JP6050840B2 - Polyether polyol composition and method for producing the same - Google Patents

Description

  The present invention relates to a polyether polyol composition, a method for producing the same, and a method for producing a polyurethane using the same.

  Conventionally, it has been widely carried out industrially to produce a polyether polyol by addition polymerization of alkylene oxide to a compound having at least one active hydrogen in the presence of an alkali metal hydroxide catalyst. However, when producing a high molecular weight polymer of alkylene oxide, particularly propylene oxide, the production of unsaturated monool is increased by side reaction, so that the quality of polyether polyol is lowered. In particular, when used as a raw material for polyurethane having good mechanical properties, it is essential to reduce unsaturated monools. As polyether polyols with reduced unsaturated monools, double metal cyano complexes (for example, see Patent Document 1). ) Or an aluminum porphyrin (for example, see Patent Document 2), a polyether polyol is known as a catalyst.

  However, merely reducing the content of the unsaturated monool may have insufficient mechanical properties when used as a polyurethane.

JP-A 63-277236 JP-A 61-197631

  An object of this invention is to provide the polyether polyol composition excellent in the mechanical physical property at the time of using as a polyurethane raw material, and its manufacturing method.

As a result of intensive studies, the present inventor has reached the following three inventions.
(I) A polyether polyol composition (S) containing a polyether polyol and diol having 3 to 6 functional groups, or containing a polyether polyol, diol and unsaturated monool having 3 to 6 functional groups The hydroxyl value [X] of (S) (unit: mg KOH / g) is 10 to 100, the unsaturated monool content [Y] of (S) (unit: meq / g) is 0 to 0.08, The diol content [Z] (unit: meq / g) of (S) is 0.04 to 0.08, and the content [α] of ethylene oxide units based on the weight of (S) is 0 to 20 weights. %, And the polyether polyol composition in which X, Y, Z, and α satisfy the relationship of the following mathematical formula (1).

(Y + Z) × (100−α) ^{/100≦5.89×X−1.27} (1)

(II) In the presence of the alkali metal hydroxide (a), the crude polyol (d1) obtained by addition polymerization of the alkylene oxide (c) to the compound (b) having 3 to 6 active hydrogens is heated. The rearrangement step [1] for obtaining the crude polyol (d2) using the allyl group in the polyol as the propenyl group, and the alkali metal hydroxide (a) in the crude polyol (d2) are adsorbed by the silicate adsorbent (e). The crude polyol (d3) obtained in the step [2] to obtain a crude polyol (d3) by treatment is acidified by adding a mineral acid (f) or a sulfonic acid group-supporting inorganic porous material (g) and water, and propenyl The manufacturing method of the polyether polyol composition of (I) including the process [3] of acid-hydrolyzing a group.
(III) A process for producing a polyurethane, comprising reacting a polyol (A) containing the polyether polyol composition (S) of (I) with a polyisocyanate (B) in the presence or absence of an additive.

  The polyurethane obtained by using the polyether polyol composition (S) of the present invention has improved mechanical properties such as elongation and hardness.

The polyether polyol composition (S) of the first invention contains a polyether polyol and diol having 3 to 6 functional groups, or a polyether polyol, diol and unsaturated monool having 3 to 6 functional groups. .
The hydroxyl value [X] of the polyether polyol composition (S) of the present invention is 10 to 100 (mgKOH / g) from the viewpoint of easy adjustment of unsaturated monool content and resin physical properties of polyurethane using the same. 15 to 60 (mgKOH / g) is preferable, and 20 to 42 (mgKOH / g) is more preferable.
The hydroxyl value in the present invention is measured by the method described in JIS K1557-1.
From the viewpoint of durability of polyurethane, the content [α] of ethylene oxide (hereinafter abbreviated as EO) units based on the weight of (S) is in the range of 0 to 20%, preferably 5 to 20%. 10 to 15% is more preferable.
In the above and below, “%” means “% by weight” unless otherwise specified.

The unsaturated monool content [Y] of the polyether polyol composition (S) is in the range of 0 to 0.08 (meq / g) and 0 to 0.05 (meq / g) from the viewpoint of durability. Is preferable, and more preferably 0 to 0.04 (meq / g). The diol content [Z] is 0.04 to 0.08 (meq / g), preferably 0.04 to 0.07, more preferably 0.04 to 0.08, from the viewpoint of the mechanical properties of the polyurethane. 0.065.
The unsaturated monool content and the diol content in the present invention are measured by the methods described in the examples described later.
The hydroxyl value [X], unsaturated monool content [Y], diol content [Z], and EO unit content [α] of the polyether polyol composition (S) must satisfy the following formula (1). It is more preferable that the numerical formula (1 ′) is satisfied.

(Y + Z) × (100−α) ^{/100≦5.89×X−1.27} (1)
(Y + Z) × (100−α) ^{/100≦5.30×X−1.27} (1 ′)

If the mathematical formula (1) is not satisfied, the mechanical properties (particularly the elongation) of the polyurethane are lowered. For example, this mathematical formula can be easily satisfied by lowering the alkylene oxide addition reaction temperature and using a highly pure alkali metal hydroxide (a) as a polymerization catalyst.
In addition, Formula (1) is a formula derived empirically from very many experimental results.

In the polyether polyol composition (S) of the first invention, for example, an alkylene oxide (c) is added to a compound (b) having 3 to 6 active hydrogens in the presence of an alkali metal hydroxide (a). The crude polyol (d1) obtained by polymerization can be easily obtained by the method for producing a polyether polyol composition of the second invention, which is treated under specific conditions.
When the polyether polyol composition (S) of the first invention is obtained by the method of the second invention, the unsaturated monool is an addition polymerization of alkylene oxide (c) to the compound (b) having 3 to 6 active hydrogens. The diol is obtained from the unsaturated monool by the step [3] of acid hydrolysis of the propenyl group described later, which is derived from what is present as a by-product in the crude polyol (d1) thus obtained.
The hydroxyl value of the unsaturated monool and diol is preferably 20 to 200 (mgKOH / g).
In addition, when the content of diol is less than the lower limit, it can be adjusted by adding diol to the polyether polyol composition (S). Examples of the diol to be added include adducts of alkylene oxides (such as alkylene oxide (c) described later) of dihydric alcohols having 2 to 20 carbon atoms (ethylene glycol, propylene glycol, 1,4-butanediol, etc.).

  In the method for producing the polyether polyol composition of the second invention, the compound (b) having 3 to 6 active hydrogens, which is an addition polymerized alkylene oxide (c), which is a raw material of the crude polyol (d1), The compound is not particularly limited as long as it is a compound having active hydrogen in the molecule, and two or more kinds may be used in combination. Examples of the group containing active hydrogen include a hydroxyl group, a carboxyl group, a mercapto group, a primary and secondary amino group. In these, a hydroxyl group is preferable.

  Specific examples of the compound (b) having 3 to 6 active hydrogens include polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids, and structures in which alkylene oxides are addition-polymerized to these active hydrogen-containing compounds. A compound etc. are mentioned and you may use 2 or more types together.

  Examples of the polyhydric alcohol include trivalent alcohols having 3 to 20 carbon atoms (aliphatic triols such as alkanetriols such as glycerin, trimethylolpropane, trimethylolethane, and hexanetriol), and 4 to 6 carbon atoms having 5 to 20 carbon atoms. Monohydric alcohols (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., alkane polyols and intra- or intermolecular dehydrates of alkanetriol; and glucose, mannose, fructose, Saccharides such as methyl glucoside and derivatives thereof), natural fat-based polyols such as castor oil, and combinations of two or more thereof.

  Examples of the polyvalent (3 to 6 valent) phenols include monocyclic polyhydric phenols such as pyrogallol and phloroglucin, condensates of phenol and formaldehyde (novolac), polyphenols, and combinations of two or more thereof.

  The amine has 3 to 6 active hydrogen atoms, and ammonia and aliphatic amines are alkanolamines having 3 to 20 carbon atoms (for example, triethanolamine), polyalkylene polyamines having 4 to 20 carbon atoms. (Dialkylenetriamine and trialkylenetetramine having 2 to 6 carbon atoms in the alkylene group, such as diethylenetriamine and triethylenetetramine) and combinations of two or more thereof may be mentioned.

  Examples of the polycarboxylic acid include aromatic polycarboxylic acids having 8 to 18 carbon atoms (such as trimellitic acid and pyromellitic acid), and mixtures of two or more thereof.

In addition, when a compound [polyether polyol] having a structure in which alkylene oxide is addition-polymerized to these active hydrogen-containing compounds is used as (b), two or more of these active hydrogen-containing compounds as raw materials are used in combination. Polyhydric alcohol is preferable.
The alkylene oxide in the alkylene oxide addition polymer is preferably an alkylene oxide having 2 to 8 carbon atoms, propylene oxide (hereinafter abbreviated as PO), EO, 1,2-, 1,3-, 1,4-, or 2, Examples include 3-butylene oxide, styrene oxide, and a combination of two or more of these (in the case of combination, random addition, block addition, or any combination thereof). PO and / or EO, especially PO is preferred.
The addition conditions of alkylene oxide are not particularly limited, and include compounds in which alkylene oxide is added at 70 to 150 ° C. in the presence of a commonly used alkali catalyst (such as an alkali metal hydroxide (a) described later). . Commercially available alkylene oxide adducts may also be used.

  Of these compounds (b) having 3 to 6 active hydrogens, preferred are polyhydric alcohols and alkylene oxide addition polymers thereof, and more preferred are glycerin, trimethylolpropane, pentaerythritol, and these. It is an alkylene oxide addition polymer of a compound.

  In the method for producing the polyether polyol composition of the second invention, the alkylene oxide (c) to be added to the compound (b) having 3 to 6 active hydrogens during the production of the crude polyol (d1) 2 to 8 are preferable, PO, EO, 1,2-, 1,3-, 1,4-, or 2,3-butylene oxide, styrene oxide, and combinations of two or more thereof (when used in combination) Can be random addition, block addition, or a combination thereof. Preferred is PO and a combination of PO and EO.

The alkali metal hydroxide (a) used as a catalyst during the production of the crude polyol (d1) is added to the compound (b) having active hydrogen, and usually after dehydration treatment (such as vacuum dehydration) (preferably active hydrogen compound) The water content is 0.1% or less), and the alkylene oxide (c) is subjected to addition polymerization.
Examples of the alkali metal hydroxide (a) include lithium, sodium, potassium, rubidium, and cesium hydroxide. From the viewpoint of the unsaturated monool produced as a by-product and cost, it is preferably a compound other than sodium hydroxide, more preferably potassium hydroxide, and particularly preferably potassium hydroxide having a purity of 95% or more.
Further, the sodium content in the alkali metal hydroxide (a) is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. When the content is 5% or less, the unsaturated monool produced as a by-product is further reduced. The analysis method of purity and sodium content may be a known method such as ion chromatography, atomic absorption analysis, or IPC method.

  The amount of the alkali metal hydroxide (a) used is preferably 0.005 to 1.5%, more preferably 0.05 to 1%, especially with respect to the weight of the polyether polyol at the end of the polymerization. Preferably it is 0.1 to 0.7%. If it is 0.005% or more, the reaction time does not become long, and if it is 1.5% or less, the reaction is easily controlled.

In the method for producing a polyether polyol composition of the present invention, the pressure in the reaction vessel at the start of introduction of the alkylene oxide (c) during production of the crude polyol (d1) is preferably 0 MPa or less. The lower limit is more preferably -0.1 MPa, and the upper limit is more preferably -0.05 MPa, particularly preferably -0.09 MPa. If the pressure at the start of introduction exceeds 0 MPa, introduction takes time and the reaction time becomes long. In addition, the pressure in this invention means the relative pressure (gauge pressure) which makes a normal pressure 0 MPa.
The reaction temperature of the alkylene oxide (c) is preferably the initial stage [the initial stage of the ripening step for completing the reaction during the introduction of the alkylene oxide (c) and after the completion of the introduction (until the internal pressure of the reaction vessel becomes 0.2 MPa or less)]. 70-95 ° C. The lower limit of the reaction temperature is more preferably 80 ° C, particularly preferably 85 ° C. When the initial reaction temperature is 70 ° C. or higher, the reaction time does not increase. There are few unsaturated monools by-produced as it is 95 degrees C or less.

After the introduction of the alkylene oxide (c), the internal pressure of the reaction vessel is usually higher than 0.2 MPa (for example, 0.3 to 4 MPa) because of the unreacted alkylene oxide (c), but gradually as the reaction proceeds. It will decline. The internal pressure of the reaction tank when the initial reaction conditions are finished and the temperature rise is started is preferably 0.2 MPa or less (more preferably 0.1 MPa or less). When the pressure is 0.2 MPa or less, there is little unsaturated monol as a by-product.
After reaching the above pressure, the temperature rise is started, but if the reaction is continued at 90 to 110 ° C., the reaction time becomes longer. In the latter period, the reaction is preferably performed at 120 to 140 ° C. More preferably, the lower limit is 125 ° C and the upper limit is 135 ° C. If it is 120 ° C or higher, the reaction time does not become long. When the temperature is 140 ° C. or lower, there is little unsaturated monol as a by-product.
The reaction (aging) is continued until the internal pressure of the reaction tank becomes constant. In the present invention, the constant internal pressure means that the change in internal pressure for 30 minutes is 0.01 MPa or less.

  Even when the polyether polyol obtained by the above production method is used as the crude polyol (d1), the alkylene oxide (c) (preferably EO) is further added by a usual reaction method, and another alkylene oxide ( c) A polyether polyol to which (especially EO) has been added may be used as the crude polyol (d1). For example, the method of adding EO at 100-150 degreeC (preferably 110-140 degreeC) to the polyether polyol containing an alkali metal hydroxide (a) is mentioned.

  The crude polyol (d1) obtained by addition polymerization of the alkylene oxide (c) is heated to obtain a crude polyol (d2) using the allyl group in the polyol as a propenyl group. The step [2] of obtaining the crude polyol (d3) by adsorbing the alkali metal hydroxide (a) in d2) with the silicate-based adsorbent (e), and the resulting crude polyol (d3) with the mineral acid ( f) Or the sulfonic acid group-carrying inorganic porous material (g) and water to make acidic conditions, and through the step [3] of acid hydrolysis of the propenyl group, the polyether polyol composition (S) of the first invention is obtained. It is done.

The reaction temperature (heating temperature) in the transfer step [1] in which the allyl group in the crude polyol (d1) after the addition polymerization reaction is transferred to the propenyl group is preferably 140 to 180 ° C, more preferably 150 to 175 ° C. Especially preferably, it is 160-170 degreeC. Above 140 ° C, the rearrangement reaction rate is fast and the reaction time does not become long. Moreover, if it is 180 degrees C or less, it will not take time for temperature rising and production efficiency will not fall.
The reaction time (heat treatment time) is preferably 1 to 6 hours.

The water content in the step [1] of rearranging an allyl group to a propenyl group is preferably 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 50 ppm or less. When the water content is 200 ppm or less, the rearrangement reaction rate is high and the reaction time does not become long.
The moisture in the present invention is measured by a Karl Fischer moisture meter (volumetric titration method).
The rearrangement of the allyl group to the propenyl group can be confirmed by, for example, ¹ H-NMR.

The crude polyol (d2) in which the allyl group is rearranged to the propenyl group is subjected to removal of the alkali metal hydroxide (a) used as a catalyst as a step [2] after the reaction is completed.
The removal of the alkali metal oxide (a) in the polyol is adsorbed using a silicate-based adsorbent (e) [synthetic magnesium silicate (for example, Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd., synthetic aluminum silicate, etc.). It is done by the processing method.
The temperature of the adsorption treatment is preferably 40 to 95 ° C. The adsorption treatment time is preferably 20 minutes to 5 hours.

To the crude polyol (d3) from which the alkali metal oxide (a) has been removed by the above method, as step [3], mineral acid (f) or sulfonic acid group-carrying inorganic porous material (g) and water are added to achieve acidic conditions, Acid hydrolysis of the propenyl group.
When the mineral acid (f) is used, the reaction temperature (heating temperature) in the acid hydrolysis step of the propenyl group is preferably 120 to 160 ° C, more preferably 130 to 160 ° C, and particularly preferably 140 to 150 ° C. Above 120 ° C, the hydrolysis rate is fast and the reaction time does not become long. Moreover, if it is 160 degrees C or less, it will not take time for temperature rising and production efficiency will not fall.
The reaction time (heat treatment time) is preferably 2 to 8 hours.
Examples of the mineral acid (f) used as the catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like. Of these, phosphoric acid is most preferable from the viewpoint of the treatment process and equipment.

When the sulfonic acid group-supporting inorganic porous material (g) is used, the reaction temperature (heating temperature) in the acid hydrolysis step of the propenyl group is preferably 50 to 170 ° C, more preferably 70 to 150 ° C, and particularly preferably 90. ~ 140 ° C. Above 50 ° C, the hydrolysis rate is fast and the reaction time does not become long. Moreover, at 170 degrees C or less, it does not take time for temperature rising and production efficiency does not fall.
The reaction time (heat treatment time) is preferably 1 minute to 8 hours.

The sulfonic acid group-supporting inorganic porous material (g) is obtained by immobilizing and supporting a sulfonic acid group-containing compound on an inorganic porous material.
As the inorganic porous body, a known inorganic porous body can be used, and examples thereof include an inorganic porous body made of one or more inorganic substances selected from the group consisting of silica, alumina, titania, magnesia and zirconia.
Specifically, silica gel as an inorganic porous material made of silica; alumina gel or the like as an inorganic porous material made of alumina; zeolite or the like as an inorganic porous material made of silica and alumina; and as an adsorbent as another inorganic porous material. Commercially available “KYOWARD” (manufactured by Kyowa Chemical Co., Ltd.), diatomaceous earth, and the like. Of these, silica, alumina and zeolite are preferable from the viewpoint of catalytic activity, and silica gel is particularly preferable.
The average pore diameter of the inorganic porous body is preferably 0.5 to 150 nm.

The method for supporting the sulfonic acid group on the inorganic porous material is not particularly limited. For example, the inorganic porous material is reacted with a sulfonic acid precursor group-containing compound (h) that can be converted into a sulfonic acid group, and then (h) And a method of converting a sulfonic acid precursor group having the sulfonic acid group into a sulfonic acid group (see JP 2011-131180 A).
Specific examples of (h) include mercapto group-containing silane coupling agents (such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane), phenyl group-containing silane coupling agents (phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyl). Dimethoxysilane and the like) and phenyl group-containing glycidyl compounds (such as phenyl glycidyl ether and nonylphenyl glycidyl ether).

The polyol polyol composition (S) obtained by the production method of the second invention is a sulfonic acid obtained by removing the mineral acid (f) used as a catalyst by further purification after the reaction of step [3], or by filtration or the like. After removing the group-supporting inorganic porous material (g), it is preferably used as various raw materials.
As a method for purifying the polyether polyol composition (S) containing the mineral acid (f), a commonly used method may be used. The catalyst is neutralized with a base such as sodium hydroxide or potassium hydroxide, and the resulting salt is filtered. There are a method of removing and an acid adsorbent [a synthetic magnesium silicate (for example, Kyoward 1000: manufactured by Kyowa Chemical Industry Co., Ltd.), a synthetic aluminum silicate, etc.]. The method is preferred.
After removing the mineral acid (f) or the sulfonic acid group-carrying inorganic porous material (g), it is preferable to perform dehydration. If necessary, dehydration is performed under heating (for example, 100 to 150 ° C.) and / or under reduced pressure (for example, −0.09 to −0.1 MPa). The moisture after dehydration is preferably 0.1% or less, more preferably 0.05% or less.

  The polyether polyol composition of the first invention can be used for various applications, but the polyol (A) containing the polyether polyol composition (S) and the polyisocyanate (B) are present in the presence of additives. It is preferably used to produce a foamed or non-foamed polyurethane by reacting under or in the absence.

As said polyol (A), you may contain other polyols (G) other than the polyether polyol composition (S) of this invention as needed.
Other polyols (G) may be those usually used as raw materials for polyurethanes, and include alkylenes such as polyhydric alcohols, polyhydric phenols, amines, and divalent or higher valent active hydrogen-containing compounds such as polycarboxylic acids. Examples thereof include compounds having a structure in which an oxide is addition-polymerized, polyhydric alcohols, and alkanolamines.
The content of the polyether polyol composition (S) in the polyol (A) used in the method for producing a polyurethane of the third invention is preferably 40% or more, more preferably 45 to 90, from the viewpoint of mechanical properties of the polyurethane. %, Particularly preferably 50 to 80%.

The method for producing polyurethane may be a commonly used method and is not particularly limited.
As said polyisocyanate (B), what is conventionally used for manufacture of a polyurethane can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

The aromatic polyisocyanate includes 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same). Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.

In the method for producing a polyurethane of the present invention, if necessary, the reaction may be carried out in the presence of an additive described below.
When producing a polyurethane foam, a foaming agent is used.
As the foaming agent, water, hydrogen atom-containing halogenated hydrocarbon, low boiling point hydrocarbon, liquefied carbon dioxide gas or the like is used, and two or more kinds may be used in combination.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa and HFC-). 365 mfc).
The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane.

The amount of the foaming agent to be used relative to 100 parts of the polyol (A) is preferably 0.1 to 30 parts, more preferably 1 to 20 parts of water. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts or less, more preferably 10 to 45 parts. The low boiling point hydrocarbon is preferably 40 parts or less, more preferably 10 to 30 parts. The amount of liquefied carbon dioxide is preferably 30 parts or less, more preferably 1 to 25 parts.
Above and below, parts mean parts by weight.

  Further, for example, urethanization catalyst (D) (tertiary amine catalyst such as triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ′, N′-tetramethylhexamethylenediamine, tetramethylethylenediamine, diamino Bicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7, and / or metal catalysts such as stannous octylate, dibutyl dilaurate Stannic acid, lead octylate, etc.), foam stabilizer (E) (dimethylsiloxane, polyether-modified dimethylsiloxane, etc.), colorant (dye, pigment), plasticizer (phthalate, adipate, etc.) , Organic fillers (from synthetic short fibers, thermoplastic or thermosetting resins Hollow microspheres), flame retardants (phosphate esters, halogenated phosphate esters, etc.), anti-aging agents (triazoles, benzophenones, etc.), antioxidants (hindered phenols, hindered amines, etc.) The reaction can be carried out in the presence of an additive.

  Regarding the usage-amount of these additives with respect to 100 parts of polyol (A), a urethanization catalyst (D) becomes like this. Preferably it is 10 parts or less, More preferably, it is 0.2-5 parts. The foam stabilizer (E) is preferably 10 parts or less, more preferably 0.5 to 5 parts. The colorant is preferably 1 part or less. The plasticizer is preferably 10 parts or less, more preferably 5 parts or less. The organic filler is preferably 50 parts or less, more preferably 30 parts or less. The flame retardant is preferably 30 parts or less, more preferably 5 to 20 parts. The anti-aging agent is preferably 1 part or less, more preferably 0.01 to 0.5 part. The antioxidant is preferably 1 part or less, more preferably 0.01 to 0.5 part. The total amount of additives used is preferably 50 parts or less, more preferably 0.2 to 30 parts.

  The isocyanate index (NCO index) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in the method for producing a polyurethane of the third invention is preferably 80 to 150, more preferably 85 to 135, and particularly preferably. Is 90-130.

Moreover, the conditions which make a polyol (A) and polyisocyanate (B) react may be the well-known conditions normally used.
For example, first, a polyol (A) containing the polyether polyol composition (S) and a predetermined amount of additives as necessary are mixed. The mixture (polyol premix) and polyisocyanate (B) are then rapidly mixed using a polyurethane low pressure or high pressure injection foamer or stirrer. The obtained mixed liquid is poured into a closed mold or an open mold (made of metal or resin) to cause urethanization reaction, and after curing for a predetermined time, it is demolded to obtain polyurethane.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

The physical property values of the obtained polyether polyol composition are shown in Table 1. The analysis was performed by measuring the hydroxyl value [X], the unsaturated monool content [Y], and the diol content [Z]. Each measuring method is as follows.
Hydroxyl value (mgKOH / g): JIS K1557-1
Unsaturated monool content (meq / g): JIS K1557-3
Diol content (meq / g): Unsaturated monool content of crude polyol (d1) (meq / g) × {propenyl group content after rearrangement step (%) / 100} × {hydrolysis rate (%) / 100}
In addition, how to obtain | require the propenyl group content (%) and hydrolysis rate (%) after a rearrangement process is as follows.
Propenyl group content (%) after rearrangement step = 100 × propenyl group content / (propenyl group content + allyl group content)
Hydrolysis rate (%) = 100-100 × (propenyl group content after hydrolysis / propenyl content after rearrangement step)
The propenyl group content and the allyl group content were determined by measuring the mixing ratio from the ratio of the proton peak derived from the propenyl group and the proton peak derived from the allyl group in ¹ H-NMR, and each content was determined from the unsaturated monool content and the mixing ratio.
In addition, in the case of a polyether polyol composition obtained by a method other than the method for producing the polyether polyol composition of the second invention, the method for measuring the diol content in addition to the above method is a polyether polyol composition. It can also be measured by subjecting the product directly to preparative gel permeation chromatography (preparative GPC) to fractionate the diol and confirming its composition by molecular weight, ¹ H-NMR analysis, hydroxyl value and the like.

Example 1
In an autoclave, 60 parts of glycerin / PO adduct [hydroxyl number conversion number average molecular weight (Mn) 600] as an active hydrogen compound was added, and high purity KOH (purity 96%, sodium content 200 ppm, the same applies hereinafter) was used as the active hydrogen compound. 5 parts were added to 100 parts and stirred under reduced pressure at 130 ° C. to uniformly dissolve and dehydrate (until the water content was 0.1% or less. The same applies to the following examples). Subsequently, 800 parts of PO was subjected to addition polymerization at a reaction temperature of 95 ° C., and 140 parts of EO was subjected to addition polymerization at a reaction temperature of 130 ° C.
The resulting crude polyol was heated up and subjected to a heating reaction at 170 ° C. for 3 hours. The moisture at the time of reaching 170 ° C. was 45 ppm. After cooling to 60 ° C., alkali adsorbent treatment [1.8% water added to the crude polyol and mixed at 85 to 90 ° C. for 30 minutes, then Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was used as the adsorbent. After adding 0.5% to the polyol and mixing at the same temperature for 30 minutes, the adsorbent was removed by filtration. The same applies to the following examples. ] Was performed. Phosphoric acid and water were added to adjust to pH 4.0, the temperature was raised, and acid hydrolysis was performed at a reaction temperature of 140 ° C. for 4 hours. After cooling to 60 ° C., acid adsorbent treatment [0.4% of Kyoward 1000 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent to the crude polyol was added and mixed at the same temperature for 30 minutes. Removed. The same applies to the following examples (excluding Example 4). ] And dehydration (dehydration was performed at 130 ° C. under a reduced pressure of −0.1 MPa until the water content was 0.1% or less. The same applies to the following examples), and the polyether polyol composition ( S-1) was obtained.
As a result of the analysis, the hydroxyl value was 25.2, the unsaturated monool content was 0.021 meq / g, and the diol content was 0.057 meq / g.

Example 2
In an autoclave, 45 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound is added, and 5 parts of the above high-purity KOH is added to 100 parts of the active hydrogen compound. Dissolved in water and dehydrated. Subsequently, 755 parts of PO was addition-polymerized at a reaction temperature of 95 ° C, and 200 parts of EO was addition-polymerized at a reaction temperature of 130 ° C.
The resulting crude polyol was heated up and subjected to a heating reaction at 170 ° C. for 3 hours. The water content at the time of reaching 170 ° C. was 90 ppm. After cooling to 60 ° C., an alkali adsorbent treatment was performed. Phosphoric acid and water were added to adjust the pH to 3.8, the temperature was raised, and acid hydrolysis was performed at a reaction temperature of 140 ° C. for 4 hours. After cooling to 60 ° C., the acid adsorbent treatment and dehydration were performed to obtain the polyether polyol composition (S-2) of the present invention.
As a result of the analysis, the hydroxyl value was 21.5, the unsaturated monool content was 0.036 meq / g, and the diol content was 0.064 meq / g.

Example 3
In an autoclave, 95 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound is added, and 5 parts of the above high-purity KOH is added to 100 parts of the active hydrogen compound. Dissolved in water and dehydrated. Subsequently, 785 parts of PO was subjected to addition polymerization at a reaction temperature of 95 ° C., and 120 parts of EO was added at a reaction temperature of 130 ° C.
The resulting crude polyol was heated up and subjected to a heating reaction at 170 ° C. for 3 hours. The moisture at the time of reaching 170 ° C. was 50 ppm. After cooling to 60 ° C., an alkali adsorbent treatment was performed. After adjusting the pH to 4.0 by adding phosphoric acid and water, the temperature was raised and acid hydrolysis was carried out at a reaction temperature of 140 ° C. for 4 hours. After cooling to 60 ° C., the acid adsorbent treatment and dehydration were performed to obtain the polyether polyol composition (S-3) of the present invention.
As a result of analysis, the hydroxyl value was 40.3, the unsaturated monool content was 0.009 meq / g, and the diol content was 0.041 meq / g.

Production Example 1
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a reflux tube, silica gel “CariACT Q-6” [average particle size: 75 to 500 μm, Fuji Silysia Chemical Ltd. )] After charging 200 parts, 400 parts of toluene as a solvent and 10 parts of water, the temperature was raised to 100 to 110 ° C. Subsequently, 100 parts of 3-mercaptopropyltrimethoxysilane was added, and the mixture was allowed to react with stirring for 8 hours under reflux. Thereafter, 15 parts of water was further added and reacted for 8 hours. The solid content was filtered off from the reaction mixture, washed three times with 400 parts of toluene and three times with 400 parts of isopropyl alcohol, and then dried at 120 ° C. under reduced pressure (−0.097 Mpa) for 5 hours to give a silane coupling agent. 220 parts of a supported inorganic porous material was obtained.
150 parts of a silane coupling agent-supporting inorganic porous material, 450 parts of water as a solvent and 150 parts of 30% hydrogen peroxide water were charged in a reaction vessel similar to the above and reacted at 80 ° C. for 8 hours. The solid content was filtered off from the reaction mixture, washed with 400 parts of methanol three times, once with 400 parts of 0.1N sulfuric acid and once with 400 parts of ion-exchanged water, and then dried under reduced pressure at 120 ° C. for 5 hours. As a result, 140 parts of a sulfonic acid group-supporting inorganic porous material was obtained.
100 parts of the sulfonic acid group-supporting inorganic porous material was charged into a reaction vessel similar to the above, and heat-treated at 180 ° C. for 24 hours. After cooling to room temperature, the sulfonic acid group-supporting inorganic porous material was washed three times with 250 parts of methanol, dried under reduced pressure (-0.097 Mpa) at 120 ° C. for 3 hours, and 190 parts of sulfonic acid group-supporting inorganic porous material (g-1). Got.

Example 4
In an autoclave, 60 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound was added, and 5 parts of the above high purity KOH was added to 100 parts of the active hydrogen compound, and the mixture was stirred uniformly at 130 ° C. under reduced pressure. Dissolved in water and dehydrated. Subsequently, 800 parts of PO was subjected to addition polymerization at a reaction temperature of 95 ° C., and 140 parts of EO was subjected to addition polymerization at a reaction temperature of 130 ° C.
The resulting crude polyol was heated up and subjected to a heating reaction at 170 ° C. for 3 hours. The moisture at the time of reaching 170 ° C. was 50 ppm. After cooling to 60 ° C., an alkali adsorbent treatment was performed. 0.5 part and water were added to 100 parts of the polyether obtained sulfonic acid group-supporting inorganic porous material (g-1), the temperature was raised, and acid hydrolysis was performed at a reaction temperature of 90 ° C. for 4 hours. After cooling to 60 ° C., the sulfonic acid group-carrying inorganic porous material (g-1) was removed and dehydrated by filtration to obtain the polyether polyol composition (S-4) of the present invention.
As a result of analysis, the hydroxyl value was 25.3, the unsaturated monool content was 0.020 meq / g, and the diol content was 0.058 meq / g.

Comparative Example 1
In an autoclave, 60 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound was added, and 5 parts of the above high purity KOH was added to 100 parts of the active hydrogen compound, and the mixture was stirred uniformly at 130 ° C. under reduced pressure. Dissolved in water and dehydrated. Subsequently, 800 parts of PO was addition-polymerized at a reaction temperature of 110 ° C, and 140 parts of EO was addition-polymerized at a reaction temperature of 130 ° C.
The obtained crude polyol was cooled to 60 ° C., then treated with an alkali adsorbent and dehydrated to obtain a comparative polyether polyol composition (S′-1).
As a result of analysis, the hydroxyl value was 24.0, the unsaturated monool content was 0.13 meq / g, and the diol content was 0.00 meq / g.

Comparative Example 2
In an autoclave, 70 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound is added, and a phosphazene compound (phosphazene base P ₄ -t-Oct solution manufactured by Aldrich) (PN) is added to 1 part of 100 parts of active hydrogen compound. .3 parts was added and stirred under reduced pressure at 100 ° C. to uniformly dissolve and dehydrate. Subsequently, 790 parts of PO was addition-polymerized at a reaction temperature of 95 ° C., and 140 parts of EO was addition-polymerized at a reaction temperature of 120 ° C.
The obtained crude polyol was cooled to 60 ° C., then treated with an alkali adsorbent and dehydrated to obtain a comparative polyether polyol composition (S′-2).
As a result of analysis, the hydroxyl value was 24.3, the unsaturated monool content was 0.022 meq / g, and the diol content was 0.00 meq / g.

Comparative Example 3
In an autoclave, 45 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound is added, and 5 parts of the above high-purity KOH is added to 100 parts of the active hydrogen compound. Dissolved in water and dehydrated. Subsequently, 755 parts of PO was addition-polymerized at a reaction temperature of 95 ° C, and 200 parts of EO was addition-polymerized at a reaction temperature of 130 ° C.
The temperature of the obtained crude polyol was raised, and a heating reaction at 170 ° C. was performed for 5 hours. After cooling to 60 ° C., an alkali adsorbent treatment was performed. After adding phosphoric acid and water to adjust to pH 3.8, the temperature was raised and acid hydrolysis was carried out at a reaction temperature of 140 ° C. for 4 hours. After cooling to 60 ° C., acid adsorbent treatment and dehydration were performed to obtain a comparative polyether polyol composition (S′-3).
As a result of analysis, the hydroxyl value was 23.2, the unsaturated monool content was 0.012 meq / g, and the diol content was 0.106 meq / g.

Comparative Example 4
In an autoclave, 50 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound is added, 5 parts of CsOH is added to 100 parts of active hydrogen compound, and the mixture is uniformly dissolved by stirring at 130 ° C. under reduced pressure. Dehydrated. Subsequently, 750 parts of PO was subjected to addition polymerization at a reaction temperature of 95 ° C., and 200 parts of EO was subjected to addition polymerization at a reaction temperature of 130 ° C.
The obtained crude polyol was cooled to 60 ° C., then treated with an alkali adsorbent and dehydrated to obtain a comparative polyether polyol composition (S′-4).
As a result of analysis, the hydroxyl value was 22.5, the unsaturated monool content was 0.032 meq / g, and the diol content was 0.00 meq / g.

Comparative Example 5
In an autoclave, 100 parts of glycerin / PO adduct (Mn600) as an active hydrogen compound was added, and a double metal cyanide complex compound (Zn ₃ [Co (CN) ₆ ] ₂ · 2.48 DME · 4.65H ₂ O · 0 0.14 part of .94ZnCl ₂ ) (DMC) was added to 100 parts of active hydrogen compound, and the mixture was stirred at 130 ° C. under reduced pressure to uniformly dissolve and dehydrate. Subsequently, 780 parts of PO was addition-polymerized at a reaction temperature of 100 ° C., and 120 parts of EO was addition-polymerized at a reaction temperature of 130 ° C.
The obtained crude polyol was cooled to 60 ° C. and then treated with an alkali adsorbent and dehydrated to obtain a comparative polyether polyol composition (S′-5).
As a result of analysis, the hydroxyl value was 40.7, the unsaturated monool content was 0.012 meq / g, and the diol content was 0.00 meq / g.

  In addition, physical properties of polyurethane foams using the polyether polyol composition (S) of the present invention and the comparative polyether polyol composition (S ′) were evaluated.

[Examples 5 to 10 and Comparative Examples 6 to 11]
The physical properties were evaluated by adding a predetermined amount of polyisocyanate (B) to the number of parts of the polyol premix shown in Table 2 [mixture of components other than polyisocyanate (B)] so that the NCO index was 100, After stirring for 6 seconds at 4000 rpm with a mechanical stirrer, the mixture was poured into a 300 mm (length) × 300 mm (width) × 100 mm (height) aluminum mold whose temperature was adjusted to 65 ° C., and the curing time was 5 minutes. And molded.
Table 2 shows the measurement results of the physical property values of each foam. The core density is a density measured by cutting out from the center of the foam into a size of 100 mm × 100 mm × 50 mm.
The polyurethane foam raw materials other than the polyether polyol compositions (S) and (S ′) synthesized in the examples and comparative examples used in the examples and comparative examples are as follows.

(1) Polyol (G-1): glycerin PO, terminal EO adduct (hydroxyl value 37.5 EO content 14.0%) / pentaerythritol PO, terminal EO adduct (hydroxyl value 37.0 EO content 17.5 %) = Polymer polyol obtained by copolymerizing styrene and acrylonitrile at styrene / acrylonitrile = 30/70 (weight ratio) in 80/20 (weight ratio). (Hydroxyl value = 24.9, volume average particle diameter (R) of polymer particles 0.4 μm.
(2) Polyol (G-2): PO adduct of sorbitol. Hydroxyl value = 490.
(3) Polyol (G-3): PO and EO random adduct of glycerin. Hydroxyl value = 24.0.
(4) Polyol (G-4): Triethanolamine. Hydroxyl value = 1130.

(5) Foaming agent (C-1): Water (6) Urethane catalyst (D-1): Ethylene glycol solution of triethylenediamine [“TEDA-L33” manufactured by Tosoh Corporation]
(7) Urethane catalyst (D-2): 70% dipropylene glycol solution of bis (dimethylaminoethyl) ether [“TOYOCAT ET” manufactured by Tosoh Corporation]
(8) Foam stabilizer (E-1): “TEGOSTAB B8738LF2” manufactured by Goldschmidt
(9) Polyisocyanate (B-1): TDI-80 / crude MDI = 80/20 (weight ratio), NCO% = 44.6

<Method for testing physical properties of foam>
The measuring method and unit of polyurethane foam physical properties are shown below.
Core density: Conforms to JIS K6400, unit is kg / m ³
Hardness (25% -ILD): Conforms to JIS K6400, unit is kgf
Rebound resilience: Conforms to JIS K6400, unit is%
Elongation: Conforms to JIS K6400, unit is%
Humid heat compression residual strain rate: Conforms to JIS K6400, unit is%

  From the above results, the polyurethane foams of Examples 5 to 10 using the polyol composition of the present invention of Examples 1 to 4 are those of Comparative Examples 6 to 11 using the comparative polyol composition of Comparative Examples 1 to 5. When the elongation properties are better than those of polyurethane foam and the hydroxyl values are similar, it can be seen that the other mechanical properties are equal or higher.

  The polyether polyol composition of the present invention is useful as a raw material for polyurethane, various industrial surfactants, cosmetics, lubricating oils, antifoaming agents, paints, polyesters and the like, particularly as a raw material for polyurethane.

Claims (5)

A polyether polyol composition (S) containing a polyether polyol and diol having 3 to 6 functional groups, or containing a polyether polyol, diol and unsaturated monool having 3 to 6 functional groups, (S) hydroxyl value [X] (unit: mg KOH / g) is 10 to 100, (S) unsaturated monool content [Y] (unit: meq / g) is 0 to 0.08, (S) The diol content [Z] (unit: meq / g) was 0.04 to 0.08, and the content [α] of ethylene oxide units based on the weight of (S) was 0 to 20% by weight. A polyether polyol composition in which X, Y, Z, and α satisfy the relationship of the following mathematical formula (1).

(Y + Z) × (100−α) ^{/100≦5.89×X−1.27} (1)
  In the presence of the alkali metal hydroxide (a), the crude polyol (d1) obtained by addition polymerization of the alkylene oxide (c) to the compound (b) having 3 to 6 active hydrogens is heated to form a polyol. The rearrangement step [1] to obtain a crude polyol (d2) using the allyl group of the above as a propenyl group, and the alkali metal hydroxide (a) in the crude polyol (d2) is adsorbed with a silicate-based adsorbent (e). The crude polyol (d3) obtained in the step [2] for obtaining the crude polyol (d3) is subjected to acidic conditions by adding a mineral acid (f) or a sulfonic acid group-supporting inorganic porous material (g) and water, and the propenyl group is converted into an acid. The manufacturing method of the polyether polyol composition of Claim 1 including the process [3] which hydrolyzes.   A crude polyol (d1) obtained by addition polymerization of an alkylene oxide (c) at an initial reaction temperature of 70 to 95 ° C., wherein the alkali metal hydroxide (a) is potassium hydroxide having a purity of 95% by weight or more is used. The manufacturing method of the polyether polyol composition of Claim 2.   The method for producing a polyether polyol composition according to claim 2 or 3, wherein the water content in the rearrangement step [1] is 200 ppm or less.   A method for producing a polyurethane, comprising reacting a polyol (A) containing the polyether polyol composition (S) according to claim 1 with a polyisocyanate (B) in the presence or absence of an additive.