JPWO2015060192A1 - Method for producing lactone polymer - Google Patents

Abstract

Provided is a method for efficiently producing a lactone polymer excellent in hue, hydrolysis resistance, and durability using a catalyst having a low environmental load. The method for producing a lactone polymer of the present invention is a method for producing a lactone polymer by ring-opening polymerization of a lactone compound to obtain a lactone polymer, and a fatty acid zinc salt having 9 or more carbon atoms as a catalyst and a lactone compound It is characterized by being used in the range of 1 to 500 ppm with respect to the total amount of initiator. As the fatty acid zinc salt having 9 or more carbon atoms constituting the catalyst, an unsaturated fatty acid zinc salt having 9 or more carbon atoms is preferable, and zinc undecylenate and / or zinc laurate are particularly preferable. Furthermore, it is preferable to use the initiator in the range of more than 0.5 mol and 120 mol or less with respect to 100 mol of the lactone compound.

Description

  The present invention relates to a method for producing a lactone polymer using a catalyst having a low environmental load. This application claims the priority of Japanese Patent Application No. 2013-220275 for which it applied to Japan on October 23, 2013, and uses the content here.

  Lactone polymers are used in a wide range of industrial fields such as resin raw materials, resin modifiers, adhesives, paints, electronic materials, and medical materials. The lactone polymer is produced, for example, by ring-opening polymerization of a lactone compound in the presence of a catalyst using an organic compound having an active hydrogen such as a hydroxyl group or an amino group as an initiator. By selecting an initiator and a catalyst, the molecular weight distribution and crystallinity of the lactone polymer can be controlled, and a lactone polymer can be produced according to the application. For example, a lactone polymer having a molecular weight of 10,000 or more is used as a resin modifier, a hot melt adhesive, a medical material utilizing its biodegradability, and various molding materials. On the other hand, lactone polymers having a molecular weight of less than 10,000 are used as raw materials for polyurethanes, polyesters and paints.

  And the organotin compound is known as a catalyst used for manufacture of the said lactone polymer (patent documents 1, 2). If the said compound is used, the lactone polymer excellent in hue, hydrolysis resistance, and durability can be efficiently manufactured by use of a small amount. However, organotin compounds may be toxic, and there is also concern about environmental impact. Therefore, there has been a demand for a method for producing a lactone polymer using a compound having a lower environmental load or toxicity as a catalyst in place of the organotin compound.

  And zinc undecylenate is known as a catalyst with lower environmental load and lower toxicity (Non-patent Document 1).

JP 2005-112941 A JP-A-6-345858

Macromolecular Rapid Communications, 2012,33,1294-1299

  However, when the present inventors manufactured a lactone polymer at the blending ratio described in Non-Patent Document 1, it was found that a lactone polymer having a yellow or light brown color was obtained, which was inferior in terms of hue. It was also found that the obtained lactone polymer had a high acid value and was insufficient in terms of hydrolysis resistance and durability.

  Accordingly, an object of the present invention is to provide a method for efficiently producing a lactone polymer excellent in hue, hydrolysis resistance and durability 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 9 or more carbon atoms, which is environmentally friendly, is used in a specific range, the lactone weight excellent in hue, hydrolysis resistance, and durability. It has been found that coalescence can be produced efficiently. The present invention has been completed based on these findings.

  That is, the present invention relates to a method for producing a lactone polymer, wherein a lactone polymer is obtained by ring-opening polymerization of a lactone compound, and a fatty acid zinc salt having 9 or more carbon atoms is used as a catalyst in the total amount of the lactone compound and the initiator. In contrast, the present invention provides a method for producing a lactone polymer, which is used in the range of 1 to 500 ppm.

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

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

  The present invention also provides the process for producing a lactone polymer as described above, wherein the initiator is used in a range of more than 0.5 mol and 120 mol or less with respect to 100 mol of the lactone compound.

  The present invention also provides a method for producing the above lactone polymer using a compound having a functional group containing active hydrogen as an initiator.

  The present invention also provides a method for producing the above lactone polymer using a polyhydric alcohol as an initiator.

  The present invention also provides a method for producing the lactone polymer, wherein the reaction temperature is 120 ° C. or higher.

  The present invention also provides a method for producing a polyurethane, wherein a lactone polymer is produced by the above-described method for producing a lactone polymer, and a polyurethane is produced by reacting the obtained lactone polymer with a polyisocyanate compound.

  The present invention also provides a lactone polymer by the method for producing a lactone polymer, and reacts the resulting lactone polymer with a hydroxyl group-containing (meth) acrylic acid ester and a polyisocyanate compound to obtain a urethane (meth) acrylate. The manufacturing method of urethane (meth) acrylate which manufactures is provided.

That is, the present invention relates to the following.
(1) A method for producing a lactone polymer, wherein a lactone polymer is obtained by ring-opening polymerization of a lactone compound. A method for producing a lactone polymer, which is used in a range of ˜500 ppm.
(2) The method for producing a lactone polymer according to (1), wherein the fatty acid zinc salt having 9 or more carbon atoms constituting the catalyst is an unsaturated fatty acid zinc salt having 9 or more carbon atoms.
(3) The method for producing a lactone polymer according to (1), wherein the fatty acid zinc salt having 9 or more carbon atoms 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 initiator is used in an amount exceeding 0.5 mol and not exceeding 120 mol with respect to 100 mol of the lactone compound.
(5) The method for producing a lactone polymer according to any one of (1) to (4), wherein a compound having a functional group containing active hydrogen is used as an initiator.
(6) The method for producing a lactone polymer according to any one of (1) to (4), wherein a polyhydric alcohol is used as an initiator.
(7) As an initiator, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, propylene glycol, 1,6-hexamethylenediol, neopentyl glycol, polyethylene glycol, trimethylolpropane, pentaerythritol And a method for producing a lactone polymer according to any one of (1) to (6), wherein at least one compound selected from dipentaerythritol is used.
(8) The method for producing a lactone polymer according to any one of (1) to (7), wherein a 3 to 16-membered lactone compound which may have an alkyl group or an alkoxy group is used as the lactone compound.
(9) As the lactone compound, at least one selected from ε-caprolactone, methylated ε-caprolactone, δ-valerolactone, and 3-ethyl-2-keto-1,4-dioxane is used (1) to (8) The manufacturing method of the lactone polymer in any one of.
(10) The method for producing a lactone polymer according to any one of (1) to (9), wherein the reaction temperature is 120 ° C. or higher.
(11) The 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 production amount of a lactone compound dimer is 0.1% or less.
(13) The 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 polyurethane produced by producing a lactone polymer by the method for producing a lactone polymer according to any one of (1) to (13), and producing a polyurethane by reacting the obtained lactone polymer with a polyisocyanate compound. Production method.
(15) A lactone polymer is produced by the method for producing a lactone polymer according to any one of (1) to (13), and the obtained lactone polymer, a hydroxyl group-containing (meth) acrylic acid ester and a polyisocyanate compound are produced. A method for producing urethane (meth) acrylate, which is reacted to produce urethane (meth) acrylate.

The method for producing a lactone polymer of the present invention uses a specific amount of a fatty acid zinc salt having 9 or more carbon atoms as a catalyst, so that it is possible to efficiently produce a lactone polymer under mild conditions while reducing the environmental burden. it can. Therefore, the method for producing a lactone polymer of the present invention is suitable as a method for industrially producing a lactone polymer.
And the lactone polymer obtained by the manufacturing method of the lactone polymer of this invention is excellent in hue, hydrolysis resistance, and durability. In addition, since the molecular weight distribution is narrow (= the mixing ratio of the low molecular weight component is low), it is possible to suppress bleed out and blooming from occurring in the final product. Furthermore, according to the method for producing a lactone polymer of the present invention, formation of a lactone compound dimer can be suppressed, and a lactone polymer having a low content of the lactone compound dimer can be obtained. Therefore, the lactone polymer obtained by the production method of the present invention is excellent in storage stability and can be suitably used as a raw material for polyurethane and urethane (meth) acrylate. If the lactone polymer obtained by the production method of the present invention is used as a raw material, it is possible to suppress the formation of deposits and the generation of odor during the production and processing of polyurethane and urethane (meth) acrylate, and durability. A final product with excellent properties can be formed.
From the above, the lactone polymer obtained by the method for producing a lactone polymer of the present invention is suitably used as a raw material for various molded products, fibers, films, sheets, raw materials for resins and elastomers, modifiers, paints, adhesives and the like. Can be used.

  The method for producing a lactone polymer according to the present invention is a method for producing a lactone polymer, wherein a lactone polymer is obtained by ring-opening polymerization of a lactone compound, and a fatty acid zinc salt having 9 or more carbon atoms and a lactone compound as a catalyst. It is characterized by being used in the range of 1 to 500 ppm with respect to the total amount of initiator. 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 as an initiator, and the monomer unit derived from the lactone compound is 50% of the total amount of the lactone polymer. Containing at least mol%. Moreover, the lactone polymer of this invention may contain the monomer unit derived from the other monomer copolymerizable with a lactone compound other than the monomer unit derived from a lactone compound.

(catalyst)
In the present invention, zinc fatty acid having 9 or more carbon atoms is used as a catalyst. Fatty acid zinc having 9 or more carbon atoms is represented, for example, by the following formula (1).
(RCOO) ₂ Zn (1)
(In the formula, R represents a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms)

  The fatty acid zinc represented by the formula (1) is a zinc salt of a fatty acid (RCOOH; R is the same as above), and examples of the fatty acid include nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, Saturated fatty acids having 9 or more carbon atoms (preferably 9 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms) such as myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid; citronellic acid, undecylenic acid, 4-dodecenoic acid , Α-linolenic acid, linoleic acid, oleic acid and the like, and unsaturated fatty acids having 9 or more carbon atoms (preferably 9 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms). These can be used individually by 1 type or in combination of 2 or more types.

  As the catalyst of the present invention, use of zinc undecylenate and / or zinc laurate provides a lactone polymer having excellent hue, hydrolysis resistance and durability and a narrow molecular weight distribution under mild conditions. It is preferable in that it can be obtained.

  The use amount of the catalyst of 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, most preferably based on the total amount of the lactone compound and the initiator. 5 to 85 ppm. By using the catalyst within the above range, a lactone polymer having excellent hue, hydrolysis resistance and durability and having a narrow molecular weight distribution can be produced efficiently. When the amount of the catalyst used is excessive, the hue, hydrolysis resistance, durability and the like of the resulting lactone polymer tend to deteriorate. On the other hand, when the amount of the catalyst used is too small, the reaction rate tends to be slow.

(Lactone compound)
Examples of the lactone compound of the present invention include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 8-hydroxyoctanoic acid lactone, 12-hydroxydodecanoic acid lactone, 13- Examples thereof include 3- to 16-membered lactone compounds such as hydroxytridecanoic acid lactone, 14-hydroxytetradecanoic acid lactone, and 15-hydroxypentadecanoic acid lactone.

  The lactone compound further includes dioxanes such as 3-ethyl-2-keto-1,4-dioxane, 1,4-dioxane-2-one, and 3-propyl-2-keto-1,4-dioxane. It is.

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

  Examples of the alkyl group include a straight chain having about 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Or a branched alkyl group is mentioned.

  Examples of the alkoxy group include about 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy group, etc. Is a lower alkoxy group having 1 to 4 carbon atoms.

  In the present invention, one of the above lactone compounds can be used alone or in combination of two or more. Of these, ε-caprolactone having a large practical value, methylated ε-caprolactone, δ-valerolactone, 3-ethyl-2-keto-1,4-dioxane and the like are preferably used.

  In the present invention, together with the lactone compound, another polymerizable monomer copolymerizable with the lactone compound (hereinafter sometimes referred to as “other monomer”) may be subjected to ring-opening polymerization. In that case, a lactone polymer having a monomer unit derived from a lactone compound and a monomer unit derived from another monomer is obtained. In addition, the ratio of the lactone compound in all the polymerizable monomers attached | subjected to ring-opening polymerization is 50 weight% or more, for example.

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

(Initiator)
In the method for producing a lactone polymer of the present invention, it is preferable to use a compound having a functional group containing active hydrogen as an initiator. Examples of the compound having a functional group containing active hydrogen include a compound containing at least one group selected from a hydroxyl group, a carboxyl group, a phosphate group, an amino group, and a thiol group. In the present invention, among them, a compound having a hydroxyl group is preferable from the viewpoint of excellent reactivity.

  Examples of the compound having a hydroxyl group include monovalent aliphatic alcohols such as methanol, ethanol, isopropanol, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and allyl alcohol; ethylene glycol, diethylene glycol, 1,3 Polyhydric alcohols such as butanediol, 1,4-butanediol, propylene glycol, 1,6-hexamethylenediol, neopentyl glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol; ethylene glycol monoacetate , Esters such as propylene glycol monoacetate and dipropylene glycol monoacetate; ethylene glycol monoalkyl Ethers; diethylene glycol monoalkyl ethers; propylene glycol monoalkyl ethers; dipropylene glycol monoalkyl ethers; butylene glycol monoalkyl ethers; phenols such as benzyl alcohol, phenol, catechol, biphenol, bisphenol A, bisphenol F, and novolak A hydroxyl group; an oligomer or polymer obtained by copolymerization or graft polymerization of a hydroxyl group-containing (meth) acrylate such as polyethylene glycol, polytetramethylene glycol, 2-hydroxyethyl (meth) acrylate, an epoxy resin containing a hydroxyl group, Examples thereof include polymer compounds such as polybutadiene containing a hydroxyl group. These can be used alone or in combination of two or more.

  In the present invention, it is particularly preferable to use a polyhydric alcohol as an initiator because a lactone polymer can be obtained more efficiently.

  The amount of the initiator used is preferably more than 0.5 mol, 120 mol or less, particularly preferably more than 1 mol, 120 mol or less, most preferably 5 to 50 mol with respect to 100 mol of the lactone compound. is there. It is possible to adjust the molecular weight of the lactone polymer obtained by controlling the molar ratio of the polymerizable monomer and the initiator.

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

  In the method for producing a lactone polymer of the present invention, any polymerization method such as bulk polymerization, solution polymerization and suspension polymerization can be employed.

  As the solvent used in the solution polymerization, for example, aromatic hydrocarbons such as toluene and xylene are preferable because they are inert to the reaction and have a high boiling point for comparison. The solvent is preferably substantially anhydrous.

  The polymerization reaction can be carried out by any method such as batch, semi-batch and continuous methods. After completion of the reaction, the reaction product can be separated and purified by, for example, separation / purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination of these.

  The reaction atmosphere is not particularly limited as long as the reaction is not inhibited. For example, the reaction is preferably performed in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere.

  Since the production method of the present invention uses the above catalyst, a lactone polymer having excellent hue (for example, hue [APHA] is 100 or less, preferably 60 or less, particularly preferably 50 or less) is obtained.

  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 used as a raw material for various molded products, it is possible to suppress the occurrence of bleeding out or blooming (exudation of low molecular weight components) in the final product.

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

  Moreover, in the manufacturing method of this invention, since the progress of a side reaction (for example, chain transfer reaction, transesterification etc.) is suppressed, it is excellent in hydrolysis resistance and an acid value is 20.0 or less (preferably 10. A lactone polymer of 0 or less, particularly preferably 5.0 or less) is obtained. Therefore, when the lactone polymer obtained by the production method of the present invention is used as a raw material, polyurethane and urethane (meth) acrylate can be produced efficiently. In addition, when a lactone polymer having a high acid value is used as a raw material, the urethanization reaction may be inhibited, and it may be difficult to efficiently produce polyurethane or urethane (meth) acrylate.

  Furthermore, in the production method of the present invention, the formation of a dimer (dimer) of a lactone compound can be reduced to, for example, 0.1% or less (preferably less than 0.05%). These contaminations can be suppressed extremely low. The dimer of the lactone compound may cause deposit formation or odor generation during the production or processing of polyurethane or urethane (meth) acrylate. By using the lactone polymer obtained by the production method of the present invention, it is possible to realize an operation with little formation of deposits and less odor during the production and processing of polyurethane and urethane (meth) acrylate.

  Since the lactone polymer obtained by the production method of the present invention also has the above characteristics, it is a raw material for various molded products, fibers, films, sheets, resins, elastomers, etc., a modifier, or a raw material for paints, adhesives, etc. It is particularly useful as a raw material for polyurethane and urethane (meth) acrylate.

[Method for producing polyurethane]
The polyurethane production method of the present invention is characterized in that a lactone polymer is produced by the above lactone polymer production method, and the resulting lactone polymer is reacted with a polyisocyanate compound to produce a polyurethane.

  Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate compounds such as diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate; Diisocyanate compounds obtained by hydrogenating aromatic isocyanate compounds among socyanate compounds (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate); such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate Examples of trivalent or higher valent isocyanate compounds; multimerized polyisocyanate compounds obtained by multiplying these compounds. These can be used alone or in combination of two or more.

  The polyurethane production method of the present invention is characterized in that the lactone polymer obtained by the above-mentioned lactone polymer production method is used as a polyol, and other conditions are the same as those of a conventionally known polyurethane production method. In the method for producing a polyurethane of the present invention, a chain extender can be used in consideration of a balance of physical properties. Examples of the chain extender include 1,3-propaneol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2- ( Hydroxymethyl) -1,3-propanediol, 3-methyl-1,5-pentanediol. These can be used alone or in combination of two or more. In addition, one or more general additives such as a catalyst, a crosslinking agent, a stabilizer, a foaming agent, a plasticizer, and a flame retardant can be used.

[Method for producing urethane (meth) acrylate]
The method for producing urethane (meth) acrylate of the present invention comprises producing a lactone polymer by the above-described method for producing a lactone polymer, and reacting the obtained lactone polymer, a hydroxyl group-containing (meth) acrylic acid ester and a polyisocyanate compound. And producing urethane (meth) acrylate.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 2- Hydroxy-3-methoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide and the like, and lactone adducts thereof [for example, manufactured by Daicel Corporation PCL-FA or PCL-FM series, etc.] can be used. Dipentaerythritol poly (meth) acrylate (for example, “DPHA” manufactured by Daicel Ornex Co., Ltd.) can also be used. These can be used alone or in combination of two or more. In this specification, “acryl” and “methacryl” may be collectively referred to as “(meth) acryl”.

  Examples of the polyisocyanate compound include the same examples as those exemplified in the above [Method for producing polyurethane].

  The method for producing a urethane (meth) acrylate according to the present invention is characterized by using a lactone polymer obtained by the above-mentioned method for producing a lactone polymer as a polyol. Other conditions include conventionally known urethane (meth) acrylates. This is the same as the manufacturing method. For example, by reacting a diisocyanate compound with a hydroxyl group-containing (meth) acrylic acid ester, a monoisocyanate compound having an isocyanate group at one end and a (meth) acryloyl group at the other end is synthesized. The compound includes a method of reacting a lactone polymer obtained by the above-described method for producing a lactone polymer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Examples 1 to 6, Comparative Examples 1 to 3 (Production of polycaprolactone diol)
According to the formulation shown in Table 1, an initiator (benzyl alcohol (BzOH) or ethylene glycol (EG)) is added to a 1 liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a condenser tube, and a temperature controller. Ε-Caprolactone (CL) was added as a lactone compound and heated to a predetermined temperature.
Next, while maintaining the reaction temperature, a predetermined amount of catalyst (zinc undecylenate, zinc laurate, or zinc octylate) is added to the reaction system to continue the reaction, and the concentration of ε-caprolactone in the reaction system is evaluated by gas chromatography. And when it became less than 1%, the reaction solution was cooled to stop the reaction to obtain polycaprolactone diol (number average molecular weight: about 3000, weight average molecular weight: about 3600).

The following items were evaluated for the obtained polycaprolactone diol. The results are summarized in Table 1.
<Molecular weight distribution: Mw / Mn>
Using a high-speed GPC apparatus, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by comparison with polystyrene standards, 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>
The amount of caprolactone dimer in the reaction system was measured using gas chromatography.
<Acid value>
Based on JIS K 0070 (1992), it measured by the neutralization titration method using phenolphthalein as an indicator.
<Hue: APHA>
Measured according to ASTM D 1209.

＊ＮＤ：不検出

* ND: Not detected

Example 7 (Production of polycaprolactone triol)
In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube and condenser, 155.0 g of trimethylolpropane (TMP), 845.0 g of ε-caprolactone (6.4 mol with respect to 1 mol of trimethylolpropane) Then, 0.050 g (50 ppm) of zinc undecylenate was charged and reacted at 160 ° C.
The concentration of ε-caprolactone in the reaction system was measured by gas chromatography. When the concentration was less than 0.2%, the reaction solution was cooled to stop the reaction, and polycaprolactone triol (1) that was liquid at room temperature was obtained.
The molecular weight distribution (Mw / Mn) and caprolactone dimer amount of the obtained polycaprolactone triol were measured by the same method as described above. The results are summarized in Table 2.

Comparative Example 4 (Production of polycaprolactone triol)
Polycaprolactone triol (2) that was liquid at room temperature was obtained in the same manner as in Example 7 except that 0.010 g (10 ppm) of tetrabutoxytitanium was used as a catalyst and the reaction was performed at 170 ° C.

Reference Example 1 (Production of polycaprolactone triol)
A polycaprolactone triol (3) liquid at room 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 reacted at 170 ° C.

The method for producing a lactone polymer of the present invention can efficiently produce a lactone polymer under mild conditions while reducing the environmental burden. Therefore, it is suitable as a method for industrially producing a lactone polymer.
And the lactone polymer obtained by the manufacturing method of the lactone polymer of this invention is excellent in hue, hydrolysis resistance, and durability. Moreover, since molecular weight distribution is narrow, it can suppress that bleed out and blooming generate | occur | produce in a final product. Furthermore, the dimer content is small and the storage stability is excellent.
If the lactone polymer obtained by the production method of the present invention is used as a raw material, it is possible to suppress the formation of deposits and the generation of odors during the production and processing of polyurethane and urethane (meth) acrylate, and durability is improved. Excellent end product can be formed.

Claims (9)

  A method for producing a lactone polymer, wherein a lactone polymer is obtained by ring-opening polymerization of a lactone compound, wherein as a catalyst, a fatty acid zinc salt having 9 or more carbon atoms is added in an amount of 1 to 500 ppm based on the total amount of the lactone compound and the initiator. A method for producing a lactone polymer, characterized by being used in a range.   The method for producing a lactone polymer according to claim 1, wherein the fatty acid zinc salt having 9 or more carbon atoms constituting the catalyst is an unsaturated fatty acid zinc salt having 9 or more carbon atoms.   The method for producing a lactone polymer according to claim 1, wherein the fatty acid zinc salt having 9 or more carbon atoms 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 120 mol or less with respect to 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 active hydrogen is used as an initiator.   The method for producing a lactone polymer according to any one of claims 1 to 4, wherein a polyhydric alcohol is used as an initiator.   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.   The manufacturing method of the polyurethane which manufactures a lactone polymer by the manufacturing method of the lactone polymer of any one of Claims 1-7, and reacts the obtained lactone polymer and a polyisocyanate compound, and manufactures a polyurethane.   A lactone polymer is produced by the method for producing a lactone polymer according to any one of claims 1 to 7, and the obtained lactone polymer, a hydroxyl group-containing (meth) acrylic acid ester and a polyisocyanate compound are reacted. The manufacturing method of urethane (meth) acrylate which manufactures urethane (meth) acrylate.