JP2007246639A - Method for producing polyvinyl alcoholic polymer having mercapto group at terminal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simply produce a polyvinyl alcoholic polymer having a high introduction ratio of a mercapto group into the terminal. <P>SOLUTION: The polyvinyl alcoholic polymer having the mercapto group(s) at one or both terminals is produced as follows. Living radical polymerization of a vinyl primary or secondary carboxylate is carried out in the presence of a dithiocarbonic acid derivative (A) composed of a specific dithiocarbonic acid ester or dithiocarbonic acid amide. A vinyl carboxylate-based polymer obtained by subsequently carrying out block copolymerization of a vinyl tertiary carboxylate, a vinyl benzoate which may have a substituent or ethylene is saponified. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polyvinyl alcohol polymer having a mercapto group at a terminal.

  Mercapto groups are highly reactive functional groups, and introduction of mercapto groups into polymers can lead to the production of functional polymers such as graft polymers and block polymers and modification of polymers by various polymer reactions. It can be possible and is very important.

  Several proposals have been made so far for producing a polymer having a mercapto group at the terminal. For example, a polymer having a thiocarboxylic acid ester group at the terminal obtained by adding a thiocarboxylic acid to a polymer having a double bond at the terminal utilizing the fact that a mercapto group is easily added to a double bond such as an olefin. A method for producing a polymer having a mercapto group at the terminal by treating the compound with an acid or an alkali (see Non-Patent Document 1) is known. However, this method has a problem that it is necessary to prepare a polymer having a double bond at the terminal in advance, which increases the number of manufacturing steps and increases the production cost.

  Further, for example, in the presence of thiocarboxylic acid, a radical polymerizable monomer is polymerized using azobisisobutyronitrile as a polymerization initiator, and the resulting polymer having a thiocarboxylic acid ester group at the terminal is treated with acid or alkali. A method for producing a polymer having a mercapto group at the terminal (see Patent Document 1) is known. However, this method has a problem that a mercapto group can be introduced only at one end, and the introduction rate at the end decreases as the polymerization rate increases.

  For example, radical polymerization of a radical polymerizable monomer using a polymerization initiator composed of thiocarboxylic acid and polysulfide, and the resulting polymer is treated with acid or alkali to produce a polymer having a mercapto group at the terminal. A method (see Patent Document 2) is known. However, in this method, when a vinyl ester such as vinyl acetate is used as the radical polymerizable monomer, it is difficult to efficiently introduce a mercapto group at the terminal, and more than 20% of the polymer does not have a mercapto group introduced at the terminal. It will be included.

JP 59-187005 A Japanese Patent No. 3256544 Makromolekular Chemie, Symposia 48/49, 317, 1991

  Accordingly, an object of the present invention is to solve the problems of the prior art as described above, and to provide a method for producing a polyvinyl alcohol polymer having a higher content of terminal mercapto groups.

（式中Ｒ^１〜Ｒ^７はそれぞれ、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ａｒ^１〜Ａｒ^４はそれぞれ、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ｘは、置換基を有してもよい炭素数１〜３０の２価の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の２価の芳香族炭化水素基を表す。）
からなる群から選ばれた少なくとも１種のジチオ炭酸誘導体（Ａ）の存在下に１級または２級カルボン酸ビニルエステルを重合し、ついで３級カルボン酸ビニルエステル、置換基を有してもよい安息香酸ビニルエステル、またはエチレンをブロック共重合して得たカルボン酸ビニルエステル系重合体を鹸化することを特徴とする下記の一般式（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）または（Ｘ）：

（式中Ｒ^８は水素または１級もしくは２級アシル基、Ｒ^９は３級アルキル基、または置換されていてもよいフェニル基を表す。）
で表される、末端にメルカプト基を有するポリビニルアルコール系重合体の製造方法に関する。 That is, the present invention
The following general formulas (I), (II), (III), (IV), (V) and (VI):

(In the formula, R ^{1 to} R ⁷ are each an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. Each of Ar ^{1 to} Ar ⁴ represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and X represents an optionally substituted substituent having 1 to 30 carbon atoms. It represents a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.)
A primary or secondary carboxylic acid vinyl ester may be polymerized in the presence of at least one dithiocarbonic acid derivative (A) selected from the group consisting of: and then a tertiary carboxylic acid vinyl ester or a substituent. The following general formula (VII), (VIII), (IX) or (X) characterized by saponifying a vinyl benzoate or a carboxylic acid vinyl ester polymer obtained by block copolymerization of ethylene:

(Wherein R ⁸ represents hydrogen or a primary or secondary acyl group, R ⁹ represents a tertiary alkyl group, or an optionally substituted phenyl group.)
It is related with the manufacturing method of the polyvinyl alcohol-type polymer which has a mercapto group at the terminal represented by these.

  According to the production method of the present invention, one end or a polyvinyl alcohol polymer having a mercapto group at a high ratio at both ends can be more easily produced, and obtained by the production method of the present invention, Polyvinyl alcohol polymers having mercapto groups at both ends are used in a wide range of applications such as production of functional polymers such as block polymers, modification of polymers by various polymer reactions, and reactive dispersion stabilizers. .

（式中Ｒ^１〜Ｒ^７はそれぞれ、置換基を有してもよい炭素数１〜２０の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ａｒ^１〜Ａｒ^４はそれぞれ、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基を表し、Ｘは、置換基を有してもよい炭素数１〜３０の２価の脂肪族炭化水素基、置換基を有してもよい炭素数６〜２０の２価の芳香族炭化水素基を表す。）
からなる群から選ばれた少なくとも１種のジチオ炭酸誘導体（Ａ）の存在下に１級カルボン酸ビニルエステルまたは２級カルボン酸ビニルエステルを重合し、ついで３級カルボン酸ビニルエステル、置換基を有してもよい安息香酸ビニルエステル、またはエチレンをブロック共重合して得たカルボン酸ビニルエステル系重合体を鹸化することにより、下記の一般式（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）または（Ｘ）

（式中Ｒ^８は水素、１級アシル基または２級アシル基、Ｒ^９は３級アルキル基、または置換されていてもよいフェニル基を表す。）
で表される末端にメルカプト基を有するポリマーを得る。本発明に用いるジチオ炭酸誘導体（Ａ）は、一般式（Ｉ）および（II）のジチオ炭酸エステル、並びに一般式（III）〜（VI）のジチオ炭酸アミドからなる。中でも、一般式（Ｉ）のジチオ炭酸エステルまたは一般式（III）もしくは（Ｖ）のジチオ炭酸アミドを用いると、一般式（VII）または（VIII）の片末端にメルカプト基を有するポリビニルアルコール系重合体が得られ、一般式（II）のジチオ炭酸エステルまたは一般式（IV）もしくは一般式（VI）のジチオ炭酸アミドを用いると、一般式（IX）または（Ｘ）の両末端にメルカプト基を有するポリビニルアルコール系重合体が得られる。この重合反応は、一般式（Ｉ）、（III）および（Ｖ）のジチオ炭酸エステルまたはジチオ炭酸アミドにおいてＲ^１とＳ原子との間、一般式（II）、（IV）または（VI）のジチオ炭酸エステルまたはジチオ炭酸アミドにおいてＸとその両側のＳ原子との間に、逐次、１級カルボン酸ビニルエステルまたは２級カルボン酸ビニルエステル、次いで３級カルボン酸ビニルエステル、置換基を有してもよい安息香酸ビニルエステルまたはエチレンが挿入されるリビングラジカル重合の機構により進行する。 The polyvinyl alcohol polymer of the present invention has the following general formulas (I), (II), (III), (IV), (V) and (VI):

(In the formula, R ^{1 to} R ⁷ are each an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. Each of Ar ^{1 to} Ar ⁴ represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and X represents an optionally substituted substituent having 1 to 30 carbon atoms. It represents a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.)
A primary carboxylic acid vinyl ester or a secondary carboxylic acid vinyl ester is polymerized in the presence of at least one dithiocarbonic acid derivative (A) selected from the group consisting of: and then a tertiary carboxylic acid vinyl ester having a substituent. May be saponified by saponifying the benzoic acid vinyl ester or the carboxylic acid vinyl ester polymer obtained by block copolymerization of ethylene, to give the following general formula (VII), (VIII), (IX) or (X )

(Wherein R ⁸ represents hydrogen, a primary acyl group or a secondary acyl group, R ⁹ represents a tertiary alkyl group or an optionally substituted phenyl group.)
The polymer which has a mercapto group at the terminal represented by this is obtained. The dithiocarbonic acid derivative (A) used in the present invention comprises dithiocarbonates of general formulas (I) and (II) and dithiocarbonate amides of general formulas (III) to (VI). In particular, when a dithiocarbonate of the general formula (I) or a dithiocarbonate amide of the general formula (III) or (V) is used, a polyvinyl alcohol-based polymer having a mercapto group at one end of the general formula (VII) or (VIII). When a dithiocarbonate of general formula (II) or dithiocarbonate amide of general formula (IV) or general formula (VI) is used, a mercapto group is added to both ends of general formula (IX) or (X). The polyvinyl alcohol polymer which has is obtained. This polymerization reaction is carried out between the R ¹ and S atoms in the dithiocarbonates or dithiocarbonates of the general formulas (I), (III) and (V), of the general formula (II), (IV) or (VI). In the dithiocarbonic acid ester or dithiocarbonic acid amide, a primary carboxylic acid vinyl ester or a secondary carboxylic acid vinyl ester, then a tertiary carboxylic acid vinyl ester, having a substituent, are successively formed between X and S atoms on both sides thereof. It proceeds by a living radical polymerization mechanism into which good vinyl benzoate or ethylene is inserted.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms of R ^{1 to} R ⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Straight chain, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. Examples thereof include branched or cyclic aliphatic hydrocarbon groups, and examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms of R ^{1 to} R ⁷ include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, Indenyl group, fluorenyl group, azulenyl group and the like can be mentioned. Among these, a methyl group, an ethyl group, or a propyl group is preferable because the dithiocarbonic acid derivative (A) can be easily produced. Moreover, as a substituent of these groups, said C1-C20 aliphatic hydrocarbon group, said C6-C20 aromatic hydrocarbon group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group , Alkoxy groups such as tert-butoxy group, aryloxy groups such as phenoxy group and naphthoxy group, halogen (F, Cl, Br, I) atoms, acetoxy group, cyano group, nitro group, sulfonic acid group, carboxyl group, amino group Examples thereof include functional groups such as a group, and are preferably substituted with a cyano group or an acetoxy group because radical generation is facilitated. These substituents may further have a substituent.

Examples of Ar ^{1 to} Ar ⁴ include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group, an azulenyl group, and the substituents for these groups include the above carbon number. 1-20 aliphatic hydrocarbon group, aromatic hydrocarbon group having 6-20 carbon atoms, alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, phenoxy group, naphthoxy group And functional groups such as an aryloxy group such as halogen (F, Cl, Br, I) atom, acetoxy group, cyano group, nitro group, sulfonic acid group, carboxyl group, and amino group. These substituents may further have a substituent.

  Examples of the divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms that may have a substituent of X include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene. Nonamethylene, decamethylene, and the like. As the substituents of these groups, the above-mentioned aliphatic hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, methoxy group, ethoxy Group, propoxy group, butoxy group, alkoxy group such as tert-butoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen (F, Cl, Br, I) atom, acetoxy group, cyano group, nitro group, sulfone Examples include functional groups such as acid groups, carboxyl groups, amino groups, etc., and it is easy to generate radicals, so cyano groups or acetoxy groups Is preferably substituted with.

  Examples of primary carboxylic acid vinyl esters include vinyl acetate, vinyl propionate, and vinyl butyrate; examples of secondary carboxylic acid vinyl esters include vinyl isopropionate and vinyl isobutyrate. Among these, vinyl acetate is used. preferable. Examples of tertiary carboxylic acid vinyl esters include vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2-ethyl-2-methylbutanoate, and among these, vinyl pivalate is preferred. Examples of the substituent of the benzoic acid vinyl ester which may have a substituent include the above aliphatic hydrocarbon group having 1 to 20 carbon atoms, the above aromatic hydrocarbon group having 6 to 20 carbon atoms, a methoxy group, and ethoxy group. Group, propoxy group, butoxy group, alkoxy group such as tert-butoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen (F, Cl, Br, I) atom, acetoxy group, cyano group, nitro group, sulfone Examples thereof include functional groups such as acid groups, carboxyl groups, and amino groups.

The primary acyl group or secondary acyl group, a tertiary alkyl group, an optionally substituted phenyl group R ⁹ in R ⁹ of the R ⁸ is determined by the monomers used.

R ⁸ is hydrogen or a mixture of hydrogen and a primary or secondary acyl group. The breakdown is arbitrarily determined based on the desired degree of saponification depending on the saponification conditions.

  Polymerization of the monomer in the presence of the dithiocarbonic acid derivative (A) can be carried out in the presence of a radical polymerization initiator by any of the bulk polymerization method, solution polymerization method, suspension polymerization method, and emulsion polymerization method. . There are no particular restrictions on the amount and method of addition of the dithiocarbonic acid derivative (A) to be present during the polymerization, and it may be added all at once or sequentially, and is appropriately determined depending on the physical properties of the target polyvinyl alcohol polymer. It should be. As the polymerization method, known methods such as a batch method, a semi-continuous method, and a continuous method can be adopted.

  As radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) ), Known radical polymerization initiators such as benzoyl peroxide and carbonate carbonate can be used. Moreover, although superposition | polymerization temperature is based also on the kind of polymerization initiator to be used, it is preferable that it exists in the range of -10-110 degreeC normally.

  The polymerization conditions of the present invention are not particularly limited, but it is preferable to use a mixed solution of a vinyl ester monomer and an inert solvent. As the inert solvent, any solvent can be used as long as it does not inhibit the polymerization. In particular, an aliphatic hydrocarbon having 4 to 20 carbon atoms, such as isobutane, pentane, hexane, heptane, cyclohexane and the like, is aromatic. Hydrocarbons such as toluene, xylene, etc., aliphatic esters having 3 to 20 carbon atoms such as methyl acetate, ethyl acetate, 2-ethylhexyl acetate, phenyl acetate, ethyl hexanoate, etc., or aromatic esters such as methyl benzoate Suitable are ethyl benzoate and the like.

  In carrying out the present invention, the charging ratio (molar ratio) of primary or secondary carboxylic acid vinyl ester and dithiocarbonic acid derivative (A) is primary or secondary carboxylic acid vinyl ester / dithiocarbonic acid derivative (A) = 25 to It is preferable to use at 8,000. The sum of m in the polymer having a mercapto group at one end of the general formula (VII) or (VIII) and l and m in the polymer having a mercapto group at both ends of the general formula (IX) or (X) is 50 to 4000 is preferable.

  In carrying out the present invention, the charge ratio (molar ratio) of primary or secondary carboxylic acid vinyl ester and radical polymerization initiator is used as primary or secondary carboxylic acid vinyl ester / radical polymerization initiator = 100 to 10,000. Is preferred.

  In carrying out the invention, the charge ratio (molar ratio) of primary or secondary carboxylic acid vinyl ester / tertiary carboxylic acid vinyl ester, primary or secondary carboxylic acid vinyl ester / vinyl benzoate which may have a substituent The ester charge ratio (molar ratio) and the primary or secondary vinyl carboxylic acid ester / ethylene charge ratio (molar ratio) are preferably 0.1 to 20, and preferably 5 to 15. . The sum of n in the polymer having a mercapto group at one end of the general formula (VII) or (VIII) and k and n in the polymer having a mercapto group at both ends of the general formula (IX) or (X) is It is preferable that it is 1-10.

  A polyvinyl alcohol polymer is produced by saponifying a vinyl acetate polymer obtained by polymerization. A methanol solution of vinyl acetate polymer is saponified using an alkali such as sodium hydroxide or potassium hydroxide as a catalyst. To manufacture.

  By the above saponification, the tertiary carboxylic acid vinyl ester block part of the polymer or the benzoic acid vinyl ester block part which may have a substituent is not hydrolyzed and the terminal carbon atom has a —CH (OH) SH structure. Thus, a polyvinyl alcohol polymer having a mercapto group at its terminal can be produced by hydrolyzing the primary carboxylic acid vinyl ester block portion and the thiocarbonylthio group. The number of terminal mercapto groups per molecule of the polyvinyl alcohol polymer obtained by the method of the present invention is preferably 0.8 or more, and more preferably 0.85 or more when having a mercapto group at one end. It is more preferable that the number is 0.9 or more. Moreover, when it has a mercapto group at both ends, it is preferably 1.6 or more, more preferably 1.7 or more, and even more preferably 1.8 or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the measuring method used for the Example and the comparative example is as follows.

(Identification of dithiocarbonic acid derivative (A))
¹ H-NMR was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL, JNM-LAMBDA-400).

(Molecular weight of polymer)
Vinyl ester in a tetrahydrofuran solvent at 40 ° C. using a gel permeation chromatograph (manufactured by Tosoh Corporation) equipped with a column (Tosoh Corporation, TSKgelGMHHR-M and TSKgelG2000HHR) and a differential refractometer (Tosoh Corporation, RI-8020). The number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer were determined in terms of polystyrene.

(Amount of mercapto group at end of polymer)
The mercapto group at the end of the polymer was determined by reacting the polymer with an aqueous iodine solution and titrating with an aqueous sodium thiosulfate solution.

(Introduction rate of mercapto group at polymer terminal)
The rate of introduction of mercapto groups at the polymer ends (hereinafter abbreviated as f) was calculated by the following mathematical formula.
f = S × Mn
(In the formula, S represents the equivalent of mercapto group per gram of polymer, and Mn represents the number average molecular weight of the polymer.)
When 100% of the mercapto group is introduced at one end of the polymer, f is 1.0, and when 100% of the functional group is introduced at both ends of the polymer, f is 2.0.

アルゴン置換した500mLの三つ口フラスコに、ブロモアセトニトリル（25.0g）、エチルキサントゲン酸カリウム（32.0g，0.20mol）、およびエタノール（250mL）を加えて、室温下１５時間攪拌した。反応溶液に水（200mL）を加え、ジエチルエーテルで抽出した。これを減圧蒸留（108℃／0.5mmHg）して標記のジチオ炭酸エステルを得た（収量29.2g，収率：91％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ4.72（q，2H），3.89（s, 2H），1.48（t，3H） [Preparation of dithiocarbonic acid derivative (A)]
Synthesis Example 1 < Synthesis of dithiocarbonate (XI)>

Bromoacetonitrile (25.0 g), potassium ethyl xanthate (32.0 g, 0.20 mol), and ethanol (250 mL) were added to a 500 mL three-neck flask purged with argon, and the mixture was stirred at room temperature for 15 hours. Water (200 mL) was added to the reaction solution, and the mixture was extracted with diethyl ether. This was distilled under reduced pressure (108 ° C./0.5 mmHg) to obtain the title dithiocarbonate (yield 29.2 g, yield: 91%).
¹ H-NMR (CDCl ₃ ): δ 4.72 (q, 2H), 3.89 (s, 2H), 1.48 (t, 3H)

アルゴン置換した50mLの二つ口フラスコに、ジチオ炭酸エステル（ＸＩ）（5.21g，50mmoL）、１，１’−アゾビス（シクロヘキサンー１−カルボニトリル）（73mg、0.30mmoL）および酢酸ビニル（8.61g、100mmol）を加えて、100℃で30分間撹拌した。
反応溶液から未反応の酢酸ビニルを留去し、カラムクロマトグラフィーにより精製して標記のジチオ炭酸エステルを得た（収量：6.47g，収率：68％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ6.68（t、1H）、4.63（q、2H）、2.55（m、2H），2.37（ｍ、2H）、2.13（s、3H）、1.42（t、3H） Synthesis Example 2 < Synthesis of dithiocarbonate (XII)>

Argon-substituted 50 mL two-necked flask was charged with dithiocarbonate (XI) (5.21 g, 50 mmoL), 1,1′-azobis (cyclohexane-1-carbonitrile) (73 mg, 0.30 mmoL) and vinyl acetate (8.61 g). , 100 mmol), and stirred at 100 ° C. for 30 minutes.
Unreacted vinyl acetate was distilled off from the reaction solution and purified by column chromatography to obtain the title dithiocarbonate (yield: 6.47 g, yield: 68%).
¹ H-NMR (CDCl ₃ ): δ 6.68 (t, 1H), 4.63 (q, 2H), 2.55 (m, 2H), 2.37 (m, 2H), 2.13 (s, 3H), 1.42 (t, 3H)

アルゴン置換した50mLの二つ口フラスコに1,9-ノナンジアール（5.23g，33.5mmol）を加え、室温でトリメチルシリルシアニド（8.93mL、67.0mmol）を加えて、室温で２時間撹拌した。ここに２N−塩酸水溶液（5mL）を加え。ジエチルエーテルで抽出して1,9-ジシアノノナン-1,9-ジオールを得た（収量：7.04g、収率99.9％）。ついでAr置換した100mL二つ口フラスコに、1,9-ジシアノノナン-1,9-ジオール（4.78g、22.7mmol）、トルエン（12mL）、メタンスルホン酸クロリド（3.86mL、49.9mmol）を加え、0℃に冷却した後、トリエチルアミン（6.96mL、49.9mmol）を滴下した。滴下終了後、室温で１２時間攪拌した後、反応液を氷水に投入し、ジエチルエーテルで有機物を抽出し、カラムクロマトグラフィーにより精製し、1,9-ジシアノ-1,9-ジメタンスルホニルノナンを得た（3.59g、収率55％）。ついでAr置換した100mL２つ口フラスコに、1,9-ジシアノ-1,9-ジメタンスルホニルノナン（732mg、2.55mmol）、エチルキサントゲン酸カリウム（818mg，5.10mmol）、およびエタノール（50mL）を加えて、室温下１５時間攪拌した。反応溶液に水（30mL）を加え、ジエチルエーテルで抽出した。これをカラムクロマトグラフィーにより精製し、標記のジチオ炭酸エステルを得た（収量907mg，収率：85％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ4.65（q、4H）、4.45（t、2H）、1.95（m、4H）、1.59（br、4H）、1.46（t、6H）、1.29（br、6H） Synthesis Example 3 < Synthesis of dithiocarbonate (XIII)>

1,9-nonanedial (5.23 g, 33.5 mmol) was added to a 50 mL two-necked flask purged with argon, trimethylsilylcyanide (8.93 mL, 67.0 mmol) was added at room temperature, and the mixture was stirred at room temperature for 2 hours. 2N hydrochloric acid aqueous solution (5 mL) was added thereto. Extraction with diethyl ether gave 1,9-dicyanononane-1,9-diol (yield: 7.04 g, yield 99.9%). Subsequently, 1,9-dicyanononane-1,9-diol (4.78 g, 22.7 mmol), toluene (12 mL), methanesulfonic acid chloride (3.86 mL, 49.9 mmol) were added to an Ar-substituted 100 mL two-necked flask. After cooling to ° C., triethylamine (6.96 mL, 49.9 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours, and then the reaction solution was poured into ice water, the organic substance was extracted with diethyl ether, purified by column chromatography, and 1,9-dicyano-1,9-dimethanesulfonylnonane was obtained. Obtained (3.59 g, 55% yield). Next, 1,9-dicyano-1,9-dimethanesulfonylnonane (732 mg, 2.55 mmol), potassium ethyl xanthate (818 mg, 5.10 mmol), and ethanol (50 mL) were added to an Ar-substituted 100 mL two-necked flask. And stirred at room temperature for 15 hours. Water (30 mL) was added to the reaction solution, and the mixture was extracted with diethyl ether. This was purified by column chromatography to obtain the title dithiocarbonate (yield 907 mg, yield: 85%).
¹ H-NMR (CDCl ₃ ): δ 4.65 (q, 4H), 4.45 (t, 2H), 1.95 (m, 4H), 1.59 (br, 4H), 1.46 (t, 6H), 1.29 (br, 6H)

アルゴン置換した50mLの二つ口フラスコに、ジチオ炭酸エステル（ＸＩＩＩ）（2.09g，5.0mmoL）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）（7.3mg、0.03mmoL）および酢酸ビニル（861mg、10mmol）を加えて、100℃で30分間撹拌した。
反応溶液から未反応の酢酸ビニルを留去し、カラムクロマトグラフィーにより精製して標記のジチオ炭酸エステルを得た（収量：1.71g，収率：58％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ6.72（dd、2H）、4.63（dq、4H）、2.71（m、2H）、2.99-2.18（m、4H）、2.13（s、6H）、1.64（m、4H）、1.54（br、4H）、1.43（t、6H）、1.27（br、6H） Synthesis Example 4 < Synthesis of dithiocarbonate (XIV)>

To a 50 mL two-necked flask purged with argon, dithiocarbonate (XIII) (2.09 g, 5.0 mmoL), 1,1′-azobis (cyclohexane-1-carbonitrile) (7.3 mg, 0.03 mmoL) and vinyl acetate ( 861 mg, 10 mmol) was added, and the mixture was stirred at 100 ° C. for 30 minutes.
Unreacted vinyl acetate was distilled off from the reaction solution and purified by column chromatography to obtain the title dithiocarbonate (yield: 1.71 g, yield: 58%).
¹ H-NMR (CDCl ₃ ): δ 6.72 (dd, 2H), 4.63 (dq, 4H), 2.71 (m, 2H), 2.99-2.18 (m, 4H), 2.13 (s, 6H), 1.64 ( m, 4H), 1.54 (br, 4H), 1.43 (t, 6H), 1.27 (br, 6H)

Example 1 <Manufacture of a polyvinyl alcohol polymer having a mercapto group at one end using dithiocarbonate (XI)>
Argon-substituted 100 mL autoclave with vinyl acetate (27.7 mL, 300 mmol), dithiocarbonate (XI) (484 mg, 3.0 mmol), and 1,1′-azobis (cyclohexane-1-carbonitrile) (7.3 mg, 0.03 mmoL) And stirred at 100 ° C. for 7 hours. After 7 hours, vinyl pivalate (4.44 mL, 30 mmol) was added, and after 10 minutes, the reaction solution was returned to room temperature and poured into hexane to obtain a polyvinyl acetate polymer (yield: 22.7 g). Mn = 8,400; Mw / Mn = 1.57. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 0.91.

Example 2 <Production of Polyvinyl Alcohol Polymer Having a Mercapto Group at One Terminal Using Dithiocarbonate (XII)>
Argon-substituted 100 mL autoclave with vinyl acetate (27.7 mL, 300 mmol), dithiocarbonate (XII) (742 mg, 3.0 mmol), and 1,1′-azobis (cyclohexane-1-carbonitrile) (7.3 mg, 0.03 mmoL) And stirred at 100 ° C. for 7 hours. After 7 hours, vinyl benzoate (4.15 mL, 30 mmol) was added, and after 10 minutes, the temperature was returned to room temperature, and the reaction solution was poured into hexane to obtain a polyvinyl acetate polymer (yield: 23.8 g). Mn = 8,800; Mw / Mn = 1.47. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 0.94.

Example 3 <Production of Polyvinyl Alcohol Polymer Having Mercapto Groups at Both Terminals Using Dithiocarbonate (XIII)>
Argon substituted 100 mL autoclave with vinyl acetate (27.7 mL, 300 mmol), dithiocarbonate (XIII) (1.26 g, 3.0 mmol), and 1,1′-azobis (cyclohexane-1-carbonitrile) (14.7 mg, 0.06 mmoL) ) And stirred at 100 ° C. for 7 hours. After 7 hours, vinyl pivalate (4.44 mL, 30 mmol) was added, and after 10 minutes, the reaction solution was returned to room temperature and poured into hexane to obtain a polyvinyl acetate polymer (yield: 20.5 g). Mn = 8,000; Mw / Mn = 1.51. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 1.82.

Example 4 <Production of Polyvinyl Alcohol Polymer Having Mercapto Groups at Both Terminals Using Dithiocarbonate (XIV)>
Argon substituted 100 mL autoclave with vinyl acetate (27.7 mL, 300 mmol), dithiocarbonate (XIII) (1.77 g, 3.0 mmol), and 1,1′-azobis (cyclohexane-1-carbonitrile) (14.7 mg, 0.06 mmol) ) And stirred at 100 ° C. for 7 hours. After 7 hours, ethylene (5 atm) was added, 10 minutes later, the temperature was returned to room temperature, and the reaction solution was poured into hexane to obtain a polyvinyl acetate polymer (yield: 22.3 g). Mn = 8,400; Mw / Mn = 1.38. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 1.88.

Comparative Example 1 <Production of polyvinyl alcohol polymer having mercapto group at one end using thioacetic acid>
To a 100 mL autoclave purged with argon, vinyl acetate (27.7 mL, 300 mmol), thioacetic acid (228 mg, 3.0 mmol), and 1,1′-azobis (cyclohexane-1-carbonitrile) (7.3 mg, 0.03 mmol) were added. Stir at 0 ° C. for 7 hours. After 7 hours, the temperature was returned to room temperature, and the reaction solution was poured into hexane to obtain a polyvinyl acetate polymer (yield: 21.2 g). Mn = 10,300; Mw / Mn = 1.79. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 0.76.

Comparative Example 2 <Production of polyvinyl alcohol polymer having mercapto groups at both ends using thioacetic acid and dibenzoyl sulfide>
Vinyl acetate (27.7 mL, 300 mmol), thioacetic acid (228 mg, 3.0 mmol), and dibenzoyl sulfide (919 mg, 3.0 mmoL) were added to an argon-substituted 100 mL autoclave, and the mixture was stirred at 60 ° C. for 7 hours. After 7 hours, the temperature was returned to room temperature, and the reaction solution was poured into hexane to obtain a polyvinyl acetate polymer (yield: 8.52 g). Mn = 8,500; Mw / Mn = 1.89. This polymer was saponified with NaOH in methanol at 40 ° C. to obtain a polyvinyl alcohol polymer. The terminal mercapto group introduction rate f was 1.47.

As is clear from the comparison between Examples 1 and 2 and Comparative Example 1 and the comparison between Examples 3 and 4 and Comparative Example 2, the use of the polymerization catalyst composition of the present invention introduces terminal mercapto groups. It can be seen that a polyvinyl alcohol polymer having a high rate can be produced.

Claims (5)

The following general formulas (I), (II), (III), (IV), (V) and (VI):

(In the formula, R ^{1 to} R ⁷ are each an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. Each of Ar ^{1 to} Ar ⁴ represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and X represents an optionally substituted substituent having 1 to 30 carbon atoms. It represents a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.)
A primary or secondary carboxylic acid vinyl ester may be polymerized in the presence of at least one dithiocarbonic acid derivative (A) selected from the group consisting of: and then a tertiary carboxylic acid vinyl ester or a substituent. The following general formula (VII), (VIII), (IX) or (X) characterized by saponifying a vinyl benzoate or a carboxylic acid vinyl ester polymer obtained by block copolymerization of ethylene:

(Wherein R ⁸ represents hydrogen or a primary or secondary acyl group, R ⁹ represents a tertiary alkyl group, or an optionally substituted phenyl group.)
The manufacturing method of the polyvinyl-alcohol-type polymer which has a mercapto group at the terminal represented by these.   M in the polyvinyl alcohol polymer of the general formula (VII) or (VIII), and the sum of l and m in the polyvinyl alcohol polymer of the general formula (IX) or (X) is 50 to 4000, The sum of n in the polyvinyl alcohol polymer of the formula (VII) or (VIII) and k and n in the polyvinyl alcohol polymer of the general formula (IX) or (X) is 1-10. 2. A method for producing a polyvinyl alcohol polymer according to 1.   The method for producing a polyvinyl alcohol polymer according to claim 1 or 2, wherein the primary or secondary vinyl carboxylic acid ester is vinyl acetate.   The method for producing a polyvinyl alcohol polymer according to any one of claims 1 to 3, wherein the tertiary carboxylic acid vinyl ester is vinyl pivalate.   The method for producing a polyvinyl alcohol polymer according to any one of claims 1 to 4, wherein the optionally substituted vinyl benzoate is vinyl benzoate.