JP2020002197A - Polyether polyol composition - Google Patents

Abstract

To provide a polyether polyol composition capable of providing a polyurethane resin having high reactivity and excellent in resin physical properties such as strength and durability.SOLUTION: There is provided a polyether polyol composition containing an alkylene oxide addition article of an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms, the polyether polyol composition contains diol (A), the number of hydrogen groups binding to a primary carbon atom of hydrogen groups of the polyether polyol composition is 55 mol% or more based on total number of hydroxyl groups in the polyether polyol composition, peak top molecular weight of the polyether polyol composition is 900 to 10000, and the diol (A) of 0.1 to 4 wt.% based on total weight of the polyether polyol composition is contained.SELECTED DRAWING: None

Description

The present invention relates to a polyether polyol composition, a method for producing the same, and a polyurethane resin which is a reaction product of the polyether polyol composition.

As a method for producing a polyether polyol, a method of reacting an alkylene oxide in the presence of a catalyst is widely known. In this production process, aldehyde is generated as a by-product and reacts with the polyol in the system to form an acetal. The generation of the acetal lowers the average number of functional groups of the polyether polyol, and inhibits the molecular weight elongation reaction during the urethanization reaction, thereby impairing the physical properties such as the strength and durability of the polyurethane resin.
In order to avoid this, a method of producing and post-treating a polyether polyol in a nitrogen atmosphere to suppress the generation of aldehyde (see Patent Document 1) or a method of removing aldehyde intermittently or continuously during the reaction ( Patent Literature 2) has been proposed.

JP 2007-204569 A JP 2009-227978 A

It has been considered that the smaller the aldehyde content, the better the polyurethane resin properties. However, this time, the low molecular weight diol obtained by hydrolyzing the acetal, if it exceeds a certain amount in the system, expands the molecular weight distribution of the polyether polyol and lowers the resin physical properties. It was found that they were taken into the hard segment and contributed to the improvement of resin properties such as strength and durability. In the prior art, the production amount of aldehyde and, consequently, low molecular weight diol could not be controlled.

The present invention provides a polyether polyol composition that not only has high reactivity but also contains a controlled specific amount of a low molecular weight diol and can provide a polyurethane resin having excellent resin properties such as strength and durability. The purpose is to do. Another object of the present invention is to provide a polyurethane resin which is a reaction product of the polyether polyol composition.

The present inventors have conducted intensive studies to solve these problems, and as a result, have reached the present invention. That is, the present invention is the following three inventions.
A polyether polyol composition containing an alkylene oxide adduct of an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms, wherein the polyether polyol composition is a diol represented by the following general formula (1): A) wherein the number of hydroxyl groups bonded to the primary carbon atoms among the hydroxyl groups of the polyether polyol composition is 55 mol% or more based on the total number of hydroxyl groups in the polyether polyol composition. The polyether polyol composition has a peak top molecular weight of 900 to 10000 as measured by gel permeation chromatography, and the diol (A) is used in an amount of 0.1 to 0.1 based on the total weight of the polyether polyol composition. A polyether polyol composition containing 4% by weight; A polyurethane resin which is a reaction product of a product and a polyisocyanate (C); and a method for producing the polyol composition, wherein an alkylene oxide is added to an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms. This is a production method having a step of performing the reaction in a plurality of times, and in the addition reaction of the alkylene oxide performed in a plurality of times, the last addition reaction is performed at a reaction temperature of 60 to 90 ° C. using a Lewis acid catalyst (D). Wherein the method comprises the step of adding an average of 3 to 8 moles of an alkylene oxide per active hydrogen atom.
HO- (AO) _n- H (1)
[In the formula, AO is a 1-methylethyleneoxy group, a 2-methylethyleneoxy group, a 1-ethylethyleneoxy group or a 2-ethylethyleneoxy group, and n is an integer of 1 to 7.]

The polyether polyol composition of the present invention can provide a polyurethane resin which is highly reactive, contains a controlled specific amount of a low molecular weight diol, and has excellent resin properties such as strength and durability.

The polyether polyol composition of the present invention is a polyether polyol composition containing an alkylene oxide adduct of an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms, and the polyether polyol composition has the following general formula: Among the hydroxyl groups of the polyether polyol composition containing the diol (A) represented by the formula (1), the number of hydroxyl groups bonded to the primary carbon atom is the number of hydroxyl groups in the polyether polyol composition. 55 mol% or more based on the total number, the peak top molecular weight of the polyether polyol composition measured by gel permeation chromatography is 900 to 10,000, and the diol (A) is the polyether polyol composition. 0.1 to 4% by weight based on the total weight of polyether poly A Lumpur composition.
HO- (AO) _n- H (1)
[In the formula, AO is a 1-methylethyleneoxy group, a 2-methylethyleneoxy group, a 1-ethylethyleneoxy group or a 2-ethylethyleneoxy group, and n is an integer of 1 to 7.]

The polyether polyol composition contains an alkylene oxide adduct of an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms, and bonds to a primary carbon atom among hydroxyl groups of the polyether polyol composition. The number of hydroxyl groups in the polyether polyol composition is 55 mol% or more based on the total number of hydroxyl groups in the polyether polyol composition, and the polyether polyol composition has a peak top molecular weight measured by gel permeation chromatography of 900%. 〜１０10000.

The active hydrogen atom is a hydrogen atom having reactivity with another compound, and is preferably a hydrogen atom bonded to any of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. Examples of the active hydrogen atom-containing compound containing an active hydrogen atom include 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 two or more active hydrogen-containing functional groups in the molecule. And the like.
In the addition of the alkylene oxide for obtaining the polyether polyol composition, the active hydrogen atom-containing compound may be a mixture of two or more of these.

Examples of the hydroxyl group-containing compound containing 2 to 8 active hydrogen atoms include water, polyhydric alcohols having 2 to 8 valences, and phenols.
Examples of the divalent to octahydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4 -Dihydric alcohols such as bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane, and trihydric alcohols such as glycerin and trimethylolpropane Pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose and the like.
Examples of phenols include phenol and cresol, examples of polyhydric phenols include pyrogallol, catechol and hydroquinone, and examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S.

Examples of the amino group-containing compound include amines, polyamines, amino alcohols and the like.
Amines containing 2 to 8 active hydrogen atoms include ammonia, alkylamines having 1 to 20 carbon atoms (such as butylamine), monoamines (such as aniline), and polyamines such as aliphatic polyamines (such as ethylenediamine and trimethylenediamine). , Hexamethylenediamine, diethylenetriamine, etc.), piperazine, heterocyclic polyamines (N-aminoethylpiperazine, etc.), alicyclic polyamines (dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines (phenylenediamine, tolylenediamine, Diethyl tolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, etc.), and alkanolamines (monoethanolamine, Ethanolamine, triethanolamine, triisopropanolamine, etc.) Others include polyamide polyamines, polyether polyamines, hydrazines (hydrazine, monoalkylhydrazine, etc.) obtained by condensation of dicarboxylic acid with an excess of polyamines, dihydrazides ( Examples thereof include succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, and the like, guanidines (butylguanidine, 1-cyanoguanidine, and the like), dicyandiamide, and a mixture of two or more of these.

Examples of the carboxyl group-containing compound containing 2 to 8 active hydrogen atoms include aliphatic monocarboxylic acids (acetic acid, propionic acid, etc.), aromatic monocarboxylic acids (benzoic acid, etc.), and aliphatic polycarboxylic acids (succinic acid, Adipic acid) and aromatic polycarboxylic acids (phthalic acid, terephthalic acid, trimellitic acid, etc.).
Examples of the polythiol compound of a thiol group-containing compound containing 2 to 8 active hydrogen atoms include divalent to octavalent polyvalent thiols (ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, , 6-hexanedithiol, 3-methylpentanedithiol, etc.).
Examples of the phosphoric acid compound containing 2 to 8 active hydrogen atoms include phosphoric acid, phosphorous acid, and phosphonic acid.

Among these active hydrogen atom-containing compounds, from the viewpoint of reactivity with the alkylene oxide, a hydroxyl group-containing compound, an amino group-containing compound, and water are preferable, and water, alcohol, and amines are more preferable.

The alkylene oxide adduct is obtained by adding an alkylene oxide to the compound containing an active hydrogen atom.
As the alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen atom-containing compound, one having 3 to 8 carbon atoms is preferable, and propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4- or Examples thereof include 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide, and a combination of two or more of these. Preferably, they are PO and BO.
When AO is used in combination, the mode of addition may be block addition or random addition.

Among the hydroxyl groups of the polyether polyol composition, the number of hydroxyl groups bonded to primary carbon atoms is 55 mol% or more based on the total number of hydroxyl groups in the polyether polyol composition.
From the viewpoint of reactivity, among the hydroxyl groups of the polyether polyol composition, the number of hydroxyl groups bonded to the primary carbon atoms is 60 mol% or more based on the total number of hydroxyl groups in the polyether polyol composition. Is preferable, and 65 mol% or more is more preferable. Among the hydroxyl groups of the polyether polyol composition, the number of hydroxyl groups bonded to primary carbon atoms is less than 55 mol% based on the total number of hydroxyl groups bonded to carbon atoms in the polyether polyol composition. If there is, the curing time of the obtained polyurethane resin becomes longer. When the number of hydroxyl groups bonded to the primary carbon atoms is less than 55 mol%, the curing time of the polyurethane resin is reduced to at least 55 mol% of the hydroxyl groups bonded to the primary carbon atoms with the polyether polyol composition. In order to make the same, it is necessary to use a large amount of a catalyst, so that a polyurethane resin excellent in resin physical properties such as strength and durability cannot be obtained.
The mole% of the hydroxyl group bonded to the primary carbon atom among all the hydroxyl groups located at the terminal of the alkylene oxide adduct is measured by an NMR method (such as the method described in JP-A-2000-344881). be able to.

Among the hydroxyl groups of the polyether polyol composition, the number of hydroxyl groups bonded to primary carbon atoms is 55 mol% or more based on the total number of hydroxyl groups bonded to carbon atoms in the polyether polyol composition. As a method for increasing the content, the addition of the AO to the active hydrogen atom-containing compound is performed by a method described in JP-A-2000-344488 [a method of adding the AO in the presence of a Lewis acid catalyst (D)]. And the like.
Examples of the Lewis acid catalyst (D) include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluoro Phenyl) borane, bis (pentafluorophenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, bis (pentafluorophenyl) borane fluoride, di (t-butyl) ) Borane fluoride, (pentafluorophenyl) borane difluoride, (t-butyl) borane difluoride, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) Aluminum difluoride , (T-butyl) aluminum difluoride and the like, and preferred are triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum, and more preferred is tris (pentafluorophenyl) aluminum. Pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum.

The polyether polyol composition has a peak top molecular weight (Mp) of 900 to 10,000 measured by gel permeation chromatography (GPC).
When the Mp of the polyether polyol composition is less than 900, the resin properties such as the strength and durability of the obtained urethane resin become insufficient, and when the Mp of the polyether polyol composition exceeds 10,000, the reaction becomes too slow. .
The Mp of the polyether polyol composition can be adjusted to the above range by adjusting the amount of AO to be added.

The GPC measurement conditions are as follows.
<GPC measurement conditions>
Apparatus: "HLC-8320GPC" [Tosoh Corporation]
Solvent: DMF, THF
Standard substance: polystyrene detector: RI
Sample concentration: 0.25%
Column stationary phase: TSKgel guardcolumn PWXL, TSKgel G6000PWXL, TSKgel G3000PWXL [all manufactured by Tosoh Corporation]
Column temperature: 40 ° C

In the polyether polyol composition, the addition of the AO to the active hydrogen atom-containing compound can be performed in a plurality of times, and a polyether composition obtained by performing the addition in two stages is preferable. When the addition of AO is performed in two steps, first, the first-stage AO is added to the active hydrogen atom-containing compound to produce an alkylene oxide adduct precursor (E). The alkylene oxide adduct precursor (E) will be described later. Then, in the second stage, AO is further added to the alkylene oxide adduct precursor (E) in the presence of the Lewis acid catalyst (D). The number of moles of AO added in the second stage of AO addition is 3 to 8 moles on average, and preferably 3 to 7 moles, per active hydrogen atom of the alkylene oxide adduct precursor (E). The number of moles of AO added in the first and second stages is appropriately selected depending on the molecular weight of the polyether polyol composition to be produced and its use. When the number of added moles of AO per active hydrogen atom of the alkylene oxide adduct precursor (E) is less than 3 moles, the number of hydroxyl groups bonded to primary carbon atoms decreases, and the curing time of the obtained polyurethane resin Becomes longer. When the number of added moles of AO exceeds 8 moles, the content of the diol (A) described later contained in the obtained polyether polyol composition increases, which adversely affects the physical properties of the obtained polyurethane resin.
The amount of the Lewis acid catalyst (D) to be used is not particularly limited, but is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 1% by weight, based on the polyether polyol composition to be produced.

The AO addition in the second step may be performed by charging and reacting the alkylene oxide adduct precursor (E), the AO and the Lewis acid catalyst (D) at a time, and reacting the alkylene oxide adduct precursor (E). The AO may be dropped and reacted with a mixture of the adduct precursor (E) and the Lewis acid catalyst (D), or the AO and the Lewis acid may be reacted with the alkylene oxide adduct precursor (E). The reaction with the catalyst (D) may be carried out separately or mixed and dropped simultaneously. From the viewpoint of controlling the reaction temperature, the AO is dropped into a mixture of the alkylene oxide adduct precursor (E) and the Lewis acid catalyst (D), or the mixture is added to the alkylene oxide adduct precursor (E). A method in which AO and the Lewis acid catalyst (D) are dropped is preferable.
The reaction temperature (content temperature) at the time of adding the AO to the alkylene oxide adduct precursor (E) is preferably from 60 ° C to 90 ° C, more preferably from 70 ° C to 90 ° C.

The polyether polyol composition of the present invention contains a diol (A) represented by the following general formula (1). The content of the diol (A) contained in the polyether polyol composition is 0.1 to 4.0% by weight based on the total weight of the polyether polyol composition.
HO- (AO) _n- H (1)
[In the formula, AO is a 1-methylethyleneoxy group, a 2-methylethyleneoxy group, a 1-ethylethyleneoxy group or a 2-ethylethyleneoxy group, and n is an integer of 1 to 7.]

When the content of the diol (A) is less than 0.1% by weight based on the total weight of the polyether polyol composition, the strength and durability of the obtained polyurethane resin are not sufficient, and 4.0% by weight. When the ratio exceeds the above range, the molecular weight distribution of the polyether polyol is expanded, and the resin properties are reduced. From the viewpoint of physical properties such as strength and durability of the obtained urethane resin, the content of the diol (A) is preferably 0.5 to 4.0% by weight based on the total weight of the polyether polyol composition. More preferably, it is 1.0 to 4.0% by weight.

The content of the diol (A) is measured as a component having a retention time of 10 to 27 minutes by gas chromatography-mass spectrometry (GC-MS) using a polyether polyol composition as a sample.
The measurement conditions of GC-MS are as follows.
<GC-MS measurement conditions>
Equipment: SIMADZU GC-17A
Column: Rtx-5 (length 30 mm, inner diameter 0.25 mm, film thickness 0.25 μm)
Evaporation chamber temperature: 150 ° C
Detector temperature: 330 ° C
Injection mode: split carrier gas: helium pressure: 150 kPa
Split ratio: 50
Column temperature: 40 ° C (5 minutes hold) → 210 ° C (10 ° C / minute temperature rise) → 300 ° C (15 ° C / minute temperature rise, 10 minute hold)
Sample solution: 40% by weight methanol solution injection volume: 1.0 μl

In order to adjust the content of the diol (A) contained in the polyether polyol composition to 0.1 to 4.0% by weight based on the total weight of the polyether polyol composition, The addition of AO to the hydrogen atom-containing compound is preferably performed in two stages, and the amount of water contained in the alkylene oxide adduct precursor (E) is adjusted, the temperature at which AO is added, or the amount of AO added is adjusted. More preferably, The adjustment method will be described later.
Further, based on the total weight of the polyether polyol composition, the content of the diol (A) is 0 based on the total weight of the polyether polyol composition with respect to the polyether polyol composition having a content of the diol (A) of less than 0.1% by weight. The diol (A) may be added later so as to be 0.1 to 4.0% by weight.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the diol (A) are preferably 1.05 to 1.25, more preferably 1.10 to 1.25. 1.20.
When the molecular weight distribution (Mw / Mn) of the diol (A) is 1.05 to 1.25, the resulting polyurethane resin has excellent tensile strength and elongation.

The molecular weight distribution (Mw / Mn) of the diol (A) can be adjusted by the amount of AO added during the production of the polyether polyol composition, the amount of water in the system, the reaction temperature, and the like. Specifically, the AO addition amount in the second stage of AO addition is set to an average of 3 to 8 mol per active hydrogen atom of the alkylene oxide adduct precursor (E), and the alkylene oxide adduct precursor before adding AO ( The polyether polyol composition containing the diol (A) having a molecular weight distribution of 1.05 to 1.25 is produced by adjusting the water content of E) to 300 ppm or less and the addition reaction temperature of AO to 60 to 90 ° C. can do. When the diol (A) is added later, the diol (A) can also be adjusted by using a plurality of diols having different molecular weight distributions (Mw / Mn) in combination.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the diol (A) were determined for each of the AO adducts having an AO addition mole number of 1 to 7 using a calibration curve from the peak area obtained by GC-MS measurement. It is obtained by calculating the content and calculating by the following formula. The measurement conditions of GC-MS are as described above.
<Calculation formula>
Molecular weight of AO1-7 mol adduct: M1-M7
AO1 to 7 mol adduct content: N1 to N7
Mn: (N1 + N2 + ... + N7) / (N1 / M1 + N2 / M2 + ... + N7 / M7)
Mw: (N1 × M1 +... + N7 × M7) / (N1 +... + N7)

The production method of the present invention is a production method including a step of performing an addition reaction of an alkylene oxide to an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms in a plurality of (preferably two) times. Of the alkylene oxide addition reaction carried out in a plurality of times, the last addition reaction is carried out using a Lewis acid catalyst (D) at a reaction temperature of 60 to 90 ° C and an average of 3 to 8 alkylene oxides per active hydrogen atom. This is a method for producing a polyether polyol composition, which is a step of adding moles.

Examples of the active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms and AO to be added include those described above. The number of added moles of AO is 3 to 8 moles on average per active hydrogen atom of the alkylene oxide adduct precursor (E), and preferably 3 to 7 moles on average from the viewpoint of reactivity.

Examples of the Lewis acid catalyst (D) include those described above. The amount of the Lewis acid catalyst (D) to be used is not particularly limited, but is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 1% by weight, based on the polyether polyol composition to be produced.

From the viewpoint of maintaining the activity of the Lewis acid catalyst (D), the peroxide value of the alkylene oxide adduct precursor (E) is 0.5 or less, and the water content is the alkylene oxide adduct precursor (E). ) Is preferably 300 ppm or less, and the CPR value is preferably 0.8 or less based on the weight of the above.
The peroxide value of the alkylene oxide adduct precursor (E) can be reduced by lowering the oxygen concentration in the step of producing the alkylene oxide adduct precursor (E). The amount of water can be adjusted by the dehydration time, the temperature, the degree of reduced pressure, and the like in the step of producing the alkylene oxide adduct precursor (E), and the CPR value is adjusted to be low by repeating filtration during alkali removal. be able to.

The peroxide value, water content, and CPR value of the alkylene oxide adduct precursor (E) can be measured by the following methods.
<Method of measuring peroxide value>
About 10 g of the alkylene oxide adduct precursor (E) is precisely weighed in 200 mL of a stoppered Erlenmeyer flask, and 25 mL of a mixed solvent of acetic acid / chloroform (3: 2) is added and dissolved. After the Erlenmeyer flask is sufficiently purged with nitrogen, 1 mL of a saturated potassium iodide standard solution is accurately added with a female pipette or a whole pipette, stoppered, shaken for 1 minute, and allowed to stand in a dark place for 5 minutes. Thereafter, 75 mL of ion-exchanged water is added, the contents are stoppered, and the mixture is vigorously shaken, and then titrated with a 0.01 mol / L sodium thiosulfate standard solution. The above operation is performed on two samples, and a blank test is performed.
The peroxide value can be calculated by the following equation.
Peroxide value = (AB) × f / S × 10
A = mL of 0.01 mol / L sodium thiosulfate standard solution required for this test B = mL number of 0.01 mol / L sodium thiosulfate standard solution required for blank test f = 0.01 mol / L sodium thiosulfate Standard solution titer S = sample amount (g)
<Method of measuring water content>
It conforms to JIS K1557-2.
<Method of measuring CPR value>
It conforms to JIS K1557-4.

The reaction temperature when adding AO to the alkylene oxide adduct precursor (E) in the presence of the Lewis acid catalyst (D) is from 60 to 90 ° C. When the reaction temperature is lower than 60 ° C., the reaction rate becomes too slow, and when the reaction temperature exceeds 90 ° C., the resin properties of the urethane resin produced from the obtained polyether polyol composition are reduced.

In the production method of the present invention, during the addition polymerization using the alkylene oxide adduct precursor (E), the AO, and the Lewis acid catalyst (D), the aldehyde and the unreacted AO are converted from a reaction mixture. Heating and / or depressurizing to continuously and / or intermittently volatilize or remove the aldehyde and the unreacted AO from the reaction mixture by heating and depressurizing to volatilize and remove in one step. It is preferred to include. Intermittent volatilization means that the AO is divided into 2 to 100 times and charged, and the reaction and volatilization are repeated for each charge. The temperature at the time of intermittent volatilization and removal may be the temperature at which the AO is added.
In the case of intermittent volatilization and removal, the reaction tank is pressurized (0.1 to 1.0 MPa) when reacting the AO, and the pressure is reduced (0.001 to 0.04 MPa) for volatilization and removal. It is good to carry out alternately. The continuous volatilization means that the volatilization and removal are performed at the same time as the AO is continuously supplied. Continuous volatilization is carried out under heating and / or reduced pressure. The temperature at the time of continuous volatilization and removal may be the temperature at which the AO is added. The degree of reduced pressure is not particularly limited, but is preferably 0.001 to 0.1 MPa, and more preferably 0.001 to 0.04 MPa.

It is preferable that the production method of the present invention further includes a step of adding an acid after the step of finally adding the alkylene oxide to the alkylene oxide adduct precursor (E). By including this step, the content of the diol (A) in the polyether polyol composition can be adjusted more accurately.

Examples of the acid include the Lewis acid catalyst (D) and phosphoric acid. The Lewis acid catalyst (D) is preferred.

The amount of the acid to be added is preferably 0.0001 to 10% by weight based on the total weight of the obtained polyether polyol composition.

The acid is added together with water for hydrolysis after the AO addition reaction is completed.

The step of adding the acid is preferably performed at 100 ° C to 200 ° C. In the step of adding the acid, water is preferably added in an amount of 1 to 20% by weight based on the total weight of the obtained polyether polyol composition.

The present invention is a polyurethane resin which is a reaction product of the above polyether polyol composition and polyisocyanate (C).
As the polyisocyanate (C), those conventionally used in the production of polyurethane can be used, and a linear aliphatic polyisocyanate (c1) having 4 to 22 carbon atoms and having 2 to 3 or more isocyanate groups, C8-C18 alicyclic polyisocyanate (c2), C8-C26 aromatic polyisocyanate (c3), C10-C18 araliphatic polyisocyanate (c4), and modification of these polyisocyanates (C5) and the like. As the polyisocyanate component (C), one type may be used alone, or two or more types may be used in combination.

Examples of the linear aliphatic polyisocyanate having 4 to 22 carbon atoms (c1) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl -2,6-diisocyanatohexanoate and the like.

Examples of the alicyclic polyisocyanate having 8 to 18 carbon atoms (c2) include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexyl. Examples include silylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms (c3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 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- And isocyanatophenylsulfonyl isocyanate.

Examples of the araliphatic polyisocyanate having 10 to 18 carbon atoms (c4) include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Examples of the modified polyisocyanate (c5) of (c1) to (c4) include the modified polyisocyanate (urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or an oxazolidone group-containing modified product having an isocyanate group content of preferably 8 to 33% by weight, more preferably 10 to 30% by weight, particularly 12 to 29% by weight, 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-modified polyisocyanates. In addition, the isocyanate group content in the present invention is measured according to JIS K 1603-1.

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

The isocyanate index [(the number of NCO groups / the number of active hydrogen atoms) × 100] in the production of the polyurethane resin of the present invention is preferably from 60 to 200, more preferably from 80 to 120, particularly preferably from 90, from the viewpoint of resin physical properties. To 115.

The polyurethane resin of the present invention may contain other components as necessary in addition to the polyether polyol composition and the polyisocyanate (C). Other components include additives such as a colorant, a curing accelerator, a diluent (thickener), an antioxidant, and an ultraviolet absorber.

Examples of the coloring agent include pigments such as inorganic pigments and organic pigments, and dyes.
Examples of the inorganic pigment include graphite, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

Organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetic anilide and pyrazolone, β-naphthol, β-oxynaphthoic acid, and β-oxynaphthoic acid. Insoluble azo pigments such as anilide, acetoacetic anilide monoazo, acetoacetic anilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; Examples thereof include polycyclic or heterocyclic compounds such as syndlinone, quinacridone, dioxane, perinone, and perylene.

As the dye, as the yellow dye, phenols, naphthols, anilines, pyrazolones, pyridones or an open-chain active methylene compound having an open-chain active methylene compound as a coupling component, or an open-chain active methylene compound as a coupling component Methine dyes such as azomethine dyes, benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro dyes, nitroso dyes, acridine dyes and acridinone dyes.

As the magenta dye, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (such as pyrrole, imidazole, thiophene and thiazole derivatives) are used as coupling components. Aryl or hetenyl azo dyes having azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye, phthalocyanine dyes and anthraquinone dyes. Examples of the coupling component include phenols, naphthols, anilines, aryl or hetenyl azo dyes having a pyrrolopyrimidinone or pyrrolotriazinone derivative (such as cI Direct Blue 14), and indigo / thioindigo dyes.

Examples of the curing accelerating catalyst include metal catalysts (for example, tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate, etc.), lead-based catalysts, etc. Catalysts (lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.), metal salts of naphthenates such as cobalt naphthenate and phenylmercury propionate, bismuth-based catalysts (bismuth tris (2-ethylhexaate) Noate), etc.)]; Amine-based catalysts [for example, triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine and diazabicycloalkenes [1,8-diazabicyclo [5,4,0] -7-undecene @ San Apro Co., Ltd.) "DBU" (registered Trademark)}] and the like; dialkylaminoalkylamines (such as dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine and dipropylaminopropylamine) or heterocyclic aminoalkylamines} Carbonates or organic acid salts (such as formate) such as 2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine; N-methylmorpholine, N-ethylmorpholine, triethylamine, diethyl Ethanolamine and dimethylethanolamine, etc.]; and mixtures of two or more thereof.

Examples of the diluent (thickening agent) include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, butyl acetate and cellosolve acetate, acetone and Solvents such as ketones such as methyl ethyl ketone and ethers such as diethylene glycol dimethyl ether and ethylene glycol dibutyl ether.

Examples of the antioxidant include a hindered phenol-based antioxidant [Irganox 1010 and Irganox 1076 (both manufactured by BASF Japan) and the like], and a hindered amine-based antioxidant [Sanol LS770 and Sanol LS-744 (all manufactured by Sankyo) ) Etc.) and a phenolic antioxidant [BHT (Tokyo Kasei)].

Examples of the ultraviolet absorber include a triazole-based ultraviolet absorber [Tinuvin 320 (manufactured by BASF Japan) and the like] and a benzophenone-based ultraviolet absorber [Siasorb UV9 (manufactured by Cyanamid) and the like].

The polyurethane resin of the present invention is obtained by reacting the above polyether polyol composition with polyisocyanate (C). The reaction method is not particularly limited, but the polyether polyol composition, the polyisocyanate (C) and, if necessary, the other components are charged into a reaction vessel having a temperature control function, and the temperature is raised to 50 to 200 ° C. for 30 to 1000 minutes. And a method in which a polyether polyol composition, a polyisocyanate (C) and, if necessary, the other components are supplied to a twin-screw extruder and continuously reacted at a temperature of 100 to 220 ° C. Can be

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples unless departing from the gist of the present invention. Unless otherwise specified, parts mean parts by weight and% means% by weight.

<Production Example 1: Production of alkylene oxide adduct precursor (E-1)>
An autoclave equipped with a stirrer and a temperature controller was charged with 266.3 parts of propylene glycol and 2.8 parts of potassium hydroxide. Next, 1133.7 parts of propylene oxide were continuously introduced at an oxygen concentration of 60 ppm while controlling the reaction temperature to be 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (E-1) had an active hydrogen atom number of 2, a hydroxyl value of 280.5, Mp400, a water content of 100 ppm, a CPR of 0.1, and a peroxide value of 0.1 meq / kg.

<Production Example 2: Production of alkylene oxide adduct precursor (E-2)>
An autoclave equipped with a stirrer and a temperature controller was charged with 311.1 parts of the polyol (E-1) synthesized in Production Example 1 and 2.8 parts of potassium hydroxide. Next, at an oxygen concentration of 60 ppm, 1088.9 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (E-2) had 2 active hydrogen atoms, a hydroxyl value of 62.5, Mp 1795, water content of 100 ppm, CPR of 0.1 and a peroxide value of 0.1 meq / kg.

<Production Example 3: Production of alkylene oxide adduct precursor (E-3)>
An autoclave equipped with a stirrer and a temperature controller was charged with 446.2 parts of the polyol (E-1) synthesized in Production Example 1 and 2.8 parts of potassium hydroxide. Next, at an oxygen concentration of 60 ppm, 953.8 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (E-3) had an active hydrogen atom number of 2, a hydroxyl value of 90.1, Mp1245, a water content of 100 ppm, a CPR of 0.7, and a peroxide value of 0.1 meq / kg.

<Production Example 4: Production of alkylene oxide adduct precursor (E-4)> 177.5 parts of propylene glycol and 2.8 parts of potassium hydroxide were charged into an autoclave equipped with a stirrer and a temperature controller. Next, at an oxygen concentration of 60 ppm, 1222.5 parts of propylene oxide were continuously charged while controlling the reaction temperature to 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (D-4) had a functional group number of 2, a hydroxyl value of 187.0, a molecular weight of 600, a water content of 200 ppm, a CPR of 0.1, and a peroxide value of 0.1 meq / kg.

<Production Example 5: Production of alkylene oxide adduct precursor (E-5)>
An autoclave equipped with a stirrer and a temperature controller was charged with 73.1 parts of sucrose and 2.8 parts of potassium hydroxide. Next, 1326.9 parts of propylene oxide were continuously introduced at an oxygen concentration of 60 ppm while controlling the reaction temperature to be 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (E-4) had eight active hydrogen atoms, a hydroxyl value of 68.6, Mp6542, a water content of 200 ppm, a CPR of 0.1 and a peroxide value of 0.4 meq / kg.

<Production Example 6: Production of alkylene oxide adduct precursor (E-6)>
An autoclave equipped with a stirrer and a temperature controller was charged with 311.1 parts of the polyol (E-1) synthesized in Production Example 1 and 2.8 parts of potassium hydroxide. Next, at an oxygen concentration of 200 ppm, 1088.9 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 14 kPa. The obtained (E-5) had an active hydrogen atom number of 2, a hydroxyl value of 62.7, Mp 1789, a water content of 1,050 ppm, a CPR of 2.0, and a peroxide value of 1.0 meq / kg.

<Production Example 7: Production of diol (A-1) for post-addition>
An autoclave equipped with a stirrer and a temperature controller was charged with 355.1 parts of propylene glycol and 2.8 parts of potassium hydroxide. Next, at an oxygen concentration of 60 ppm, 1044.9 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 100 to 110 ° C. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The obtained (A-1) had 2 active hydrogen atoms, a hydroxyl value of 374.0, and Mp300.

<Example 1>
In an autoclave equipped with a stirrer and a temperature controller, 1166.3 parts of (E-2) obtained in Production Example 2 and 0.07 part of tris (pentafluorophenyl) borane were charged, and purged with nitrogen. Next, at an oxygen concentration of 70 ppm, 233.6 parts of propylene oxide were continuously charged while controlling the reaction temperature to 60 to 90 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The obtained polyether polyol composition (B-1) has 2 active hydrogen atoms, a hydroxyl value of 56.1, Mp2000, a content of hydroxyl groups bonded to primary carbon atoms of 63 mol%, diol (A) Was 0.15% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.13.

<Example 2>
In an autoclave equipped with a stirrer and a temperature controller, 1172.6 parts of (E-2) obtained in Production Example 2 and 0.07 part of tris (pentafluorophenyl) borane were charged and purged with nitrogen. Next, 227.3 parts of propylene oxide were continuously introduced at an oxygen concentration of 70 ppm while controlling the reaction temperature to be 60 to 90 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The obtained polyether polyol composition (B-2) has 2 active hydrogen atoms, a hydroxyl value of 56.3, Mp1993, a content of a hydroxyl group bonded to a primary carbon atom of 57 mol%, and a diol (A). Was 0.40% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.15.

<Example 3>
An autoclave equipped with a stirrer and a temperature controller was charged with 810.8 parts of (E-3) obtained in Production Example 3 and 0.07 part of tris (pentafluorophenyl) borane, and the atmosphere was replaced with nitrogen. Next, at an oxygen concentration of 60 ppm, 589.1 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 60 to 90 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The obtained polyether polyol composition (B-3) has 2 active hydrogen atoms, a hydroxyl value of 56.1, Mp2000, a content of a hydroxyl group bonded to a primary carbon atom of 68 mol%, and a diol (A). Was 3.80% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.19.

<Comparative Example 1>
In an autoclave equipped with a stirrer and a temperature controller, 1166.3 parts of (E-2) obtained in Production Example 2 and 0.07 part of tris (pentafluorophenyl) borane were charged, and purged with nitrogen. Next, propylene oxide was introduced at an oxygen concentration of 60 ppm while controlling the reaction temperature to be 50 to 60 ° C. Propylene oxide was charged in 20 batches, charged for 10 minutes, then reduced in pressure at 3.0 kPa for 15 minutes, and a process of distilling off low-boiling volatile components such as aldehyde was repeatedly performed. When the total amount of propylene oxide charged reached 233.6 parts, the charging was stopped, and when the pressure in the kettle became constant, depropylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The resulting polyether polyol composition (B-8) had 2 active hydrogen atoms, a hydroxyl value of 56.4, Mp 1989, a hydroxyl group content of 63 mol% bonded to a primary carbon atom, and a diol (A). Was 0.05% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.02.

<Example 4>
A four-necked flask equipped with a stirrer was charged with 700 parts of (B-8) obtained in Comparative Example 1 and 2.45 parts of tripropylene glycol (manufactured by Nacalai Tesque) as a diol (A) component, followed by purging with nitrogen. Thereafter, the mixture was stirred at room temperature until it became uniform. The resulting polyether polyol composition (B-4) had 2 active hydrogen atoms, a hydroxyl value of 56.6, Mp 1989, a hydroxyl group content of 63 mol% bonded to a primary carbon atom, and a diol (A). Was 0.4% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.03.

<Example 5>
In a four-necked flask equipped with a stirrer, 700 parts of (B-8) obtained in Comparative Example 1, 1.23 parts of Sannicks PP-200 (manufactured by Sanyo Chemical Industries) as a diol (A) component, and 1.23 parts of Knicks PP-400 (manufactured by Sanyo Chemical Industries, Ltd.) was charged, and the mixture was replaced with nitrogen. The resulting polyether polyol composition (B-5) had 2 active hydrogen atoms, a hydroxyl value of 56.6, Mp 1989, a hydroxyl group content of 63 mol% bonded to a primary carbon atom, and a diol (A). Was 0.4% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.35.

<Example 6>
An autoclave equipped with a stirrer and a temperature controller was charged with 785.0 parts of (E-4) obtained in Production Example 4 and 0.07 part of tris (pentafluorophenyl) borane, and the atmosphere was replaced with nitrogen. Next, at an oxygen concentration of 70 ppm, 614.9 parts of propylene oxide were continuously charged while controlling the reaction temperature to 60 to 90 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The obtained polyether polyol composition (B-6) has 2 active hydrogen atoms, a hydroxyl value of 112, Mp1002, a content of a hydroxyl group bonded to a primary carbon atom of 69 mol%, and a diol (A) content. The amount was 3.0% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.16.

<Example 7>
An autoclave equipped with a stirrer and a temperature controller was charged with 1138.2 parts of (E-5) obtained in Production Example 5 and 0.07 part of tris (pentafluorophenyl) borane, and the atmosphere was replaced with nitrogen. Next, at an oxygen concentration of 70 ppm, 258.3 parts of propylene oxide were continuously charged while controlling the reaction temperature to 60 to 90 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The resulting polyether polyol composition (B-7) had 8 active hydrogen atoms, a hydroxyl value of 56.0, Mp8014, a content of a hydroxyl group bonded to a primary carbon atom of 63 mol%, and a diol (A). Was 0.30% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.14.

<Comparative Example 2>
An autoclave equipped with a stirrer and a temperature controller was charged with 259.9 parts of (E-1) obtained in Production Example 1 and 0.07 part of tris (pentafluorophenyl) borane, and the atmosphere was replaced with nitrogen. Next, at an oxygen concentration of 60 ppm, 1140.1 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 70 to 80 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. 72.0 parts of ion-exchanged water and 0.02 parts of tris (pentafluorophenyl) borane were charged to the obtained polyether polyol, and the mixture was purged with nitrogen. After stirring at 140 ° C. for 30 minutes to perform an acetal decomposition reaction, dehydration and dealdehyde were performed at a pressure of 3.0 kPa. The resulting polyether polyol composition (B-9) had 2 active hydrogen atoms, a hydroxyl value of 56.5, Mp1986, the content of a hydroxyl group bonded to a primary carbon atom was 68 mol%, and the diol (A) Was 6.0% by weight, and the molecular weight distribution of the diol (A) was Mw / Mn = 1.25.

<Comparative Example 3>
In an autoclave equipped with a stirrer and a temperature controller, 1166.3 parts of (E-2) obtained in Production Example 2 and 3.5 parts of potassium hydroxide were charged and purged with nitrogen. Next, at an oxygen concentration of 60 ppm, 233.6 parts of propylene oxide were continuously introduced while controlling the reaction temperature to 100 to 110 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 100 ° C. and a pressure of 3.0 kPa. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. Thereafter, (A-1) obtained in Production Example 7 was added in an amount of 0.4% by weight and stirred at room temperature until the mixture became uniform. The resulting polyether polyol composition (B-10) had 2 active hydrogen atoms, a hydroxyl value of 56.1, Mp2000, a content of 2 mol% of hydroxyl groups bonded to primary carbon atoms, and a diol (A). Was 0.40% by weight, and the molecular weight distribution Mw / Mn of the diol (A) was 1.11.

<Comparative Example 4>
In an autoclave equipped with a stirrer and a temperature controller, 1212.3 parts of (E-2) obtained in Production Example 2 and 3.5 parts of potassium hydroxide were charged and purged with nitrogen. Next, at an oxygen concentration of 60 ppm, 184.2 parts of ethylene oxide were continuously introduced while controlling the reaction temperature to be 125 to 135 ° C. After the entire amount was charged, when the pressure in the kettle became constant, propylene oxide was removed at 130 ° C. and a pressure of 3.0 kPa. After alkali removal of the obtained crude polyol containing the catalyst using aluminum silicate and magnesium silicate, dehydration was performed at 130 ° C. and a pressure of 3.0 kPa. The resulting polyether polyol composition (B-11) had an active hydrogen number of 2, a hydroxyl value of 56.1, Mp2000, a hydroxyl group content of 68% bonded to a primary carbon atom, and a diol (A) content of 68%. The content was 0.0% by weight.

<Comparative Example 5>
In an autoclave equipped with a stirrer and a temperature controller, 1166.3 parts of (E-6) obtained in Production Example 6 and 0.07 part of tris (pentafluorophenyl) borane were charged, and purged with nitrogen. Next, at an oxygen concentration of 70 ppm, 233.6 parts of propylene oxide were continuously added while controlling the reaction temperature to be 70 to 80 ° C., but the reaction did not proceed easily, so it was judged that production was difficult and the production was interrupted. did.

<Production of isocyanate group-terminated urethane prepolymer (F) for main agent>
In a four-necked flask equipped with a stirrer and a temperature controller, 850.7 parts of a glycerin PO adduct [Sannicks GH-3000NS manufactured by Sanyo Chemical Industry Co., Ltd.] is charged, and 130 ° C. under reduced pressure (3 kPa). For 1 hour. Thereafter, the mixture was cooled to 50 ° C., and 149.3 parts of 2,4-toluene diisocyanate [“TDI-80” manufactured by Tosoh Corporation) was charged. After the temperature was gradually raised to 70 ° C. with stirring under a nitrogen stream, and the reaction was carried out for 10 hours, the mixture was cooled to room temperature to obtain an isocyanate group-terminated urethane prepolymer (F). The isocyanate group content measured according to JIS K 1558 was 3.6%.

<Manufacture of polyurethane resin sheet>
The R value (NCO group / OH group molar ratio) of the isocyanate group-terminated urethane prepolymer (F) and the polyether polyols obtained in Examples 1 to 7 and Comparative Examples 1 to 4 is 1.05. And Neostan U-28 was added as a catalyst to the urethane resin in the number of copies shown in Tables 1 and 2. After mixing at room temperature, defoaming was performed with a centrifuge. The obtained urethane resin was poured into a polypropylene tray of 11 × 17.5 cm so as to have a thickness of 1 mm, and cured at room temperature overnight. After the resin was cured, surface IR measurement was performed, and it was confirmed that the peak of the unreacted NCO terminal at 2200 to 2350 cm -1 disappeared.

<Evaluation of polyurethane resin sheet>
Using the obtained urethane resin sheet, the tensile rupture strength was evaluated. The evaluation was performed according to JIS K 7311-1995. The same evaluation was performed after the heat resistance test and the water resistance test.
<Evaluation of heat resistance of urethane resin sheet>
The urethane resin sheet was allowed to stand in a dryer at 110 ° C. for 5 days. After 5 days, the urethane resin sheet taken out was cooled to 23 ± 2 ° C. to obtain a urethane resin sheet after the heat resistance test. The measurement of the tensile rupture strength of the urethane resin sheet after the heat resistance test was performed in accordance with JIS K 7311-1995.
<Evaluation of water resistance of urethane resin sheet>
The urethane resin sheet was immersed in a 10% aqueous sodium hydroxide solution, and allowed to stand in a dryer at 70 ° C. for 5 days. After 5 days, the urethane resin sheet taken out was wiped off and dried to obtain a urethane resin sheet after the water resistance test. The measurement of the tensile rupture strength of the urethane resin sheet after the water resistance test was performed in accordance with JIS K 7311-1995.
The evaluation results are shown in Tables 1 and 2.

By using the polyether polyol composition of the present invention, a polyurethane resin having excellent resin properties such as strength and durability can be obtained. This polyurethane resin can be used in various applications such as urethane foam, urethane elastomer, urethane coating material, sealing material and the like. Examples of urethane foam include cushioning materials for automobiles and backing materials for automobiles, examples of urethane elastomers include casting potting materials, and examples of coating materials include adhesives and paints.

Claims (5)

A polyether polyol composition containing an alkylene oxide adduct of an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms, wherein the polyether polyol composition is a diol represented by the following general formula (1): A)
Among the hydroxyl groups of the polyether polyol composition, the number of hydroxyl groups bonded to primary carbon atoms is 55 mol% or more based on the total number of hydroxyl groups in the polyether polyol composition,
The peak top molecular weight measured by gel permeation chromatography of the polyether polyol composition is 900 to 10,000,
A polyether polyol composition containing the diol (A) in an amount of 0.1 to 4% by weight based on the total weight of the polyether polyol composition.
HO- (AO) _n- H (1)
[In the formula, AO is a 1-methylethyleneoxy group, a 2-methylethyleneoxy group, a 1-ethylethyleneoxy group or a 2-ethylethyleneoxy group, and n is an integer of 1 to 7.] The polyether polyol composition according to claim 1, wherein a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the diol (A) is 1.05 to 1.25. A polyurethane resin, which is a reaction product of the polyether polyol composition according to claim 1 and a polyisocyanate (C). A method for producing a polyether polyol composition according to claim 1 or 2,
A production method comprising a step of performing an addition reaction of an alkylene oxide to an active hydrogen atom-containing compound containing 2 to 8 active hydrogen atoms in a plurality of divided times,
Of the alkylene oxide addition reactions carried out in a plurality of times, the last addition reaction is performed using a Lewis acid catalyst (D) at a reaction temperature of 60 to 90 ° C and an average of 3 to 8 mol of alkylene oxide per active hydrogen atom. A method for producing a polyether polyol composition, which is a step of adding. The method for producing a polyether polyol according to claim 4, further comprising a step of adding an acid after the last addition reaction.