JP4771737B2 - Method for producing a polymer having a polyvinyl ether moiety and an organopolysiloxane moiety - Google Patents

Description

The present invention relates to a process for producing a polymer comprising a polyvinyl ether moiety and an organopolysiloxane moiety, and more particularly to a process for reacting an organohydrogenpolysiloxane and a vinyl ether monomer in the presence of a ruthenium catalyst.

  Polyvinyl ether is a polymer compound used in electronic component materials, lubricants, adhesives, etc., and conventionally polymerizes vinyl ether monomers using Lewis acid catalysts such as protonic acids, carbonium ion salts, metal halides, etc. It is synthesized by.

When a reactive silicon functional group is introduced into the terminal of the polyvinyl ether, it becomes possible to bond another compound via the functional group, leading to an improvement in the functionality of the polyvinyl ether. For example, a cationic polymerization method using chlorosilane and metal halide (HgCl ₂ ) is known (Non-patent Document 1). However, this method has a problem that a chloro group bonded to a silicon atom is easily hydrolyzed to generate hydrochloric acid.

As a method for solving such a drawback, a method is known in which hydrosilane is activated by a transition metal catalyst to introduce a silicon functional group at the end of polyvinyl ether. For example, a reaction using a cobalt catalyst (Non-patent Document 2), a reaction using a platinum catalyst (Patent Document 1), and a reaction using a ruthenium catalyst (Patent Document 2 and Non-Patent Document 3) are disclosed.

Patent Document 1 discloses a method of polymerizing a vinyl ether monomer by heating a mixture of a vinyl ether monomer, a platinum catalyst, and an organohydrogenpolysiloxane. The organohydrogenpolysiloxane is a polymerization promoter. It is only used as. An organopolysiloxane having a vinyl ether functional group is also considered to be effective as a vinyl ether monomer, but it is not preferable because an intermolecular polymerization reaction proceeds to give a crosslinked organopolysiloxane.

As a polymerization reaction using a ruthenium catalyst, a method for producing a polyether by polymerizing a cyclic ether and a method for producing a silalkylenesiloxane by polymerizing a cyclic siloxane are also known (Patent Documents 3 and 4).

   The ruthenium catalysts described in Patent Document 2 and Non-Patent Document 3 are considered to act on Si—H bonds of hydrosilane to activate hydrogen atoms. That is, it is necessary for the ruthenium catalyst to interact with the Si—H bond. Therefore, it is expected that a hydrogen atom is hardly activated when there is a large substituent that sterically inhibits such an interaction. In fact, as the hydrosilane, only those having a phenyl group and a methyl group as substituents are used.

However, surprisingly, contrary to the above prediction, the present inventors can activate a predetermined organohydrogenpolysiloxane using a ruthenium catalyst, polymerize vinyl ether, and bond it to the organohydrogenpolysiloxane. It was found (Non-Patent Document 4).
Kajiura et al., J. Polym. Sci. A., 11, 1109 (1972) Crivello et al., J. Polym. Sci. A., 30, 31-39 (1992) Nagashima et al., Organometallics, 23, 5779-5786 (2004) Organometallic Chemistry Conference Proceedings, page 428, published October 6, 2004 JP-A-6-172444 JP 2004-238484 A JP 2001-59021 A PCT / JP00 / 07531 publication

  However, the above studies were still only at the laboratory level for organopolysiloxanes with limited structure. Therefore, an object of the present invention is to provide a method for efficiently producing a polymer having an organopolysiloxane portion and a polyvinyl ether portion from various organohydrogenpolysiloxanes and vinyl ether monomers.

That is, the present invention provides an organohydrogenpolysiloxane having at least one Si—H bond, and a vinyl ether represented by the following formula (1) in a molar amount larger than the total molar amount of the Si—H bond. ,
R ¹ ₂ C═C (R ¹ ) —OR ² (1)
^{(R 1} in formula (1) each independently represent hydrogen atom, the carbon number 1-10, an alkyl group, an aryl group, or an aralkyl group, ^{R 2} is the carbon number 1-10, an alkyl group, an aryl Group, aralkyl group, or silyl group),
This is a method for producing a polymer in which polyvinyl ether is bonded to the organopolyhydrogenpolysiloxane residue by reacting in the presence of a polynuclear ruthenium carbonyl complex having 2 to 4 ruthenium atoms.

The organohydrogenpolysiloxane used in the method of the present invention can be represented by the following general formula.
R ³ _a H _b SiO _{(4-ab) / 2}
R ³ is independently an alkyl group, aryl group, or aralkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, which may be substituted with a halogen atom. a and b are numbers less than 4, respectively, where a + b <4. Preferably 1.0 ≦ a ≦ 2.5 and 0.001 ≦ b ≦ 1.0, more preferably 1.0 ≦ a ≦ 2.0 and 0.005 ≦ b ≦ 1.0.

Examples of R ³ include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, and decyl groups; alkyl groups such as cyclopentyl groups and cyclohexyl groups; An alicyclic hydrocarbon group; an aryl group such as a phenyl group and a tolyl group; a fluorine-substituted alkyl group such as a trifluoropropyl group, a nonafluorohexyl group, and a heptadecylfluorodecyl group. Preferably, R ³ is an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a trifluoropropyl group.

ここで、Ｒ⁴は水素原子または上述のＲ³であり、但し、ｄが０のときはＲ⁴の少なくとも一方が水素原子である。式（２）において、ｃは０〜１０００の整数、ｄは０〜１０００の整数である。得られるポリマーに、ポリオルガノポリシロキサンの特性をより反映させるために、ｃ＋ｄは２〜２０００の整数、好ましくは２〜１０００、より好ましくは１０〜５００である。 The structure of the organohydrogenpolysiloxane may be any one of a linear form represented by the following formula (2), a cyclic form represented by the formula (3), and a branched form represented by the formula (4). good.

Here, R ⁴ is a hydrogen atom or R ³ described above, provided that when d is 0, at least one of R ⁴ is a hydrogen atom. In Formula (2), c is an integer of 0 to 1000, and d is an integer of 0 to 1000. In order to further reflect the characteristics of polyorganopolysiloxane in the obtained polymer, c + d is an integer of 2 to 2000, preferably 2 to 1000, more preferably 10 to 500.

In Formula (3), e is an integer of 0-8, f is an integer of 1-8, e + f is an integer of 3-10, Preferably it is an integer of 4-8. In the formula (4), g is 0 or 1, h is an integer of 3 or 4, and g + h is 4.

Preferably, a linear organohydrogenpolysiloxane represented by the formula (2) is used. The linear organohydrogenpolysiloxane may contain a side chain structure such as R ³ SiO _1.5 units and SiO ₂ units as long as it does not inhibit the reaction in the present invention. Further, in the methyl hydrogen polysiloxane of the formula (2), the position of Si—H is not particularly limited.

More preferably, in the above formula (2), methyl hydrogen polysiloxane represented by formula (5), wherein R ³ is a methyl group, and c and d are 1 to 1000, formula (2) Wherein d = 0, c is an integer of 2 to 2000, preferably an integer of 2 to 1000, more preferably an integer of 10 to 500, and R ^{4 at} both ends is a hydrogen atom. Or a methyl hydrogen polysiloxane represented by the formula (7) in which R ^{4 at the} same terminal is a hydrogen atom.

The catalyst in the method of the present invention is a polynuclear ruthenium carbonyl complex having 2 to 4 ruthenium atoms, preferably trinuclear ruthenium coordinated with acenaphthylene represented by the following formula (A) having 3 ruthenium atoms. A carbonyl complex or a trinuclear ruthenium carbonyl complex coordinated with azulene represented by the following formula (B).

The vinyl ether monomer used in the method of the present invention is represented by the formula (1).
R ¹ ₂ C = C (R ¹ ) -OR ² (1)
Here, R ¹ is, independently of each other, a hydrogen atom, an optionally substituted alkyl group, an aryl group, or an aralkyl group having 1 to 10 carbon atoms, and R ² is an optionally substituted carbon number. 1-8 alkyl groups, aryl groups, aralkyl groups, or silyl groups.

Examples of R ¹ include alkyl groups such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; cyclopentyl group, and cyclohexyl group. A saturated alicyclic hydrocarbon group such as a group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a phenethyl group. Preferably R ¹ is a hydrogen atom.

Examples of R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and Alkyl groups such as decyl groups; saturated alicyclic hydrocarbon groups such as cyclopentyl groups and cyclohexyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups and phenethyl groups; trimethylsilyl groups and triethylsilyl groups And a silyl group such as a t-butyldimethylsilyl group. Preferably R ² is an alkyl group.

The reaction between the Si-H bond in the organohydrogenpolysiloxane and the vinyl ether monomer is represented by the following formula.
Si-H + n ・ R ¹ ₂ C = C (R ¹ ) -OR ² ≡ Si-{(R ¹ ₂ ) CC (R ¹ ) (OR ² )} _n -H
In the above formula, n is an integer of 2 or more. However, when there are a plurality of SiH bonds in one molecule, n may be one.

これらのポリマーは、オルガノポリシロキサンと、ポリビニルエーテル双方の特性を有し、例えば、化粧料、コーティング剤、界面活性剤への応用が期待される。 When the organohydrogenpolysiloxanes of the above formulas (2) to (7) are used, polymers represented by the following formulas (8) to (13) can be obtained.

These polymers have characteristics of both organopolysiloxane and polyvinyl ether, and are expected to be applied to, for example, cosmetics, coating agents, and surfactants.

In the method of the present invention, the ruthenium catalyst is preferably used in a range of 1/1000 to 1/10 mol with respect to 1 mol of the SiH bond of the organohydrogenpolysiloxane. Even if the amount is less than the lower limit, that is, a large amount of ruthenium catalyst is used, the reaction rate does not increase. On the other hand, if the upper limit is exceeded, the polymerization time becomes too long. Preferably, the ruthenium catalyst amount is in the range of 1/500 to 1/10, more preferably 1/200 to 1/10 mol, and most preferably 1/150 to 1/50, relative to 1 mol of SiH bonds.

The vinyl monomer is preferably added in several portions without being added at once. The additional addition is carried out after the reaction of the already added vinyl monomer has progressed to some extent, preferably after the reaction has almost ended. The progress of the reaction can be confirmed by measuring the residual vinyl monomer in the reaction mixture by, for example, ^H NMR. The amount of addition at one time is preferably 100 to 5,000 mol, more preferably 500 to 2,000 mol with respect to 1 mol of the catalyst. Even if the amount is less than the lower limit, that is, the amount of ruthenium catalyst is increased with respect to the monomer, the reaction rate does not increase. It is added once in the above addition amount, and after confirming that the reaction of the added vinyl ether is completed, the next addition is performed, and this is repeated until the polymerization no longer proceeds. The total amount of vinyl monomer addition will typically be in the range of 100 to 100,000 moles, more typically 5,000 to 50,000 moles per mole of catalyst. Even if the total amount is added all at once, unreacted monomer tends to remain.

  As the reaction solvent, ether solvents, aromatic solvents, alcohol solvents and the like can be used, and ether solvents such as 1,4-dioxane and tetrahydrofuran are preferable. As the molecular weight of the organohydrogenpolysiloxane increases, the solubility decreases. In order to achieve a homogeneous reaction, it is necessary to set reaction conditions by appropriately combining an increase in the amount of solvent and an increase in reaction temperature.

  Since the catalyst of the present invention has high activity, the desired product can be obtained at a very mild reaction temperature of 0 to 100 ° C. The reaction temperature is preferably 20 to 60 ° C. The reaction time is not particularly limited, but typically, the vinyl ether polymerization reaction does not proceed within 30 minutes to 10 hours, more typically 30 minutes to 3 hours after the addition of vinyl ether.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the following examples, NMR measurement was performed using a Lambda 600 spectrometer manufactured by JEOL Ltd. The infrared absorption spectrum was measured using FT / IR-550 manufactured by JASCO Corporation. The molecular weight and molecular weight distribution of the product were determined by GPC (column: Concatenated Shodex GPC-KF-804L and KF-805L; eluent THF; molecular weight calculation standard: polystyrene standard sample). ²⁹ Si-NMR was used as a compound identification method. INEPT measurement (measured with J value of 204 Hz) is a measurement method that detects only the peak of silicon atom having Si-H group, and the peak is not detected by INEPT measurement of ²⁹ SiNMR of the polymer produced. Corresponds to the disappearance of the Si-H group. On the other hand, DEPT measurement (measured with J value of 11 Hz) detects peaks of all silicon species regardless of functional groups. Compared with the raw material organohydrogenpolysiloxane, the product has no signal based on Si-H groups, and a signal of Si bonded to an alkyl group is observed. In the following results, multiple ²⁹ Si signals were observed in the DEPT measurement, which is due to the mixture of polymers with different tacticities.

30mＬ二口フラスコに、磁気撹拌子、前記式（Ａ）で示される触媒（以下、AceRu₃(CO)₇と略す、2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.056mＬ）をマイクロシリンジで加えて錯体を溶解した。この錯体溶液に、1,1,1,3,3,5,5-ヘプタメチルトリシロキサン（0.018ｍL, 0.066 mmol）を加えて30分撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、１０００当量ｔ−ブチルビニルエーテル（以下、t-BVEと略す、0.43 mL, 3.3 mmol, 1000e.q.）を加え、室温で撹拌した。発熱を伴う溶液の粘度の急激な増加が観察された。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して28000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリマー（8.02g）を得た。生成したポリマーを¹HNMR, ¹³CNMR, ²⁹SiNMR, IRで測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。
Mn = 10000, Mw = 20000, Mw/Mn = 1.98(GPC、ポリスチレン換算)
Mn = 94000(¹HNMR)
Mn = 122000(理論)（これは、消費したモノマー/使用したシロキサンのモル数から算出した値であり、以下において同様である）。
²⁹SiNMR(119MHz, C₆D₆, r.t.)
(Dept J=11Hz) δ7.38、 7.12、7.02(OSiMe₃), -20.6, -20.83, -21.29, -21.75, -21.83, -21.95, -22.00(その他、複数のタクティシティによる複数のピークが表れた)
(Inept J=204Hz) Si-H peak( -7.03ppm )の消失を確認した。
IR Si-H peak( 2127cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): ポリマー鎖に基くシグナル: δ 0.84〜1.51 (br, 9H, CH₃ of ^tBu), 1.52〜2.45 (ポリマー鎖に基くbr, 2H, CH₂ ), 3.49〜4.17 (ポリマー鎖に基くbr,1H, CH), 末端シリル基の小さなピークがδ 0.02〜0.09, 0.09〜0.12, 0.12〜0.21 に観察された(いずれもbr-s, 積分比8:4:5, 21H, SiMe)
¹³C NMR (150 MHz, C₆D₆, r.t.) ポリマー鎖のピークのみ以下のシフトに観察された: ・ 28.41〜30.68 (CH₃ of ^tBu), 44.74〜47.43 (ポリマー鎖のCH₂), 66.35〜68.94 (ポリマー鎖のCH), 72.52〜74.12(C of ^tBu)(S/Nが悪いため、Si-Me基の¹³Cシグナルは確認できなかった。） Example 1
Reaction of 1,1,1,3,3,5,5-heptamethyltrisiloxane with t-butyl vinyl ether (t-BVE)

A magnetic stirring bar and a catalyst represented by the above formula (A) (hereinafter abbreviated as AceRu ₃ (CO) ₇ , 2.15 mg, 0.0033 mmol) were added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.056 mL) was added with a microsyringe to dissolve the complex. When 1,1,1,3,3,5,5-heptamethyltrisiloxane (0.018 mL, 0.066 mmol) is added to this complex solution and stirred for 30 minutes, the color of the solution changes from dark orange to light orange. did. Next, 1000 equivalent t-butyl vinyl ether (hereinafter abbreviated as t-BVE, 0.43 mL, 3.3 mmol, 1000 e.q.) was added and stirred at room temperature. A rapid increase in the viscosity of the solution with an exotherm was observed. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalents of t-BVE were newly added, and this was repeated until the polymerization did not proceed (28000 equivalents relative to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain a polymer (8.02 g). When the produced polymer was measured by ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR, disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained.
Mn = 10000, Mw = 20000, Mw / Mn = 1.98 (GPC, polystyrene equivalent)
Mn = 94000 ⁽¹ HNMR)
Mn = 122000 (theoretical) (this is a value calculated from the number of moles of monomer consumed / number of siloxanes used, and so on).
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
(Dept J = 11Hz) δ 7.38, 7.12, 7.02 (OSiMe ₃ ), -20.6, -20.83, -21.29, -21.75, -21.83, -21.95, -22.00 (Other multiple peaks due to multiple tacticities (Appears)
(Inept J = 204 Hz) The disappearance of Si-H peak (−7.03 ppm) was confirmed.
IR Si-H peak (2127cm ^-1 ) Disappeared.
¹ H NMR (600 MHz, C ₆ D ₆ , rt): Signal based on polymer chain: δ 0.84 to 1.51 (br, 9H, CH ₃ of ^t Bu), 1.52 to 2.45 (br, 2H, CH based on polymer chain ₂ ), 3.49 to 4.17 (br, 1H, CH based on polymer chain), small peaks of terminal silyl groups were observed at δ 0.02 to 0.09, 0.09 to 0.12, 0.12 to 0.21 (both br-s, integral ratio) (8: 4: 5, 21H, SiMe)
Only ¹³ C NMR (150 MHz, C ₆ D ₆ , rt) polymer chain peaks were observed with the following shifts: 28.41-30.68 (CH ₃ of ^t Bu), 44.74-47.43 (CH _{2 of} polymer chain), 66.35 to 68.94 (CH of polymer chain), 72.52 to 74.12 (C of ^t Bu) (S / N was poor, so ¹³ C signal of Si-Me group could not be confirmed.)

30mＬ二口フラスコに、磁気撹拌子、AceRu₃(CO)₇（2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.056 mＬ）をマイクロシリンジで加えて錯体を溶解した。この錯体溶液に、1,1,3,3,5,5-ヘキサメチルトリシロキサン（0.008ｍL, 0.033 mmol）を加えて30分撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、１０００当量のt-BVE（0.43 mL, 3.3 mmol,）を加え、室温で撹拌した。発熱を伴う溶液の粘度の急激な増加が観察された。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して18000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリマー（4.05g）を得た。生成したポリマーを¹HNMR, ¹³CNMR, ²⁹SiNMR, IRで測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。
Mn = 9000, Mw = 16000, Mw/Mn = 1.84(GPC、ポリスチレン換算)
Mn = 111000(¹HNMR)
Mn = 124000(理論)
²⁹SiNMR(119MHz, C₆D₆, r.t.)
Dept J=11Hz δ-21.63, -21.72(その他、複数のタクティシティによる複数のピークが表れた)
Inept J=210Hz Si-H peak( -6.40ppm )の消失を確認した。
IR Si-H peak( 2126cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): ポリマー鎖に基くシグナル: δ 0.93〜1.45 (br, 9H, CH₃ of ^tBu), 1.55〜2.21 (ポリマー鎖に基づくbr,2H, CH₂), 3.54〜3.94 (ポリマー鎖のブロードな1H, CH), 末端シリル基の小さなピークがδ0.09〜0.21に観察された (m, 18H, SiMe) ¹³C NMR (150 MHz, C₆D₆, r.t.) ポリマー鎖のピークのみ以下のシフトに観察された: δ 28.33〜30.83 (CH₃ of ^tBu), 44.83〜47.30 (ポリマー鎖のCH₂), 66.08〜68.61 (ポリマー鎖のCH ), 72.25〜74.67(C of ^tBu)。 S/Nが悪いため、Si-Me基の13Cシグナルは確認できなかった。 Example 2
Reaction of 1,1,3,3,5,5-hexamethyltrisiloxane with t-BVE

A magnetic stirring bar, AceRu ₃ (CO) ₇ (2.15 mg, 0.0033 mmol) was added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.056 mL) was added with a microsyringe to dissolve the complex. When 1,1,3,3,5,5-hexamethyltrisiloxane (0.008 mL, 0.033 mmol) was added to this complex solution and stirred for 30 minutes, the color of the solution changed from dark orange to light orange. Next, 1000 equivalent of t-BVE (0.43 mL, 3.3 mmol,) was added and stirred at room temperature. A rapid increase in the viscosity of the solution with an exotherm was observed. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalent t-BVE was newly added, and this was repeated until the polymerization did not proceed (18000 equivalents relative to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain a polymer (4.05 g). When the produced polymer was measured by ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR, disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained.
Mn = 9000, Mw = 16000, Mw / Mn = 1.84 (GPC, polystyrene equivalent)
Mn = 111000 ⁽¹ HNMR)
Mn = 124000 (theory)
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
Dept J = 11Hz δ-21.63, -21.72 (In addition, multiple peaks due to multiple tacticities appeared)
The disappearance of Inept J = 210 Hz Si-H peak (−6.40 ppm) was confirmed.
IR Si-H peak (2126cm ^-1 ) Disappeared.
¹ H NMR (600 MHz, C ₆ D ₆ , rt): Signal based on polymer chain: δ 0.93 to 1.45 (br, 9H, CH ₃ of ^t Bu), 1.55 to 2.21 (br, 2H, CH based on polymer chain ₂ ), 3.54 to 3.94 (broad 1H, CH of the polymer chain), a small peak of the terminal silyl group was observed at δ 0.09 to 0.21 (m, 18H, SiMe) ¹³ C NMR (150 MHz, C ₆ D ₆ , rt) Only the peak of the polymer chain was observed with the following shift: δ 28.33-30.83 (CH ₃ of ^t Bu), 44.83-47.30 (CH _{2 of the} polymer chain), 66.08-68.61 (CH of the polymer chain), 72.25-74.67 (C of ^t Bu). Due to poor S / N, 13C signal of Si-Me group could not be confirmed.

30mＬ二口フラスコに、磁気撹拌子、AceRu₃(CO)₇（2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.056 mＬ）をマイクロシリンジで加えて錯体を溶解した。この錯体溶液に、メチルハイドロジェンポリシロキサン（0.021ｍL, 0.033 mmol）を加えて30分撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、1000当量のt-BVE（0.43 mL, 3.3 mmol, 1000e.q.）を加え、室温で撹拌した。発熱を伴う溶液の粘度の急激な増加が観察された。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して20000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリマー（4.85g）を得た。生成したポリマーを¹HNMR, ¹³CNMR, ²⁹SiNMR, IRで測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。図１に¹H-NMスペクトル、図２に¹³C-NMRスペクトル、図３にD DEPTスペクトル、図４にINEPTスペクトル、図５にIRスペクトル（右側は出発原料のシロキサンのスペクトル）、図６にGPCチャートを示す。
Mn = 6000, Mw = 12000, Mw/Mn = 1.95(GPC 、ポリスチレン換算)
Mn = 130000(¹HNMR)
Mn = 150000(理論)
²⁹SiNMR(119MHz, C₆D₆, r.t.)
(Dept J=11Hz) δ-15.31, -20.34, -21.28, -21.63, -21.75, -21.86, -21.91, -22.09, -22.31(その他、図３に示すように複数のタクティシティによる複数のピークが表れた)
(Inept J=198Hz) Si-H peak( -6.83ppm )の消失を確認した。
IR Si-H peak( 2127cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): .): ポリマー鎖に基くシグナル: δ 0.91〜1.46 (b, br, 9H, CH₃ of ^tBu), 1.57〜2.12 (ポリマー鎖のc, br, 2H, CH₂), 3.57〜3.95 (ポリマー鎖のbr，1H, CH), 末端シリル基の小さなピークが・ 0.09〜0.19に観察された(a, m, 48H, SiMe) ¹³C NMR (150 MHz, C₆D₆, r.t.) ポリマー鎖のピークのみ以下のシフトに観察された: δ28.33〜30.62 (B, CH₃ of ^tBu), 45.17〜47.09 (ポリマー鎖のC, CH₂), 66.49〜68.56 (ポリマー鎖のD, CH), 72.38〜74.05(E, C of ^tBu), 1.33, 2.14(SiCH₃) Example 3
Reaction of t-BVE with methylhydrogenpolysiloxane containing SiH groups at both ends

A magnetic stirring bar, AceRu ₃ (CO) ₇ (2.15 mg, 0.0033 mmol) was added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.056 mL) was added with a microsyringe to dissolve the complex. When methylhydrogenpolysiloxane (0.021 mL, 0.033 mmol) was added to this complex solution and stirred for 30 minutes, the color of the solution changed from dark orange to light orange. Next, 1000 equivalent of t-BVE (0.43 mL, 3.3 mmol, 1000 e.q.) was added, and the mixture was stirred at room temperature. A rapid increase in the viscosity of the solution with an exotherm was observed. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalent t-BVE was newly added, and this was repeated until the polymerization did not proceed (20,000 equivalents relative to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain a polymer (4.85 g). When the produced polymer was measured by ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR, disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained. ¹ H-NM spectrum in FIG. 1, ¹³ C-NMR spectrum in FIG. 2, D DEPT spectrum in FIG. 3, INEPT spectra in Figure 4, IR spectrum in FIG. 5 (right spectrum of the siloxane starting material), 6 A GPC chart is shown.
Mn = 6000, Mw = 12000, Mw / Mn = 1.95 (GPC, polystyrene equivalent)
Mn = 130000 ⁽¹ HNMR)
Mn = 150000 (theory)
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
(Dept J = 11Hz) δ-15.31, -20.34, -21.28, -21.63, -21.75, -21.86, -21.91, -22.09, -22.31 (In addition, multiple peaks with multiple tacticities as shown in Fig. 3 Appeared)
(Inept J = 198 Hz) The disappearance of Si-H peak (−6.83 ppm) was confirmed.
IR Si-H peak (2127cm ^-1 ) Disappeared.
¹ H NMR (600 MHz, C ₆ D ₆ , rt):.): Signal based on polymer chain: δ 0.91 ~ 1.46 (b, br, 9H, CH ₃ of ^t Bu), 1.57 ~ 2.12 (c of polymer chain , br, 2H, CH ₂ ), 3.57 to 3.95 (br, 1H, CH of polymer chain), small peak of terminal silyl group was observed at 0.09 to 0.19 (a, m, 48H, SiMe) ¹³ C NMR (150 MHz, C ₆ D ₆ , rt) Only the peak of the polymer chain was observed in the following shift: δ 28.33-30.62 (B, CH ₃ of ^t Bu), 45.17-47.09 (C, CH _{2 of the} polymer chain ), 66.49-68.56 (D, CH of polymer chain), 72.38-74.05 (E, C of ^t Bu), 1.33, 2.14 (SiCH ₃ )

30mＬ二口フラスコに、磁気撹拌子、AceRu₃(CO)₇（2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.10mＬ）をマイクロシリンジで加えて錯体を溶解した。この錯体溶液に、リビング重合で合成したオリゴジメチルシロキサン（Mn = 858 (¹HNMR), 0.062ｍL, 0.066 mmol）を加えて30分、40℃で撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、1000当量のt-BVE（0.43 mL, 3.3 mmol,）を加え、40℃で撹拌した。溶液の粘度の増加が観察された。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して4000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリ（t-BVE）（0.96g）を得た。生成したポリマーの¹HNMR, ¹³CNMR, ²⁹SiNMR, IRスペクトルを測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。
Mn = 15000(¹HNMR)
Mn = 15900(理論)
²⁹SiNMR(119MHz, C₆D₆, r.t.)
(Dept J=11Hz) δ7.96（OSiMe₂n-Bu), -20.22, -21.34, -21.52, -21.55, -21.60, -21.75, -22.21(その他、複数のタクティシティによる複数のピークが表れた)
(Inept J=198Hz) Si-H peak(-6.60, -6.64ppm)の消失を確認した。
IR Si-H peak( 2125cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): ポリマー鎖に基くシグナル: δ 0.97〜1.54 (br, 9H, CH₃ of ^tBu), 1.61〜2.19 ポリマー鎖のブロードな2H, CH₂), 3.65〜4.08 (ポリマー鎖のbr,1H, CH), 末端シリル基の小さなピークが・ 0.13(bs), 0.16(bs), 0.17〜0.25(bm), に観察された( 33H, SiMe), 0.55〜0.62(n-Bu のブロードな2H, CH₂), 0.88〜0.93(br, 3H, CH₃ of n-Bu) ¹³C NMR (150 MHz, C₆D₆, r.t.): δ 29.20〜30.41 (CH₃ of ^tBu), 45.07〜47.13 (ポリマー鎖のCH₂), 66.50〜68.82 (ポリマー鎖のCH ), 72.59〜74.05(n-Bu のC), 26.73, 25.85, 18.30, 14.03 (n-Bu), 2.13, 1.43, 1.37, 1.34, 0.40 (SiCH₃) Example 4
Reaction of oligodimethylsiloxane synthesized by living polymerization with t-BVE

A magnetic stirring bar, AceRu ₃ (CO) ₇ (2.15 mg, 0.0033 mmol) was added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.10 mL) was added with a microsyringe to dissolve the complex. To this complex solution, oligodimethylsiloxane (Mn = 858 ( ¹ HNMR), 0.062 mL, 0.066 mmol) synthesized by living polymerization was added and stirred for 30 minutes at 40 ° C. The color of the solution changed from dark orange to light orange. And changed. Next, 1000 equivalent of t-BVE (0.43 mL, 3.3 mmol,) was added, and the mixture was stirred at 40 ° C. An increase in the viscosity of the solution was observed. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalents of t-BVE was newly added, and this was repeated until the polymerization did not proceed (4000 equivalents to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain poly (t-BVE) (0.96 g). As a result of measuring ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR spectrum of the produced polymer, the disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained.
Mn = 15000 ⁽¹ HNMR)
Mn = 15900 (theory)
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
(Dept J = 11Hz) δ7.96 (OSiMe ₂ n-Bu), -20.22, -21.34, -21.52, -21.55, -21.60, -21.75, -22.21 (Other multiple peaks due to multiple tacticity appear ()
(Inept J = 198 Hz) The disappearance of Si-H peak (-6.60, -6.64 ppm) was confirmed.
The disappearance of IR Si-H peak (2125 cm ⁻¹ ) was confirmed.
¹ H NMR (600 MHz, C ₆ D ₆ , rt): Signal based on polymer chain: δ 0.97 to 1.54 (br, 9H, CH ₃ of ^t Bu), 1.61 to 2.19 Polymer chain broad 2H, CH ₂ ) , 3.65 ~ 4.08 (br, 1H, CH of polymer chain), small peaks of terminal silyl groups were observed at 0.13 (bs), 0.16 (bs), 0.17 ~ 0.25 (bm), (33H, SiMe), 0.55-0.62 (n-Bu broad 2H, CH ₂ ), 0.88-0.93 (br, 3H, CH ₃ of n-Bu) ¹³ C NMR (150 MHz, C ₆ D ₆ , rt): δ 29.20-30.41 (CH ₃ of ^t Bu), 45.07 to 47.13 (CH _{2 of} polymer chain), 66.50 to 68.82 (CH of polymer chain), 72.59 to 74.05 (C of n-Bu), 26.73, 25.85, 18.30, 14.03 (n- Bu), 2.13, 1.43, 1.37, 1.34, 0.40 (SiCH ₃ )

30mＬ二口フラスコに、磁気撹拌子、AceRu₃(CO)₇（2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.056 mＬ）をマイクロシリンジで加えて錯体を溶解した。この錯体溶液に、テトラメチルシクロシロキサン（0.004ｍL, 0.017 mmol）を加えて30分撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、1000当量のt-BVE（0.43 mL, 3.3 mmol,）を加え、室温で撹拌した。発熱を伴う溶液の粘度の急激な増加が観察された。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して17000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリマー（2.12g）を得た。生成したポリマーを¹HNMR, ¹³CNMR, ²⁹SiNMR, IRで測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。
Mn = 8600, Mw = 16000, Mw/Mn = 1.92(GPC 、ポリスチレン換算)
Mn = 37000(¹HNMR)
Mn = 130000(理論)消費したモノマー/使用したSiloxaneのモル数から算出した値である。
²⁹SiNMR(119MHz, C₆D₆, r.t.)
(Dept J=11Hz) δ-21.78, -21.86 (Siがタクティシティの影響のため複数のピークが表れる)
(Inept J=198Hz) Si-H peak( -31.69, -31.72, -32.01, -32.38ppm、cis, trans体 )の消失を確認
IR Si-H peak( 2128cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): ポリマー鎖に基くシグナル: δ0.81〜1.40 (br, 9H, CH₃ of ^tBu), 1.45〜2.14 (ポリマー鎖のブロードな2H, CH₂), 3.43〜3.88 (ポリマー鎖のブロードな1H, CH), 末端シリル基の小さなピークがδ 0.11に観察された (s, 12H, SiMe) ¹³C NMR (150 MHz, C₆D₆, r.t.): δ 28.88〜30.44 (^tBu のCH₃ ), 45.01〜47.16 (ポリマー鎖のCH₂), 66.49〜68.85 (ポリマー鎖のCH), 72.55〜73.81(^tBu のC), 1.29, 1.21(SiCH₃) Example 5
Polymerization of tetramethylcyclosiloxane and t-BVE

A magnetic stirring bar, AceRu ₃ (CO) ₇ (2.15 mg, 0.0033 mmol) was added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.056 mL) was added with a microsyringe to dissolve the complex. When tetramethylcyclosiloxane (0.004 mL, 0.017 mmol) was added to this complex solution and stirred for 30 minutes, the color of the solution changed from dark orange to light orange. Next, 1000 equivalent of t-BVE (0.43 mL, 3.3 mmol,) was added and stirred at room temperature. A rapid increase in the viscosity of the solution with an exotherm was observed. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalents of t-BVE was newly added, and this was repeated until the polymerization did not proceed (17000 equivalents relative to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain a polymer (2.12 g). When the produced polymer was measured by ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR, disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained.
Mn = 8600, Mw = 16000, Mw / Mn = 1.92 (GPC, polystyrene equivalent)
Mn = 37000 ⁽¹ HNMR)
Mn = 130000 (theoretical) Calculated from the number of moles of consumed monomer / siloxane used.
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
(Dept J = 11Hz) δ-21.78, -21.86 (Several peaks appear due to the influence of tacticity in Si)
Confirmed the disappearance of (Inept J = 198Hz) Si-H peak (-31.69, -31.72, -32.01, -32.38ppm, cis, trans isomers)
IR Si-H peak (2128cm ^-1 ) Disappeared.
¹ H NMR (600 MHz, C ₆ D ₆ , rt): Signal based on polymer chain: δ0.81 to 1.40 (br, 9H, CH ₃ of ^t Bu), 1.45 to 2.14 (broad polymer chain 2H, CH ₂ ), 3.43 to 3.88 (broad 1H, CH of the polymer chain), a small peak of terminal silyl group was observed at δ 0.11 (s, 12H, SiMe) ¹³ C NMR (150 MHz, C ₆ D ₆ , rt ): δ 28.88-30.44 (CH _{3 of} ^t Bu), 45.01-47.16 (CH _{2 of} polymer chain), 66.49-68.85 (CH of polymer chain), 72.55-73.81 (C of ^t Bu), 1.29, 1.21 (SiCH ₃ )

30mＬ二口フラスコに、磁気撹拌子、AceRu₃(CO)₇（2.15mg, 0.0033 mmol）を加えて、フラスコ内をアルゴン雰囲気に置換した。1,4-ジオキサン（0.2mＬ）をガスタイトシリンジで加えて錯体を溶解した。この錯体溶液に、上記のメチルハイドロジェンポリシロキサン（0.11ｍL, 0.022mmol）を加えて30分、40℃で撹拌すると、溶液の色が濃橙色からうすい橙色へと変化した。つぎに、1000当量のt-BVE（0.43 mL, 3.3 mmol,）を加え、40℃で撹拌した。H-NMRでt-BVE の残量がほぼ認められなくなった後に、新たに1000当量t-BVE を加え、重合が進まなくなるまでこれを繰り返した（錯体に対して2000等量）。反応後に溶液を10^-3Torrの減圧下で乾燥させることにより、ポリ（t-BVE）（0.35g）を得た。生成したポリマーを¹HNMR, ¹³CNMR, ²⁹SiNMR, IRで測定したところSi-Hピークの消失が確認され、対応するポリマーの構造に適合したシグナルが得られた。
Mn = 20000(¹HNMR)
Mn = 21000(理論) （消費したモノマー／使用したシロキサンのモル数から算出した値である）
²⁹SiNMR(119MHz, C₆D₆, r.t.)
(Dept J=11Hz) δ7.56・OSiMe₃), -21.03, -21.08, -21.48, -21.65, -21.81(その他のSiがタクティシティの影響のため複数のピークが表れる)
(Inept J=239Hz) Si-H peak(-37.21ppm)の消失を確認した。
IR Si-H peak( 2160cm^-1 )の消失を確認した。
¹H NMR (600 MHz, C₆D₆, r.t.): ポリマー鎖に基くシグナル: δ 1.07〜1.53 (br, 9H, CH₃ of ^tBu), 1.68〜2.22 (ポリマー鎖のブロードな2H, CH₂), 3.68〜4.08 (ポリマー鎖のbr,1H, CH), 末端シリル基の小さなピークがδ 0.09〜0.43に観察された (m, 387H, SiMe) ¹³C NMR (150 MHz, C₆D₆, r.t.): δ28.30〜30.90 (CH₃ of ^tBu), 45.39〜47.20 (ポリマー鎖のCH₂), 66.55〜68.79 (ポリマー鎖のCH), 72.71〜73.98(C of ^tBu), 0.96(bs), 1.09(bs), 1.18, 1.22, 1.35(bs), 1.59, 1.94(SiCH₃) Example 6
Polymerization of side chain Si-H group-containing methylhydrogenpolysiloxane and t-BVE

A magnetic stirring bar, AceRu ₃ (CO) ₇ (2.15 mg, 0.0033 mmol) was added to a 30 mL two-necked flask, and the inside of the flask was replaced with an argon atmosphere. 1,4-Dioxane (0.2 mL) was added with a gas tight syringe to dissolve the complex. When the above-mentioned methyl hydrogen polysiloxane (0.11 mL, 0.022 mmol) was added to this complex solution and stirred at 40 ° C. for 30 minutes, the color of the solution changed from dark orange to light orange. Next, 1000 equivalent of t-BVE (0.43 mL, 3.3 mmol,) was added, and the mixture was stirred at 40 ° C. After almost no remaining amount of t-BVE was observed by H-NMR, 1000 equivalent t-BVE was newly added, and this was repeated until the polymerization did not proceed (2000 equivalents to the complex). After the reaction, the solution was dried under reduced pressure of 10 ⁻³ Torr to obtain poly (t-BVE) (0.35 g). When the produced polymer was measured by ¹ HNMR, ¹³ CNMR, ²⁹ SiNMR, and IR, disappearance of the Si-H peak was confirmed, and a signal suitable for the structure of the corresponding polymer was obtained.
Mn = 20000 ⁽¹ HNMR)
Mn = 21000 (theory) (value calculated from the number of moles of monomer consumed / number of siloxanes used)
²⁹ Si NMR (119 MHz, C ₆ D ₆ , rt)
(Dept J = 11Hz) δ7.56 ・ OSiMe ₃ ), -21.03, -21.08, -21.48, -21.65, -21.81 (multiple peaks appear due to tacticity of other Si)
(Inept J = 239 Hz) The disappearance of Si-H peak (-37.21 ppm) was confirmed.
IR Si-H peak (2160cm ^-1 ) Disappeared.
¹ H NMR (600 MHz, C ₆ D ₆ , rt): Signal based on polymer chain: δ 1.07 to 1.53 (br, 9H, CH ₃ of ^t Bu), 1.68 to 2.22 (polymer chain broad 2H, CH ₂ ), 3.68 to 4.08 (br, 1H, CH of polymer chain), a small peak of terminal silyl group was observed at δ 0.09 to 0.43 (m, 387H, SiMe) ¹³ C NMR (150 MHz, C ₆ D ₆ , rt): δ 28.30-30.90 (CH ₃ of ^t Bu), 45.39-47.20 (CH _{2 of} polymer chain), 66.55-68.79 (CH of polymer chain), 72.71-73.98 (C of ^t Bu), 0.96 (bs ), 1.09 (bs), 1.18, 1.22, 1.35 (bs), 1.59, 1.94 (SiCH ₃ )

  According to the method of the present invention, a polymer having an organopolysiloxane moiety and a polyvinyl ether moiety can be efficiently obtained. The polymer may be useful for cosmetics, coating agents, surfactants and the like.

3 is a ¹ H-NM spectrum of the polymer obtained in Example 3. 3 is a ¹³ C-NMR spectrum of the polymer obtained in Example 3. 3 is a DEPT spectrum of the polymer obtained in Example 3. 4 is an INEPT spectrum of the polymer obtained in Example 3. FIG. 2 shows the IR spectrum of the polymer obtained in Example 3 and the IR spectrum of the starting siloxane. 4 is a GPC chart of the polymer obtained in Example 3.

Claims (6)

An organohydrogenpolysiloxane having at least one Si—H bond, and a vinyl ether represented by the following formula (1) in a molar amount larger than the total molar amount of the Si—H bond:
R ¹ ₂ C═C (R ¹ ) —OR ² (1)
(In Formula (1), R ¹ is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and R ² is an alkyl group having 1 to 10 carbon atoms, aryl. Group, aralkyl group, or silyl group),
A method for producing a polymer in which polyvinyl ether is bonded to the organopolyhydrogenpolysiloxane residue by reacting in the presence of a polynuclear ruthenium carbonyl complex having 2 to 4 ruthenium atoms. [1] A step of mixing the polynuclear ruthenium carbonyl complex and the organohydrogenpolysiloxane in an amount such that the polynuclear ruthenium carbonyl complex is 1/200 to 1/10 mol with respect to 1 mol of the SiH bond of the organohydrogenpolysiloxane. And [2] adding vinyl ether to the mixture obtained in step [1] in an amount of 100 to 5,000 mol per mol of the polynuclear ruthenium carbonyl complex,
[3] After the added vinyl ether is no longer detected by ¹ H-NMR, repeated addition of new vinyl ether in an amount of 100 to 5,000 moles per mole of the polynuclear ruthenium carbonyl complex is repeated. Process,
The method of claim 1 comprising: The method according to claim 1 or 2, wherein the organohydrogenpolysiloxane has 4 to 500 silicon atoms. The method according to any one of claims 1 to 3, wherein the organohydrogenpolysiloxane is represented by the following formula (2).

(R ³ is, independently of one another, an alkyl group having 1 to 30 carbon atoms, an aryl group, or an aralkyl group, which may be substituted with a halogen atom, and R ⁴ is a hydrogen atom or R ³ , provided that d When is 0, at least one of R ⁴ is a hydrogen atom, c is an integer of 0 to 1000, d is an integer of 0 to 1000, provided that 2 ≦ c + d) The method according to any one of claims 1 to 4, wherein the vinyl ether is t-butyl vinyl ether. Catalyst, any one SL mounting method of claim 1, wherein the polynuclear ruthenium-carbonyl complex represented by the following formula (A) or the following formula (B).

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