JP5618194B2 - Azacalix [3] pyridinium salt, method for producing the same, and method for producing polyalkylene glycol using the same - Google Patents

Description

  The present invention relates to a novel azacalix [3] pyridinium salt expected to be useful as a reagent for various reactions, a method for producing the same, and a method for producing polyalkylene glycol using the same. A novel azacalix [3] pyridinium salt obtained from a hydrogen compound and an azacalix [3] pyridine having a specific substituent on each of a benzene ring and a pyridine ring, from the azacalix [3] pyridinium salt The present invention relates to a method for producing a polyalkylene glycol simply and with high activity by carrying out a ring-opening polymerization reaction of an alkylene oxide.

  The cyclic cyclophane N ′, N ″, N ′ ″-tris (p-tolyl) azacalix [3] (2,6) pyridine has strong basicity (pKa = 23.1) It has been reported that a pyridinium salt is formed by reaction with hexafluorophosphoric acid due to its strong proton scavenging ability (see, for example, Non-Patent Document 1). In addition, if an electron-donating substituent can be introduced onto the pyridine ring of N ′, N ″, N ′ ″-tris (p-tolyl) azacalix [3] (2,6) pyridine, a base The trial calculation result using the chemical calculation that the property is further improved has been reported (for example, see Non-Patent Document 2). Since these compounds have strong basicity, application as novel organic base catalysts is expected.

  Examples of the reaction using an organic base catalyst include alkylation of secondary amine, alkylation of phenylacetonitrile, α, β-epoxy ester formation reaction by condensation reaction of aldehyde and α-haloester, alkylene oxide Ring-opening (polymerization) reactions are known. In particular, in the ring-opening polymerization reaction of alkylene oxide, polyalkylene glycol, which is a raw material of polyurethane used as polyurethane elastomers, adhesives, paints, polyurethane foams, etc., is produced. It has been broken.

  Examples of typical polymerization catalysts used in the ring-opening polymerization reaction of alkylene oxides include anionic polymerization catalysts such as alkali metal compounds, alkaline earth metal compounds, and phosphazene compounds; phosphoric acid, Lewis acid, and organic ligands thereof. Cationic polymerization catalysts such as compounds, trifluoromethyl sulfonates and tetrakispentafluorophenyl borate salts; coordination polymerization catalysts such as double metal cyanides are known. Proazaphosphatran base known as a barcade catalyst is also a strong basic compound and has been proposed as a production catalyst for polyalkylene glycol (see, for example, Patent Document 1).

Eur. J. Org. Chem., 2006, pp. 3314-3316 ORGANIC LETTERS, 2007, Vol. 9, No. 6, pp. 1101-1104

Japanese Patent Laying-Open No. 2005-232377 (refer to the claims)

  However, N ′, N ″, N ′ ″-tris (p-tolyl) azacalix [3] (2,6) pyridine proposed in Non-Patent Document 1 has a strong basicity. However, since its basicity is insufficient, active hydrogen cannot be extracted from the active hydrogen compound, and N ′, N ″, N ″ ′-tris (p-tolyl) azacalix [3] (2 6) Since a pyridinium salt could not be produced, it could not be used as a catalyst for producing polyalkylene glycol.

  In addition, with regard to the compound proposed in Non-Patent Document 2, the actual situation is that neither the actually synthesized example nor the basicity is known at all.

  In addition, it is difficult to produce a polyalkylene glycol with a molecular weight of 1000 or more and a narrow molecular weight distribution in the cationic polymerization catalyst used in the ring-opening polymerization reaction of alkylene oxide, and a cyclic compound is generated by a side reaction. There was a problem. In addition, the coordination polymerization catalyst has a problem that it is difficult to uniformly carry out addition polymerization of ethylene oxide uniformly to the terminal of the polyalkylene glycol, and crystalline polyethylene oxide is easily produced as a by-product. Furthermore, since an anionic polymerization catalyst by-produces water and alcohol, it is necessary to perform a ring-opening polymerization reaction after removing these by-products.

  The proazaphosphatolan base proposed in Patent Document 1 is capable of ring-opening polymerization of alkylene oxide and is efficient, but has low thermal stability as a catalyst for producing polyalkylene glycol and low catalytic activity. There was a problem.

  As a result of intensive studies on the above problems, the present inventors have found that a novel azacalix [3] pyridinium salt having a specific substituent on each of a benzene ring and a pyridine ring is useful for various reactions, particularly It became a catalyst for the production of polyalkylene glycol, has high activity also for the ring-opening polymerization reaction of alkylene oxide, and found that polyalkylene glycol can be produced efficiently, leading to the completion of the present invention. .

  That is, the present invention relates to an azacalix [3] pyridinium salt represented by the following general formula (1), a method for producing the same, and a method for producing a polyalkylene glycol using the azacalix [3] pyridinium salt.

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an electron donating group, R ₂ represents an electron donating group which may be the same as or different from R _1, and n is 1 to 8) Y ^n- represents a hydroxy anion; an alcohol having 1 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms having 2 to 8 hydroxyl groups, a saccharide or a derivative thereof, and 1 to 8 at the terminal shows the polyalkylene oxides having a number average molecular weight from 200 to 50,000 having hydroxyl group, an alkoxy anion or a carboxy anion derived from a carboxylic acid having 1 to 20 carbon atoms having 1-6 carboxyl groups derived from. here, The electron donating group is an aliphatic or aromatic alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, an unsubstituted or alkyl-substituted group having 4 to 7 carbon atoms. Selected from the group consisting of a cyclic amino group, 1,1,3,3-tetramethylguanidino group, iminotris (dimethylamino) phosphoranyl group, and an alkoxy anion derived from a saccharide or a derivative thereof is glucose An alkoxy anion derived from a group selected from the group consisting of sorbitol, dextrose, fructose, and sucrose.

  The novel azacalix [3] pyridinium salt of the present invention efficiently produces polyalkylene glycol useful as a raw material for a reaction agent for various reactions as an organic base catalyst, especially as a polyurethane elastomer, adhesive, paint, foam, etc. Its value is extremely high as a catalyst for producing polyalkylene glycol which can be produced well.

  The present invention will be described in detail below.

  The novel azacalix [3] pyridinium salt of the present invention is an azacalix [3] pyridinium salt having a structure represented by the general formula (1).

And R < ₁ > shows the substituent on a benzene ring, and represents a hydrogen atom, a C1-C10 alkyl group, or an electron-donating group each independently. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, Examples thereof include n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Among them, raw materials are easy to obtain, and they are highly active as reactive agents and applied to various reactions. Is expected to be hydrogen or a methyl group. Here, when R ₁ is an alkyl group having more than 10 carbon atoms, it is difficult to obtain an azacalix [3] pyridinium salt itself.

  Examples of the electron donating group include, independently of each other, an aliphatic or aromatic alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, an unsubstituted or alkyl-substituted group having 4 to 7 carbon atoms. Cyclic amino group, 1,1,3,3-tetramethylguanidino group, iminotris (dimethylamino) phosphoranyl group, and examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, Examples thereof include an n-butoxy group and a phenoxy group. Examples of the dialkylamino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a di (isopropyl) amino group, Di (n-butyl) amino group, di (isobutyl) amino group, di (2-butyl) amino group, di (n-pentyl) amino group, di n-hexyl) amino group, di (n-heptyl) amino group, di (n-octyl) amino group, di (n-nonyl) amino group, di (n-decyl) amino group and the like. Examples of the unsubstituted or alkyl-substituted cyclic amino group having 4 to 7 include a pyrrolidinyl group, a 2,5-dimethylpyrrolidinyl group, a piperidinyl group, and a 2,6-dimethylpiperidinyl group. .

R ₂ represents a substituent on the pyridine ring, and each independently represents an electron-donating substituent which may be the same as or different from R _1, and specific examples thereof are the same as those for R ₁ above. Can be mentioned. Among them, a dimethylamino group, a pyrrolidinyl group, and a piperidinyl group are preferable because the raw materials are easily obtained and the activity as a reactant is high and application to various reactions is expected.

  n shows the real number of 1-8. Here, when n is less than 1 or when n exceeds 8, it is practically difficult to obtain an azacalix [3] pyridinium salt.

Y ^n- represents a hydroxy anion, an alcohol having 1 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms having 2 to 8 hydroxyl groups, a saccharide, a saccharide derivative, or a 1 to 8 hydroxyl group at a terminal. An alkoxy anion derived from a polyalkylene oxide having a number average molecular weight of 200 to 50,000 and a carboxy anion derived from a C 1-20 carboxylic acid having 1 to 8 carboxyl groups. Here, when Y ⁿ⁻ is other than these, the azacalix [3] pyridinium salt cannot be expected as a reactant. Moreover, since n is a real number of 1 to 8 as described above, Y ⁿ⁻ does not necessarily require that all functional groups are alkoxy anions and carboxy anions. The functional group only needs to be an alkoxy anion or a carboxy anion. For example, when n = 1, Y ⁿ⁻ may be a single functional group including a hydroxy anion, a monovalent alkoxy anion, and a monovalent carboxy anion. It may be a divalent alcohol whose group is alkoxy anionized, polypropylene glycol having three hydroxyl groups whose functional group is alkoxy anionized, or the like.

  Examples of the alkoxy anion derived from the alcohol having 1 to 20 carbon atoms include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, sec-butoxy anion, tert-butoxy anion, Isopentyloxy anion, tert-pentyloxy anion, n-octyloxy anion, lauryloxy anion, cetyloxy anion, cyclopentyloxy anion, cyclohexyloxy anion, allyloxy anion, crotyloxy anion, methylvinylcarbyloxy anion, benzyl Oxyanion, 1-phenylethyloxyanion, triphenylcarbyloxyanion, cinnamyloxyanion, etc. Examples of the alkoxy anion derived from a C2-C20 polyhydric alcohol having one hydroxyl group include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, , 4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, trimethylolmelamine, pentaerythritol, dipentaerythritol, etc. Examples of the alkoxy anion derived from a saccharide or a derivative thereof include, for example, an alkoxy anion derived from glucose, sorbitol, dextrose, fructose or sucrose. Examples of alkoxy anions derived from polyalkylene oxides having a number average molecular weight of 200 to 50000 having 1 to 8 hydroxyl groups at the terminals include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexa Mention may be made of alkoxy anions derived from methylene glycol or copolymers thereof.

  Examples of the carboxy anion derived from a carboxylic acid having 1 to 8 carboxyl groups and having 1 to 20 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid, and phenyl. Acetic acid, dihydrocinnamic acid, cyclohexanecarboxylic acid, benzoic acid, paramethylbenzoic acid, 2-carboxynaphthalene, succinic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butanetetracarboxylic acid, phthalic acid, Derived from isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, N, N-diethylcarbamic acid, N-carboxypyrrolidone, N-carboxyaniline, N, N′-dicarboxy-2,4-toluenediamine Carboxy anions.

Among these, since it is particularly excellent in the ring-opening reactivity of alkylene oxide, it becomes an azacalix [3] pyridinium salt that is excellent as a catalyst for producing polyalkylene glycol. Therefore, as Y ⁿ⁻ , ethylene glycol, propylene glycol, 1 Alkoxy anion derived from polyhydric alcohols such as 1,4-butanediol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol; alkoxy anion derived from glucose, sorbitol, dextrose, fructose, sucrose sugars or derivatives thereof Polyethylene glycol, polypropylene glycol or copolymers thereof having a number average molecular weight of 200 to 10,000 having 2 to 6 ends and 2 to 6 hydroxyl groups at the ends An alkoxy anion derived from a polyalkylene oxide is preferred.

  The novel azacalix [3] pyridinium salt of the present invention can be produced by reacting an azacalix [3] pyridine represented by the following general formula (2) with an active hydrogen compound.

(However, R ₁ and R ₂ are the same as those in the general formula (1).)
Examples of the azacalix [3] pyridine include N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) (4-dimethylaminopyridine), N, N ′, N ″. -Tris (phenyl) azacalix [3] (2,6) (4-diethylaminopyridine), N, N ', N "-tris (phenyl) azacalix [3] (2,6) [4-di (n -Propyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) (4-diisopropylaminopyridine), N, N ′, N ″ -tris (phenyl) aza Calix [3] (2,6) [4-di (n-butyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) (4-diisobutylaminopyridine ), N, N ', N "-Tris Phenyl) azacalix [3] (2,6) [4-di (n-pentyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) [4- Di (n-hexyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) [4-di (n-heptyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) [4-di (n-octyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2, 6) [4-Di (n-nonyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) [4-di (n-decyl) aminopyridine], N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) (4-pyrrolidinyl Pyridine), N, N ′, N ″ -tris (phenyl) azacalix [3] (2,6) (4-piperidinylpyridine), N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-dimethylaminopyridine), N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-diethylaminopyridine), N, N ', N ″ -tris (p-tolyl) azacalix [3] (2,6) [4-di (n-propyl) aminopyridine], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-diisopropylaminopyridine), N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) [4-di (n-butyl) amino Pyridine], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2 6) [4-Di (n-pentyl) aminopyridine], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) [4-di (n-hexyl) aminopyridine ], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) [4-di (n-heptyl) aminopyridine], N, N ′, N ″ -tris (p -Tolyl) azacalix [3] (2,6) [4-di (n-octyl) aminopyridine], N, N ', N "-tris (p-tolyl) azacalix [3] (2,6) [4-di (n-nonyl) aminopyridine], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) [4-di (n-decyl) aminopyridine], N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine), N, N ′, N -Tris (p-tolyl) azacalix [3] (2,6) (4-piperidinylpyridine) and the like. Particularly, since it has excellent ring-opening reactivity of alkylene oxide, it is used for producing polyalkylene glycol. Since an azacalix [3] pyridinium salt excellent as a catalyst is obtained, N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-dimethylaminopyridine), N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine), N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-piperidinylpyridine) is preferred, and N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) is more preferred. preferable.

  The active hydrogen compound may be any compound having active hydrogen in the molecule, such as water; formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid. , Carboxylic acids having 1 to 20 carbon atoms such as phenylacetic acid, dihydrocinnamic acid, cyclohexanecarboxylic acid, benzoic acid, paramethylbenzoic acid, 2-carboxynaphthalene; oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipine Polyvalent carboxylic acids having 2 to 8 carbon atoms having 2 to 20 carbon atoms such as acid, itaconic acid, butanetetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid; N, N-diethylcarbamic acid, N-carboxypyrrolidone, N-carboxyaniline, N, N′-dicarboxy Carbamates such as -2,4-toluenediamine; methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol , Lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbinol, cinnamyl alcohol, etc. Alcohols: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanedio 1,2-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, trimethylolmelamine, pentaerythritol, dipentaerythritol, etc. Polyhydric alcohols having 2 to 8 hydroxyl groups; sugars such as glucose, sorbitol, dextrose, fructose or sucrose or derivatives thereof; phenols, 2-naphthol, 2,6-dihydroxynaphthalene, bisphenol A and the like having 6 to 6 carbon atoms 20 aromatic compounds having 1 to 3 hydroxyl groups; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, or copolymers thereof having 1 to 8 ends, 1 And polyalkylene oxides having a number average molecular weight of 200 to 50,000 having 8 hydroxyl groups.

  Among them, ethylene glycol, propylene glycol, and 1,4-butanediol are obtained because an azacalix [3] pyridinium salt that is excellent as a catalyst for producing polyalkylene glycol is obtained because of excellent ring opening reactivity of alkylene oxide. Polyhydric alcohols having 2 to 8 carbon atoms having 2 to 20 carbon atoms such as trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol; sugars such as glucose, sorbitol, dextrose, fructose and sucrose; Polyethylene glycol, polypropylene glycol or copolymers thereof, etc., which are polyalkylene oxides having a number average molecular weight of 200 to 10,000 having 2 to 6 ends and 2 to 6 hydroxyl groups at the ends. It is preferred.

  Further, the reaction ratio of azacalix [3] pyridine and active hydrogen compound in producing azacalix [3] pyridinium salt from the azacalix [3] pyridine and active hydrogen compound is arbitrary, and among them, the reactant, In particular, since an azacalix [3] pyridinium salt having excellent characteristics as a catalyst for producing a polyalkylene glycol can be obtained, the active hydrogen compound is in a range of 0.2 to 1000 mol with respect to 1 mol of azacalix [3] pyridine. The reaction is preferably carried out in the range of 1 to 500 mol, particularly in the range of 10 to 300 mol. At this time, the azacalix [3] pyridinium salt of the present invention is represented by the general formula (1), n is a real number of 1 to 8, and the reaction of azacalix [3] pyridine with active hydrogen of an active hydrogen compound. Is a reversible reaction, the number of active hydrogens of azacalix [3] pyridine and the active hydrogen compound need not be equivalent.

  When the azacalix [3] pyridinium salt represented by the general formula (1) of the present invention is produced by reacting the azacalix [3] pyridine represented by the general formula (2) with an active hydrogen compound, an aprotic compound is used. Polar solvents may be used. Examples of the aprotic polar solvent include dimethyl sulfoxide, dimethylformamide, acetamide, formamide, hexamethylphosphoric triamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone. Among them, dimethyl sulfoxide is preferable because it is excellent in solubility of the active hydrogen compound, azacalix [3] pyridine, the reaction proceeds efficiently, and the solvent can be easily removed. In addition, the amount of the aprotic polar solvent used at that time may be appropriately selected and used. Usually, it is in the range of 5 to 50 liters, more preferably in the range of 10 to 30 liters per mole of azacalix [3] pyridine. It is preferable that

  The atmosphere for producing the azacalix [3] pyridinium salt is to prevent the azacalix [3] pyridine, active hydrogen compound, and the generated azacalix [3] pyridinium salt from coming into contact with moisture in the air. For the purpose, it is desirable to carry out in an atmosphere of an inert gas such as nitrogen, helium or argon.

  The reaction temperature for producing the azacalix [3] pyridinium salt of the present invention from azacalix [3] pyridine and an active hydrogen compound is any temperature as long as the azacalix [3] pyridinium salt can be produced. For example, a range of 20 to 160 ° C., a range of 50 to 150 ° C., particularly a range of 80 to 130 ° C. is preferable. Moreover, as reaction time in that case, it is 30 hours or less normally, and also it is preferable that it is the range of 0.1-24 hours.

  When an azacalix [3] pyridinium salt represented by the general formula (1) of the present invention is used as a catalyst for producing a polyalkylene glycol, polyalkylene glycol is produced as a by-product during the production of the catalyst like an anionic polymerization catalyst. A catalyst can be easily produced by mixing active hydrogen compounds and azacalix [3] pyridine to form an azacalix [3] pyridinium salt without the need for water or alcohol removal, and ring-opening polymerization of alkylene oxide. Reaction can be performed to produce polyalkylene glycol.

  The method for producing polyalkylene glycol by ring-opening polymerization of alkylene oxide using the azacalix [3] pyridinium salt represented by the general formula (1) of the present invention as a catalyst for producing polyalkylene glycol will be described in detail below. .

  Here, any alkylene oxide may be used as long as it belongs to the category of alkylene oxide, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or cyclohexene. Among them, there can be mentioned epoxy compounds such as oxides. Among them, ethylene oxide, propylene oxide, 1,2-butylene oxide or styrene oxide is preferable because it becomes a polyalkylene glycol having excellent characteristics as a raw material for polyurethane. And / or propylene oxide. Moreover, the said alkylene oxide may be used independently and may use 2 or more types together. When using together, the method of adding several alkylene oxide simultaneously, the method of adding sequentially, the method of adding sequentially, etc. can be taken.

  The reaction temperature for carrying out the ring-opening polymerization in producing the polyalkylene glycol may be any temperature at which the ring-opening polymerization proceeds, for example, 20 to 160 ° C. Among them, the ring-opening polymerization is carried out efficiently to carry out side reactions. The temperature is preferably 50 to 150 ° C., particularly preferably 80 to 130 ° C., because it is possible to produce a polyalkylene glycol having excellent properties. Further, the reaction pressure is sufficient if ring-opening polymerization proceeds, and is, for example, in the range of 0.001 to 1.5 MPa, more preferably 0.01 to 1.0 MPa, particularly 0.1 to 0. The range is preferably 5 MPa. The reaction time may be appropriately selected depending on the amount of catalyst or the polymerization temperature or pressure, and is usually 0.1 to 30 hours, preferably 0.5 to 24 hours.

  The atmosphere for producing the polyalkylene oxide can be carried out in an atmosphere of an inert gas such as nitrogen or argon if necessary.

  When carrying out the ring-opening polymerization reaction of alkylene oxide, it is also possible to use a solvent if necessary, and the solvent at that time is not limited as long as it does not inhibit the ring-opening polymerization reaction, For example, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, 1,3-dioxane and anisole; dimethyl sulfoxide and N, N-dimethyl Examples include aprotic polar solvents such as formamide, hexamethylphosphoramide, N, N′-dimethylimidazolidinone, and the like.

  Further, when producing a polyalkylene glycol using the azacalix [3] pyridinium salt represented by the general formula (1) of the present invention, it is conventionally known for the purpose of reducing the burden of removing the initiator after polymerization. These initiators may be used in combination.

  In addition, when the polyalkylene glycol is produced using the azacalix [3] pyridinium salt represented by the general formula (1) of the present invention as a polyalkylene glycol production catalyst, the aza represented by the general formula (2) is used. Since the reaction between calix [3] pyridine and the active hydrogen, hydroxyl group and carboxyl group, is a reversible reaction, it is possible to efficiently generate active species of ring-opening polymerization reaction, and the production of polyalkylene glycols with excellent catalytic efficiency can be achieved. Since it becomes possible, it is preferable to manufacture polyalkylene glycol by using together the azacalix [3] pyridinium salt shown by General formula (1), and an active hydrogen compound. Examples of the active hydrogen compound at that time include 2 to 8 hydroxyl groups having 2 to 20 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. Polyhydric alcohols having: sugars such as glucose, sorbitol, dextrose, fructose, sucrose or derivatives thereof; polyethylene glycol, polypropylene glycol or copolymers thereof having 2 to 6 ends and 2 to 6 at the ends Mention may be made of polyalkylene oxides having a number average molecular weight of 200 to 10,000 having a single hydroxyl group. The mixing ratio of the active hydrogen compound at that time is particularly excellent in the production efficiency of the polyalkylene glycol, so that it is 0.1 to 10,000 per 1 mol of the azacalix [3] pyridinium salt represented by the general formula (1). It is preferable that it is mol, and it is especially preferable that it is 10-500 mol. The active hydrogen compound may be added to the azacalix [3] pyridinium salt during or before the ring-opening polymerization reaction, or a large excess is required when preparing the azacalix [3] pyridinium salt. It is also possible to prepare an active hydrogen compound in a state where an unreacted active hydrogen compound coexists.

  The obtained polyalkylene glycol can be purified by a conventional purification method such as treatment with an acid, carbon dioxide, acid-type ion exchange resin, or the like, or washing with water, an organic solvent or a mixture thereof.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The evaluation / measurement methods used in the examples are shown below.

~ NMR spectrum measurement ~
Measurement was performed using a nuclear magnetic resonance spectrum measuring apparatus (270 MHz-NMR: (trade name) EX-270 manufactured by JEOL Ltd.) and DMSO-d6 (manufactured by Aldrich) as a heavy solvent.

~ Measurement of hydroxyl value ~
It measured according to the measuring method of JISK1557.

~ Measurement of molecular weight distribution ~
Using gel permeation chromatography (GPC) (manufactured by Tosoh Corp., (trade name) HLC8020GPC), tetrahydrofuran was used as a solvent, and the number average molecular weight (Mn) as a standard polystyrene conversion value from an elution curve measured at 40 ° C, The weight average molecular weight (Mw) was measured, and the molecular weight distribution (Mw / Mn) was calculated.

~ Organic element analysis ~
Measurement was performed using an elemental analyzer (manufactured by Perkin-Elmer, (trade name) 2400 CHN Elemental Analyzer).

~ Activity of catalyst for polyalkylene glycol production ~
The catalytic activity when the obtained azacalix [3] pyridinium salt was used as a catalyst for producing polyalkylene glycol was calculated by the following formula.
Catalytic activity = A / (B × C)
(Here, A is the amount of alkylene oxide (g) subjected to the ring-opening polymerization reaction, and calculated from A = (weight of polyalkylene glycol obtained) − (weight of active hydrogen compound + weight of catalyst). (The amount of catalyst for producing polyalkylene glycol (mol), and C is the reaction time (min).)

~ Active hydrogen compounds ~
Polyols such as polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sanniks GP-1000: number of hydroxyl groups = 3, molecular weight = 1000), polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sanniks GP-400: number of hydroxyl groups = 3, molecular weight = 400).

  Synthesis Example 1 (Synthesis of 2,6-dibromo-4-pyrrolidinylpyridine)

J. et al. Med. Chem. , 2003, 46, pp. According to the method described in 1273 to 1276, 1.5 g (5.1 mmol, 93% yield) of 2,6-dibromo-4-nitropyridine was obtained in 3 steps from 1.3 g (5.5 mmol) of 2,6-dibromopyridine. Was obtained as a white solid.
A 25 ml Schlenk tube equipped with a magnetic rotor was charged with 0.12 g (5 mmol) of sodium hydride and 3.5 ml of dehydrated dimethylformamide. The resulting mixture showed a light blue color. After adding 0.42 g (5 mmol) of pyrrolidine to this solution, 1.41 g (5 mmol) of synthesized 2,6-dibromo-4-nitropyridine was added, and the reaction was performed with stirring at room temperature for 2 hours. After completion of the reaction, water was added to quench the reaction, followed by extraction with ethyl acetate. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The concentrated residue was isolated by silica gel column chromatography using hexane / ethyl acetate = 10/1 to 5/1 as a developing solvent. 1.1 g (yield 73%) of a white solid having a purity of 99% or more was obtained.
As a result of analysis, the obtained compound was 2,6-dibromo-4-pyrrolidinylpyridine.
270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 2.04 (t, 4H), 3.27 (t, 4H), 6.48 (s, 2H)

  Synthesis Example 2 (Synthesis of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) pyridine)

SYNLETT, 2005, No. 2, pp. According to the method described in H.263-266, 1.34 g (yield 82%) of a pale yellow solid was obtained.
As a result of analysis, this pale yellow solid was N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) pyridine.
270 MHz ¹ H-NMR measurement results; δ (CDCl ₃ ): 2.42 (s, 9H), 6.08 (d, 6H), 7.17 (t, 3H), 7.28 to 7.36 ( m, 12H)
FAB-MS: 547 (M)

  Synthesis Example 3 (Synthesis of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine))

In a 200 ml four-necked flask equipped with a magnetic rotor, 8.3 g (10.2 mmol) of potassium carbonate, 180 mg (12.5 mmol) of cuprous bromide, 4-pyrrolidinyl-2 obtained in Synthesis Example 1, N, N-bis (6-bromo-4-pyrrolidinylpyridyl) toluidine 557 mg (1.0 mmol) synthesized from 6-dibromopyridine and toluidine, and N, N′-di (p-toluyl) -2,6 358 mg (1.0 mmol) of -diamino-4-pyrrolidinylpyridine was added and the mixture was brought to a nitrogen atmosphere. 100 ml of nitrobenzene was added and a reflux tube was attached. After the inside of the reflux tube was also in a nitrogen atmosphere, the oil bath was heated to 240 ° C. The reaction was continued with heating and stirring at 240 ° C. for 3 hours. After 3 hours, the raw materials N, N′-di (p-toluyl) -2,6-diamino-4-pyrrolidinylpyridine and N, N-bis (6-) were analyzed by thin layer chromatography (propylamine-modified silica gel). The disappearance of bromo-4-pyrrolidinylpyridyl) toluidine was confirmed. Thereafter, the oil bath was removed and the mixture was allowed to cool to room temperature (23 ° C.). Nitrobenzene was removed in the range of 60-90 ° C. under 1 Torr vacuum. The resulting black-brown viscous liquid was separated and purified by column chromatography (propylamine-modified silica gel, eluent: hexane / ethyl acetate = 7/3, chloroform, acetonitrile in this order), and the powder obtained by removing the solvent The body was washed with diethyl ether to obtain 442 mg (yield 53%) of a pale yellow solid.
As a result of NMR measurement, the obtained pale yellow solid was protonated with N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine). (The counter anion is a Br anion).
270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ); 1.84 (s, 9H), 2.50 (s, 12H), 2.89 (s, 12H), 4.89 (s, 6H) 7.25 (d, 6H), 7.41 (d, 6H), 21.03 (s, 1H)
ESI-MS; Positive: 754 (m / z)
150 mg of a proton adduct of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) obtained by the above cyclization reaction was magnetically used. In addition to a two-necked eggplant flask with a rotor, a nitrogen atmosphere was established. 100 ml of chloroform and 150 ml of 2.5 wt% sodium hydroxide aqueous solution (pH: 13.8) were added and reacted at room temperature. Thereafter, the operation of removing the aqueous layer and reacting again by adding 150 ml of 2.5 wt% sodium hydroxide aqueous solution was repeated 5 times. Finally, after removing the aqueous layer, the chloroform solution was removed under reduced pressure of 1 Torr. As a result of NMR analysis, the obtained reddish-brown solid was deprotonated N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine). I confirmed that there was.
270 MHz ¹ H-NMR measurement result; δ (DMSO-d6): 1.80 (s, 9H), 2.27 (s, 12H), 2.98 (s, 9H), 5.66 (s, 6H) ), 7.05 (d, 6H), 7.125 (d, 6H)

Example 1
As an active hydrogen compound, 0.2 g (0.2 mmol) of polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) was heated and dried, and charged into a 50 ml Schlenk tube substituted with nitrogen. It is. And 300 mg of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) obtained by the same method as in Synthesis Example 3. 4 mmol) was dissolved in 4 ml of dimethyl sulfoxide, and the resulting solution was pressed into a Schlenk tube at a nitrogen pressure using a polytetrafluoroethylene tube. The mixture was stirred at 25 ° C. for 24 hours. After 24 hours, NMR of the mixture was measured. As a result, N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) was all protons. After confirming that it was changed to an adduct, azacalix [3] pyridinium salt (R ₁ represented by the general formula (1) is a methyl group, R ₂ is a pyrrolidinyl group, n is 2, and Y ⁿ⁻ is 3 Two of the hydroxyl groups in the above are alkoxy anions of polypropylene glycol having a molecular weight of 1000, which are alkoxy anions.
270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ); 1.84 (s, 9H), 2.50 (s, 12H), 2.89 (s, 12H), 4.89 (s, 6H) 7.25 (d, 6H), 7.41 (d, 6H), 21.03 (s, 1H)

Example 2
24 mg (0.4 mmol) of acetic acid is used instead of 0.2 g (0.2 mmol) of polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: number of functional groups = 3, molecular weight = 1000) as an active hydrogen compound The same operation as in Example 1 was performed except that. After 0.5 hours, the mixture was allowed to cool to room temperature and then NMR was measured. As a result, N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrroline) was measured. It was confirmed that all of the dinypyridines were converted to proton adducts, and azacalix [3] pyridinium salt (R ₁ in the general formula (1) was a methyl group, R ₂ was a pyrrolidinyl group, n = 1, Y ⁿ⁻ is an acetoxy anion).

Example 3
As an active hydrogen compound, 1.0 g (1 mmol) of polypropylene glycol (manufactured by Sanyo Chemical Co., Ltd., (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) is taken in a 200 ml glass autoclave and nitrogen at a pressure of 0.1 MPa. The inside of the autoclave was purged with nitrogen using a gas. 0.75 g (1 mmol) of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) obtained by the same method as in Synthesis Example 3 Is dissolved in 10 ml of dimethyl sulfoxide, the dimethyl sulfoxide solution is press-fitted into the autoclave with nitrogen, and polypropylene glycol and N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) ( 4-Pyrrolidinylpyridine) was stirred at room temperature for 24 hours to carry out the reaction, and an azacalix [3] pyridinium salt (wherein R ₁ in the general formula (1) is a methyl group and R ₂ is a pyrrolidinyl group) , N is 1, and Y ⁿ⁻ is one of three hydroxyl groups, which is an alkoxy anion of a polypropylene glycol having a molecular weight of 1000, which is an alkoxy anion.
Thereafter, the temperature in the autoclave was raised to 110 ° C., and 7 g (0.12 mol) of propylene oxide was sequentially added over 1 hour so that the internal pressure became 0.3 MPa or less. After the supply of propylene oxide was stopped, the mixture was aged for 1 hour, and while maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 5.7 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 4900 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 41 g / (mol Min).

Example 4
Except for the active hydrogen compound, 0.092 g (1 mmol) of glycerin instead of 1.0 g (1 mmol) of polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) The same operation as in Example 3 was performed. At room temperature for 24 hours stirring the reaction was carried out Azakarikkusu [3] _{R 1} is a methyl group represented by the pyridinium salt (formula (1), _{R 2} is a pyrrolidinyl group, with n is ^{1, Y n-of} glycerin alkoxy anion There is.)
Thereafter, the temperature in the autoclave was raised to 110 ° C., and 7 g (0.58 mol) of propylene oxide was sequentially added over 1 hour so that the internal pressure became 0.3 MPa or less. After stopping the supply of propylene oxide, the mixture was aged for 1 hour, and at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 4.1 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 3600 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 28 g / (mol Min).

Example 5
The same operation as in Example 3 was performed except that the polymerization reaction temperature of propylene oxide was changed from 110 ° C to 120 ° C. While maintaining the temperature at 120 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 6.5 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 5700 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 48 g / (mol). Min).

Example 6
The same operation as in Example 3 was performed except that the polymerization reaction temperature of propylene oxide was changed from 110 ° C to 90 ° C. While maintaining the temperature at 90 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 3.9 g of polyalkylene oxide. The obtained polypropylene glycol had a molecular weight of 3000 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a catalyst for producing polyalkylene glycol was 26 g / (mol). Min).

Example 7
As an active hydrogen compound, polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: number of functional groups = 3, molecular weight = 1000) 1.0 g (1 mmol) instead of polypropylene glycol (manufactured by Sanyo Chemical, (Product Name) Sannix GP-400: Azacalix [3] pyridinium salt (general formula) except that the number of functional groups = 3, molecular weight = 400) was changed to 0.4 g (1 mmol). (1) R ₁ is a methyl group represented by, R ₂ is pyrrolidinyl radical, n is 1, Y ^n-1 pieces of the three number of hydroxyl groups is in the alkoxy anion of polypropylene glycol having a molecular weight = 400 is an alkoxy group There is.)
Thereafter, 5.8 g (0.1 mol) of propylene oxide was sequentially added over 1 hour so that the internal pressure became 0.3 MPa or less. It was aged for 1 hour after the supply of propylene oxide was stopped. While maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 4.8 g of polypropylene glycol. The obtained polypropylene glycol had a molecular weight of 4500 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a catalyst for producing polyalkylene glycol was 33 g / (mol). Min).

Example 8
After operating in the same manner as in Example 7, the temperature was lowered to 50 ° C. and propylene oxide was removed under reduced pressure. Thereafter, the temperature was raised again to 110 ° C., and 5 g of ethylene oxide was sequentially supplied over 1 hour so that the pressure became 0.4 MPa or less. After feeding ethylene oxide, the mixture was aged at 110 ° C. for 2 hours. While maintaining at 110 ° C., ethylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 6.3 g of a polypropylene glycol / polyethylene glycol copolymer. The obtained polypropylene glycol / polyethylene glycol had a molecular weight of 5500 and a molecular weight distribution (Mw / Mn) of 1.06.

Example 9
As an active hydrogen compound, 180 mg (0.18 mmol) of polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) in a 200 ml glass autoclave and nitrogen at a pressure of 0.1 MPa The inside of the autoclave was purged with nitrogen using a gas. N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) 135 mg (0.18 mmol) obtained by the same method as in Synthesis Example 3 Is dissolved in 4 ml of dimethyl sulfoxide, the dimethyl sulfoxide solution is pressed into an autoclave with nitrogen, and polypropylene glycol and N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) ( 4-Pyrrolidinylpyridine) was stirred at room temperature for 24 hours to carry out the reaction, and an azacalix [3] pyridinium salt (wherein R ₁ in the general formula (1) is a methyl group and R ₂ is a pyrrolidinyl group) , n is 1, Y ^n-1 pieces of the three hydroxyl groups are alkoxy anion of polypropylene glycol having a molecular weight of 1000 which is alkoxy anion.) to give the
Then, 0.82 g (0.82 mmol) of polypropylene glycol (manufactured by Sanyo Chemical Industries, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) was placed in the autoclave, and the temperature was raised to 110 ° C. The mixture was warmed, and 7 g (0.12 mol) of propylene oxide was sequentially added over 3 hours so that the internal pressure became 0.3 MPa or less. After stopping the supply of propylene oxide, the mixture was aged for 1 hour, and at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 4.9 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 4900 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 90 g / (mol Min).

Example 10
The same operation as in Example 9 was carried out, and an azacalix [3] pyridinium salt (in the general formula (1), R ₁ was a methyl group, R ₂ was a pyrrolidinyl group, n was 1, and Y ⁿ⁻ was three hydroxyl groups. 1 is an alkoxy anion of a polypropylene glycol having a molecular weight of 1000, which is an alkoxy anion.
Thereafter, 4.82 g (4.82 mmol) of polypropylene glycol (manufactured by Sanyo Chemical Industries, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) was placed in the autoclave, and the temperature was raised to 110 ° C. The mixture was warmed and 33 g (0.58 mol) of propylene oxide was sequentially added over 7 hours so that the internal pressure became 0.3 MPa or less. After stopping the supply of propylene oxide, the mixture was aged for 3 hours, and while maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 23.8 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 4900 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 176 g / (mol). Min).

Example 11
The active hydrogen compound was changed to polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sanniks GP-1000: hydroxyl number = 3, molecular weight = 1000) 180 mg (0.18 mmol) instead of glycerol 17 mg (0.18 mmol). The same operation as in Example 9 was performed. At room temperature for 24 hours stirring the reaction was carried out Azakarikkusu [3] _{R 1} is a methyl group represented by the pyridinium salt (formula (1), _{R 2} is a pyrrolidinyl group, with n is ^{1, Y n-of} glycerin alkoxy anion There is.)
Thereafter, 0.442 (4.82 mmol) of glycerin was placed in the autoclave, the temperature was raised to 110 ° C., and 33 g (0.58 mol) of propylene oxide was added for 7 hours so that the internal pressure became 0.3 MPa or less. Over time. After stopping the supply of propylene oxide, the mixture was aged for 3 hours, and while maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 16.8 g of polypropylene glycol. The obtained polypropylene glycol had a molecular weight of 3600 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a catalyst for producing a polyalkylene glycol was 151 g / (mol). Min).

Example 12
Polypropylene glycol (manufactured by Sanyo Kasei, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) 5.0 g (5 mmol) as an active hydrogen compound was placed in a 200 ml glass autoclave and nitrogen at a pressure of 0.1 MPa. The inside of the autoclave was purged with nitrogen using a gas. N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) 135 mg (0.18 mmol) obtained by the same method as in Synthesis Example 3 Is dissolved in 4 ml of dimethyl sulfoxide, the dimethyl sulfoxide solution is pressed into an autoclave with nitrogen, and polypropylene glycol and N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) ( 4-Pyrrolidinylpyridine) was stirred at room temperature for 24 hours to carry out the reaction, and an azacalix [3] pyridinium salt (wherein R ₁ in the general formula (1) is a methyl group and R ₂ is a pyrrolidinyl group) , N is 1, and Y ⁿ⁻ is an alkoxy anion of polypropylene glycol).
Thereafter, the temperature in the autoclave was raised to 110 ° C., and 33 g (0.58 mol) of propylene oxide was sequentially added over 7 hours so that the internal pressure became 0.3 MPa or less. After stopping the supply of propylene oxide, the mixture was aged for 3 hours, and while maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 23.8 g of polypropylene glycol. The obtained polypropylene glycol has a molecular weight of 4900 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a polyalkylene glycol production catalyst was 176 g / (mol). Min).

Example 13
As an active hydrogen compound, except that polypropylene glycol (manufactured by Sanyo Chemical Industries, (trade name) Sannix GP-1000: hydroxyl number = 3, molecular weight = 1000) 5.0 g (5 mmol) was replaced with glycerin 0.46 g (5 mmol). The same operation as in Example 12 was performed. At room temperature for 24 hours stirring the reaction was carried out Azakarikkusu [3] _{R 1} is a methyl group represented by the pyridinium salt (formula (1), _{R 2} is a pyrrolidinyl group, with n is ^{1, Y n-of} glycerin alkoxy anion There is.)
Thereafter, the temperature in the autoclave was raised to 110 ° C., and 33 g (0.58 mol) of propylene oxide was sequentially added over 7 hours so that the internal pressure became 0.3 MPa or less. After stopping the supply of propylene oxide, the mixture was aged for 3 hours, and while maintaining at 110 ° C., propylene oxide and dimethyl sulfoxide were removed under reduced pressure to obtain 16.8 g of polypropylene glycol. The obtained polypropylene glycol had a molecular weight of 3600 and a molecular weight distribution (Mw / Mn) of 1.05. At this time, the catalytic activity of the azacalix [3] pyridinium salt as a catalyst for producing a polyalkylene glycol was 151 g / (mol). Min).

Comparative Example 1
Instead of 1 mmol of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine), N, N ′, Production of polypropylene glycol was attempted by the same operation as in Example 3 except that 7 mmol of N ″ -tris (p-tolyl) azacalix [3] (2,6) pyridine was used.
The obtained polypolypropylene glycol was 5.1 g, and the ring-opening polymerization reaction of propylene oxide did not proceed.

Comparative Example 2
Instead of N, N ′, N ″ -tris (p-tolyl) azacalix [3] (2,6) (4-pyrrolidinylpyridine) (1 mmol), 2,8,9-triisopropyl2, Except for using 0.75 g (2.5 mmol) of 5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (manufactured by Ardrich), the same operation as in Example 3 was performed, 3.1 g of polypropylene glycol was obtained.
The obtained polypropylene glycol had a molecular weight of 2400 and a molecular weight distribution (Mw / Mn) of 1.06, and the activity of the catalyst was only 7 g / (mol · min).

  The novel azacalix [3] pyridinium salt of the present invention efficiently produces a polyalkylene glycol useful as an organic base catalyst as a reactant for various reactions, particularly as a raw material for polyurethanes such as polyurethane elastomers, adhesives, paints, and foams. This is expected as a catalyst for polyurethane production that can be performed.

Claims (8)

Azakarikkusu characterized in that it is represented by the following general formula (1) [3] pyrid two Umushio.

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an electron donating group, R ₂ represents an electron donating group which may be the same as or different from R _1, and n is 1 to 8) Y ^n- represents a hydroxy anion; an alcohol having 1 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms having 2 to 8 hydroxyl groups, a saccharide or a derivative thereof, and 1 to 8 at the terminal shows the polyalkylene oxides having a number average molecular weight from 200 to 50,000 having hydroxyl group, a carboxy anion derived from a carboxylic acid having 1 to 20 carbon atoms having an alkoxy anion or 1-8 carboxyl groups derived from. here, The electron donating group is an aliphatic or aromatic alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, an unsubstituted or alkyl-substituted group having 4 to 7 carbon atoms. Selected from the group consisting of a cyclic amino group, 1,1,3,3-tetramethylguanidino group, iminotris (dimethylamino) phosphoranyl group, and an alkoxy anion derived from a saccharide or a derivative thereof is glucose An alkoxy anion derived from a group selected from the group consisting of sorbitol, dextrose, fructose, and sucrose. A method for producing an azacalix [3] pyridinium salt represented by the following general formula (1), wherein an azacalix [3] pyridine represented by the following general formula (2) is reacted with an active hydrogen compound.

(Wherein, R ₁ represents a hydrogen atom, an alkyl group or an electron donating group having 1 to 10 carbon atoms, R ₂ represents a good electron-donating group be the same or different and R _1. Here, an electron-donating The group includes an aliphatic or aromatic alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, an unsubstituted or alkyl-substituted cyclic amino group having 4 to 7 carbon atoms, 1,1, It is selected from the group consisting of a 3,3-tetramethylguanidino group and an iminotris (dimethylamino) phosphoranyl group.

(Wherein, _{R 1} and _{R 2} are the same as the above-mentioned general formula (2), n indicates the actual number of 1 to ^{8, Y n-hydroxy} anion; alcohols having 1 to 20 carbon atoms, 2-8 Alkoxy anion derived from polyhydric alcohols having 2 to 20 carbon atoms, saccharides or derivatives thereof, polyalkylene oxides having 1 to 8 hydroxyl groups and number average molecular weight of 200 to 50000, or 1 A carboxy anion derived from a carboxylic acid having 1 to 20 carbon atoms and having 1 to 20 carbon atoms , wherein the alkoxy anion derived from a saccharide or a derivative thereof consists of glucose, sorbitol, dextrose, fructose, and sucrose. An alkoxy anion derived from one selected from the group. ) The method for producing an azacalix [3] pyridinium salt according to claim 2, wherein the reaction is carried out in an aprotic polar solvent at 20 to 160 ° C. The method for producing an azacalix [3] pyridinium salt according to claim 3, wherein the aprotic polar solvent is dimethyl sulfoxide. A catalyst for producing a polyalkylene glycol, comprising an azacalix [3] pyridinium salt represented by the following general formula (1).

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an electron donating group, R ₂ represents an electron donating group which may be the same as or different from R _1, and n is 1 to 8) Y ^n- represents a hydroxy anion; an alcohol having 1 to 20 carbon atoms, a polyhydric alcohol having 2 to 20 carbon atoms having 2 to 8 hydroxyl groups, a saccharide or a derivative thereof, and 1 to 8 at the terminal shows the polyalkylene oxides having a number average molecular weight from 200 to 50,000 having hydroxyl group, a carboxy anion derived from a carboxylic acid having 1 to 20 carbon atoms having an alkoxy anion or 1-8 carboxyl groups derived from. here, The electron donating group is an aliphatic or aromatic alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, an unsubstituted or alkyl-substituted group having 4 to 7 carbon atoms. Selected from the group consisting of a cyclic amino group, 1,1,3,3-tetramethylguanidino group, iminotris (dimethylamino) phosphoranyl group, and an alkoxy anion derived from a saccharide or a derivative thereof is glucose An alkoxy anion derived from a group selected from the group consisting of sorbitol, dextrose, fructose, and sucrose. 6. The polyalkylene glycol according to claim 5, wherein in the general formula (1), R ₁ is a hydrogen atom or a methyl group and R ₂ is a azacalix [3] pyridinium salt which is a pyrrolidinyl group. Catalyst for production. A method for producing a polyalkylene glycol, comprising ring-opening polymerization of at least one alkylene oxide in the presence of the catalyst for producing a polyalkylene glycol according to claim 5 or 6. The method for producing a polyalkylene glycol according to claim 7, wherein ring-opening polymerization of at least one alkylene oxide is performed in the presence of the catalyst for producing polyalkylene glycol according to claim 5 or 6 and an active hydrogen compound. .