JPH1081745A - New polyalcohol and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyalcohol excellent in oxygen barrier and to provide a method for producing the polyalcohol. SOLUTION: An alternating copolymer of ethylene and carbon monoxide is reduced with potassium boron hydride in a mixed solvent of hexafluoroisopropanol and water at <=10 deg.C or reduced with hydrogen in the presence of a catalyst comprising a ruthenium compound, a trialkylphosphine and an acid to produce a polyalcohol composed of >=95% of a regular unit shown by the formula -CH2 -CH2 CH(OH)- and a melting point in the range of 130 deg.C to 145 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyalcohol obtained by reducing an alternating copolymerized polyketone of ethylene and carbon monoxide, and a method for producing the same. The obtained polyalcohol is useful as an oxygen-barrier resin material such as a packaging material.

[0002]

2. Description of the Related Art A polyalcohol obtained by reduction of an alternating copolymer polyketone of ethylene and carbon monoxide is
(1) European Polymer Journal (Euro
Pean Polymer Journal), Volume 9,
669 pages (1973) (hereinafter referred to as Reference (1)
Abbreviated. ) And (2) JP-A-1-204929.
(Hereinafter abbreviated as Document (2)). In the literature (1), the formula (I) is obtained by reducing an alternating copolymerized polyketone of ethylene and carbon monoxide with sodium borohydride.

[0003]

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[0004] 1,2-glycol as a heterogeneous structure having a regular unit structure of 1.23 to 1.56 mol%
Containing polyalcohol. In addition, in Example 1 of Reference (2), a linear alternating copolymer of ethylene and carbon monoxide produced using a palladium catalyst composition was prepared in a mixed solvent of hexafluoroisopropanol and ethanol at 15 to 40 ° C. Reduction with sodium borohydride at a reaction temperature in the range of from 94 to 97% of the ordered units of the formula (I),
It is stated that a polyalcohol at 17 ° C. was produced. Here, molecular impurities other than the ordered unit represented by the formula (I) are said to have a substituted 2,5-tetrahydrofuran structure. According to this document, the film-form formed from the polyalcohol exhibits a certain degree of barrier properties and is useful as a multi-layer laminate for packaging materials and containers for foods, medicines and cosmetics, which usually causes oxidative deterioration when exposed to air. Is described.

[0005]

The document (1) has no description about the use of polyalcohol. In Document (2), there is no description about data relating to the oxygen barrier property required for the above-mentioned applications, and no mention is made of the relationship between the physical properties of polyalcohol and the oxygen barrier property. An object of the present invention is to provide a novel polyalcohol which is obtained by reducing an alternating copolymerized polyketone of ethylene and carbon monoxide and has excellent oxygen barrier properties, and a method for producing the same.

[0006]

Means for Solving the Problems The present inventors diligently studied a method for reducing an alternating copolymerized polyketone of ethylene and carbon monoxide, and determined the relationship between the physical properties of the obtained polyalcohol and the oxygen barrier property. As a result, surprisingly, polyalcohols containing 95% or more of the ordered unit represented by the formula (I) and having a melting point in the range of 130 ° C. to 145 ° C. are very excellent. The inventors have found that they exhibit oxygen barrier properties, and have completed the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The alternating copolymer polyketone of ethylene and carbon monoxide as a raw material of the polyalcohol of the present invention is produced, for example, by performing a polymerization reaction using a palladium compound as a catalyst by a known method. Can be. This polymerization reaction is carried out, for example, by the Journal of American Chemical Society (Journal of Amer).
ican Chemical Society), No. 1
Volume 04, 3520 pages (1982), Journal
Of Organometallic Chemistry (Journ
al of Organometallic Chem
Istry), 417, 235 pages (1991)
It is described in.

The polyalcohol of the present invention is obtained by reducing an alternating copolymerized polyketone of ethylene and carbon monoxide.

[0009]

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It is characterized by containing 95% or more of the ordered units represented by the formula (1) and having a melting point in the range of 130 ° C. to 145 ° C. The polyalcohol of the present invention not only has excellent oxygen barrier properties, but also has a melting point of 130 ° C to 14 ° C.
Since it is between 5 ° C., common sealant materials used at a heat sealing temperature of 120 ° C. or higher, for example, ethylene-
It is possible to form a composite such as a dry laminate with a vinyl acetate copolymer, LLDPE, or the like, and is an oxygen barrier material superior to known polyalcohols having a melting point of 117 ° C.

The present inventors have found the following two methods for producing the polyalcohol of the present invention. One is to alternately copolymerize polyketone of ethylene and carbon monoxide in a mixed solvent of hexafluoroisopropyl alcohol and water using potassium borohydride in the presence of potassium hydroxide at a temperature of 10 ° C or less. The other is a method of reducing (hereinafter, referred to as a method A). The other method is to convert the same alternating copolymerized polyketone of ethylene and carbon monoxide into hydrogen in the presence of a catalyst comprising a ruthenium compound, a trialkylphosphine and an acid. This is a method of reducing (hereinafter, referred to as method B). Next, these methods will be described in order.

The production of the polyalcohol of the present invention by the method A is carried out, for example, by dissolving an alternating copolymerized polyketone of ethylene and carbon monoxide in hexafluoroisopropanol,
After adding an aqueous solution of potassium hydroxide thereto, the reaction temperature is maintained at 10 ° C. or lower, and a mixed aqueous solution of potassium borohydride and potassium hydroxide is added to the solution of the alternating copolymerized polyketone.

The amount of hexafluoroisopropanol to be used may be any as long as it dissolves the polyketone of alternating copolymerization of ethylene and carbon monoxide, which is a raw material, but is 5 to 50 parts by weight per 1 part by weight of alternating copolymerized polyketone. Is preferred. If the amount is too small, the raw material alternately copolymerized polyketone cannot be dissolved, so that the reaction does not proceed smoothly. If the amount is too large, the production efficiency deteriorates. The amount of the aqueous potassium hydroxide solution to be added to this solution is not particularly limited as long as the pH after mixing is 7 or more.
It is preferable to use a solution consisting of 1 to 0.1 part by weight and 0.01 to 0.1 part by weight of water. The amount of the potassium borohydride used as the reducing agent is preferably 1 to 5 parts by weight based on 1 part by weight of the alternating copolymerized polyketone. The amount of potassium hydroxide used is suitably from 0.1 to 1 part by weight based on 1 part by weight of potassium borohydride. The amount of water for dissolving potassium borohydride and potassium hydroxide is not particularly limited as long as it dissolves them, but 5 to 20 parts by weight per 1 part by weight of potassium borohydride is appropriate.

After completion of the reaction, an acid such as hydrochloric acid or acetic acid is added to the reaction mixture to release the polyalcohol.
It can be separated from the solvent by common separation means, for example, operations such as precipitation, extraction, and solvent evaporation. Further, if necessary, the polyalcohol can be purified by general purification means, for example, reprecipitation, extraction and washing.

The production of the polyalcohol of the present invention by the method B can be carried out, for example, by subjecting an alternating copolymerized polyketone of ethylene and carbon monoxide to hydrogen reduction in the presence of a catalyst prepared from a ruthenium compound, a trialkylphosphine and an acid. It is implemented by doing.

In the present method, a ruthenium compound represented by the general formula (I
I)

[0017]

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Wherein R is the same or different and each represents an alkyl group having 1 to 12 carbon atoms, and a catalyst comprising an acid and an acid. The ruthenium compound is not particularly limited as long as it provides a catalyst that dissolves in the reaction system, and ruthenium oxides, hydroxides, inorganic acid salts, organic acid salts, halides or complex compounds can be used. Specifically, ruthenium dioxide, ruthenium dihydroxide, ruthenium acetate, ruthenium chloride,
Dichlorobis (cyclooctadiene) ruthenium, ruthenium acetylacetonate, pentacarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridedodecacarbonylruthenium and the like. The amount of these ruthenium compounds to be used is 0.1 to 100 mg atom, preferably 0.5 to 100 mg ruthenium per mole of carbonyl group in the raw material alternating copolymerized polyketone.
10 milligram atoms. If the amount of the ruthenium compound used is too small, the reaction rate becomes slow, and if it is too large, it is economically disadvantageous from the viewpoint of catalyst cost.

General formula (II)

[0020]

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(Wherein R is the same or different and each represents an alkyl group having 1 to 12 carbon atoms). Examples of the phosphine compound represented by trimethylphosphine, triethylphosphine, tri (n-butylphosphine) and tri ( n-octyl phosphine), tri (n-dodecyl phosphine), dimethyl (n-butyl) phosphine, tri (i-propyl) phosphine, tricyclohexyl phosphine, etc., and, particularly, triethyl phosphine and tri (n-butyl phosphine). And phosphine having an n-alkyl group having 2 to 8 carbon atoms, such as tri (n-octylphosphine). The amount of the phosphine compound varies depending on the kind of the phosphine compound used, but is 1 to 10 mmol, preferably 3 to 6 mmol, per 1 mg atom of ruthenium. If the amount of the phosphine compound is too small, the polyalcohol of the present invention having a high melting point cannot be obtained. If the amount is too large, the reaction activity decreases.

As the acid to be added to the catalyst, an inorganic acid or an organic acid or a salt thereof is used. For example, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, borofluoric acid, fluorosulfonic acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, phenylphosphonic acid, paratoluenesulfonic acid, acetic acid, propionic acid, benzoic acid, etc. can give. The activity of the catalyst varies depending on the strength of the acid, and it is particularly preferable to use an acid having a pKa of 5 or less or a salt thereof. Where pK
a indicates the logarithm of the reciprocal of the acid dissociation constant measured in an aqueous solution at 25 ° C. Thus, the numerical values of typical compounds can be known. The amount of the acid used varies depending on the type and the type and amount of the organic phosphorus compound.
Mmol, preferably 0.5 to 10 mmol. If the amount of the acid or its salt is too small, sufficient catalytic activity is not exhibited, and if it is too large, the polyalcohol of the present invention having a high melting point cannot be obtained.

The solvent used in the present method is not particularly limited as long as it dissolves the catalyst generated in the reaction system and is inert to the hydrogen reduction reaction. For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, n-octyl alcohol,
Cyclohexanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether,
Alcohols such as diethylene glycol monomethyl ether; ethers such as tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; and sulfur-containing compounds such as dimethyl sulfone and sulfolane. These solvents may be used alone or in combination of two or more. A preferred solvent is sulfolane or a mixed solvent containing the same. As a component of the mixed solvent containing sulfolane, water; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, n-octyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol Alcohols such as monomethyl ether; ethers such as tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; A desirable mixed solvent is water. The mixing ratio is optional, but the ratio of sulfolane / water is 9/1 to 1/9, preferably 7/3 to 3/7. Similarly, one or more other solvents can be used in a mixture with sulfolane in an arbitrary ratio. The amount of the solvent used is 0.1 to 80% by weight as the concentration of the raw material polyketone,
It is preferably from 1 to 50% by weight, particularly preferably from 5 to 20% by weight. If the concentration is too high, the solution viscosity becomes high, so that sufficient stirring becomes difficult. If the concentration is too low, it is economically disadvantageous in terms of reaction efficiency and solvent recovery.

The reaction temperature is 30-300 ° C., preferably 1
The temperature is from 00 to 250 ° C, particularly preferably from 150 to 180 ° C. If the temperature is too low, the reaction rate is disadvantageous, and if it is too high, the selectivity is disadvantageous. The reaction is carried out under a hydrogen atmosphere at normal pressure or under pressure, but an inert gas such as nitrogen or argon may coexist. The reaction pressure is 1 to 500 atm, preferably 20 to 300 atm, particularly preferably 50 to 200 atm.
Atmospheric pressure. Too low a pressure is disadvantageous in terms of reaction rate, and too high is disadvantageous in terms of equipment and operating costs. 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, semi-continuous and continuous methods.

The polyalcohol thus obtained is removed by a general separation means, for example, if necessary, a procedure such as adsorption and extraction of the catalyst from the reaction mixture, followed by precipitation, extraction and solvent distillation. It can be separated from the solvent by the operation. Further, if necessary, the polyalcohol can be purified by general purification means, for example, reprecipitation, extraction and washing.

[0026]

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 In a 1-liter flask equipped with a stirrer, 5.0 g of an alternating copolymerized polyketone of ethylene and carbon monoxide (hereinafter sometimes abbreviated as polyketone) and 200 g of hexafluoroisopropanol were placed. The mixture was stirred to dissolve the polyketone. To this, a solution of 3.75 g of potassium hydroxide in 7.0 g of water was added, and the internal temperature was cooled to 0 to 5 ° C. 12.5 g of potassium borohydride and 3.7 of potassium hydroxide
A solution in which 5 g was dissolved in 175 g of water was added dropwise over about 2 hours. At this time, the internal temperature was kept at 10 ° C. or less. After dropping,
After stirring was continued at 10 ° C. or lower for 1 hour, acetic acid (70 ml) was added. After the solvent was distilled off under reduced pressure, the residue was sufficiently washed with water. The obtained white solid is 180m in methanol.
The solution was added dropwise to 1 liter of acetone. The white precipitate was separated by filtration and dried under reduced pressure to obtain a polyalcohol. The yield is 90% based on the raw material polyketone
Met. According to NMR analysis, the polyalcohol contains 98% of a regular unit represented by the formula (I).
C analysis revealed that its melting point was 142 ° C. Further, the oxygen transmission rate of the polyalcohol film is 0.023 cc · 20 at a temperature of 20 ° C. and a relative humidity of 65%.
μ / m ² · day · atm. Ethylene under the same conditions
The oxygen permeation rate of the vinyl alcohol copolymer (ethylene 32 mol%) film is 0.3 cc · 20 μ / m ² · day · a
tm, indicating that the polyalcohol has excellent oxygen barrier properties.

Example 2 In a stainless steel autoclave having a capacity of 300 ml and equipped with a stirrer, 16.5 g of an alternating copolymerized polyketone of ethylene and carbon monoxide, and ruthenium acetylacetonate 0.2
66 g, 0.676 g of tri (n-butylphosphine),
0.106 g of phenylphosphonic acid and 150 ml of a mixture of sulfolane and water (volume ratio 60/40) 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, the autoclave was heated until the internal temperature reached 160 ° C., and then hydrogen was added to the autoclave at a total pressure of 150 atm.
The heating and stirring were continued for 0 hours. After the completion of the reaction, the content was extracted from the reactor into acetone under hydrogen pressure. The precipitated polymer was separated by filtration, washed three times with acetone, and dried under reduced pressure to obtain a polyalcohol. The yield was 92% based on the starting polyketone. NMR analysis revealed that the polyalcohol contained 96% of the ordered unit represented by the formula (I), and its melting point was found to be 135 ° C. by DSC analysis. The oxygen transmission rate of the polyalcohol film is 0.06 cc at a temperature of 20 ° C. and a relative humidity of 65%.
・ 20 μ / m ²・ day ・ atm.

Example 3 0.810 g of tri (n-butylphosphine) was used in place of 0.676 g of tri (n-butylphosphine), and the reaction time was changed to 10 hours and 2 hours.
The reaction was performed in the same manner as in Example 2 except that the time was changed to 0 hour. The yield of the obtained polyalcohol was 90% based on the raw material alternating copolymerized polyketone. According to NMR analysis, the polyalcohol contains 97% of a regular unit represented by the formula (I).
It was found to be 1 ° C. Further, the oxygen transmission rate of the present polyalcohol film was 0.025 cc · 20 μ / m ² · day · atm at a temperature of 20 ° C. and a relative humidity of 65%.

[0030]

According to the present invention, a novel polyalcohol having excellent oxygen barrier properties can be produced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Keizo Michihata 2045-1, Sazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.

Claims (4)

[Claims] 1. A compound of formula (I) obtained by reducing an alternating copolymerized polyketone of ethylene and carbon monoxide. Contains 95% or more of the ruled unit represented by
A novel polyalcohol characterized by being in the range of 0 ° C to 145 ° C. 2. The novel polyalcohol according to claim 1, wherein the melting point is in the range from 135 ° C. to 145 ° C. 3. An alternating copolymerized polyketone of ethylene and carbon monoxide is reduced at a temperature of 10 ° C. or lower using potassium borohydride in the presence of potassium hydroxide in a mixed solvent of hexafluoroisopropanol and water. The method for producing a novel polyalcohol according to claim 1 or 2, wherein 4. The method according to claim 1, wherein the alternating copolymer polyketone of ethylene and carbon monoxide is hydrogen reduced in the presence of a catalyst prepared from a ruthenium compound, a trialkylphosphine and an acid. For producing a novel polyalcohol.