JPH09235370A - Production of polyalcohol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyalcohol having a high grade gas barrier property and high in an OH content in high selectivity in a state little in the by- production of tetrahydrofuran rings by hydrogenating a polyketone obtained from a specific polyolefin and carbon monoxide in a specified solvent. SOLUTION: This method for producing a polyalcohol comprises hydrogenating (A) a polyketone (e.g. an alternating copolymer having an A2 copolymerization degree of 49-50 equivalent %) in the presence of (C) a hydrogenation catalyst in (B) sulfolane or a solvent consisting mainly of the sulfolane (e.g. the mixture of the sulfolane with water). The polyketone (A) is obtained by copolymerizing (A1 ) an olefin consisting mainly of ethylene, such as ethylene alone or the mixture of the ethylene with propylene, with (A2 ) carbon monoxide e.g. in the presence of a catalyst containing a transition metal compound as a component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyketone obtained by copolymerizing an olefin mainly composed of ethylene and carbon monoxide in the presence of a hydrogen reduction catalyst to be useful as a gas barrier material. To a method for producing various polyalcohols.

[0002]

2. Description of the Related Art There are several known methods for producing a polyalcohol by hydrogenating a polyketone obtained by copolymerizing an olefin mainly containing ethylene with carbon monoxide in a solvent in the presence of a catalyst. However, since the solubility of polyketone in a solvent varies greatly depending on the production method, first, the production methods of polyketone are classified, and the relationship between the polyketone obtained by each production method and the solubility in a solvent will be described. The production method of polyketone, which is a copolymer of ethylene and carbon monoxide, or two or more kinds of ethylene-based olefins and carbon monoxide, includes (1) a copolymerization method using a free radical initiator or γ-ray irradiation, And (2) a copolymerization method using a transition metal catalyst (Advance in Polymer Science (Adv. Poly).
m. Sci. ), 1986, 73/74, p. 125), but in the present specification, a copolymerization method using a free radical initiator (hereinafter, this is abbreviated as A method), a copolymerization method by γ-ray irradiation (hereinafter , This is abbreviated as Method B), and a copolymerization method using a transition metal compound catalyst (hereinafter, this is abbreviated as Method C).

In particular, various studies have been carried out on copolymerized polyketones of ethylene and carbon monoxide.
We will compare each method mainly. In the method A or the method B, the polyketone in which the copolymerization ratio of ethylene and carbon monoxide is changed in the copolymer polyketone is produced by changing the reaction temperature, the reaction pressure and the composition of the reaction mixture. The method C has a big difference in that a polyketone having a copolymerization ratio of ethylene and carbon monoxide of 1: 1 in which ethylene and carbon monoxide are completely copolymerized alternately is obtained.

Journal of the American Chemical Society (J. Am. Chem. Soc.,), 74,
1509 (1952), regarding the measurement of the molecular weight of polyketones, "benzene is used as the solvent for most polyketones. The ratio of ethylene to carbon monoxide is 3: 1.
The molecular weight was measured in dioxane, since polyketones below or below were not completely soluble in benzene. It is described. Further, in Table 1 in which the reaction pressure, the carbon monoxide ratio and the molecular weight of the polyketone are compared, it is described that the polyketone having a carbon monoxide ratio of 44.9% is insoluble. Therefore, the polyketone synthesized by Method A has a ratio of ethylene to carbon monoxide of 3: 1 or less,
It is understood that it is soluble in dioxane but partially insoluble in benzene, and becomes insoluble in dioxane when the carbon monoxide ratio reaches 44.9%.

Regarding the synthesis by the B method,
Of Polymer Science (J. Polym. Sc
i. ) Part A-1 (Part A-1), 1966,
Volume 4, page 29. The copolymerization ratio of ethylene and carbon monoxide is controlled by the reaction pressure, reaction mixture composition, irradiation intensity, reaction temperature and the like. Regarding the relationship between the carbon monoxide copolymerization rate of the produced polyketone and its solubility in a solvent, the carbon monoxide copolymerization rate was 33%.
˜43% is insoluble in benzene, xylene, decalin, carbon tetrachloride, dimethylformamide, etc., and is soluble in α-chlornaphthalene and o-dichlorobenzene at 130 ° C., but the carbon monoxide copolymerization rate is 43 to 48. % Polyketone became only partially soluble in these solvents,
It is described that when the content exceeds%, it does not dissolve at all. Fibrous Science Institute Annual Report, No. 12, p. 72 (1959) shows that when ethylene and carbon monoxide are irradiated with γ-rays at relatively low pressure (50 atm), the molar ratio of ethylene and carbon monoxide is almost 1. A polyketone close to: 1 was obtained, which was described to have a main chain in which ethylene and carbon monoxide were arranged alternately and regularly.
On page 17 (1960), polyketone having a copolymerization ratio of ethylene and carbon monoxide of 1: 1 obtained by γ-ray irradiation at a relatively high pressure of 150 atm was cyclohexanone,
It is insoluble in toluene, dioxane, tetrahydrofuran, chloroform, dimethylformamide, o-dichlorobenzene, etc., but m-
It is stated that the compound was dissolved in three kinds of solvents of cresol, o-toluidine and o-chlorophenol under heat. Japanese Patent Sho 40-
No. 25268, the above-mentioned Textile Research Institute Annual Report, No. 13
Regarding the solubility of the polyketone in a solvent, which is reported in the publication, it is described that it is slightly soluble in m-cresol at high temperature. That is, the copolymer by the method B has a significantly lower solubility in a solvent as the copolymerization rate of carbon monoxide increases, that is, the higher the alternating copolymerizability of ethylene and carbon monoxide increases, and at a low temperature, It will be understood that it will become completely insoluble in the solvent.

Regarding the synthesis method by the C method, for example, Journal of Organometallic Chemistry (J. Organomet. Chem.), Volume 417,
235 (1991) and Journal of Polymer Science (J. Polym. Sci.) Part A (Part A), Polymer Chemistry (Poly).
m. Chem. ), 1992, Vol. 30, p. 2735, the latter is a common copolymer polyketone which is soluble in m-cresol, hexafluoroisopropanol, trifluoroacetic acid and trichloroacetic acid, It is described that it does not dissolve in an organic solvent.
In addition, the American Chemical Society Journal (J. Am. Chem. So
c. ), 104, 3520 (1982), alternating copolymers of ethylene and carbon monoxide are described as being substantially insoluble in common organic solvents.

Next, a method for producing a polyalcohol by reducing the polyketones synthesized by the method A, the method B and the method C with hydrogen in the presence of a catalyst in a solvent will be described. A reduction method using a polyketone synthesized by the method A as a raw material is described in US Pat. No. 2,495,292 and British Patent 598,
145, JP-A-1-149828, JP-A-5-339367, and JP-A-6-49203.
No., published in Japanese Unexamined Patent Publication No.

The method disclosed in US Pat. No. 2,495,292 uses a polyketone having a copolymerization ratio of ethylene and carbon monoxide of 1.3 to 45: 1 with dioxane as a solvent. The method disclosed in British Patent No. 598,145 describes a hydrocarbon solvent and dioxane,
Preferably, 1,4-dioxane is used, and the copolymerization ratio of ethylene and carbon monoxide is 4 in the examples.
For polyketone of 5: 1, decahydronaphthalene has a copolymerization ratio of ethylene and carbon monoxide of 1.3 to 1.
Dioxane is used for the 7: 1 polyketone. JP-A-1-149828 discloses the use of an aliphatic alcohol having 1 to 6 carbon atoms and / or diethylene glycol for a polyketone having a carbonyl group content of 1 to 50 equivalent%, and JP-A-5-339367. Also, Japanese Patent Application Laid-Open No. 6-49203 discloses use of ethers or a mixed solvent mainly containing polyketone having a carbonyl group content of 1 to 50 equivalent%. Regarding the synthesis of a copolymer of two or more kinds of ethylene-based olefins and carbon monoxide, Japanese Patent Application Laid-Open No. HEI-2: 2
The content of the carbonyl group is 1 to 5 in JP-A-232228.
0 equivalent%, CH ₂ CH ₂ group is 30 to 49 equivalent%, CH 2
With respect to the polyketone having 20 to 1 equivalent% of (CH ₃ ) CH ₂ groups, examples using at least one solvent selected from methanol, cyclohexanol and diethylene glycol are disclosed.

Although a hydrogen reduction method using a polyketone synthesized by the method B as a raw material and a catalyst is not known, Japanese Patent Publication No. 40-25268 and European Polymer Journal (Eur. Polym. J.), vol. 9, 669. Page (1973) discloses a method of reducing polyketones with sodium borohydride in a suspension in methanol.

Regarding the alternating copolymerized polyketone synthesized by the method C, hexafluoroisopropanol or alcohol, ether or alcohol is used in which a catalyst composition obtained by the reaction of a metal hydride and a nickel compound is disclosed in JP-A-1-204929. A hydrogen reduction method using ether is disclosed.

[0011]

[Patent Document 1] Japanese Patent Application Laid-Open No. 1-14982
As described in JP-A No. 8 and JP-A-5-339367, in order to impart a high gas barrier property to a polyalcohol obtained by reducing a polyketone, the alcohol content in the polymer is increased. Are considered necessary. For this purpose, it is necessary to use a polyketone having a high carbon monoxide copolymerization ratio as a raw material and to suppress the formation of a tetrahydrofuran ring which is a byproduct of the reduction reaction. This tetrahydrofuran ring is derived from the hemiacetal that is generated when the polyketone is partially reduced and a carbonyl group and a hydroxyl group coexist, and when the polyketone is not dissolved in a solvent, the polyketone and the reducing agent or reduction catalyst It is presumed that the tetrahydrofuran ring is likely to be generated because contact is suppressed.

However, US Pat. No. 2,495,292, British Patent No. 598,145, and JP-A No. 1-11, which relate to hydrogenation of a polyketone polymerized by the method A.
49928, JP-A-5-339367, JP-A-6-49203, and JP-A-2-23222.
The method described in Japanese Patent No. 8 has a problem in applying it to hydrogenation of a poorly soluble polyketone synthesized by Method B or Method C. The method using dioxane as a solvent described in U.S. Pat. No. 2,495,292 and British Patent 598,145 is disclosed in JP-A-1-14982.
In JP-A-8, it was additionally tested as Comparative Example 1, and it was found that 17% of the tetrahydrofuran ring was by-produced. The methods described in JP-A-1-149828, JP-A-5-339367 and JP-A-6-49203 are all methods applied only to the polyketone synthesized by Method A, and will be described later. As shown in Comparative Examples 1 to 3, it was found that it cannot be applied to the polyketone synthesized by the C method, or even if it can be applied, the production rate of the tetrahydrofuran ring is high and it is not practical. JP-A-2-232228
The method described in the publication relates to a ternary polyketone composed of ethylene, propylene and carbon monoxide. As shown in Comparative Example 4, by mixing propylene, the regularity of the molecular structure is disturbed and the solubility in the solvent is improved. Therefore, this solvent system is used as it is with ethylene having a high carbon monoxide copolymerization rate. It cannot be applied to polyketones composed of carbon oxide.

The polyketone synthesized by Method B has never been attempted to undergo hydrogen reduction using a catalyst. A hydrogen reduction method using a catalyst composition obtained by the reaction of a metal hydride of an alternating copolymerized polyketone synthesized by Method C and a nickel compound is described in JP-A-1-204929, and hexafluoroisopropanol or alcohol, ether. Or it is said that alcohol ether is used. However, as described in Example 9, the hydrogen reduction method is not practical because 50% of the carbonyl groups are not reduced and only about 10% of the hydroxyl groups are produced. .

Therefore, an object of the present invention is to find a solvent which dissolves polyketone having a high copolymerization ratio of carbon monoxide including alternating copolymerized polyketone, which is produced by the A method, the B method or the C method. By carrying out a reduction reaction in a polymer, a polyalcohol having a high gas barrier property is synthesized, in which the contact between the polyketone and the catalyst is promoted and the formation of the tetrahydrofuran ring is suppressed to increase the alcohol content in the polymer. To provide a method.

[0015]

According to the present invention, there is provided a method for producing a polyalcohol by hydrogen-reducing a polyketone obtained by copolymerizing an olefin mainly composed of ethylene and carbon monoxide in the presence of a catalyst. The above object can be achieved by providing a method for producing a polyalcohol, which comprises performing the reduction reaction in a sulfolane or a solvent mainly containing sulfolane. As a result of conducting a search for a solvent that dissolves the alternating copolymerized polyketone obtained by the method C, which was said to be insoluble in a general organic solvent as described above, the present inventors surprisingly found that Sulfolane or a mixed solvent composed mainly of sulfolane that can be used on an industrial scale has excellent solubility, hydrogen reduction occurs rapidly in the solvent, and the selectivity is high, and further the above alternating copolymer. It was found that polyalcohol can be produced not only from the copolymer obtained by the method A or the method B, but the present invention has been completed.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material for producing a polyalcohol in the present invention is a polyketone obtained by copolymerizing an olefin mainly containing ethylene and carbon monoxide. This polyketone is obtained, for example, by radically copolymerizing ethylene and carbon monoxide, or two or more kinds of olefins mainly composed of ethylene and carbon monoxide, and as a known method, US Pat. No. 2,495,286. Description, JP-A-53-128690 and JP-A-53-128
The method disclosed in Japanese Patent No. 691 is cited. Further, regarding the method for producing an alternating copolymer having a high carbon monoxide copolymerization rate, for example, an alternating copolymer of ethylene and carbon monoxide,
Alternatively, a method for producing an alternating copolymer of two or more olefins mainly composed of ethylene and carbon monoxide with a catalyst containing a transition metal compound as a component is disclosed in JP-A-59-197427 and JP-A-61-91226. Japanese Patent Laid-Open No. Sho 62-2
No. 32434, No. 62-53332, No. 63-3025, and No. 63-105031.
JP-A-63-132937, JP-A-1-
149829 and Japanese Patent Laid-Open No. 2-67319. As the olefin other than ethylene, any olefin copolymerizable by the above method can be used, and propylene, 1-butene, 1-octene, isobutene, butadiene, 1,7-octadiene, vinyl acetate, styrene, acrylic acid can be used. Examples thereof include methyl, methyl methacrylate and N-vinylpyrrolidone. The polymerization ratio of ethylene and an olefin other than ethylene is not particularly limited as long as ethylene is 50 mol% or more. The present invention is not limited in any way by the method for producing the above polyketone as a raw material and its carbon monoxide copolymerization rate, in order to obtain a polyalcohol having a high hydroxyl group content, the carbon monoxide copolymerization rate is Copolymer in the range of 49 to 60 equivalent%, preferably in the range of 49 to 50 equivalent%, more preferably alternating copolymer, even more preferably alternating copolymerization with a catalyst containing a transition metal compound as a component. The prepared polyketone is a suitable raw material.

As the hydrogen reduction catalyst, a heterogeneous or homogeneous catalyst generally used in hydrogenation reaction can be used. Examples of heterogeneous catalysts are Raney nickel, nickel metal, or nickel catalysts supported on one or more carriers selected from diatomaceous earth, silica, alumina, etc .; Raney cobalt, cobalt metal, or diatomaceous earth, silica, Cobalt catalyst supported on one or more carriers selected from alumina and the like; Adkins-type copper chromium to which Raney copper, copper metal, and, if necessary, one or more promoter components such as manganese and barium are added. Catalysts and other catalysts mainly composed of copper oxides; ruthenium catalysts supported on ruthenium metal, ruthenium oxide, or one or more carriers selected from diatomaceous earth, silica, alumina, carbon and the like;
Palladium metal, palladium oxide, or a palladium catalyst supported on one or more carriers selected from diatomaceous earth, silica, alumina, carbon, etc .; from rhodium metal, rhodium oxide, diatomaceous earth, silica, alumina, carbon, etc. Examples thereof include a rhodium catalyst supported on one or more selected carriers. On the other hand, examples of the homogeneous catalyst include ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium, dihydridotetrakis (triphenylphosphine) ruthenium, and ruthenium dodecacarbonyl; and rhodium complexes such as chlorotris (triphenylphosphine) rhodium. be able to. In any case, an alkali metal salt, an alkaline earth metal salt, an amine, or the like is added as necessary for improving the activity, or, for example, iron,
It can be modified with other metals or metal compounds such as manganese, rhenium and molybdenum. The amount of the catalyst used varies depending on the type of the catalyst used, but is 0.0001 to 50% by weight, preferably 0.001 to 5% by weight, based on the mixture of the raw material polyketone and the solvent. If the amount of the catalyst is less than 0.0001% by weight, it is disadvantageous in terms of reaction time, and if it is more than 50% by weight, it is disadvantageous in terms of cost and recovery operation.

The present invention is characterized in that sulfolane or a mixed solvent mainly containing sulfolane is used as a solvent for the hydrogen reduction reaction. As components of the mixed solvent mainly containing sulfolane, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, octyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol; tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol Ethers such as dimethyl ether; ethylene glycol monomethyl ether,
Diol monoethers such as diethylene glycol monomethyl ether; and the like. A desirable mixed solvent is water. The mixing ratio is arbitrary in the range of 50% by weight or more of sulfolane, but preferably sulfolane /
The ratio of water is 100/0 to 60/40. Similarly, one or more other mixed solvents may also be used as sulfolane 5
It can be used by arbitrarily mixing it in the range of 0% by weight or more. The amount of the solvent used is 0.1 to 80% by weight, preferably 1 to 50% by weight, particularly preferably 5 to 5% by weight as the concentration of the raw material polyketone.
It is 20% by weight. If the concentration is higher than 80% by weight, the solution viscosity becomes high, so that sufficient stirring becomes difficult and
If it is less than wt%, it is economically disadvantageous in terms of reaction efficiency and solvent recovery.

The reaction temperature is 30 to 300 ° C., preferably 1
The temperature is from 00 to 250 ° C, particularly preferably from 150 to 200 ° C. If the temperature is lower than 30 ° C, the reaction rate will be 30%.
If the temperature is higher than 0 ° C, it is disadvantageous in terms of selectivity. The reaction is carried out in a hydrogen atmosphere or under pressure, but an inert gas such as nitrogen or argon may coexist. Reaction pressure is 1-5
The pressure is 00 atm, preferably 20 to 300 atm, particularly preferably 50 to 200 atm. If the pressure is lower than 1 atm, it is disadvantageous in the reaction rate, and if it is higher than 500 atm, it is disadvantageous in terms of equipment and operating cost. In addition, hydrogen may be added so as to replenish the hydrogen consumed in the reaction, or the reaction may be performed while flowing hydrogen at all times. The reaction can be carried out by any of batch method, semi-continuous method and continuous method. The catalyst may be dispersed in a stirring tank, or a catalyst-immobilized reaction system such as a fixed bed may be used.

The polyalcohol thus obtained is separated, extracted, after the catalyst is removed from the reaction mixture by an ordinary separation means such as centrifugation, filtration, adsorption, extraction, etc., if necessary. It can be separated from the solvent by an operation such as evaporation of the solvent. Further, if necessary, the polyalcohol can be purified by general purification means, for example, reprecipitation, extraction and washing.

[0021]

Next, the method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

EXAMPLE 1 3 g of an alternating copolymer of ethylene and carbon monoxide, 1.2 g of Raney cobalt as a hydrogenation catalyst, and sulfolane and water as a reaction solvent were placed in a 100 ml stainless steel autoclave equipped with a stirrer. Mixture (volume ratio 80/2
0) 30 ml was charged and the reactor was sealed. After the inside of the system was replaced with hydrogen gas at room temperature, hydrogen was injected to 100 atm. While stirring the inside of the autoclave, the autoclave was heated until the internal temperature reached 150 ° C., after which hydrogen was added and heating and stirring was continued for 15 hours at a total pressure of 150 atm. After the reaction was completed, the reactor was cooled and the pressure was released, and then the reactor was opened and the contents were collected. After removing the catalyst, the reaction solution was dropped into acetone to obtain a white solid. The yield based on the raw material polyketone was 90%. Structural analysis of the product by NMR spectrum analysis revealed that the conversion rate of the carbonyl group was 100% and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 92/8.

Example 2 Reaction was carried out in the same manner as in Example 1 except that the mixture of sulfolane and water (volume ratio 80/20) was replaced with the mixture of sulfolane and water (volume ratio 90/10). I went. The yield of the obtained white solid based on the raw material polyketone was 81%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 94/6. there were.

Example 3 0.5 g of an alternating copolymer of ethylene and carbon monoxide was placed in a stainless steel autoclave equipped with a stirrer and having a volume of 100 ml.
g, Raney cobalt 1.0 g as a hydrogenation catalyst, and sulfolane 50 ml as a reaction solvent were charged, and the reactor was sealed. After the inside of the system was replaced with hydrogen gas at room temperature, hydrogen was injected to 100 atm. While stirring the inside of the autoclave, heat the autoclave until the internal temperature reaches 180 ° C,
After that, hydrogen was added and heating and stirring was continued at a total pressure of 150 atm for 15 hours. After completion of the reaction, after cooling the reactor and releasing the pressure,
The reactor was opened and the contents were collected. After removing the catalyst, the solvent was partially removed from the reaction solution under reduced pressure. The obtained concentrated liquid was added dropwise to acetone to obtain a white solid. The yield based on the raw material polyketone was 81%. When the structure of the product was analyzed by NMR spectrum analysis, the conversion rate of the carbonyl group was 100%, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 94/6.

Example 4 Instead of the alternating copolymer of ethylene and carbon monoxide, an alternating copolymer of ethylene and propylene and carbon monoxide (composition ratio 47/3/50) was used as a raw material, and the reaction temperature was changed. 180
The reaction was carried out in the same manner as in Example 3 except that the temperature was changed to 150 ° C. The yield of the obtained white solid with respect to the raw material polyketone was 85%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and CH (O
The ratio of H) structure to tetrahydrofuran ring structure is 94 /
It was 6.

Example 5 Instead of the alternating copolymer of ethylene and carbon monoxide, an alternating copolymer of ethylene and 1-butene and carbon monoxide (composition ratio 47/3/50) was used as a raw material to carry out the reaction. Temperature 180
The reaction was carried out in the same manner as in Example 3 except that the temperature was changed to 150 ° C. The yield of the obtained white solid with respect to the raw material polyketone was 83%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and CH (O
The ratio of H) structure to tetrahydrofuran ring structure is 94 /
It was 6.

Example 6 Example 3 was repeated except that copper chromium oxide modified with manganese and barium was used as a catalyst instead of Raney cobalt.
The reaction was performed by the same operation as. The yield of the obtained white solid based on the raw material polyketone was 80%.
From the spectrum analysis, the conversion rate of the carbonyl group was 100%, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 91/9.

Example 7 The reaction was carried out in the same manner as in Example 3 except that ruthenium supported on γ-alumina (supported amount: 5% by weight) was used as a catalyst instead of Raney cobalt. The yield of the obtained white solid based on the raw material polyketone was 75%.
From the R spectrum analysis, the conversion rate of carbonyl group is 100%
And the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 90/10.

Example 8 Instead of an alternating copolymer of ethylene and carbon monoxide, a copolymer of ethylene and carbon monoxide having a carbon monoxide copolymerization rate of 45 equivalent% was used as a raw material, and sulfolane was used as a solvent. Instead of a mixture of sulfolane and water (volume ratio 90/1
The reaction was carried out by the same procedure as in Example 3 except that 0) was used. The yield of the obtained white solid with respect to the raw material polyketone was 90%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 93/7. there were.

Example 9 Example 9 was carried out except that a copolymer of ethylene and carbon monoxide having a carbon monoxide copolymerization rate of 48 equivalent% was used as a raw material instead of the alternating copolymer of ethylene and carbon monoxide. The reaction was carried out by the same operation as in Example 3. The yield of the obtained white solid with respect to the raw material polyketone was 93%, and the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis.
The ratio of the H (OH) structure to the tetrahydrofuran ring structure was 92/8.

Example 10 Instead of the alternating copolymer of ethylene and carbon monoxide, a copolymer of ethylene and carbon monoxide having a carbon monoxide copolymerization rate of 49 equivalent% was used as a raw material, and sulfolane was used as a solvent. Instead of a mixture of sulfolane and water (volume ratio 80/2
The reaction was carried out by the same procedure as in Example 3 except that 0) was used. The yield of the obtained white solid with respect to the raw material polyketone was 95%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 92/8. there were.

Example 11 Example 11 was carried out except that a copolymer of ethylene and carbon monoxide having a carbon monoxide copolymerization rate of 55 equivalent% was used as a raw material instead of the alternating copolymer of ethylene and carbon monoxide. The reaction was carried out by the same operation as in Example 3. The yield of the obtained white solid with respect to the raw material polyketone was 95%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and C
The ratio of the H (OH) structure to the tetrahydrofuran ring structure was 90/10.

Example 12 Instead of the alternating copolymer of ethylene and carbon monoxide, a copolymer of ethylene and propylene and carbon monoxide (composition ratio 49
/ 3/48) was used as the raw material, and the reaction was carried out by the same operation as in Example 3 except that the reaction temperature was changed from 180 ° C to 150 ° C. The yield of the obtained white solid with respect to the raw material polyketone was 82%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and CH (OH)
The ratio of the structure to the tetrahydrofuran ring structure was 94/6.

Example 13 Instead of the alternating copolymer of ethylene and carbon monoxide, a copolymer of ethylene and 1-butene and carbon monoxide (composition ratio 47
/ 5/48) as the raw material, the reaction temperature was changed from 180 ° C. to 150 ° C., and the mixture of sulfolane and water (volume ratio 90/10) was used instead of sulfolane as the solvent. The reaction was performed by the same operation. The yield of the obtained white solid with respect to the raw material polyketone was 80%, the conversion rate of the carbonyl group was 100% from the NMR spectrum analysis, and the ratio of the CH (OH) structure to the tetrahydrofuran ring structure was 94/6. there were.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that cyclohexanol was used as the solvent instead of the mixture of sulfolane and water (volume ratio 80/20). The weight of the obtained white solid was 2.55 g, but it was confirmed from the result of NMR spectrum analysis that this was not the polyalcohol but the unreacted starting polyketone.

Comparative Example 2 Diethylene glycol was used as a solvent in place of the mixture of sulfolane and water (volume ratio 80/20), and the reaction temperature was 150.
The reaction was carried out by the same operation as in Example 1 except that the temperature was changed to 180 ° C. The yield of the obtained white solid based on the raw material polyketone was 70%, and the ratio of the CH (OH) structure and the tetrahydrofuran ring structure was 60/40 based on the NMR spectrum analysis.

Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that 1,3-dioxolane was used as the solvent instead of the mixture of sulfolane and water (volume ratio 80/20). The weight of the obtained white solid was 2.49 g, but it was confirmed from the result of NMR spectrum analysis that this was not a polyalcohol but an unreacted raw material polyketone.

Comparative Example 4 Reaction was carried out in the same manner as in Example 1 except that the solvent was a mixture of methanol and water (volume ratio 70/30) instead of the mixture of sulfolane and water (volume ratio 80/20). I went. The weight of the obtained white solid was 2.49 g, but it was confirmed from the result of NMR spectrum analysis that this was not a polyalcohol but an unreacted raw material polyketone.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, in the reduction of a polyketone obtained by copolymerizing an olefin mainly containing ethylene with carbon monoxide in the presence of a hydrogen reduction catalyst, an alternating carbon monoxide having a high copolymerization rate is obtained. By making it possible to use the copolymerized polyketone as a raw material and improving the selectivity in the hydrogen reduction reaction, it is possible to obtain a polyalcohol having a low tetrahydrofuran ring content and thus a high hydroxyl group content and a high gas barrier property. It can be manufactured.

Claims (11)

[Claims] 1. A method for producing a polyalcohol by reducing a polyketone obtained by copolymerizing an olefin containing ethylene as a main component and carbon monoxide in the presence of a hydrogen reduction catalyst, wherein sulfolane or the main component is used. A method for producing a polyalcohol, which comprises performing the reduction reaction in a solvent. 2. The method for producing a polyalcohol according to claim 1, wherein the olefin containing ethylene as a main component is ethylene. 3. The method for producing a polyalcohol according to claim 2, wherein the copolymerization ratio of carbon monoxide in the polyketone is 49 to 60 equivalent%. 4. The method for producing a polyalcohol according to claim 3, wherein the copolymerization ratio of carbon monoxide in the polyketone is 49 to 50 equivalent%. 5. The method for producing a polyalcohol according to claim 4, wherein the polyketone is an alternating copolymer. 6. The method for producing a polyalcohol according to claim 5, wherein the polyketone is an alternating copolymer polymerized by a catalyst containing a transition metal compound as a component. 7. The ethylene-based olefin is ethylene or propylene.
The method for producing a polyalcohol according to 1. 8. The method for producing a polyalcohol according to claim 7, wherein the copolymerization ratio of carbon monoxide in the polyketone is 49 to 50 equivalent%. 9. The method for producing a polyalcohol according to claim 8, wherein the polyketone is an alternating copolymer. 10. The method for producing a polyalcohol according to claim 9, wherein the polyketone is an alternating copolymer polymerized by a catalyst containing a transition metal compound as a component. 11. The solvent according to claim 1, wherein the solvent is a mixture of sulfolane and water.
The method for producing a polyalcohol according to one of the items.