JPH10158388A - Modified polyetherpolyol and production of polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyol capable of giving polyurethane resins excellent in hardness, impact resilience, permanent compression strain resistance, hydrothermal-resistant durability, etc., by limiting the OH value, monool content and modified diol content of the polyol within specific ranges, respectively. SOLUTION: This modified polyetherpolyol has an OH value of 3-180mgKOH/ g and contains a monool and a modified diol in amounts of <=50mol% and 1-20mol%, respectively. The modified polyetherpolyol is obtained by addition- polymerizing an alkylene oxide compound to an active hydrogen compound in the presence of an alkali metal compound, a composite metal cyanide complex or a phosphazene compound, adjusting the concentration of an alkali metal compound containing Cs and Rb as metal components to 2-30% per OH in the polyol in the obtained reaction solution, heating the adjusted solution to a temperature of 120-170 deg.C to thermally rearrange the allyl unsaturated group in the monool into a propenyl unsaturated group (Z), and subsequently heating the reaction solution at a temperature of 70-130 deg.C in an acidic condition to hydrolyze the group Z.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a specific modified polyether polyol and a polyurethane resin. More specifically, the present invention transposes an allyl unsaturated group in a polyether polyol to a propenyl unsaturated group, particularly in the presence of an alkali metal compound containing cesium and rubidium as a metal component, and then hydrolyzes with an aqueous solution of an inorganic acid. And a method for producing a polyurethane resin using the modified polyether polyol. Polyether polyols include flexible and rigid polyurethane foams and elastomers, paints, sealants, flooring,
In addition to being used as a raw material for polyurethane resins such as adhesives, it is widely used as a raw material for surfactants.

[0002]

2. Description of the Related Art In anionic polymerization of propylene oxide catalyzed by potassium hydroxide and sodium hydroxide,
Part of propylene oxide is isomerized to allyl alcohol in the presence of the catalyst, and an allyl unsaturated group-containing monol in which propylene oxide is added to this allyl alcohol is formed. It is known that the formation of a monool lowers the average number of functional groups of a polyether polyol, inhibits a molecular weight extension reaction during a urethanization reaction, and impairs the mechanical properties of a polyurethane resin.

[0003] In order to reduce the content of by-product monols, a method of modifying an unsaturated group monool in a polyether polyol into a modified diol is being studied in addition to improving the alkylene oxide polymerization catalyst. Japanese Patent Application Laid-Open No. 4-153219 discloses that a crude polyether polyol containing an alkaline catalyst (caustic potash) is adjusted to pH 2 to 4 by adding a mineral acid aqueous solution to 80 to 80%.
It is described that a heat treatment at 150 ° C. provides a polyether polyol having a reduced unsaturated group. However, the total degree of unsaturation of the obtained polyether polyol was 0.027 meq. / G,
Significant unsaturated components are present. Further, it is described that the allyl compound also undergoes rearrangement and hydrolysis to the propenyl compound under acidic conditions, but the hydrolysis rate of the allyl compound under acidic conditions is slight within the range examined by the present inventors.

In the conventional method for producing a polyether polyol, most of the unsaturated groups are allyl groups, and almost no propenyl groups are present. It is known that a part of the allyl unsaturated group is rearranged to a propenyl unsaturated group by increasing the polymerization temperature, but the rearrangement ratio is low.

A method for acid-hydrolyzing a propenyl unsaturated group has been described in J. A. Am. Chem. Soc. , 8
1, 3374-3379 (1959). 0.1-0.5 potassium hydroxide per polyol
Heated at 120-160 ° C., followed by acid hydrolysis with 5% sulfuric acid. The unsaturated group concentration in the polyol obtained by this method is 0.011 meq. / G, and the monool content in the polyether polyol used for the modification is large, so that the modified diol content generated by this reaction is also large, and the mechanical properties of the polyurethane decrease in the monool content. It has not improved significantly. Within the range examined by the present inventors, the modified diol content is preferably 20 mol% or less.

[0006] Am. Chem. Soc. , 83,1
In 701 to 1704 (1961), an experiment of thermal rearrangement of an allylic unsaturated group to a propenyl unsaturated group is performed by potassium-t-butoxide in a temperature range of 150 to 175 ° C., but 97% is converted to a propenyl unsaturated group. 24
Since it requires more time, the production time becomes longer for industrial use, which is not preferable.

[0007] Chem. Soc. Chem. Com
m. , 694-695 (1978) teaches a method of rearranging an allyl unsaturated compound into a propenyl unsaturated group compound using an iridium compound, but is not suitable for industrial use because the catalyst is expensive.

As described in detail above, a method of rearranging a monol at an allyl unsaturated group in a polyether polyol to a propenyl unsaturated group and hydrolyzing it is known. Polyether polyols catalyzed by alkali metal hydroxides such as sodium hydroxide have a high content of monool having an unsaturated group component. It was found that the physical properties of the polyurethane reacted with the above did not improve.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently producing a monool as an unsaturated group component and a specific modified polyether polyol having a reduced content of a modified diol, and the modified polyether. An object of the present invention is to provide a method for producing a polyurethane resin using a polyol.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, using an alkali metal consisting of cesium and rubidium, a mono-ol having an allylic unsaturated group in a polyether polyol is not propenyl-free. It has been found that polyether polyols having a low content of monol and diol can be obtained by rearrangement to a saturated group and then hydrolysis with an inorganic acid catalyst, thereby completing the present invention.

The above object is achieved by the present invention described below. That is, the first gist disclosed by the present invention is that the hydroxyl value OHV is 3 to 180 mgKOH / g, the monool content is 5 mol% or less, and the modified diol content is 1 to 20 mol%. It is a modified polyether polyol characterized by the following.

[0012] A second gist of the present invention relates to a method for producing a modified polyether polyol, comprising: (1) the following method of adding an alkylene oxide compound to an active hydrogen compound, and a) a method of using an alkali metal compound. B) a method using a double metal cyanide complex, or c) a method using a phosphazene compound, and (2) cesium and rubidium in the reaction solution obtained in the above addition polymerization step. An adjusting step of adjusting the concentration of an alkali metal compound as a metal component to 2 to 30 mol% based on 1 mol of hydroxyl groups in the polyether polyol; (3) heating the adjusted reaction solution to a temperature of 120 to 170 ° C. to prepare a monool A thermal rearrangement step of rearranging an allyl unsaturated group in the compound into a propenyl unsaturated group, and (4) The reaction solution after the thermal rearrangement is 70-130 ° C. under acidic conditions.
A hydrolyzing step of hydrolyzing the propenyl unsaturated group in the monol by heating the monool to a modified polyether polyol.

Further, a third gist of the present disclosure is a polyurethane resin obtained by reacting the modified polyether polyol with an organic polyisocyanate, and a method for producing the polyurethane resin.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for addition-polymerizing an alkylene oxide to an active hydrogen compound using an alkali metal compound will be described.

The active hydrogen compound of the present invention includes, for example, polyhydric alcohols, polyhydric phenols, polyamines and alkanolamines. For example, ethylene glycol,
2 such as propylene glycol and 1,4-butanediol
Polyhydric alcohols, glycerin, monoethanolamine,
Alkanolamines such as diethanolamine and triethanolamine, polyhydric alcohols such as trimethylolpropane and pentaerythritol, sugars such as sorbitol, sucrose and methylglucoside, fatty acid amines such as ethylenediamine, and aromatics such as toluylenediamine and diphenylmethanediamine Aliphatic amines, alkanolamines such as triethanolamine and diethanolamine, phenols such as bisphenol A and novolak, and water. Further, compounds obtained by addition-polymerizing an alkylene oxide to these active hydrogen compounds by a conventionally known method can also be used.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and the like. These may be used alone or in combination. Particularly preferred cyclic ethers are alkylene oxides having 2 to 4 carbon atoms, particularly a combination of propylene oxide and ethylene oxide.

The alkali metal compounds refer to cesium and rubidium compounds. The cesium and rubidium compounds may be used after being dried or used in the form of an aqueous solution, regardless of the form.

In the present invention, the alkali metal compound containing cesium and rubidium as the metal component means that the ratio of cesium to the sum of cesium and rubidium is 70 or more and 9 or more.
9.99 mol% or less, and the sum of cesium and rubidium in all metal components is 96 wt% or more. Such compounds include, for example, inorganic salts such as hydroxides, halides, carbonates and bicarbonates, and alkali metal alkoxides such as methoxide and ethoxide.

The addition amount is usually 0.05 to 0.5 mol per 1 mol of the active hydrogen compound. The temperature for addition polymerization is 60 to 98 ° C, and the maximum pressure during the reaction is 4 kgf.
/ Cm ² G (493 kPa) or less.

Next, an addition polymerization step using a double metal cyanide complex will be described. Double metal cyanide (hereinafter D
The complex described in US Pat. No. 4,477,589 can be used as the complex. Among the,
Complexes in which zinc chloride, 1,2-dimethoxyethane and water are present as ligands in hexacyanocobalt zinc are preferred. In the DMC complex, addition polymerization of propylene oxide is possible, but in the presence of the complex, addition polymerization of ethylene oxide to polyether polyol is impossible. For ethylene oxide addition polymerization, the complex must be chemically decomposed with an alkali metal after the propylene oxide addition polymerization, and the addition polymerization of ethylene oxide must be performed in the presence of the same catalyst (alkali metal). Therefore, the use of an alkali metal compound composed of cesium and rubidium is effective in decomposing a DMC complex, and also enables rearrangement of a monool at the terminal of an allyl unsaturated group to a propenyl unsaturated group.

The amount added depends on the molecular weight of the active hydrogen compound used as the polymerization initiator. For example, when polypropylene glycol having a number average molecular weight of 1000 is used as the active hydrogen compound, the amount is 0.05 parts by weight based on 100 parts by weight of the polypropylene glycol.

The temperature for the addition polymerization is 40 to 120 ° C.
The maximum pressure during the reaction was 4 kgf / cm ² G (493
kPa) or less. The other conditions are the same as in the case where the alkali metal compound is used, and the description is omitted.

Next, an addition polymerization step using a phosphazene compound will be described. The phosphazene compound in the present invention includes the following chemical formula (1) and chemical formula (2)
Are exemplified. That is,

[0024]

Embedded image (However, a, b, c and d in the formula are each a positive integer of 3 or less or 0, but a, b, c and d are not simultaneously 0. R is the same or different. A hydrocarbon group having 1 to 10 carbon atoms, in which two Rs on the same nitrogen atom may be bonded to each other to form a ring structure, ^m represents the number of phosphazenium cations, and X ^{m -.} the hydroxy anion, halogen anion, alkoxy anion, aryloxy anion or carboxy anion) and a compound represented by,

[0025]

Embedded image (Where l, m, and n in the formula are each a positive integer of 0 or 3 or less, and
Never be. D is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, a thiol residue, a thiophenol residue, a monosubstituted amino group, a disubstituted amino group or a 5- to 6-membered cyclic amino group. Group. Q is a hydrocarbon group having 1 to 20 carbon atoms. Further, two Ds on the same phosphorus atom or on two different phosphorus atoms may be bonded to each other, and D and Q may be bonded to each other to form a ring structure. ).

As the phosphazene compound, for example, a mono {tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium} halogen compound corresponding to the chemical formula (1) (where a =
1, b = 1, c = 1, d = 1, R is a methyl group. ).

Next, the Fluka corresponding to the chemical formula (2)
Brand name phosphazene base P <t / 4> -tO
ct), that is, [1-tert-octyl] -4-, 4
-, 4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphanilideneamino] -2
λ ⁵ , 4λ ⁵ -catenadi (phosphazene) (wherein, in the formula (2), l = m = n = 1, D is a dimethylamino group, and Q is a 1-tert-octyl group).

The method for synthesizing these phosphazene compounds is described in "Phosphorus-Nitrogen Compound" by A.H.
1972 or Reinhard Schlesinger, "Nylichen Hemy Technique Laboratorium" 38
Vol. 10, Nos. 1214-12226, 1990 and the like. By conducting the addition polymerization of the alkylene oxide with the phosphazene compound at a reaction temperature in the range of 40 to 120 ° C., the monool at the terminal of the allyl unsaturated group can be reduced.

The concentration used in the polymerization reaction is the active hydrogen compound 1
Since it is within the range of ⁴ to 20 × 10 ^-4 mol with respect to mol, the basicity is weak in order to transfer the allyl unsaturated group to the propenyl unsaturated group. Therefore, an alkali metal compound consisting of cesium and rubidium is added, and propenyl is added. It is preferable to carry out a rearrangement reaction to an unsaturated group.

The temperature for addition polymerization is 40 to 120 ° C.
The maximum pressure during the reaction was 4 kgf / cm ² G (493
kPa) or less. The other conditions are the same as in the case where the alkali metal compound is used, and the description is omitted.

Next, the post-treatment of the reaction solution obtained by addition polymerization by the above three methods will be described.

(Adjustment step) The alkali metal compound containing cesium and rubidium as the metal component used when the terminal of the allyl unsaturated group in the polyether polyol is rearranged to the terminal of the propenyl unsaturated group is based on the hydroxyl group concentration of the polyether polyol. 2 to 30 mol% is suitable, preferably 5 to 25 mol%, more preferably 10 to 18 mol%.
mol%. If the amount is less than 2 mol%, the time required for propenyl rearrangement becomes longer and the productivity is lowered, so that it is not suitable for the purpose of the present invention. On the other hand, if it exceeds 30 mol%, the amount of salt after neutralization with an aqueous solution of an inorganic acid increases, which is not economical.

(Thermal Rearrangement Step) The reaction temperature in the rearrangement to the propenyl unsaturated group is preferably from 120 to 170 ° C.
More preferably, it is 135 to 170 ° C. Most preferably, it is 150 to 165 ° C. If the temperature is lower than 120 ° C., the time required for dislocation increases. If the temperature exceeds 170 ° C., it takes time to raise the temperature to a predetermined temperature, so that the production efficiency is reduced. The time required for the rearrangement reaction to the propenyl unsaturated group in this temperature range depends on the reaction scale, but generally ranges from 3 to 6 times.
Time is enough. Before the rearrangement reaction, auxiliary agents such as an antioxidant and a thermal deterioration inhibitor can also be used as appropriate.

(Hydrolysis step) An aqueous solution having an inorganic acid in an amount of 2 to 5 times the amount of an alkali metal compound containing cesium and rubidium as a metal component was added to the monool in the polyether polyol rearranged to a propenyl unsaturated group. Thereafter, hydrolysis is performed at a reaction temperature of 70 to 130 ° C. to produce a modified diol. When the amount of the inorganic acid is less than 2 mol times,
The hydrolysis reaction time is undesirably long. 5mo
If it is more than 1-fold, the odor becomes severe and the amount of peroxide increases. Although it depends on the reaction scale within the reaction temperature range, the time required for hydrolysis is generally at least 2 hours.

The inorganic acid is selected, for example, from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, sulfurous acid and mixtures thereof, and phosphoric acid and sulfuric acid are most preferred. In carrying out the hydrolysis, it is desirable to use 2 to 50 parts by weight of water with respect to 100 parts by weight of the polyether polyol which has undergone 100% propenyl rearrangement. Ion exchange water can be used as water. As an acid compound other than the inorganic acid, oxalic acid, trichloroacetic acid, toluenesulfonic acid, metasulfonic acid, dichloroacetic acid and the like can be used as necessary.

Propionaldehyde is produced in the course of acid hydrolysis. Since the boiling point of propionaldehyde is 48 ° C. at normal pressure, it can be easily removed from the polyether polyol when dehydrating in a subsequent step.

An adsorbent is used to remove excess inorganic acids and salts. As the adsorbent, synthetic magnesium silicate is preferably used, and Tomix AD-60 is used.
0, Tomix AD-700 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward 400, Kyoward 500, and Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.). As other removal methods, known methods such as a water washing method and an ion exchange method can be used. The temperature at the time of adsorption is usually 40 to 130 ° C.

The conditions for removing propionaldehyde in parallel with the adsorption are usually at 40 to 130 ° C. and 10 mmHg.
abs. It is as follows.

Further, the reaction solution after the hydrolysis may be washed with the extract. Usually, washing is performed at 20 to 90 ° C. Examples of the extract include water alone and a mixture of water and an organic compound.
More specifically, hydrocarbon compounds such as n-hexane and toluene, chloroform, and methylene chloride are included in the organic compounds.

Next, the polyether polyol obtained by washing is dried under reduced pressure. Usually 70 to 12 as specific conditions
0 ° C., 10 mmHg abs. The following are exemplified.

The hydroxyl value of the polyether polyol obtained according to the above method is in the range of 3 to 180 mgKOH / g, particularly preferably 5 to 60 mgKOH / g. Most preferably, it is 10 to 50 mgKOH / g. The monool content in the polyether polyol is 5 mo
1% (0.02 meq./g in total unsaturation).

In particular, 3 mol% (0.01 in total unsaturation)
meq. / G) is preferred. Most preferably, the monol content is 1 mol% (0.003 m
eq. / G, detection limit). This polyol has a diol content of 1 to 20 mol%.

The modified polyether polyol obtained in the present invention is reacted with an organic polyisocyanate to form a foaming agent such as a non-foaming polyurethane resin such as an elastomer or a sealing or water, a foam stabilizer such as an organosilicon surfactant, and a crosslinking agent. It is also applicable to urethane foams obtained in the presence of other auxiliaries such as agents.

As the organic polyisocyanate, any known organic polyisocyanate used for producing polyurethane can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), isomer mixture in 65/35 weight ratio (TDI-65 / 35), crude tolylene diisocyanate containing polyfunctional tar (polyfunctional tar is a by-product of isocyanate production, Group in the molecule
It is a mixture of tar-like substances containing more than one. same as below. ), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,
2,2′-diphenylmethane diisocyanate, any isomer mixture of diphenylmethane diisocyanate, 3
Crude diphenylmethane diisocyanate (polymeric MDI) containing core or higher polyfunctional tar, toluidine diisocyanate, xylylene diisocyanate,
Examples include hexamethylene diisocyanate, carbodiimide-modified and buret-modified products of these organic polyisocyanates, and prepolymers obtained by modifying these with polyols or monools alone or in combination. The above-mentioned organic polyisocyanates can be used in a mixture at an arbitrary ratio.

As the catalyst, all those usually used in the production of polyurethane can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'
Organic metal catalysts such as tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine and salts of triethylenediamine; Examples include tin, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

These catalysts can be arbitrarily mixed and used. The amount of the catalyst used is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the polyether polyol composition. In addition, a flame retardant, a plasticizer, a colorant, and the like can be added as needed.

[0047]

EXAMPLES Examples of the present invention will be shown below to clarify the present invention, but the present invention is not limited to these examples.

A 50% by weight aqueous solution of cesium hydroxide from Kemetal was used as a polymerization catalyst for alkylene oxide and a catalyst for modifying monol. The cesium purity of the product is 9
9.96% by weight and rubidium purity is 0.05% by weight (hereinafter abbreviated as cesium hydroxide). The polymerization of the polyether polyol and the diolation reaction of the unsaturated group component were all performed in a pressure-resistant autoclave equipped with a stirrer.

The monol content and the diol content in the polyether polyol were determined from the area ratio of the chromatogram obtained by using high performance liquid chromatography under the following measurement conditions (Table 1).

[0050]

[Table 1] The chromatogram of the polyether polyol was taken, and determined from the peak area intensity detected by a differential refraction system (manufactured by JASCO Corporation).

The total degree of unsaturation, which indicates the monool content, is JI
It was determined by the method described in S K 1557. Also, the hydroxyl value of the polyether polyol is determined according to JIS K 1557.
Determined by

Example 1 1 mol of propylene glycol
0.15 mol of “cesium hydroxide” was added to 1 l of the mixture, and the mixture was dehydrated under reduced pressure at 85 ° C. and 10 mmHg or less for 3 hours.
/ G until propylene oxide was added. Next, “cesium hydroxide” was added so that the concentration of cesium and rubidium was 12 mol% with respect to the concentration of hydroxyl groups in the polyether polyol, and the water content in the system was reduced to 0.0
Dehydration under reduced pressure was performed until the content became 8% by weight or less. The temperature was raised to 160 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 3 hours. After that, phosphoric acid was added to 4 mo of the total base component concentration.
added as an aqueous solution of 75.2% by weight so as to be 1-fold,
Then 1 to 100 parts by weight of polyether polyol
0 parts by weight of ion-exchanged water was added.

After heating and stirring at 110 ° C. for 2 hours to carry out hydrolysis, 3 parts by weight of a synthetic adsorbent KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts by weight of polyether polyol, and excess was added. At 110 ° C. and 5 mmHg or less while adsorbing phosphoric acid and cesium phosphate
After drying under reduced pressure for a time, the generated propionaldehyde was also removed. The hydroxyl value of the polyether polyol after the purification treatment was 28.7 mgKOH / g, the monool content was below the detection limit, and the diol content was 4 mol% (total unsaturation was 0.0015 meq./g).

Example 2 Double metal cyanide prepared according to US Pat. No. 4,477,589 with respect to 100 parts by weight of a polyether polyol Diol 1000 (manufactured by Mitsui Toatsu Chemicals, Inc.) obtained by addition polymerization of propylene glycol and propylene oxide. Complex (Zn ₃ [Co (CN) ₆ ] _2.
2.48DME · 4.65H ₂ 0 · 0.94ZnCl ₂
Here, DME is an abbreviation for 1,2-dimethoxyethane. ) Was added thereto, and the mixture was dehydrated under reduced pressure at 105 ° C. and 5 mmHg or less for 3 hours, followed by addition polymerization of propylene oxide at a reaction temperature of 95 ° C. until the hydroxyl value reached 18.4 mgKOH / g. Next, “cesium hydroxide” was added so that the concentration of cesium and rubidium was 16 mol% with respect to the hydroxyl group concentration of the polyether polyol, and dehydration under reduced pressure was performed until the water content in the system became 0.08% by weight or less. The temperature was raised to 145 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 6 hours.

Thereafter, the phosphoric acid was added to the total base component concentration of 3.5.
An aqueous solution of 75.2% by weight was added so as to be mol times, and then 20 parts by weight of ion-exchanged water was added to 100 parts by weight of the polyether polyol. After heating and stirring at 110 ° C. for 2 hours for hydrolysis, the synthetic adsorbent KW
-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) is added in an amount of 5 parts by weight based on 100 parts by weight of the polyether polyol. Drying under reduced pressure was performed for 3 hours, and the generated propionaldehyde was also removed. The polyether polyol after purification treatment has a hydroxyl value of 18.8 mgKOH / g and a monol content of 1 mol.
%, Diol content is 8 mol% (total unsaturation is 0.0
027 meq. / G).

Example 3 0.012 mol of a phosphazene base P <t / 4> -t-Oct (trade name, manufactured by Fluka) adjusted to 1.00 M in n-hexane was added to 1 mol of glycerin. 85 ° C, 10mmHg
Thereafter, after dehydration under reduced pressure for 3 hours, addition polymerization of propylene oxide was carried out at a reaction temperature of 70 ° C. until the hydroxyl value became 30.1 mgKOH / g. Then, the reaction temperature 80
The addition polymerization of ethylene oxide is carried out at ℃
6.2 mg KOH / g of polyether polyol was obtained. Next, “cesium hydroxide” was added so that the concentration of cesium and rubidium was 13 mol% with respect to the concentration of hydroxyl groups of the polyether polyol, and the water content in the system was reduced to 0.02%.
Dehydration under reduced pressure was performed until the content became 8% by weight or less. The temperature was raised to 138 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 4 hours. Thereafter, phosphoric acid was added to a total base component concentration of 2.8.
An aqueous solution of 75.2% by weight was added so as to be mol times, and 5 parts by weight of ion-exchanged water was added to 100 parts by weight of the polyether polyol.

After heating and stirring at 110 ° C. for 2 hours for hydrolysis, 4 parts by weight of a synthetic adsorbent KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts by weight of polyether polyol, and excess was added. 110 ° C., 5 mmHg or less while adsorbing phosphoric acid and cesium phosphate
Drying under reduced pressure was performed under the conditions of time, and the generated propionaldehyde was also removed. The hydroxyl value of the polyether polyol after the purification treatment is 26.6 mgKOH / g, the monool content is below the detection limit, and the diol content is 7 mol%.
(Total degree of unsaturation was 0.0019 meq./g).

(Comparative Examples) The following comparative examples are shown. These are modified polyether polyols in which potassium hydroxide is used as a polymerization catalyst for alkylene oxide, and the unsaturated group-terminated monool in the resulting polyether polyol is diolated. It is.

Comparative Example 1 1 mol of propylene glycol
0.25 mol of potassium hydroxide per 1 l in the form of a 50% aqueous solution was added, and the mixture was dehydrated under reduced pressure at 85 ° C. and 10 mmHg or less for 3 hours.
Addition polymerization of propylene oxide was carried out until 8.5 mgKOH / g. Next, a 50% aqueous potassium hydroxide solution was added so that the potassium concentration of the polyether polyol was 16 mol% with respect to the hydroxyl group concentration, and dehydration was performed under reduced pressure until the water content in the system became 0.08% by weight or less. 600 ppm of t-butylhydroxytoluene as an antioxidant was added to the polyether polyol, the temperature was raised to 160 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 6 hours. Then, phosphoric acid was added to 4 mol of the total base component concentration.
And added as an aqueous solution of 75.2% by weight, and then added to 10 parts by weight of polyether polyol.
Parts by weight of ion-exchanged water were added.

After heating and stirring at 110 ° C. for 3 hours for hydrolysis, 4 parts by weight of a synthetic adsorbent KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts by weight of polyether polyol, and excess was added. At 110 ° C and 5 mmHg or less while adsorbing phosphoric acid and potassium phosphate
After drying under reduced pressure for a time, the generated propionaldehyde was also removed. The hydroxyl value of the polyether polyol after the purification treatment was 28.9 mgKOH / g, the monool content was 6 mol%, and the diol content was 26 mol% (total unsaturation was 0.0225 meq./g).

Comparative Example 2 A 50% aqueous solution of 0.4 parts by weight of potassium hydroxide was added to 100 parts by weight of a polyether polyol Diol 1000 (manufactured by Mitsui Toatsu Chemicals, Inc.) obtained by addition polymerization of propylene glycol to propylene glycol. After dehydration under reduced pressure at 105 ° C., 5 mmHg or less for 3 hours, a hydroxyl value of 1 was obtained at a reaction temperature of 105 ° C.
Addition polymerization of propylene oxide was performed until the concentration reached 7.5 mgKOH / g. Next, a 50% aqueous potassium hydroxide solution was added so that the potassium concentration of the polyether polyol was 18 mol% with respect to the hydroxyl group concentration, and dehydration was performed under reduced pressure until the water content in the system became 0.08% by weight or less. 600 ppm of t-butylhydroxytoluene as an antioxidant was added to the polyether polyol, the temperature was raised to 160 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 6 hours. Thereafter, the phosphoric acid was added to a total base component concentration of 3.5 m.
It was added as an aqueous solution of 75.2% by weight so as to be 1 times as much as ol, and then 20 parts by weight of ion-exchanged water was added to 100 parts by weight of the polyether polyol.

After heating and stirring at 103 ° C. for 3 hours for hydrolysis, 4 parts by weight of a synthetic adsorbent KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts by weight of polyether polyol, and excess was added. At 110 ° C and 5 mmHg or less while adsorbing phosphoric acid and potassium phosphate
After drying under reduced pressure for a time, the generated propionaldehyde was also removed. The hydroxyl value of the polyether polyol after the purification treatment was 18.7 mgKOH / g, the monool content was 3 mol%, and the diol content was 32 mol% (total unsaturation was 0.0153 meq./g).

[Comparative Example 3] 0.25 mol of potassium hydroxide was added to 1 mol of glycerin in the form of a 50% aqueous solution, and the mixture was dehydrated under reduced pressure at 105 ° C and 7 mmHg or less for 3 hours. Value is 30.5mg
Addition polymerization of propylene oxide was carried out until KOH / g. Then, addition polymerization of ethylene oxide was carried out at a reaction temperature of 110 ° C. to obtain a hydroxyl value of 26.1 mgKOH / g.
Was obtained. Then, a 50% aqueous solution of potassium hydroxide was added so that the potassium concentration was 13 mol% with respect to the hydroxyl group concentration of the polyether polyol, and dehydration was performed under reduced pressure until the water content in the system became 0.08% by weight or less. 600 ppm of t-butylhydroxytoluene as an antioxidant was added to the polyether polyol, the temperature was raised to 162 ° C. while supplying nitrogen, and the mixture was heated and stirred at the same temperature for 4 hours. Thereafter, phosphoric acid was added as a 75.2% by weight aqueous solution so as to be 3.1 mol times the total base component concentration, and 5 parts by weight of ion-exchanged water was added to 100 parts by weight of the polyether polyol.

After heating and stirring at 110 ° C. for 2 hours for hydrolysis, 4 parts by weight of a synthetic adsorbent KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts by weight of polyether polyol, and excess was added. 110 ° C., 5 mmHg or less while adsorbing phosphoric acid and cesium phosphate
Drying under reduced pressure was performed under the conditions of time, and the generated propionaldehyde was also removed. The hydroxyl value of the polyether polyol after the purification treatment is 26.9 mgKOH / g, the monool content is 6 mol%, and the diol content is 31 mol%
(Total unsaturation was 0.0221 meq./g).

The hydroxyl value, monool content and diol content of the polyether polyols obtained in Examples and Comparative Examples are shown in Table 2. CsOH used as the alkylene oxide polymerization catalyst was "cesium hydroxide", DM
C is a double metal cyanide complex, PN is a phosphazene compound, and KOH is an abbreviation for potassium hydroxide.

[0066]

[Table 2] The hydroxyl value and the total degree of unsaturation were measured according to JIS K1557. In converting the polyether polyol obtained in the present invention into a urethane resin, Examples 1 and 2 and Comparative Examples 1 and 2 were reacted with 4,4'-diphenylmethane diisocyanate (manufactured by Mitsui Toatsu Chemicals, Inc.). An isocyanate group-terminated prepolymer was synthesized to prepare an elastomer using 1,4-butanediol (manufactured by Wako Pure Chemical Industries) as a chain extender.

4,4′-Diphenylmethane diisocyanate was added to the polyether polyols of Examples 1 and 2 and Comparative Examples 1 and 2, and the mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere, and the NCO% of the prepolymer was 6%. 1.0 was obtained. Thereafter, the temperature of the depolymerized depolymerized prepolymer was maintained at 65 ° C., and 1,4-butanediol was added in a constant temperature room at 22 ° C. so as to have an isocyanate index (ratio of isocyanate group concentration to hydroxyl group concentration) of 1.05. As a catalyst, a 1% by weight solution of dibutyltin dilaurate in dioctylphthalic acid was used in an amount of 0.40 part by weight based on 100 parts by weight of the prepolymer. After stirring with a stirrer for 1 minute, the mixed solution was poured into an aluminum mold (for forming a cylinder having a diameter of 30 mm and a depth of 12 mm), and the mixture was stirred under a nitrogen atmosphere for 10 minutes.
Cured at 0 ° C. for 24 hours. After curing, the molded product was cured in a constant temperature room at 22 ° C. for one week, and a physical property test was performed.

Hardness (Shore A), rebound resilience and 70
Measurement of permanent compression strain at ℃ x 22 hours is based on JIS K-
6301. The result obtained with the polyether polyol of Example 1 was obtained in Example 4, the result obtained in Example 2 was obtained in Example 5, and the results of Comparative Example 1 were similarly obtained in Comparative Example 4, and Comparative Example 2 was obtained. This was Comparative Example 5. Table 3 summarizes the results.

[0069]

[Table 3] Comparing the examples with the comparative examples, the polyurethane elastomer using the polyether polyol having a monol and a diol content of the present invention is superior in both hardness, rebound resilience and permanent compression set to a modified product of a polyether polyol obtained with a KOH catalyst. You can see that it is.

The physical properties of the polyurethane foam were evaluated using the polyether polyol of the present invention. In addition to the polyether polyol of the present invention, the following raw materials shown in (Table 4) were used.

[0071]

[Table 4] The physical properties were measured according to JIS K-6301 and JIS
Performed according to K-6401.

A resin solution was prepared by mixing the polyether polyols of Example 3 and Comparative Example 3 with the components shown in Table 5 below.

[0073]

[Table 5] The isocyanate was mixed with 100 parts by weight of the above resin solution so that the isocyanate index became 1.00, and immediately adjusted to 60 ° C. in an internal size of 400 × 400 × 100.
mm, and the lid was closed to foam. 100 ℃
After heating and curing in a hot air oven for 7 minutes, the foam was removed from the mold. Table 6 shows the physical properties of the obtained foam.

The results using the polyether polyol obtained in Example 3 are shown in Example 6, and the results using the polyether polyol obtained in Comparative Example 3 are shown in Comparative Example 6.

[0075]

[Table 6] From the above results, it can be seen that the polyurethane foam produced using the polyether polyol obtained according to the present invention has high hardness and excellent resistance to wet heat.

[0076]

As described in detail above, the modified polyether polyol according to the present invention is reacted with an organic polyisocyanate to produce a polyurethane resin having excellent physical properties such as hardness, rebound resilience and durability. it can.

Claims (9)

[Claims] 1. A hydroxyl value OHV of 3 to 180 mg KOH.
/ G, a monool content of 5 mol% or less, and a modified diol content of 1 to 20 mol%. 2. The method for producing a modified polyether polyol, wherein: (1) the following method of addition-polymerizing an alkylene oxide compound with an active hydrogen compound; a) a method using an alkali metal compound; and b) a double metal cyanide complex. Or c) a method using a phosphazene compound, and (2) adjusting the concentration of an alkali metal compound containing cesium and rubidium as a metal component in the reaction solution obtained in the addition polymerization step to a polyether polyol. (3) heating the adjusted reaction solution to a temperature of 120 to 170 ° C. to convert the allyl unsaturated group in the monol into a propenyl unsaturated group by adjusting the reaction solution to a temperature of 120 to 170 ° C. And (4) subjecting the reaction solution after the thermal rearrangement to 70-1 under acidic conditions. 0 ℃
2. The process for producing a modified polyether polyol according to claim 1, comprising a hydrolysis step of hydrolyzing the propenyl unsaturated group in the monol by heating the monool. 3. The method according to claim 1, wherein in the hydrolysis step, the reaction solution after the hydrolysis is brought into contact with an adsorbent under reduced pressure and heating conditions to remove excess acid, and at the same time, propionaldehyde is removed by evaporation. A method for producing the modified polyether polyol according to claim 2. 4. The method according to claim 2, wherein, in the hydrolysis step, the reaction solution after the hydrolysis is washed with an extract, and the obtained polyether polyol phase is dried under reduced pressure to remove water. A method for producing a modified polyether polyol. 5. The conditions for the addition polymerization of the alkylene oxide compound are such that the reaction temperature when using an alkali metal compound is 60 to 98 ° C. and the reaction temperature when using a double metal cyanide complex or a phosphazene compound is 4.
The modified polyether polyol according to any one of claims 2 to 4, wherein the temperature is 0 to 120 ° C and the maximum pressure during the reaction is 4 kgf / cm ² G (493 kPa) or less in any case. Production method. 6. The phosphazene compound represented by the following chemical formula (1): (However, a, b, c and d in the formula are each a positive integer of 3 or less or 0, but a, b, c and d are not simultaneously 0. R is the same or different. A hydrocarbon group having 1 to 10 carbon atoms, in which two Rs on the same nitrogen atom may be bonded to each other to form a ring structure, ^m represents the number of phosphazenium cations, and X ^{m -} the preparation of hydroxy anion, halogen anion, alkoxy anion, modified polyether polyol according to any one of claims 2 to 5, characterized in that a compound represented by) represents an aryloxy anion or carboxy anion. Method. 7. The phosphazene compound represented by the following chemical formula (2): (Where l, m, and n in the formula are each a positive integer of 0 or 3 or less, and
Never be. D is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, a thiol residue, a thiophenol residue, a monosubstituted amino group, a disubstituted amino group or a 5- to 6-membered cyclic amino group. Group. Q is a hydrocarbon group having 1 to 20 carbon atoms. Further, two Ds on the same phosphorus atom or on two different phosphorus atoms may be bonded to each other, and D and Q may be bonded to each other to form a ring structure. The method for producing a modified polyether polyol according to any one of claims 2 to 5, wherein the compound is represented by the following formula: 8. A polyurethane resin obtained by reacting the modified polyether polyol with an organic polyisocyanate. 9. A method for producing a polyurethane resin, comprising reacting the modified polyether polyol with an organic polyisocyanate to obtain the polyurethane resin.