KR870001646B1 - Process for production polyether polyol - Google Patents

Abstract

This invention relates to polyether polyol which has good elasticity even at low temp.. Tetrahydrofurane is copolymerized with polyhydric alcohol to give polyether polyol containing 50-99.5 wt.% of oxitetramethylene group. The copolymerization is catalized by heteropoly acid containing 0.1-15 water molecules per one heteropoly anion. The polyhydric alcohol is ethylene glycol, propyleneglycol, 1,3-propanediol or 1,4-butane diol.

Description

Method for producing polyether polyol

Figure 1 shows the ¹ H-NMR spectrum of the copolymerized polyether glycol of ethylene glycol and THF described in Example 1 (measured at 400 MHz by a JEOL JNM-GX 400 NMR apparatus).

2 shows copolymerized polyether glycol ¹³ C-NMR spectra of acetylated ethylene glycol and THF with terminal hydroxyl groups as measured in Example 1 (measured by JEOL JNM-GX 400NMR apparatus).

3 is a process diagram of a continuous polymerization apparatus that may be used to practice the present invention.

4 shows the ¹ H-NMR spectrum of copolymerized polyether glycol of 1,6-hexane diol and THF as described in Example 2 (measured at 400 MHz by JEOL JNM-GX 400NMR apparatus).

FIG. 5 shows the ¹ H-NMR spectrum of copolymerized polyether glycol of neopentylglycol and THF described in Example 8 (measured at 400 MHz by JEOL JNM-GX 400NMR apparatus).

FIG. 6 shows the ¹ H-NMR spectrum of copolymerized polyether glycol of bis- (2-hydroxyethyl) -n-butyl-amine and THF described in Example 13 (at 200 MHz by JEOL FX 200 NMR apparatus) Measure).

* Explanation of symbols for main parts of the drawings

1: polymerization tank 2: phase separation tank

3: distillation column

The present invention copolymerizes polyhydric alcohol and tetrahydrofuran (hereinafter referred to as "THF") having two or more hydroxyl groups in one molecule using heteropoly acid and / or salt thereof as a catalyst, or polyhydric alcohol and tetrahydrofuran and copolymerized therewith. It relates to a process for copolymerizing possible cyclic ethers to produce novel polyether polyols.

For polyether glycol, which is a starting material of polyurethane used in spandex or synthetic leather, polyoxytetra methylene glycol (hereinafter referred to as "PTMG"), which is a homopolymer of THF, has been used primarily. However, soft segments of urethane elastomers using PTMG tend to crystallize at low temperatures and cause problems in physical properties at low temperatures, such as insufficient recovery after stretching under tension.

In order to solve this problem, a copolymer of THF and a cyclic ether as a polyether glycol instead of PTMG has been studied, but ring-opening polymerization of cyclic ether or ring-opening polymerization of cyclic ether or synthesis of cyclic ether is difficult. For reasons such as these, there are restrictions on the type of the copolymer and no satisfactory results are obtained.

Moreover, in general, the ring-opening polymerizability is low, and the method of obtaining the copolymer which has a hydroxyl group at the sock end at once by copolymerizing with polyhydric alcohol and copolymerizing with THF is not known yet. Although there is a known example of co-opening epichlorohydrin in THF (Japanese Patent Publication No. 32200/1973), the polyhydric alcohol added in this method is thought to act only at the initiation of the reaction. Combined.

In order to solve the above problems, the inventors of the present invention have found a catalyst capable of synthesizing polyether glycol by copolymerizing diol with THF to complete the present invention.

The present invention is to copolymerize tetrahydrofuran with a polyhydric alcohol having two or more hydroxyl groups in one molecule by using a heteropoly-acid and / or a salt thereof in which 0.1 to 15 molecules of one heteropoly-anionic water are present on the catalyst as a catalyst. Or 0.5 to 99.5% by weight of an oxy tetramethylene group derived from tetrahydrofuran by copolymerizing a mixture of a polyhydric alcohol having two or more hydroxyl groups in one molecule with other cyclic ethers and tetrahydrofuran copolymerizable therewith. Provided are a process for producing a polyetherpolyol having and novel polyether glycols synthesized thereby.

The present invention relates to a novel reaction in which a copolymerization reaction proceeds only with THF and a polyhydric alcohol, and the polyhydric alcohol residue in the resulting polyether glycol is not limited to the end of the molecule but may be contained in the molecule. Furthermore, in the present invention, it is not necessary to add water as starting material in the reaction system, and it is not necessary to hydrolyze by adding water, but the terminal can be directly converted to an OH group. In addition, the catalyst can be recycled for reuse. As described above, the present invention has new characteristics that have not been realized in the past.

Such a polymerization reaction can be accomplished by first using heteropoly-acid as a catalyst and presenting 0.1 to 15 molecules of water on one catalyst per heteropoly-anion.

In general, in addition to the disadvantage that the type of cyclic ether available can be limited in the copolymerization reaction between cyclic ether and THF, it is more likely to proceed as a block polymerization reaction due to the difference in the degree of polymerization reaction between THF and cyclic ether. Therefore, there is a disadvantage that polyether glycol of good low crystallinity as a soft segment for an elastomer cannot be easily obtained. For example, 6-membered cyclic ether tetrahydropyran cannot be copolymerized, and 7-membered cyclic ether oxetane is also known to have a very low copolymerization possibility with THF. On the other hand, the reactivity of 3- or 4-membered cyclic ethers such as ethylene oxide or oxetane is extremely high compared to THF, so that a product in which block ethylene oxide or oxetane is block polymerized can be easily obtained.

According to the method of the present invention, various polyhydric alcohols can be used as comonomers with THF, and the copolymer can be obtained in an optionally bonded state to the polymer chain. Most of these copolymers have a lower melting point and lower crystallinity than PTMG of the same molecular weight, and when used as soft segments for elastomers, good elasticity can be recovered even at low temperatures.

As the alcohol having two or more hydroxyl groups in one molecule used in the present invention, any alcohol can be used. Provided that it does not have a substituent that inhibits the catalytic activity of the present invention. Preferred polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6 Dihydroxyalkanes such as -hexanediol, neopentylglycol, 2-methyl-1,4-butanediol, hexanediol, heptanediol and the like; Trihydroxyalkane such as trihydroxyheptane, trihydroxyoctane, glycerin and the like; Polyalkylene glycols such as diemethyl glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like.

Particularly preferred among the polyhydric alcohols are dihydric alcohols.

As the polyhydric alcohol, low molecular weight polymers of polyether polyols derived by the process of the present invention using the polyhydric alcohols exemplified above may also be used. Moreover, low molecular weight polymers of PTMG can also be used as polyhydric alcohols. The low molecular weight polymer is not particularly limited as long as it has a lower molecular weight than the polymer to be synthesized. However, for example, when a polymer having a molecular weight of 600 or more is synthesized, it should have an average molecular weight of 100 to 500, while an average molecular weight should be 100 to 1000 when a polymer having an average molecular weight of 1200 or more is synthesized. The use of the low molecular weight polymer in the reaction as a reactant for polymerization by recycling the oligomer separated by extraction or distillation from the polyether polyol synthesized according to the reaction of the present invention is a good example. Low molecular weight polymers are preferably added at no more than 10% by weight to the monomer of the starting material.

By having a monohydric alcohol as the alcohol in the reaction system, an alkoxy group can be introduced at the terminal of the polymer.

As the polyhydric alcohol, a nitrogen-containing polyhydric alcohol having a moiety containing a secondary amine or tertiary amine or a salt thereof in the molecule can be used, in which case a polymer containing nitrogen is obtained. The nitrogen-containing polyhydric alcohol is not particularly limited, but a compound having a hydroxyl group in each of the disubstituents on the nitrogen atom is preferable because of a polyether containing a nitrogen atom in the main chain which can be preferably used as a starting material for the elastomer. This is because glycol can be obtained. Preferred examples of the nitrogen-containing polyhydric alcohols have the following structures such as diethanolamine and N-methyl-diethanol amine.

Wherein R ₁ and R ₂ are — (CH ₂ ) _n — (n is 2-10), —CH ₂ CH ₂ —O—CH ₂ CH _2, and —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ ; R ₃ is selected from an alkyl group having 1 to 10 carbon atoms and a hydrogen atom.

On the other hand, the polyhydric alcohol may be a polyhydroxysulfide having a sulfur atom in the molecule. In this case, a polymer containing sulfur is obtained. The polyhydroxysulfide is not particularly limited but preferred examples are represented by the following structures, such as 2,2'-thiodiethanolamine and 3,3'-thiodipropanolamine.

HO-R ₁ -SR ₂ -OH

Wherein R ₁ and R ₂ are — (CH ₂ ) _n — (n is 2 to 10), —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, and —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ Selected from CH ₂ .

If the nitrogen-containing polyhydric alcohol or polyhydroxyalkylene sulfide is present in the reaction system at a molar amount of 4 times the heteropoly-anion, it is preferable to use the compound in an amount of 4 times or less of the heteropoly-anion because the polymerization activity is lower. .

The cyclic ether to be used in the present invention may be a 3-membered equivalent ether such as ethylene oxide, propylene oxide, isobutylene oxide, epichlorohydrin or the like; 4-membered cyclic ether, such as oxetane, 3, 3- dimethyl oxetane, 3-methane oxetane, 3, 3-bis (chloromethyl)-oxetane; 5-membered cyclic ethers such as methyl tetrahydrofuran, 1,3-dioxolane and the like; 6-membered cyclic ethers such as trioxane and derivatives thereof; 7-membered cyclic ethers such as oxepan and derivatives thereof; Bicyclic 5-membered ethers such as 1,4-epoxycyclohexane and the like; Macrocyclic ethers such as 15-crown-3, 20-crown-4 and the like; And oligomeric cyclic ethers which are polymers of THF or copolymers of THF and alkylene oxides.

The composition of the starting materials for the process of the invention is not particularly limited, but 0.5 to 99.9% by weight of THF is good, particularly preferably 10 to 99% by weight. When copolymerized with both cyclic ethers and polyhydric alcohols in addition to THF, the ratio of cyclic ethers and polyhydric alcohols other than THF in the starting material is not particularly limited, but polyhydric alcohols can use two times or more moles of cyclic ether better than THF.

Heteropoly-acid and salts thereof in the present invention condensate salts of oxyacids and oxyacids with other components such as P, Si, As, Ge, B, Ti, Ce, Co and at least one Mo, W and V oxide And the atomic ratio of the former to the latter is from 2.5 to 12.

Examples of these catalysts are 12-molybdophosphoric acid, 5-molybdo-2-phosphoric acid, 12- tungstophosphoric acid, 12-molybdo-tungstophosphoric acid, 6-molybdo-6-tungstophosphoric acid, 12 Molybdo-banadophosphoric acid, 11-molybdo-1-banadophosphoric acid, 12-molybdo tungsutobanadophosphoric acid, 12-tungstovanadophosphoric acid, 12-molybdateobophosphoric acid, 12- Tungstosilicate, 12-molybdosilicate, 12-molybdo tungstosilicate, 12-molybdo tungsutovanadosilicate, 12- tungstoboric acid, 12-molybdoboric acid, 12-molybdate Stoboric acid, 12-molybdobanadoboric acid, 12-molybdo tungstobanadoboric acid, 9-molybdate nickel acid, 6-molybdocobaltic acid, 6- tungstocobaltic acid, 11-molybdate Dobiic acid, 12- tungstobisic acid, 12- tungstogermanic acid, 18- tungsto-2- arsenic acid, 18-molybdo-2-phosphate, 9-molybdophosphoric acid, 18- tungsto-2-phosphate, 12- titanomolybdic acid, 12-ceriomolybdic acid, 18-molybdo-2-phosphate and salts thereof.

Among these, 12-molybdate phosphoric acid, 18-molybdo-2-phosphate, 9-molybdophosphoric acid, 12- tungstophosphoric acid, 18- tungsto-2-phosphate, 11-molybdo-1 Banadophosphoric acid, 12-molybdo tungstosane, 6-molybdo-6-tungstophosphoric acid, 12-molybdo tungsutobanadophosphoric acid, 12-tungstobanadophosphorus, 12-molybdodo Tungstic silicate, 12-molybdo tungstosilicate, 12-molybdo tungstobanadosilicate, 12- tungstoboric acid, 12-molybdoboric acid, 12-molybdo tungstoboronic acid, 12-mol Libdobanadoboronic acid, 12-molybdoungstomanadoboric acid, 12-tungstogermanic acid and 12-tungstobisic acid.

The type of salt is not particularly limited. For example, metals belonging to group I of the periodic table (e.g., Li, Na, K, Rb, Cs, Cu, Ag, Au, etc.), group II metals (e.g., Mg, Ca, Sr, Ba, Zn, Cd, Hg, etc.), Group III metals (eg Sc, La, Ce, Al, Ga, In, etc.), Group VIII metals (eg Fe, Co, Ni, Ru, Pd, Pt, etc.) and other metals (eg Sn, Pb, Mn) Metal salts of Bi, etc .; Or ammonium salts; Amine young etc. can be used.

Representative examples of these salts include 12- tungstophosphate-1-lithium (LiH ₂ PW ₁₂ O ₄₀ ), 12- tungstophosphate- ₂ -lithium (Li ₂ HPW ₁₂ O ₄₀ ), 12- tungstophosphate-1-sodium (NaH ₂ PW ₁₂ O ₄₀ ), 12- tungstophosphate- ₂ -potassium (K ₂ HPW ₁₂ O ₄₀ ), 12- tungstophosphate-2- cesium Cs ₂ HPW ₁₂ O ₄₀ ), 12- tungstophosphate- 2-Silver (Ag ₂ HPW ₁₂ O ₄₀ ), 12-Tungstophosphate-1-Magnesium (MgHPW ₁₂ O ₄₀ ), 12-Tungstophosphate-1-Calcium (CaHPW ₁₂ O ₄₀ ), 12-Tungstophosphate- 1-zinc (ZnHPW ₁₂ O ₄₀ ), 12- tungstophosphate-1-nickel (NiHPW ^I ₂ O ₄ ⁰ ), 12- tungstosilicate-1-nickel (NiHSiW ₁₂ O ₄₀ ), 12- tungstosilicate- 2-lithium (Li ₂ H ₂ SiW ₁₂ O ₄₀ ), 12- tungstosilicate- ₂ -silver (Ag ₂ H ₂ SiW ₁₂ O ₄₀ ), 12- tungstosilicate-1-magnesium (MgH ₂ SiW ₁₂ O ₄₀ ), 12- tungstosilicate-1-aluminum (AlHSiW ₁₂ O ₄₀ ), 12- tungstosilicate-2-indium (InHSiW ₁₂ O ₄₀ ), 12- tungstosilicate- ₁ -gallium (GaHSiW _{1 2} O ₄₀ ), 12-molybdophosphate-1-lithium (LiH ₂ PM ₁₂ O ₄₀ ), 12-molybdophosphate-1-magnesium) MgHPM ₁₂ O ₄₀ ), 12-tungstophosphate-2-ammonium ((NH ₄ ) ₂ HPW ₁₂ O ₄₀ ), 12-tungstosilicate-1-tetramethylamine (N (CH ₃ ) ₄ H ₃ SiW ₁₂ O ₄₀ ), 12-tungstophosphate-1-iron (FePW ₁₂ O ₄₀ ), 12- tungstophosphate-1-bismuth (BiPW ₁₂ O ₄₀ ), 12- tungstophosphate-1-aluminum (AlPW ₁₂ O ₄₀ ), 12- tungstophosphate-1-chrome (CrPW ₁₂ O ₄₀ ), 12- tungstophosphate-1-gallium (GaPW ₁₂ O ₄₀ ), and 12- tungstophosphate-1-indium (INPWO ₄₀ ). Mixtures with heteropoly-acids may also be used.

Heteropoly-acid salts may be prepared by titrating an aqueous solution of heteropoly-acid with carbonates or nitrates, ammonia, amines and the like of various metals and then evaporating to dryness.

These heteropoly-acids or salts thereof can also be used as catalysts in reduced form.

In general, heteropoly-acids or salts thereof are present in a coordinated state of 20 to 40 molecules of water per molecule, but in this case there is no polymerization activity. Number of coordinated water molecules (molar ratio of water coordinated to heteropoly-anions), such as when the catalyst is dried to alter the polymerization activity, the molecular weight of water present on the catalyst per one heteropoly-anionic sugar is less than 15, in particular up to 8 It was found by chance that when reduced, polymerization activity appeared, and furthermore, the ability of the polyhydric alcohol to be activated to form a copolymer with THP, in which the residual polyhydric alcohol was bound inside the polymer chain, was demonstrated. If the molar ratio of water to heteropoly-anions present on the catalyst is 0.1 or less, the effect of the terminal hydroxylation reaction is inferior, so the ratio needs to be in the range of 0.1 to 15. Depending on the composition of the starting material and the heteropoly-acid or salt thereof used, the catalyst in which water coexists in an amount within this range is not uniformly dissolved in the starting material solution in the polymerization system. However, it exists as a catalyst liquid phase forming a two-liquid phase with a starting material as an organic phase or a solid phase.

If the water content is increased above this ratio, the polymerization activity disappears and the heteropoly-acid can be dissolved homogeneously in the starting material solution. In particular, the polymerization system generally forms a two-liquid phase of the catalyst liquid phase and the starting material organic phase when water is present in a ratio of 1 to 15 molecules per heteropoly-anion.

If the amount of water is reduced below the ratio of about 1, the catalyst becomes a solid phase. However, even if water is present in a ratio of 1 to 15 molecules per heteropoly-anion, some heteropoly-acid salts do not form a liquid phase but remain in a solid phase. Otherwise, the catalyst is often dissolved evenly without forming a two-liquid phase even if the polyhydric alcohol concentration in the starting material is very high. When the ratio is in the range of 1 to 8, a polyether polyol which can be used well as a starting material of the elastomer and has an average molecular weight of 600 to 3500 can be obtained.

The molecular weight and polymerization activity of the resulting polymers vary with the molar ratio of water to the heteropoly-anions present on the catalyst, the relationship of which depends on the type of catalyst used. Therefore, it is preferable to carry out the reaction with an optimum amount of water which can be easily determined according to each condition and purpose.

In the present invention, the water present on the catalyst is expected to exist in the coordinated state of the catalyst when the catalyst is in the solid phase, while the catalyst is expected to be dispersed or coordinated in the catalyst state when the catalyst is in the liquid phase. do. Here, the number of coordinated water molecules is defined as the value of the total number of water molecules in the catalyst liquid phase divided by the number of heteropoly-anions present when the catalyst is in the solid phase.

The number of coordinated water molecules can be controlled by heating the heteropoly-acid or salt thereof to a temperature higher than the disintegration temperature or by maintaining it at a relatively low temperature and reduced pressure.

Since the disintegration temperature of the catalyst depends on the special catalyst used, the heating temperature depends on the catalyst but is generally between 100 ° C and 320 ° C. It is also possible to control the number of coordinating water molecules so that they can be increased from a lean state than required by supplementing the amount of water needed to mix with the starting material for polymerization such as THF.

In this reaction, water is produced when the polyhydric alcohol is introduced into the polymer chain via an ether bond, so that the polymerization activity is lowered if the water content in the system exceeds 15 times mole of the heteropoly-anion. Therefore, it is necessary to determine the molar ratio of the polyhydric alcohol to be reacted to THF and the catalyst so that the amount of coordinated water molecules does not exceed 15 by the water produced in the system in an amount greater than the amount consumed as polymer ends. When it is desirable to further enhance the molar ratio of alcohol / THF, the water can be removed by distillation or other means of maintaining the number of water molecules coordinated in heteropoly-anions to 15 or less. Therefore, the copolymerization ratio of alcohol can be promoted.

On the other hand, if the water molecular weight is less than that consumed as the end of the polymer, the number of coordinated water molecules in the catalyst decreases as the reaction proceeds, so that the obtained polymer increases in molecular weight over time. Therefore, it is preferable to carry out the reaction while controlling the content of water in the catalyst phase to a certain level by the addition of a polyhydric alcohol or water.

The amount of catalyst used is not particularly limited, but the polymerization rate is slow even if the amount of catalyst in the reactor is small, so it is used at 0.01 to 20 times the weight of the starting material (preferably 0.1 to 3 times the weight).

When the reaction is carried out in a two-liquid system with a volume of at least 10% (preferably more than 30%) of the total liquid phase volume in the reactor, the polymer having a very narrow molecular weight distribution can be obtained after the reaction from the starting organic phase. have. The mechanism by which polymers with narrow molecular weight distributions are produced is not fully understood, but two liquids are used to selectively transfer polymers with a specific or higher molecular weight to selectively transfer polymers having a lower molecular weight than those remaining in the catalyst liquid phase. It is expected to be due to the selective extraction possessed by the offset. For this reason, if the ratio of the catalyst liquid phase occupied throughout the liquid phase is low, selective extraction through the molecular weight level of the polymer by the two-liquid phase is lowered and a narrow molecular weight distribution is not obtained.

As the carrier of the catalyst, a carrier capable of absorbing heteropoly-acid or a salt thereof (e.g. activated charcoal, silica alumina, alumina, etc.) may be used, and the catalyst may be used as a bed or a fixed bed. . The separation between the polymer and the catalyst obtained by using the supported catalyst can be easily carried out with the amount of catalyst dissolved on a very low polymer. Accordingly, the purification step can be greatly simplified. As a carrier, activated charcoal has particularly good adsorptivity to heteropoly-acids and salts thereof.

The reactants to be provided for the polymerization should not contain impurities such as peracids and the like.

The reaction temperature is particularly good at -10 to 120 ° C, especially 30 to 80 ° C, because if the temperature is too high, the degree of polymerization tends to be lower and the polymer yield is also lower. The yield will suddenly decrease if the temperature exceeds 120 ° C. The reaction temperature is lower below -10 ° C.

The time required for the reaction is 0.5 to 50 hours depending on the amount of catalyst and the reaction temperature. The reaction pressure can be atmospheric pressure, pressurized or reduced pressure.

In the process of the present invention, the reaction may be carried out while stirring the cyclic ether with a catalyst in which the number of water molecules coordinated with the polyhydric alcohol and THF or polyhydric alcohol, THF and the cyclic ether is pre-determined.

The reactor may include those conventionally used, such as tank devices, tower devices. It is also possible to use a batch device or a continuous device.

When the catalyst is in the solid phase, the catalyst can be removed by filtration, or in the liquid phase, it can be separated into two phases by phase separation. When uniformly dissolved, the polyether polyol can be removed by extracting and then removing the unreacted monomer by distillation. You can get it. The obtained polymer is purified by washing or adsorbent treatment to obtain a product. The catalyst can be used repeatedly, if necessary, after readjusting the coordinated water molecule number.

The composition of the copolymer can be varied in the range of 0.5 to 99.5% by weight of the components of the oxytetramethylene group derived from THE.

Compositions of the preferred copolymers for use as starting materials for elastomers, such as polyurethane elastomers, comprise from 10 to 99.5% by weight of oxytetramethylene groups (particularly from 50 to 98% by weight, particularly preferably from 70 to 95% by weight). . When the copolymer contains oxytetramethylene groups in an excess of 99.5% by weight, the difference in physical and chemical properties from PTMG, the homopolymer of THE, becomes very small.

When alkylene glycol having 5 or more carbon atoms such as 1,5-pentanediol or 1,6-hexanediol is used as a polyhydric alcohol, it is composed of a unit represented by the following structural formula (I) and a unit represented by the following structural formula (II) And polyether glycols having hydroxyl groups at both ends of the molecule.

(Where n is an integer of 5 or more).

Polyetherglycol having a molar ratio of unit (I) to unit (II) of 99: 1 to 5: 1 and an average molecular weight of 500 to 10,000 is a soft segment for an elastomer such as polyurethane, polyester, polyamide, etc. It can be used well. Above all, polymers having a molar ratio of unit (I) to unit (II) of 50: 1 to 5: 1 and an average molecular weight of 500 to 3500 are particularly good as soft segments for elastomers.

When neopentyl glycol is a polyhydric alcohol, it is possible to obtain a polyether glycol composed of a unit of formula (I) and a unit of formula (III), wherein both ends of the molecule are hydroxyl groups:

Polyether glycols having a molar ratio of unit (I) to unit (III) of 99: 1 to 5: 1, an average molecular weight of 500 to 10,000, and a melting point of 18 ° C. or less are difficult to crystallize even if the polymer has a large molecular weight. It can be used well as soft segments for elastomers such as polyesters, polyamides and the like. The elastomer using the polyether glycol as a soft segment is excellent in elastic recovery even on a scale. The average molecular weight thereof is preferably 500 to 3500.

On the other hand, when the nitrogen-containing alcohol has a moiety containing a secondary amine or tertiary amine or a salt thereof in the molecule, a polyether polyol containing nitrogen can be obtained. When a compound having the following structure is used as the polyhydric alcohol containing nitrogen:

[Wherein R ₁ and R ₂ are-(CH ₂ ) _n- (n is 2-10), -CH ₂ CH ₂ -O-CH ₂ CH ₂ and -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -is selected from; R ₃ is selected from a hydrogen atom and an alkyl group having 1 to 10 carbon atoms], a polyether glycol composed of a unit of formula (I) and a unit of formula (IV) below, wherein both ends of the molecule are hydroxyl groups Can be obtained:

[Wherein R ₁ , R ₂ and R ₃ are each as defined above].

Polyetherglycols having a molar ratio of unit (I) to unit (IV) of 99: 1 to 5: 1 and an average molecular weight of 500 to 10,000 are good as soft segments for elastomers such as polyurethanes, polyesters, polyamides, and the like. Can be used. The average molecular weight thereof is preferably 500 to 3500. Elastomers and polyetherglycols synthesized using them as starting materials generally suffer from defects such as yellowing or reduced strength when exposed to oxygen, NO _x gas, and heat. As a method for preventing such fever, stabilizers such as phenol compounds, amine compounds, sulfur compounds, etc. are mixed, but the amount of stabilizers used is limited due to the compatibility with the polymer, and the added stabilizers bleed on the polymer surface. It has the disadvantage of reducing the effect of stabilizer. Polyuhetan synthesized using such nitrogen-containing polyether glycol is hardly yellowed even when exposed to NO _x gas and has excellent dyeability. This is because the amine structure is bonded in the molecule and the amine structure is present in the soft segment, so that the dyeability is excellent.

The sulfur-containing polyether polyols obtained when using polyhydroxyalkylsulfides as polyhydric alcohols are very stable even when exposed to oxygen, light, heat and the like, and are good as soft segments for elastomers such as polyurethanes, polyesters, polyamides and the like. Is used. The average molecular weight thereof is preferably 500 to 3500.

According to the process of the invention, various polyhydric alcohols can be copolymerized with THF and moreover the polyhydric alcohol is optionally copolymerized in the chain formed by ring-opening polymerization of THF. Therefore, most of the polyether polyols obtained have low crystallinity in PTMG, and the elastomers obtained by using the compounds as soft segments are excellent in elastic recovery even at low temperatures. In addition, according to the method of the present invention, amine groups or sulfur atoms can be introduced into the polymer chain to synthesize polyalkyleneether polyols having heat resistance and yellowing resistance not found in PTMG.

Furthermore, according to the process of the present invention, another advantage not known in the art is that the polyalkyleneetherpolyol can be synthesized in one step, which does not require a hydrolysis step, and the catalyst used can be used repeatedly.

The invention is described in more detail in the following examples.

Example 1

200 g of THF containing 350 ppm H ₂ O and 8.5 g of ethylene glycol were introduced into a vessel equipped with a stirring means and a reflux condenser. 100 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) heated at 300 ° C. for 3 hours was added again to make anhydride. (The number of moles of ethylene glycol is about four times the number of moles of tungstophosphoric acid, and the amount of water produced when ethylene glycol is copolymerized is a terminal OH group, four times the number of moles of tungstophosphoric acid, although the amount consumed is not calculated). The temperature was fixed at 60 ° C. and stirring continued for 4 h under a nitrogen atmosphere, then the mixture was separated in two phases by setting at room temperature. Unreacted THF was distilled off to the upper layer to give transparent viscous polymer 42G.

The polymer obtained was found to have an average molecular weight of 1500 as measured by gel permeation chromatography (GPC).

The polymer had a melting point of 10 ° C. lower than that of PTMG with the same average molecular weight as measured by a differential injection calorimeter (PERKIN-ELMER DSC-2) (temperature rise rate 4 ° C./min). The ¹ H-NMR spectrum (400 MHz) of the obtained polymer is shown in the first roughness, where the abscissa indicates chemical shift (ppm) when using tetramethylsilane as the reference material.

As a result of the detailed analysis, the polymer was a polyether glycol formed by copolymerization of ethylene glycol and THF at a mole ratio of ethylene glycol / THF of 1/9, and the ratio of oxydimethylene group to oxymethylene group present at the terminal of the molecule was 26:74.

의 β-위치 탄소가 69.1ppm의 위치에서 존재 하지만, 이 중합체중 말단 아세티리의 β-위치 탄소는 68.5ppm으로 존재하는데 이는 말단기로 부터 연속적으로 존재하지 않는 단위체 임을 뜻하는 것이다.In addition, the ¹³ C-NMR spectrum of the polymer having hydroxyl groups acetylated at both ends is shown in FIG. 2, where the abscissa indicates chemical shift (ppm) when using tetramethylsilane as reference material. When the oxydimethylene group is continuously present from the terminal, the terminal acetyl group

Although the β-position carbon of is present at 69.1 ppm, the β-position carbon of the terminal acethyri in this polymer is present at 68.5 ppm, meaning that it is a unit that does not exist continuously from the terminal group.

From the above results it can be inferred from the above results that ethylene glycol is optionally copolymerized rather than blocks.

Example 2

As shown in FIG. 3, polymerization was carried out by using a continuous polymerization apparatus. First, 200 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ .3.5H ₂ O) having a volume of 300 ml and having 3.5 of water coordinated in polymerization tank 1 having a stirring means and a reflux condenser were introduced. As shown in Table 1, 150 g of a monomer mixture containing a predetermined amount of diol and THF was added and the mixture was stirred. The polymerization tank temperature was fixed at 60 ° C., and the mixture containing the predetermined amount of diol and THF was continuously fed at a rate of 32 ml / hr while continuing stirring for 4 hours under a nitrogen atmosphere. The mixture in the polymerization tank was introduced into phase separation tank 2 and the separated upper layer was removed by flooding and the catalyst phase in the lower layer was circulated to the polymerization tank to carry out the reaction again. As such, it was carried out continuously for 100 hours. Unreacted THF was removed by distillation from distillation column 3 from the overflowing supernatant to obtain a polymer. As such, all the polymers were found to be polyetherglycols having an OH group at the terminal end of which the diol molecule average 1 was optionally copolymerized in one molecule of the polymer. The composition of starting materials when using various diols is shown in Table 1.

The ¹ H-NMR spectrum (measured by JEOL JNM-GX 400 nuclear magnetic resonance apparatus) of polyether glycol prepared by copolymerization of THF and 1,6-hexane diol is shown in FIG. 4, and the abscissa indicates tetramethyl as a reference When silane is used, it shows chemical shift (ppm).

TABLE 1

* 1) Measured with a non-injection calorimeter at a temperature rise rate of 4 ° C / min.

Example 3

200 g of THF containing 350 ppm and 10.6 g of 1,3-propanediol were introduced into a vessel equipped with a stirring means and a reflux condenser. As shown in Table 2, 100 g of the catalyst made in anhydrous state was added thereto. Stirring was continued for 4 hours at 60 ° C. under a nitrogen atmosphere, and the mixture was allowed to stand at room temperature to separate into two phases. Unreacted THF was removed by distillation from the upper layer to obtain a copolymer copolymerized with 1,3-propanol. The yield of the obtained polymer is shown in Table 2. The number of water coordinated to the catalyst during the reaction was 0.5 to 4.

TABLE 2

Example 4 and Comparative Example 1

200 g of THF and 1,3-propanediol were introduced into the vessel equipped with the stirring means and the reflux condenser as shown in Table 3. Then 100 g of tungstophosphoric acid was adjusted with the number of coordinated water adjusted to 2. After stirring was continued for 4 hours at 60 DEG C under nitrogen atmosphere, the mixture was allowed to stand at room temperature and separated into two phases. Unreacted TFH was distilled off from the top layer to obtain a polymer. Table 3 shows the average molecular weight and the course of polymerization determined by GPC.

TABLE 3

* 1) The number of water molecules coordinated in the catalyst was 15 or more.

Example 5

As shown in FIG. 3, polymerization can be carried out by using a continuous polymerization apparatus. First, 200 g of ₁₂ -tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ .3.5H ₂ O) with coordination bond number 3.5 was introduced up to 300 ml of polymerization tank 1 with stirring means and reflux condenser. 150 g of a monomer mixture containing 1.8% by weight of 1,4-butanediol and THF was added and the mixture was stirred. The temperature of the polymerization tank was kept at 60 ° C. and stirring was continued for 4 hours under a nitrogen atmosphere, and the mixture containing 1.8% by weight of 1,4-butanediol and THF was continuously supplied at a rate of 32 ml / hr. The liquid was circulated from the lower layer of the phase separation tank 2 to the reaction tank, and the reaction was performed while the upper layer after the phase separation was removed by flooding. Unreacted THF was distilled off from the flooded upper layer to obtain PTMG. Unreacted 1,4-butane diol was hardly detected. After continuous operation for 100 hours, 850 g of PTMG having an average molecular weight of 1750 was obtained.

Example 6

100 g of THF having a water content of 350 ppm, 3 g of 1,4-butanediol and 6 g of PTMG oligomer having an average molecular weight of 600 were added to the vessel provided with the stirring means. Again 50 g of 12- tungstosilicate-1-lithium (LiH ₃ SiW ₁₂ O ₄₀ ) was added. The vessel was sealed and stirring continued at 60 ° C. for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was left to separate into two liquid phases, and then the lower catalyst phase was separated.

Unreacted THF was distilled off from the upper layer to obtain 31 g of PTMG having an average molecular weight of 1800.

Example 7

Into a vessel equipped with a stirring means and a reflux condenser, 200 g of THF containing 350 ppm H ₂ O, 8.0 g of propylene oxide and 13 g of 1,4-butanediol were introduced. 100 g of tungstoin (H ₃ PW ₁₂ O ₄₀ ) acid, heated at 300 ° C. for 3 hours and made anhydrous, was added thereto. The temperature was brought to 60 ° C. and stirring continued for 4 hours under a nitrogen atmosphere, then the mixture was separated into two phases by standing at room temperature. Unreacted THF was distilled off from the upper layer to obtain 49 g of a clear, viscous polymer. The obtained polymer was found to be polyalkylene ether glycol having an OH group at the end of the molecule and two molecules of propylene oxide copolymerized on average of one molecule.

The average molecular weight was measured to 1500 by GPC.

Example 8

vis/

n)는 1.58로 밝혀졌다.As shown in FIG. 3, polymerization was carried out by a continuous polymerization apparatus. First, 3.0 g of THF and 1.8 wt% of neopentyl glycol were introduced into a polymerization tank 1 having a volume of 10 L and having a stirring means and a reflux condenser. The mixture was heated to 300 ° C. while stirring to add 8.0 kg of tungsutophosphate (H ₃ PW ₁₂ O ₄₀ ) made of anhydride to prepare a liquid catalyst. The volume of the liquid catalyst was about 6.3 liters. Again at 60 ° C., THF and neopentyl glycol 1.8 wt% containing 200 ppm of water were supplied to the vessel at a rate of 1 L / hr. The liquid in the overflowed polymerization tank was phase separated in Phase Separation Tank 2, followed by polymerization to recover the organic phase starting material of the upper layer, and the liquid catalyst was recycled to the polymerization tank. Unreacted THF was recovered by vacuum distillation from the starting material of the organic phase to obtain 27.8 kg of the polymer. Analysis of the polymer revealed that the average 1 molecule of neopentylglycol per molecule of the polymer having OH groups in the sock end is an optionally copolymerized polyalkylene ether glycol. The average molecular weight was found to be 1970 and the molecular weight distribution (

vis /

n) was found to be 1.58.

n은 OH기를 정량분석 함으로써 측정된 평균 분자량이고

vis는 점성 평균 분자량이며 40℃에서 측정된 점도와 관련된 다음식으로 부터 계산된 것이다.here,

n is the average molecular weight measured by quantitative analysis of OH groups

vis is the viscosity average molecular weight and is calculated from the following equation with respect to the viscosity measured at 40 ° C.

vis=antilog(0.493 log점도(cp)+3.0646)

vis = antilog (0.493 log viscosity (cp) +3.0646)

vis/

n)는 상기 방법에 따라 결정 되었다.The molecular weight distribution (unless otherwise indicated in the examples below)

vis /

n) was determined according to the above method.

The polymer was found to have a melting point of 10 ° C. as measured by a differential injection calorimeter (PERKIN-ELMER DSC-2 MODEL). The ¹ H-NMR spectrum of this polymer is shown in Figure 5, where the abscissa indicates chemical shift (ppm) when using tetramethylsilane as reference material.

Example 9 and Comparative Example 2

Into a vessel equipped with a stirring means and a reflux condenser, 200 g of THF containing 100 ppm of H ₂ O and 4.2 g of ethylene glycol were introduced. 100 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ .nH ₂ O) adjusted to the specific number of coordination water by heating at 150 to 250 ° C. for 0.5 to 2 hours was added to the mixture. After stirring was continued for 4 hours at 60 ° C. under a nitrogen atmosphere, the mixture was allowed to stand at room temperature and separated into two phases.

Unreacted THF was distilled off from the upper layer to obtain copolymerized polyether glycol of ethylene glycol and THF. The polymerization results are shown in Table 4. Average molecular weight was measured by GPC.

TABLE 4

Example 10

Into a vessel equipped with a stirring means, 100 g of THF containing 300 ppm of water, 2 g of 1,3-propanediol and a low molecular weight polymer (average molecular weight: 600) of polyether polyol were introduced, where 1,3-propanediol and THFsms 1 It is copolymerized in the molar ratio of 8 :. 50 g of tungstosilic acid (H ₃ PW ₁₂ O ₄₀ .2H ₂ O) with coordination bond number adjusted to 2 was added to the mixture. Stirring was continued at 60 ° C. for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was allowed to stand at room temperature, separated into two liquid phases, and then the lower catalyst layer was separated.

Unreacted monomer was removed from the upper phase by distillation to obtain 30 g of polyether glycol having an average molecular weight of 1750. Unreacted 1,3-propane diol was not detected, so it can be assumed that all 1,3-propane diols were copolymerized.

Example 11

100 g of THF containing 30 ppm water, 2 g of 1,3-propanediol, 5 g of low molecular weight polymer (average molecular weight: 600) of polyether polyol and 2 g of oligomeric cyclic ether of the following structural formula were introduced into a vessel equipped with a stirring means, wherein 1 , 3-propanediol and THF are copolymerized in a molar ratio of 1: 8:

Next, 50 g of tungsto silicic acid (H ₃ SiW ₁₂ O ₄₀ .2H ₂ O) with coordination bond number adjusted to 2 was added to the mixture.

Stirring was continued at 60 ° C. for 10 hours under nitrogen atmosphere. After the reaction, the mixture was left at room temperature to separate into two liquid phases. Unreacted monomer was distilled off from the upper phase to obtain 35 g of polyether glycol having an average molecular weight of 2000. This polymer phase contained 0.15 g oligomeric cyclic ether and the catalyst phase was found to contain 0.1 g of the same cyclic ether. As a result, it is assumed that most oligomeric cyclic ethers can be copolymerized to the polymer. Since unreacted 1,3-propanediol was not detected, it can be assumed that all 1,3-propanediol can be copolymerized.

Example 12

10 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ · 30H ₂ O) having a coordination bond number of 30 was dissolved in 100 g of THF. 50 g of activated charcoal of granules were added to the solution and then mixed for 1 hour at room temperature. Activated charcoal was filtered, dried and heated at 300 ° C. for 3 hours to obtain a supported catalyst. 50 g of the supported catalyst, 160 g of THF containing 50 ppm of H ₂ O and 1.0 g of ethylene glycol were introduced into an air-mild stainless steel vessel. After replacing with nitrogen gas, the vessel was sealed and vibrated continuously for 24 hours in a vibrator maintained at 60 ° C. Then, the catalyst supported on the activated charcoal was filtered off, and unreacted monomer was distilled off from the filtrate to obtain 12 g of polyether glycol copolymerized with ethylene glycol and THF.

Example 13

Into a vessel equipped with a stirring means and a reflux condenser, 200 g of THF containing 350 ppm H ₂ O and 11.2 g of bis- (2-hydroxyethyl) -n-butylamine having the following structural formula were introduced:

100 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) made from anhydride by heating at 300 ° C. for 3 hours was added. Stirring was continued for 6 hours at 60 ° C. under nitrogen atmosphere. The reaction mixture became two-liquid phase, reacted at room temperature and left to separate in two phases. Unreacted THF was distilled off from the top phase to give 60.3 g of a clear, viscous polymer. Elemental analysis and ¹ H-NMR measurement of the obtained polymer revealed that the polymer was a polyether glycol copolymerized with a ratio of bis- (2-hydroxyethyl) -n-butylamine and THF 1/25. The ¹ H-NMR spectrum of the polymer is shown in Figure 6, where the abscissa represents the chemical shift (ppm) when using tetramethylsilane as the reference material.

The obtained polymer was also found to contain unreacted bis- (2-hydroxyethyl) -n-butylamine by gas chromatography. The molecular weight measurement of the polymer by gel permeation chromatography revealed that the average molecular weight was 1700.

Example 14

The various amines shown in Table 5 were introduced into a vessel equipped with agitation means and a reflux condenser with 200 g of THF containing 350 ppm H ₂ O. Again, 100 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) made from anhydride was added by heating at 300 ° C. for 3 hours. After stirring was continued for 6 hours at 60 ° C. under a nitrogen atmosphere, the mixture was left to separate into two phases. Unreacted THF was removed from the top phase to obtain a polymer in which the amine was copolymerized with THF. Table 5 shows the composition of the starting materials introduced, the polymer yield after the reaction, and the nitrogen content in the obtained polymer.

TABLE 5

Example 15

Into a vessel equipped with a stirring means and a reflux condenser, 200 g of THF containing 350 ppm of H ₂ O and 8.2 g of thiodiethanol [HO-CH ₂ CH ₂ -S-CH ₂ CH ₂ -OH] were introduced. 100 g of tungstophosphoric acid made from anhydride by heating at 300 DEG C for 3 hours was added. Stirring was continued at 60 ° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was in two phases and left after reaction to separate into two phases. Unreacted THF was distilled off from the top layer to yield 14 g of a clear, viscous polymer. Elemental analysis of the polymer by fluorescence X-rays and measurement of ¹ H-NMR revealed that the polymer was polyetherglycol copolymerized at a molar ratio of 1/22 of thiodiethanol / THF. It was found that unreacted monomer was not present in the polymer obtained. The polymer obtained by measurement by gel permeation chromatography (GPC) was found to have an average molecular weight of 2000.

Example 16

Into a vessel equipped with a stirring means and a reflux condenser, 200 g of THF containing 350 ppm H ₂ O and various thioglycols shown in Table 6 were introduced. Then, 100 g of anhydrous tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) was added by heating at 300 ° C. for 3 hours. Stirring was continued at 60 ° C. for 6 hours under a nitrogen atmosphere. The reaction mixture became a two-liquid phase, which was left to react and separated into two phases.

Unreacted THF was distilled off from the upper phase to obtain a polymer copolymerized with thioglycol and THF. Table 6 shows the types of thioglycol, the composition of the starting materials, and the polymer yield after the reaction.

TABLE 6

Example 17

50 g of THF having a water content of 30 ppm in a vessel provided with a stirring means; 1 g of 1,3-propanediol and 15 g of a low molecular weight polymer (average molecular weight: 600) of polyether glycol prepared by copolymerization at a molar ratio of 1,3-propanediol and THF 1: 8 were introduced.

As a next step, 50 g of tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ 1H ₂ O) in which the binding number of the vessel was adjusted to 1 was added to the mixture, followed by reaction at 60 ° C. for 20 hours under a nitrogen atmosphere. After the reaction, 250 g of H ₂ O and 250 g of chloroform were added to the mixture, followed by phase separation into two phases. From the chloroform phase, unreacted monomer and chloroform were removed by vacuum distillation to give 25 g of polymer. The polymer was found to be polyether glycol copolymerized with 1,3-propanediol and THF in a molar ratio of 1: 8 and an average molecular weight of 1950. Analysis of the polymer obtained by gel permeation chromatography (GPC) revealed that a low molecular weight polymer of polyether glycol added as starting material was consumed. Therefore, it is assumed that the polymer was used for the copolymerization reaction with THF.

[Example 1]

Polyurethane films were prepared by using PTMG as a starting material and reference material of the copolymerized polyether glycol as shown in Table 7. To the polyether glycol was added 0.55 times mole of 4,4'-diphenylmethane diisocyanate for synthesizing the prepolymer, followed by dissolving the prepolymer with 5 times the weight of the prepolymer in dimethylacetamide solvent, and then freed isocyanate. Polyurethane was prepared by reacting an equimolar number of amines (mixture of ethylenediamine and diethylamine: molar ratio of diethylamine / ethylenediamine and diethylamine 0.128 / L) at 70 ° C. for 3 hours. The resulting polyurethane has a molecular weight of about 70,000. The polyurethane was made into a film having a thickness of 0.125 mm and a width of 1 mm, and then its low temperature recovery rate (the film recovered after 10 seconds at 10 ° C. from the stretching state up to 100% for 16 hours at 10 ° C.). As a result, it is shown in Table 7 and Table 7 shows that the low-temperature recoverability of the copolymerized polyether glycol compared to the polyurethane film using PTMG.

TABLE 7

* 1) Average molecular weight by OH value measurement

* 2) Recovery rate after 10 seconds at 10 ℃ after stretching the film to 100% for 16 hours at 10 ℃

Claims (26)

Tetrahydrofuran by copolymerizing tetrahydrofuran with a polyhydric alcohol having two or more hydroxyl groups per molecule using a heteropoly acid or salt thereof containing 0.1 to 15 molecules of water per heteropoly-anion or a mixture of heteropolyacids and salts thereof as a catalyst Process for producing a polyether polyol having a content of 50 to 99.5% by weight of oxytetramethylene group derived from. The method of claim 1 wherein the amount of water present in the catalyst is in the range of 1 to 8 molecules per one heteropoly-anion. The method according to any one of claims 1 to 2, wherein the polyhydric alcohol is a dihydric alcohol having 2 to 10 carbon atoms. The dihydric alcohol according to claim 3, wherein the dihydric alcohol is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentylglycol , 2-methyl-1,4-butanediol, hexanediol, heptanediol and octanediol alone or a mixture of two or more thereof. The method according to claim 1, wherein the polyhydric alcohol has a moiety comprising a secondary amine or a tertiary amine or a salt thereof in the molecule thereof. The method according to claim 5, wherein the polyhydric alcohol having a moiety containing a secondary amine or a tertiary amine in the molecule has the following structure:

In the above, R ₁ and R ₂ is-(CH ₂ ) _n- (where n is 2-10), -CH ₂ CH ₂ -O-CH ₂ CH ₂ and -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -is selected from; R ₃ is selected from hydrogen and alkyl groups having 1 to 10 carbon atoms. The method of claim 1 wherein the polyhydric alcohol is poly hydroxy alkylsulfide. 8. The method of claim 7, wherein the polyhydroxyalkylsulfide has the following structure. HO-R ₁ -SR ³ -OH In the above, R ₁ and R ₂ are-(CH ₂ ) _n- (where n is 2-10), -CH ₂ CH ₂ -O-CH ₂ CH ₂ -and -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -is selected from. The method according to claim 1, wherein as at least part of the polyhydric alcohol, a low molecular weight polymer of polyether polyol obtained by copolymerizing tetrahydrofuran and polyhydric alcohol is used. The reaction according to any one of claims 1 to 2, wherein the polymer forms a two-liquid phase of the organic phase starting material and the liquid catalyst, and the reaction is carried out in a two-liquid system in which the liquid catalyst is present in at least 10% by volume of the total liquid phase in the reactor. A process for recovering polyether glycols from the organic phase of a hugh starting material. The process according to any of the preceding claims, wherein the catalyst or catalyst-containing phase is recovered by separation and repeated use in the polymerization reaction. 10. The catalyst of any one of claims 1, 2, 5, 7, and 9, wherein the catalyst comprises at least one oxide selected from Mo, W and V and P, Si, As, Ge, B, Ti. , A heteropoly-acid formed by condensation of an element selected from Ce and Co with an oxy-acid. 13. The heteropoly-acid according to claim 12, wherein the heteropoly-acid is 12-molybdoic acid, 18-molybdo-2-phosphoric acid, 9-molybdophosphoric acid, 12- tungstophosphoric acid, 18- tungsto-2-phosphoric acid, 11- Molybdo-1-banadophosphoric acid, 12-molybdo tungstophosphoric acid, 6-molybdo-6-tungstophosphoric acid, 12-molybdo tungstobanadophosphoric acid, 12-tungstobanadophosphoric acid, 12-molybdosilicate, 12-tungstosilicate, 12-molybdo tungstosilicate, 12-molybdotungstobanadosilicate, 12-tungstoboric acid, 12-molybdoboric acid, 12-molybdate Do tungstoboronic acid, 12-molybdovanadoboric acid, 12-molybdo tungstobanadoboric acid, 12- tungstogermanic acid and 12- tungstobisic acid alone or a mixture of two or more compounds selected therefrom How to feature. Mixtures of tetrahydrofuran and other cyclic ethers copolymerizable therewith with heteropoly-acids or salts thereof containing 0.1 to 15 molecules of water per one heteropoly-anion, or mixtures of heteropolyacids and salts thereof, per molecule A method for producing a polyether polyol containing 50 to 99.5% by weight of an oxytetramethylene group derived from tetrahydrofuran by copolymerizing with a polyhydric alcohol having a hydroxyl group. 15. The process of claim 14, wherein the amount of water present on the catalyst is between 1 and 5 molecules per one heteropoly-anion. The process according to any one of claims 14 to 15, wherein the polyhydric alcohol is a dihydric alcohol having 2 to 10 carbon atoms. 17. The dihydric alcohol according to claim 16, wherein the dihydric alcohol is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanol, 1,5-pentanediol, neopentylg A recall, 2-methyl-1,4-butanediol, hexanediol, heptanediol and octanediol alone or a mixture of two or more thereof. The method according to claim 14, wherein the polyhydric alcohol has a moiety comprising a secondary amine or a tertiary amine or a salt thereof in the molecule. 19. The method of claim 18, wherein the polyhydric alcohol having a moiety comprising a secondary amine or a tertiary amine in the molecule has the following structure.

In the above, R ₁ and R ₂ is-(CH ₂ ) _n- (where n: 2-10), -CH ₂ CH ₂ -O-CH ₂ CH ₂ and -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -is selected from; R ₃ is selected from hydrogen and alkyl groups having 1 to 10 carbon atoms. 15. The method of claim 14, wherein the polyhydric alcohol is polyhydroxy alkylsulfide. 21. The method of claim 20, wherein the polyhydroxyalkylsulfide has the following structure. HO-R ₁ -SR ₂ -OH In the above, R ₁ and R ₂ is-(CH ₂ ) _n- (where n: 2 to 10), -CH ₂ CH ₂ -O-CH ₂ CH ₂ and -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -is selected from. The polyether polyol obtained by copolymerizing tetrahydrofuran, other cyclic ether copolymerizable therewith, and polyhydric alcohol as at least part of the polyhydric alcohol, wherein the polyether polyol uses a low molecular weight polymer or is at least a portion of the cyclic ether. A method characterized by using an oligomeric cyclic ether obtained by copolymerizing furan, other cyclic ethers copolymerizable therewith and a polyhydric alcohol. The process according to any one of claims 14 to 15, wherein the polymer forms a two-liquid phase of the organic phase starting material and the liquid catalyst, and the reaction is carried out in a two-liquid system in which the liquid catalyst is present in at least 10% by volume of the total liquid phase in the reactor. Recovering polyether glycol from the organic phase of the starting material after the reaction. The process according to any one of claims 14 to 15, wherein the catalyst or catalyst-containing phase is recovered by separation and used repeatedly in the polymerization reaction. 23. The catalyst of any one of claims 14, 15, 18, 20 and 22, wherein the catalyst comprises at least one oxide selected from Mo, W and V and P, Si, As, Ge, B, Ti. , A heteropoly-acid formed by condensation of an element selected from Ce and Co with an oxy-acid. 26. The process of claim 25, wherein the heteropoly-acid is 12-molybdophosphoric acid, 18-molybdo-2-phosphoric acid, 9-molybdophosphoric acid, 12- tungstophosphoric acid, 18- tungsto-2-phosphoric acid, 11- Molybdo-1-banadophosphoric acid, 12-molybdo tungstophosphoric acid, 6-molybdo-6-tungstophosphoric acid, 12-molybdo tungstobanadophosphoric acid, 12-tungstobanadophosphoric acid, 12-molybdosilicate, 12-tungstosilicate, 12-molybdo tungstosilicate, 12-molybdotungstobanadosilicate, 12-tungstoboric acid, 12-molybdoboric acid, 12-molybdate Do tungstoboronic acid, 12-molybdobanadoboric acid, 12-molybdo tungstobanadoboric acid, 12- tungstogermanic acid and 12- tungstobisic acid alone or a mixture of two or more compounds selected from them. Characterized in that the method.

Images