JP2017179363A - Manufacturing method of polyol and manufacturing method of urethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high reactive and high molecular weight polyol and a urethane resin using the same and a manufacturing method of polyol capable of providing a polyurethane resin good in water resistance.SOLUTION: There is provided a manufacturing method of polyoxyalkylene polyol or monool (B) having a process for ring opening addition polymerizing 1,2-alkylene oxide (J) having 3 to 8 carbon atoms with intermediate polyoxyalkylene polyol or monool (G) obtained by ring opening addition polymerizing 1,2-alkylene oxide (R) having 3 to 8 carbon atoms with polyoxyalkylene polyol or monool (Q) in presence of a composite metal cyanide complex catalyst (F), in presence of a compound (H) having a specific chemical structure as a polymerization catalyst to obtain the polyoxyalkylene polyol or monool (B) and a manufacturing method of a urethane resin using the same.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a highly reactive and high molecular weight polyol, and a method for producing a urethane resin having excellent water resistance using the polyol.

Polyurethane resin is a resin that uses polyol component and polyisocyanate component as raw materials and has excellent stretchability and elasticity, so it can be used in a wide range of applications such as molding materials, paints, adhesives, sealing agents, synthetic leather, artificial leather and elastic fibers. Has been used. In that case, a urethane resin can be obtained from a polyol component extender (curing agent) and a urethane prepolymer having an isocyanate group, but the polyol component extender has various types from a relatively low molecular weight to a high one. A polyol is used.
As a method for producing a polyol used for a polyurethane resin, a method using a double metal cyanide complex catalyst (DMC catalyst) is known (Patent Documents 1 to 3).
When 1,2-propylene oxide is subjected to ring-opening polymerization in the presence of this composite metal cyanide complex catalyst, a poly (oxypropylene) polyol having a high molecular weight and a low degree of unsaturation can be synthesized.

However, the poly (oxypropylene) polyol has a terminal hydroxyl group primary conversion rate of 10% or less, and 90% or more is a secondary hydroxyl group. Therefore, this polyol has low reactivity with the isocyanate group of the polyisocyanate component.

In order to increase the reactivity with the isocyanate group, the terminal hydroxyl group needs to be changed from a secondary hydroxyl group to a primary hydroxyl group. For this purpose, a method has been reported in which poly (oxypropylene) polyol synthesized in the presence of the double metal cyanide complex catalyst is further subjected to ring-opening polymerization of ethylene oxide to make the terminal hydroxyl group a primary hydroxyl group ( Patent Document 4).
However, since the polyethylene oxide portion is hydrophilic, this method can only yield polyols with low water resistance. Therefore, there is a problem that the resin physical properties of the urethane resin using this polyol are greatly reduced by moisture or the like.

Further, it has been reported that when a catalyst having a specific chemical structure is used, a poly (oxypropylene) polyol having a terminal hydroxyl group primary conversion of 50% or more can be obtained without adding ethylene oxide (Patent Document 5). .
However, when this catalyst is used, a polyol having a number average molecular weight of 6000 or more cannot be synthesized.

Japanese Patent Laid-Open No. 9-59373 JP-A-10-36500 US Pat. No. 5,527,880 Japanese Patent Laid-Open No. 5-025267 Japanese Patent No. 3076032

  An object of the present invention is a method for producing a polyol having a high reactivity with a urethane prepolymer and a high molecular weight polyol, which can obtain a polyurethane resin having good water resistance; and the polyoxyalkylene polyol or mono It is providing the manufacturing method of the polyurethane resin (E) which has the process of making all (B) and a urethane prepolymer (D) react.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides the intermediate polyoxyalkylene polyol or monool (G) obtained in the presence of the double metal cyanide complex catalyst (F) as a polymerization catalyst represented by the following general formula (1), (2) or (3). 1,2-alkylene oxide (J) is subjected to ring-opening addition polymerization using a compound (H) represented by the following formula to obtain a polyoxyalkylene polyol or monool (B): It is a manufacturing method of oars.

[In the formulas (1), (2) and (3), X represents a boron atom or an aluminum atom, F represents a fluorine atom, and R ³ represents a substituted group represented by the following general formula (4). And a tertiary alkyl group represented by the following general formula (5), which may be the same or different. ]

[In Formula (4), Y represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different; k represents a number of 0-5. , K is 2 or more, the plurality of Y may be the same or different. ]

[In the formula (5), R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ]

  The polyol obtained by the production method of the present invention is highly reactive with a urethane prepolymer and has a high molecular weight. When this polyol is used as an extender and reacted with the urethane prepolymer, the water resistance is good. A polyurethane resin can be obtained.

The method for producing the polyoxyalkylene polyol or monool (B) of the present invention comprises the following two steps.
Step 1: In the presence of a double metal cyanide complex catalyst (F), 1,2-alkylene oxide (R) is subjected to ring-opening addition polymerization to polyoxyalkylene polyol or monool (Q) as a raw material, and intermediate polyoxyalkylene is obtained. A polyol or monool (G) is produced. The reaction product (G) can be used in Step 2 as it is without purification.
Step 2: In the presence of the compound (H) represented by the general formula (1), (2) or (3) as a polymerization catalyst, 1,2-alkylene oxide is added to the intermediate polyoxyalkylene polyol or monool (G). (J) is subjected to ring-opening addition polymerization to obtain a polyoxyalkylene polyol or monool (B).
The production method of the polyoxyalkylene polyol or monool (Q) is not particularly limited, but the 1,2-alkylene oxide (M) is directly opened on the active hydrogen-containing compound (A) by the double metal cyanide complex catalyst (F). Addition polymerization is generally inefficient and has a long induction period. Therefore, after the ring-opening addition polymerization of 1,2-alkylene oxide (M) to the active hydrogen-containing compound (A) in the presence of an alkali catalyst, the polyoxyalkylene polyol or monool (N) is subjected to an alkali catalyst treatment step. The method of producing is preferred.

Hereinafter, each step will be described.
Production method of polyoxyalkylene polyol or monool (Q) As the compound (A), for example, a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, a phosphoric acid compound; And a compound having an active hydrogen-containing functional group, and a mixture of two or more thereof.

Examples of the hydroxyl group-containing compound include water, monovalent alcohol, divalent to octavalent polyhydric alcohol, phenols and polyhydric phenols. Specifically, monohydric alcohols such as methanol, ethanol, butanol, octanol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol , Dihydric alcohols such as diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4′-hydroxycyclohexyl) propane; Trivalent alcohols such as glycerin and trimethylolpropane; pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sho 4-8 such as sugar Phenols such as phenol and cresol; polyphenols such as pyrogallol, catechol and hydroquinone; bisphenols such as bisphenol A, bisphenol F and bisphenol S; polybutadiene polyol; castor oil type Polyols: Polyalkyl (meth) acrylate (co) polymers, polyfunctional (eg, 2-100 functional groups) polyols such as polyvinyl alcohols, and the like.

Examples of the amino group-containing compound include amines, polyamines, amino alcohols and the like. Specifically, ammonia; monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine; piperazine, N-aminoethyl Heterocyclic polyamines such as piperazine; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine Aromatic amines such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and other alkanolamines; Polyamide polyamine obtained by condensation of boric acid and excess polyamines; polyether polyamine; hydrazines (hydrazine, monoalkyl hydrazine, etc.), dihydrazides (succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, etc. ), Guanidines (butyl guanidine, 1-cyanoguanidine and the like); dicyandiamide and the like; and a mixture of two or more of these.

Examples of carboxyl group-containing compounds include aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatic polycarboxylic acids such as succinic acid and adipic acid; phthalic acid, terephthalic acid and trimellit Examples thereof include aromatic polycarboxylic acids such as acids; polycarboxylic acid polymers (functional group number: 2 to 100) such as (co) polymers of acrylic acid. Examples of the polythiol compound of the thiol group-containing compound include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 3-methylpentanedithiol, and the like. Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

Of these active hydrogen-containing compounds (A), a hydroxyl group-containing compound, an amino group-containing compound, and water are preferable, and water, alcohol, and amine are particularly preferable.

Alkali catalysts include alkali metal hydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (sodium methylate, potassium methylate, etc.), alkali metal simple substances (metal potassium, etc.), alkali metals Examples thereof include carbonates (such as potassium carbonate and sodium carbonate) and mixtures of two or more thereof. Among these, from the viewpoint of productivity, preferred is an alkali metal hydroxide, and more preferred is potassium hydroxide.

In the ring-opening addition polymerization of 1,2-alkylene oxide (M), the amount of the alkali catalyst used is not particularly limited, but is preferably 0.05 with respect to the weight of the intermediate polyoxyalkylene polyol or monool (N) to be produced. It is -1.5 weight%, More preferably, it is 0.1-0.7 weight%. If it is 0.05% by weight or more, the reaction time does not become long, and if it is 1.5% by weight or less, the reaction is easily controlled.

Examples of the 1,2-alkylene oxide (M) include a C3-C8 alkylene group or cycloalkylene group which may have a halogen atom or an aryl group.
Specific examples of (M) include 1,2-propylene oxide (hereinafter sometimes referred to as PO), 1,2-butylene oxide, 1,2-cyclohexene oxide, epichlorohydrin, styrene oxide, and the like. Two or more kinds may be used in combination. Among these, 1,2-propylene oxide, 1,2-butylene oxide, epichlorohydrin, and styrene oxide are preferable. (M) may be one type or a mixture of two or more types.

The reaction temperature for ring-opening addition polymerization of 1,2-alkylene oxide (M) to the active hydrogen-containing compound (A) in the presence of an alkali catalyst is 80 ° C to 200 ° C, preferably 100 ° C to 180 ° C. As the reaction equipment, generally, a stirring tank equipped with a Max blend, paddle blade, inclined paddle blade, turbine blade, squid blade and the like is used.

When (M) is added to (A), three types (A), (M), and an alkali catalyst may be charged and reacted at once, or a mixture of (A) and an alkali catalyst may be ( M) may be dropped and reacted, or (M) and an alkali catalyst may be dropped and reacted in (A). From the viewpoint of controlling the reaction temperature, a method of dropping (M) into a mixture of (A) and an alkali catalyst, or dropping (M) and an alkali catalyst into (A) is preferable.
In this step, it is necessary to remove the alkali catalyst. As a method for removing the catalyst, there is a method using an adsorbent and, if necessary, a filter aid.

The adsorbent and the filter aid are not particularly limited as long as they are usually used, and oxides of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 or Examples include hydroxides, complex salts of one or more elements selected from Group 1, Group 2, Group 13 and Group 14, silicates, and natural products containing these, and combinations of two or more May be.

Examples of Group 1 elements constituting the compound include sodium and potassium. Examples of Group 2 elements include magnesium, calcium, and barium. Examples of the Group 13 element include aluminum. Examples of the Group 14 element include silicon.
Specifically, examples of the oxide of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 include MgO and Al ₂ O ₃ . Examples of the hydroxide of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 include Al (OH) ₃ .xH ₂ O. Examples of the composite salt of one or more elements selected from Group 1, Group 2, Group 13, and Group 14 include Mg ₄ . ₅ Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg ₀ . ₇ Al ₀ . ₃ O ₁ . ₁₅ , Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and Mg ₀ . ₇ Al ₀ . ₃ O ₁ . ₁₅ etc. are mentioned. Examples of the silicate include synthetic magnesium silicate and synthetic aluminum silicate. Diatomaceous earth etc. are mentioned as a natural product containing these.

Preferred as the adsorbent is an oxide or hydroxide of one or more elements selected from Group 1, Group 2 and Group 13 and one type selected from Group 1, Group 2 and Group 13. A complex salt of the above elements, more preferably a complex salt of one or more elements selected from Group 2 and Group 13.

Preferred as filter aids are oxides or hydroxides of Group 14 elements, complex salts containing at least Group 14 elements and optionally Group 2 and / or Group 13 elements, and diatomaceous earth It is.

In the polyoxyalkylene polyol or monool (Q), the number of added moles of 1,2-alkylene oxide (M) is 1 or more, preferably 2 to 70. Moreover, the number average molecular weight of (N) is 100 to 4000, preferably 200 to 3000, and more preferably 300 to 2000.

Process 1
The composition of the double metal cyanide complex catalyst (F) (hereinafter sometimes referred to as DMC catalyst) is known, and examples thereof include zinc hexacyanocobalt (III), zinc hexacyanoferrate (III), and hexacyanoiron. (II) Nickel acid, hexacyanocobalt (III) cobalt acid, and others. Of these, zinc hexacyanocobalt (III) is particularly preferable.

The DMC catalyst (F) used in the present invention contains an organic complexing agent. In general, the complexing agent should be soluble in water. Suitable complexing agents are well known to those skilled in the art and are added during the preparation of the catalyst or immediately after precipitation. Usually an excess of complexing agent is used. A preferred complexing agent is a water-soluble heteroatom-containing organic compound capable of forming a complex with a double metal cyanide. Suitable complexing agents include, but are not limited to, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof. Preferred complexing agents are water soluble aliphatic alcohols selected from the group consisting of ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. Of these, t-butyl alcohol is particularly preferable.

A method for producing the DMC catalyst (F) is known and can be produced, for example, by the method described in JP-A-9-59373. In the ring-opening addition polymerization of 1,2-alkylene oxide (R), the amount of (F) used is not particularly limited, but is 10 to 1000 ppm based on the weight of the intermediate polyoxyalkylene polyol or monool (G) to be produced, Preferably it is 30-500 ppm.

The polyoxyalkylene polyol or monool (B) of the present invention is obtained by the method described in JP-A-9-59373, for example, in the presence of a double metal cyanide complex catalyst (DMC catalyst). After the ring opening reaction of 1,2-alkylene oxide (R) with (Q), it is represented by the above general formula (1), (2) or (3) as it is by the method described in JP-A-2000-344881. In the presence of the compound (H), 1,2-alkylene oxide (J) can be subjected to a ring-opening addition reaction, and the terminal can be made primary.

1,2-alkylene oxide (R) is C3-C12 alkylene oxide which may have a halogen atom or an aryl group, or cycloalkylene oxide.
Specific examples include the same as the above 1,2-alkylene oxide (R).
(R) may be one type or a mixture of two or more types.

The reaction temperature for ring-opening addition polymerization of 1,2-alkylene oxide (R) to polyoxyalkylene polyol or monool (Q) in the presence of DMC catalyst (F) is 60 ° C to 250 ° C, preferably 80 ° C to 180 ° C. More preferably, it is 90 degreeC-140 degreeC. As the reaction equipment, generally, a stirring tank equipped with a Max blend, paddle blade, inclined paddle blade, turbine blade, squid blade and the like is used.

The intermediate polyoxyalkylene polyol or monool (G) can be used as it is for the ring-opening addition polymerization in Step 2 without being treated. Moreover, it can also refine | purify as needed.
Purification methods include adsorption using an adsorbent selected from synthetic silicates (magnesium silicate, aluminum silicate, etc.), ion exchange resins, activated clay, amines, alkali metal hydroxides, phosphoric acid, lactic acid. A neutralization method using an organic acid such as succinic acid, adipic acid or acetic acid or a salt thereof, or an inorganic acid such as sulfuric acid, nitric acid or hydrochloric acid, or a method using a neutralization method and an adsorption method in combination can be used.
Further, a water addition method by adding water in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the reaction product may be used alone or in combination with the adsorption method.

In the intermediate polyoxyalkylene polyol or monool (G), the number of added moles of 1,2-alkylene oxide (R) is from 10 mol to 1000 mol, preferably from 50 mol to 200 mol, per active hydrogen. The number average molecular weight of (G) is 6,000 to 60,000, preferably 6,500 to 20,000, and more preferably 7,000 to 10,000.

Process 2
Examples of the polymerization catalyst include the compound (H) represented by the general formula (1), (2), or (3).
Specific examples include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluorophenyl) borane, bis (Pentafluorophenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, bis (pentafluorophenyl) fluoroborane, di (t-butyl) fluoroborane, (Pentafluorophenyl) difluoroborane, (t-butyl) difluoroborane, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) aluminum difluoride, (T-Buchi ) Aluminum difluoride, etc., and preferred are triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, and more preferred is tris (pentafluorophenyl). Boran.
Although the usage-amount of (H) is not specifically limited, it is 1-100000 ppm with respect to the weight of the intermediate | middle polyoxyalkylene polyol or monool (G) to manufacture, Preferably it is 10-10000 ppm.

1,2-alkylene oxide (J) is C3-C12 alkylene oxide which may have a halogen atom or an aryl group, or cycloalkylene oxide.
As a specific example, the same thing as said 1, 2- alkylene oxide (M) is mentioned.
(J) may be a single species or a mixture of two or more species.
(J) may use the same compound as (M) or (L), or may use a different compound.

The reaction temperature for the ring-opening addition polymerization of 1,2-alkylene oxide (J) to the intermediate polyoxyalkylene polyol or monool (G) in the presence of the compound (H) as a catalyst is usually 0 ° C. to 250 ° C., preferably It is 20 to 180 ° C, more preferably 50 to 90 ° C. As the reaction equipment, generally, a stirring tank equipped with a Max blend, paddle blade, inclined paddle blade, turbine blade, squid blade and the like is used.

When (J) is added to (G), three types (G), (J) and (H) may be charged and reacted together, or a mixture of (G) and (H). (J) may be dropped and reacted, or (J) and (H) may be dropped and reacted to (G). From the viewpoint of controlling the reaction temperature, a method of dropping (J) into a mixture of (G) and (H) or dropping a mixture of (J) and (H) into (G) is preferred.

The polyoxypropylene polyol or monool (B) obtained by the production method of the present invention is an alkylene oxide adduct of an active hydrogen-containing compound (A) represented by the following general formula (7), and has a number average The molecular weight is 6,000 to 60,000, and 50 mol% or more of the —AO—H group, which is a hydroxyl group-containing group located at the terminal, is a primary hydroxyl group-containing group represented by the following general formula (6). Polyoxyalkylene polyol or monool (B).

[In General Formula (7), R ¹ is an m-valent group obtained by removing active hydrogen from water, an alcohol compound, a phenol compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, or a phosphate compound; Is an alkylene or cycloalkylene group having 3 to 12 carbon atoms which may have a halogen atom or an aryl group; A is an alkylene group having 3 to 12 carbon atoms which may have a halogen atom or an aryl group; Is a number of 1 or 2 to 100; p is a number of 1 or more, q is a number of 1 or more, and p + q is 100 to 1050. ]

[In General Formula (6), R ² is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may have a halogen atom. ]

Specific examples of the polyoxyalkylene polyol (B1) or monool (B2) include water propylene oxide adduct, methanol propylene oxide adduct, glycerin propylene oxide adduct, ammonia propylene oxide adduct, and the like. .

In the polyoxyalkylene polyol or monool (B), the ratio of the primary hydroxyl group-containing group represented by the above general formula (7) to the total hydroxyl groups at the terminals (this is the terminal hydroxyl group in this specification). (Also referred to as the primary ratio) is 50% or more. When the ratio is low, the reactivity as the polyol component is insufficient. The primary hydroxylation rate of the terminal hydroxyl group is calculated by measuring the sample in advance by pretreatment for esterification and then measuring by 1 H-NMR method.

The total degree of unsaturation (according to JISK-1557) of the polyoxyalkylene polyol or monool (B) is 0.05 meq / g or less. When it is 0.05 meq / g or less, the resin physical properties and thermal stability of the resin synthesized using the polyoxyalkylene polyol (B1) are improved.

The content of the low molecular diol having a number average molecular weight of 200 or less contained in the polyoxyalkylene polyol or monool (B) is 2% by weight or less. When the low molecular diol content is 2% by weight or less, the resin physical properties and thermal stability of the resin synthesized using (B1) are improved. The content of this low molecular diol is calculated by GPC measurement.

The urethane prepolymer (D) can be produced by reacting the polyoxyalkylene polyol (B1) obtained by the production method of the present invention with the organic polyisocyanate (C).
As organic polyisocyanate (C), what is conventionally used for manufacture of polyurethane can be used, C6-C18 alicyclic polyisocyanate (C1), C4-C22 aliphatic polyisocyanate (C2) ), Aromatic polyisocyanate having 8 to 26 carbon atoms (C3), aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms (C4), modified products of these polyisocyanates (C5), and the like. An organic polyisocyanate (C) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the alicyclic polyisocyanate (C1) having 6 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the aliphatic polyisocyanate (C2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexacene. Methylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanate Hexanoate is mentioned.

  Examples of the aromatic polyisocyanate (C3) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude TDI. 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate and m- or p -Isocyanatophenylsulfonyl isocyanate.

  Examples of the araliphatic polyisocyanate (C4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  As the modified polyisocyanate (C5) of (C1) to (C4), the modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate) Group or oxazolidone group-containing modified product, etc .; free isocyanate group content is usually 8 to 33% by weight, preferably 10 to 30% by weight, especially 12 to 29% by weight), for example, modified MDI (urethane modified MDI, carbodiimide modified) MDI and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

Among these, organic diisocyanates are preferable from the viewpoint of physical properties of the obtained resin, more preferable are aromatic diisocyanates having 8 to 26 carbon atoms, and aliphatic diisocyanates having 10 to 18 carbon atoms, and particularly preferable are MDI and TDI.

The isocyanate group content of the urethane prepolymer (D) is preferably in the range of 1.5 to 7% by weight. Urethane prepolymer (D) may be used individually by 1 type, or may use 2 or more types together.

A polyurethane resin (E) can be produced by reacting the urethane prepolymer (D) with a chain extender (K).

Examples of the chain extender (K) include water, polyhydric alcohols having 2 to 20 carbon atoms, and polyamine compounds having a chemical formula amount of less than 500.

  Among the polyhydric alcohols having 2 to 20 carbon atoms as the chain extender (K), the aliphatic dihydric alcohol having 2 to 8 carbon atoms and 3 having 3 to 20 carbon atoms are preferable from the viewpoint of tensile strength and elongation. And more preferred are ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin and trimethylolpropane, and particularly preferred are ethylene glycol, 1,3-propanediol and 1,4-butanediol.

  Examples of polyamine compounds having a chemical formula amount of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, Poly (n = 2-6) alkylene (carbon number 2-6) poly (n = 3-7) amine, etc.] such as pentaethylenehexamine and hexaethyleneheptamine], alicyclic polyamines having 6-20 carbon atoms ( 1,3- or 1,4-diaminocyclohexane, 4,4′- or 2,4′-dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines having 6 to 20 carbon atoms (1,3- or 1,4 -Phenylenediamine, 2,4- or 2,6-tolylene diamine And 4,4'- or 2,4'-methylenebisaniline), C3-C20 heterocyclic polyamines (2,4-diamino-1,3,5-triazine, piperazine and N-aminoethyl) Piperazine, etc.), hydrazine or derivatives thereof [dibasic acid dihydrazide, etc. (adipic acid dihydrazide, etc.)] and amino alcohols having 2 to 20 carbon atoms (ethanolamine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine, etc.) ) And the like. Of these, aromatic diamines having 6 to 20 carbon atoms are preferable from the viewpoint of strength and elongation of the obtained polyurethane resin, and 4,4'-diaminodiphenylmethane is more preferable.

By using the polyol component containing the polyoxyalkylene polyol (B1) obtained by the production method of the present invention as an essential component as the polyol component of the polyurethane resin, the polyol component is hydrophobic and highly reactive with the isocyanate compound. It has the characteristic of being sex. That is, the urethane resin derived from the production method of the present invention is characterized by high reactivity with isocyanate during production and low humidity dependency of resin physical properties (such as tensile strength and elongation at break).

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, parts indicate parts by weight.

<Measurement of number average molecular weight>
The number average molecular weight of the polyoxyalkylene polyol or monool (B) was calculated from the following formula. The hydroxyl value was measured according to JIS K1557-1.
Number average molecular weight (g / mol) = (56100 × m) / hydroxyl value where m is the number of functional groups in (B).
The content of the low molecular diol having a number average molecular weight of 200 or less based on the weight of the polyoxyalkylene polyol or monool (B) was determined by GPC measurement.

<Determination of reaction end point in resin curing reaction>
The end point of the resin curing reaction can be determined by surface IR measurement. First, a part of urethane resin under curing was cut out every 12 hours, and surface IR measurement was immediately performed. When unreacted NCO ends remain, a peak appears at 2200 to 2350 cm ⁻¹ . The time when this peak disappeared was taken as the end point of the resin curing reaction, and the time was taken as the curing time.

<Water resistance evaluation of urethane resin sheet>
The urethane resin sheet was immersed in a 10% aqueous sodium hydroxide solution and allowed to stand for 5 days in a 70 ° C. dryer. The urethane resin sheet taken out after 5 days was wiped off and dried to obtain a urethane resin sheet after the water resistance test. The tensile strength at break and elongation at break of the urethane resin sheet after the water resistance test were measured according to JIS K 7311.

Production Example 1 [Synthesis of DMC catalyst]
Potassium hexacyanocobaltate (20 g) was charged into a beaker and dissolved in ion-exchanged water (350 g) (Solution 1). In another beaker, zinc chloride (62.5 g) was charged and dissolved in ion-exchanged water (100 g) (solution 2). Solution 1 was heated to 55 ° C., and solution 2 was mixed dropwise while stirring, and then a 50:50 (weight ratio) mixture (500 g) of t-butyl alcohol and ion-exchanged water was added and stirred for 30 minutes. did. In a separate beaker, ion-exchanged water (500 g), t-butyl alcohol (5 g), and propylene glycol PO adduct [Sanix PP-2000, manufactured by Sanyo Chemical Industries, Ltd.] (5 g) are uniformly mixed. (Solution 3).
Solution 3 was added to the water-soluble slurry of zinc hexacobaltate obtained above and stirred at 50-60 ° C. for 3 minutes. The obtained product was filtered, and the collected solid cake was added with t-butyl alcohol (350 g), ion-exchanged water (150 g), propylene glycol PO adduct [Sanix Chemicals Co., Ltd. “SANNICS PP-2000 ]] (5 g) was charged. After redispersion after stirring for 3 minutes, the PO cake of t-butyl alcohol (500 g) and propylene glycol [Sanix PP-2000, manufactured by Sanyo Chemical Industries, Ltd.] (2.5 g) of the mixture was charged. The mixture was stirred for 3 minutes to redisperse and then filtered to obtain a solid cake. The obtained solid catalyst was dried under reduced pressure at 60 ° C. under a pressure of 2.7 kPa until there was no change in weight. The yield of the obtained double metal cyanide complex catalyst (DMC catalyst) (F-1) was 32.5 g.

Production Example 2 [Sanix PP-2000 synthesis]
Although SANNICS PP-2000 can be generally obtained as an industrial product, it can be produced by the following method.
Into an autoclave equipped with a stirrer and a temperature controller, 76.0 parts of propylene glycol and 4.0 parts of potassium hydroxide were charged, and then 1921.6 parts of propylene oxide was stirred so that the reaction temperature became 100 to 110 ° C. It was continuously fed while being controlled. The crude polyol containing the catalyst was charged with 40.0 parts of water and 40.0 parts of an alkali adsorbent “Kyoward 600” (manufactured by Kyowa Chemical Industry Co., Ltd.), heated to 90 ° C., and stirred for 1 hour. Thereafter, the charged KW-600 was removed with a filter with a filter paper, and the polyol after filtration was dehydrated at 130 ° C. and a pressure of 2.7 kPa to obtain a poly (oxypropylene) polyol having a hydroxyl value of 56.1. Obtained.

Production Example 3 [Production of main component isocyanate group-terminated urethane prepolymer (D-1)]
In a reaction vessel equipped with a stirrer and a temperature controller, 850.7 parts of a glycerin PO adduct [“SANNICS GH-3000NS” manufactured by Sanyo Chemical Industries, Ltd.] was charged, and 1 at 130 ° C. under reduced pressure (4 kPa). Time dehydration was performed. Thereafter, the mixture was cooled to 50 ° C. and charged with 149.3 parts of 2,4-toluene diisocyanate [“TDI-80” manufactured by Tosoh Corporation]. While stirring under a nitrogen stream, the temperature was gradually raised to 70 ° C. and reacted for 10 hours, and then cooled to room temperature to obtain an isocyanate group-terminated urethane prepolymer (D-1). The isocyanate group content measured according to JIS K 1558 was 3.6%.

Example 1 [Synthesis of polyoxypropylene diol (B-1) having a molecular weight of 6000]
Propylene glycol (A-1) PO adduct [Sanix PP-2000] manufactured by Sanyo Chemical Industries, Ltd.] (Q-1) 315.0 parts and the above production example in an autoclave equipped with a stirrer and a temperature controller After charging 0.10 parts of the double metal cyanide complex catalyst (DMC catalyst) (F-1) produced in Step 1, the temperature in the reactor was raised to 95 ° C., and 31.5 parts of PO was added with stirring. . After 1.5-3 hours, the pressure in the reactor dropped rapidly. This indicates that the catalyst has been activated.
Thereafter, 598.5 parts of PO was continuously added under stirring while controlling the reaction temperature to be 90 to 100 ° C. After the PO charge was complete, the reaction mixture was stirred at 95 ° C. until the pressure was constant. This mixture was vacuum stripped at 100 ° C. for 0.5 hour, and unreacted PO was removed from the reactor to obtain a polyoxypropylene diol (G-1 having a molecular weight of 6000 and a terminal group primary conversion of 7%. )

Subsequently, 0.050 part of tris (pentafluorophenyl) borane (H-1) was charged into the same reactor, and the temperature in the reactor was increased to 75 ° C. Thereafter, 54.8 parts of PO was continuously added under stirring while controlling the reaction temperature to be 70 to 80 ° C. Next, 75.3 parts of water was added, the temperature was raised to 140 ° C., and the mixture was stirred for 1 hour. Thereafter, polyoxypropylene diol (B-1) was obtained by dehydration at 130 ° C. and a pressure of 2.7 kPa.
(B-1) The terminal hydroxyl group primary ratio is 59%, the molecular weight is 6070, the total unsaturation is 0.0 meq / g, and the content of the low molecular diol having a number average molecular weight of 200 or less is 0.37% by weight. there were.

Example 2 [Synthesis of polyoxypropylene diol (B-2) having a molecular weight of 20,000 to 20,000]
94.3 parts of the PO adduct of propylene glycol (A-1) [“Sanix PP-2000” manufactured by Sanyo Chemical Industries, Ltd.] (Q-1) and the above production example in an autoclave equipped with a stirrer and a temperature controller After charging 0.10 part of the double metal cyanide complex catalyst (DMC catalyst) (F-1) prepared in Step 1, the temperature in the reactor was raised to 95 ° C., and 42.5 parts of PO was added with stirring. . After 1.5-3 hours, the pressure in the reactor dropped rapidly. This indicates that the catalyst has been activated.
Thereafter, 808.3 parts of PO was continuously added under stirring while controlling the reaction temperature to be 90 to 100 ° C. After the PO charge was complete, the reaction mixture was stirred at 95 ° C. until the pressure was constant. This mixture was vacuum stripped at 100 ° C. for 0.5 hour, and unreacted PO was removed from the reactor, whereby polyoxypropylene diol (G-2 having a molecular weight of 20050 and a terminal group primary conversion of 9% was obtained. )

Subsequently, 0.050 part of tris (pentafluorophenyl) borane (H-1) was charged into the same reactor, and the temperature in the reactor was increased to 75 ° C. Thereafter, 54.8 parts of PO was continuously added under stirring while controlling the reaction temperature to be 70 to 80 ° C. Next, 75.3 parts of water was added, the temperature was raised to 140 ° C., and the mixture was stirred for 1 hour. Then, polyoxypropylene diol (B-2) was obtained by performing dehydration at 130 ° C. and a pressure of 2.7 kPa.
The terminal hydroxyl group primary conversion ratio of (B-2) is 56%, the molecular weight is 20100, the total unsaturation is 0.03 meq / g, and the content of low molecular diol having a number average molecular weight of 200 or less is 0.45% by weight. there were.

Comparative Example 1 [Synthesis of polyoxypropylene / oxyethylenediol (B′-1) having a molecular weight of 6000 to 600]
Propylene glycol (A-1) PO adduct [“Sanix PP-2000” manufactured by Sanyo Chemical Industries, Ltd.] (Q-1) 331.0 parts and the above production example in an autoclave equipped with a stirrer and a temperature controller After charging 0.10 parts of the double metal cyanide complex catalyst (DMC catalyst) (F-1) prepared in Step 1, the temperature in the reactor was raised to 95 ° C., and 31.1 parts of PO was added with stirring. . After 1.5-3 hours, the pressure in the reactor dropped rapidly. This indicates that the catalyst has been activated.
Thereafter, 591.5 parts of PO was continuously added under stirring while controlling the reaction temperature to be 90 to 100 ° C. After the PO charge was complete, the reaction mixture was stirred at 95 ° C. until the pressure was constant. This mixture was vacuum stripped at 100 ° C. for 0.5 hour, and unreacted PO was removed from the reactor to obtain a polyoxypropylene diol having a molecular weight of 5760 and a terminal group primary ratio of 7%.
Subsequently, 2.0 parts of potassium hydroxide was charged into the same reactor, and 44.3 parts of ethylene oxide was continuously charged under stirring so as to control the reaction temperature to 125 to 135 ° C. 20.0 parts of water and 20.0 parts of an alkali adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the crude polyol containing the catalyst, and the temperature was raised to 90 ° C. and stirred for 1 hour. Thereafter, the charged KW-600 was removed with a filter with a filter paper, and the polyol after filtration was dehydrated at 130 ° C. and a pressure of 2.7 kPa to obtain polyoxypropylene / oxyethylenediol (B′-1). Obtained.
(B′-1) had a terminal hydroxyl group primary ratio of 61%, a molecular weight of 6030, a total degree of unsaturation of 0.0 meq / g, and an EO content of 4.4% by weight.

Comparative Example 2 [Synthesis of polyoxypropylene / oxyethylenediol (B′-2) having a molecular weight of 20,000 to 20,000]
99.5 parts of the PO adduct of propylene glycol (A-1) [“Sanix PP-2000” manufactured by Sanyo Chemical Industries, Ltd.] (Q-1) and the above production example in an autoclave equipped with a stirrer and a temperature controller After charging 0.10 parts of the double metal cyanide complex catalyst (DMC catalyst) (F-1) prepared in Step 1, the temperature in the reactor was raised to 95 ° C., and 44.3 parts of PO was added with stirring. . After 1.5-3 hours, the pressure in the reactor dropped rapidly. This indicates that the catalyst has been activated. Thereafter, 840.9 parts of PO was continuously added under stirring while controlling the reaction temperature to be 90 to 100 ° C. After the PO charge was complete, the reaction mixture was stirred at 95 ° C. until the pressure was constant. This mixture was subjected to vacuum stripping at 100 ° C. for 0.5 hour, and unreacted PO was removed from the reactor to obtain polyoxypropylene diol having a molecular weight of 19790 and a terminal group primary conversion of 9%.
Subsequently, 2.0 parts of potassium hydroxide was charged into the same reactor, and 13.1 parts of ethylene oxide was continuously charged with stirring so as to control the reaction temperature to 125 to 135 ° C. 20.0 parts of water and 20.0 parts of an alkali adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the crude polyol containing the catalyst, and the temperature was raised to 90 ° C. and stirred for 1 hour. Thereafter, the charged KW-600 is removed by a filter with a filter paper, and the polyol after filtration is dehydrated at 130 ° C. and a pressure of 2.7 kPa to obtain polyoxypropylene / oxyethylenediol (B′-2). Obtained. (B′-2) had a terminal hydroxyl group primary ratio of 60%, a molecular weight of 2,050, a total unsaturation of 0.0 meq / g, and an EO content of 1.3% by weight.

Example 3 [Synthesis of Urethane Resin Sheet (E-1)]
15.4 parts of the isocyanate group-terminated urethane prepolymer (D-1) obtained in Production Example 3, 44.6 parts of the polyoxypropylene diol (B-1) obtained in Example 1, Neostan U-600 06 parts were mixed and defoamed with a centrifuge. The obtained urethane resin (E-1) was poured into an 11 × 17.5 cm polypropylene tray to a thickness of 1 mm and cured at room temperature overnight.
Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point.
The resulting urethane resin sheet had a curing time of 48 hours, a tensile strength at break of 0.22 MPa, and an elongation at break of 342%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.17 MPa, and the elongation at break was 355%.

Example 4 [Synthesis of Urethane Resin Sheet (E-2)]
6.4 parts of urethane prepolymer (D-1), 53.6 parts of polyoxypropylene diol (B-2) obtained in Example 2 and 0.06 part of Neostan U-600 were mixed and centrifuged. Defoaming was performed. The obtained urethane resin (E-2) was poured into an 11 × 17.5 cm polypropylene tray to a thickness of 1 mm and cured at room temperature overnight. Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point.
The resulting urethane resin sheet had a curing time of 180 hours, a tensile strength at break of 0.15 MPa, and an elongation at break of 900%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.11 MPa, and the elongation at break was 930%.

Comparative Example 3 [Synthesis of Urethane Resin Sheet (E′-1)]
Urethane prepolymer (D-1) 15.4 parts, polyoxypropylene diol (G-1) 44.6 parts produced during the production of Example 1 (B-1), Neostan U-600 0.06 parts Were mixed and defoamed with a centrifuge. The obtained urethane resin (E′-1) was poured into an 11 × 17.5 cm polypropylene tray to a thickness of 1 mm and cured at room temperature overnight. Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point.
The resulting urethane resin sheet had a curing time of 60 hours, a tensile strength at break of 0.15 MPa, and an elongation at break of 200%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.11 MPa, and the elongation at break was 250%.

Comparative Example 4 [Synthesis of Urethane Resin Sheet (E′-2)]
6.4 parts of urethane prepolymer (D-1), 53.6 parts of reoxypropylene diol (G-2) produced during the production of (B-2) of Example 2, 0.06 part of Neostan U-600 Were mixed and defoamed with a centrifuge. The obtained urethane resin (E′-2) was poured into an 11 × 17.5 cm polypropylene tray to a thickness of 1 mm and cured at room temperature overnight. Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point. The obtained urethane resin sheet had a curing time of 216 hours, a tensile breaking strength of 0.11 MPa, and an elongation at break of 750%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.08 MPa, and the elongation at break was 800%.

Comparative Example 5 [Synthesis of Urethane Resin Sheet (E′-3)]
15.4 parts of the isocyanate group-terminated urethane prepolymer (D-1) obtained in Production Example 3, 44.6 parts of the polyoxypropylene diol (B′-1) obtained in Comparative Example 1, Neostan U-6600 0.06 part was mixed and defoamed with a centrifuge. The obtained urethane resin (E′-3) was poured into an 11 × 17.5 cm polypropylene tray so as to have a thickness of 1 mm, and was cured overnight at room temperature.
Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point.
The resulting urethane resin sheet had a curing time of 48 hours, a tensile strength at break of 0.24 MPa, and an elongation at break of 350%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.10 MPa, and the elongation at break was 370%.

Comparative Example 6 [Synthesis of Urethane Resin Sheet (E′-4)]
6.4 parts of the isocyanate group-terminated urethane prepolymer (D-1) obtained in Production Example 3, 53.6 parts of the polyoxypropylene diol (B′-2) obtained in Comparative Example 2, Neostan U-6600 0.06 part was mixed and defoamed with a centrifuge. The obtained urethane resin (E′-3) was poured into an 11 × 17.5 cm polypropylene tray so as to have a thickness of 1 mm, and was cured overnight at room temperature.
Thereafter, it was cured at room temperature, a part of the sample was cut every 12 hours, and surface IR measurement was immediately performed. The time when the peak of unreacted NCO terminal at 2200 to 2350 cm ⁻¹ disappeared was taken as the reaction end point.
The resulting urethane resin sheet had a curing time of 180 hours, a tensile strength at break of 0.16 MPa, and an elongation at break of 880%. The tensile strength at break of the urethane resin sheet after the water resistance test was 0.07 MPa, and the elongation at break was 870%.

The measurement of tensile strength at break and elongation at break of the urethane resin sheet was performed according to JIS K 7311.

The physical properties of the polyoxyalkylene polyols or monools obtained in Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 1.
In addition, Table 2 summarizes the curing times of Examples 3 and 4 and Comparative Examples 3 to 6 and the physical properties of the obtained urethane resin sheets.

When Example 3 using a polyol (B-1) having a molecular weight of about 6000 is compared with Comparative Example 3 using a polyol (G-1), Example 3 using (B-1) of the present invention is compared. The curing time is shorter. Similarly, when Example 4 using a polyol (B-2) having a molecular weight of around 20,000 is compared with Comparative Example 4 using a polyol (G-2), (B-2) of the present invention is used. In Example 4, the curing time was shorter.
Furthermore, the tensile break strength of the urethane resin sheets (E-1) and (E-2) of Examples 3 and 4 obtained using (B-1) and (B-2) of the present invention after the water resistance test is shown. While the retention rate was 72% or more, the urethane resin sheets (E′-3) and (E′-4) of Comparative Examples 5 and 6 were defective with a retention rate of 44% or less.

The polyoxyalkylene polyol or monool (B) obtained by the production method of the present invention can be applied to various uses such as polyurethane foam and polyurethane resin. As polyurethane foam, cushioning materials for automobiles, backing materials for automobiles, etc., as polyurethane resins, sealing materials, waterproofing coating films, paints, inks, coating agents, adhesives, heat insulating materials, artificial leather, synthetic leather, textile products and automobiles Examples include parts.

Claims (5)

Intermediate polyoxy obtained by ring-opening addition polymerization of C3-C8 1,2-alkylene oxide (R) to polyoxyalkylene polyol or monool (Q) in the presence of a double metal cyanide complex catalyst (F) In the presence of the compound (H) represented by the following general formula (1), (2) or (3) as a polymerization catalyst in the alkylene polyol or monool (G), 1,2-alkylene having 3 to 8 carbon atoms A process for producing a polyoxyalkylene polyol or monool (B), which comprises a step of ring-opening addition polymerization of oxide (J) to obtain a polyoxyalkylene polyol or monool (B).

[In the formulas (1), (2) and (3), X represents a boron atom or an aluminum atom, and F represents a fluorine atom, respectively. R ³ represents an optionally substituted phenyl group represented by the following general formula (4) or a tertiary alkyl group represented by the following general formula (5), and may be the same or different. ]

[In Formula (4), Y represents a hydrogen atom, a C1-C4 alkyl group, a halogen atom, a nitro group, or a cyano group. k represents an integer of 0 to 5, and when k is 2 or more, the plurality of Y may be the same or different from each other. ]

Wherein (5) represents a R ^4, R ^5, R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms. ] The number average molecular weight of the polyoxyalkylene polyol or monool (B) is 6,000 to 60,000, and 50 mol% or more of the hydroxyl group-containing group located at the terminal of (B) is represented by the following general formula (6). The manufacturing method of the polyoxyalkylene polyol or monool of Claim 1 which is the primary hydroxyl group containing group represented.

[In General Formula (6), R ² is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may have a halogen atom. ] The method for producing a polyoxyalkylene polyol or monool according to claim 1 or 2, wherein the double metal cyanide complex catalyst (F) is zinc hexacyanocobalt (III). The method for producing a polyoxyalkylene polyol or monool according to any one of claims 1 to 3, wherein the compound (H) is tris (pentafluorophenyl) borane. The manufacturing method of the polyurethane resin (E) which has a process with which the polyoxyalkylene polyol or monool (B) obtained by the manufacturing method in any one of Claims 1-4 is made to react with a urethane prepolymer (D).