrix agent, and 2.0 mg of sodium iodide as an ionizing agent, and prepare a solution for measurement. After coating on the target plate, it was dried at room temperature for about 100 minutes.

< ¹ H-NMR>
The obtained polymer was subjected to ¹ H-NMR measurement under the following conditions.
Apparatus: Nuclear magnetic resonance apparatus (400 MHz) manufactured by JEOL Ltd.
Measurement solvent: heavy dichloromethane, heavy chloroform.
Sample preparation: Several mg to several tens of mg of the obtained polymer were dissolved in a measurement solvent.

<IR>
The obtained polymer was subjected to IR measurement under the following conditions.
Apparatus: JASCO Fourier transform infrared spectrophotometer (FT/IR-6100)
Sample preparation: Approximately 2 mg of sample was diluted with approximately 300 mg of dry potassium bromide (KBr). The mixture was ground with a mortar and pestle and molded.

<Element content ratio O/S ratio>
A photoelectron spectrometer manufactured by JEOL (JPS-9010TR, XPS device, light source: Mg, X-ray output: 400 W) was measured using a sample formed by spin-coating 0.25 ml of the polymer solution onto a silicon wafer. The O/S ratio was calculated by measuring the peak intensity derived from the 2p orbital of the sulfur atom and the peak intensity derived from the 1s orbital of the oxygen atom, and calculating the integral ratio thereof. If necessary, the peak intensity derived from the 1s orbital of carbon atoms was also measured, and the O/S ratio was calculated in consideration of the result. The method of measurement, the position of binding energy, etc. were referred to Handbook of X-ray Photoelectron Spectroscopy (JEOL, March 1991).
By 1H-NMR measurement, when the sulfide and sulfoxide peaks could be separated, the O/S ratio was calculated by calculating the integral ratio of each.

<Binding energy>
Using a sample formed by spin-coating 0.25 ml of the polymer solution on a silicon wafer, a photoelectron spectrometer manufactured by JEOL (JPS-9010TR, XPS device) was used to determine the 2p3/2 orbit of sulfur atoms. Binding energy was measured from the peak position.

<Organic Elemental Analysis>
The obtained polymer was subjected to elemental analysis using the following equipment.
Apparatus: Jay Science Lab JM10.

<Transmittance>
(Sample preparation)
In the examples, the polymer (sulfide-containing polymer obtained in the production example) subjected to the oxidation reaction was adjusted to a concentration of 5% by mass with chloroform. polymer), a solution was prepared by dissolving each polymer in hexafluoro-2-propanol to a concentration of 5% by mass. The resulting solution was spin-coated on a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., S1111) that hardly absorbs visible light at about 500 rpm for 60 s, dried at 100 ° C. for 10 minutes to form a thin film (thickness 1 μm).
(measurement)
The transmittance of the obtained thin film was measured with a spectrophotometer (UV-visible/infrared spectrophotometer V-700 series manufactured by JASCO Corp.). In order to evaluate the visible light transmittance, the transmittance at 400 nm was used for comparison. Air was used as a control sample. The above transmittance is parallel line transmittance.

<Transmittance after heating>
The thin film used in the evaluation of the transmittance of the thin film was heated at 260° C. for 10 minutes, and the transmittance of the thin film after heating was measured as a sample. The measurement method and conditions are the same as those for <Transmittance of thin film> above.

(Synthesis of monomer)
[Synthesis Example 1]
Water (98 mL), o-toluenethiol (2-methylbenzenethiol) (18.2 g, 0.147 mol), tetrabutylammonium iodide (54.3 mg, 0.147 mmol) were added to a 500 mL three-necked flask, and , 30% hydrogen peroxide solution (15.2 mL, 0.147 mol) was added dropwise at 1 mL/min, and stirred at 60° C. for 2 hours. After cooling to room temperature, the supernatant (aqueous layer) was removed, an aqueous sodium thiosulfate solution was added, the mixture was stirred at room temperature for 2 hours, and the supernatant (aqueous layer) was removed. The reaction solid was filtered, washed with pure water and methanol in that order, and vacuum-dried to recover bis(2-methylphenyl)disulfide. Yield was 98%. It was confirmed to be bis(2-methylphenyl)disulfide (2,2′-dimethyldiphenyldisulfide) by ¹ H-NMR, ¹³ C-NMR and FAB-MS.

[Synthesis Example 2]
Synthetic reaction was carried out under the same conditions as in Synthesis Example 1, except that the raw material in Synthesis Example 1 was changed to p-toluenethiol (4-methylbenzenethiol) instead of o-toluenethiol, and bis(4-methylphenyl ) The disulfide was obtained in 98% yield. It was confirmed to be bis(4-methylphenyl)disulfide (4,4′-dimethyldiphenyldisulfide) by ¹ H-NMR, ¹³ C-NMR and FAB-MS.

(Synthesis of sulfide-containing polymer)
[Production Example 1]
In a 500 mL three-necked flask, diphenyl disulfide (131.00 g, 0.6 mol), bis(2-methylphenyl) disulfide (36.01 g, 0.15 mol) obtained in Synthesis Example 1 above, iron chloride ( III) Add (6.05 g, 37.30 mmol), (+)-CSA (1.73 g, 7.46 mmol), Na ₂ S ₂ O ₈ (1.78 g, 7.46 mmol) and heat at 160°C. Oxidative polymerization was carried out by stirring the reaction solution for 40 hours with air bubbling (100 mL/min). After cooling to room temperature, a black solid polymer (Ps1) was obtained in 92% yield. The structure of the obtained polymer (Ps1) was identified by ¹ H-NMR, GPC, ICP, XPS and MALDI. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.18 (m, 23H), 2.25 (m, 3H), weight average molecular weight (Mw) was 2400, and ICP By analysis, the iron content was 21500 ppm. XPS measurement shows a peak at 160.3-164.9 eV, and peak separation can separate peaks at 160.3-164.9 eV (sulfide) and 163.5-164.9 eV (disulfide). was 93:7. Further, repeated peaks of m/z 107.98 and m/z 122.04 were observed by MALDI measurement, and -C ₆ H ₄ S- and -C ₆ H ₃ (CH ₃ )S- It was confirmed that the polymer contained

[Production Example 2]
The monomer in Production Example 1 was changed to bis(4-methylphenyl)disulfide obtained in Synthesis Example 2 above instead of bis(2-methylphenyl)disulfide, and the reaction time was changed to 60 hours. A polymerization reaction was carried out under the same conditions as in Example 1 to obtain a polymer (Ps2) with a yield of 94%. The structure of the obtained polymer (Ps2) was identified by ¹ H-NMR, GPC, ICP, XPS and MALDI. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.20 (m, 23H), 2.25 (m, 3H), weight average molecular weight 3040, and ICP analysis confirmed iron The content was 22500 ppm. By XPS measurement, a peak was observed at 160.1-164.8 eV, and by peak separation, peaks could be separated into 160.1-164.8 eV (sulfide) and 163.5-164.8 eV (disulfide), sulfide and disulfide. was 95:5. Further, MALDI measurement showed repeated peaks at m/z 107.95 and m/z 122.02, and the constituent element (A) was -C ₆ H ₄ S- and -C ₆ H ₃ (CH ₃ )S-. It was confirmed that the polymer contained

[Example 1]
In a 100 ml eggplant flask, the polymer (Ps1) (1.1 g) obtained in Production Example 1 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 1.0 mL of pure water (THF: water=10:1) was added and stirred for 5 minutes. Then, trichloroisocyanuric acid (TCCA) (0.369 g) was added while cooling the eggplant flask with an ice-cooling bath, and the mixture was stirred for 2 hours. After completion of the reaction, methanol (40 mL) was gradually added to the reaction solution to precipitate a product, and the precipitate in the reaction solution was filtered by Kiriyama and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain polymer (Po1) powder. The structure of the obtained polymer (Po1) was identified by ¹ H-NMR, XPS, ICP, IR and elemental analysis. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 15H) δ = 7.56 (m, 8H), 2.35 (m, 3H), from IR A peak derived from sulfone was observed near 1350 cm ⁻¹ and 1170 cm ⁻¹ and a peak derived from sulfoxide was observed near 1050 cm ⁻¹ . The structure was assumed to be -S(=O ₂ )Cl.

[Example 2]
1.1 g of the polymer (Ps2) obtained in Production Example 2 and THF (1.0 M, 10 mL) as a solvent were added to a 100 mL eggplant flask, and after stirring for 10 minutes, 1.0 mL of pure water (THF: water = 10:1) was added and stirred for 5 minutes. Then, while cooling the eggplant flask with an ice bath, TCCA (0.369 g) was added, and after stirring for 2 hours, zinc powder (0.131 g) was added, and the mixture was stirred at room temperature for 16 hours. After completion of the reaction, methanol (40 mL) was gradually added to the reaction solution to precipitate a product, and the precipitate in the reaction solution was filtered by Kiriyama and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain polymer (Po2) powder. The structure of the obtained polymer (Po2) was identified by ¹ H-NMR, XPS, ICP, IR and elemental analysis. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 9H) δ = 7.56 (m, 14H), 2.35 (m, 3H), from IR , a mercapto-derived peak was observed near 2570 cm ⁻¹ , and elemental analysis confirmed that the chlorine atom content in the polymer was below the detection limit and the terminal structure was —SH.

[Example 3]
Into a 100 ml eggplant flask, the polymer (Ps1) (1.1 g) obtained in Production Example 1 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 0.5 mL of pure water was added. minutes. Next, NaClO.5H ₂ O (0.987 g) was added while cooling the eggplant flask with an ice-cooling bath, and concentrated hydrochloric acid (0.5 mL) was gradually added. 131 g) was added and stirred at room temperature for 16 hours. After completion of the reaction, methanol (40 mL) was gradually added to the reaction solution to precipitate a product, and the precipitate in the reaction solution was filtered by Kiriyama and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain a polymer (Po3) powder. The structure of the obtained polymer (Po3) was identified by ¹ H-NMR, XPS, ICP and IR. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 7H) δ = 7.56 (m, 12H), 2.35 (m, 3H), from IR , a mercapto-derived peak was observed near 2570 cm ⁻¹ , confirming that the terminal structure was —SH.

[Example 4]
In a 100 ml eggplant flask, the polymer (Ps1) (1.1 g) obtained in Production Example 1 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 1.0 mL of pure water (THF: water=10:1) was added and stirred for 5 minutes. Then, while cooling the eggplant flask with an ice bath, TCCA (0.369 g) was added, and after stirring for 2 hours, triethylamine (TEA) (0.506 g) was added and stirred at room temperature for 30 minutes. Furthermore, 1 mL of aqueous ammonia (25%) was added as an introduced amine, and the mixture was stirred for 2 hours. After completion of the reaction, methanol (40 mL) acidified with 5% hydrochloric acid was gradually added to the reaction solution to precipitate the product. The precipitate in the reaction solution was filtered by Kiriyama, and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain a polymer (Po4) powder. The structure of the obtained polymer (Po4) was identified by ¹ H-NMR, XPS, ICP and elemental analysis. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 5H) δ = 7.56 (m, 14H), 2.35 (m, 3H), XPS measurement , a peak is seen at 160.5-168.8 eV, and by peak separation, 160.5-163.8 eV (sulfide) and 160.9-168.8 eV (sulfoxide), 166.0-168.8 eV (sulfone) The peak area ratio of sulfide, sulfoxide and sulfone is 22:72:6, and the chlorine atom content in the polymer is below the detection limit and the nitrogen atom content is 0.77 by elemental analysis. %, and the terminal structure was confirmed to be -S(=O ₂ )NH ₂ .

[Example 5]
Into a 100 ml eggplant flask, the polymer (Ps2) (1.1 g) obtained in Production Example 2 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 1.0 mL of pure water (THF: water=10:1) was added and stirred for 5 minutes. Then, while cooling the eggplant flask with an ice bath, TCCA (0.369 g) was added, and after stirring for 2 hours, zinc powder (0.131 g) was added, and the mixture was stirred at room temperature for 30 minutes. Furthermore, acrylic acid (AA) (0.144 g) was added dropwise as an alkyne reactant for the enethiol reaction, and the mixture was stirred for 16 hours. After completion of the reaction, methanol (40 mL) was gradually added to the reaction solution to precipitate a product, and the precipitate in the reaction solution was filtered by Kiriyama and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain a polymer (Po5) powder. The structure of the obtained polymer (Po5) was identified by ¹ H-NMR, XPS, ICP and IR. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ=7.19 (m, 29H) δ=7.56 (m, 32H), 2.35 (m, 8H), 2. 52 (m, 2H), 3.11 (m, 2H), peaks derived from carboxyl groups were observed near 1690 cm ⁻¹ by IR, confirming that the terminal structure is —SCH ₂ CH ₂ COOH.

[Example 6]
Into a 100 ml eggplant flask, the polymer (Ps1) (1.1 g) obtained in Production Example 1 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 1.0 mL of pure water (THF: water=10:1) was added and stirred for 5 minutes. Next, TCCA (0.369 g) was added while cooling the eggplant flask with an ice bath, and after stirring for 2 hours, 10 mL of NMP was added as a solvent, and then K ₂ CO ₃ (0.691 g) was added, Stirred at room temperature for 30 minutes. After stirring, diallylamine (DAA) was added dropwise as an amine, and the mixture was stirred at room temperature for 16 hours. After completion of the reaction, methanol (40 mL) acidified with 5% hydrochloric acid was gradually added to the reaction solution to precipitate the product. The precipitate in the reaction solution was filtered by Kiriyama, and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain polymer (Po6) powder. The structure of the obtained polymer (Po6) was identified by ¹ H-NMR, XPS, ICP, IR and elemental analysis. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ=7.19 (m, 35H) δ=7.56 (m, 26H), 2.35 (m, 8H), 3. 81 (m, 4H), 5.09 (m, 4H), 5.57 (m, 2H), from IR, peaks derived from allyl groups near 990 cm ^-1 , sulfone near 1350 cm ^-1 and 1170 cm ^-1 A peak derived from sulfoxide was observed near 1050 cm ⁻¹ , and it was confirmed by elemental analysis that the chlorine atom content in the polymer was below the detection limit and the nitrogen atom content was 0.48%. Part of the structure was confirmed to be -S(=O ₂ )N(CH ₂ CH=CH ₂ ) ₂ .

[Example 7]
In a 100 ml eggplant flask, the polymer (Ps1) (1.1 g) obtained in Production Example 1 and THF (1.0 M, 10 mL) as a solvent were added. After stirring for 10 minutes, 1.0 mL of pure water (THF: water=10:1) was added and stirred for 5 minutes. Then, TCCA (1.38 g) was added while the eggplant flask was ice-cooled in an ice-cooling bath, and the mixture was stirred for 2 hours. Further, 1 mL of aqueous ammonia (25%) was added and stirred for 2 hours. After completion of the reaction, methanol (40 mL) acidified with 5% hydrochloric acid was gradually added to the reaction solution to precipitate the product. The precipitate in the reaction solution was filtered by Kiriyama, and washed with methanol and pure water. Then, the obtained powder was vacuum-dried at room temperature to obtain a polymer (Po7) powder. The structure of the obtained polymer (Po7) was identified by ¹ H-NMR, XPS, ICP and elemental analysis. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.56 (m, 19H), 2.35 (m, 3H), 160.8-168.9 eV from XPS measurement Peaks can be seen, and the peaks can be separated into 160.8-163.6 eV (sulfide), 160.8-168.9 eV (sulfoxide), and 166.0-168.9 eV (sulfone). The peak area ratio of sulfone was 2:92:6, and elemental analysis confirmed that the chlorine atom content in the polymer was below the detection limit and the nitrogen atom content was 0.80%. was -S(=O ₂ )NH ₂ .

[Comparative Example 1]
Into a 50 ml eggplant flask, 0.33 g of the polymer (Ps1) obtained in Production Example 1 was added and dissolved in 3.0 mL of chloroform. Then, 65% meta-chloroperbenzoic acid (mCPBA) (0.796 g) was slowly added to the eggplant flask and stirred at room temperature for 16 hours. Thereafter, the reaction solution was added dropwise to 20 mL of a methanol solution acidified with hydrochloric acid to precipitate an oxidized product. The precipitate was filtered by Kiriyama, washed with methanol and water in that order, and dried in a vacuum to obtain a brown polymer (PoC1). The structure of the obtained polymer (PoC1) was identified by ¹ H-NMR, XPS and ICP. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.56 (m, 19H), 2.35 (m, 3H), peak at 161.8-168.5 eV from XPS measurement was observed, and the peaks could be separated into 161.8-168.5 eV (sulfoxide) and 161.8-163.5 eV (sulfide) by peak separation, and the peak area of sulfoxide and sulfide was 97:3.

[Comparative Example 2]
In a 300 ml eggplant flask, 6.73 g of the polymer (Ps1) obtained in Production Example 1 was added, added to 60.9 mL of cyclopentyl methyl ether (CPME), and dissolved at 70°C. A solution prepared by adding 66.7 mg of 1,1,1-trifluoroacetone to 6.12 mL of 60% hydrogen peroxide water was added to the obtained polymer solution, and the mixture was stirred at 60° C. for 18 hours.
A mixed solvent of 122 mL of methanol and 122 mL of water was added to the polymer solution after stirring, and the solid matter was filtered, washed with water and methanol, and dried under vacuum to obtain a brown polymer (PoC2). The structure of the obtained polymer (PoC2) was identified by ¹ H-NMR, XPS and ICP. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.56 (m, 19H), 2.35 (m, 3H), peaks at 161.2-168.9 eV. By peak separation, the peaks could be separated into 161.2-168.9 eV (sulfoxide) and 161.2-163.8 eV (sulfide), and the peak area of sulfoxide and sulfide was 96:4.

[Comparative Example 3]
In a 50 ml eggplant flask, 1.10 g of the polymer (Ps1) obtained in Production Example 1 was added, dissolved in a mixed solvent of 10 mL of tetrahydrofuran and 0.5 mL of methanol, sodium borohydride (0.151 g) was added, Stir at room temperature for 6 hours. After stirring, the solvent was removed by vacuum. Then, 10 mL of cyclopentyl methyl ether (CPME) was added and dissolved at 70°C. A solution prepared by adding 12.3 mg of 1,1,1-trifluoroacetone to 0.030 mL of 60% hydrogen peroxide solution was added to the obtained polymer solution, and the mixture was stirred at 60° C. for 18 hours. The polymer solution after stirring was added dropwise to 400 mL of a 3% methanol solution acidified with hydrochloric acid to precipitate, and the solid matter was filtered, washed with water and methanol, and dried in a vacuum to obtain a polymer (PoC3). . The structure of the obtained polymer (PoC3) was identified by ¹ H-NMR, XPS and ICP. As a result, ¹ H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 13H) δ = 7.56 (m, 6H), 2.35 (m, 3H), XPS measurement A peak can be seen at 160.3-168.1 eV, and peak separation can separate peaks at 160.3-167.8 eV (sulfide) and 164.6-167.8 eV (sulfoxide). The peak area ratio was 30:70.

[Comparative Example 4]
In a 50 ml eggplant flask, 1.10 g of the polymer (Ps1) obtained in Production Example 1 was added, dissolved in a mixed solvent of 10 mL of tetrahydrofuran and 0.5 mL of methanol, sodium borohydride (0.151 g) was added, Stir at room temperature for 6 hours. After stirring, 1 mL of hydrochloric acid methanol solution was added dropwise, and the mixture was stirred for 30 minutes. The polymer solution after stirring was added dropwise to 400 mL of a 3% methanol solution acidified with hydrochloric acid to precipitate, and the solid matter was filtered, washed with water and methanol, and dried in a vacuum to obtain a polymer (PoC4). . The structure of the obtained polymer (PoC4) was identified by 1H-NMR, XPS, ICP and IR. As a result, 1H-NMR (CD ₂ Cl ₂ , 400 MHz, ppm): δ = 7.19 (m, 19H), 2.35 (m, 3H), 160.1-163.7 eV (sulfide ) peak, and a peak derived from a mercapto group was observed near 2570 cm ⁻¹ by IR, confirming that the terminal structure is —SH.

Table 1 shows the evaluation results of the polymers (Po1) to (Po7) and (PoC1) to (PoC4) obtained in Examples 1 to 7 and Comparative Examples 1 to 4, respectively. From Table 1, the polymers obtained in the comparative examples had low transmittance after heating, but all the polymers obtained in the examples had high transmittance after heating.

Claims (4)

A method for producing a sulfur-containing polymer having a sulfoxide skeleton in its main chain,
Using at least one compound selected from the group consisting of hypochlorous acid, hypochlorite, and compounds capable of generating hypochlorous acid, oxidizing a sulfur-containing polymer having a sulfide skeleton in its main chain. A method for producing a sulfur-containing polymer, comprising an oxidation step. 2. The method for producing a sulfur-containing polymer according to claim 1, further comprising a polymer terminal control step. 3. The method for producing a sulfur-containing polymer according to claim 2, wherein the polymer terminal control step uses a reducing substance or a basic substance. Further comprising a polymerization step of obtaining a sulfur-containing polymer having a sulfide skeleton in the main chain by polymerizing a monomer component containing a sulfur-containing monomer, the sulfur-containing polymer according to any one of claims 1 to 3 Coalescing manufacturing method.