JP2008031147A - Modified free-acid type heteropolyacid, modified heteropolyacid salt and free-acid type heteropolyacid-based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a free-acid type heteropolyacid-based polymer usable as an acid catalyst to be readily recovered and reused. <P>SOLUTION: The modified free-acid type heteropolyacid represented by general formula (1) H<SB>m</SB>[XY]-nH<SB>2</SB>O (1) [X is a heteropolyanion in which a backbone constituent atom is partially deficient; Y is a metal group containing a reactive organic functional group; n is an integer of ≥1; m is an integer of ≥1 and is the absolute value of negative charge determined from [XY] in the general formula (1)] is homopolymerized or copolymerized to give the free-acid type heteropolyacid-based polymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a modified free acid type heteropolyacid that can be used as an acid catalyst, a modified heteropolyacid salt as an intermediate material thereof, and a free acid type heteropolyacid polymer using the heteropolyacid.

  Heteropolyacid salts have a structure in which skeleton constituent atoms such as W and Mo are coordinated through oxygen atoms centered on heteroatoms such as P, Si, As, Ge, and S in which four oxygen atoms are coordinated. is there. It is known that the heteropolyacid salt having such a structure can be partially substituted with a different metal by deleting a part of the skeleton constituent atoms. Such a deficient heteropoly acid salt and a heteropoly acid salt substituted with a different oxidation metal having a lower oxidation number have a negative charge density on the surface, which is higher than that of a normal heteropoly acid salt. It is used as

  There are many examples of catalyst utilization of deficient and substituted heteropolyacid salts, many of which are used as oxidation catalysts. For example, an oxidation reaction of alcohol by a Ru substituent is known (Patent Document 1).

However, what is important for industrial use and has been put into practical use is the use as an acid catalyst using a free acid type heteropolyacid obtained by exchanging the countercation of the heteropolyanion with H ⁺ . For example, ring-opening polymerization of tetrahydrofuran is mentioned (Patent Document 2).

Many examples of heteropolyacids as acid catalysts that are useful for industrial applications often use unsubstituted free acid types. For _{example, H 3 [PW 12 O 40} ], H 3 [PMo 12 O 40], H 4 [SiW 12 O 40], H 4 [SiMo 12 O 40] , and the like.

JP 2003-261493 A (Claims) JP 59-215320 A (Example)

  However, these acid catalysts using heteropolyacids are dissolved in a solvent, and there is a problem that they are difficult to recover and reuse.

  In addition, since free acid type heteropolyacid has excellent proton transport ability, it is expected to be used as an antistatic agent when it is contained in a coating film, but it is prone to bleed out from the coating film and cannot maintain antistatic performance. was there.

  Accordingly, a method of physically immobilizing the heteropolyacid by mixing with a carrier such as a polymer or silica, and a method of immobilizing the heteropolyacid to the quaternary ammonium salt type silane coupling agent by an electrostatic charge effect are conceivable.

  However, there is a problem that the bleed-out cannot be sufficiently prevented by the method of physically mixing, and the bleed-out can be prevented by substitution with a compound having a stronger charge in the method of fixing by electrostatic charge action. There was a problem that it could not be prevented.

  Therefore, the present invention provides a modified free acid type heteropolyacid that can solve the above problems by homopolymerization or copolymerization, a heteropolyacid salt that is an intermediate material thereof, and a free acid type heteropolyacid using the heteropolyacid. An object is to provide an acid polymer.

  The modified free acid type heteropolyacid of the present invention that solves the above-mentioned problems is one in which a metal group having a reactive organic functional group is introduced into a partially deficient site of the skeleton constituent atom of the heteropolyacid.

The modified free acid heteropolyacid of the present invention is represented by the general formula (1).
H _m [XY] · nH ₂ O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, and Y is a metal group having a reactive organic functional group. n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and is the absolute value of the negative charge determined from [XY] in the general formula (1). ]

  In addition, the modified heteropolyacid salt of the present invention is one in which a metal group having a reactive organic functional group is introduced into a partially deficient site of the skeleton constituent atom of the heteropolyacid salt.

The modified heteropolyacid salt of the present invention is represented by the general formula (2).
R _m [XY] (2)
[Wherein, R is selected from the group of Bu ₄ N ⁺ , Me ₂ NH ₂ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , and X is a heteropolyanion in which a part of the skeleton constituent atoms is missing] Y is a metal group having a reactive organic functional group. m is an integer of 1 or more, and is an absolute value of the negative charge determined from [XY] in the general formula (2). ]

  The free acid heteropolyacid polymer of the present invention is obtained by homopolymerizing or copolymerizing the modified free acid heteropolyacid.

  The modified free acid type heteropolyacid of the present invention can be easily obtained by homopolymerization or copolymerization because a metal group having a reactive organic functional group is introduced at a part of the deficient site of the skeleton constituting atom of the heteropolyacid. It can be a polymer.

  The free acid heteropolyacid polymer of the present invention, which is a polymer, has an acid catalyst that can be easily recovered and reused, an antistatic agent that hardly causes bleed out from the coating film, and bleed out from the separator. It can be suitably used as a proton transfer agent to be contained in a separator of a fuel cell that hardly occurs.

  The modified heteropolyacid salt of the present invention can easily obtain the modified free acid type heteropolyacid of the present invention by cation exchange.

  Embodiments of the present invention will be described below.

  First, an embodiment of the modified free acid heteropolyacid of the present invention will be described. The modified free acid type heteropolyacid of the present invention is obtained by introducing a metal group having a reactive organic functional group into a partially deficient site of the skeleton constituting atom of the heteropolyacid.

  Such a modified free acid type heteropolyacid has a metal group having a reactive organic functional group introduced in the deficient portion of the skeleton constituent atom, so it can be homopolymerized itself or has a reactive functional group By copolymerizing with other monomer / polymer / heteropolyacid, a free acid type heteropolyacid polymer can be obtained.

Examples of such a modified free acid type heteropolyacid include those represented by the general formula (1).
H _m [XY] · nH ₂ O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, and Y is a metal group having a reactive organic functional group. n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and is the absolute value of the negative charge determined from [XY] in the general formula (1). ]

X in the general formula (1) represents a heteropolyanion in which a part of the skeleton constituent atoms is missing. Examples of such heteropolyanions include P ₂ W ₁₇ O ₆₁ , PW ₁₁ O ₃₉ , γ-PW ₁₀ O ₃₆ , SiW ₁₁ O ₃₉ , γ-SiW ₁₀ O ₃₆ , and GeW ₁₁ O ₃₉ .

  Y in the general formula (1) represents a metal group having a reactive organic functional group.

  Examples of the reactive organic functional group include a hydroxyl group, a (meth) acryl group, a vinyl group, an epoxy group, a styryl group, a (meth) acryloxy group, an amino group, a mercapto group, and an isocyanate group. Among these functional groups, the (meth) acryl group, vinyl group, styryl group, and (meth) acryloxy group, which are groups having an unsaturated double bond, are homopolymerized themselves or have an unsaturated double bond. This is preferable in that it can be easily copolymerized with other monomers, polymers and heteropolyacids. Among these, it is particularly preferable to use a (meth) acryl group.

  Examples of the metal group include hydrolysates of metal alkoxides and metal chlorides. Among these, a hydrolyzate of a metal alkoxide is preferable in the process for producing a modified heteropolyacid.

  Specific examples of the hydrolyzate of metal alkoxide include hydrolysates such as silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconium coupling agents. Among these, it is preferable to use a hydrolyzate of a silane coupling agent from the viewpoint of the variety of reactive functional groups, good handleability, and availability. Specific examples of the metal chloride include titanium chloride, silyl chloride, and tin chloride.

Specific examples of Y in the general formula (1) include {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O, {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O, {CH ₂ CHSi } ₂ O, {CH ₂ CHC ₆ H ₄ Si} ₂ O, {CH ₂ (O) CHCH ₂ O (CH ₂ ) ₃ Si} ₂ O, {NH ₂ (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si } ₂ O, {NH ₂ (CH ₂ ) ₃ Si} ₂ O, {SH (CH ₂ ) ₃ Si} ₂ O, {OCN (CH ₂ ) ₃ Si} ₂ O, and the like. Further, those in which Si of Y is changed to Ti, Al, or Zr are also included.

Further, as shown by the general formula (1), the counter cation of the heteropolyanion of the general formula (1) is H ⁺ . Thus, by using a free acid type heteropolyacid having a counter cation as H ⁺ , the catalytic activity as an acid catalyst can be improved. Further, the free acid type heteropolyacid can be used as an antistatic agent having excellent antistatic performance, and further, by containing it in the separator of the fuel cell, the proton transport ability of the fuel cell can be improved. .

Specific examples of the modified free acid heteropolyacid represented by the general formula (1) include those represented by the following general formula (3).
H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O (3)

  The modified free acid type heteropolyacid of the general formula (1) can be obtained, for example, by introducing a metal group having a reactive organic functional group as described above into a partially deficient site of the skeleton constituent atom of the heteropolyacid. Can do.

Specifically, a skeletal constituent atom such as K ₁₀ [P ₂ W ₁₇ O ₆₁ ] separately synthesized is partly dissolved in a solution in which a metal alkoxide having a reactive organic functional group is dissolved in a mixture of water and alcohol. Add the stoichiometric amount of the missing heteropolyacid salt and stir. Next, the pH of the solution is adjusted to about 3 or less with hydrochloric acid. By this operation, the metal alkoxide is hydrolyzed in the reaction system, and the hydrolyzate is introduced into a partially deficient site of the skeleton constituent atom of the heteropolyacid salt by a dehydration condensation reaction. A counter cation such as Me ₂ NH ₂ ⁺ is then added to the resulting solution to form a heteropolyacid salt as a precipitate. The produced precipitate can be filtered off and sufficiently dried under vacuum to obtain a modified heteropolyacid salt as a powder. Next, using a cation exchange resin (Amberlite 120NBA: Rohm & Haas, etc.), the counter cation of the heteropolyacid salt is cation-exchanged, whereby the general formula (1) having H ⁺ as the counter cation The modified free acid type heteropolyacid can be produced.

  In addition, the heteropolyacid salt in which the skeleton constituent atoms are partially lost can be obtained by referring to known literature. For example, R.A. Contant, Inorg. Synth. 27, 104, 1990. (America).

Next, an embodiment of the modified heteropolyacid salt of the present invention will be described. The modified heteropolyacid salt of the present invention is obtained by introducing a metal group having a reactive organic functional group into a partially deficient site of the skeleton constituent atom of the heteropolyacid salt. Such a modified heteropolyacid salt becomes an intermediate material of the above-described free acid heteropolyacid of the present invention. Specifically, the modified free acid heteropolyacid of the present invention described above can be obtained by substituting the counter cation of the modified heteropolyacid salt with H ⁺ using a cation exchange resin.

Examples of such a modified heteropolyacid salt include those represented by the general formula (2).
R _m [XY] (2)
[Wherein, R is selected from the group of Bu ₄ N ⁺ , Me ₂ NH ₂ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , X is a heteropolyanion in which a part of the skeleton constituent atoms is partially lost Y is a metal group having a reactive organic functional group. m is an integer of 1 or more, and is an absolute value of the negative charge determined from [XY] in the general formula (2). ]

  X and Y in the general formula (2) are the same as X and Y in the general formula (1) described above. Such modified heteropolyacid salts may also be hydrates.

  The method for producing the modified heteropolyacid salt of the present invention is the same as the method for producing the modified free acid heteropolyacid of the present invention described above, except for cation exchange which is the final step.

  Next, an embodiment of the free acid type heteropolyacid polymer of the present invention will be described. The free acid type heteropolyacid polymer of the present invention is obtained by homopolymerizing or copolymerizing the above-described modified free acid type heteropolyacid of the present invention.

  The polymerization can be performed by reaction of a reactive organic functional group. In the case of copolymerization, the partner monomer / polymer / heteropolyacid may be any one having a functional group capable of reacting with the reactive organic functional group of the modified free acid type heteropolyacid. Examples of such monomers, polymers, and heteropolyacids include hydroxyl groups, (meth) acryl groups, vinyl groups, epoxy groups, styryl groups, (meth) acryloxy groups, amino groups, mercapto groups, and isocyanato groups in the side chain. What you have.

  Hereinafter, a copolymerization reaction between a modified free acid type heteropolyacid obtained by introducing a metal group having an unsaturated double bond and another monomer having an unsaturated double bond (acrylic monomer) will be described as an example. .

  First, prepare a three-necked flask containing a predetermined amount of reaction solvent, a modified free acid type heteropolyacid introduced with a metal group having an unsaturated double bond, a general-purpose acrylic monomer and a polymerization initiator, and react while stirring. The system is replaced with nitrogen. After nitrogen substitution, the flask is added to a 75 ° C. oil bath and the system is heated. The mixture is heated and stirred for 4 hours while keeping the temperature of the oil bath at 75 ° C. After 4 hours, the reaction solution is allowed to cool to room temperature, and the solution is added dropwise to a large amount of methanol to reprecipitate the polymer. After stirring overnight, the precipitate is separated and sufficiently dried by suction, whereby a free acid heteropolyacid polymer obtained by copolymerizing a modified free acid heteropolyacid and an acrylic monomer can be obtained.

  The above-described polymerization method is based on a solution polymerization method, but can also be performed by a different polymerization method such as bulk polymerization.

  For example, a UV-curable acrylic oligomer, acrylic monomer, and modified free acid type heteropolyacid introduced with a metal group having a reactive organic functional group are uniformly mixed, and the photopolymerization initiator is uniformly mixed. Dissolve in. At this time, a solvent in which each component is dissolved may be used for viscosity adjustment.

  Next, by irradiating the prepared solution with ultraviolet light (if a diluting solvent is used, the solvent is removed by hot air drying before ultraviolet irradiation), the ultraviolet curable acrylic oligomer, the acrylic monomer, and the reactivity A free acid heteropolyacid polymer obtained by copolymerizing a modified free acid heteropolyacid into which a metal group having an organic functional group is introduced can be obtained. In addition, when irradiating an ultraviolet-ray to a solution, it is preferable to arrange | position to a desired shape by apply | coating a solution on base materials, such as a polyester film, and making it a thin film, or pouring into a type | mold. According to this bulk polymerization method, the ratio of the heteropolyacid component can be increased, which is preferable in that the catalyst activity, antistatic performance, and proton transport performance can be improved.

  The shape of the free acid type heteropolyacid polymer can be properly used according to the application. When used as an acid catalyst, it is preferably in the form of fine particles having excellent handleability. In this case, the average particle diameter of the fine particles is preferably 0.1 to 100 μm. By setting the average particle diameter in such a range, it is possible to facilitate the catalytic reaction and improve the handleability.

  As described above, the free acid type heteropolyacid polymer of the present invention can be obtained by homopolymerizing or copolymerizing the modified free acid type heteropolyacid of the present invention. The modified free acid type heteropolyacid and other heteropolyacids) are preferably 15% by weight or more of the whole polymer, more preferably 30% by weight or more, and further preferably 50% by weight or more. The upper limit is preferably 80% by weight or less.

  Such a free acid type heteropolyacid polymer of the present invention can be used as an acid catalyst that can be easily recovered and reused. Examples of the catalytic reaction include esterification reaction, alkylation reaction, acylation reaction of various compounds, alkene hydration reaction, alkene oxidation reaction, and the like. Furthermore, the free acid type heteropolyacid polymer of the present invention can be used as an antistatic agent that hardly causes bleed-out from a coating film, and a proton transport agent that is contained in a fuel cell separator that hardly causes bleed-out from a separator. it can. When used as an antistatic agent or proton transporting agent, the free acid type heteropolyacid polymer of the present invention may be formed into a single coating to form an antistatic layer or a separator, but may be mixed with another resin or the like. A coating film or a separator may be formed.

  The following examples further illustrate the present invention. “Parts” and “%” are based on weight unless otherwise specified.

[Example 1]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

Heteropolyacid salt modified with hydrolyzate of metal alkoxide having methacrylic group ((Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 6H ₂ O) production method will be described.

475 μL (2.0 mmol) of γ-methacryloxypropyltrimethoxysilane (CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ) was added to a mixed solvent of 150 mL of methanol and 50 mL of pure water. (R. Constant, Inorg. Synth., 27, 104, 1990) 5.0 g (1 mmol) of one-deficient Dawson-type Tungstopolyacid salt K ₁₀ [α ₂ -P ₂ W ₁₇ O ₆₁ ] · 19H ₂ O synthesized according to (R. Constant, Inorg. Synth., 27, 104, 1990). added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 30 minutes, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 70 mL using a rotary evaporator. An excessive amount of Me ₂ NH ₂ Cl (5.5 g, 67 mmol) was added to the concentrate to precipitate a powder. The precipitated powder was collected with a glass filter (G4) and sufficiently dried under vacuum to obtain 3.98 g (yield: 81.6%) of the target product as a white powder.

<FT-IR {KBr disk}>
1702 (m), 1629 (br, m) [H ₂ O], 1466 (m) [Me ₂ NH ₂ ], 1412 (w), 1327 (w), 1304 (w), 1186 (m), 1088 ( s), 1039 (m), 954 (s), 922 (w), 793 (vs), 566 (w), 527 (m) cm ⁻¹

^<31 P NMR>
{Solvent D ₂ O, 22.6 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-10.3, -13.3 ppm

^<1 H NMR>
{Solvent D ₂ O, 21.3 ° C, external standard: TSP substitution method}
δ 0.93-0.94, 1.93, 2.01-1.05, 2.74, 4.28-4.29, 5.69, 6.15 ppm

< ^13C NMR>
{Solvent D ₂ O, 26.3 ° C, external standard: DSS substitution method}
δ 19.3, 23.2, 36.5, 69.0, 128.4, 138.0 ppm

<CHN elemental analysis>
(Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 6H ₂ O

From the characterization results, it can be seen that the target product was synthesized as a single species.
Using this compound as a precursor, free acid was synthesized.

<Heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H Modified by Hydrolyzate of Metal Alkoxide Having Reactive Organic Functional Group Production of ₂ O (Substitution of Counter Cation of Modified Heteropolyacid Salt Obtained above)>

Heteropolyacid salt (Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 6H ₂ O 0.4 g (0.082 mmol) prepared above ) Was dissolved in 60 mL of pure water on a hot water bath. After cooling to room temperature, the drug was passed through 100 mL of an H ⁺ charged cation exchange resin (Amberlite 120NBA: Rohm and Haas). Furthermore, 100 mL of pure water was poured, and the liquid that came out was dried using a rotary evaporator. Furthermore, 0.3 g (yield: 80%) of the target product was obtained as an orange-yellow powder by vacuum drying.

<FT-IR {KBr disk}>
1686 (m), 1629 (br, w) [H ₂ O], 1419 (w), 1368 (w), 1306 (w), 1238 (w), 1189 (br, w), 1090 (s), 1039 (M), 957 (s), 915 (m), 805 (br, vs), 597 (w), 566 (w), 531 (m) cm ⁻¹

^<31 P NMR>
{Solvent D ₂ O, 23.1 ° C, external standard: 25% H ₃ PO ₄ aq. Replacement method}
δ-10.3, -13.3 ppm

^<1 H NMR>
{Solvent D ₂ O, 21.4 ° C, external standard: TSP substitution method}
δ 0.89-0.92, 1.91, 1.97-2.04, 4.25-4.26, 5.67, 6.13 ppm

< ^13C NMR>
{Solvent D ₂ O, 25.2 ° C, external standard: DSS substitution method}
δ9.72, 19.4, 23.3, 69.1, 128.5-129.0, 138.1, 172.0 ppm

<Solid ²⁹ Si NMR>
{CPMAS: 40 Hz, standard: substitution method polydimethylsilane-solid (-37.0 ppm), RT}
δ-53.0 ppm

<CHN elemental analysis>
H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O

From the result of the above characterization, it was confirmed that the target heteropoly acid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O was produced. confirmed.

<Coordination of heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O obtained in Example 1 and methyl methacrylate (MMA) Production of polymer>

30 mL of CH ₃ CN was added to a three-necked flask equipped with a cooling pipe, a nitrogen introduction pipe, and a thermometer, and the heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) _{3] obtained above.} Si} ₂ O] · 20H ₂ O 8 g (1.80 mmol) was dissolved. Further, 12 g (84 mmol) of methyl methacrylate (MMA) was added, and 0.03 g of azobisisobutyronitrile as a polymerization initiator was added and purged with nitrogen. After purging, the three-necked flask was placed in an oil bath and the internal temperature was kept at 75 ° C. for 4 hours. 500 mL of methanol was added to the solution with increased viscosity, and the precipitated powder was recovered by decantation and sufficiently dried in vacuum. 6.6 g (yield: 33.0%) of the target polymer was obtained as a white powder.

<FT-IR>
2994 (w), 2950 (w), 1723 (m), 1434 (m), 1386 (m), 1239 (s), 1190 (s), 1144 (s), 962 (m), 910 (m), 838 (m), 809 (m), 749 (m) cm ^-1

_{^{<31 P NMR in CD 3 CN}} >
δ-9.1, -12. 2 ppm

From the result of the above characterization, the heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O and MMA are copolymerized. It was confirmed that a free acid type heteropolyacid polymer was obtained.

[Example 2]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

First, a method for producing a heteropolyacid salt (Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ (CH ₂ CHSi) ₂ O] · 7H ₂ O modified with a hydrolyzate of a metal alkoxide having a vinyl group will be described. To do.

One-deficient Dawson-type Tungstopolyacid salt synthesized according to the same literature as Example 1 by adding 310 μL (2.0 mmol) of vinyltrimethoxysilane (CH ₂ CHSi (OCH ₃ ) ₃ ) to a mixed solvent of methanol 150 mL and pure water 50 mL 5.0 g (1 mmol) of K ₁₀ [α ₂ -P ₂ W ₁₇ O ₆₁ ] .19H ₂ O was added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 70 mL using a rotary evaporator. An excessive amount of Me ₂ NH ₂ Cl (5.5 g, 67 mmol) was added to the concentrate to precipitate a powder. The precipitated powder was collected by a membrane filter, washed twice with 5 mL of methanol, and further washed twice with 50 mL of diethyl ether. Further, 3.17 g (yield: 67.6%) of the target product was obtained as a fine white yellowish green powder by sufficiently sucking and drying.

<FT-IR {KBr disk}>
1617 (m), 1465 (s), 1437 (w), 1405 (W), 1272 (w), 1232 (w), 1090 (vs), 1069 (w), 1040 (s), 1017 (w), 954 (m), 919 (m), 792 (Br, s), 622 (w), 596 (w), 583 (w), 566 (w), 528 (m), 483 (w) cm ⁻¹

^<31 P NMR>
{Solvent D ₂ O, 23.4 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-10.3, -13.3 ppm

^<1 H NMR>
{Solvent D ₂ O, 23.5 ° C, Internal standard: DSS}
δ 6.05-6.12, 6.30, 6.33-6.35 ppm

< ^13C NMR>
{Solvent D ₂ O, 26.0 ° C, external standard: DSS substitution method}
δ36.5, 130.6, 140.5 ppm

^<29 Si NMR>
{Solvent DMSO-d ₆ , 26.0 ° C, external standard: TMS substitution method}
δ-67.6 ppm

< ¹⁸³ W NMR>
{Solvent DMSO-d ₆ , 20.0 ° C, external standard: saturated Na ₂ WO ₄ aq. Replacement method}
δ-116.6, −161.7, −163.6, −164.1, −173.3, −178.9, −198.6, −317.3 ppm

<CHN elemental analysis>
(Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ (CH ₂ CHSi) ₂ O] · 7H ₂ O

  From the characterization results, it can be seen that the target product was obtained as a single species. Using this compound as a precursor, free acid was synthesized.

<Production of heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ (CH ₂ CHSi) ₂ O] · 22H ₂ O modified with a hydrolyzate of metal alkoxide having a reactive organic functional group>

The heteropoly acid salt (Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {(CH ₂ CHSi) ₂ O}] · 7H ₂ O 2.0 g (0.43 mmol) prepared above was dissolved in 30 mL of pure water. . The drug was passed through 100 mL of the same cation exchange resin as in Example 1 charged with H ⁺ . Further, 100 mL of pure water was passed through and the liquid that came out was dried using a rotary evaporator. Furthermore, 1.66 g (yield: 82.3%) of the target product as a yellow powder could be obtained by vacuum drying.

<FT-IR {KBr disk}>
1617 (m), 1406 (m), 1271 (w), 1090 (vs), 1043 (m), 956 (s), 916 (s), 797 (br, s), 566 (w), 529 (m ), 484 (w) cm ^-1

^<31 P NMR>
{Solvent D ₂ O, 22.8 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-10.4, -13.4 ppm

^<1 H NMR>
{Solvent D ₂ O, 23.0 ° C, external standard: DSS substitution method}
δ 5.98-6.10, 6.27-6.29, 6.31-6.33 ppm

< ^13C NMR>
{Solvent D ₂ O, 26.1 ° C, external standard: DSS substitution method}
δ130.5, 140.4 ppm

<CHN elemental analysis>
H ₆ [P ₂ W ₁₇ O ₆₁ (CH ₂ CHSi) ₂ O] .22H ₂ O

From the result of the above characterization, it was confirmed that the target heteropoly acid H ₆ [P ₂ W ₁₇ O ₆₁ (CH ₂ CHSi) ₂ O] · 22H ₂ O was produced.

[Example 3]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

Heteropolyacid salt ((Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 5H ₂ O modified with hydrolyzate of metal alkoxide having an acrylic group ) Will be described.

445 μL (2.0 mmol) of _3- alkoxypropyltrimethoxysilane (CH ₂ CHCOO (CH ₂ ) ₃ Si (OMe) ₃ ) was added to a mixed solvent of 150 mL of methanol and 50 mL of pure water according to the same literature as in Example 1. 5.0 g (1 mmol) of synthesized single-deficient Dawson-type tungstopolyacid salt K ₁₀ [α ₂ -P ₂ W ₁₇ O ₆₁ ] · 19H ₂ O was added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 70 mL using a rotary evaporator. An excessive amount of Me ₂ NH ₂ Cl (5.5 g, 67 mmol) was added to the concentrate to precipitate a powder. The precipitated powder was collected by a membrane filter, washed twice with 5 mL of methanol, and further washed twice with 50 mL of diethyl ether. Further, by sufficiently sucking and drying, 3.48 g (yield: 72.1%) of the target product as a fine white yellowish green powder could be obtained.

<FT-IR {KBr disk}>
1713 (m), 1616 (m), 1465 (m), 1413 (w), 1298 (w), 1217 (w), 1088 (s), 1069 (w), 1039 (m), 1018 (w), 955 (vs), 921 (s), 795 (br, vs), 750 (m), 715 (m), 570 (w), 529 (w) cm ⁻¹

^<31 P NMR>
{Solvent D ₂ O, 21.6 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-10.2, -13.3 ppm

^<1 H NMR>
{Solvent D ₂ O, 21.8 ° C, external standard: DSS substitution method}
δ 0.91-0.95, 2.01-2.06, 4.27-4.31, 5.94-5.97, 6.21-6.28, 6.41-6.45 ppm

< ^13C NMR>
{Solvent DMSO-d ₆ , 25.1 ° C, external standard: TMS substitution method}
δ 8.57, 21.8, 66.0, 128.2, 131.1, 165.3 ppm

< ¹⁸³ W NMR>
{Solvent DMSO-d ₆ , 18.3 ° C, external standard: saturated Na ₂ WO ₄ aq. Replacement method}
δ-115.9, -118.6, -162.7, -166.6, -173.4, -179.8, -199.8, -320.1 ppm

<CHN elemental analysis>
(Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 5H ₂ O

  From the characterization results, it can be seen that the target product was obtained as a single species. Using this compound as a precursor, free acid was synthesized.

<Production of heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O modified with a hydrolyzate of metal alkoxide having a reactive organic functional group >

The heteropolyacid salt (Me ₂ NH ₂ ) ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 5H ₂ O 2.0 g (0.41 mmol) prepared above is purified water. Dissolved in 30 mL. The drug was passed through 100 mL of the same cation exchange resin as in Example 1 charged with H ⁺ . Further, 100 mL of pure water was passed through and the liquid that came out was dried using a rotary evaporator. Further, 1.59 g (yield: 78.9%) of the target product as a yellow powder could be obtained by vacuum drying.

<FT-IR {KBr disk}>
1698 (m), 1618 (m), 1416 (w), 1301 (w), 1225 (w), 1089 (m), 1038 (m), 954 (vs), 917 (s), 793 (br, vs ), 570 (w), 529 (w) cm ⁻¹

^<31 P NMR>
{Solvent D ₂ O, 21.4 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-10.3, -13.3 ppm

^<1 H NMR>
{Solvent D ₂ O, 23.0 ° C, external standard: DSS substitution method}
δ 0.89-0.93, 1.99-2.03, 4.26-4.28, 5.92-5.95, 6.20-6.27, 6.38-6.44 ppm

< ^13C NMR>
{Solvent D ₂ O, 25.6 ° C, external standard: DSS substitution method}
δ 6.93, 23.2, 68.8, 129.6, 133.9, 170.6 ppm

<CHN elemental analysis>
H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O

From the results of the above characterization, it was confirmed that the target heteropoly acid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O was produced.

[Example 4]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

A method for producing a heteropolyacid salt (Bu ₄ N) ₃ [PW ₁₁ O ₃₉ (CH ₂ CHSi) ₂ O] modified with a hydrolyzate of a metal alkoxide having a vinyl group will be described.

One-deficient Keggin-type Tungstopoly synthesized by adding 310 μL (2.0 mmol) of vinyltrimethoxysilane (CH ₂ CHSi (CH ₃ O) ₃ ) to a mixed solvent of 150 mL of methanol and 50 mL of pure water according to the same literature as in Example 1. 3.0 g (1 mmol) of acid salt K ₇ [PW ₁₁ O ₃₉ ] · 8H ₂ O was added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 70 mL using a rotary evaporator. To this concentrated liquid, 5.5 g (17 mmol) of an excessive amount of Bu ₄ NBr was added to precipitate a powder. The precipitated powder was collected with a membrane filter and then washed three times with 50 mL of pure water, 50 mL of methanol, and 50 mL of diethyl ether. Further, by sufficiently sucking and drying, the desired product was obtained as a white powder in 3.16 g (yield: 44.7%).

<FT-IR {KBr disk}>
1482 (w), 1467 (w), 1459 (w), 1420 (w), 1381 (w), 1111 (m), 1065 (m), 1038 (m), 995 (m), 963 (vs), 870 (s), 823 (s), 791 (m), 620 (w), 522 (w) cm ⁻¹

^<31 P NMR>
{Solvent CD ₃ CN, 21.9 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-13.3 ppm

^<1 H NMR>
{Solvent DMSO-d ₆ , 25.1 ° C, internal standard: TMS}
δ 6.04, 6.16-6.17, 6.22-6.26 ppm

< ^13C NMR>
{Solvent DMSO-d ₆ , 25.3 ° C, external standard: TMS substitution method}
δ129.6, 137.4 ppm

^<29 Si NMR>
{Solvent DMSO-d ₆ , 25.2 ° C, external standard: TMS substitution method}
δ-65.6 ppm

<CHN elemental analysis>
(Bu ₄ N) ₃ [PW ₁₁ O ₃₉ (CH ₂ CHSi) ₂ O]

  From the characterization results, it can be seen that the target product was obtained as a single species.

[Example 5]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

Method for producing heteropolyacid salt (Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] modified by hydrolyzate of metal alkoxide having methacryl group explain.

Example 1 by adding 475 μL (2.0 mmol) of γ-methacryloxypropyltrimethoxysilane (CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ) to a mixed solvent of 150 mL of acetonitrile and 50 mL of pure water. 3.0 g (1 mmol) of one-deficient Keggin type tungstopolyacid salt K ₇ [PW ₁₁ O ₃₉ ] · 8H ₂ O synthesized according to the same literature as above was added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 70 mL using a rotary evaporator. To this concentrated solution, 8.6 g (27 mmol) of an excessive amount of Bu ₄ NBr was added to precipitate a powder. The precipitated powder was collected with a membrane filter and then washed three times with 50 mL of pure water, 50 mL of methanol, and 50 mL of diethyl ether. Further, by sufficiently sucking and drying, the desired product was obtained as a white powder in 3.16 g (yield: 44.7%).

<FT-IR {KBr disk}>
1716 (m), 1474 (m), 1458 (m), 1382 (w), 1320 (w), 1297 (w), 1169 (m), 1111 (s), 1065 (s), 1037 (s), 995 (s), 963 (vs), 870 (vs), 824 (vs), 712 (s), 585 (m), 521 (m)) cm ⁻¹

^<31 P NMR>
{Solvent CD ₃ CN, 21.9 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-12.6 ppm

^<1 H NMR>
{Solvent DMSO-d ₆ , 25.1 ° C, internal standard: TMS}
δ 1.09 (H1), 1.22, 1.63, 1.86, 4.40 (H3), 5.82, 6.30 (H4a or H4b) ppm

< ^13C NMR>
{Solvent DMSO-d ₆ , 25.3 ° C, external standard: TMS substitution method}
δ 7.91 (C1), 13.2, 19.0, 22.9, 17.7 (C7), 21.5 (C2), 65.7 (C3), 125.2 (C6), 135.7 (C5), 166.2 (C4) ppm

^<29 Si NMR>
{Solvent DMSO-d ₆ , 25.2 ° C, external standard: TMS substitution method}
δ-51.8 ppm

< ¹⁸³ W NMR>
{Solvent DMSO-d ₆ , 22.4 ° C, external standard: saturated Na ₂ WO ₄ aq. }
δ-98.0 (2W), -102.9 (2W), -107.0 (1W), -120.7 (2W), -197.6 (2W), -250.0 (2W) ppm

<CHN elemental analysis>
(Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O]

  From the characterization results, it can be seen that the target product was obtained as a single species.

[Example 6]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

A method for producing a heteropolyacid salt (Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] modified with a hydrolyzate of a metal alkoxide having an acrylic group will be described.

Example: 445 μL (2.0 mmol) of γ-acryloxypropyltrimethoxysilane (CH ₂ C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ) was added to a mixed solvent of 150 mL of acetonitrile and 50 mL of pure water. 1 deficient Keggin-type tungstopolyacid salt K ₇ [PW ₁₁ O ₃₉ ] · 8H ₂ O synthesized according to the same literature as 1 was added in an amount of 3.0 g (1 mmol). The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 30 mL using a rotary evaporator. To this concentrated solution, 8.6 g (27 mmol) of an excessive amount of Bu ₄ NBr was added to precipitate a powder. The precipitated powder was collected with a membrane filter and then washed three times with 50 mL of pure water, 50 mL of methanol, and 50 mL of diethyl ether. Furthermore, by sufficiently sucking and drying, the target product was obtained as a white powder in 2.42 g (yield: 65.4%).

<FT-IR {KBr disk}>
1718 (m), 1474 (m), 1459 (m), 1381 (m), 1274 (m), 1194 (m), 1111 (m), 1065 (m), 1037 (m), 963 (s), 869 (s), 823 (s), 521 (w), 420 (w) cm ⁻¹

^<31 P NMR>
{Solvent DMSO-d ₆ , 21.8 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-13.1 ppm

^<1 H NMR>
{Solvent DMSO-d ₆ , 25.1 ° C, external standard: TMS substitution method}
δ 0.77, 1.84, 4.14, 5.92, 6.20, 6.30 ppm

< ^13C NMR>
{Solvent DMSO-d ₆ , 25.7 ° C, external standard: TMS substitution method}
δ 7.9, 21.5, 65.5, 128.2, 130.9, 165.2 ppm

^<29 Si NMR>
{Solvent DMSO-d ₆ , 25.1 ° C, external standard: TMS substitution method}
δ-51.9 ppm

<CHN elemental analysis>
(Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O]

  From the characterization results, it can be seen that the target product was obtained as a single species.

[Example 7]
<Production of heteropolyacid salt modified with hydrolyzate of metal alkoxide having reactive organic functional group>

A method for producing a heteropolyacid salt (Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ OCHCH ₂ O (CH ₂ ) ₃ Si} ₂ O] modified with a hydrolyzate of a metal alkoxide having an epoxy group will be described. .

560 μL (2.54 mmol) of ₃ -glycidoxypropyltrimethoxysilane (CH ₂ OCHCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ) was added to a mixed solvent of 150 mL of acetonitrile and 30 mL of pure water, and Example 1 3.0 g (1 mmol) of one-deficient Keggin-type tungstopolyacid salt K ₇ [PW ₁₁ O ₃₉ ] · 8H ₂ O synthesized according to the same literature was added. The pH was adjusted to 1.8 using 1M hydrochloric acid. After stirring for 2 hours, unreacted powder was removed with a membrane filter, and the filtrate was concentrated to about 30 mL using a rotary evaporator. To this concentrated solution, 8.6 g (27 mmol) of an excessive amount of Bu ₄ NBr was added to precipitate a powder. The precipitated powder was collected with a membrane filter and then washed three times with 50 mL of pure water, 50 mL of methanol, and 50 mL of diethyl ether. Further, by sufficiently sucking and drying, the target product was obtained as a white powder in 1.10 g (yield: 29.7%).

<FT-IR {KBr disk}>
1701 (m), 1474 (m), 1458 (m), 1420 (m), 1383 (m), 1111 (m), 1065 (m), 1036 (m), 963 (s), 869 (s), 823 (s), 525 (w) cm ⁻¹

^<31 P NMR>
{Solvent CD ₃ CN, 23.3 ° C, external standard: 25% H ₃ PO ₄ aq. Capillary}
δ-12.6 ppm

^<1 H NMR>
{Solvent CD ₃ CN, 23.3 ° C, internal standard: TMS}
δ 0.81, 1.82, 2.53, 2.71, 3.32, 3.43, 3.55, 3.70 ppm

< ^13C NMR>
{Solvent CD ₃ CN, 25.3 ° C, external standard: TMS substitution method}
δ 7.97, 22.3, 43.4, 50.1, 71.0, 72.1 ppm

^<29 Si NMR>
{Solvent DMSO-d ₆ , 26.1 ° C, external standard: TMS substitution method}
δ-51.4 ppm

<CHN elemental analysis>
(Bu ₄ N) ₃ [PW ₁₁ O ₃₉ {CH ₂ OCHCH ₂ O (CH ₂ ) ₃ Si} ₂ O]

  From the characterization results, it can be seen that the target product was obtained as a single species.

  Next, the heteropolyacids obtained in Example 1 and Example 3 were respectively polymerized to produce free acid type heteropolyacid polymers.

<Preparation of Polymer of Heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O Obtained in Example 1>

Initiation of polymerization with 1 g of heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O obtained in Example 1 above in a 15 mL Schlenk flask 0.002 g of azobisisobutyronitrile as an agent was dissolved in 1 mL of CH ₃ CN. This container was immersed in liquid nitrogen to freeze the reaction solvent inside. After confirming that the reaction solvent was frozen, the inside of the container was degassed for 10 minutes using a suction pump from Schlenkcock. When the deaeration was completed, the Schlenk cock was closed, and the container was removed from the liquid nitrogen while keeping the interior of the container in a vacuum state, and returned to room temperature. The vessel was then immersed in an oil bath at 75 ° C. and the polymerization reaction was carried out for 15 hours. As the polymerization progressed, the polymer powder gradually precipitated. After the completion of the polymerization reaction, the precipitated powder was recovered and washed with a large amount of CH ₂ CN, and then the powder was sufficiently vacuum dried. 0.18 g (yield: 18.0%) of the target polymer was obtained.

<FT-IR {KBr disk}>
1699 (m), 1653 (m), 1558 (w), 1541 (w), 1506 (w), 1489 (w), 1473 (w), 1456 (w), 1396 (w), 1269 (w), 1090 (s), 1041 (w), 958 (vs), 918 (s), 810 (br), 528 (w) cm ⁻¹

<Solid ³¹ P NMR>
{25.0 ° C, external standard: (NH ₄ ) HPO ₄ substitution method}
δ-9.17, -12.0 ppm

As a result of the above characterization, a heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} ₂ O] · 20H ₂ O polymer (free acid type heteropoly acid system) Polymer).

<Preparation of Polymer of Heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O Obtained in Example 3>

Heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O 1 g obtained in Example 3 and azobis as a polymerization initiator were placed in a 15 mL Schlenk flask. 0.002 g of isobutyronitrile was dissolved in 1 mL of CH ₃ CN. This container was immersed in liquid nitrogen to freeze the reaction solvent inside. After confirming that the reaction solvent was frozen, the inside of the container was degassed for 10 minutes using a suction pump from Schlenkcock. When the deaeration was completed, the Schlenk cock was closed, and the container was removed from the liquid nitrogen while keeping the interior of the container in a vacuum state, and returned to room temperature. The vessel was then immersed in an oil bath at 75 ° C. and the polymerization reaction was carried out for 15 hours. As the polymerization progressed, the polymer powder gradually precipitated. After the polymerization reaction, the precipitated powder was collected and washed with a large amount of CH ₃ CN, and then the powder was sufficiently dried in vacuum. 0.46 g (yield: 46.0%) of the target polymer was obtained.

<FT-IR {KBr disk}>
1716 (w), 1699 (w), 1684 (w), 1652 (w), 1588 (w), 1541 (w), 1508 (w), 1473 (w), 1458 (w), 1396 (w), 1200 (w), 1090 (m), 1041 (m), 955 (s), 918 (s), 796 (br), 663 (w) cm ⁻¹

<Solid ³¹ P NMR>
{25.3 ° C., external standard: (NH ₄ ) HPO ₄ substitution method}
δ-9.29, -12.5 ppm

As a result of the above characterization, the heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O polymer (free acid type heteropoly acid polymer) It was confirmed that there was.

The free acid type heteropolyacid polymer obtained as described above (the heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ Si} obtained in Example 1) ₂ O] · 20H ₂ O and methyl methacrylate (MMA) copolymer, heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ (CH ₃ ) CCOO (CH ₂ ) ₃ obtained in Example 1 The polymer of Si} ₂ O] · 20H ₂ O and the heteropolyacid H ₆ [P ₂ W ₁₇ O ₆₁ {CH ₂ CHCOO (CH ₂ ) ₃ Si} ₂ O] · 25H ₂ O obtained in Example 3 The solid acid strength of the polymer was evaluated with a Hammett indicator.

A methanol solution of Hammett indicator (1,9-diphenyl-1,3,6,8-nonatetraen-5-one, pKa = -3.0) was adjusted to a concentration of 4.0 × 10 ⁻⁵ mol / L. When the above polymer was added to this solution and the coloration of the polymer surface was confirmed, no coloration was observed in the supernatant solution for all, but only the polymer surface was colored red based on the indicator. Was confirmed. From this, it was confirmed that the polymer can act as a strong solid acid catalyst having a pKa of −3.0 or more, and it was confirmed that there was no bleed out from the polymer because it was immobilized by a covalent bond. . These free acid type heteropolyacid salt polymers can be recovered by filtration and can be reused as an acid catalyst.

On the other hand, a normal non-polymerized heteropolyacid (for example, H ₃ [PW ₁₂ O ₄₀ ] · 12H ₂ O) is colored by a Hammett indicator, but is dissolved in methanol and used as a solid acid catalyst. It was something that could not be done.

Claims (5)

  A modified free acid type heteropolyacid obtained by introducing a metal group having a reactive organic functional group into a partially deficient site of a skeleton constituent atom of a heteropolyacid. The modified free acid type heteropolyacid according to claim 1, which is represented by the general formula (1).
H _m [XY] · nH ₂ O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, and Y is a metal group having a reactive organic functional group. n is an integer greater than or equal to 1, m is an integer greater than or equal to 1, and is the absolute value of the negative charge determined from [XY] in the general formula (1). ]   A modified heteropolyacid salt in which a metal group having a reactive organic functional group is introduced into a partially deficient site of a skeleton constituent atom of a heteropolyacid salt. The modified heteropolyacid salt according to claim 3, which is represented by the general formula (2).
R _m [XY] (2)
[Wherein, R is selected from the group of Bu ₄ N ⁺ , Me ₂ NH ₂ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , and X is a heteropolyanion in which a part of the skeleton constituent atoms is missing] Y is a metal group having a reactive organic functional group. m is an integer of 1 or more, and is an absolute value of the negative charge determined from [XY] in the general formula (2). ]   A free acid heteropolyacid polymer obtained by homopolymerization or copolymerization of the modified free acid heteropolyacid according to claim 1 or 2.