JP7072344B2 - Polyurethane-forming composition - Google Patents

Description

The present invention relates to polyurethane-forming compositions.

Polyalkylene oxide is frequently used as one of the raw materials for polyurethane. Polyurethane obtained by mixing polyalkylene oxide and isocyanate compounds and reacting them is mainly used for coating materials, adhesives / adhesives, sealing materials, and elastomers. , Widely used for various purposes.

This polyalkylene oxide is industrially produced by addition polymerization of alkylene oxide using potassium hydroxide as a catalyst. However, when a high molecular weight polyalkylene oxide is produced by this method, the obtained polyalkylene oxide contains a large amount of monool having a single-ended double bond (unsaturated group) as a by-product.
Here, when a polyurethane is to be obtained using a polyalkylene oxide, if the ratio of monool in the polyalkylene oxide is increased, the polyurethane obtained by the reaction with the isocyanate compound does not have a high molecular weight and is obtained. When the polyurethane is subjected to tensile deformation, the elongation is reduced, and as a result, the strength at the time of tensile break is also reduced.

Further, in order to obtain polyurethane using polyalkylene oxide, there is also a method using a prepolymer having a terminal isocyanate group obtained by reacting a terminal hydroxyl group of the polyalkylene oxide with a polyfunctional isocyanate compound. Even if a polyurethane is to be obtained by this method, when a polyalkylene oxide having a high monool ratio is used, the molecular weight does not increase, and the mechanical properties of the obtained polyurethane have the same problems as described above. Occurs.

Furthermore, when polyurethane is to be obtained using polyalkylene oxide having a high proportion of monool or a prepolymer using it, the crosslink density in polyurethane decreases, so that the elastic recovery after deformation, which is a characteristic of polyurethane, is achieved. Is scarce, and the rebound resilience, hysteresis loss, and compression set of polyurethane of polyurethane are reduced.

Therefore, in polyurethane using polyalkylene oxide, it is extremely important to reduce monool in polyalkylene oxide (lower the degree of unsaturation). Since monool has a low molecular weight, if the amount of monool in the polyalkylene oxide is reduced, the amount of the low molecular weight component in the polyalkylene oxide is also reduced.

Under the above background, as a polyalkylene oxide containing a small amount of monool, a polyalkylene oxide obtained by using a complex metal cyanide complex as a catalyst is known (see, for example, Patent Documents 1 and 2). However, the polyalkylene oxides described in Patent Documents 1 and 2 have a wide molecular weight distribution, and the catalysts described in Patent Documents 1 and 2 also have a problem that ethylene oxide, which is frequently used in the field as an alkylene oxide, is difficult to adapt. ..

Further, as a polyalkylene oxide containing a small amount of monool, a polyalkylene oxide obtained by using a specific phosphazenium salt as a catalyst is known (see, for example, Patent Documents 3, 4, and 5). However, even with the polyalkylene oxides described in Patent Documents 3, 4, and 5, monool is still abundant.

Further, as a polyalkylene oxide containing a small amount of monool, a polyalkylene oxide obtained by using a catalyst composed of a phosphazene compound and triisobutylaluminum is also known (see, for example, Non-Patent Document 1). However, the polyalkylene oxide described in Non-Patent Document 1 also has a wide molecular weight distribution.

Here, when a polyurethane is to be obtained by using a polyalkylene oxide having a small amount of monool but a wide molecular weight distribution or a prepolymer obtained by using the polyalkylene oxide, the molecular weight distribution of the obtained polyurethane is widened and the crosslinked structure is also non-uniform. (The molecular weights between the cross-linking points are not uniform), which makes it difficult to stabilize the product properties.

US Pat. No. 5,235,114 Japanese Unexamined Patent Publication No. 4-59825 Japanese Patent No. 3497054 (Japanese Unexamined Patent Publication No. 10-77289) Japanese Patent No. 3905638 (Japanese Unexamined Patent Publication No. 11-106500) Japanese Patent No. 5663856 (Japanese Unexamined Patent Publication No. 2010-150514)

Polymer Chemistry, 2012, 3, 1189.

The present invention has been made in view of the above background technique, and an object thereof is repulsive elasticity and hysteresis based on the fact that the tensile elongation and tensile breaking strength are larger than those of conventional polyurethane, and the elastic recovery force after deformation is excellent. It is an object of the present invention to provide a polyurethane composed of a polyurethane-forming composition having good loss and compression set and stable physical properties thereof, and a reaction product thereof.

As a result of diligent studies to solve the above problems, the present inventors have made polyalkylene oxides and isocyanate compounds having a high molecular weight, a small amount of monool (low degree of unsaturatedity), a narrow molecular weight distribution, and a small amount of low molecular weight components. We have found that a prepolymer obtained from a composition consisting of a composition comprising, a polyurethane obtained from the composition, a prepolymer obtained from the composition consisting of the polyalicyrene oxide and an isocyanate compound, and a polyurethane obtained using the same can lead to a solution to the problem. The invention was completed.

That is, the present invention relates to a composition comprising a polyalkylene oxide and an isocyanate compound as shown below, and a prepolymer and a polyurethane obtained from the composition.

[1] A polyurethane-forming composition containing a polyalkylene oxide (A) and an isocyanate compound (B) satisfying all of the following i) to iv).
i) Degree of unsaturation is 0.020 meq / g or less ii) Mw / Mn is 1.10 or less ii) Mh / f is 1,000 or more iv) Mh / 3 or less The area ratio of molecular weight is 2.0% or less ( However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is Mn, the weight average molecular weight is Mw, the highest peak molecular weight is Mh, and the number of functional groups of polyalkylene oxide is f).
[2] The molecular weight of the polyalkylene oxide (A) calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is in the range of 1000 to 50,000 g / mol. The composition according to the above [1].

[3] The isocyanate compound (B) is at least one selected from the group consisting of aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof [3]. 1] or the composition according to [2].

[4] The composition according to any one of the above [1] to [3], which comprises a prepolymer composed of a reaction product of a polyalkylene oxide (A) and an isocyanate compound (B).

[5] Polyurethane comprising the reaction product of the composition according to any one of the above [1] to [4].

The polyurethane composed of the reaction product of the polyurethane forming composition of the present invention has higher tensile elongation and tensile breaking strength than the conventional polyurethane, and has excellent elastic recovery force after deformation, such as impact resilience, hysteresis loss, and compression set. Is good, and those various physical properties can be stably obtained.

It is a figure which shows the calculation method of the area ratio of the low molecular weight component of a polyalkylene oxide in an Example. It is a figure (enlarged view) which shows the calculation method of the area ratio of the low molecular weight component of a polyalkylene oxide in an Example.

The polyurethane-forming composition of the present invention contains a polyalkylene oxide (A) and an isocyanate compound (B) that satisfy all of the following i) to iv).
i) Unsaturation degree is 0.020 meq / g or less ii) Mw / Mn is 1.10 or less ii) Mh / f is 1,000 or more iv) Mh / 3 or less The area ratio of molecular weight is 2.0% or less ( However, using polystyrene as a standard substance, the number average molecular weight obtained from gel permeation chromatography measurement is Mn, the weight average molecular weight is Mw, the highest peak molecular weight is Mh, and the number of functional groups of polyalkylene oxide is f).
In the present invention, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is "Mn", the weight average molecular weight is "Mw", the highest peak molecular weight is "Mh", and the number of functional groups of polyalkylene oxide. Let be "f".

The amount of monool of the polyalkylene oxide (A) is 0.020 meq / g or less, preferably 0.010 meq / g or less in terms of unsaturation. When the degree of unsaturation becomes larger than 0.020 meq / g, the molecular weight of polyurethane does not increase due to the reaction with the isocyanate compound, including the case where the prepolymer composed of the polyalkylene oxide is used, and the crosslink density also increases. Since it is lowered, the tensile elongation and the tensile breaking strength are lowered, and the impact resilience, the hysteresis loss, and the compression set are also deteriorated, which is not preferable.

The Mw / Mn of the polyalkylene oxide (A) is 1.10 or less, preferably 1.08 or less. When Mw / Mn is larger than 1.10, the molecular weight distribution when polyurethane is formed by reaction with the isocyanate compound is widened and the crosslinked structure is non-uniform, including the case where the prepolymer composed of the polyalkylene oxide is used. The molecular weight between the cross-linking points is not uniform), which makes it difficult to stabilize the product properties, which is not preferable.

The Mh / f of the polyalkylene oxide (A) is 1,000 or more, preferably 1,500 or more. Mh / f is one of the indexes related to the molecular weight of polyalkylene oxide. When Mh / f is smaller than 1,000, the crosslink density becomes excessively high when polyurethane is formed by reaction with an isocyanate compound, which is a characteristic of polyurethane. This is not preferable because the flexibility, which is one of the above, deteriorates.

In the polyalkylene oxide (A), the area ratio of the molecular weight of Mh / 3 or less is 2.0% or less, preferably 1.0% or less. The index of Mh / 3 or less indicates the small amount of low molecular weight components in the polyalkylene oxide including monool, and when the area ratio of the molecular weight of Mh / 3 or less is larger than 2.0%, the polyalkylene The amount of low molecular weight components containing monool in the oxide increases, and when polyurethane is formed by reaction with an isocyanate compound, the molecular weight does not increase and the crosslink density also decreases, so that tensile elongation and tensile breaking strength decrease, and repulsion occurs. It is not preferable because the elasticity, hysteresis loss, and compression set are also deteriorated.

The polyalkylene oxide (A) preferably has a molecular weight of 1000 to 50,000 g / mol as a molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof, and is preferably 3000 to 30000 g. It is particularly preferable that it is / mol.

The polyalkylene oxide (A) can be obtained, for example, by performing ring-opening polymerization of the alkylene oxide using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid.

Examples of the phosphazene compound include a phosphazenium salt represented by the following general formula (1).

(In the above general formula (1), R ¹ and R ² are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, a ring structure in which R ¹ and R ² are bonded to each other, R ^1s or each other. R ² represents a ring structure in which each other is bonded to each other. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. Is 2 when is a carbon atom and 3 when Y is a phosphorus atom.)
Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group and a t-butyl group. , Cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, Cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like can be mentioned.

Further, examples of the case where R ¹ and R ² are bonded to each other to form a ring structure include, for example, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indrill group, an isoindrill group and the like.

As a ring structure in which ^R1s or ^R2s are bonded to each other, for example, a ring structure in which one substituent becomes an alkylene group such as an ethylene group, a propylene group or a butylene group and the other substituent is bonded to each other. Can be mentioned.

Among these, R ¹ and R ² are preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint that they are alkylene oxide polymerization catalysts having particularly excellent catalytic activity and the raw materials are easily available.

Further, X ⁻ in the phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

Examples of the alkoxy anion having 1 to 4 carbon atoms include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion, t-butoxy anion and the like.

Examples of the alkyl carboxy anion having 2 to 5 carbon atoms include acetoxy anion, ethyl carboxy anion, n-propyl carboxy anion, isopropyl carboxy anion, n-butyl carboxy anion, isobutyl carboxy anion, t-butyl carboxy anion and the like. Can be done.

Among these, hydroxy anion and hydrogen carbonate anion are particularly preferable as X ⁻ because it is an alkylene oxide polymerization catalyst having excellent catalytic activity.

Specific examples of the phosphazenic compound include tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydroxide, and tetrakis (1,1). , 3,3-Tetra (n-propyl) guanidino) Phosphonium Hydroxide, Tetrakiss (1,1,3,3-Tetraisopropylguanidino) Phosphonium Hydroxide, Tetrakiss (1,1,3,3-Tetra (n-butyl) ) Phosphonium Hydroxide, Tetrakiss (1,1,3,3-Tetraphenylguanidino) Phosphonium Hydroxide, Tetrakiss (1,1,3,3-Tetrabenzylguanidino) Phosphonium Hydroxide, Tetrakiss (1,3-dimethyl) Imidazolidine-2-imino) Phosphonium Hydroxide, Tetrakiss (1,3-dimethylimidazolidine-2-imino) Phosphonium Hydroxide, Tetrakiss (1,1,3,3-Tetramethylguanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1) , 1,3,3-Tetraethylguanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,1,3,3-Tetra (n-propyl) Guanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,1,3,3-Tetraisopropylguanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,1,3,3-Tetra (n-butyl) guanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,1,3,3-Tetraphenylguanidino) Phosphonium Hydrogen Carbonate, Tetrax (1,1,1 3,3-Tetrabenzylguanidino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,3-dimethylimidazolidine-2-imino) Phosphonium Hydrogen Carbonate, Tetrakiss (1,3-dimethylimidazolidine-2-imino) Phosphonium Hydrogen Carbonate, etc. Phosphonium Salt can be exemplified.

In addition, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (diethylamino) phosphoranilideneamino] phosphonium hydroxydo, tetrakis [tris (din-propylamino) phosphoranilideneamino] phosphonium hydroxydo Do, Tetrakiss [Tris (diisopropylamino) phosphoranylideneamino] phosphonium hydroxide, Tetrakiss [Tris (di-n-butylamino) phosphoranilideneamino] phosphonium hydroxide, Tetrakiss [Tris (diphenylamino) phosphoranilideneamino] phosphonium Hydroxide, Tetrakiss [Tris (1,3-dimethylimidazolidine-2-imino) Phosphoranilideneamino] Phosphonium Hydroxide, Tetrakiss [Tris (dimethylamino) Phosphoranilideneamino] Phosphonium Hydrogen Carbonate, Tetrakiss [Tris (diethylamino) Phosphoranilidene Amino] Phosphonium Hydrogen Carbonate, Tetrakiss [Tris (di n-propylamino) Phosphoranilidene Amino] Phosphonium Hydrogen Carbonate, Tetrakiss [Tris (diisopropylamino) Phosphoranilidene Amino] Phosphonium Hydrogen Carbonate, Tetrakiss [Tris (Di n) -Butylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diphenylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (1,3-dimethylimidazolidine-2-imino) phosphoranilideneamino] Phosphazenium salts such as phosphonium hydrogen carbonate can be exemplified.

Further, 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) phosphoranilideneamino) -2λ5,4λ5-catenadi (phosphazene) can be exemplified. can.

Among these, tetrakis (1,1,3,3-tetramethylguanidino) phosphazenium hydroxide and tetrakis (1,1,3,3-) are the catalysts for producing polyalkylene oxides with excellent catalytic performance. Tetramethylguanidino) phosphazenium hydrogen carbonate, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide are particularly preferred.

Examples of Lewis acid include aluminum compounds, zinc compounds, boron compounds and the like.

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum and the like. Organic aluminum; aluminoxane such as methylaluminoxane, isobutylaluminoxan, and methyl-isobutylaluminoxan; inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide can be mentioned.

Examples of the zinc compound include organic zinc such as dimethylzinc, diethylzinc and diphenylzinc; and inorganic zinc such as zinc chloride and zinc oxide.

Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, trifluoroborane and the like.

Among these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is particularly preferable, because it is an alkylene oxide polymerization catalyst having excellent catalytic performance.

The ratio of the phosphazene compound to the Lewis acid in the alkylene oxide polymerization catalyst is arbitrary as long as the action as the alkylene oxide polymerization catalyst is exhibited, and is not particularly limited, but among them, the polymerization catalyst having particularly excellent catalytic performance. Therefore, it is preferable that the phosphazene compound: Lewis acid = 1: 0.002 to 500 (molar ratio).

The active hydrogen-containing compound is not particularly limited, and examples thereof include water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group.

Examples of the hydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and triol. Examples thereof include methylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoecrose, glucose, 2-naphthol, bisphenol and the like.

Examples of the amine compound include ethylenediamine, N, N'-dimethylethylenediamine, piperidine, piperazine and the like.

Examples of the carboxylic acid compound include benzoic acid and adipic acid.

Examples of the thiol compound include ethanedithiol and butanedithiol.

Examples of the polyether polyol having a hydroxyl group include a polyether polyol having a molecular weight of 200 to 3000.

Then, these active hydrogen-containing compounds may be used alone or in combination of several kinds.

Since the polyalkylene oxide (A) can be efficiently produced, the phosphazene compound is preferably 0.001 to 0.1 mol, more preferably 0.001 to 0.1 mol, based on 1 mol of the active hydrogen in the active hydrogen-containing compound. It is particularly preferably 0.05 mol. Further, since the polyalkylene oxide (A) can be efficiently produced, the Lewis acid is preferably 0.001 to 0.1 mol with respect to 1 mol of the active hydrogen in the active hydrogen-containing compound, and 0. It is particularly preferably 001 to 0.05 mol.

The method for preparing the alkylene oxide polymerization catalyst can be any method as long as the polyalkylene oxide (A) is possible, and is not particularly limited. For example, a method of mixing a phosphazene compound and a Lewis acid can be mentioned. In that case, for example, benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like may be used as the solvent.

Further, in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and Lewis acid, an active hydrogen-containing compound is used as an initiator, and when the alkylene oxide is subjected to ring-opening polymerization, the phosphazene compound, Lewis acid, and the active hydrogen-containing compound are simultaneously mixed. Any method may be used, such as a method of mixing the other two components with one of these components, a method of mixing the other one component with two of these components, and the like.

Among them, since it is excellent in catalytic performance, it is particularly preferable to mix a phosphazene compound and an active hydrogen-containing compound, and then mix Lewis acid to carry out ring-opening polymerization of the alkylene oxide. In that case, heating / depressurization treatment may be performed, and the temperature of the heat treatment may be, for example, 50 to 150 ° C., preferably 70 to 130 ° C., and the pressure during the decompression treatment may be set. Can be, for example, 50 kPa or less, preferably 20 kPa or less.

In the method for producing the polyalkylene oxide (A), the alkylene oxide is not particularly limited, and examples thereof include an alkylene oxide having 2 to 20 carbon atoms. Specific examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxide, styrene oxide, and cyclohexene oxide.

Among these, ethylene oxide and propylene oxide are preferable because alkylene oxide is easily available and the obtained polyalkylene oxide (A) has a high industrial value.

The alkylene oxide may be used alone or in combination of two or more. When two or more kinds are mixed and used, for example, the first alkylene oxide may be reacted and then the second alkylene oxide may be reacted, or two or more kinds of alkylene oxides may be reacted at the same time. ..

In the method for producing the polyalkylene oxide (A), the polymerization pressure is preferably in the range of 0.05 to 1.0 MPa, preferably in the range of 0.1 to 0.6 MPa. In the production of the polyalkylene oxide, the polymerization temperature is preferably in the range of 50 to 140 ° C, preferably in the range of 60 to 130 ° C.

In the method for producing the polyalkylene oxide (A), the polymerization can be carried out in a solvent or in the absence of a solvent. Examples of the solvent used include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like. Preferably, it is carried out in a solvent-free environment.

In the method for producing the polyalkylene oxide (A), since it is an efficient method for producing the polyalkylene oxide, it is preferable that the catalytic activity is 200 g / mol · min or more, and particularly 300 g / mol · min. It is preferable that the above is shown.

In the composition of the present invention, the isocyanate compound (B) to be combined with the alkylene oxide (A) is not particularly limited, and for example, an aromatic isocyanate compound, an aliphatic isocyanate compound, an alicyclic isocyanate compound, and polyisocyanate derivatives thereof and the like. Can be mentioned.

Among these, examples of the aromatic isocyanate compound include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI) and phenylenedi isocyanate (m-, p-phenylenedi isocyanate). Or a mixture thereof, 4,4'-diphenyldiisocyanate, diphenylmethanediisocyanate (4,4'-, 2,4'or 2,2'-diphenylmethanediisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI). ), 4,4'-Diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra Methylxylylene diisocyanate or a mixture thereof) (TMXDI), ω, ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalenedi isocyanate or a mixture thereof) (NDI) ), Triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, polymethylenepolyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4 '-Diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like can be mentioned.

Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, and butylene diisocyanate (tetramethylene diisosianate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene). Diisocyanis), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanismethyl capate, lysine diisocyanate, lysine ester triisisocyanis, Examples thereof include 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate.

Examples of the monocyclic alicyclic isocyanate compound include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and the like. 3-Isocyanate Methyl-3,5,5-trimethylcyclohexylisocyanate (isophoronediisocyanate, IPDI), methylenebis (cyclohexylisocyanate (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate or these) Mixture) (hydrogenated MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, bis (isocyanatemethyl) cyclohexane (1,3- or 1,4-bis (1,3- or 1,4-bis) Isocyanatemethyl) cyclohexane or a mixture thereof) (hydroisocyanate XDI), dimerate diisocyanate, transcyclohexane1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), etc. Can be mentioned.

Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, siisocyanatomethylbicycloheptane, and di (diisocyanatomethyl) tricyclodecane.

Examples of derivatives of these polyisocyanates include multimers of the above isocyanate compounds (dimeric, trimeric, pentameric, hepatic, uretidinedione, ureitoneimine, isocyanurate-modified, polycarbodiimide, etc.). , Urethane modified product (for example, urethane modified product obtained by modifying or reacting a part of isocyanate group in the above isocyanate compound or multimer with monool or polyol), Biuret modified product (for example, by reaction between the above isocyanate compound and water). Biuret modified product to be produced, etc.), allophanate modified product (for example, allophanate modified product produced by reaction of the isocyanate compound with a monool or polyol component, etc.), urea modified product (for example, by reaction of the isocyanate compound with diamine). Examples thereof include urea-modified products (such as urea-modified products) and oxadiazine-trione (for example, oxadiazine-trione produced by the reaction of the above-mentioned isocyanate compound with carbon dioxide gas and the like).

The above isocyanate compound or its derivative may be used alone or in combination of two or more.

The composition of the present invention can include, for example, a prepolymer consisting of a reaction product of a polyalkylene oxide (A) and an isocyanate compound (B). Specifically, such a prepolymer contains a urethane bond obtained by reacting a polyalkylene oxide (A) with a bifunctional or higher functional isocyanate compound as an isocyanate compound (B), and has a terminal. An example is a prepolymer having an isocyanate group. Polyurethane can also be obtained by reacting the composition containing the isocyanate-terminated prepolymer with the polyalkylene oxide (A). Further, it is also possible to prepare a composition composed of this prepolymer and water and react both components to obtain a polyurethane having a urea bond (hereinafter referred to as "polyurethane urea"). Regarding this polyurethane urea, even if water is not intentionally mixed with the prepolymer, by holding the prepolymer in the air, the moisture in the air permeates the prepolymer, and the permeated water permeates the prepolymer. Polyurethane urea can also be obtained by reacting with. Obtaining polyurethane urea in this way is referred to as "moisture curing" in the present technical field. Therefore, this prepolymer can also be used in moisture curing applications for making polyurethane ureas.

When the prepolymer is obtained by reacting the polyalkylene oxide (A) with the composition containing the polyfunctional isocyanate compound as the isocyanate compound (B), for example, 150, as long as it does not affect the composition. The composition can be heated up to ° C, dioctyltin dilaurate, dibutyltin dilaurate, triethylamine, triethylenediamine, stanas octate, dibutyltin di-2-ethylhexanoate, sodium o-phenylphenate, potassium oleate, tetra. Addition of catalysts such as (2-ethylhexyl) titanate, stannic chloride, ferric chloride, antimony trichloride can accelerate the reaction between the polyalkylene oxide and the isocyanate compound to obtain a prepolymer in a short time. can.

The composition of the present invention may contain various additives as long as the effects of the present invention are not impaired, and the effect of the blended additives is expected in the resulting polyurethane. Examples of various additives include dyes, organic pigments, inorganic pigments, inorganic reinforcing materials, plasticizers, processing aids such as acrylic processing aids, ultraviolet absorbers, light stabilizers, lubricants, waxes, and crystal nucleating agents. , Mold release agent, hydrolysis inhibitor, antifogging agent, dustproof agent, rust preventive agent, ion trapping agent, flame retardant, flame retardant aid, inorganic filler, organic filler and the like.

The composition of the present invention can be used for various purposes, and the use is not particularly limited, but for example, coating agents / coatings, adhesives / adhesives, sealants, and the like. The English acronyms for these four applications, such as thermoplastic or thermosetting elastomers, can be suitably used for applications referred to as CASE in the art.

Among these, due to the characteristics of polyurethane composed of the reaction product of the composition of the present invention, it can be used as a coating material in many applications such as building / public structures, woodworking, ships, and intermediate coating of automobiles. can.

Further, due to the characteristics of polyurethane composed of the reaction product of the composition of the present invention, the adhesive may be, for example, a laminated laminated material for flexible packaging materials, that is, a food laminated bag for snacks, boil, retort, and a detergent. It can be used for bonding non-food laminated bags such as wrapping, floor warming floors, and flooring in the construction field, and for bonding solar cell backsheets, liquid crystal TVs, and other batteries in the electronics field. can.

In addition, due to the characteristics of polyurethane composed of reaction products of the composition of the present invention, in the use of sealing materials, building exteriors such as sealing of ALC panels and sashes, jointing of RC walls, skeletons under tiles and outside windows Sealing for frames, sealing for water and gypsum boards in building interiors, sealing for building materials such as waterproof bases and roofs, and sealing for special vehicles such as cold storage cars and automobile window frames. Can be used as a gasket in electrical / electronic equipment, communication equipment, particularly hardwall equipment.

Further, due to the characteristics of polyurethane composed of the reaction product of the composition of the present invention, in the application of elastomer, high pressure hoses, fire hoses, pesticide hoses, hoses such as painting hoses, pneumatic tubes are used as thermoplastic elastomers. , Hydraulic tube, fuel tube, dialysis tube, arterial / vein / heart tube, etc., scratch prevention film / sheet for automobiles, scratch prevention film for instrument panel skin material sofa, air mat, nursing bed sheet, diaphragm, keyboard Sheets, rubber screens, conveyor belts, gaskets, synthetic leather, elastic sheets, flexible films, tarpaulins, clothing, air mats, life jackets, wet suits, hot melts, diaper supplies, packing cushioning films, medical surgical films, etc.・ Sheets, various gears, various grips, solid tires, casters, rollers, anti-vibration / soundproof parts, pickers, bushes, bearings, anti-slip, building materials, packing, caps, watch belts, connectors, rubber screens, printed drums. , Gris cover, hammer, dust cover, film parts, ball joints and other industrial parts, instrument panel skin, gear knob skin, console box skin, leather seats, bumper / side molding, tail lamp seal, snow chain, bush, dust cover, gear , Bearings, caps, ball joints, pedal stoppers, door lock strikers, spring covers, anti-vibration parts and other automobile parts, conveyor belts, timing belts, round belts, V-belts, flat belts and other belts, power / communication cables , ABS sensor cable for automobiles, robot cable, industrial cable, computer wiring, etc., as well as sports shoes, mountain climbing shoes, ski shoes, ski boards, snowboards, motocross boots, safety shoes, high heels, snorkels. , Foot fins, golf ball covers, non-slip stairs, road pole cones, roller skate wheels, various tags, sailboard supplies, ski parts, various ropes, binders, medical dressing materials, catheters, medical ropes, adhesive plasters, etc. For a wide range of applications, and as thermosetting elastomers, papermaking, iron plate rolling rolls, printing, small rolls for office equipment, platen rolls, rolls such as skate rollers, solid tires, casters, battery forklifts, work carriers, work carriers For (pared lift, etc.), Wheels such as industrial truck wheels, idlers for conveyor belts, guide rolls and prairie springs for cables and belts, belt shock absorbers, belts such as oil seals, OA equipment such as cleaning grades for electronic equipment parts and copying machines, It can be used for secondary processing materials such as round bars, pipes, square columns, plates, sheets, etc., and also for a wide range of applications such as various gears, connection ring liners, pump linings, impeller cyclone cones, cyclone liners, polishing pads, etc. Can be used for.

Furthermore, in addition to these uses called CASE, it can be used for leather, spandex, various inks, etc. due to the characteristics of polyurethane composed of the reaction product of the composition of the present invention.

The polyurethane composed of the reaction product of the composition of the present invention can be produced, for example, by reacting the polyalkylene oxide (A) contained in the composition of the present invention with the isocyanate compound (B).

Hereinafter, the present invention will be described with reference to Examples, but the present Examples do not limit the present invention in any way. First, a method for analyzing polyalkylene oxides will be described.

(1) Molecular weight of polyalkylene oxide (unit: g / mol)
Using a gel permeation chromatograph (GPC) (HLC8020, manufactured by Tosoh Corporation), measurement was performed at 40 ° C. using tetrahydrofuran as a solvent, polystyrene was used as a standard substance, and the number average molecular weight (Mn) and weight of the polyalkylene oxide. The average molecular weight (Mw) and the highest peak molecular weight (Mh) were calculated.

Further, the hydroxyl value d (unit: mgKOH / g) of the polyalkylene oxide was measured by the method described in JIS K-1557. The number of functional groups of the obtained polyalkylene oxide was set to e, and the molecular weight of the polyalkylene oxide was calculated by the following formula.

Molecular weight = (56100 / d) x e.

(2) Molecular weight distribution of polyalkylene oxide (unit: dimensionless)
From the Mn and Mw calculated by the above method, the molecular weight distribution (Mw / Mn) of the polyalkylene oxide was calculated.

(3) Area ratio of low molecular weight component of polyalkylene oxide (unit:%)
The area ratio of the low molecular weight component having a molecular weight (Mh / 3) or less obtained by dividing Mh calculated by the above method by 3 was calculated.

(4) Degree of unsaturation of polyalkylene oxide (unit: meq / g)
The degree of unsaturation of the polyalkylene oxide was calculated by the method described in JIS K-1557.

Here, an example of synthesizing the phosphazenium salt used in the examples will be described.

<Synthesis Example 1>: Synthesis of phosphazenium salt A A 2-liter four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere, 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added, and the mixture was stirred at 20 ° C. .. While maintaining stirring, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise, the temperature was raised to 100 ° C., and 107 g (0) of 1,1,3,3-tetramethylguanidine was further added. .92 mol) was added dropwise. The obtained white slurry solution was stirred at 100 ° C. for 14 hours, cooled to 80 ° C., 250 ml of ion-exchanged water was added, and the mixture was stirred for 30 minutes. When the stirring was stopped, all the slurry was dissolved and a two-phase solution was obtained. The obtained two-phase solution was separated into oil and water, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the obtained aqueous phase, oil-water separation was performed, and the dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water.

The obtained dichloromethane solution is transferred to a 2 liter four-necked flask equipped with a stirring blade, 900 g of 2-propanol is added, and then the temperature is raised to 80 to 100 ° C. under normal pressure to remove dichloromethane. bottom. The obtained 2-propanol solution was allowed to cool to 60 ° C. with stirring, and then 31 g (0.47 mol) of 85 wt% potassium hydroxide was added and reacted at 60 ° C. for 2 hours. By cooling the temperature to 25 ° C. and removing the precipitated by-product salt by filtration, the target phosphazenium salt A [R1 in the above general formula ( ¹ ) is a methyl group, ^R2 is a methyl group, and X ^- is A 2-propanol solution of hydroxy anion, Y is a carbon atom, and a is a phosphazenium salt corresponding to 2] was obtained in a concentration of 25% by weight and a yield of 92%.

<Synthesis Example 2>: Synthesis of phosphazenium salt B A 100 ml Schlenk tube equipped with a magnetic rotor is placed under a nitrogen atmosphere, and 5.7 g (7.4 mmol, Aldrich) of tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium chloride is used. ), 16 ml of 2-propanol was added, and the mixture was stirred and dissolved at 25 ° C. A solution of 85% by weight potassium hydroxide 0.53 g [8.1 mmol, 1.1 mol equivalent to tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium chloride] in 2-propanol while maintaining stirring. Was added. After stirring at 25 ° C. for 5 hours, the precipitated by-product salt is removed by filtration to form the desired phosphazenium salt B [R ¹ is a methyl group, R ² is a methyl group, and X ⁻ in the above general formula (1). A 2-propanol solution of hydroxy anion, Y is a phosphorus atom, and a is a phosphazenium salt corresponding to 3] was obtained in a concentration of 17% by weight and a yield of 98%.

Further, a polymerization example of the polyalkylene oxide used in the examples will be described.

<Polymerization Example 1>: Polymerization example of polyalkylene oxide [A1] 18 g (active hydrogen) of a polyether polyol (Sanniks GP1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) in a 0.2 liter autoclave equipped with a stirring blade under a nitrogen atmosphere. (Amount 54 mmol), 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 was added. The internal temperature was set to 80 ° C., and the reduced pressure treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. ..

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and the reaction was carried out while intermittently supplying 92 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., 18 g of ethylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. To obtain 127 g of colorless and odorless polyalkylene oxide. The degree of unsaturation of the obtained polyalkylene oxide is 0.006 meq / g, the molecular weight distribution is 1.06, Mh / f is 3,700 g / mol, and the area ratio of low molecular weight components of Mh / 3 or less is 0.1%. Met. The obtained polyalkylene oxide was designated as [A1].

<Polymerization Example 2>: Polymerization example of polyalkylene oxide [A2] 18 g (active hydrogen amount) of a polyether polyol (Sanniks GP1000 manufactured by Sanyo Kasei Kogyo Co., Ltd.) in a 0.2 liter autoclave equipped with a stirring blade under a nitrogen atmosphere. 54 mmol), 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 was added. The internal temperature was set to 80 ° C., and the reduced pressure treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol / l hexane solution of aluminum isopropoxide (Al (OiPr) ₃ ) was added, the internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to perform alkylene oxide. A polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and the reaction was carried out while intermittently supplying 92 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., 18 g of ethylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. To obtain 127 g of colorless and odorless polyalkylene oxide. The degree of unsaturation of the obtained polyalkylene oxide is 0.005 meq / g, the molecular weight distribution is 1.08, Mh / f is 3,500 g / mol, and the area ratio of low molecular weight components of Mh / 3 or less is 1.4%. Met. The obtained polyalkylene oxide was designated as [A2].

<Polymerization Example 3>: Polymerization Example of Polyalkylene Oxide [A3] 18 g (active hydrogen amount 54 mmol) of a polyether polyol (Sanniks GP1000 manufactured by Sanyo Kasei Kogyo Co., Ltd.) in a 0.2 liter autoclave equipped with a stirring blade under a nitrogen atmosphere. ), 2.0 g (0.45 mmol) of a 17 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 was added. The internal temperature was set to 80 ° C., and the reduced pressure treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. ..

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and the reaction was carried out while intermittently supplying 92 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., 18 g of ethylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. To obtain 127 g of colorless and odorless polyalkylene oxide. The degree of unsaturation of the obtained polyalkylene oxide is 0.006 meq / g, the molecular weight distribution is 1.06, Mh / f is 3,700 g / mol, and the area ratio of low molecular weight components of Mh / 3 or less is 0.1%. Met. The obtained polyalkylene oxide was designated as [A3].

The results of the above polymerization examples are also shown in Table 1.

<Preparation of composition>
The composition of the present invention contains a polyalkylene oxide (A) and an isocyanate compound (B) as essential components. Here, even if only the two components of the polyalkylene oxide (A) and the isocyanate compound (B) are used, the chemical reaction between the two components proceeds to obtain polyurethane, but in this case, the reaction rate is slow. Since the reaction rate between the two components is increased by adding a catalyst to the composition containing the polyalkylene oxide (A) and the isocyanate compound (B), a small amount of catalyst was added here. As the catalyst, a solution of triethylene diamine in dipropylene glycol at a concentration of 33% by weight (TEDA-L33 manufactured by Tosoh Corporation) was used.

As the isocyanate compound, a commercially available polyphenylene polymethylene polyisocyanate (Tosoh Coronate C-1331) was used. The NCO group content of C-1331 is 32.5% by weight.

Table 2 shows a list of the materials constituting the composition used in the examples and the blending amount thereof. In the above composition, the total amount of isocyanate groups (NCO groups) in the composition reacts with the NCO groups. The isocyanate compounds were mixed so that the ratio of the available isocyanate group-reactive groups (NCO-reactive groups), that is, NCO / NCO-reactive groups = 1.0.

Further, the composition shown in Table 2 was stirred and mixed at 1400 rpm for 1 minute using a small high-speed stirrer (PRIMIX manufactured by PRIMIX Corporation) to obtain a stirred mixture of the composition.

<Method of measuring physical properties of polyurethane>
Evaluation of elastic recovery.
The room temperature liquid stirring mixing composition obtained above was sandwiched between two parallel plates of a rotary leometer (a solid meter manufactured by UBM) equipped with a parallel plate (parallel plate), and nitrogen was inside the apparatus. By keeping the temperature at 25 ° C. in an atmosphere, the polyalkylene oxide in the composition and the isocyanate compound react with each other over time, and polyurethane is obtained between the parallel plates of the rotary leometer. While the composition was held between the parallel plates, the parallel plates were occasionally vibrated at a strain amount of 1% and a frequency of 10 Hz, and the storage elastic modulus of the composition (polyurethane) was measured.

For the obtained polyurethane, the storage elastic modulus measured at 25 ° C. is determined by the crosslink density of the polyurethane, and the larger the crosslink density of the polyurethane, the larger the storage elastic modulus of the polyurethane. Here, the storage elastic modulus is related to the elastic recovery of polyurethane, and the larger the storage elastic modulus, the greater the elastic recovery. Therefore, the storage elastic modulus is used as an index of elastic recovery, and the storage elastic modulus is elastic when the storage elastic modulus becomes stable over time, that is, when the reaction between the polyalkylene oxide and the isocyanate compound is assumed to be completed. It was used as an index of resilience.

Evaluation of tensile elongation at break and tensile strength at break.
The composition obtained above by stirring and mixing in a liquid state at room temperature was added dropwise to a SUS plate in a room temperature environment, and the SUS plate was placed in a small oven at 50 ° C. together with the SUS plate and held for 1 day to obtain a sheet-shaped polyurethane. A predetermined test piece is prepared from this polyurethane sheet, and the test piece is subjected to tensile deformation under the following conditions to obtain the elongation until the sample breaks (tensile fracture elongation) and the stress at that time (tensile fracture strength). It was measured.

Test piece: Dumbbell AS1822
Tensile environment: constant temperature (23 ° C), constant humidity (50% RH)
Tensile speed: 200 mm / min
Specimen thickness: Approximately 1 mm.

Example 1.
As shown in Table 2, [A1] was used as the polyalkylene oxide, the composition (A1-composition) shown in Table 2 was made into polyurethane by the above method, and the physical characteristics of polyurethane were measured by the above method. The physical characteristics of the obtained polyurethane are shown in Table 3.

Example 2.
As shown in Table 2, [A2] was used as the polyalkylene oxide, the composition (A2-composition) shown in Table 2 was made into polyurethane by the above method, and the physical characteristics of polyurethane were measured by the above method. The physical characteristics of the obtained polyurethane are shown in Table 3.

Example 3.
As shown in Table 2, [A3] was used as the polyalkylene oxide, the composition (A3-composition) shown in Table 2 was made into polyurethane by the above method, and the physical characteristics of polyurethane were measured by the above method. The physical characteristics of the obtained polyurethane are shown in Table 3.

Next, a polymerization example of the polyalkylene oxide used in the comparative example will be described.

<Polymerization Example 4>: Polymerization example of the polyalkylene oxide [B1] used in the comparative example 18 g (18 mmol) of a polyether polyol (Sanniks GP1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) in a 0.2 liter autoclave under a nitrogen atmosphere. , 0.54 g (0.27 mmol) of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and the reaction was carried out while intermittently supplying 92 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., 18 g of ethylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. To obtain 127 g of colorless and odorless polyalkylene oxide. The degree of unsaturation of the obtained polyalkylene oxide is 0.026 meq / g, the molecular weight distribution is 1.12, Mh / f is 3,300 g / mol, and the area ratio of low molecular weight components of Mh / 3 or less is 3.7%. Met. The obtained polyalkylene oxide was designated as [B1].

<Polymerization Example 5>: Polymerization example of the polyalkylene oxide [B2] used in the comparative example 18 g (active hydrogen) of a polyether polyol (Sanniks GP1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) in a 0.2 liter autoclave under a nitrogen atmosphere. (Amount 54 mmol), 500 mg (4.5 mmol) of a 50 wt% aqueous solution of potassium hydroxide (KOH) was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 110 ° C., and the reaction was carried out while intermittently supplying 108 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. 125 g of colorless and odorless polyalkylene oxide was obtained. The degree of unsaturation of the obtained polyalkylene oxide was 0.090 meq / g, the molecular weight distribution was 1.32, Mh / f was 3300 g / mol, and the area ratio of low molecular weight components of Mh / 3 or less was 13.0%. rice field. The obtained polyalkylene oxide was designated as [B2].

<Polymerization Example 6>: Polymerization example of the polyalkylene oxide [B3] used in the comparative example A 0.2 liter autoclave was placed under a nitrogen atmosphere, and 6 g (active hydrogen) of a polyether polyol (Sanniks GP1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used. Amount 18 mmol), and the phosphazene P4 base 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) phosphoranilideneamino) -2λ5,4λ5-catenadi 18 ml (18 mmol) of a 1.0 mol / l hexane solution of (phosphazene) was added. The internal temperature was set to 80 ° C., and the reduced pressure treatment was performed at 0.5 kPa. Then, 18 ml (36 mmol) of a 2.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and the reaction was carried out while intermittently supplying 37 g of propylene oxide so as to maintain the reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. 42 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 10 g / mol · min, the degree of unsaturation of the obtained polyalkylene oxide is 0.016 meq / g, the molecular weight distribution is 1.36, Mh / f is 3,300 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 3.7%. The obtained polyalkylene oxide was designated as [B3].
The results of the above polymerization examples are also shown in Table 4.

A composition was obtained in the same manner as in the above <Preparation of composition> except that the polyalkylene oxide shown in Table 5 was used. Table 5 also shows a list of the materials constituting the composition used in the comparative example and the blending amount thereof.

As in the examples, the above composition also contains an isocyanate group-reactive group (NCO group) that can react with the NCO group, including the total amount of the isocyanate group (NCO group) in the composition and the hydroxyl group (OH group) contained in water. The isocyanate compound was blended so that the ratio of NCO-reactive group), that is, NCO / NCO-reactive group = 1.0.

Polyurethane was prepared from the above composition by the same method and conditions as in Examples, and the physical characteristics of polyurethane were measured by the same method as in Examples.

Comparative example 1.
As shown in Table 5, [B1] was used as the polyalkylene oxide, the composition (B1-composition) shown in Table 5 was made into polyurethane by the same method as in Examples, and the physical characteristics of polyurethane were obtained by the same method as in Examples. It was measured. The physical characteristics of the obtained polyurethane are shown in Table 6. In [B1], the degree of unsaturation, the area ratio of low molecular weight components of Mw / Mn and Mh / 3 or less is larger than the claimed range, and the polyurethane has a higher degree than that of the examples. The storage elastic modulus, which is an index of elastic recovery, was small, and the tensile elongation at break and the tensile strength at break were also small.

Comparative example 2.
As shown in Table 5, [B2] was used as the polyalkylene oxide, the composition shown in Table 5 (B2-composition) was made into polyurethane by the same method as in Examples, and the physical characteristics of polyurethane were obtained by the same method as in Examples. It was measured. The physical properties of the obtained polyurethane are also shown in Table 6. In [B2], the degree of unsaturation, the area ratio of the low molecular weight components of Mw / Mn and Mh / 3 or less are larger than the claimed range, and compared with the examples. The storage elastic modulus, which is an index of the elastic recovery of polyurethane, was small, and the tensile elongation at break and the tensile strength at break were also small.

Comparative example 3.
As shown in Table 5, [B3] was used as the polyalkylene oxide, the composition shown in Table 5 (B3-composition) was made into polyurethane by the same method as in Examples, and the physical characteristics of polyurethane were obtained by the same method as in Examples. It was measured. The physical properties of the obtained polyurethane are also shown in Table 6. In [B3], the area ratio of the low molecular weight component of Mw / Mn and Mh / 3 or less is larger than the claimed range, and the elastic recovery of the polyurethane is compared with the examples. The storage elastic modulus, which is an index of physical characteristics, was small, and the tensile elongation at break and the tensile strength at break were also small.

Example 4
A composition was prepared by mixing polyalkylene oxide [A1] and 4,4'-diphenyldiisocyanate as an isocyanate compound at a molar ratio of 1: 1.2, and dioctyltin dilaurate (U810 manufactured by Nitto Kasei Co., Ltd.) was prepared as a catalyst for the composition. ) Was added at 200 ppm, and the compositions were kept at 110 ° C. for 8 hours to obtain a prepolymer [A1-P]. Place this prepolymer [A1-P] on the lower plate (plate) of a rotary leometer (polylique meter manufactured by UBM) with a parallel plate (parallel plate), open the device door, and keep it at room temperature. , The prepolymer [A1-P] was kept in contact with the atmosphere, that is, in a state where the moisture in the atmosphere could permeate the prepolymer [A1-P] for 7 days, and then permeated with the prepolymer [A1-P]. As a result of the reaction of water, a polyurethane having a urea bond (polyurethane urea) was obtained. After that, the upper flat plate of the rotary leometer was brought into close contact with the polyurethane urea, the device door was closed, and the inside of the device in which the polyurethane urea was sandwiched between the upper and lower parallel plates was kept at 25 ° C. under a nitrogen atmosphere. Then, the parallel flat plate sandwiched with the polyurethane urea was vibrated at a strain amount of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane urea was measured, and this storage elastic modulus was used as an index of elastic recovery. Further, the prepolymer [A1-P] is dropped onto the SUS plate in a room temperature environment, and the prepolymer [A1-P] is in contact with the atmosphere, that is, the prepolymer [A1-P] is infiltrated with water in the atmosphere. It was kept in a moist state for 7 days to obtain a sheet-shaped polyurethane urea. From this polyurethane urea sheet, tensile elongation at break and tensile strength at break were measured in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3. The physical characteristics of the obtained polyurethane urea are shown in Table 7.

Comparative example 4.
A prepolymer [B2-P] and a polyurethane urea were prepared in the same manner as in Example 4 except that [B2] was used as the polyalkylene oxide, and the storage elastic modulus, tensile elongation at break and tensile strength at break were measured. The physical properties of the obtained polyurethane urea are shown in Table 7, and [B2] was obtained from [B2] because the degree of unsaturation, the area ratio of low molecular weight components of Mw / Mn and Mh / 3 or less was larger than the claimed range. The polyurethane urea using the prepolymer [B2-P] had a smaller storage elasticity, which is an index of elastic recovery of polyurethane, and a smaller tensile elongation at break and tensile strength at break, as compared with Examples.

The composition consisting of the polyalkylene oxide, the isocyanate compound, and water in the present invention and the prepolymer and polyurethane obtained from the composition are a coating agent (paint) adhesive, a sealing material, a thermosetting elastomer, a thermoplastic elastomer, that is, 4 It can be suitably used for various uses centering on the use called CASE in the field by taking the English acronym for one use.

Claims (5)

A polyurethane-forming composition containing a polyalkylene oxide (A) and an isocyanate compound (B) satisfying all of the following i) to iv).
i) Degree of unsaturation is 0.006 meq / g or less ii) Mw / Mn is 1.08 or less ii) Mh / f is 1,000 or more iv) Mh / 3 or less The area ratio of molecular weight is 2.0% or less (However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is Mn, the weight average molecular weight is Mw, the highest peak molecular weight is Mh, and the number of functional groups of polyalkylene oxide is f). The polyalkylene oxide (A) is characterized in that the molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is in the range of 1000 to 50,000 g / mol. The composition according to claim 1. Claim 1 or claim, wherein the isocyanate compound (B) is at least one selected from the group consisting of an aromatic isocyanate compound, an aliphatic isocyanate compound, an alicyclic isocyanate compound, and a polyisocyanate derivative thereof. Item 2. The composition according to Item 2. The composition according to any one of claims 1 to 3, which comprises a prepolymer comprising a reaction product of a polyalkylene oxide (A) and an isocyanate compound (B). A polyurethane comprising the reaction product of the composition according to any one of claims 1 to 4.

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