JP2003147073A - Method of producing polyether polyol copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing polyether polyol copolymers that can arbitrarily change the content of the O(CH2 )x group in the main chains of polyether polyol copolymer that has a proper crystallinity and is suitable as a raw material for elastomers and simultaneously can change the molecular weight of the copolymers. SOLUTION: The polyether polyol copolymer is produced by polymerizing (1) a ring ether represented by general formula (I) (wherein x is an integer of 2-10), (2) a diol represented by general formula (II) HO-(CH2 )x -OH [x has the same meaning as in general formula (I)] and (3) other polyols in the presence of an acid catalyst.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyether polyol copolymer, in particular, O (CH ₂₎ in the polyether polyol copolymer containing an _x group units essential structural units, O (CH _{2) x} groups The present invention relates to a method for producing a polyether polyol copolymer, the content ratio of which can be adjusted to a desired range.

[0002]

2. Description of the Related Art Polyether polyols are polyether glycols having hydroxyl groups at both ends and are generally produced by ring-opening polymerization of cyclic ethers. In order to modify the physical properties of the polyether polyol, methods for producing various polyether polyol copolymers by copolymerizing using a cyclic ether and a diol have been studied.
When a polyether polyol copolymer is obtained by copolymerization using a specific cyclic ether and a diol, the oxypolymethylene group (O
When the content of (CH ₂ ) _x group) is designed to be a desired content and copolymerization is carried out, the content of the oxypolymethylene group becomes the desired content, but the polyether obtained from the cyclic ether and diol When the molecular weight of the polyol copolymer cannot be adjusted to the target molecular weight and the molecular weight of the polyether polyol copolymer is to be adjusted to the target molecular weight, the oxypolymethylene group in the polyether polyol copolymer is The content cannot be adjusted to the target content. Among polyether glycols having hydroxyl groups at both ends, a compound having a particularly industrial meaning is polytetramethylene ether glycol (hereinafter PTMEG) produced by ring-opening polymerization of tetrahydrofuran (hereinafter THF). PTMEG has an oxytetramethylene group, spandex,
It is widely used as a material for coating materials such as synthetic leather and optical fibers. However, elastomers using PTMEG, especially PTMEG with a high molecular weight, tend to crystallize at low temperature or during long-term storage, and physical properties at low temperatures are not sufficient, or physical properties change from design physical properties during storage. There was a problem.

As a solution to this problem, instead of using PTMEG which is a homopolymer of THF, a copolymerized P obtained by copolymerizing THF and other cyclic ether is used.
It has been proposed to use TMEG. By copolymerizing THF and other cyclic ethers, the purpose is to disturb the molecular arrangement and reduce the crystallinity. For example, in Japanese Examined Patent Publication No. 4-20013, a copolymer of THF and 3-methyloxetane is used. Japanese Patent Publication No. 7-116276 discloses a polymerized PTMEG, which is a copolymerized PTMEG of THF and 3-alkyltetrahydrofuran. However, in the method using these ring-opening copolymerization reaction, a cyclic ether compound other than THF is required as a copolymerization component, and there are limits to the types of cyclic ethers that can be used due to the difficulty in synthesizing the cyclic ether compound, When the cyclic ether and the polyol are compared, the cyclic ether tends to be expensive in terms of manufacturing cost.

Another method for synthesizing copolymerized PTMEG is to use glycols instead of cyclic ether as a component to be copolymerized with THF. Since glycols are cheaper and have more kinds than cyclic ethers, the range of molecular design of copolymerized PTMEG can be widened. Specifically, Japanese Patent Publication No. 7-13139 discloses that
Disclosed is a method for producing a polyether polyol from THF and glycol by using a heteropoly acid in which 15 molecules or less of water are coordinated or present per molecule as a catalyst.

On the other hand, when the copolymerized PTMEG is used as an elastomer raw material, it is very important to control the ratio of the copolymerized components other than THF. When the proportion of the copolymerization component is small, the crystallinity of PTMEG remains strong, and the improvement of the low temperature characteristics and storage stability of the target elastomer becomes insufficient. Further, when the proportion of the copolymerization component is large, the low temperature characteristics and the storage stability can be improved, but the physical properties are greatly affected and, for example, the tensile strength is extremely lowered.

However, when the copolymerization of THF and glycol is carried out to obtain a copolymerized PTMEG having a desired molecular weight, the charging ratio of THF and glycol is uniquely determined, and therefore the proportion of oxytetramethylene groups in the copolymerized PTMEG. Is also constant. That is, when the copolymerization is carried out using THF and glycol, the content of the oxytetramethylene group at the time of the ring-opening of THF is designed to the desired content, and the copolymerization is carried out. However, the molecular weight of the copolymerized PTMEG obtained from THF and glycol cannot be adjusted to the desired molecular weight, and if the molecular weight of the copolymerized PTMEG is adjusted to the desired molecular weight, It becomes impossible to adjust the content of the oxytetramethylene group in PTMEG to the target content. This phenomenon also applies to the above Japanese Patent Publication No. 7-13139, and it has been impossible to obtain a copolymerized PTMEG in which the content of the oxytetramethylene group and the molecular weight of the copolymerized PTMEG are changed. On the other hand, even when a cyclic ether other than THF is used as a raw material, the content of the oxyalkylene group derived from the cyclic ether contained in the obtained polyether polyol copolymer and the molecular weight of the obtained copolymer are simultaneously controlled. If possible, a material having desired physical properties can be easily obtained, but no such report has been made so far.

[0007]

DISCLOSURE OF THE INVENTION The present invention is directed to O (CH 2) in the main chain of a polyether polyol copolymer obtained as a raw material for an elastomer and having a suitable crystallinity.
₂ ) It is an object of the present invention to provide a method for producing a polyether polyol copolymer in which the content of _x groups can be arbitrarily changed, and at the same time, the molecular weight of the copolymer can be changed.

[0008]

The present invention is directed to O (CH ₂ ) _x
In producing a polyether polyol copolymer having a group unit as an essential constitutional unit, in copolymerizing a specific cyclic ether and other polyol in the presence of an acid catalyst, a structure in which the specific cyclic ether is ring-opened This finding was made based on the finding that the above problem can be effectively solved by using the diol in combination.

That is, the present invention provides (1) a cyclic ether represented by the following general formula (I):

[Chemical 2] (Wherein, x is an integer from 2 to 10) (2) the following general formula (II) diol represented by and HO- (CH _{2) x} -OH (II) (wherein, x is as described above (3) A method for producing a polyether polyol copolymer, which comprises copolymerizing another polyol in the presence of an acid catalyst. The present invention also includes (1) tetrahydrofuran, (2) 1,4-butanediol and (3).
Provided is a method for producing a polyether polyol copolymer, which comprises copolymerizing another polyol in the presence of an acid catalyst.

[0010] The present invention also, O (CH ₂₎ a polyether polyol copolymer containing _x group O (CH ₂₎ for adjusting the _x group content, method for producing said polyether polyol copolymer The use of the combination of the cyclic ether represented by the general formula (I) and the diol represented by the general formula (II) in. The present invention also provides, O (CH ₂₎ a polyether polyol copolymer containing _x group O (CH ₂₎ for adjusting the _x group content, and tetrahydrofuran in the manufacturing method of the polyether polyol copolymer 1 The use of a combination of 4,4-butanediol is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic ether that can be used in the production method of the present invention is represented by the following general formula (I).

[Chemical 3]

Wherein x is 2-10, preferably 2-4,
Particularly preferably, it is an integer of 4. Where general formula (I)
The methylene group therein may be substituted with a C ₁ -C ₄ alkyl group. The alkyl group may be linear or branched.
The substitution with the alkyl group may be mono-substituted or poly-substituted and is not particularly limited, but mono-substituted is preferred. The substitution position by the alkyl group is not particularly limited, but it is preferable that the methylene groups on both sides of the oxygen atom contained in the cyclic ether are not simultaneously substituted. Specifically, ethylene oxide, propylene oxide, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, oxepane, butene-1-oxide, butene-2-oxide,
Examples thereof include, but are not limited to, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and the like. Of these, tetrahydrofuran is preferred.

The diol which can be used in the production method of the present invention is represented by the following general formula (II). During _{HO- (CH 2) x -OH (} II) formula, x it is as described above. In the diol represented by the general formula (II), the cyclic ether of the general formula (I) is C ₁ -C.
_When substituted with a ₄ alkyl group, the diol of general formula (II) is also substituted at the corresponding position with the same C ₁ -C ₄ alkyl group. Specific examples of such diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,2-propanediol and 2- Examples include, but are not limited to, methyl-1,3-propanediol, neopentyl glycol, 2-methyl-1,4-butanediol and the like. this house,
1,4-butanediol is preferred.

As the polyether polyol obtained by the production method of the present invention, those represented by the following general formula (1) are preferable. _{H- (O (CH 2) x} ) m - (OR) a polyether polyol represented by _n -OH (1) General formula (1) may be alternating copolymers in random copolymer in the block copolymer. In the general formula (1), m and n represent integers satisfying m + n ≦ 100. R is not limited as long as it is different from the O (CH ₂ ) _x group derived from the cyclic ether of the general formula (I) having a specific x to be used and the diol of the general formula (II) having a ring-opening structure. Absent. For example, in the cyclic ether of the general formula (I) and the diol of the general formula (II), x = 4
And when the methylene group is not alkyl substituted,
R may be any group other than the tetramethylene group. Also, R
May be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which each structure is mixed, may be cyclic or chain, and may contain a hetero atom such as nitrogen, oxygen, sulfur, or silicon. Also, a mixture of several kinds of groups may be used. In the general formula (1), the ratio of m and n is 0.5 ≦ m / (m
+ N) ≦ 0.99.

The other polyol, which is a raw material of the group represented by (OR) in the above general formula (1), is appropriately selected from the physical properties of the elastomer and is not particularly limited. For example, when tetrahydrofuran is used as the cyclic ether of the general formula (I) and 1,4-butanediol is used as the diol of the general formula (II), other polyols other than 1,4-butanediol are, for example, Ethylene glycol, 1,3-propanediol, 1,5-pentanediol and the like can be used without limitation.

Specific examples of such other polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,9. -Nonanediol, 1,2-propanediol, 2-methyl-1,
3-propanediol, neopentyl glycol, 2-
Methyl-1,4-butanediol, 3-methyl-1,5
-Pentanediol, (3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and 3,9-diethanol-2,4 , 8,10-Tetraoxaspiro [5,5] undecane and other spiroglycols, 1,4
-Cyclohexanedimethanol, 1,4-dihydroxymethylbenzene, bisphenol A, bisphenol F, polyoxyalkylene glycol, thiodiethylene glycol, alcohol-modified polydimethylsiloxane,
Examples thereof include alkylene oxide adducts of polydimethylsiloxane.

Of these, ethylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,
5-pentanediol, 1,6-hexanediol,
1,9-nonanediol, 1,2-propanediol,
2-methyl-1,3-propanediol, neopentyl glycol, 2-methyl-1,4-butanediol, 3
-Methyl-1,5-pentanediol spiroglycol, 1,4-cyclohexanedimethanol and 1,4-dihydroxymethylbenzene are preferred. Here, examples of the alcohol-modified polydimethylsiloxane include polydimethylsiloxane having hydroxyl groups at both ends, and examples thereof include alcohol-modified silicone PSF-475.
With the trade name of No. 1, a commercially available product from Toshiba Silicon Co., Ltd. can be used. The amount used can be appropriately selected depending on the physical properties of the intended elastomer, but the content ratio of O (CH ₂ ) _x groups in the obtained polyether polyol is preferably 50 to 99% in terms of molar ratio, and further Preferably 75-97% mol, most preferably 80-
It is 95 mol%.

The acid catalyst used in the present invention is not particularly limited as long as it is a catalyst capable of directly reacting the cyclic ether represented by the general formula (I) and the diol-containing polyol represented by the general formula (II). There is no. For example, 1) a heteropoly acid or a salt thereof in which the amount of water coordinated or present is defined, or a catalyst in which these are supported on a carrier, 2) a portion composed of zirconia and / or hydrous zirconia having a tetragonal structure, and alumina and Examples of the carrier include a molded carrier composed of a portion composed of water-containing alumina, and a catalyst containing a sulfuric acid component supported on the carrier.
The amount of the acid catalyst used is not particularly limited, but is 0.1 to 70 per 100 parts by weight of the cyclic ether represented by the general formula (I).
It is preferably part by weight, more preferably 10 to 60 parts by weight.

In the present invention, a heteropoly acid or a salt thereof which regulates the amount of coordinated or existing water, or a catalyst in which these are supported on a carrier means that one molecule of heteropoly acid contains not more than 15 molecules of water. A coordinated catalyst,
A catalyst in which 8 molecules or less of water is present or coordinated with 1 molecule of the heteropolyacid is preferable because it exhibits rapid activity. Further, it is preferable that 0.1 molecule or more of water is present or coordinated with 1 molecule of the heteropolyacid in the reaction system. Such a catalyst is described in, for example, Japanese Patent Publication No. 10-506137.

The coordination water number of the catalyst can be controlled by a method such as heating a commonly available heteropolyacid having a coordination water number of 20 to 40 at 250 ° C. for 3 hours. Water is produced by the reaction in which the polyol used in the present invention and the diol represented by the general formula (II) are incorporated into the polymer chain by an ether bond. The activity disappears. Therefore, the amount of water in which the heteropolyacid is coordinated or present before the reaction and the amount of water produced during the polymerization are 1
The molar ratio of the diol represented by the general formula (II) and the other polyol to be used and the amount of coordinated water and / or existing water of the heteropolyacid before the reaction are adjusted so as not to exceed 5 times by mole. Is good. Further, it is preferable to remove water from the system by distillation or another method so that the amount of water in the system does not exceed 15 times the molar amount of the heteropolyacid.

The heteropolyacid usable in the present invention includes at least one oxide of Mo, W and V,
Other elements such as P, Si, As, Ge, B, Ti, C
It is a general term for oxyacids produced by condensation of oxyacids such as e and Co, and the former atomic ratio to the latter is preferably 2.5-12. Specific examples of these heteropolyacids include phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdniobic acid, silicotungstic acid, silicomolybdic acid, silicomolybdotungstic acid, Cimolybdo tungstovanadic acid, germanium tungstic acid, borotungstic acid, boromolybdic acid, boomolybdotungstic acid, boomolybdovanadic acid, boomolybdotungstovanadic acid, cobalt molybdic acid, cobald tungstic acid, arsenic molybdic acid , Arsenic tungstic acid, titanium molybdic acid, cerium molybdic acid, and the like.

A tetragonal zirconia and / or hydrous zirconia part used in the present invention, a shaped carrier composed of alumina and / or hydrous alumina part, and a sulfuric acid content carried on the carrier. The catalyst containing is a catalyst described in International Publication No. WO98 / 9727, and the production method includes aluminum hydroxide and / or hydrated oxide, zirconium oxide and / or hydrated oxide, Further, the sulfuric acid-containing compound is kneaded and molded, and the obtained molded product is fired at a temperature at which tetragonal structure zirconia is obtained. Alternatively, aluminum hydroxide and / or hydrated oxide, zirconium hydroxide and / or hydrated oxide, and a sulfuric acid-containing compound are kneaded and molded, and the obtained molded product is tetragonal structure zirconia. By firing at a temperature at which
Carrying a Group 9 or Group 10 metal component, followed by 3
A method of firing at 00 to 700 ° C can be used.
It is preferable that the surface area of the catalyst is 150 m ² / g or more. Further, as the aluminum hydroxide and / or hydrated oxide used for producing the catalyst, a catalyst obtained by using aluminum hydrated oxide having a boehmite structure is preferable.

As a concrete production method, as an aluminum hydroxide and / or a hydrated oxide, in order to improve the crush strength and the specific surface area of the catalyst, usually a powder, preferably an average particle diameter of 0.5 to It is preferable to use a shape of 50 μm, particularly 0.5 to 20 μm. The zirconium hydroxide and / or hydrated oxide may be prepared by any method, but generally, these salts and organometallic compounds such as oxychlorides, alcoholates, chlorides, sulfates, nitrates and oxysulfates are used. It can be obtained by neutralizing or hydrolyzing a salt or the like, and in order to improve the crushing strength and the specific surface area of the catalyst, it is usually a powder, preferably an average particle size of 0.5 to 50 μm.
It is preferable to use a shape of m, particularly 0.5 to 20 μm. The zirconium hydroxide and / or hydrated oxide and / or salt thereof may contain other metal hydroxide / or hydrated oxide and / or salt.
Other metals include titanium, hafnium, vanadium,
Chromium, manganese, iron, silicon, tin, aluminum and gallium are preferred. Compounds of these metals may be composite metal compounds. However, as the zirconium hydroxide or hydrated oxide, those having substantially only zirconium as the metal component are preferably used.

Examples of the sulfuric acid-containing compound for producing the catalyst include sulfuric acid, ammonium sulfate, sulfurous acid, ammonium sulfite, thionyl chloride and the like. Ammonium sulfate and ammonium sulfite are preferable because of low corrosiveness of the production apparatus. The sulfuric acid-containing compound may be used as it is or as a solution such as an aqueous solution. The weight of the sulfuric acid-containing compound blended during the production of the catalyst depends on the amount of the aluminum oxide and / or hydrated oxide before firing, the amorphous zirconium hydroxide and / or hydrated oxide, and the sulfuric acid-containing compound. The total weight is preferably 3 to 30% by weight, particularly 5 to 20% by weight, which is preferable because the catalyst activity can be improved.

For kneading during the production of the catalyst, any kneading machine generally used for preparing the catalyst may be used. Usually, water is added to the raw materials and the mixture is preferably used by a stirring blade, but the order of adding the raw materials and additives is not particularly limited. Water is usually added at the time of kneading, but as liquids to be added, ethanol, 2-
An organic solvent such as propanol, acetone, methyl ethyl ketone or methyl isobutyl ketone may be used. There is no particular limitation on the temperature during kneading and the kneading time. The molding method after kneading is not particularly limited, and a molding method generally used for catalyst preparation can be used. In particular, extrusion molding using a screw type extruder or the like is preferably used because it can be efficiently molded into an arbitrary shape such as a pellet shape or a honeycomb shape. The size of the molded product is not particularly limited, but the cross-sectional length (diameter) is usually 0.5 to 10 mm, and the length (overall length) is 0.5.
It is possible to easily obtain one having a size of about 15 mm. Since the crushing strength after firing is greatly influenced by kneading, it is desirable to preliminarily determine the water content, the kneading time, the electric power amount, and the like during the above kneading. The calcination is performed in a gas atmosphere such as air or nitrogen gas at a temperature at which zirconium having a tetragonal structure is obtained. When using pseudo-phemite alumina,
The preferred firing temperature is 450 to 800 ° C, especially 500 to 8
The temperature is 00 ° C, more preferably 600 to 800 ° C, and the preferable firing time is 0.5 to 10 hours.

Group 8, Group 9 used in the manufacture of the catalyst,
The metal components selected from Group 10 include platinum and palladium.
Radium, ruthenium, nickel, etc. are preferably used.
That is in the form of a compound rather than the metal itself
Is preferably used. As these metal compounds,
It can be used as an anhydride or a hydrate.
Furthermore, these metal compounds may be used alone or in combination of two or more.
It can be a stuff. There is no limitation on the method of supporting the catalyst
However, there are no impregnation methods such as spraying and dipping, and ion exchange methods.
Which is preferably used. The strong acidity of this catalyst HO (Hamet
Acidity function) is stronger than -11.93, and the specific surface area is
150m²/ G or more is preferable. High catalytic activity
In order to obtain crush strength, the specific surface area is preferably 20
0m ²/ G or more, especially 200 m²/ G ~ 300m²/ G
Is preferred.

As the monomer used in the present invention, a cyclic ether represented by the general formula (I), a diol represented by the general formula (II), and other polyols are essential components, but O (CH ₂ ) Cyclic ethers other than the ether used as the cyclic ether represented by the general formula (I) can be used in combination to the extent that the excellent characteristics of the _x group are not lost. Examples of the cyclic ether other than the specific cyclic ether represented by the general formula (I) include ethylene oxide, oxetane, oxepane, propylene oxide, butene-1-oxide,
Butene-2-oxide, cyclohexene oxide, styrene oxide, epichlorohydrin, 3,3-bischloromethyloxetane, 2-methyltetrahydrofuran,
3-methyltetrahydrofuran may be mentioned. Two or more kinds of these cyclic ethers can be used. The amount of the cyclic ether represented by the general formula (I) is 10
It is preferably 25 parts by weight or less, and more preferably 15 parts by weight or less per 0 parts by weight.

The copolymerization reaction is preferably carried out under atmospheric pressure to increased pressure, more preferably atmospheric pressure, in the range of -20 to 100 ° C, and more preferably 40 to 70 ° C. The reaction time is not particularly limited, but it is preferably about 2 to 12 hours. Further, the number average molecular weight of the obtained polyether polyol copolymer is preferably 500 to 5,000, more preferably 650 to 4,000.

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the following examples, the molecular weight was measured by gel permeation chromatography (GPC) and the melting point was measured by a differential scanning calorimeter (DSC).

Preparation Example 1 Preparation of Catalyst A Commercially available phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ · 26H
₂ O) was calcined at 250 ° C. for 2 hours to obtain phosphotungstic anhydride (catalyst A).

Examples 1 to 3 Catalyst A 50 g, THF 1
00 g of 1,3-propanediol and 1,4-butanediol in the amounts shown in Table 1 were placed in a glass container and reacted at 60 ° C. under atmospheric pressure for 6 hours while stirring under a nitrogen atmosphere. After the reaction was completed, the catalyst was removed from the reaction solution, and unreacted THF was distilled off.
The MEG was obtained directly. This copolymerized PTMEG is GPC
As a result of the measurement in step 1, the obtained PTMEG contained neither unreacted 1,3-propanediol nor 1,4-butanediol monomer. The unreacted T
As a result of analyzing the liquid containing HF by gas chromatography, it was found that neither 1,3-propanediol nor 1,4-butanediol was contained. The results are shown in Table 1.

(Comparative Examples 1-2) Catalyst A 50 g, THF 1
00 g of 1,3-propanediol and 1,4-butanediol in the amounts shown in Table 1 were placed in a glass container and reacted at 60 ° C. under atmospheric pressure for 6 hours while stirring under a nitrogen atmosphere. After the reaction is completed, the catalyst is removed from the reaction solution
When HF was distilled off, a copolymerized PTM with hydroxyl groups at both ends
EG was obtained directly. This copolymerized PTMEG was analyzed and evaluated, and the results are shown in Table 1. In Table 1, PDO is 1,3-
Propanediol and BDO are 1,4-butanediol. Further, in Tables 1 to 3, the term “acquired amount” means that the charged THF
It is the number of g of the obtained copolymerized PTMEG per g.

[0032]

[Table 1] Table 1 Note: The content is P in the polyether polyol copolymer.
It is the mol% of the DO monomer unit.

As can be seen from the melting point item in Table 1, in the production method of the present invention, the content of 1,3-propanediol can be changed while the molecular weight of the copolymerized PTMEG is kept substantially constant.

Examples 4 to 9 The same reaction as in Example 1 was carried out except that the following polyol was used in an equimolar amount in place of 1,3-propanediol. The results are shown in Table 2. In Table 2, 2MePD is 2-methyl-1,3-propanediol HDO is 1,6-hexanediol 3MePD is 3-methyl-1,5-pentanediol CHDM is cyclohexanedimethanol DHMB is 1,4-dihydroxymethylbenzene. SPG is spiroglycol (3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-
Tetraoxaspiro [5,5] undecane)

[0035]

[Table 2] Table 2 Note: Content is 2 in the polyether polyol copolymer
It is the mol% of monomer units such as MePD.

(Examples 10 to 11) The reaction was carried out in the same manner as in Example 1 except that 1,3-propanediol and 1,4-butanediol were used in the amounts shown in Table 3. The results are shown in Table 3. (Comparative Example 3) The reaction was performed in the same manner as in Example 1 except that the amount of 1,4-butanediol described in Table 3 was used. The results are shown in Table 3.

[Table 3] Table 3 Note: The content is P in the polyether polyol copolymer.
It is the mol% of the DO monomer unit.

[0037]

INDUSTRIAL APPLICABILITY In the production method of the present invention, the proportion of the diol represented by the general formula (II) is changed so that the polyether polyol copolymer can have suitable crystallinity suitable as an elastomer. The content of O (CH ₂ ) _x groups in the main chain can be arbitrarily changed, and at the same time, the molecular weight of the polyether polyol copolymer can be changed. Specifically, (3) the content of monomer units derived from other polyols can be changed while keeping the molecular weight of the obtained polyether polyol copolymer substantially constant, while the obtained polyether polyol copolymer is obtained. It is possible to change the molecular weight while keeping the content of the monomer unit derived from (3) other polyols therein to be substantially constant.

Claims (18)

[Claims] 1. A cyclic ether represented by the following general formula (I): (Wherein, x is an integer from 2 to 10) (2) the following general formula (II) diol represented by and HO- (CH _{2) x} -OH (II) (wherein, x is as described above (3) A method for producing a polyether polyol copolymer, which comprises copolymerizing another polyol in the presence of an acid catalyst. 2. The production method according to claim 1, wherein x is an integer of 2 to 4 in the general formulas (I) and (II). 3. The production method according to claim 1, wherein x is 4 in the general formulas (I) and (II). 4. A cyclic ether 1 represented by the general formula (I)
The manufacturing method according to claim 1, wherein 0.1 to 70 parts by weight of the acid catalyst is used per 00 parts by weight. 5. The production method according to claim 1, wherein the copolymerization is performed in the range of −20 to 100 ° C. 6. The production method according to claim 1, wherein a polyoxyalkylene glycol copolymer having a number average molecular weight of 500 to 5000 is produced. 7. The method according to claim 1, wherein the content ratio of O (CH ₂ ) _x groups in the resulting polyether polyol copolymer is 50 to 99 mol%. 8. The content ratio of O (CH ₂ ) _x group is 75 to 97.
The production method according to claim 7, which is mol%. 9. The method according to claim 1, wherein the acid catalyst is a heteropoly acid.
8. The manufacturing method according to claim 8. 10. Other polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1, 2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, spiroglycol, 1,4-cyclohexane Dimethanol,
At least one polyol selected from the group consisting of 1,4-dihydroxymethylbenzene, bisphenol A, bisphenol F, polyoxyalkylene glycol, thiodiethylene glycol, alcohol-modified polydimethylsiloxane and alkylene oxide adduct of polydimethylsiloxane. Item 10. The method according to any one of Items 1 to 9. 11. (1) Tetrahydrofuran, (2)
A method for producing a polyether polyol copolymer, which comprises copolymerizing 1,4-butanediol and (3) another polyol in the presence of an acid catalyst. 12. O (CH ₂₎ a polyether polyol copolymer containing _x group O (CH ₂₎ for adjusting the _x group content, claim the method for producing the polyether polyol copolymer 1 Use of a cyclic ether of the general formula (I) according to claim 1 and a diol of the general formula (II) according to claim 1. 13. In the general formulas (I) and (II), x
13. The use according to claim 12, wherein is an integer from 2 to 4. 14. In the general formulas (I) and (II), x
13. The use according to claim 12, wherein 4 is 4. 15. A polyether polyol copolymer having a number average molecular weight of 500 to 5,000.
Use according to any one of claims. 16. The use according to claim 12, wherein the content ratio of O (CH ₂ ) _x groups in the polyether polyol copolymer is 50 to 99 mol%. 17. The use according to claim 12, wherein the production method uses an acid catalyst. 18. O (CH ₂₎ a polyether polyol copolymer containing _x group O (CH ₂₎ for adjusting the _x group content, and tetrahydrofuran in the manufacturing method of the polyether polyol copolymer 1 Use of a combination of 4,4-butanediol.