JPH0859800A - Method for producing lactone-based polyol - Google Patents

Abstract

(57) [Summary] [Structure] A polyol compound having an active hydrogen atom is used as an initiator in the presence of a tertiary amine compound having a pKa value of 11 or more and containing no active hydrogen in the molecule,
A method for producing a lactone-based polyol, which comprises subjecting a substituted or unsubstituted δ-valerolactone to ring-opening addition polymerization. [Effect] The lactone-based polyol produced according to the present invention is useful as a raw material for providing polyurethane and elastomer that are soft and have excellent hydrolysis resistance, and are useful as sheets, films, rolls, gears, solid tires, belts, hoses, Tube, packing material, anti-vibration material, shoe sole,
It can be effectively used as a resin raw material for a wide variety of uses such as sports shoes, machine parts, automobile parts, sports goods, elastic fibers, artificial leather, fiber treatment agents, adhesives, coating agents, binders and paints.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lactone polyol by ring-opening polymerization of lactone.

[0002]

Polyester polyols having hydroxyl groups at both ends obtained by ring-opening polymerization of substituted or unsubstituted δ-valerolactone using a compound having two active hydrogen atoms as an initiator are ε-caprolactone. Polycaprolactone obtained by ring-opening polymerization of
Like the polyester polyol obtained by polycondensation of dicarboxylic acid and diol, it is a useful compound as a raw material for polyurethane, polyester elastomer and the like.

Among them, poly (β-methyl-δ-obtained by ring-opening polymerization of β-methyl-δ-valerolactone
Valerolactone) polyol (hereinafter abbreviated as PMVL) is a liquid having fluidity at room temperature, and is far superior to other polyester polyols in terms of easiness of handling. It is also useful as a raw material for providing polyurethane and polyester elastomers that are soft and have excellent hydrolysis resistance, and are produced on an industrial scale.

The reaction to obtain a lactone-based polyol by ring-opening addition of a substituted or unsubstituted δ-valerolactone to a compound having an active hydrogen atom such as polyether polyol, polyester polyol, polycarbonate polyol is usually sulfuric acid, Mineral acids such as phosphoric acid, alkali metals such as lithium, sodium and potassium, hydroxides, carbonates and bicarbonates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium carbonate and calcium oxide, n-butyllithium Alkyl metal compounds such as p-toluenesulfonic acid, acidic ion exchange resins, solid acids such as activated clay, tetraisopropyl titanate, tetrabutyl titanate, tetraphenyl tin,
It is carried out in the presence of a catalyst such as an organic metal such as tetraoctyl tin or diphenyl tin dilaurate. (JP-A-60-5
No. 5026, JP-A-64-85968) Generally, when the produced polymer is thermally stable, there is no problem even if the catalyst used during the reaction remains. However, the lactone-based polyol obtained according to the above-mentioned known method is relatively thermodynamically unstable because it contains a substituted or unsubstituted δ-valerolactone in the molecule, and therefore, it was used in the reaction. If the catalyst remains, the stability may be deteriorated during storage, or an undesired side reaction may be caused when the polymeric material is subsequently produced using the lactone-based polyol. In order to prevent this, it is conceivable to remove the catalyst substance by washing the obtained lactone-based polyol with water or the like, but it is usually not easy to remove the catalyst component.

When a lactone-based polyol is produced using a solid acid catalyst such as an acidic ion exchange resin or activated clay, the catalyst can be easily removed by filtration.
Since it is difficult to avoid mixing impurities that elute from a small amount of solid acid catalyst, etc., the stability of the lactone-based polyol may be impaired during storage, or it may be desirable when a polymer substance is produced by a subsequent polymerization reaction. Or cause no side reaction.

Therefore, for example, JP-A-60-55026
In the case of producing PMVL using the catalysts described in JP-A No. 64-85968, etc.
After carrying out the reaction using a solvent which dissolves MVL and is immiscible with water, the reaction solution is washed several times with water, or the reaction is carried out in the absence of the solvent, and the solvent is added to the reaction solution and then water is added. A method is employed in which the solvent and water are removed, preferably by washing under pressure several times, followed by liquid separation.

[0007]

However, according to the studies by the present inventors, a substituted or unsubstituted δ-valerolactone is subjected to ring-opening addition using a polyether polyol such as polypropylene glycol or polytetramethylene glycol as an initiator. It was found that it is very difficult to remove the catalyst from the lactone-based polyol obtained by washing with water.

Further, the above-mentioned method requires a dedicated facility for removing the catalytic substance, or has a disadvantage that when the catalytic substance is removed, it is necessary to treat a huge amount of waste water having a high COD value. have. Moreover, this method requires facilities to recover, purify and store the solvent used.

The advantage of the ring-opening addition polymer is that unlike the polycondensate, water is not produced as a by-product during the production, so that the amount of water contained in the product is small and the dehydration operation during use becomes unnecessary. However, washing the product with water also eliminates this advantage.

An object of the present invention is to solve these problems and propose a method for industrially producing a polymer from a substituted or unsubstituted δ-valerolactone.

[0011]

Conventionally, when a ring-opening addition reaction of substituted or unsubstituted δ-valerolactone is carried out using a tertiary amine compound catalyst such as pyridine or quinoline, the reaction is It was supposed not to happen. (Lecture Polymerization Theory 7, Takeo Saegusa) As a result of intensive investigations by the present inventors, in the case of using a tertiary amine compound having a pKa value of 11 or more and having no active hydrogen in the molecule, Not only does the ring-opening addition reaction of the substituted or unsubstituted δ-valerolactone proceed at an industrially satisfactory reaction rate, but it is also distilled from a polymer containing the substituted or unsubstituted δ-valerolactone as a component. As a result, they have found that the catalyst component can be easily removed, and have completed the present invention.

That is, according to the present invention, in the presence of a tertiary amine compound having a pKa value of 11 or more and having no active hydrogen in the molecule, active hydrogen atoms such as polyether polyol, polyester polyol and polycarbonate polyol are added. It is a method for producing a lactone-based polyol by ring-opening addition polymerization of δ-valerolactone which may have a substituent, using the possessed polyol compound as an initiator.

Specific examples of the tertiary amine compound used in the present invention include 1,8-diazabicyclo (5.4.0) undecene-7. The preferred amount of the tertiary amine compound used is 0.001 to 1 based on the weight of the substituted or unsubstituted δ-valerolactone.
It is 0% by weight, preferably 0.01 to 3% by weight.

In the present invention, specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, ethylene oxide and tetrahydrofuran. And a block or random copolymer of the above.

Further, as the polyester polyol, specifically, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,4
-Butanediol, 1,3-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,
Saturated diols such as 9-nonanediol, 1,10-decanediol and neopentyl glycol and saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and cyclohexanedicarboxylic acid Examples thereof include those obtained by condensation polymerization of alicyclic dicarboxylic acid, phthalic acid, terephthalic acid, dicarboxylic acid such as aromatic dicarboxylic acid such as isophthalic acid, and the like.

Further, as the polycarbonate polyol, specifically, polytetramethylene carbonate,
Examples thereof include polypentamethylene carbonate, polyhexamethylene carbonate, polycyclohexanedimethylene carbonate, polynonamethylene carbonate and the like.

As the polyol compound having an active hydrogen atom used in the present invention, there are polyether polyol, polyester polyol, polycarbonate polyol and the like, and one kind or two or more kinds thereof can be used.

The δ-valerolactone used in the present invention may be substituted, and examples of the substituent in this case are lower alkyl groups such as methyl group and ethyl group. Specific examples of δ-valerolactone having these substituents include β-methyl-δ-valerolactone and β-ethyl-
δ-valerolactone, γ, γ-dimethyl-δ-valerolactone and the like.

In the method of the present invention, the molecular weight of the resulting polymer can be arbitrarily adjusted by adjusting the molar ratio of the substituted or unsubstituted δ-valerolactone to the polyol compound having an active hydrogen atom. Is.

The reaction according to the present invention is usually carried out in an atmosphere of an inert gas such as nitrogen, helium or argon. In carrying out this reaction, it is desirable that the substituted or unsubstituted δ-valerolactone, polyether polyol, polyester polyol, polycarbonate polyol and the like have the water content lowered as much as possible. Similarly, it is desirable that the water content of the tertiary amine compound is as low as possible.

This reaction is usually carried out in the presence or absence of a solvent at a temperature of -20 ° C or higher.
Valerolactone is not always thermally stable, so it is better to select a temperature condition that does not exceed 200 ° C.
A more preferable temperature condition is 20 ° C to 80 ° C.

This reaction is usually carried out without using a solvent, but it can also be carried out using a solvent. Solvents that can be used for this purpose are organic solvents that do not have active hydrogen, specifically, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran,
Examples thereof include ethers such as dioxane, and halogenated hydrocarbons such as dichloromethane and chloroform. When these solvents are also used, it is desirable to reduce the water content as much as possible prior to their use. In the present invention, the reaction mixture obtained by the reaction can be used as it is as a raw material for the next reaction, but the catalyst and the unreacted substituted or unsubstituted δ-valerolactone are removed to give a polyether polyol or polyester polyol. It is desirable to purify and use an adduct of δ-valerolactone which is substituted or unsubstituted with a polycarbonate polyol or the like. The treatment of this reaction mixture is, for example,
This can be done by treating the reaction mixture as it is under a reduced pressure condition using a thin film evaporator. The unreacted substituted or unsubstituted δ-valerolactone and the tertiary amine compound recovered during the treatment can be directly fed to the next polymerization system.

The method for producing a lactone-based polyol according to the present invention is widely applicable not only when the initiator is a polyether polyol, polyester polyol or polycarbonate polyol but also to a compound having an active hydrogen atom such as a hydroxyl group and an amino group. .

The lactone polyol produced by the present invention is a polyether polyol used as an initiator,
It reduces the crystallization tendency of polyester polyols, polycarbonate polyols and the like. It is also useful as a raw material for providing polyurethanes and elastomers that are soft and have excellent hydrolysis resistance, and include sheets, films, rolls, gears, solid tires, belts, hoses, tubes, packing materials, vibration damping materials, and soles. It can be effectively used as a resin raw material for a wide variety of uses such as sports shoes, machine parts, automobile parts, sports goods, elastic fibers, artificial leather, fiber treatment agents, adhesives, coating agents, binders and paints.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 A separable flask having a content of 500 ml equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and the dehydrated polytetramethylene glycol (molecular weight: 1000)
100 g and 245 g of previously dehydrated β-methyl-δ-valerolactone were charged and immersed in a bath at 30 ° C. with stirring under a nitrogen atmosphere. Thereafter, 2.5 g of 1,8-diazabicyclo (5.4.0) undecene-7 (manufactured by San-Apro), which had been dehydrated in advance from a dropping funnel, was immediately added. After the dropping was completed, stirring was continued at 30 ° C to 35 ° C for 36 hours. The reaction mixture became a viscous liquid, and β-methyl-δ-valerolactone in this polymer was analyzed by liquid chromatography and found to be 41.7 g.

The obtained polymer was treated with a wiper type thin film distillation apparatus under the conditions of 180 ° C. and 1 torr or less to obtain 297 g of a colorless and transparent viscous liquid.

When measured by 1 H-NMR, its chemical shift confirmed that this liquid was a lactone-based polyol obtained by ring-opening addition polymerization of β-methyl-δ-valerolactone with polytetramethylene glycol (molecular weight 1000). Was done.

This product has a hydroxyl value of 36.5 mg KOH
/ G and the acid value was 0.3 mgKOH / g, the molecular weight was 3050.

Further, from the elemental analysis result, the residual N content is 0.
It was 02%.

Example 2 A separable flask having a content of 500 ml equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then the dehydrated polyhexamethylene carbonate (molecular weight: 750)
150 g and 340 g of previously dehydrated β-methyl-δ-valerolactone were charged and immersed in a bath at 60 ° C. with stirring under a nitrogen atmosphere. After that, 2.7 g of 1,8-diazabicyclo (5.4.0) undecene-7 (manufactured by San-Apro Ltd.) dehydrated in advance from a dropping funnel was quickly added. After the dropping was completed, stirring was continued at 60 ° C. to 65 ° C. for 24 hours. The reaction mixture became a viscous liquid, and β-methyl-δ-valerolactone in this polymer was analyzed by liquid chromatography and found to be 75.3 g.

The obtained polymer was treated with a wiper type thin film distillation apparatus under the conditions of 180 ° C. and 1 torr or less to obtain 410 g of a colorless and transparent viscous liquid.

When measured by 1 H-NMR, its chemical shift confirmed that this liquid was a lactone-based polyol obtained by ring-opening addition polymerization of β-methyl-δ-valerolactone with polyhexamethylene carbonate (molecular weight 750). Was done.

This product has a hydroxyl value of 53.6 mg KOH
/ G and the acid value was 0.3 mgKOH / g, the molecular weight was 2082.

Furthermore, from the elemental analysis results, the residual N content was 0.
It was 02%.

Example 3 A separable flask having a content of 500 ml equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then dehydrated in advance to the flask. Adipate (Molecular weight 80
0) 100 g and 350 g of previously dehydrated δ-valerolactone were charged, and the mixture was stirred under a nitrogen atmosphere while stirring 45
Immerse in a bath at ℃. Then, 3 g of 1,8-diazabicyclo (5.4.
0) Undecene-7 (manufactured by San-Apro) was immediately added. After completion of dropping, stirring was further continued at 45 ° C. for 36 hours. The reaction mixture became a viscous liquid, and the δ
-Valerolactone was analyzed by liquid chromatography and found to be 68.5 g.

The obtained polymer was treated with a wiper type thin film distillation apparatus under the conditions of 180 ° C. and 1 torr or less to obtain 376 g of a colorless and transparent viscous liquid.

When measured by 1 H-NMR, its chemical shift confirmed that this liquid was a lactone-based polyol obtained by ring-opening addition polymerization of 1,9-nonanediol adipate (molecular weight 800) with δ-valerolactone. It was

This product has a hydroxyl value of 36.3 mg KOH
/ G and acid value 0.5 mgKOH / g, the molecular weight was 3050.

Further, from the elemental analysis result, the residual N content was 0.
It was 02%.

Comparative Example 1 A separable flask having a content of 500 ml equipped with a thermometer, a dropping funnel, a stirrer, and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and the dehydrated polytetramethylene glycol (molecular weight: 1000)
120 g and 300 g of previously dehydrated β-methyl-δ-valerolactone were charged and immersed in a bath at 60 ° C. with stirring under a nitrogen atmosphere. Thereafter, 2 ml of a 25% n-butyllithium hexane solution (manufactured by Nippon Alkyl Aluminum Co., Ltd.) was quickly added from the dropping funnel. After the dropping, exotherm was observed, but after the internal temperature reached 60 ° C to 65 ° C, stirring was continued for further 5 hours.

The reaction mixture became a viscous liquid, and β-methyl-δ-valerolactone in this polymer was analyzed by liquid chromatography and found to be 54 g.

To the obtained polymerization liquid, 600 ml of toluene was added and washed with 250 ml of water 5 times.

The COD of the wastewater generated during this operation is 172
Since it was as high as 0 ppm, it was incinerated. After washing with water, toluene was distilled off with a rotary evaporator, and then the wiper type thin film distillation apparatus was used to remove the toluene at 180 ° C. and 1 torr.
A colorless and transparent viscous liquid that is processed under the following conditions 3
55 g was obtained.

The recovered toluene has an acid value of 0.5 KOH.
Since it was as high as mg / g, it was incinerated.

When measured by 1 H-NMR, its chemical shift confirmed that this liquid was a lactone-based polyol obtained by ring-opening addition polymerization of β-methyl-δ-valerolactone with polytetramethylene glycol (molecular weight 1000). Was done.

This product has a hydroxyl value of 36.5 mgKOH
/ G and the acid value was 0.3 mgKOH / g, the molecular weight was 3050.

Further, the Li content was 2.5 ppm by the atomic absorption method.

[0049]

The lactone-based polyol produced by the present invention reduces the crystallization tendency of polyether polyol, polyester polyol, polycarbonate polyol and the like used as an initiator. It is also useful as a raw material for providing polyurethanes and elastomers that are soft and have excellent hydrolysis resistance, and include sheets, films, rolls, gears, solid tires, belts, hoses, tubes, packing materials, vibration damping materials, and soles. Sports shoes, machine parts, automobile parts, sports equipment, elastic fiber, artificial leather,
It can be effectively used as a resin raw material for a wide variety of uses such as a fiber treating agent, an adhesive, a coating agent, a binder, and a paint.

Claims (3)

[Claims] 1. A substituted or unsubstituted δ is prepared by using a polyol compound having an active hydrogen atom as an initiator in the presence of a tertiary amine compound having a pKa value of 11 or more and containing no active hydrogen in the molecule. -A method for producing a lactone-based polyol, which comprises subjecting valerolactone to ring-opening addition polymerization. 2. The method for producing a lactone-based polyol according to claim 1, wherein the polyol compound having an active hydrogen atom is one kind or two or more kinds of a polyether polyol, a polyester polyol and a polycarbonate polyol. 3. The substituted or unsubstituted δ-valerolactone is β-methyl-δ-valerolactone.
2. The method for producing a lactone-based polyol according to 2.