WO2021040014A1 - 高分子材料、その製造方法、及び高分子材料組成物 - Google Patents

高分子材料、その製造方法、及び高分子材料組成物 Download PDF

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WO2021040014A1
WO2021040014A1 PCT/JP2020/032729 JP2020032729W WO2021040014A1 WO 2021040014 A1 WO2021040014 A1 WO 2021040014A1 JP 2020032729 W JP2020032729 W JP 2020032729W WO 2021040014 A1 WO2021040014 A1 WO 2021040014A1
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polymer material
group
polymer
sulfur
substituent
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French (fr)
Japanese (ja)
Inventor
研一 小柳津
元康 平井
雨舜 孫
貫太 松島
潤一 中村
川瀬　健夫
輝久 藤林
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Waseda University
Nippon Shokubai Co Ltd
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Waseda University
Nippon Shokubai Co Ltd
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Priority to US17/636,279 priority Critical patent/US12338327B2/en
Priority to CN202080059476.6A priority patent/CN114269809A/zh
Priority to JP2021543078A priority patent/JP7257530B2/ja
Publication of WO2021040014A1 publication Critical patent/WO2021040014A1/ja
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Priority to JP2023060064A priority patent/JP7695970B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/18—Polysulfoxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/08—Polysulfonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Definitions

  • the present invention relates to a polymer material, a method for producing the same, and a polymer material composition. More specifically, the present invention relates to a polymer material having reduced coloring in the visible light region, a high refractive index, and a small light dispersion, a method for producing the same, and a polymer material composition.
  • a high refractive index material a polycarbonate having an aromatic ring and a polymer material having a fluorene skeleton are known.
  • a refractive index adjusting material for improving the light extraction efficiency of an LED and a lens material for an imaging system a material having a large Abbe number, that is, a material having a small light dispersion is required.
  • a material having such a high refractive index and small light dispersion a material into which sulfur molecules and halogen molecules have been introduced, a material containing metal oxide nanoparticles, and the like have been developed.
  • thermosetting material As a material containing sulfur, a thermosetting material has been conventionally developed as a lens material for eyeglasses.
  • the thermosetting material has a demerit that the number of steps increases when molding and processing, and a thermoplastic material has been required in terms of productivity.
  • Patent Document 1 has a repeating unit containing a benzene ring in which the hydrogen atom of 2 is substituted with a methyl group and a sulfur atom in the main chain, and has a dispersity of 3.0 or more, so that it is in a solution state.
  • a molding material having excellent moldability is described.
  • Patent Document 2 is excellent in moldability in a solution state by containing a polymer having a repeating unit containing a benzene ring in which one hydrogen atom is substituted with a methyl group and a sulfur atom in the main chain.
  • a molding material capable of forming an optical member having a high refractive index is described.
  • the present inventor has studied various polymer materials having a high refractive index and a small light dispersion.
  • a polymer having a sulfoxide skeleton in the main chain coloring in the visible light region is suppressed and the high refractive index is high. It was found that it could be a polymer material with small light dispersion. Further, they have found that such a polymer material can be efficiently obtained by polymerizing a monomer component containing a sulfur-containing monomer using a specific oxidizing agent, and have completed the present invention. It was.
  • the present invention is a polymer material characterized by having a sulfoxide skeleton in the main chain.
  • the polymer material further has an aromatic ring structure having a substituent in the main chain.
  • the polymer material preferably has a structural unit represented by the following general formula (1).
  • a 1 represents a divalent aromatic hydrocarbon group having a substituent.
  • the structural unit represented by the general formula (1) is preferably the structural unit represented by the following general formula (1-1).
  • R may have the same or different halogen atom, hydroxyl group, or substituent, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, aryl group, aralkyl. It represents a group or a sulfur-containing substituent.
  • N represents the number of R and is an integer of 1 to 4).
  • the polymer material preferably has an element ratio (O / S) of oxygen atom O to sulfur atom S of 0.1 to 1.5.
  • the polymer material preferably has a glass transition temperature of 80 to 250 ° C.
  • the polymer material is preferably a thermoplastic polymer material.
  • the polymer material is preferably for optics.
  • the present invention is also a polymer material composition, which comprises the above-mentioned polymer material and a metal oxide.
  • the present invention is also a method for producing a polymer material described above, wherein the production method uses a step of polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer and an oxidizing agent.
  • the production of a polymer material comprising a step of oxidizing the sulfur-containing polymer, wherein the oxidizing agent is at least one selected from the group consisting of peroxide and chloric acid. It's also a method.
  • the present invention it is possible to provide a polymer material in which coloring in the visible light region is reduced, the refractive index is high, and the light dispersion is small.
  • the polymer material of the present invention can be suitably used for optical applications such as imaging lens materials. Further, according to the method for producing a polymer material of the present invention, the above-mentioned polymer material can be efficiently produced.
  • the polymer material of the present invention is characterized by having a sulfoxide skeleton in the main chain. Since the polymer material of the present invention has a sulfoxide skeleton in the main chain, coloring in the visible light region (380 to 800 nm) is reduced, the refractive index is high, and the light dispersion is reduced, because the sulfoxide structure is introduced. By doing so, the reduction of the refractive index is suppressed, and the absorption band in the visible region disappears due to the n- ⁇ * transition of the lawn pair on sulfur, so that the coupling of the sp2 orbital can be broken. It is presumed that this is because the transparency in the visible light region is improved.
  • the polymer material of the present invention has a sulfoxide skeleton in the main chain.
  • the polymer material of the present invention is a polymer having a sulfoxide skeleton in the main chain.
  • the polymer material preferably further has an aromatic ring structure having a substituent in the main chain.
  • the aromatic ring structure is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a biphenyl ring, a diphenyl ring, and a triphenyl ring.
  • a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, and a triphenyl ring are preferable.
  • the aromatic ring structure preferably contains an aromatic ring structure having 6 to 20 carbon atoms, and has a carbon number of 6 to 20. It is more preferable to contain an aromatic ring structure of 6 to 18, further preferably to contain an aromatic ring structure having 6 to 12 carbon atoms, and even more preferably to include a benzene ring.
  • the above-mentioned "having an aromatic ring structure in the main chain” means that the aromatic ring structure itself is on the main chain.
  • the following formula (a) represents a case where a naphthalene ring is present on the main chain. In this case, the main chain has an aromatic ring structure having 10 carbon atoms.
  • the following formula (b) represents a case where a biphenyl ring is present on the main chain. In this case, the main chain has an aromatic ring structure having 12 carbon atoms.
  • the following formula (c) represents a case where a benzene ring is present on the main chain and the benzene ring has a substituent (phenyl group) having 6 carbon atoms.
  • substituent having the aromatic ring structure examples include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a sulfur-containing substituent and the like.
  • the substituent of the aromatic ring structure may further have a substituent.
  • the substituent having the aromatic ring structure is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an aryl group which may have a halogen atom, a hydroxyl group, or a substituent. , Alkoxy group, or sulfur-containing substituent.
  • the substituent having the aromatic ring structure may have a substituent, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, in that the refractive index of the polymer material can be further increased.
  • An alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms. Is even more preferable, and a methyl group is particularly preferable.
  • the polymer material preferably has a structural unit represented by the following general formula (1) (hereinafter, also referred to as “constituent unit (A)”).
  • a 1 represents a divalent aromatic hydrocarbon group having a substituent.
  • the divalent aromatic hydrocarbon group represented by A 1 is a divalent group having the above aromatic ring structure, for example, a phenylene group, a naphthylene group, an anthrylene group, a triphenylene group, a biphenylene group, a phenanthrylene group and the like. Can be mentioned. Of these, a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a triphenylene group are preferable, and a phenylene group is more preferable, in that the light dispersion of the polymer material becomes smaller.
  • Examples of the substituent contained in the divalent aromatic hydrocarbon group include the same substituents as those contained in the aromatic ring structure, and preferably have a halogen atom, a hydroxyl group, or a substituent. , An alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or a sulfur-containing substituent.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a bromine atom is preferable.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a hexyl group and the like. Of these, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is even more preferable.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, a phenoxy group, a cyclohexyloxy group, a benzyloxy group and the like.
  • an alkoxy group having 1 to 6 carbon atoms is preferable, and a methoxy group is more preferable.
  • aryl group examples include a phenyl group, a naphthyl group, a biphenyl group and the like. Of these, a phenyl group is preferable.
  • 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.
  • aralkyl group examples include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenyloctyl group and the like.
  • the carbon number of the aralkyl group is preferably 7 to 14, and more preferably 7 to 9.
  • sulfur-containing substituent examples include a thioalkyl group and a thioaryl group. Of these, a thioalkyl group is preferable.
  • the sulfur-containing substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
  • the alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing substituent may further have a substituent, and the substituent is preferably an alkyl group from the viewpoint of solubility, and is a metal oxide. From the viewpoint of dispersibility, halogen atoms and hydroxyl groups are preferably mentioned.
  • the alkyl group having 1 to 18 carbon atoms and the sulfur-containing substituent are examples of the substituents of the divalent aromatic hydrocarbon group in that the refractive index and the number of abbreviations can be further increased. More preferably, a methyl group and a thioalkyl group are further preferable, and a methyl group is particularly preferable.
  • a hydroxyl group and a sulfur-containing substituent are more preferable, and a hydroxyl group, a thioalkyl group and a thioaryl group are more preferable in that the dispersibility of the metal oxide can be improved. Further preferred, a hydroxyl group is particularly preferred.
  • the number of substituents contained in the divalent aromatic hydrocarbon group is not particularly limited, but it is preferably as small as possible in that the refractive index of the polymer material is further increased, and specifically, 1 to 6 are used. It is preferably present, more preferably 1 to 3, and even more preferably 1.
  • the structural unit (A) is preferably a structural unit represented by the following general formula (1-1) in that the refractive index of the polymer material is higher and the light dispersion is smaller.
  • R may have the same or different halogen atom, hydroxyl group, or substituent, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, aryl group, aralkyl. It represents a group or a sulfur-containing substituent.
  • N represents the number of R and is an integer of 1 to 4).
  • R represents a substituent, and may have a halogen atom, a hydroxyl group, or a substituent, and is an alkyl group having 1 to 18 carbon atoms, carbon. Represents an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent of the number 1 to 18.
  • each substituent represented by R is the same as the substituent contained in the above divalent aromatic hydrocarbon group, and specific examples and preferred embodiments thereof are also the same. ..
  • n represents the number of substituents R and is an integer of 1 to 4. n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 in that the refractive index becomes even higher.
  • the structural unit represented by the general formula (1-1) is more preferably the structural unit represented by the following general formula (1-1-1).
  • R is the same as R in the above general formula (1-1).
  • the type and preferred embodiment of the substituent represented by R in the general formula (1-1-1) are the same as those represented by R in the general formula (1-1).
  • the ratio of the structural unit (A) is preferably 1 to 100% by mass with respect to 100% by mass of all the structural units of the polymer, and from the viewpoint that the transparency can be further increased. It is more preferably 5% by mass or more, further preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 30% by mass or more, and the refractive index. From the viewpoint that it can be made higher, it is more preferably 80% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the polymer material may have only one type of the structural unit (A), or may have two or more types.
  • the polymer material may have other structural units (B) in addition to the structural unit (A) as long as the effects of the present invention are not affected.
  • the other structural unit (B) for example, a structural unit represented by the following general formula (2) is preferably mentioned.
  • a 2 represents a divalent aromatic hydrocarbon group.
  • a 2 in the formula represents a divalent aromatic hydrocarbon group having no substituent.
  • Examples of the divalent aromatic hydrocarbon group represented by A 2 include groups similar to the divalent aromatic hydrocarbon group represented by A 1 in the general formula (1).
  • the structural unit represented by the general formula (2) is preferably the structural unit represented by the following general formula (2-1).
  • the configuration represented by the following general formulas (3) and (4) is used from the viewpoint of increasing the refractive index. Units and the like can be mentioned.
  • Equation (3) and (4) in, A 3 and A 4 are the same or different and each represents an aromatic hydrocarbon group which may have a substituent.
  • the divalent aromatic hydrocarbon group represented by A 3 and A 4 divalent represented by A 1 in the general formula (1)
  • Groups similar to aromatic hydrocarbon groups can be mentioned. Among them, the divalent aromatic hydrocarbon group represented by A 3 and A 4, phenylene group, naphthylene group, anthrylene group, biphenylene group, triphenylene group is preferably a phenylene group is more preferable.
  • the divalent aromatic hydrocarbon group represented by A 3 and A 4 may have, the divalent aromatic hydrocarbon represented by A 1 in the above general formula (1) is used.
  • examples thereof include those similar to the substituents of the hydrogen group.
  • the substituent contained in the divalent aromatic hydrocarbon group a methyl group and a thioalkyl group are preferable, and a methyl group is more preferable, in that the refractive index and the Abbe number can be further increased.
  • a hydroxyl group, a thioalkyl group and a thioaryl group are more preferable, and a hydroxyl group is particularly preferable, in that the dispersibility of the metal oxide can be improved.
  • a divalent aromatic hydrocarbon group represented by A 3 and A 4 is a phenylene group, the phenylene group has a substituent
  • the position of the substituent is preferably the same as the position of the substituent of the phenylene group on the main chain in the structural unit represented by the above general formula (1-1-1).
  • the ratio of the structural unit (B) is preferably 0 to 99% by mass, more preferably 10% by mass or more, based on 100% by mass of all the structural units of the polymer. , 20% by mass or more is further preferable, 40% by mass or more is further preferable, 50% by mass or more is particularly preferable, and transparency can be further improved. It is more preferably 95% by mass or less, further preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 70% by mass or less.
  • the polymer material may have only one type of the structural unit (B), or may have two or more types. When there are two or more kinds of the structural units (B), the ratio of the structural units (B) is the total amount thereof.
  • the molar ratio [(A): (B)] of the structural unit (A) to the structural unit (B) is from 1: 0 to higher in terms of transparency and refractive index. It is preferably 1: 100, more preferably 1: 0.1 to 1:10, and even more preferably 1: 1 to 1: 5.
  • the molar ratio of the constituent units (B) is the total amount of the two or more types of constituent units (B).
  • the polymer material may be an alternating copolymer of the structural unit (A) and the structural unit (B), a block copolymer, or a random copolymer. ..
  • the polymer material preferably has an element ratio (O / S) of oxygen atom O to sulfur atom S of 0.1 to 1.5.
  • the elemental ratio of the oxygen atom O to the sulfur atom S is the elemental ratio (O / S) of the oxygen atom O bonded to the sulfur atom S of the main chain and the sulfur atom S of the main chain.
  • the sulfur atom S in the main chain means the sulfur atom S of —SO— in the main chain in the structural unit represented by the general formula (1) or (2).
  • the structural unit represented by the general formula (3) means the sulfur atom S of —S— in the main chain
  • the structural unit represented by the general formula (4) is ⁇ SO 2 in the main chain.
  • -Sulfur atom S means.
  • the oxygen atom bonded to the sulfur atom S of the main chain is specifically, for example, the oxygen atom O of —SO— in the main chain in the structural unit represented by the general formula (1) or (2).
  • the element ratio (O / S) is more preferably 0.3 or more, further preferably 0.7 or more, and further increasing the refractive index in that the transparency can be further increased. It is more preferably 1.3 or less, and even more preferably 1.1 or less, in that it can be increased.
  • the element ratio is measured by evaluating the peak intensities of the 1s orbital (O1s) of the oxygen atom, the 1s orbital (C1s) of the carbon atom, and the 2p orbital (S2p) of the sulfur atom using an X-ray photoelectron spectrometer (XPS). This can be obtained by the method described in the examples described later.
  • the polymer material preferably has a glass transition temperature (Tg) of 80 to 250 ° C.
  • Tg glass transition temperature
  • the glass transition temperature is more preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and 200 ° C. or lower from the viewpoint of facilitating molding processing from the viewpoint of increasing heat resistance. Is more preferable.
  • the glass transition temperature is defined as the baseline from the DSC curve obtained by raising the temperature from room temperature to 250 ° C. (heating rate 10 ° C./min) in a nitrogen gas atmosphere using a differential scanning calorimeter (DSC). It can be obtained by a method of evaluating by the intersection of tangents at an inflection point, and specifically, it can be obtained by the method described in Examples described later.
  • the polymer material preferably has an SO binding energy of 163 eV to 167 eV.
  • the SO binding energy can be obtained by evaluating the position of the peak top of the 2p3 / 2 orbital of the sulfur atom obtained by measuring by X-ray photoelectron spectroscopy (XPS), and will be described in detail later. It can be obtained by the method described in the examples.
  • the weight average molecular weight (Mw) of the polymer material is preferably 500 to 10,000,000. When the weight average molecular weight is in the above range, it can be suitably used as an optical material.
  • the weight average molecular weight is more preferably 1000 or more, further preferably 3000 or more, still more preferably 10000 or more, and 1,000,000 or less from the viewpoint of reducing melt viscosity, from the viewpoint of improving mechanical properties. Is more preferable, and 100,000 or less is further preferable.
  • the dispersity (weight average molecular weight / number average molecular weight) of the polymer material is preferably 1 to 10. When the degree of dispersion is in the above range, molding becomes easy.
  • the dispersity 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 the number average molecular weight can be determined by measuring by a gel permeation chromatography (GPC) method, and specifically, can be determined by the method described in Examples described later.
  • the degree of dispersion can be determined by dividing the weight average molecular weight by the number average molecular weight.
  • the polymer material preferably has a refractive index of 1.69 or more.
  • the refractive index is more preferably 1.7 or more, and further preferably 1.71 or more.
  • the refractive index is measured by forming a film having a thickness of 50 nm using the above polymer material as a measurement sample, using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific), and using a Na D line (589 nm). Specifically, it can be obtained by the method described in Examples described later.
  • the polymer material preferably has an Abbe number of 10 or more. When the Abbe number is in the above range, the light dispersion is small and an optical material suitable for a lens can be obtained.
  • the Abbe number is more preferably 15 or more, further preferably 18 or more, and even more preferably 20 or more.
  • the Abbe number is preferably 60 or less, and more preferably 55 or less, from the viewpoint of adjusting the light dispersibility.
  • the Abbe number is formed by forming a film using the polymer material, and using the spectroscopic ellipsometer, D line (589.3 nm), F line (486.1 nm), and C line ( The refractive index at 656.3 nm) can be measured and obtained by using the following calculation formula, and specifically, it can be obtained by the method described in Examples described later.
  • Abbe number (v D ) (n D -1) / (n F -n C )
  • n D , n F , and n C represent the refractive indexes of Fraunhofer on the D line (589.3 nm), F line (486.1 nm), and C line (658.3 nm), respectively.
  • the polymer material preferably has a visible light transmittance of 70% or more.
  • the visible light transmittance is more preferably 80% or more, more preferably 85% or more, and further preferably 88% or more.
  • the visible light transmittance is a parallel line transmittance, and a spectrophotometer (for example, by using a thin film having a thickness of 0.02 mm made of the above polymer material or by standardizing the thickness to 0.02 mm).
  • the polymer material preferably has an absorbance of 0.010 or less at a wavelength of 360 nm.
  • the absorbance is more preferably 0.008 or less, and even more preferably 0.005 or less.
  • the absorbance can be determined by measuring the absorbance of a solution obtained by dissolving the polymer material in a chloroform solution using an ultraviolet-visible-infrared spectrophotometer such as V-700 series manufactured by JASCO Corporation. Can be obtained by the method described in Examples described later.
  • the polymer material of the present invention is preferably a thermoplastic polymer material.
  • the polymer material of the present invention has physical properties such as suppressed coloring in the visible light region, high refractive index, small light dispersion, and excellent heat resistance. Therefore, it is an optical material such as a lens. It is useful for various purposes described later. These applications require thin film formability with excellent film thickness homogeneity and high-precision molding processability for complex shapes, but if it is thermoplastic, these requirements can be satisfied by a simple process. Workability can be achieved.
  • the method for producing the polymer material of the present invention is not particularly limited as long as it can produce the polymer having a sulfoxide skeleton in the main chain described above, and is a monomer component containing a sulfur-containing monomer. Can be polymerized by a known method. Among them, in that a polymer having a sulfoxide skeleton in the main chain can be efficiently produced, a step of polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer and an oxidizing agent are used.
  • the oxidizing agent is preferably a peroxide and / or a chloric acid.
  • the oxidant comprises a step of polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer and a step of oxidizing the sulfur-containing polymer using an oxidizing agent.
  • a method for producing a polymer material which is at least one selected from the group consisting of, peroxide, and chloric acid, is also one of the present inventions.
  • Process (1) The method for producing a polymer material of the present invention first includes a step of polymerizing a monomer component containing a sulfur-containing monomer to obtain a sulfur-containing polymer.
  • the sulfur-containing monomer is not particularly limited as long as it is a monomer containing a sulfur atom, but in the production method of the present invention, a sulfur-containing polymer can be obtained by oxidatively polymerizing the sulfur-containing monomer.
  • a sulfur-containing polymer can be obtained by oxidatively polymerizing the sulfur-containing monomer.
  • Preferred examples of the sulfur-containing monomer from which a sulfur-containing polymer can be obtained by such oxidative polymerization include a disulfide compound and a thiol compound. Specific examples thereof are represented by the following general formula (5).
  • the diaryldisulfide compound to be used and the thioaryl compound represented by the following formula (6) are more preferable.
  • a 5 and A 6 are the same or different and each represents a monovalent aromatic hydrocarbon group having a substituent.
  • the monovalent aromatic hydrocarbon group represented by A 5 and A 6 is a monovalent group based on the divalent aromatic hydrocarbon group represented by A 1 in the general formula (1). Is the same group as.
  • the substituents and their numbers of the monovalent aromatic hydrocarbon groups represented by A 5 and A 6 are the divalent aromatic hydrocarbon groups represented by A 1 in the general formula (1). It is the same as the substituent having.
  • the diaryldisulfide compound is preferably a compound represented by the following general formula (5-1).
  • the thioaryl compound is preferably a compound represented by the following general formula (6-1).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different, and are hydrogen atom and halogen.
  • R 1 to At least one of R 4 and R 5 to R 8 may have a halogen atom, a hydroxyl group, or a substituent, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and the like.
  • Aryl group, alkoxy group, or sulfur-containing substituent may have the above-mentioned substituents, respectively, according to the above-mentioned general formula (1-). It is preferable that it is the same as that represented by R in 1).
  • a diphenyl disulfide compound represented by the following general formula (7) is preferable.
  • R 9 may have a halogen atom, a hydroxyl group, or a substituent, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or sulfur. Represents a containing substituent.
  • the R 9 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • the disulfide compound can also be prepared by oxidizing a thiol compound. Therefore, in the polymerization step of the step (1), a thiol compound can also be used as a precursor of the disulfide compound. A disulfide compound can be obtained by oxidatively binding two molecules of a thiol compound.
  • the thiol compound is not particularly limited as long as it is a precursor of the above-mentioned disulfide compound, but a thiophenol compound represented by the above formula (6-1) is preferably mentioned, and is represented by the following general formula (8). Thiophenol compounds are more preferred.
  • R 9 is the same as R 9 in the general formula (7).
  • the method for obtaining the disulfide compound by oxidizing the thiol compound is not particularly limited, and a known method such as a method for oxidizing with hydrogen peroxide, iodine or the like can be used.
  • the sulfur-containing monomer may further contain a compound containing an unsubstituted disulfide compound and / or an unsubstituted thiol compound.
  • the unsubstituted disulfide compound diphenyl disulfide is preferably mentioned.
  • the unsubstituted thiol compound benzenethiol is preferably mentioned.
  • the amount of the unsubstituted disulfide compound and the unsubstituted thiol compound added may be appropriately set so that the content ratio of each of the above-mentioned structural units in the polymer material is within a desired range.
  • the monomer component used to obtain the sulfur-containing polymer may contain only one type of the sulfur-containing monomer, or may contain two or more types of the sulfur-containing monomer.
  • the polymerization step of the above step (1) is preferably oxidative polymerization.
  • the above-mentioned oxidative polymerization is not particularly limited, and can be carried out by a known method such as oxidative polymerization using a quinone compound or oxidative polymerization using a metal compound such as a vanadium compound.
  • the above-mentioned oxidative polymerization is preferably carried out by using a quinone-based oxidizing agent represented by the following general formulas (9) and / or (10) in that the transparency can be further improved. .. It is preferable to use a metal compound from the viewpoint that the amount used for the monomer component is small and the amount of waste is small.
  • X 1 , X 2 , X 3 and X 4 are the same or different, and have a hydrogen atom, a chlorine atom, a bromine atom, a nitrile group, and an alkyl group having 1 to 8 carbon atoms. , An aralkyl group, or an aryl group. X 1 and X 2 , and X 3 and X 4 may be bonded to each other to form a ring having 6 to 8 carbon atoms.)
  • quinone-based oxidant represented by the general formula (9) or (10) include 2,3-dichloro-5,6-dicyano-parabenzoquinone (DDQ), 2,3. 5,6-Tetrachloroparabenzoquinone (chloranyl), 2,3,5,6-tetrabromobenzoquinone (bromanyl), 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 (ortrochloranyl) , 3,4,5,6-tetrabromoortobenzoquinone (orthobromanyl), 3,4,5,6-
  • the amount of the quinone-based oxidizing agent added is preferably 0.1 to 3 mol, more preferably 0.8 to 1.5 mol, based on 1 mol of the sulfur-containing monomer used. It is more preferably 0.9 to 1.1 mol.
  • an acid may be further added.
  • the quinone-based oxidizing agent acts, the quinone-based compound becomes a dianion of hydroquinone, but when an acid is added, the dianion can be stabilized and the oxidizing power can be maintained.
  • the acid is not particularly limited, and is, for example, sulfuric acid, acetic acid, methanesulfonic acid, benzenesulphonic acid, toluenesulphonic acid, trifluoromethanesulphonic acid, 1,1,2,2-tetrafluoroethanesulphonic acid, trifluoroacetic acid. , Perfluoropropionic acid, perfluorobutyric acid and the like. Of these, trifluoroacetic acid is preferable in terms of increasing the acidity. Only one kind of the above acid may be used, or two or more kinds may be used.
  • the amount of the acid added is preferably 10 to 1000 mol, more preferably 50 to 500 mol, and more preferably 80 to 120 mol, based on 100 mol of the total amount of the quinone-based oxidizing agent to be added. Is more preferable.
  • the reaction temperature is not particularly limited as long as it is a temperature at which the polymerization proceeds, but is preferably 0 to 200 ° C., more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher, from the viewpoint that the above-mentioned oxidative polymerization is likely to proceed. It is preferable, and 180 ° C. or lower is more preferable, and 150 ° C. or lower is further preferable, in that side reactions can be suppressed.
  • the reaction 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 reaction of the above step (1).
  • Preferred solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachlorethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3. -Dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate and the like can be mentioned.
  • a monomer component containing a sulfur-containing monomer may be sequentially added during the polymerization reaction.
  • the above-mentioned thiol compound may be oxidatively polymerized to obtain a disulfide compound, and then the obtained disulfide compound may be oxidatively polymerized.
  • the method for producing a polymer material of the present invention then includes a step of oxidizing the sulfur-containing polymer obtained in step (1) using a specific oxidizing agent.
  • the oxidizing agent include at least one selected from the group consisting of peroxide and chloric acid.
  • the peroxide examples include metachloroperbenzoic acid, hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, t-butyl hydroperoxide and the like.
  • the oxidizing agent is preferably a peroxide, and is preferably metachloroperbenzoic acid or hydrogen peroxide, in that it can be dissolved in the same solvent as the solvent capable of dissolving the sulfur-containing polymer. More preferred. It is more preferable that the oxidizing agent is metachloroperbenzoic acid in terms of not using water in which the polymer is precipitated and in terms of suppressing oxidation of sulfoxide with an excess oxidizing agent.
  • hydrogen peroxide is used as the peroxidant, it is preferable to use a phase transfer catalyst such as trifluoroacetone while suppressing the amount of water from the viewpoint of suppressing the precipitation of the polymer. ..
  • the amount of the oxidizing agent added is not particularly limited as long as the desired oxidation reaction of sulfur atoms proceeds, but is usually 0.1 to 10 mol with respect to 1 mol of sulfur atoms in the sulfur-containing polymer. Is more preferable, 0.5 to 5 mol is more preferable, and 0.8 to 1.5 mol is further preferable.
  • the reaction temperature of the oxidation reaction is not particularly limited as long as it is a temperature at which the desired oxidation reaction proceeds, but it is preferably 0 to 200 ° C., more preferably 10 ° C. or higher, in that the oxidation reaction easily proceeds. It is more preferably 15 ° C. or higher, more preferably 180 ° C. or lower, and further preferably 150 ° C. or lower in terms of suppressing side reactions.
  • the reaction 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 oxidation reaction of the step (2), and as the solvent, a solvent similar to the solvent used in the polymerization step of the step (1) can be preferably mentioned.
  • the cleaning method is not particularly limited, and examples thereof include a method of cleaning with water, an acid, a base, or the like.
  • the polymer may be filtered or washed with a solvent in order to remove the unreacted product.
  • the solvent is not particularly limited, but the same solvent as the reaction solvent can be used.
  • the method for producing a polymer material may include other steps in addition to the above steps (1) and (2).
  • Examples of the other steps include a aging step, a neutralization step, a dilution step, a drying step, a concentration step, a purification step, and the like. These steps can be performed by a known method.
  • the polymer material of the present invention can be combined with other components to form a polymer material composition.
  • the other components are not particularly limited, and may be appropriately selected from known components according to the purpose and use of the polymer material composition.
  • a metal oxide is combined with the above polymer material, the transparency is significantly improved.
  • Such a polymer material and a polymer material composition characterized by containing a metal oxide are also one of the present inventions.
  • the content of the polymer material is preferably 10 to 100% by mass based on 100% by mass of the total solid content of the polymer material composition, and 20% by mass in that the permeability and the refractive index can be further improved.
  • the above is more preferable, and 50% by mass or more is further preferable.
  • the content is preferably 99% by mass or less, more preferably 95% by mass or less, and 85% by mass or less, in that the viscosity of the polymer material at the time of injection can be kept low. It is even more preferably 80% by mass or less, and most preferably 60% by mass or less.
  • the metal oxide examples include titanium oxide; silicon dioxide; zirconium oxide; aluminum oxide; magnesium oxide; barium titanate, barium titanate, strontium titanate, barium titanate, zirconium titanate, zirconium titanate, and zirconic acid.
  • Perovskite-type oxides such as lead titanate; boron nitride; aluminum hydroxide; aluminum titanate and the like can be mentioned. Only one of these may be used, or two or more thereof may be used in combination. Among them, zirconium oxide, titanium oxide, and silicon dioxide are more preferable, and the polymer material composition is more preferable in that the transparency can be further improved and the polymer material composition can be low-line expanded.
  • Zirconium oxide and titanium oxide are more preferable from the viewpoint of improving the refractive index of silicon oxide.
  • a perovskite type oxide is preferable in that it has a high relative permittivity and the polymer material composition can be suitably used as a ferroelectric material and a piezoelectric material.
  • Boron nitride, aluminum hydroxide, and aluminum titanate are preferable in that they have high thermal conductivity and the polymer material composition can be suitably used as a heat radiating material.
  • the shape of the metal oxide is not particularly limited and may be indefinite, particle-like, plate-like, fibrous or the like, but particle-like is preferable.
  • the average particle size of the metal oxide is preferably 1 nm or more and 1000 nm or less. When the average particle size of the metal oxide is in the above range, the transparency in the visible light region and the infrared region can be improved.
  • the average particle size of the metal oxide is more preferably 5 nm or more, further preferably 10 nm or more, still more preferably 100 nm or less, and further preferably 50 nm or less.
  • the average particle size is about 10 to 1000 individual particles (about 10 to 1000 times) by observing the metal oxide with SEM (magnification: 1000 to 100,000 times, preferably 10,000 times) and analyzing the obtained image.
  • the content of the metal oxide is not particularly limited, and can be appropriately set according to the purpose and application of the polymer material composition.
  • the content of the metal oxide is 10 parts by mass or more with respect to 100 parts by mass of the polymer material in that the transparency can be further improved and the line expansion can be performed. It is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and most preferably 80 parts by mass or more.
  • the content of the metal oxide is preferably 90 parts by mass or less, preferably 80 parts by mass or less, with respect to 100 parts by mass of the polymer material. It is more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.
  • the polymer material compositions include, for example, pigments, dyes, antioxidants, ultraviolet absorbers, IR cut agents, reactive diluents, light stabilizers, plasticizers, and non-reactive compounds.
  • Chain transfer agent thermal polymerization initiator, anaerobic polymerization initiator, polymerization inhibitor, inorganic filler, organic filler, adhesion improver such as coupling agent, heat stabilizer, antibacterial / antifungal agent, flame retardant, Matters, antifoaming agents, leveling agents, wetting / dispersing agents, anti-settling agents, thickeners, anti-sagging agents, anti-coloring agents, emulsifiers, anti-slip / scratch inhibitors, anti-skin agents, desiccants, anti-skin It may contain components such as a stain, an antistatic agent, a conductive agent (electrostatic aid), and a solvent. Only one of these components may be used, or two or more of these components may be used, or two or more of
  • the polymer material composition when it is for an optical material, it may contain other components as appropriate depending on the use of the optical material.
  • specific examples of the above other components include ultraviolet absorbers, IR cut agents, reactive diluents, pigments, washing agents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, defoamers and the like. Is preferably mentioned.
  • the polymer material composition preferably has a glass transition temperature (Tg) of 80 to 250 ° C.
  • Tg glass transition temperature
  • the glass transition temperature is more preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and 200 ° C. or lower from the viewpoint of facilitating molding processing from the viewpoint of increasing heat resistance. 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 material described above.
  • the polymer material composition preferably has a refractive index of 1.69 or more.
  • the refractive index is in the above range, it can be suitably applied as an optical material or the like.
  • the refractive index is more preferably 1.70 or more, and further preferably 1.71 or more.
  • the refractive index can be obtained by the same method as the method for measuring the refractive index of the polymer material described above.
  • the polymer material composition preferably has an Abbe number of 10 or more.
  • the Abbe number is more preferably 15 or more, further preferably 18 or more, and even more preferably 20 or more.
  • the Abbe number is more preferably 60 or less, and further preferably 55 or less, from the viewpoint of adjusting the light dispersibility.
  • the Abbe number can be obtained by the same method as the method for measuring the Abbe number of the polymer material described above.
  • the polymer material composition preferably has a visible light transmittance of 70% or more.
  • the visible light transmittance is more preferably 80% or more, more preferably 85% or more, and further preferably 88% or more.
  • the visible light transmittance is a parallel line transmittance, and can be obtained by the same method as the method for measuring the visible light transmittance of the polymer material described above.
  • the method for producing the polymer material composition is not particularly limited, and the polymer material, the metal oxide, and if necessary, other components are mixed to obtain the polymer material composition.
  • Obtainable examples include known means such as a bead mill, a roll mill, a ball mill, a jet mill, a kneader, and a blender.
  • the polymer material of the present invention is preferably a thermoplastic polymer material, and the polymer material composition containing the polymer material is also preferably thermoplastic. Since the polymer material composition of the present invention contains the above-mentioned polymer material, it has physical properties such as suppression of coloring in the visible light region, high refractive index, small light dispersion, and excellent heat resistance. If the polymer material composition is also thermoplastic, the molding processability becomes good, and it becomes easy to apply it to various applications requiring the above-mentioned physical properties.
  • the polymer material and polymer material composition of the present invention are materials in which coloring in the visible light region is suppressed, have a high refractive index, and have a small light dispersion, so that coloring in the visible light region is small and the refractive index is small. It is suitably used for applications that require high light dispersion and low light dispersion.
  • the polymer material and polymer material composition of the present invention are preferably used for optics, and specifically, for example, an imaging lens, an optical material (member), a mechanical component material, an electric / electronic component material, and an automobile. It is used for various purposes such as parts materials, civil engineering and building materials, molding materials, as well as paint and adhesive materials. Among them, it is particularly preferably used for optical materials, optodevice members, display device members and the like. Specific examples of such applications include eyeglass lenses, imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-vehicle cameras, light beam condensing lenses, lenses such as light diffusion lenses, and LEDs.
  • the polymer material and the polymer material composition of the present invention are also excellent in heat resistance, filters such as heat-resistant materials, ferroelectric materials, heat-dissipating materials, battery material separators, gas separation membranes and liquid separation membranes are used. It can also be suitably used for the like.
  • the polymer material and the polymer material composition of the present invention are preferably thermoplastic, easy to mold, and excellent in productivity.
  • the polymer material and the polymer material composition of the present invention can be suitably used as a molding material, and can be suitably used as a thermoplastic polymer material and a thermoplastic composition.
  • the molding method is not particularly limited, and examples thereof include generally known methods for processing thermoplastic resins such as injection molding, extrusion molding, T-die method, and inflation method. Further, it may be formed into a desired shape by a method such as casting or coating.
  • the shape is not particularly limited, and various known shapes such as a lens, a sheet, and a film can be mentioned.
  • the polymer material and the polymer material composition of the present invention have a high refractive index, low light dispersibility, and suppression of coloring in the visible light region. Therefore, it can be suitably used for optical applications and the like. It also has excellent productivity. Further, according to the method for producing a polymer material of the present invention, the above-mentioned polymer material can be easily obtained.
  • Each measurement method used in this example is as follows. ⁇ Weight average molecular weight (Mw), number average molecular weight (Mn), dispersity (Mw / Mn)> The weight average molecular weight and the number average molecular weight of the polymer were determined by measurement under the following conditions by gel permeation chromatography (GPC) method. The degree of dispersion was calculated by dividing the weight average molecular weight by the number average molecular weight.
  • GPC gel permeation chromatography
  • the wavelength (450 nm) and the angle of incidence (75 °) of the incident light are preset values, and the complex refractive index is obtained.
  • the refractive index at 190-2000 nm is calculated, and the refractive index at the wavelength of 589.3 nm is obtained. It was.
  • a film having a film thickness of 50 ⁇ m was obtained by the same method as the above-mentioned measurement of the refractive index.
  • the refractive index of the obtained film was measured using a spectroscopic ellipsometer UVISEL manufactured by HORIBA Scientific Co., Ltd., using D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm).
  • the Abbe number (v D ) was calculated by using the following formula (A).
  • n D , n F , and n C indicate the refractive indexes of Fraunhofer's D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm), respectively.
  • ⁇ Absorvity of solution> The absorbance at 200 to 800 nm was measured using an ultraviolet-visible-infrared spectrophotometer (V-700 series, cell used: cell with an optical path length of 1 cm) manufactured by JASCO Corporation.
  • V-700 series ultraviolet-visible-infrared spectrophotometer
  • a chloroform solution (0.01 mg / ml) of a polymer or a polymer material composition was used.
  • Tg ⁇ Glass transition temperature (Tg)>
  • ⁇ Glass transition temperature (Tg)> Using a differential scanning calorimeter manufactured by Seiko Electronics Co., Ltd., using ⁇ -alumina as a reference, the DSC curve obtained by raising the temperature from room temperature to 250 ° C. at a heating rate of 10 ° C./min is used as the baseline. It was evaluated and obtained by the intersection of the tangents at the inflection point.
  • ⁇ Thin film transmittance> The polymer before main chain oxidation is dissolved in chloroform at 5 wt%, and the polymer after main chain oxidation is dissolved in hexafluoro-2-propanol at 5 wt%. Using an organic solvent that can dissolve the polymer, the polymer is dissolved at about 5%. A dissolved solution was prepared. The obtained solution was spin-coated on a glass substrate having almost no absorption of visible light at about 500 rpm for 60 s and dried at 100 ° C. for 10 minutes to form a thin film (thickness 1 ⁇ m).
  • the transmittance of the obtained thin film was measured by a spectrophotometer (UV-Visible-infrared spectrophotometer V-700 series manufactured by JASCO Corporation). In order to evaluate the visible light transmittance, the transmittance at 400 nm and the average transmittance at 400 to 700 nm were compared. In addition, air was used as a control sample.
  • a spectrophotometer UV-Visible-infrared spectrophotometer V-700 series manufactured by JASCO Corporation.
  • the thin film used for evaluating the transmittance of the thin film was heated at 260 ° C. for 10 minutes, and the transmittance after heating was measured by the same method as the method for evaluating the transmittance of the thin film. It is preferable that the transmittance difference before and after heating is small and the visible light transmittance is high because the heat resistance is good.
  • Example 1 (Synthesis Example 1) ⁇ Synthesis of monomer> Chloroform (300 ml) and m-toluenethiol (24.8 g, 0.2 mol) are added to a 1000 ml conical beaker, and a methanol solution (300 ml) containing iodine (25.4 g, 0.1 mol) is further added. Stir at room temperature for hours. Then, an aqueous sodium thiosulfate solution was added to remove iodine, and the solvent was distilled off.
  • reaction solution was dispersed in diethyl ether, separated and washed in the order of hydrochloric acid aqueous solution (3% by mass), sodium hydroxide aqueous solution (5% by mass), and pure water, dehydrated, solvent removed, and vacuum dried, and then bis (3-). Methylphenyl) disulfide was recovered. The yield was 80%. The structure was confirmed by 1 1 H-NMR, 13 C-NMR and FAB-MS.
  • polymerization solution After removing the by-products in the polymerization solution with a glass filter, the polymerization solution was added dropwise to hydrochloric acid acidic methanol to precipitate the produced polymer, and the polymer was filtered through a glass filter to recover the precipitate as a powder. Then, it was washed with potassium hydroxide aqueous solution (0.1M), pure water, and methanol in order, and vacuum dried to obtain polymer A having a repeating unit represented by the following formula (A).
  • Polymer A was identified by 1 1 H-NMR and 13 C-NMR.
  • the weight average molecular weight Mw of the obtained polymer A was 2700, and Mn was 1300.
  • the glass transition temperature was 73 ° C.
  • the refractive index was 1.79.
  • the element ratio (O / S) of oxygen atom O to sulfur atom S was 0.92 (0.92 / 1).
  • the SO binding energy peaked at 165 eV and 163 eV, and the peaks could be separated into 164-168 eV (sulfoxide) and 162-168 eV (sulfide) by peak separation, and the peak area of sulfoxide and sulfide was 47.8 vs. 4. It was 4.
  • x was 0.08 and y was 0.92.
  • Example 2 10 mg of the thermoplastic polymer material A-1 obtained above and 28.6 mg of a zirconia nanoparticle dispersion (particle size 11 nm, solid content 70% in solution methyl ethyl ketone) were added to 1,1,2,2-tetra. It was dissolved in 1 ml of chloroethane to obtain a thermoplastic composition (polymer material composition).
  • Comparative Example 1 A thermoplastic polymer material was obtained in the same manner as in Example 1 except that the [oxidation reaction of the polymer main chain] was not performed in Example 1. That is, the polymer A in Example 1 corresponds to the thermoplastic polymer material of Comparative Example 1.
  • thermoplastic polymer material was obtained in the same manner as in Example 1 except that the [oxidation reaction of the polymer main chain] was carried out by the following method.
  • [Oxidation reaction B of polymer main chain] In a 50 ml eggplant flask, the polymer A (0.302 g) obtained above was added to 10 mL of a chloroform solution (1M) of metachlorobenzoic acid (mCPBA), and the mixture was stirred and oxidized at room temperature for 20 hours. Next, the reaction solution was added dropwise to hydrochloric acid acidic methanol, centrifuged, and vacuum dried to obtain a polymer (thermoplastic polymer material) B-1 having a repeating unit represented by the formula (B-1).
  • the yield was 104%.
  • Polymer A thermoplastic polymer material of Comparative Example 1
  • polymer A-1 thermoplastic polymer material of Example 1
  • polymer B-1 comparative example obtained in the above Examples and Comparative Examples.
  • Table 1 shows the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), O / S ratio, and SO bond energy of (2) thermoplastic polymer materials).
  • thermoplastic polymer material and the thermoplastic composition (polymer material composition) obtained in the above Examples and Comparative Examples the refractive index, Abbe number, absorbance, and glass transition temperature ( Tg) was measured. The results obtained are shown in Table 2.
  • Comparative Example 2 the refractive index, Abbe number, and absorbance could not be measured because the obtained thermoplastic polymer material was not dissolved in the solvent.
  • FIGS. 1 to 4 the measurement data of the refractive index and the absorbance of the thermoplastic polymer materials obtained in Example 1 and Comparative Example 1 are shown in FIGS. 1 to 4, respectively.
  • thermoplastic polymer material having a sulfoxide skeleton in the main chain (Example 1) and the thermoplastic composition containing the thermoplastic polymer material (Example 2) have a sulfoxide skeleton in the main chain.
  • the refractive index is slightly lower than that of the thermoplastic polymer material (Comparative Examples 1 and 2), the refractive index is 1.69 or more, the Abbe number is high, and the absorbance value at a wavelength of 360 nm is small. , It was confirmed that the coloring in the visible light region was low.
  • Example 3 ⁇ Synthesis of polymer> In ⁇ Polymer Synthesis> of Example 1, instead of using diphenyl disulfide and bis (3-methylphenyl) disulfide, only bis (3-methylphenyl) disulfide (10.92 g, 44.41 mmol) was used.
  • Polymer C was obtained by synthesizing in the same manner as in Polymer A of Example 1 except that the reaction time was 40 hours. Polymer C was identified by 1 1 H-NMR and 13 C-NMR. The weight average molecular weight Mw of the obtained polymer C was 6500, and Mn was 1650. The SO binding energy was 162-164 eV. That is, S had 100% sulfide. The yield of Polymer C was 65%.
  • X in the formula (A) was 0.
  • the transmittance of the thin film and the transmittance of the polymer A-1 obtained in Example 1 and the polymer C-1 obtained in Example 3 after the heating test were evaluated by the above-mentioned method. Further, as a comparative example, the same evaluation was performed using the polymer A (Comparative Example 1) and the polymer C (Comparative Example 3) before the oxidation reaction. The results are shown in Table 3.
  • Example 4 (Synthesis of bromo-containing polymer D)
  • PMPS poly (2,6-dimethyl disulfide), 2.7242 g, 20 mmol, 0.2 M
  • NBS N-bromosuccinimide, 3.5998 g, 20 mmol, 1 eq.
  • AIBN azoisobutyronitrile, 98.526 mg, 0.6 mmol, 0.03 eq.
  • PMPS Poly (2,6-dimethyl disulfide), 2.7242 g, 20 mmol, 0.2 M
  • NBS N-bromosuccinimide, 3.5998 g, 20 mmol, 1 eq.
  • AIBN azoisobutyronitrile, 98.526 mg, 0.6 mmol, 0.03 eq.
  • PMPS nitrogen was aerated (bubbling) for 30 minutes.
  • the SO and SO 2 amounts of each polymer were measured by infrared absorption spectroscopy (IR), and the OH, Br and CH 3 amounts were measured by 1 H-NMR.
  • IR infrared absorption spectroscopy
  • OH, Br and CH 3 amounts were measured by 1 H-NMR.
  • Tg glass transition temperature of each polymer
  • n D refractive index at the D line (589.3 nm) of Fraunhofer
  • v D Abbe number
  • the obtained hybrid solution was formed by drop casting on a glass substrate or spin coating on a silicon wafer so as to have the thickness shown in Table 5, respectively, and under reduced pressure at 60 ° C. for 2 hours at 150 ° C.
  • a hybrid membrane was prepared by heating and drying in 1 hour.
  • the obtained hybrid film was evaluated by the above method for the absorbance at 400 nm with respect to the film thickness, the refractive index (n D ) at the Fraunhofer D line (589.3 nm), and the Abbe number (v D). The results are shown in Table 5.
  • FIG. 5 shows a diagram showing measurement data of the refractive index of the polymer material compositions of Experimental Examples 1 and 4 in Examples. In the figure, the solid line shows Experimental Example 1 and the broken line shows Experimental Example 4.
  • FIG. 6 shows photographs of the hybrid membranes obtained in Experimental Examples 1 to 4 in Examples.
  • the polymer material composition containing the polymer material and the metal oxide of the example has high transparency in which coloring in the visible light region is suppressed, has a high refractive index, and has a small light dispersion. It was confirmed that.

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JP2023002372A (ja) * 2021-06-22 2023-01-10 株式会社日本触媒 硫黄含有重合体の製造方法
JP2023008136A (ja) * 2021-07-05 2023-01-19 株式会社日本触媒 重合体含有組成物
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