TW201527349A - Production method for lactone polymer - Google Patents

Abstract

Provided is a method for the efficient manufacture of a lactone polymer having excellent hue, resistance to hydrolysis, and durability, using a catalyst having a low environmental load. This production method for a lactone polymer involves obtaining a lactone polymer through ring-opening polymerization of a lactone compound, wherein the production method for a lactone polymer is characterized in that a C9 or greater fatty acid zinc salt is used as the catalyst, in a range of 1-500 ppm with respect to the total amount of the lactone compound and the initiator. The C9 or greater fatty acid zinc salt constituting the catalyst is preferably a C9 or greater unsaturated fatty acid zinc salt, and especially preferably zinc undecylenate and/or zinc laurate. The initiator is preferably used in an amount in the range of more than 0.5 mole, but not more than 120 moles, per 100 moles of the lactone compound.

Description

Method for producing lactone polymer

The present invention relates to a process for producing a lactone polymer using a catalyst having a low environmental burden. The present application claims the priority of Japanese Patent Application No. 2013-220275, filed on Jan. 23, 2013 in Japan, and the content is hereby incorporated.

The lactone polymer is used in a wide range of industrial fields such as a resin raw material, a resin modified material, an adhesive, a coating material, an electronic material, and a medical material. The lactone polymer is produced, for example, by ring-opening a polymerized lactone compound in the presence of a catalyst, using an organic compound having an active hydrogen such as a hydroxyl group or an amine group as a starting agent. The molecular weight distribution and crystallinity of the lactone polymer can be controlled by selecting the initiator and the catalyst, and the lactone polymer can be produced in accordance with the use. For example, a lactone polymer having a molecular weight of 10,000 or more is used as a resin-modified material, a hot-melt adhesive, a biodegradable medical material, and various molding materials. On the other hand, lactone polymers having a molecular weight of less than 10,000 are being used as raw materials for polyurethanes, polyesters, and coatings.

Then, an organotin compound is known as a catalyst used for the production of the lactone polymer (Patent Documents 1 and 2). When the above compound is used, it is possible to efficiently produce a lactone polymer having a good hue, hydrolysis resistance, and durability by using a small amount. But there is Machine tin compounds are toxic and are also concerned about environmental impacts. Therefore, a method of producing a lactone polymer by using an environmentally burdensome and less toxic compound instead of an organotin compound as a catalyst is being sought.

Then, as a catalyst having a low environmental burden and low toxicity, zinc undecylenate is known (Non-Patent Document 1).

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2005-112941

Patent Document 2 Japanese Patent Laid-Open No. Hei 6-345858

Non-patent literature

Non-Patent Document 1 Macromolecular Rapid Communications, 2012, 33, 1294-1299

However, when the present inventors produced a lactone polymer in the blending ratio described in Non-Patent Document 1, a lactone polymer exhibiting yellow and light brown color was obtained, and it was found that the color was inferior. Further, it has been found that the obtained lactone polymer has a high acid value and is insufficient in hydrolysis resistance and durability.

Accordingly, an object of the present invention is to provide a method for efficiently producing a lactone polymer having a good hue, hydrolysis resistance, and durability by using a catalyst having low environmental burden and low toxicity.

As a result of intensive studies to solve the above problems, the present inventors have found that when a fatty acid zinc salt having a carbon number of 9 or more which is excellent in the environment is used in a specific range, it is possible to efficiently produce a hue, hydrolysis resistance, and durability. Good lactone polymer. The present invention has been completed based on these findings.

That is, the present invention provides a method for producing a lactone polymer, which is a method for producing a lactone polymer of a lactone polymer by ring-opening a polymerized lactone compound, which is characterized in that it is relative to a lactone compound and As the total amount of the initiator, a zinc salt of a fatty acid having 9 or more carbon atoms is used as a catalyst in the range of 1 to 500 ppm.

Furthermore, the present invention provides a method for producing a lactone polymer, wherein a zinc salt of a fatty acid having a carbon number of 9 or more constituting a catalyst is a zinc salt of an unsaturated fatty acid having 9 or more carbon atoms.

Further, the present invention provides the method for producing a lactone polymer, wherein the zinc salt of a fatty acid having a carbon number of 9 or more constituting the catalyst is zinc undecylenate and/or zinc laurate.

Still further, the present invention provides a process for producing the above lactone polymer, wherein the initiator is used in a range of more than 0.5 mol and less than 120 mol per 100 mol of the lactone compound.

Further, the present invention provides a process for producing the aforementioned lactone polymer, wherein a compound having a functional group containing an active hydrogen is used as a starter.

Still further, the present invention provides a process for producing the aforementioned lactone polymer, wherein a polyol is used as a starter.

Further, the present invention provides a process for producing the above lactone polymer, wherein the reaction temperature is 120 ° C or higher.

Further, the present invention provides a method for producing a polyurethane, which comprises producing a lactone polymer by the method for producing a lactone polymer, and reacting the obtained lactone polymer with a polyisocyanate compound to produce a polymer. Carbamate.

Further, the present invention provides a method for producing a urethane (meth) acrylate which is produced by the method for producing a lactone polymer described above, which comprises obtaining a lactone polymer and containing a hydroxyl group. The (meth) acrylate and the polyisocyanate compound are reacted to produce a urethane (meth) acrylate.

That is, the present invention relates to the following.

(1) A method for producing a lactone polymer, which is a method for producing a lactone polymer of a lactone polymer by ring-opening a polymerized lactone compound, characterized by: a lactone compound and an initial As the total amount of the agent, a zinc salt of a fatty acid having 9 or more carbon atoms is used as a catalyst in a range of 1 to 500 ppm.

(2) The method for producing a lactone polymer according to (1), wherein the zinc salt of a fatty acid having a carbon number of 9 or more constituting the catalyst is a zinc salt of an unsaturated fatty acid having 9 or more carbon atoms.

(3) The method for producing a lactone polymer according to (1), wherein the zinc salt of a fatty acid having a carbon number of 9 or more constituting the catalyst is zinc undecylenate and/or zinc laurate.

(4) The method for producing a lactone polymer according to any one of (1) to (3), wherein the use is carried out in a range of more than 0.5 mol and less than 120 mol per 100 mol of the lactone compound. Starting agent.

(5) A method for producing a lactone polymer according to any one of (1) to (4), wherein a compound having a functional group containing an active hydrogen is used as a starter.

(6) A method for producing a lactone polymer according to any one of (1) to (4), wherein a polyol is used as a starter.

(7) The method for producing a lactone polymer according to any one of (1) to (6), wherein a method selected from the group consisting of ethylene glycol, diethylene glycol, 1,3-butylene glycol, and 1, 4 is used. A compound of at least one of butylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol is used as a starter.

(8) A process for producing a lactone polymer according to any one of (1) to (7), wherein a lactone compound which may also have a 3-16 ring of an alkyl group and an alkoxy group is used as a lactone compound .

(9) The method for producing a lactone polymer according to any one of (1) to (8), wherein a method selected from the group consisting of ε-caprolactone, methylated ε-caprolactone, and δ-valerolactone is used. And 3-ethyl-2-keto-1,4-di At least one of the alkane is a lactone compound.

(10) A method for producing a lactone polymer according to any one of (1) to (9), wherein the reaction temperature is 120 ° C or higher.

(11) A method for producing a lactone polymer according to any one of (1) to (10), wherein a lactone polymer having an acid value of 20.0 or less is obtained.

(12) The method for producing a lactone polymer according to any one of (1) to (11), wherein the amount of the dimer of the lactone compound is 0.1% or less.

(13) A method for producing a lactone polymer according to any one of (1) to (12), wherein a lactone polymer having a hue (APHA) (according to ASTM D 1209) of 100 or less is obtained.

(14) A method for producing a polyurethane, which comprises the method for producing a lactone polymer according to any one of (1) to (13), wherein the lactone polymer is produced. The lactone polymer reacts with the polyisocyanate compound to produce a polyurethane.

(15) A method for producing a urethane (meth) acrylate, wherein the lactone polymer is produced by the method for producing a lactone polymer according to any one of (1) to (13) The obtained lactone polymer and the hydroxyl group-containing (meth) acrylate and the polyisocyanate compound are reacted to produce a urethane (meth) acrylate.

Since the lactone polymer of the present invention is produced by using a specific amount of a fatty acid zinc salt having a carbon number of 9 or more as a catalyst, it is possible to reduce the environmental burden and efficiently produce a lactone polymer under mild conditions. Therefore, the method for producing a lactone polymer of the present invention is suitable as a method for industrially producing a lactone polymer.

Then, the lactone polymer obtained by the method for producing a lactone polymer of the present invention is excellent in hue, hydrolysis resistance, and durability. Further, since the molecular weight distribution is narrow (=the mixing ratio of the low molecular weight component is low), it is possible to suppress bleeding and blooming in the final product. Further, according to the method for producing a lactone polymer of the present invention, formation of a dimer of a lactone compound can be suppressed, and a lactone polymer having a small dimer content of a lactone compound can be obtained. Therefore, by The lactone polymer obtained by the production method of the present invention has good storage stability and can be suitably used as a raw material of a polyurethane and a urethane (meth) acrylate. Then, if the lactone polymer obtained by the production method of the present invention is used as a raw material, deposition can be suppressed at the time of production or processing of the polyurethane and the urethane (meth) acrylate. The formation and the generation of odor can form a final product with good durability.

From the above, the lactone polymer obtained by the method for producing a lactone polymer of the present invention can be suitably used as a raw material, a modified material, or a modified material as various molded articles, fibers, films, sheets, resins, and elastomers. Raw materials such as paints and adhesives.

The method for producing a lactone polymer of the present invention is a method for producing a lactone polymer of a lactone polymer by ring-opening a polymerized lactone compound, characterized by a total of a lactone compound and a starter The amount of the zinc salt of a fatty acid having 9 or more carbon atoms is used as a catalyst in the range of 1 to 500 ppm. The lactone polymer obtained by the production method of the present invention is an oligomer or polymer formed by ring-opening polymerization of one or more molecules of a lactone compound by an initiator, and contains a total amount of 50 moles of the lactone polymer. More than 100% of the monomer units derived from the lactone compound. Further, the lactone polymer of the present invention may contain, in addition to the monomer unit derived from the lactone compound, a monomer unit derived from another monomer which can be copolymerized with the lactone compound.

(catalyst)

In the present invention, zinc fatty acid having a carbon number of 9 or more is used as a catalyst. The zinc fatty acid having a carbon number of 9 or more is represented by the following general formula (1), for example.

(RCOO) ₂ Zn (1)

(In the formula, R represents a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms)

The zinc salt of the fatty acid represented by the above formula (1) is a zinc salt of a fatty acid (RCOOH; R is the same as the above), and examples of the fatty acid include capric acid, capric acid, undecanoic acid, lauric acid, and thirteen carbonic acid. a saturated fatty acid having 9 or more carbon atoms (preferably a carbon number of 9 to 20, particularly preferably 10 to 18) of myristic acid, pentadecic acid, palmitic acid, heptadecanoic acid, stearic acid, etc.; citronellic acid, ten Monocarboic acid, 4-dodecenoic acid, α-linolenic acid, linoleic acid, oleic acid, etc. have a carbon number of 9 or more (preferably a carbon number of 9 to 20, particularly preferably 10 to 18). Unsaturated fatty acids, etc. These can be used alone or in combination of two or more.

As a catalyst of the present invention, zinc undecylenate and/or zinc laurate is used as a lactone polymer which can obtain a hue, hydrolysis resistance, and durability with a narrow molecular weight distribution under mild conditions. It is better.

The amount of the catalyst used in the present invention is in the range of 1 to 500 ppm, preferably 5 to 200 ppm, more preferably 5 to 150 ppm, particularly preferably 5 to 130 ppm, based on the total amount of the lactone compound and the initiator. The best is 5~85ppm. By using a catalyst in the above range, a lactone polymer having a good hue, hydrolysis resistance, and durability and a narrow molecular weight distribution can be efficiently produced. If the amount of the catalyst used is excessive, the obtained phase of the lactone polymer will deteriorate, such as the hue, hydrolysis resistance, and durability. to. On the other hand, if the amount of the catalyst used is too small, the reaction rate tends to be slow.

(lactone compound)

The lactone compound of the present invention may, for example, be α-lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 8-hydroxyoctanolactone, 12- a 3 to 16 ring lactone compound such as hydroxydodecanolide, 13-hydroxytridecyl lactone, 14-hydroxytetradecanolactone or 15-hydroxypentadecanolide.

The lactone compound can further comprise 3-ethyl-2-keto-1,4-di Alkane, 1,4-two Alkan-2-one, 3-propyl-2-keto-1,4-di Two of the alkane Alkanes.

These lactone compounds may have a substituent such as an alkyl group or an alkoxy group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a fluorenyl group. A linear or branched chain alkyl group having a carbon number of about 1 to 10 or the like.

The alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tertiary butoxy group, a pentyloxy group or a hexyloxy group. A lower alkoxy group having a carbon number of about 1 to 10 (preferably, a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 4).

In the present invention, the above lactone compounds can be used alone or in combination of two or more. Among them, ε-caprolactone and methylated ε-caprolactone, δ-valerolactone, 3-ethyl-2-keto-1,4-di which are of great practical value are preferably used. Alkane, etc.

The present invention may also be subjected to ring-opening polymerization together with a lactone compound, other polymerizable monomers (hereinafter referred to as "other monomers") which are copolymerizable with the lactone compound. When this is the case, a lactone polymer having a monomer unit derived from a lactone compound and a monomer unit derived from another monomer can be obtained. Further, the proportion of the lactone compound in all the polymerizable monomers subjected to ring-opening polymerization is, for example, 50% by weight or more.

Examples of the other monomer include lactide and trimethylene carbonate. These can be used alone or in combination of two or more.

(starting agent)

The method for producing a lactone polymer of the present invention is preferably a compound having a functional group containing an active hydrogen as a starting agent. The compound having a functional group containing an active hydrogen may, for example, be a compound containing at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a phosphoric acid group, an amine group, and a fluorenyl group. In the present invention, from the viewpoint of good reactivity, a compound having a hydroxyl group is preferred.

Examples of the compound having a hydroxyl group include methanol, ethanol, isopropanol, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and allyl alcohol. 1 yuan aliphatic alcohol; ethylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, neopentyl glycol, polyethylene Polyols such as alcohol, trimethylolpropane, pentaerythritol, dipentaerythritol; esters such as ethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate; ethylene glycol monoalkyl ether Diethylene glycol monoalkyl ethers; propylene glycol monoalkyl ethers; dipropylene glycol monoalkyl ethers; butanediol monoalkyl ethers; benzyl alcohol, phenol, a phenolic hydroxyl group such as catechol, biphenol, bisphenol A, bisphenol F, novolak, etc.; polyethylene glycol, polytetramethylene glycol, hydroxyl group of (meth)acrylic acid, etc. An oligomer or a polymer obtained by copolymerizing a (meth) acrylate or a lactone, a polymer compound containing a hydroxyl group, a polymer compound such as a hydroxyl group-containing polybutadiene, or the like. These can be used alone or in combination of two or more.

In the present invention, from the viewpoint of obtaining the lactone polymer more efficiently, it is preferred to use a polyol as a starter.

The amount of the starting agent used is preferably more than 0.5 mol and less than 120 mol, more preferably more than 1 mol and less than 120 mol, and most preferably 5 to 50, relative to 100 mol of the lactone compound. Moor. The molecular weight of the obtained lactone polymer can be adjusted by controlling the molar ratio of the polymerizable monomer and the starter.

The reaction temperature of the method for producing a lactone polymer of the present invention is preferably 120 ° C or higher, particularly preferably 120 to 210 ° C, and most preferably 150 to 200 ° C. If the reaction temperature is too low, the reaction rate tends to be slow. On the other hand, if the reaction temperature is too high, the coloration due to the transesterification reaction or the decomposition reaction of the formed polymer proceeds, and it becomes difficult to obtain a lactone polymer having a good hue and a narrow molecular weight distribution. . Further, the reaction time is, for example, about 3 to 30 hours, preferably 4 to 24 hours. Further, the reaction pressure is about 0.7 to 1.5 atm.

Further, in the method for producing a lactone polymer of the present invention, any polymerization method of bulk polymerization, solution polymerization and suspension polymerization can also be employed.

As the solvent used for the solution polymerization, for example, an aromatic hydrocarbon such as toluene or xylene is preferred because it is inert to the reaction and has a high boiling point. The solvent is expected to be substantially anhydrous.

The above polymerization reaction can also be carried out in any one of batch, semi-batch, continuous, and the like. After completion of the reaction, the reaction product can be isolated and purified by means of separation and purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or the like.

The reaction environment is not particularly limited as long as it does not hinder the reaction, and it is preferred to carry out the reaction in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere.

In the production method of the present invention, a lactone polymer having a good hue (for example, a hue [APHA] of 100 or less, preferably 60 or less, particularly preferably 50 or less) can be obtained by using the above-mentioned catalyst.

Further, the lactone polymer obtained by the production method of the present invention has a narrow molecular weight distribution (weight average molecular weight / number average molecular weight) (for example, less than 1.35, preferably less than 1.30). Therefore, when it is used as a raw material of various molded articles, it is possible to suppress bleeding and blooming (leakage of low molecular weight components) in the final product.

The production method of the present invention is capable of obtaining a lactone polymer having a weight average molecular weight of, for example, about 200 to 100,000, and preferably 200 to 10,000. The weight average molecular weight can be controlled by adjusting the molar ratio of the lactone compound and the starter.

Further, the production method of the present invention can be obtained by suppressing the progress of side reactions (for example, chain transfer reaction, transesterification reaction, etc.). A lactone polymer having good hydrolysis resistance and an acid value of 20.0 or less (preferably 10.0 or less, particularly preferably 5.0 or less). Therefore, when the lactone polymer obtained by the production method of the present invention is used as a raw material, the polyurethane and the urethane (meth)acrylate can be efficiently produced. Further, in the case where a lactate polymer having a high acid value is used as a raw material, the urethanization reaction is hindered, and it becomes difficult to efficiently produce a polyurethane and an aminocarboxylic acid. The case of ester (meth) acrylate.

Further, the production method of the present invention can reduce the formation of a dimer of a lactone compound to, for example, 0.1% or less (preferably less than 0.05%), and can extremely inhibit the polymerization of the dimer into the lactone. Things. The dimer of the lactone compound may be a cause of deposition or odor during the production or processing of the polyurethane and the urethane (meth) acrylate. By using the lactone polymer obtained by the production method of the present invention, formation of deposition can be achieved at the time of production or processing of the polyurethane or urethane (meth) acrylate, and Odor-less operation.

The lactone polymer obtained by the production method of the present invention has the above-described characteristics, and is used as a raw material, a modified material, a paint, an adhesive, or the like of various molded articles, fibers, films, sheets, resins, and elastomers. A raw material (particularly a raw material of a polyurethane, a urethane (meth) acrylate) is useful.

[Method for Producing Polyurethane]

A method for producing a polyurethane according to the present invention, which is characterized in that a lactone polymer is produced by the method for producing a lactone polymer, and a obtained lactone polymer and a polyisocyanate compound are reacted to produce a polymer. Carbamate.

Examples of the polyisocyanate compound include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 1,3-diisocyanate, and 1,4-diisocyanate. D-xylylene ester, terephthalic acid diisocyanate, naphthyl 1,5-diisocyanate, phenyl diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate, diisocyanate-4,4'-dibenzyl ester, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4 a diisocyanate compound such as trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate; or a diisocyanate compound obtained by hydrogenating an aromatic isocyanate compound in the diisocyanate compound ( For example, a diisocyanate compound such as hydrogenated diphenyl isocyanate or hydrogenated diphenylmethane diisocyanate; or a trivalent or higher isocyanate compound such as triphenylmethane triisocyanate or dimethylene triphenyl triisocyanate; Multi-quantitative polyisocyanate compound obtained by multi-quantification Wait. These can be used alone or in combination of two or more.

The method for producing a polyurethane of the present invention is characterized in that a lactone polymer obtained by the above-described method for producing a lactone polymer is used as a polyalcohol, and other conditions are similar to those of a conventionally known polyamine group. The method of producing a formate is the same. The method for producing a polyurethane of the present invention can use a chain extender in consideration of the balance of physical properties. Examples of the chain extender include 1,3-propanol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, and 2-ethyl group. -2-(Hydroxymethyl)-1,3-propanediol, 3-methyl-1,5-pentanediol. These can be used alone or in combination of two or more. Others can also use one or more types A usual additive such as a catalyst, a crosslinking agent, a stabilizer, a foaming agent, a plasticizer, and a flame retardant.

[Method for producing urethane (meth) acrylate]

A method for producing a urethane (meth) acrylate according to the present invention, which is characterized in that a lactone polymer is produced by the method for producing a lactone polymer, and the obtained lactone polymer and a hydroxyl group are obtained. The (meth) acrylate and the polyisocyanate compound are reacted to produce a urethane (meth) acrylate.

As the hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or ethylene glycol mono(meth)acrylate can be used. , propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, N-hydroxymethyl(meth)acrylamide, N - Hydroxy (meth) acrylamide or the like or such lactone adducts (for example, PCL-FA or PCL-FM series manufactured by DAICEL Co., Ltd.). Further, dipentaerythritol poly(meth)acrylate (for example, "DPHA" manufactured by DAICEL-ALLNEX Co., Ltd.) can also be used. These can be used alone or in combination of two or more. In the present specification, the case where "acrylic group" and "methacrylic group" are collectively referred to as "(meth)acrylic group" is used.

The polyisocyanate compound is the same as the one exemplified in the above [method of producing a polyurethane).

A method for producing a urethane (meth) acrylate according to the present invention, characterized in that a lactone polymer obtained by the above-described method for producing a lactone polymer is used as a polyalcohol, and other conditions are The conventionally known urethane (meth) acrylate is produced in the same manner. package Containing, for example, by reacting a diisocyanate compound and a hydroxyl group-containing (meth) acrylate to synthesize a monoisocyanate compound having an isocyanate group at one end and a (meth) acrylonitrile group at the other end, and the isocyanate compound A method of reacting a lactone polymer obtained by the above-described method for producing a lactone polymer.

[Examples]

The invention is more specifically described by the following examples, but the invention is not limited by the examples.

[Examples 1 to 6 and Comparative Examples 1 to 3] (manufacture of polycaprolactone diol)

In a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirring device, a cooling tube, and a temperature regulator, an initiator (benzyl alcohol (BzOH) or ethylene glycol (EG)) was added according to the formulation shown in Table 1 and The ε-caprolactone (CL) of the lactone compound is heated to a predetermined temperature.

Next, the reaction temperature is maintained, and a catalytic amount (zinc undecylenate, zinc laurate, or zinc octoate) is added to the reaction system to continue the reaction, and ε- in the reaction system is evaluated by a gas chromatograph. When the concentration of caprolactone is less than 1%, the reaction liquid is cooled to stop the reaction, and polycaprolactone diol (number average molecular weight: about 3,000, weight average molecular weight: about 3,600) is obtained.

The following items were evaluated for the obtained polycaprolactone diol. The summary results are shown in Table 1.

<Molecular weight distribution: Mw/Mn>

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by comparison with polystyrene standards using a high-speed GPC apparatus, and the ratio was used as an index of molecular weight distribution.

The measurement conditions are as follows.

Measuring device: High-speed GPC device "HLC-8220GPC", manufactured by Tosoh Corporation

Mobile phase: tetrahydrofuran

<dimer amount>

A gas chromatograph was used to determine the amount of caprolactone dimer in the reaction system.

<acid price>

It was measured by neutralization titration using phenolphthalein as an indicator in accordance with JIS K 0070 (1992).

<Hue: APHA>

Determined in accordance with ASTM D 1209.

[Example 7] (Manufacture of polycaprolactone triol)

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a condenser, 155.0 g of trimethylolpropane (TMP) and 845.0 g of ε-caprolactone (with respect to 1 mol of trimethylolpropane) of 6.4 m were placed. Ear), 0.050 g (50 ppm) of zinc undecylenate, and the reaction was allowed to proceed at 160 °C.

The concentration of ε-caprolactone in the reaction system was measured by a gas chromatograph, and when the temperature became less than 0.2%, the reaction liquid was cooled to stop the reaction, and polycaprolactone triol (1) which was liquid at normal temperature was obtained.

The molecular weight distribution (Mw/Mn) and the amount of caprolactone dimer of the obtained polycaprolactone triol were measured in the same manner as above. The summary results are shown in Table 2.

[Comparative Example 4] (Manufacture of polycaprolactone triol)

A polycaprolactone triol (2) having a liquid at normal temperature was obtained in the same manner as in Example 7 except that 0.010 g (10 ppm) of titanium tetrabutoxide was used as a catalyst and the reaction was allowed to proceed at 170 °C.

[Reference Example 1] (Manufacture of polycaprolactone triol)

A polycaprolactone triol (3) having a liquid at normal temperature was obtained in the same manner as in Example 7 except that 0.010 g (10 ppm) of tin octylate was used as a catalyst and the reaction was allowed to proceed at 170 °C.

[Industry use possibility]

The method for producing a lactone polymer of the present invention is capable of efficiently producing a lactone polymer while reducing environmental burden and under mild conditions. Therefore, it is suitable as a method of industrially producing a lactone polymer.

Then, the lactone polymer obtained by the method for producing a lactone polymer of the present invention has a good hue, hydrolysis resistance, and durability. Further, since the molecular weight distribution is narrow, it is possible to suppress bleeding and blooming of the final product. Further, the dimer content is small and the storage stability is good.

When the lactone polymer obtained by the production method of the present invention is used as a raw material, deposition formation can be suppressed at the time of production or processing of the polyurethane or urethane (meth) acrylate. Or the generation of odor, and can form a final product with good durability.

Claims (9)

A method for producing a lactone polymer, which is a method for producing a lactone polymer of a lactone polymer by ring-opening a polymerized lactone compound, characterized by a total of a lactone compound and a starter The amount of the zinc salt of a fatty acid having 9 or more carbon atoms is used as a catalyst in the range of 1 to 500 ppm. The method for producing a lactone polymer according to claim 1, wherein the fatty acid zinc salt having a carbon number of 9 or more constituting the catalyst is a zinc salt of an unsaturated fatty acid having 9 or more carbon atoms. The method for producing a lactone polymer according to claim 1, wherein the zinc salt of the fatty acid having a carbon number of 9 or more constituting the catalyst is zinc undecylenate and/or zinc laurate. The method for producing a lactone polymer according to any one of claims 1 to 3, wherein the initiator is used in a range of more than 0.5 mol and less than 120 mol per 100 mol of the lactone compound. The method for producing a lactone polymer according to any one of claims 1 to 4, wherein a compound having a functional group containing an active hydrogen is used as a starter. The process for producing a lactone polymer according to any one of claims 1 to 4, wherein a polyol is used as a starter. The method for producing a lactone polymer according to any one of claims 1 to 6, wherein the reaction temperature is 120 ° C or higher. A method for producing a polyurethane, which is produced by the method for producing a lactone polymer according to any one of claims 1 to 7, wherein the obtained lactone polymer and the polymer are obtained. The isocyanate compound is reacted to produce a polyurethane. A method for producing a urethane (meth) acrylate by the method for producing a lactone polymer according to any one of claims 1 to 7, wherein the obtained lactone polymer is obtained The ester polymer is reacted with a hydroxyl group-containing (meth) acrylate and a polyisocyanate compound to produce a urethane (meth) acrylate.