Method for producing polymer, and solid

Abstract

To provide a method for producing a polymer by which the content of residual bisphenol compound can be further decreased, and to provide a solid that contains a polymer and exhibits a reduced content of residual bisphenol compound.SOLUTION: A method for producing polymer comprising: step 1 selected from step 1X and step 1Y; and step 2 of contacting a solid product obtained in the step 1 with a solvent selected from the group consisting of a solvent represented by formula (S1) (e.g., acetone) and a solvent represented by formula (S2) (e.g., acetonitrile).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polymer and a solid product. [Background technology]

[0002] Polyarylates containing repeating units derived from an aromatic diol compound and repeating units derived from an aromatic dicarboxylic acid compound, and polycarbonates containing repeating units derived from an aromatic diol compound and repeating units derived from phosgene, are excellent in heat resistance, mechanical strength, etc., and are widely used industrially. For example, Patent Document 1 discloses a polyarylate having a predetermined structure produced from an aromatic diol compound and an aromatic dicarboxylic acid compound as raw materials, and a method for producing the same. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6914727 Summary of the Invention [Problem to be solved by the invention]

[0004] Bisphenol A, a type of aromatic diol compound, is subject to regulation as an endocrine disrupting substance. Recently, there has been a gradual increase in the number of bisphenol compounds other than bisphenol A (e.g., bisphenols B, S, F, and AF) that are subject to regulation. In accordance with the above-mentioned restrictions on bisphenol compounds, it is desired to further reduce the content of bisphenol compounds, which are raw material components, remaining in the polymer (hereinafter also referred to as "residual bisphenol compounds") in polyarylates and polycarbonates synthesized using bisphenol compounds as raw material components.

[0005] The present inventors have conducted research with reference to the method for producing polyarylate described in Patent Document 1 and have found that there is room for further reducing the content of residual bisphenol compounds in polyarylate.

[0006] Therefore, an object of the present invention is to provide a method for producing a polymer that can further reduce the content of residual bisphenol compounds. Another object of the present invention is to provide a solid product that contains a polymer and has a low content of residual bisphenol compounds. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] Step 1 selected from Step 1X and Step 1Y; A method for producing a polymer, comprising: a step 2 of contacting the solid product obtained in the step 1 with a solvent selected from the group consisting of a solvent represented by formula (S1) described below and a solvent represented by formula (S2) described below. Process 1X: A process of reacting a compound represented by formula (a1) described later with a compound selected from the group consisting of a compound represented by formula (b) described later and a compound represented by formula (c) described later, by an interfacial polymerization method using an aqueous phase and an organic phase, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A1) described later and a repeating unit selected from a repeating unit represented by formula (B) described later and a repeating unit represented by formula (C) described later from the organic phase. Process 1Y: a step of reacting a compound represented by formula (a2) described later with a compound represented by formula (d) described later in the presence of an organic solvent, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A2) described later and a repeating unit represented by formula (D) described later from the organic phase. [2] The method for producing a polymer according to [1], wherein the solvent represented by the formula (S1) is acetone or methyl ethyl ketone, and the solvent represented by the formula (S2) is acetonitrile or propionitrile. [3] The method for producing a polymer according to [1] or [2], wherein the polymer obtained in the step 1X contains a repeating unit represented by the formula (B). [4] In the above formula (a1) and the above formula (A1), R 11 represents a branched alkyl group having 4 or more carbon atoms which may have a substituent, or a linear alkyl group having 3 or more carbon atoms which may have a substituent, R 12 represents a hydrogen atom, an optionally substituted linear alkyl group, or an optionally substituted alkyl group, In the above formula (a2) and the above formula (A2), R 21 represents a branched alkyl group having 4 or more carbon atoms which may have a substituent, or a linear alkyl group having 3 or more carbon atoms which may have a substituent, R 22 represents a hydrogen atom, a linear alkyl group which may have a substituent, or an aryl group which may have an alkyl group substituted therewith. [1] The method for producing a polymer according to any one of [1] to [3]. [5] In the above formula (a1) and the above formula (A1), R 11 represents a 2-methylpropyl group, and R 12 represents a methyl group, and R 13 and R 14 represents a hydrogen atom, In the above formula (a2) and the above formula (A2), R 21 represents a 2-methylpropyl group, and R 22 represents a methyl group, and R 23 and R 24 The method for producing a polymer according to any one of [1] to [4], wherein represents a hydrogen atom. [6] A solid material containing a polymer including a repeating unit represented by the formula (A1) described later, a repeating unit represented by the formula (B) described later, and a repeating unit represented by the formula (C) described later, A solid material having a content of a compound represented by the formula (a1-OH) described below of 100 mass ppm or less relative to the total mass of the solid material. [7] A solid containing a polymer containing a repeating unit represented by the formula (A2) described later and a repeating unit represented by the formula (D) described later, A solid material having a content of a compound represented by the formula (a2-OH) described below of 100 mass ppm or less relative to the total mass of the solid material. [Effects of the Invention]

[0009] According to the present invention, a method for producing a polymer that can further reduce the content of residual bisphenol compounds can be provided. Furthermore, according to the present invention, it is possible to provide a solid product that contains a polymer and has a low content of residual bisphenol compounds. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0011] In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0013] As used herein, when a polymer has multiple repeating units of the same designation (represented by the same general formula), each repeating unit may be the same or different.

[0014] In this specification, the weight average molecular weight (Mw) of a polymer is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). Tetrahydrofuran is a preferred eluent for GPC. A preferred embodiment of the weight average molecular weight is a polystyrene-equivalent value measured using tetrahydrofuran as the eluent.

[0015] The bonding direction of the divalent groups shown in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-OZ" or "XO-CO-Z".

[0016] [Polymer manufacturing method] The method for producing the polymer of the present invention comprises the steps of: Step 1 selected from Step 1X and Step 1Y described below; and Step 2, in which the solid product obtained in Step 1 is contacted with a solvent (hereinafter also referred to as "specific solvent") selected from the group consisting of a solvent represented by formula (S1) described below and a solvent represented by formula (S2) described below. The polymer obtained through Step 1X and Step 2 is a polymer (hereinafter also referred to as "specific polyarylate") containing a repeating unit represented by formula (A1) and a repeating unit selected from a repeating unit represented by formula (B) and a repeating unit represented by formula (C), and the polymer obtained through Step 1Y and Step 2 is a polymer (hereinafter also referred to as "specific polycarbonate") containing a repeating unit represented by formula (A2) and a repeating unit represented by formula (G). According to the production method of the present invention having such a configuration, it is possible to significantly reduce the amount of bisphenol compounds used as raw material components remaining in the resulting polymer. That is, it is possible to further reduce the content of the remaining bisphenol compounds (in the production of the specific polyarylate, this corresponds to the compound represented by the formula (a1-OH) described below, and in the production of the specific polycarbonate, this corresponds to the compound represented by the formula (a2-OH) described below) remaining in the resulting polymer. Although the mechanism of the above-mentioned effect of the present invention is not entirely clear, it is believed that the content of the residual bisphenol compounds could be significantly reduced by further carrying out a step (step 2) of contacting the solid product obtained in step 1 with a specific solvent. That is, it is believed that the specific solvent has a significantly higher permeability into the specific polyarylate or specific polycarbonate than methanol, which is a commonly used cleaning solvent, and has the effect of making it easier to extract the specific residual bisphenol compounds.

[0017] Hereinafter, a further reduction in the content of residual bisphenol compounds in the polymer obtained by the production method of the present invention will also be referred to as "the effect of the present invention being superior." The methods for producing the specific polyarylate and the specific polycarbonate will be described below.

[0018] [Method for producing specific polyarylate] The method for producing the specific polyarylate of the present invention includes steps 1X and 2. Step 1X: A step of reacting a compound represented by formula (a1) with a compound selected from the group consisting of compounds represented by formula (b) and compounds represented by formula (c) by an interfacial polymerization method using an aqueous phase and an organic phase, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A1) and a repeating unit selected from a repeating unit represented by formula (B) and a repeating unit represented by formula (C) from the organic phase. Step 2: A step of contacting the solid product obtained in Step 1X with a specific solvent

[0019] <Specific polyarylate> First, the specific polyarylate produced by the above-mentioned production method will be described below. The specific polyarylate is a polymer containing a repeating unit represented by formula (A1) (hereinafter also referred to as "repeating unit I-A1") and a repeating unit selected from a repeating unit represented by formula (B) and a repeating unit represented by formula (C) (hereinafter also referred to as "repeating unit II").

[0020] (Repeating unit I-A1) The repeating unit I-A1 is a repeating unit represented by formula (A1).

[0021] [ka]

[0022] In formula (A1), R 11 and R 12 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, provided that R 11 and R 12 The total number of carbon atoms is 3 or more.

[0023] R 11 and R 12 Examples of the hydrocarbon group represented by the formula (I) which may have a substituent include a linear or branched alkyl group which may have a substituent, and an aryl group which may have a substituent, and among these, a linear or branched alkyl group which may have a substituent is preferred. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and even more preferably 4 to 10 carbon atoms.

[0024] R 11 and R 12The substituent that the linear or branched alkyl group represented by the formula (I) may have is not particularly limited, and examples thereof include an alkoxy group, an acyl group, and an acyloxy group. The alkyl group moiety contained in the alkoxy group, acyl group, and acyloxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and the alkyl group moiety contained in the alkoxy group, acyl group, and acyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. R 11 and R 12 The linear or branched alkyl group represented by the formula (I) preferably has no substituent.

[0025] The number of ring atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 12, and particularly preferably 6 to 10. The aryl group may be either monocyclic or polycyclic. The substituent that the aryl group may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an acyl group, and an acyloxy group. The alkyl group moiety contained in the alkyl group, alkoxy group, acyl group, and acyloxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group moiety contained in the alkyl group, alkoxy group, acyl group, and acyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. R 11 and R 12 Specific examples of the optionally substituted aryl group represented by the formula (I) include a phenyl group, a 4-methoxyphenyl group, a 4-acetoxyphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0026] R 11 Among these, a branched alkyl group having 4 or more carbon atoms which may have a substituent, or a linear alkyl group having 3 or more carbon atoms which may have a substituent, is preferred. R 11The number of carbon atoms in the branched alkyl group having 4 or more carbon atoms represented by the following formula is preferably 4 to 20, more preferably 4 to 15, still more preferably 4 to 10, particularly preferably 4 to 8, and particularly preferably 4 to 6. R 11 Examples of branched alkyl groups having 4 or more carbon atoms and represented by the formula (I) include a 1-methylpropyl group, a 2-methylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 4-methylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1,3-dimethylpentyl group, a 1,4-dimethylpentyl group, a 2,4,4-trimethylpentyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, a 3-methylhexyl group, and an 11-methyldodecyl group.

[0027] R 11 Among these, the branched alkyl group having 4 or more carbon atoms represented by the formula (I) is preferably a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-ethylpentyl group, a 1-ethylhexyl group, a 1-ethylheptyl group, or a 2,4,4-trimethylpentyl group, more preferably a 2-methylpropyl group, a 1-ethylbutyl group, a 1-ethylpentyl group, a 2,4,4-trimethylpentyl group, or a 1-ethylheptyl group, and even more preferably a 2-methylpropyl group, a 1-ethylbutyl group, a 1-ethylpentyl group, or a 2,4,4-trimethylpentyl group. R 11 The branched alkyl group having 4 or more carbon atoms represented by the following formula may have the above-mentioned substituent, but it is also preferable that it has no substituent.

[0028] R 11 The linear alkyl group having 3 or more carbon atoms, represented by the following formula (I), preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms. R 11 The linear alkyl group having 3 or more carbon atoms represented by the formula (I) may have the above-mentioned substituent, but it is also preferable that it has no substituent.

[0029] R 12 Among these, a hydrogen atom, a linear alkyl group which may have a substituent, or an aryl group which may have an alkyl group as a substituent is preferred, and a hydrogen atom or a linear alkyl group is more preferred. R 12 The number of carbon atoms in the linear alkyl group represented by the formula (I) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. 12 Specific examples of the linear alkyl group represented by the formula (I) are preferably a methyl group or an ethyl group, and more preferably a methyl group. R 12 The linear alkyl group represented by the formula (I) may have the above-mentioned substituent, but it is also preferable that it has no substituent.

[0030] R 12 The aryl group optionally substituted with an alkyl group represented by the formula (I) is preferably a phenyl group or a naphthyl group optionally substituted with an alkyl group.

[0031] R 13 and R 14 each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and among these, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred. The alkyl group is preferably linear or branched, and is preferably linear. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. R 13 and R 14 The substituents that the alkyl group represented by the formula (I) may have are not particularly limited, and examples thereof include the above-mentioned R 11 and R 12 The substituents may be the same as those that may be possessed by the linear or branched alkyl group represented by the following formula: R13 and R 14 The alkyl group represented by the formula (I) preferably has no substituent.

[0032] R 13 and R 14 The optionally substituted aryl group represented by R 11 and R 12 The meaning and preferred embodiments are also the same as those of the optionally substituted aryl group represented by the following formula:

[0033] In the above formula (A), R 11 and R 12 may be bonded to each other to form an alicyclic ring which may have a substituent. The alicyclic ring may be either a monocyclic ring or a polycyclic ring. The number of ring members in the alicyclic ring is, for example, preferably 6 to 20, and more preferably 6 to 18. The substituent that the alicyclic ring may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an acyl group, and an acyloxy group. The alkyl group moiety contained in the alkyl group, alkoxy group, acyl group, and acyloxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group moiety contained in the alkyl group, alkoxy group, acyl group, and acyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. However, R 11 and R 12 When the number of ring atoms in the alicyclic ring formed by bonding together is 6 or less, the alicyclic ring has an alkyl group as a substituent, or R 13 and R 14 At least one of these groups represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

[0034] Specific examples of repeating unit I-A1 are shown below.

[0035] [ka]

[0036]

change

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045] The lower limit of the content of the repeating unit I-A1 is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on all repeating units of the specific polyarylate. The upper limit of the content of the repeating unit I-A1 is preferably 60% by mass or less, based on all repeating units of the specific polyarylate.

[0046] (Repeating unit II) The repeating unit II is a repeating unit selected from the repeating units represented by formula (B) and the repeating units represented by formula (C).

[0047] <Repeating unit represented by formula (B)> [ka]

[0048] In formula (B), L 11 represents a single bond or an oxygen atom.

[0049] <Repeating unit represented by formula (C)> [ka]

[0050] The repeating unit II preferably contains a repeating unit represented by formula (B) in that the effects of the present invention are more excellent.

[0051] The lower limit of the content of repeating unit II is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on all repeating units of the specific polyarylate. The upper limit of the content of repeating unit II is preferably 50% by mass or less, based on all repeating units of the specific polyarylate. The repeating unit II may be of one type or of two or more types. When two or more types of repeating unit II are used, the above content represents the total content.

[0052] The weight average molecular weight of the specific polyarylate is preferably from 50,000 to 250,000, more preferably from 80,000 to 180,000, and even more preferably from 100,000 to 150,000.

[0053] <Process 1X> In step 1X, a repeating unit I-A1 raw material and a repeating unit II raw material are reacted (polycondensation reaction) by an interfacial polymerization method using an aqueous phase and an organic phase, and then a solid product containing the specific polyarylate is obtained. In step 1X, the mixing ratio of the repeating unit I-A1 raw material and the repeating unit II raw material is preferably, for example, 0.5 to 1.5 moles of the repeating unit II raw material per mole of the repeating unit I-A1 raw material. Step 1X is preferably a step of reacting (polycondensation reaction) a repeating unit I-A1 raw material with a repeating unit II raw material by an interfacial polymerization method using an aqueous phase and an organic phase, and then obtaining a solid product containing the specific polyarylate by a reprecipitation method or a method of distilling off the organic solvent contained in the organic phase.

[0054] (Raw material ingredients) The raw material components of the repeating unit I-A1 and the repeating unit II will be described below.

[0055] The repeating unit I-A1 raw material is a compound represented by formula (a1).

[0056] [ka]

[0057] R in formula (a1) 11 , R 12 , R 13 , and R 14 is R in formula (A1). 11 , R 12 , R 13 , and R 14 The same definition and preferred embodiments are also the same. In addition, R 11 and R12 The total number of carbon atoms is 3 or more. Also, R 11 and R 12 may be bonded to each other to form an alicyclic ring which may have a substituent. 11 and R 12 When they are bonded to each other to form an alicyclic ring having 6 or less ring atoms, the alicyclic ring has an alkyl group as a substituent, or R 13 and R 14 At least one of R represents an alkyl group which may have a substituent or an aryl group which may have a substituent. 11 and R 12 A preferred embodiment of the optionally substituted alicyclic ring which may be formed by bonding together is R 11 and R 12 are the same as the preferred embodiments of the optionally substituted alicyclic ring which may be formed by bonding together.

[0058] X 11 and X 12 each independently represents a hydrogen atom, a sodium atom, a lithium atom, a potassium atom, or a cesium atom.

[0059] Specific examples of the compound represented by formula (a1) include compounds obtained by substituting an oxygen atom at a position having a bond connecting the repeating units in the compounds exemplified as specific examples of repeating unit I-A1 with -OX (X represents a hydrogen atom, an atom, a sodium atom, a lithium atom, a potassium atom, or a cesium atom).

[0060] The raw material for repeating unit II is a compound selected from the group consisting of compounds represented by formula (b) (raw material components for the repeating unit represented by formula (B) above) and compounds represented by formula (c) (raw material components for the repeating unit represented by formula (C) above).

[0061] [ka]

[0062] In formula (b), L 11 represents a single bond or an oxygen atom. 11 and Y 12 each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0063] [ka]

[0064] In formula (c), Y 13 and Y 14 each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0065] (Step 1X procedure) In step 1X, a specific polyarylate is synthesized by interfacial polymerization. Interfacial polymerization is a polymerization method for obtaining polyester (polyarylene) by mixing a repeating unit II raw material dissolved in a water-immiscible organic solvent with a repeating unit I-A1 raw material dissolved in an alkaline aqueous solution. Literature related to interfacial polymerization includes W. M. EARECKSON, J. Poly. Sci., XL399, 1959, and Japanese Patent Publication No. 40-001959. Compared to solution polymerization, interfacial polymerization has a faster reaction rate, which can suppress hydrolysis of the repeating unit II raw material (e.g., hydrolysis of acid halides), making it easier to obtain a high molecular weight resin.

[0066] The interfacial polymerization method in step 1X may be the following method A. This is an especially effective method when the repeating unit II raw material is insoluble or has low solubility in the organic phase solvent. Method A As the aqueous phase, an alkaline aqueous solution of the repeating unit I-A1 raw material is prepared, followed by the addition of a polymerization catalyst. At this time, the repeating unit I-A1 raw material and / or its metal salt (phenoxide) do not need to be completely dissolved in the alkaline aqueous solution of the repeating unit I-A1 raw material. Furthermore, as the organic phase, only an organic solvent that is incompatible with water and dissolves the polymer is mixed with the alkaline solution and stirred to form a suspension. A solid repeating unit II raw material, such as a powder, is added to the alkaline aqueous solution, and the polymerization reaction is carried out. Method A has three advantages. The first advantage is that the repeating unit II raw material is not previously prepared as a solution or solvent suspension, so that hydrolysis of the repeating unit I-A1 raw material can be suppressed until it is mixed with the alkaline aqueous solution. The second advantage is that since no solvent suspension is handled, the complicated procedure of transferring the solvent suspension to mix it with an alkaline aqueous solution can be avoided. The third advantage is that organic solvents can be saved. To avoid handling the repeating unit II raw material as a solvent suspension, it is possible to dilute it with a large amount of solvent to form a solution. In contrast, in Method A, in which a solid repeating unit II raw material is added, the amount of organic solvent used can be reduced because there is no need to completely dissolve the repeating unit II raw material itself. As a result, production efficiency is improved and organic solvents can be saved. The polymerization catalyst may be added in advance to the aqueous phase or to the organic phase. Examples of alkalis used in preparing the aqueous alkali solution of the repeating unit I-A1 raw material include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of alkali used is generally 2 to 5 times the number of moles of the repeating unit I-A1 raw material, i.e., 1 to 2.5 equivalents relative to the hydroxyl groups.

[0067] The interfacial polymerization method in step 1X may be the following method B. 《Method B》 The organic phase is prepared by mixing the repeating unit II raw material with an organic solvent that is incompatible with water but dissolves the polymer, and stirring to obtain a suspension. Meanwhile, in a separate container, an alkaline aqueous solution of the repeating unit I-A1 is prepared as the aqueous phase, followed by the addition of a polymerization catalyst. The resulting aqueous phase is added to the suspension to carry out the polymerization reaction. The reproducibility of the polymerization process can be improved by preparing a suspension of the repeating unit II raw material in an organic solvent in advance using Method B. Furthermore, compared to the reverse procedure of adding a solvent suspension of the repeating unit II raw material to an alkaline aqueous solution of the repeating unit I-A1 raw material, Method B does not include a step of transferring the solvent suspension, which reduces the complexity of the operation and the risk of hydrolysis of the repeating unit II raw material during the step of transferring the solvent suspension.

[0068] In the production method of the present invention, the following method C may be used. 《Method C》 In the general interfacial polymerization method described above, an alkaline aqueous solution of the repeating unit I-A1 raw material is prepared as the aqueous phase, followed by the addition of a polymerization catalyst, while a solution or solvent suspension of the repeating unit II raw material is prepared as the organic phase, which is then added to the alkaline aqueous solution to carry out the polymerization reaction.

[0069] In the above methods A to C, the temperature and reaction time of the reaction solution during the polymerization reaction can be set appropriately, and the polymerization reaction is preferably carried out at a temperature of 50° C. or less for 1 to 8 hours with stirring.

[0070] In the interfacial polymerization, a terminal-capping agent may be used during the polymerization in order to control the molecular weight of the polymer. Also, in order to control the properties of the polymer, it is preferable that the terminals of the polymer are blocked with a monohydric phenol, a monohydric acid chloride, a monohydric alcohol, a monocarboxylic acid, or the like. Examples of monohydric phenols used as such end-capping agents include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2-phenyl-2-(4-hydroxyphenyl)propane (sometimes referred to as "p-(α-cumyl)phenol"), 2-phenyl-2-(2-hydroxyphenyl)propane, and 2-phenyl-2-(3-hydroxyphenyl)propane. Examples of monovalent acid chlorides used as end-capping agents include benzoyl chloride, methanesulfonyl chloride, phenyl chlorocarbonate, acetyl chloride, and lauroyl chloride. Examples of monohydric alcohols used as end-capping agents include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol. Examples of monovalent carboxylic acids used as end-capping agents include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid. Among these, it is preferable to cap the ends with a monohydric phenol or a monoacid chloride, and it is more preferable to cap the ends with p-tert-butylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, benzoyl chloride, or acetyl chloride.

[0071] Examples of the polymerization catalyst for interfacial polymerization include quaternary ammonium salts such as tributylbenzylammonium halide, tetrabutylammonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide; and quaternary phosphonium salts such as tributylbenzylphosphonium halide, tetrabutylphosphonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide. Among these, tributylbenzylammonium halide, tetrabutylammonium halide, tributylbenzylphosphonium halide, and tetrabutylphosphonium halide are preferred in terms of facilitating polymerization.

[0072] Examples of solvents that can be used for the organic phase in interfacial polymerization include chlorine-based solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; aromatic hydrocarbons such as toluene, benzene, xylene, and anisole; tetrahydrofuran; etc. Among these, dichloromethane and o-dichlorobenzene are preferred as organic solvents for the organic phase. If the repeating unit II raw material is insoluble or has low solubility in the organic solvent of the organic phase, other organic solvents can be used. The organic solvent of the organic phase is preferably insoluble in water, but a part of the organic phase can be replaced with an organic solvent that is also soluble in water for the purposes of improving the solubility of the repeating unit II raw material in the organic phase, or for the purposes of increasing the efficiency of the polymerization reaction, suppressing hydrolysis of the repeating unit II raw material, and obtaining a polymer of the desired molecular weight. Examples of organic solvents that are effective in improving the solubility of the repeating unit II raw material in the organic phase include tetrahydrofuran, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), 1,4-dioxane, and 1,3-dioxolane. A higher polymer concentration relative to the organic solvent in the organic phase is preferable from the viewpoint of productivity. The amount of polymer relative to the liquid volume of the organic phase is preferably 2% by mass or more, more preferably 6% by mass or more, and even more preferably 10% by mass or more. The amount of polymer relative to the total amount of the aqueous phase and organic phase is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.

[0073] It is preferable that the reaction liquid obtained after the polymerization reaction is subjected to a liquid separation operation to remove the aqueous phase, acetic acid is added to the obtained polymer solution to terminate the polymerization, and then the polymer solution is washed by repeatedly stirring with water to remove ionic components contained in the polymer solution, such as sodium ions, potassium ions, lithium ions, chloride ions, and the polymerization catalyst. The water used for washing may be acidic or basic, and it is preferable to wash repeatedly until the waste washing water becomes neutral.

[0074] Next, a polymer solid product is obtained from the organic phase. Specific methods include adding the obtained polymer solution dropwise to a poor solvent (reprecipitation method) or distilling off the organic solvent from the polymer solution. The main component of the solid product is a solid polymer, but the solid product may also typically contain residual monomers (including residual bisphenol compounds) contained in the polymer, alkaline components, and impurities derived from the polymerization catalyst (hereinafter, these are also collectively referred to as "residual monomers, etc.").

[0075] When the method of dropping a polymer solution into a poor solvent is carried out, the polymer content in the polymer solution is preferably 7% by mass or less based on the total mass of the polymer solution. The volume of the poor solvent is preferably three times or more the volume of the polymer solution. Examples of poor solvents include lower alcohols such as methanol, ethanol, and isopropyl alcohol, as well as hexane. By carrying out the treatment of dropping the polymer solution into the poor solvent, the content of residual monomers and the like in the obtained solid product (that is, residual monomers and the like contained in the polymer) can be reduced to a certain degree. In order to reduce the content of residual monomers, etc. as much as possible in this step, it is preferable to set the immersion time in the poor solvent after the precipitation treatment in the poor solvent to 1 minute or more. Furthermore, when trimethylbenzylammonium halide or triethylbenzylammonium halide, which has a relatively low polymerization activity, is used as the polymerization catalyst, it is preferable to set the immersion time to 3 minutes or more. The above procedure of dropping the polymer solution into a poor solvent, dissolving the precipitated polymer in the solvent again, and adding the polymer to the poor solvent for precipitation may be repeated. However, because the procedure of dissolving the polymer in the solvent again and re-precipitating is complicated, it is also preferable to not repeat the reprecipitation procedure and instead carry out the step of contacting the polymer with a specific solvent in Step 2 described below. Step 2 described below is simple and can significantly contribute to reducing the amount of residual phenolic compounds. It is preferable to perform a drying treatment after filtering off the polymer precipitated by dropping the polymer solution into a poor solvent. The drying treatment is preferably performed at a temperature and for a time period that allows the solvent to be removed.

[0076] As described in paragraph

[0066] of Japanese Patent No. 5211469, various methods can be selected for distilling off the organic solvent from the polymer solution. For example, a method of obtaining a film by heating and removing the organic solvent, or a method of obtaining a polymer powder by evaporating the organic solvent while maintaining the polymer solution in a suspended state in water, may be used. When distilling off the organic phase, the polymer solution may contain water used for washing. For example, when methylene chloride is used as the organic solvent for the organic phase in the interfacial polymerization reaction, the polymer solution contains the produced polymer and methylene chloride, but may also contain water used for washing. Furthermore, when water is contained in the polymer solution when distilling off the organic phase, the polymer may be obtained by further filtering after distilling off the organic phase. It is also preferable to further subject the polymer precipitated by the treatment of distilling off the organic solvent from the polymer solution to a drying treatment. The treatment temperature and treatment time of the drying treatment are preferably such that the organic solvent can be removed. Of the above methods for obtaining a solid product, a method in which the organic solvent is distilled off from the polymer solution is preferred from the viewpoint of reducing the amount of organic solvent used.

[0077] In the solid product obtained through step 1X, the content of the residual bisphenol compound is typically 250 mass ppm or more relative to the total mass of the solid product. The content (mass ppm) of the residual bisphenol compound in the solid product can be measured by the same method as the method for measuring the content (mass ppm) of the residual bisphenol compound in the specific polyarylate described below. The above-mentioned residual bisphenol compound refers to a compound represented by the formula (a1-OH).

[0078] [ka]

[0079] R in formula (a1-OH) 11 ~R 14 are R in formula (a1), respectively. 11 ~R 14 is synonymous with.

[0080] <Process 2> Step 2 is a step of contacting the polymer-containing solid product obtained in Step 1X with a specific solvent. The specific solvent is a solvent selected from the group consisting of solvents represented by formula (S1) and solvents represented by formula (S2). By undergoing step 2, the solid product is washed, and the content of residual bisphenol compounds contained in the solid product is significantly reduced. In other words, the content of residual bisphenol compounds in the produced polymer is significantly reduced.

[0081] [ka]

[0082] In formula (S1), R S1 represents an alkyl group having 1 to 5 carbon atoms. RS1 The alkyl group represented by the formula (I) is preferably linear or branched, more preferably linear. The solvent represented by formula (S1) is preferably acetone or methyl ethyl ketone.

[0083] [ka]

[0084] In formula (S2), R S2 represents an alkyl group having 1 to 5 carbon atoms. R S2 The alkyl group represented by the formula (I) is preferably linear or branched, more preferably linear. The solvent represented by formula (S2) is preferably acetonitrile or propionitrile.

[0085] (Step 2) The treatment method for bringing the solid product into contact with the specific solvent is not particularly limited, and for example, a method of stirring a mixture of the solid product and the specific solvent can be mentioned. The content of the solid product is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the mixed liquid. The temperature during stirring of the mixed liquid can be appropriately set, but is preferably 10 to 100° C., more preferably 20 to 80° C. The stirring time of the mixed liquid can be appropriately set, but is preferably 0.1 to 10 hours, more preferably 1 to 5 hours.

[0086] The treatment of bringing the solid product into contact with the specific solvent may be carried out once or multiple times. After washing the solid product with the specific solvent, the solid product is filtered out from a mixed solution containing the solid product and the specific solvent. It is also preferable to subject the solid product filtered out from the mixed solution to a drying treatment. The treatment temperature and treatment time of the drying treatment are preferably those that can remove the specific solvent. By passing through the above step 2, the specific polyarylate is obtained.

[0087] In the specific polyarylate obtained through step 2, the upper limit of the content of residual bisphenol compounds (compounds represented by the above formula (a1-OH)) is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, and even more preferably 10 ppm by mass or less, relative to the total mass of the specific polyarylate. The lower limit of the content of residual bisphenol compounds is often more than 0 ppm by mass, relative to the total mass of the specific polyarylate.

[0088] The content (ppm by mass) of the residual bisphenol compound (compound represented by the above formula (a1-OH)) in the specific polyarylate can be measured by dissolving the specific polyarylate in a good solvent for the specific polyarylate (e.g., N-methyl-2-pyrrolidone), adding a poor solvent for the specific polyarylate (e.g., methanol) to the resulting solution to cause reprecipitation, and then measuring the supernatant by HPLC (high performance liquid chromatography). Specifically, 50 mg of the specific polyarylate was dissolved in 1 mL of N-methyl-2-pyrrolidone. Then, methanol was added to bring the volume to 10 mL. The supernatant, which reprecipitated the specific polyarylate, was filtered to obtain a filtrate. The resulting filtrate was used for HPLC analysis using an ODS column as the separation column, water containing phosphoric acid and acetonitrile as the eluent, and a sample injection volume of 10 μL. A photodiode array detector was used as the detection device, and the detection wavelength was set to 280 nm to determine the content (ppm by mass) of residual bisphenol compounds in the specific polyarylate. When detecting the mass of the remaining bisphenol compounds by HPLC analysis, a calibration curve showing the relationship between the area of ​​the peak derived from the remaining bisphenol compounds and the mass of the compound is prepared in advance, and the mass of the remaining bisphenol compounds is calculated from the results of the obtained HPLC analysis, and the content (ppm by mass) of the remaining bisphenol compounds in the specific polyarylate is calculated taking into account the amount of sample injected into the HPLC.

[0089] [Method for producing specific polycarbonate] The method for producing the specific polycarbonate of the present invention includes steps 1Y and 2. (Step 1Y) A step of reacting a compound represented by formula (a2) with a compound represented by formula (d) in the presence of an organic solvent, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A2) and a repeating unit represented by formula (D) from the organic phase. (Step 2) A step of contacting the solid product obtained in the above step 1 with a solvent (specific solvent) selected from the group consisting of a solvent represented by formula (S1) and a solvent represented by formula (S2).

[0090] <Specific polycarbonate> First, the specific polycarbonate produced by the above-mentioned production method will be described below. The specific polycarbonate is a polymer containing a repeating unit represented by formula (A2) (hereinafter also referred to as "repeating unit I-A2") and a repeating unit represented by formula (D) (hereinafter also referred to as "repeating unit III").

[0091] (Repeating unit I-A2) The repeating unit I-A2 is a repeating unit represented by formula (A2).

[0092] [ka]

[0093] In formula (A2), R 21 and R 22 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R 21 and R 22 The total number of carbon atoms is 3 or more. R in formula (A2) 21 , R 22 , R 23 , and R 24 are R in formula (A1), respectively. 11 , R 12 , R 13 , and R 14 The same definition and preferred embodiments are also the same.

[0094] R 21 and R 22may be bonded to each other to form a ring. The ring may be either a monocyclic or polycyclic ring, and may have a substituent. The ring may be either an aromatic ring or an alicyclic ring, with an alicyclic ring being preferred. The number of ring members in the ring is, for example, preferably 6 to 20, and more preferably 6 to 18.

[0095] The lower limit of the content of repeating unit I-A2 is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total repeating units of the specific polycarbonate. The upper limit of the content of repeating unit I-A2 is preferably 50% by mass or less, based on the total repeating units of the specific polycarbonate.

[0096] Specific examples of the repeating unit I-A2 include the same as the specific examples of the repeating unit I-A1 described above.

[0097] (Repeating unit III) The repeating unit III is a repeating unit represented by formula (D). (Repeating unit represented by formula (D))

[0098] [ka]

[0099] The lower limit of the content of repeating unit III is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total repeating units of the specific polycarbonate. The upper limit of the content of repeating unit III is preferably 50% by mass or less, based on the total repeating units of the specific polycarbonate.

[0100] The weight average molecular weight of the specific polycarbonate is preferably from 50,000 to 250,000, more preferably from 80,000 to 180,000, and even more preferably from 100,000 to 150,000.

[0101] <Process 1Y> In step 1Y, the repeating unit I-A2 raw material and the repeating unit III raw material are reacted (polycondensation reaction) in the presence of an organic solvent, and then a solid product containing the specific polycarbonate is obtained. In step 1Y, the mixing ratio of the repeating unit I-A2 raw material and the repeating unit III raw material is preferably, for example, 0.5 to 1.5 moles of the repeating unit III raw material per mole of the repeating unit I-A2 raw material. Step 1Y is preferably a step of reacting the repeating unit I-A2 raw material with the repeating unit III raw material in the presence of an organic solvent (polycondensation reaction), and then obtaining a solid product containing the specific polycarbonate by distilling off the organic solvent or by a reprecipitation method.

[0102] (Raw material ingredients) The raw material components of the repeating unit I-A2 and the repeating unit III will be described below.

[0103] The raw material for the repeating unit I-A2 is a compound represented by formula (a2).

[0104] [ka]

[0105] R in formula (a2) 21 , R 22 , R 23 , and R 24 is R in formula (A2) 21 , R 22 , R 23 , R, and R 24 The same definition and preferred embodiments are also the same. In addition, R 21 and R 22 The total number of carbon atoms is 3 or more. Also, R 21 and R 22 may be bonded to each other to form a ring. 21 and R 22A preferred embodiment of the ring that may be formed by bonding together is R 21 and R 22 are the same as the preferred embodiments of the ring which may be formed by bonding to each other.

[0106] X 21 and X 22 each independently represents a hydrogen atom, a sodium atom, a lithium atom, a potassium atom, or a cesium atom.

[0107] Specific examples of the compound represented by formula (a2) include compounds obtained by substituting an oxygen atom at a position having a bond connecting the repeating units in the compounds exemplified in the upper part as specific examples of repeating unit I-A1 with -OX (X represents a hydrogen atom, sodium atom, lithium atom, potassium atom, or cesium atom).

[0108] The repeating unit III raw material is a compound represented by formula (d) (a raw material component of the repeating unit represented by formula (D) above).

[0109] [ka]

[0110] In formula (d), Z 11 and Z 12 each independently represents a chlorine atom, a trichloromethoxy group (-OCCl3), a methoxy group, or a phenyloxy group.

[0111] (Step 1Y procedure) In step 1Y, the method for polymerizing (polycondensing) the repeating unit I-A2 raw material and the repeating unit III raw material in the presence of an organic solvent is not particularly limited, and any known method can be used.

[0112] An example of the polymerization method in Step 1Y is a method in which the repeating unit I-A2 and the repeating unit III raw material are polymerized in the presence of pyridine or in the presence of pyridine and another organic solvent. The other organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, benzene, xylene, and anisole. Another example is an interfacial polymerization method in which a sodium salt of bisphenol is reacted with phosgene in the presence of methylene chloride and water. In the reaction solution during the polymerization reaction, the total content of the raw material components is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, based on the total mass of the reaction solution. The temperature and reaction time of the reaction solution during the polymerization reaction can be appropriately set, and the polymerization reaction is preferably carried out at a temperature of 60°C or less for 1 to 8 hours with stirring.

[0113] After the polymerization reaction, it is preferable to terminate the polymerization by adding water or an alcohol to the reaction solution, or by adding the reaction solution to water or an alcohol. Alternatively, the quenched reaction solution may be subjected to a separation operation to remove the aqueous phase, and the resulting polymer solution may be washed by repeatedly stirring with water to remove ionic components contained in the polymer solution, such as sodium ions, potassium ions, lithium ions, chloride ions, and the polymerization catalyst. The water used for washing may be acidic or basic, and it is preferable to wash repeatedly until the washing waste water becomes neutral.

[0114] Next, a polymer solid product is obtained from the organic phase. Specific methods include a method in which the polymer solution obtained by the above-mentioned procedure is dropped into a poor solvent (reprecipitation method), or a method in which the organic solvent is distilled off from the polymer solution obtained by the above-mentioned procedure. The main component of the solid product is a solid polymer, but the solid product may also typically contain residual monomers (including residual bisphenol compounds) contained in the polymer, alkaline components, and impurities derived from the polymerization catalyst (such as residual monomers).

[0115] When the method of dropping a polymer solution into a poor solvent is carried out, the polymer content in the polymer solution is preferably 7% by mass or less relative to the total mass of the polymer solution. The volume of the poor solvent is preferably three times or more the volume of the polymer solution. Examples of poor solvents include lower alcohols such as methanol, ethanol, and isopropyl alcohol, weak acid aqueous solutions such as dilute hydrochloric acid, and hexane. The poor solvent may be used singly or in combination of two or more. By carrying out the treatment of dropping the polymer solution into the poor solvent, the content of residual monomers and the like in the obtained solid product (that is, residual monomers and the like contained in the polymer) can be reduced to a certain degree. In order to reduce the content of residual monomers and the like as much as possible in this step, it is preferable to set the immersion time in the poor solvent after the precipitation treatment in the poor solvent to 1 minute or more. The above procedure of dropping the polymer solution into a poor solvent, dissolving the precipitated polymer in the solvent again, and adding the polymer to the poor solvent for precipitation may be repeated. However, because the procedure of dissolving the polymer in the solvent again and re-precipitating is complicated, it is also preferable to not repeat the reprecipitation procedure and instead carry out the step of contacting the polymer with a specific solvent in Step 2 described below. Step 2 described below is simple and can significantly contribute to reducing the amount of residual phenolic compounds. It is preferable that the polymer precipitated by dropping the polymer solution into a poor solvent is filtered, and then the polymer is washed with water and dried. The drying temperature and time are preferably such that the solvent can be removed.

[0116] As described in paragraph

[0066] of Japanese Patent No. 5211469, various methods can be selected for distilling off the organic solvent from the polymer solution. For example, a method of obtaining a film by heating and removing the organic solvent, or a method of obtaining a polymer powder by evaporating the organic solvent while maintaining the polymer solution in a suspended state in water, may be used. When distilling off the organic phase, the polymer solution may contain water used for washing. For example, when methylene chloride is used as the organic solvent for the organic phase in the interfacial polymerization reaction, the polymer solution contains the produced polymer and methylene chloride, but may also contain water used for washing. Furthermore, when water is contained in the polymer solution when distilling off the organic phase, the polymer may be obtained by further filtering after distilling off the organic phase. It is also preferable to further subject the polymer precipitated by the treatment of distilling off the organic solvent from the polymer solution to a drying treatment. The treatment temperature and treatment time of the drying treatment are preferably such that the organic solvent can be removed. Of the above methods for obtaining a solid product, a method in which the organic solvent is distilled off from the polymer solution is preferred from the viewpoint of reducing the amount of organic solvent used.

[0117] In the solid product obtained through step 1Y, the content of residual bisphenol compounds is typically 250 mass ppm or more relative to the total mass of the solid product. The content (mass ppm) of residual bisphenol compounds in the solid product can be measured by the same method as the method for measuring the content (mass ppm) of residual bisphenol compounds in the specific polyarylate described above. The above-mentioned residual bisphenol compounds refer to compounds represented by the formula (a2-OH).

[0118] [ka]

[0119] R in formula (a2-OH) 21 ~R 24 are R in formula (a2), respectively. 21 ~R24 is synonymous with.

[0120] The polymerization method may be the interfacial polymerization method described in detail in Step 1X, and can be carried out in the same manner.

[0121] (Step 2) The treatment method for bringing the solid product into contact with the specific solvent is not particularly limited, and for example, a method of stirring a mixture of the solid product and the specific solvent can be mentioned. The specific procedure of step 2 is the same as that of step 2 in the method for producing the specific polyarylate, and the preferred embodiments are also the same. By going through the above step 2, the specific polycarbonate is obtained.

[0122] In the specific polycarbonate obtained through step 2, the upper limit of the content of residual bisphenol compounds (compounds represented by formula (a2-OH)) is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, and even more preferably 10 ppm by mass or less, relative to the total mass of the specific polycarbonate. The lower limit of the content of residual bisphenol compounds is often more than 0 ppm by mass, relative to the total mass of the specific polycarbonate. The content (ppm by mass) of residual bisphenol compounds in the specific polycarbonate can be measured by the same method as the method for measuring the content (ppm by mass) of residual bisphenol compounds in the specific polyarylate described above.

[0123] [Solids] The present invention also relates to a solid body. [First solid] The first solid material of the present invention is a solid material containing a polymer (specific polyarylate) containing a repeating unit represented by formula (A1), a repeating unit represented by formula (B), and a repeating unit represented by formula (C), The content of the compound represented by the formula (a1-OH) is 100 mass ppm or less relative to the total mass of the solid material. The repeating unit represented by formula (A1), the repeating unit represented by formula (B), the repeating unit represented by formula (C), and the compound represented by formula (a1-OH) are as described above.

[0124] The first solid material is obtained by the above-mentioned method for producing the specific polyarylate. In other words, the first solid material is essentially a specific polyarylate, and the content of residual bisphenol compounds contained as impurities (the content of compounds represented by formula (a1-OH)) is 100 mass ppm or less relative to the total mass of the solid material. The content of the specific polyarylate is preferably 95.0% by mass or more, more preferably 97.0% by mass or more, and even more preferably 99.0% by mass or more, based on the total mass of the first solid material. The content of the specific polyarylate is often less than 100% by mass, based on the total mass of the first solid material. The upper limit of the content of the compound represented by formula (a1-OH) is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, based on the total mass of the first solid material. The lower limit of the content of the compound represented by formula (a1-OH) is often more than 0 ppm by mass, based on the total mass of the first solid material. The content (ppm by mass) of the compound represented by formula (a1-OH) in the first solid material can be measured by a method similar to the method for measuring the content (ppm by mass) of the residual bisphenol compound in the specific polyarylate described in detail in the production method for the specific polyarylate.

[0125] [Second solid] The second solid material of the present invention is a solid material containing a polymer (specific polycarbonate) containing a repeating unit represented by formula (A2) and a repeating unit represented by formula (D), The content of the compound represented by the formula (a2-OH) is 100 mass ppm or less relative to the total mass of the solid material. The repeating unit represented by formula (A2), the repeating unit represented by formula (D), and the compound represented by formula (a2-OH) are as described above.

[0126] The second solid material is obtained by the above-mentioned method for producing the specific polycarbonate. In other words, the second solid material is essentially a specific polycarbonate, and the content of residual bisphenol compounds contained as impurities (the content of compounds represented by formula (a2-OH)) is 100 mass ppm or less relative to the total mass of the second solid material. The content of the specific polycarbonate is preferably 95.0% by mass or more, more preferably 97.0% by mass or more, and even more preferably 99.0% by mass or more, based on the total mass of the second solid material. The content of the specific polycarbonate is often less than 100% by mass, based on the total mass of the second solid material. The upper limit of the content of the compound represented by formula (a2-OH) is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, relative to the total mass of the second solid material. The lower limit of the content of the compound represented by formula (a2-OH) is often more than 0 ppm by mass, relative to the total mass of the second solid material. The content (ppm by mass) of the compound represented by formula (a2-OH) in the second solid material can be measured by a method similar to the method for measuring the content (ppm by mass) of the residual bisphenol compound in the specific polyarylate described in detail in the production method for the specific polyarylate.

[0127] [Application] The polymer, the first solid material, and the second solid material obtained by the method for producing a polymer of the present invention can be used, for example, as a coating film that requires heat resistance and abrasion resistance. The coating film may be composed of one or more selected from the polymer obtained by the polymer production method of the present invention, a first solid, and a second solid. Alternatively, the coating film may contain other components in addition to the polymer obtained by the polymer production method of the present invention, the first solid, and the second solid (hereinafter also referred to as "specific polymer"). Examples of other components include functional components that impart desired functionality to the coating film. Examples of composite coating films containing functional materials include low-moisture permeable films such as those described in JP 2016-069468 A. Adding a phenolic compound to a specific polymer as a functional material can enhance compatibility between the specific polymer and the functional material, thereby effectively reducing moisture permeability. Another example of a composite coating film containing a functional material is an organic device. The organic device comprises a specific polymer as a binder and a functional material such as a charge transport material. It is preferable that the specific polymer and the functional material exhibit high compatibility. The coating film of the present invention can also be preferably used as, for example, a metal wire coating film and a protective film for a polarizing plate in a display device. [Example]

[0128] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0129] Example 1 <Preparation of Polymer (1)> Polymer (1) was prepared according to the following scheme.

[0130] [ka]

[0131] A suspension was prepared by adding 11.4493 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (Honshu Chemical Industry Co., Ltd.), 0.1750 g of 2,3,5-trimethylphenol (Tokyo Chemical Industry Co., Ltd.), 0.0572 g of sodium hydrosulfite (Fujifilm Wako Pure Chemical Industries, Ltd.), and 230 mL of water to a reaction vessel equipped with a stirrer. 4.8378 g of sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.1981 g of benzyltributylammonium chloride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 150 mL of water were added to this suspension at room temperature (20°C) under stirring, and the mixture was stirred for 30 minutes under a nitrogen atmosphere until the solids were mostly dissolved. To this aqueous solution, a mixture of 12.0000 g of 4,4'-biphenyldicarbonyl chloride (Tokyo Chemical Industry Co., Ltd.) and 210 mL of methylene chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) was added. After the addition was completed, the reaction was allowed to proceed for 4 hours with stirring at room temperature (20°C) under a nitrogen atmosphere. The polymerized solution was diluted with 300 mL of methylene chloride, and the aqueous phase was removed. After washing with a dilute aqueous acetic acid solution and ion-exchanged water, the solution was poured into 2 L of methanol (Fujifilm Wako Pure Chemical Industries, Ltd.) to precipitate the polymer. The precipitated polymer was filtered and dried at 50°C, yielding 17.8 g of a solid product containing polymer (1). The remaining amount of bisphenol at this point (the content (ppm by mass) of the remaining bisphenol compound (the compound represented by the above formula (a1-OH)) relative to the total mass of the solid product before carrying out step 2; hereinafter also referred to as "residual bisphenol amount (1)") was measured according to the procedure described below. Furthermore, 15.0 g of a solid product containing polymer (1) and 150 mL of acetone were mixed in a reaction vessel equipped with a stirrer and stirred at room temperature for 2 hours. Thereafter, the mixture was suction filtered, washed with 150 mL of acetone, and dried at 50°C to obtain 14.8 g of a solid containing polymer (1) after acetone washing. The amount of bisphenol remaining in the solid content containing the polymer (1) obtained after washing with acetone (the content (ppm by mass) of the remaining bisphenol compound (compound represented by the above formula (a1-OH)) relative to the total mass of the solid after carrying out step 2; hereinafter also referred to as "residual bisphenol amount (2)") was measured according to the procedure described below.

[0132] <Procedure for determining residual bisphenol amounts (1) and (2)> The residual amount of bisphenol (1) and the residual amount of bisphenol (2) were each quantified by the following method. The method for quantifying the residual amount of bisphenol (2) will be described below as an example, but the residual amount of bisphenol (1) was also measured by the same method. The polymer-containing solid (50 mg) was dissolved in 1 mL of N-methyl-2-pyrrolidone. Methanol was then added to bring the volume to 10 mL, and the polymer was reprecipitated. The supernatant was filtered and used for this analysis. HPLC analysis was performed using an ODS column as the separation column, water containing phosphoric acid and acetonitrile as the eluent, and the sample injection volume was 10 μL. A photodiode array detector was used as the detection device, and the detection wavelength was 280 nm. In detecting the mass of the remaining bisphenol compounds by HPLC analysis, a calibration curve showing the relationship between the area of ​​the peak derived from the remaining bisphenol compounds and the mass of the compound was prepared in advance, and the mass of the remaining bisphenol compounds was calculated from the results of the obtained HPLC analysis. Taking into account the amount of sample injected into the HPLC, the content (ppm by mass) of the remaining bisphenol compounds in the specific polyarylate was calculated. The results were evaluated according to the following criteria based on the measured values. The results are shown in Table 1.

[0133] (Evaluation criteria) "A": 0 mass ppm or more, less than 10 mass ppm "B": 10 mass ppm or more, less than 50 mass ppm "C": 50 mass ppm or more, less than 100 mass ppm "D": 100 mass ppm or more, less than 250 mass ppm “E”: ≧250 mass ppm

[0134] Example 2 <Preparation of Polymer (2)> A solid material containing polymer (2) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (2), the amount of bisphenol remaining in the solid product containing polymer (2) and the amount of bisphenol remaining in the solid material containing polymer (2) were each quantified using the same procedures as in Example 1.

[0135] [ka]

[0136] Example 3 <Preparation of Polymer (3)> A solid material containing polymer (3) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (3), the amount of bisphenol remaining in the solid product containing polymer (3) and the amount of bisphenol remaining in the solid material containing polymer (3) were each quantified using the same procedures as in Example 1.

[0137] [ka]

[0138] Example 4 <Preparation of Polymer (4)> A solid material containing polymer (4) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (4), the amount of bisphenol remaining in the solid product containing polymer (4) and the amount of bisphenol remaining in the solid material containing polymer (4) were each quantified using the same procedures as in Example 1.

[0139] [ka]

[0140] Example 5 <Preparation of Polymer (5)> A solid material containing polymer (5) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (5), the amount of bisphenol remaining in the solid product containing polymer (5) and the amount of bisphenol remaining in the solid material containing polymer (5) were each quantified using the same procedures as in Example 1.

[0141] [ka]

[0142] Example 6 <Preparation of Polymer (6)> A solid material containing polymer (6) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (6), the amount of bisphenol remaining in the solid product containing polymer (6) and the amount of bisphenol remaining in the solid material containing polymer (6) were each quantified using the same procedures as in Example 1. The composition ratio of the following four repeating units in polymer (6) is 25 mol% / 25 mol% / 25 mol% / 25 mol%. The bisphenol residual amount (1) and the bisphenol residual amount (2) are the total residual amounts of the raw material components corresponding to the first and second repeating units from the left.

[0143] [ka]

[0144] Example 7 <Preparation of polymer (7)> A solid material containing polymer (7) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (7), the amount of bisphenol remaining in the solid product containing polymer (7) and the amount of bisphenol remaining in the solid material containing polymer (7) were each quantified using the same procedures as in Example 1.

[0145] [ka]

[0146] Example 8 <Preparation of Polymer (1)> Polymer (1) was prepared according to the following scheme.

[0147] [ka]

[0148] A suspension was prepared by adding 11.4493 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (Honshu Chemical Industry Co., Ltd.), 0.1750 g of 2,3,5-trimethylphenol (Tokyo Chemical Industry Co., Ltd.), 0.0572 g of sodium hydrosulfite (Fujifilm Wako Pure Chemical Industries, Ltd.), and 230 mL of water to a reaction vessel equipped with a stirrer. 4.8378 g of sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.1981 g of benzyltributylammonium chloride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 150 mL of water were added to this suspension at room temperature (20°C) under stirring, and the mixture was stirred for 30 minutes under a nitrogen atmosphere until the solids were mostly dissolved. To this aqueous solution, a mixture of 12.0000 g of 4,4'-biphenyldicarbonyl chloride (Tokyo Chemical Industry Co., Ltd.) and 210 mL of methylene chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) was added. After the addition was completed, the reaction was allowed to proceed for 4 hours under stirring at room temperature (20°C) under a nitrogen atmosphere. The polymerized solution was diluted with 300 mL of methylene chloride, and the aqueous phase was removed. The solution was washed with a dilute aqueous acetic acid solution and ion-exchanged water. The resulting organic phase and 300 mL of ion-exchanged water were heated under reduced pressure to distill off the methylene chloride. The ion-exchanged water was filtered off and further dried at 50°C, yielding 18.0 g of a solid product containing polymer (1). The amount of bisphenol remaining at this point (1) was measured according to the procedure described above. Furthermore, 15.0 g of a solid product containing polymer (1) and 150 mL of acetone were mixed in a reaction vessel equipped with a stirrer and stirred at room temperature for 2 hours. Thereafter, the mixture was suction filtered, washed with 150 mL of acetone, and dried at 50°C to obtain 14.8 g of a solid product containing polymer (1) after acetone washing. The amount of bisphenol remaining (2) in the resulting solid containing polymer (1) after washing with acetone was measured according to the procedure described above.

[0149] Example 9 A solid material containing polymer (1) was obtained in the same manner as in the preparation of polymer (1) in Example 1, except that the washing solvent was changed to methyl ethyl ketone. In addition, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid material containing polymer (1) were each quantified using the same procedures as in Example 1.

[0150] Example 10 A solid material containing polymer (1) was obtained in the same manner as in the preparation of polymer (1) in Example 1, except that the washing solvent was changed to acetonitrile. In addition, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid material containing polymer (1) were each quantified using the same procedures as in Example 1.

[0151] Example 11 A solid material containing polymer (1) was obtained in the same manner as in the preparation of polymer (1) in Example 1, except that the washing solvent was changed to propionitrile. In addition, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid material containing polymer (1) were each quantified using the same procedures as in Example 1.

[0152] Example 12 <Preparation of polymer (8)> Polymer (8) was prepared according to the following scheme:

[0153] [ka]

[0154] A reaction vessel equipped with a stirrer was charged with 24.68 g of 1,1-bis(4-hydroxyphenyl)cyclohexane (Tokyo Chemical Industry Co., Ltd.) and 68 mL of pyridine (anhydrous) (Fujifilm Wako Pure Chemical Industries, Ltd.), and a nitrogen atmosphere was created. With stirring, the internal temperature was raised to 50°C, and a solution of 12.50 g of triphosgene (Tokyo Chemical Industry Co., Ltd.) and 24 mL of toluene (anhydrous) (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 4 hours. After stirring at 50°C for 3 hours, the mixture was cooled to room temperature. The reaction solution was carefully added to an ice-cooled mixture of methanol and dilute hydrochloric acid, resulting in reprecipitation. After washing with water and drying at 50°C, 21.02 g of a solid product containing polymer (8) was obtained. The remaining amount of bisphenol (1) at this point (the content (ppm by mass) of the remaining bisphenol compound (the compound represented by the above formula (a2-OH)) relative to the total mass of the solid product before carrying out step 2) was measured according to the procedure described above. Furthermore, 15.0 g of a solid product containing polymer (8) and 150 mL of acetone were mixed in a reaction vessel equipped with a stirrer and stirred at room temperature for 2 hours. Thereafter, the mixture was suction filtered, washed with 150 mL of acetone, and dried at 50°C to obtain 14.8 g of a solid product containing polymer (8) after acetone washing. The residual bisphenol amount (2) of the obtained solid containing polymer (8) after acetone washing (the content (ppm by mass) of the remaining bisphenol compound (compound represented by the above formula (a2-OH)) relative to the total mass of the solid after carrying out step 2) was measured according to the procedure described above.

[0155] Example 13 <Preparation of polymer (9)> A solid material containing polymer (9) was obtained in the same manner as in Example 12, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (9), the amount of bisphenol remaining in the solid product containing polymer (9) and the amount of bisphenol remaining in the solid material containing polymer (9) were each quantified using the same procedures as in Example 12.

[0156] [ka]

[0157] Example 14 In the preparation of polymer (1) in Example 1, the step of obtaining a solid containing polymer (1) by washing was changed from "15.0 g of a solid product containing polymer (1) and 150 mL of acetone were placed in a reaction vessel equipped with a stirrer, mixed, and stirred at room temperature for 2 hours" to "15.0 g of a solid product containing polymer (1) and 450 mL of acetone were placed in a reaction vessel equipped with a stirrer, mixed, and stirred at 50°C for 4 hours." Except for this, a solid containing polymer (1) was obtained by the same procedure as in Example 1. Furthermore, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid containing polymer (1) were each quantified by the same procedure as in Example 1.

[0158] Comparative Example 1 A solid material containing polymer (1) was obtained in the same manner as in the preparation of polymer (1) in Example 1, except that the washing solvent was changed to methanol. In addition, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid material containing polymer (1) were each quantified using the same procedures as in Example 1.

[0159] Comparative Example 2 A solid material containing polymer (1) was obtained in the same manner as in the preparation of polymer (1) in Example 8, except that the washing solvent was changed to methanol. In addition, following the synthesis of polymer (1), the amount of bisphenol remaining in the solid product containing polymer (1) and the amount of bisphenol remaining in the solid material containing polymer (1) were each quantified using the same procedures as in Example 8.

[0160] Comparative Example 3 Following the teachings of Japanese Patent No. 6914727, a solid product containing polyester resin A of Synthesis Example 1 was synthesized.

[0161] [ka]

[0162] The amount of bisphenol remaining at this point (1) was measured according to the procedure described above. Furthermore, 15.0 g of a solid product containing polyester resin A and 150 mL of methanol were mixed in a reaction vessel equipped with a stirrer and stirred at room temperature for 2 hours. Thereafter, the mixture was suction filtered, washed with 150 mL of methanol, and dried at 50°C to obtain 14.7 g of a solid product containing polyester resin A after methanol washing. The amount of bisphenol remaining (2) in the resulting solid matter containing polyester resin A after washing with methanol was measured according to the procedure described above.

[0163] Comparative Example 4 A solid material containing polymer (8) was obtained in the same manner as in the preparation of polymer (8) in Example 12, except that the washing solvent was changed to methanol. In addition, following the synthesis of polymer (8), the amount of bisphenol remaining in the solid product containing polymer (8) and the amount of bisphenol remaining in the solid material containing polymer (8) were each quantified using the same procedures as in Example 12.

[0164] Comparative Example 5 A solid material containing polymer (9) was obtained in the same manner as in the preparation of polymer (9) in Example 13, except that the washing solvent was changed to methanol. In addition, following the synthesis of polymer (9), the amount of bisphenol remaining in the solid product containing polymer (9) and the amount of bisphenol remaining in the solid material containing polymer (9) were each quantified using the same procedures as in Example 13.

[0165] Comparative Example 6 <Preparation of polymer (10)> A solid material containing polymer (10) was obtained in the same manner as in Example 1, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (10), the amount of bisphenol remaining in the solid product containing polymer (10) and the amount of bisphenol remaining in the solid material containing polymer (10) were each quantified using the same procedures as in Example 1. The composition ratio of the following four repeating units in polymer (10) is 50 mol % / 25 mol % / 25 mol %. The bisphenol residual amount (1) and the bisphenol residual amount (2) are the residual amounts of the raw material components corresponding to the first ones from the left.

[0166] [ka]

[0167] Comparative Example 7 <Preparation of polymer (11)> A solid material containing polymer (11) was obtained in the same manner as in Example 12, except that the raw material components were changed as shown in the following scheme. In addition, following the synthesis of polymer (11), the amount of bisphenol remaining in the solid product containing polymer (11) and the amount of bisphenol remaining in the solid material containing polymer (11) were each quantified using the same procedures as in Example 12.

[0168] [ka]

[0169] Table 1 below shows the weight average molecular weight of the obtained polymer, and the residual bisphenol amounts (1) and (2). In Table 1, in the column "Polyarylate or Polycarbonate", if the obtained polymer is polyarylate, it is indicated as "A", and if it is polycarbonate, it is indicated as "B".

[0170] [Table 1]

[0171] From the results in Table 1, it is clear that the polymers obtained by the production methods of the Examples have a significantly reduced content of residual bisphenol compounds in the polymers. Comparison of the Examples has confirmed that in the synthesis of a polymer obtained through Step 1X and Step 2, when the specific solvent in Step 2 is a solvent represented by formula (S1), the content of residual bisphenol compounds in the polymer can be further reduced.

Claims

1. Step 1 selected from Step 1X and Step 1Y; and step 2 of contacting the solid product obtained in step 1 with a solvent selected from the group consisting of a solvent represented by formula (S1) and a solvent represented by formula (S2). 【Chemical 1】 In formula (S1), R Ｓ１ represents an alkyl group having 1 to 5 carbon atoms. 【Chemistry 2】 In formula (S2), R Ｓ２ represents an alkyl group having 1 to 5 carbon atoms. Process 1X: A process of reacting a compound represented by formula (a1) with a compound selected from the group consisting of compounds represented by formula (b) and compounds represented by formula (c) by an interfacial polymerization method using an aqueous phase and an organic phase, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A1) and a repeating unit selected from the repeating unit represented by formula (B) and the repeating unit represented by formula (C) from the organic phase. 【Chemistry 3】 In formula (a1), R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R １１ and R １２ The total number of carbon atoms in R is 3 or more. １３ and R １４ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. １１ and X １２ R each independently represents a hydrogen atom, a sodium atom, a lithium atom, a potassium atom, or a cesium atom. １１ and R １２ may be bonded to each other to form an alicyclic ring which may have a substituent. １１ and R １２ When they are bonded to each other to form an alicyclic ring having 6 or less ring atoms, the alicyclic ring has an alkyl group as a substituent, or R １３ and R １４ At least one of these groups represents an alkyl group which may have a substituent or an aryl group which may have a substituent. 【Chemistry 4】 In formula (b), L １１ represents a single bond or an oxygen atom. １１ and Y １２ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 【Chemistry 5】 In formula (c), Y １３ and Y １４ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 【Chemistry 6】 In formula (A1), R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R １１ and R １２ The total number of carbon atoms in R is 3 or more. １３ and R １４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. １１ and R １２ may be bonded to each other to form an alicyclic ring. １１ and R １２ are bonded to each other to form an alicyclic ring having 6 or less ring atoms which may have a substituent, the alicyclic ring has an alkyl group as a substituent, or １３ and R １４ At least one of these groups represents an alkyl group which may have a substituent or an aryl group which may have a substituent. 【Chemistry 7】 In formula (B), L １１ represents a single bond or an oxygen atom. 【Chemistry 8】 Process 1Y: a step of reacting a compound represented by formula (a2) with a compound represented by formula (d) in the presence of an organic solvent, and then obtaining a solid product containing a polymer containing a repeating unit represented by formula (A2) and a repeating unit represented by formula (D) from the organic phase; 【Chemistry 9】 In formula (a2), R ２１ and R ２２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ２１ and R ２２ The total number of carbon atoms in R is 3 or more. ２３ and R ２４ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ２１ and X ２２ R each independently represents a hydrogen atom, a sodium atom, a lithium atom, a potassium atom, or a cesium atom. ２１ and R ２２ may be bonded to each other to form a ring. 【Chemistry 10】 In formula (d), Z １１ and Z １２ each independently represents a chlorine atom, a trichloromethoxy group, a methoxy group, or a phenyloxy group. 【Chemistry 11】 In formula (A2), R ２１ and R ２２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ２１ and R ２２ The total number of carbon atoms in R is 3 or more. ２３ and R ２４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ２１ and R ２２ may be bonded to each other to form a ring. 【Chemistry 12】

2. 2. The method for producing a polymer according to claim 1, wherein the solvent represented by formula (S1) is acetone or methyl ethyl ketone, and the solvent represented by formula (S2) is acetonitrile or propionitrile.

3. The method for producing a polymer according to claim 1 or 2, wherein the polymer obtained in step 1X contains a repeating unit represented by formula (B).

4. In the formula (a1) and the formula (A1), R １１ represents a branched alkyl group having 4 or more carbon atoms which may have a substituent, or a linear alkyl group having 3 or more carbon atoms which may have a substituent, R １２ represents a hydrogen atom, an optionally substituted linear alkyl group, or an optionally substituted alkyl group, In the formula (a2) and the formula (A2), R ２１ represents a branched alkyl group having 4 or more carbon atoms which may have a substituent, or a linear alkyl group having 3 or more carbon atoms which may have a substituent, R ２２ The method for producing a polymer according to claim 1 or 2, wherein represents a hydrogen atom, a linear alkyl group which may have a substituent, or an aryl group which may have an alkyl group substituted thereon.

5. In the formula (a1) and the formula (A1), R １１ represents a 2-methylpropyl group, and R １２ represents a methyl group, R １３ and R １４ represents a hydrogen atom, In the formula (a2) and the formula (A2), R ２１ represents a 2-methylpropyl group, and R ２２ represents a methyl group, R ２３ and R ２４ The method for producing a polymer according to claim 1 or 2, wherein represents a hydrogen atom.

6. A solid material comprising a polymer including a repeating unit represented by formula (A1), a repeating unit represented by formula (B), and a repeating unit represented by formula (C), A solid material, wherein the content of the compound represented by formula (a1-OH) is 100 mass ppm or less relative to the total mass of the solid material. 【Chemistry 13】 In formula (A1), R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R １１ and R １２ The total number of carbon atoms in R is 3 or more. １３ and R １４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. １１ and R １２ may be bonded to each other to form an alicyclic ring. １１ and R １２ are bonded to each other to form an alicyclic ring having 6 or less ring atoms which may have a substituent, the alicyclic ring has an alkyl group as a substituent, or １３ and R １４ At least one of these groups represents an alkyl group which may have a substituent or an aryl group which may have a substituent. 【Chemistry 14】 In formula (B), L １１ represents a single bond or an oxygen atom. 【Chemistry 15】 【Chemistry 16】 In formula (a1-OH), R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R １１ and R １２ The total number of carbon atoms in R is 3 or more. １３ and R １４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. １１ and R １２ may be bonded to each other to form an alicyclic ring which may have a substituent. １１ and R １２ When they are bonded to each other to form an alicyclic ring having 6 or less ring atoms, the alicyclic ring has an alkyl group as a substituent, or R １３ and R １４ At least one of these groups represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

7. A solid material comprising a polymer containing a repeating unit represented by formula (A2) and a repeating unit represented by formula (D), A solid material, wherein the content of the compound represented by the formula (a2-OH) is 100 ppm by mass or less relative to the total mass of the solid material. 【Chemistry 17】 In formula (A2), R ２１ and R ２２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ２１ and R ２２ The total number of carbon atoms in R is 3 or more. ２３ and R ２４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ２１ and R ２２ may be bonded to each other to form a ring. 【Chemistry 18】 【Chemistry 19】 In formula (a2), R ２１ and R ２２ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ２１ and R ２２ The total number of carbon atoms in R is 3 or more. ２３ and R ２４ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ２１ and R ２２ may be bonded to each other to form a ring.

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