阅读说明：本技术 共聚物以及聚氨酯的制备方法 (Method for producing copolymer and polyurethane ) 是由 松本明洋 青木良和 佐藤刚 于 2020-09-15 设计创作，主要内容包括：一种共聚物以及聚氨酯的制备方法。提供一种能够容易地控制内酯聚合物的分子量,能够容易且完全地去除作为残留催化剂的废酸,着色或杂质的生成少并且在工业上非常简单且无浪费地制备高质量的聚醚的方法。本发明涉及一种五元环环状醚(A)和内酯类(B)的共聚物的制备方法,其特征在于,在10℃～50℃的温度范围内进行共聚反应,将杂多酸作为催化剂,将含有羟基、氨基、巯基的含有活性氢原子的化合物作为反应引发剂(C)使用,并且并用三元环至四元环环状醚(D)。(A method for preparing copolymer and polyurethane. A process for producing a high-quality polyether which is industrially very simple and free from waste, while easily controlling the molecular weight of a lactone polymer, easily and completely removing waste acid as a residual catalyst, and producing little coloration or impurities. The present invention relates to a method for producing a copolymer of a five-membered cyclic ether (A) and a lactone (B), characterized by carrying out a copolymerization reaction at a temperature of 10 ℃ to 50 ℃, using a heteropoly acid as a catalyst, using a compound containing a hydroxyl group, an amino group, and a mercapto group and containing an active hydrogen atom as a reaction initiator (C), and using a three-to four-membered cyclic ether (D) in combination.)

1. A process for producing a copolymer of a five-membered cyclic ether (A) and a lactone (B), wherein,

copolymerization is carried out at a temperature of 10 to 50 ℃ and a three-to four-membered cyclic ether (D) is used in combination with a heteropoly acid as a catalyst and a compound containing a hydroxyl group, an amino group and a mercapto group and having an active hydrogen atom as a reaction initiator (C).

2. The method for producing a copolymer according to claim 1, wherein,

the five-membered cyclic ether (A) is a tetrahydrofuran, and the amount of the five-membered cyclic ether (A) added is 1 to 90 mol% based on the total mole number of the five-membered cyclic ether (A) and the lactone (B).

3. The method for producing a copolymer according to claim 1, wherein,

the lactone (B) may have a substituent and is beta-propiolactone, gamma-butyrolactone, delta-valerolactone or epsilon-caprolactone, and the amount of the lactone (B) added is 1 to 90 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

4. The method for producing a copolymer according to claim 1, wherein,

the reaction initiator (C) is a hydroxyl compound having at least one hydroxyl group, and is added in an amount of 0 to 20 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

5. The method for producing a copolymer according to claim 1, wherein,

the three-to four-membered cyclic ether (D) is an epoxide or an oxetane, and is added in an amount of 0.1 to 50 mol% based on the total mole number of the five-membered cyclic ether (A) and the lactone (B).

6. The method for producing a copolymer according to claim 1, wherein,

the catalyst is untreated heteropoly acid, and the addition amount of the catalyst is 0.01-2 mol% relative to the total mol number of the five-membered cyclic ether (A) and the lactone (B).

7. The method for producing a copolymer according to claim 1, wherein,

a process for producing a copolymer of a five-membered cyclic ether (A) and a lactone (B), which comprises subjecting to a copolymerization reaction at a temperature of 10 to 50 ℃ in the presence of a catalyst comprising 0.01 to 2 mol% of a heteropolyacid and a reaction initiator (C) comprising 0 to 5 mol% of a hydroxy compound having at least one hydroxy group, and in combination 40 to 80 mol% of a tetrahydrofuran-based five-membered cyclic ether (A), 20 to 60 mol% of an epsilon-caprolactone-based lactone (B) and 5 to 20 mol% of a three-to four-membered cyclic ether (D), based on the total mole number of the five-membered cyclic ether (A) and the lactone (B).

8. A process for the preparation of a polyurethane, wherein,

reacting the copolymer obtained by the production method according to any one of claims 1 to 7 and a polyisocyanate compound to produce a polyurethane.

Technical Field

The invention relates to a preparation method of a five-membered cyclic ether and lactone copolymer.

Background

Cyclic ethers such as Tetrahydrofuran (THF) have been known to be polymerized by cationic catalysts such as protonic acids, lewis acids, and ionic complexes. In addition, lactones such as β -propiolactone or ∈ -caprolactone are known to be easily polymerized by both cationic catalysts and anionic catalysts. The polymer such as polytetramethylene ether glycol or polycaprolactone glycol obtained in this way is a useful material as a soft segment of a polyurethane resin or a polyester resin.

Polytetramethylene ether glycol has a polyether as a main chain, and a lactone-type ring-opening polymer such as polycaprolactone glycol has a polyester as a main chain, and therefore, they have advantages and disadvantages contrary to each other in hydrolysis resistance, heat resistance, light resistance, and the like. As a solution to compensate for these shortfalls, polyether polyester diols obtained by copolymerization of THF and lactones may be considered. However, THF and lactones differ greatly in polymerizability and it is difficult to copolymerize them. As a method for copolymerizing THF and epsilon-caprolactone, a method using lewis acid as a catalyst is known (non-patent document 1), but the obtained copolymer has high blockiness, that is, THF and epsilon-caprolactone cannot be polymerized randomly, and a compound such as a block copolymer of polytetrahydrofuran and polyepsilon-caprolactone or a mixture of polytetramethylene ether and polycaprolactone diol is obtained.

To solve these problems, a method for copolymerizing THF and epsilon-caprolactone characterized by using boron trifluoride (BF) as a Lewis acid in a catalyst has been reported₃) And a tri-to quaternary cyclic ether in combination with a tertiary ring, a fuming sulfuric acid, a fluorosulfuric acid, or the like (for example, patent document 1).

Further, a method of copolymerizing a lactone and a cyclic ether by using an anion ring-opening polymerization catalyst such as tetrabutyl titanate or by performing a reaction at a high temperature of 100 to 200 ℃ has been reported (for example, patent document 2).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. Sho 63-178131 No. Heng

Patent document 2: japanese patent laid-open No. 2019-23256 publication No.

Non-patent document

Non-patent document 1: "Journal of Polymer (Polymer Journal)", (Japan), 1971, volume 3, No. 3, page 389-393

Disclosure of Invention

The molecular weight of the copolymer cannot be controlled only by using three-membered to four-membered cyclic ethers in combination, and thus a copolymer of a target molecular weight cannot be obtained. Further, catalyst systems such as boron trifluoride, fuming sulfuric acid, and fluorosulfuric acid have a problem that they require fluorination treatment or treatment of a large amount of waste acid in the subsequent treatment. Further, since a side reaction such as a transesterification reaction occurs simultaneously with the high-temperature anionic polymerization, and a large amount of oligomer is contained, the conventional production method has a problem that the molecular weight of the copolymer cannot be controlled, a large amount of waste acid is treated, and the polymerization at a high temperature generates impurities due to the side reaction.

In view of the above circumstances, the present inventors have conducted extensive studies and as a result have found a production method capable of copolymerizing a five-membered ring cyclic ether and a lactone by a polymerization process using a three-to four-membered ring cyclic ether as an initiator under a condition that the amount of a heteropoly acid catalyst to be used is reduced to a trace amount, and have completed the present invention.

Namely, the copolymer of the present invention is prepared as follows.

[1] A process for producing a copolymer of a five-membered cyclic ether (A) and a lactone (B), wherein a copolymerization reaction is carried out at a temperature in the range of 10 ℃ to 50 ℃, a Lewis acid and/or a solid acid (preferably a heteropoly acid) is used as a catalyst, a compound containing an active hydrogen atom and having a hydroxyl group, an amino group or a mercapto group is optionally used as a reaction initiator (C), and a three-to four-membered cyclic ether (D) is used in combination.

[2] The method for producing a copolymer according to [1], wherein the five-membered cyclic ether (A) is a tetrahydrofuran, and the amount (blending ratio) of the five-membered cyclic ether (A) is 1 to 90 mol% based on the total mole number of the five-membered cyclic ether (A) and the lactone (B).

[3] The process for producing a copolymer according to [1], wherein the lactone (B) may have a substituent and is β -propiolactone, γ -butyrolactone, δ -valerolactone or ∈ -caprolactone, and the amount of the lactone (B) added (the blending ratio) is 1 to 90 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

[4] The method for producing a copolymer according to [1], wherein the reaction initiator (C) is a hydroxyl compound having one or more hydroxyl groups, and is added in an amount of 0 to 20 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

[5] The process for producing a copolymer according to [1], wherein the three-to four-membered cyclic ether (D) is an epoxide or an oxetane, and the amount of the three-to four-membered cyclic ether (D) is 0.1 to 50 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

[6] The process for producing a copolymer according to [1], wherein the catalyst is an untreated heteropoly acid and is added in an amount of 0.01 to 2 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B).

[7] The process for producing a copolymer according to [1], wherein the copolymer is produced by a copolymerization reaction of a five-membered cyclic ether (A) and a lactone (B) at a temperature of 10 ℃ to 50 ℃, and wherein a heteropoly acid is used as a catalyst in an amount of 0.01 to 2 mol% based on the total mole number of the five-membered cyclic ether (A) and the lactone (B), a hydroxy compound having one or more hydroxy groups is used as a reaction initiator (C) in an amount of 0 to 5 mol%, and a tetrahydrofuran-based five-membered cyclic ether (A), an epsilon-caprolactone-based lactone (B) in an amount of 20 to 60 mol% and a three-to four-membered cyclic ether (D) in an amount of 5 to 20 mol% are used in combination.

[8] A production method of polyurethane, wherein a copolymer obtained by the production method of any one of [1] to [7] and a polyisocyanate compound are allowed to react to produce polyurethane.

The preparation method of the copolymer of five-membered cyclic ether and lactone can simply adsorb and remove heteropoly acid through ion exchange resin under the condition of not processing heteropoly acid and using trace amount, and then can obtain the copolymer of five-membered cyclic ether and lactone only by distilling off unreacted cyclic ether. The method for producing a copolymer of a five-membered cyclic ether and a lactone of the present invention does not require a step such as a hydrolysis operation or a washing operation, and therefore, it is an extremely simple production method which does not require any treatment of waste acid or waste water produced.

In addition, the method for producing the copolymer of five-membered cyclic ether and lactone of the present invention determines the optimum polymerization reaction temperature depending on the kind and amount of the initiator, the quality and molecular weight of the target polymer, and the like, and therefore the polymerization reaction can be carried out in an inert organic solvent. Further, the copolymer obtained at a temperature of 50 ℃ or lower is free from quality deterioration, such as coloration, caused by side reactions.

In addition, the method for producing a copolymer of a five-membered cyclic ether and a lactone of the present invention can easily control the molecular weight by changing the amount of the catalyst used and the amount of the initiator added, and thus can control the molecular weight of the copolymer.

Thus, the process for producing the copolymer of a five-membered cyclic ether and a lactone of the present invention is an excellent process which is industrially very simple and free from waste and which enables to obtain a polyether of high quality.

Detailed Description

The present invention will be described in more detail with reference to preferred embodiments.

Specific examples of the lactone compounds (B) include β -propiolactone, β -butyrolactone, β -valerolactone, γ -butyrolactone, γ -valerolactone, γ -octanolide, δ -valerolactone, β -methyl- δ -valerolactone, δ -stearolactone (δ -stearolactone), ε -caprolactone, 2-methyl- ε -caprolactone, 4-methyl- ε -caprolactone, ε -octanolide and ε -palmitolactone.

Examples of the 3 to 4-membered cyclic ether (D) include epoxides such as ethylene oxide, propylene oxide and epichlorohydrin, and oxetanes such as 3-methyloxetane and 3, 3-bis (chloromethyl) -oxetane.

When the 3 to 4-membered cyclic ether (D) is used, the amount thereof to be added is preferably 0.1 to 50 mol%, particularly preferably 0.1 to 10 mol%, based on the total mole number of the five-membered cyclic ether (a) and the lactone (B). When the 3-to 4-membered cyclic ether (D) is not used, the compound is a mixture of a cyclic ether polymer and a lactone polymer without copolymerization. When the 3 to 4-membered cyclic ether (D) is more than 50 mol%, the composition ratio of the polymer is greatly changed, which results in deterioration of physical properties, and a large amount of unreacted materials is generated, which is not preferable because it requires cost for removal.

Examples of the five-membered cyclic ether (A) include tetrahydrofuran compounds such as tetrahydrofuran, 2-methyltetrahydrofuran and 3-methyltetrahydrofuran, and dioxolane.

The method for producing the copolymer of the five-membered cyclic ether (A) and the lactone (B) is characterized in that, when the five-membered cyclic ether (A) is used, the amount thereof to be added is preferably 1 to 90 mol%, particularly preferably 10 to 80 mol%, based on the total mole number of the five-membered cyclic ether (A) and the lactone (B).

The compound containing an active hydrogen atom is a compound containing a hydroxyl group, an amino group and a mercapto group, and is used as the reaction initiator (C). Examples of the hydroxyl group-containing compound include aliphatic alcohols such as methanol, ethanol, propanol, n-butanol, second butanol, third butanol, allyl alcohol and 2-hydroxyethyl methacrylate, aromatic alcohols such as benzyl alcohol and benzyl methanol, alicyclic alcohols such as cyclohexanol and trimethylhexanol, polyhydric alcohols such as ethylene glycol, propylene glycol, 1, 4-butanediol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, glycerin, trimethylolpropane, cyclohexanediol and xylylene glycol, and various other phenols, organic carboxylic acids and amino group-containing compounds including aliphatic primary amines such as methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-and tert-butyl groups and corresponding aliphatic secondary amines such as dialkylamines, secondary amines such as dialkyl amines, and the like, Aliphatic, aromatic, alicyclic and heterocyclic polyamines such as aniline, toluidine (tolulidine), diphenylamine, cyclohexylamine and piperidine, and aliphatic, aromatic, alicyclic and heterocyclic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, o-, m-or p-phenylenediamine, 1, 4-cyclohexanediamine, piperazine, diethylenetriamine and 4,4 ', 4 ″ -methylenetriphenylamine (4, 4', 4 ″ -methylidyne trianiline). Examples of the mercapto group-containing compound include aliphatic thiols such as methyl-, ethyl-, propyl-, and butyl-, aromatic thiols such as benzyl thiol, ethylene dithioglycol (ethylene dithioglycol), xylylene glycol (xylylene glycol), mercaptoethanol, and the like.

The method for producing the copolymerization method of the five-membered cyclic ether (a) and the lactone (B) is characterized in that when a polyhydric alcohol is used as the initiator (C), the amount thereof to be used is preferably 0 to 20 mol% (preferably 0 mol% is excluded), and particularly preferably 0.1 to 1.0 mol% with respect to the total mol number of the five-membered cyclic ether (a) and the lactone (B). When the initiator (C) is used in an amount of more than 20 mol%, the molecular weight of the product is small and a sufficient polymer body is not produced. When the initiator (C) is not used, the molecular weight cannot be controlled and a compound of a target molecular weight cannot be obtained.

Examples of the solid acid used in the present invention include silica, titania, zirconia, alumina, and heteropolyacids (for example, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and silicomolybdic acid). Examples of the lewis acid include metal or nonmetal halides such as boron trifluoride, phosphorus pentafluoride, antimony pentachloride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Further, as a form of the catalyst using them, boron trifluoride, antimony pentachloride and the like, and a complex of a linear ether and a cyclic ether such as diethyl ether, tetrahydrofuran and the like may be mentioned.

The method for producing the copolymer of the five-membered cyclic ether (a) and the lactone (B) is characterized in that the amount of the lewis acid and/or the solid acid catalyst used in the present invention is preferably 2 mol% or less, and particularly preferably 0.1 mol% to 1.0 mol% based on the total mole number of the five-membered cyclic ether (a) and the lactone (B). Characterized in that the amount of the catalyst used is extremely small, and therefore, the removal thereof is also easy. When the catalyst is used in an amount of more than 2 mol%, heat generation may be significant and the molecular weight distribution is greatly broadened, and in addition, side reactions cause quality deterioration, such as coloration, to be significant. Further, it is difficult to remove the catalyst by an ion exchange resin, and therefore, a water washing step is required, and cost is required for removing the catalyst, which is not preferable.

In carrying out the present invention, the polymerization reaction temperature is preferably 50 ℃ or lower, particularly preferably 0 to 40 ℃, but the optimum temperature depends on the kind and amount of the initiator (C), the mass, molecular weight, etc. of the objective polymer, and is usually 20 to 40 ℃. The polymerization reaction may also be carried out in an inert organic solvent. In bulk polymerization at a relatively low temperature, crystallization is likely to occur while the polymerization is carried out, and therefore, it is preferable to carry out the polymerization in an inert organic solvent such as benzene, toluene, or xylene. At a temperature higher than 100 ℃, the molecular weight distribution is greatly broadened, and not only does a side reaction cause quality deterioration, such as coloration, conspicuous. On the other hand, the polymerization reaction time depends on the reaction rate and varies depending on the temperature, the kind and the amount of the initiator (C) used. Usually, it is set to 2 to 10 hours or more. In this polymerization system, in order to simplify the purification operation of the polymer and improve the quality, it is preferable to conduct the polymerization until unreacted lactone disappears, and sufficient aging is required.

The method for producing the polyurethane resin using the copolymer of the five-membered cyclic ether (a) and the lactone-based compound (B) obtained in the present invention is not particularly limited, and the polyurethane resin can be produced by a known method or the like. For example, the polyisocyanate component may be added together with the polyol, the chain extender, and the organic metal catalyst to carry out the reaction, or the extension reaction may be carried out by adding the chain extender after the polyol and the polyisocyanate component are reacted to obtain an isocyanate group-terminated prepolymer.

Examples of the polyisocyanate compound include aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups.

Specific examples thereof include polyisocyanates such as Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (MDI), Xylylene Diisocyanate (XDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HMDI). Here, MDI is preferable in terms of easy availability and control of the reaction with hydroxyl groups.

Examples of the chain extender include low molecular weight glycols such as 1, 3-propanediol, 1, 4-butanediol, and 1, 5-pentanediol.

The organic metal catalyst is not particularly limited, and specific examples thereof include organic tin catalysts such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride and dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate and bismuth naphthenate. Among them, preferred compounds are organotin catalysts, and more preferred is dibutyltin dilaurate.

When the amount of the copolymer of the five-membered cyclic ether (A) and the lactone-type (B) is 100.0 parts by weight, the amount of the organometallic catalyst used is usually in the range of 0.0001 to 5.0 parts by weight, more preferably in the range of 0.001 to 3.0 parts by weight.

The measurement method used in the present invention is described below.

[ method for measuring number average molecular weight (Mn) of copolymer of five-membered cyclic ether and lactone ]

The number average molecular weight (Mn) of the lactone polymer of the present invention can be measured, for example, by gel permeation chromatography (hereinafter, abbreviated as GPC) under the following conditions.

The device comprises the following steps: TOSOH HPLC-8320gPC (manufactured by Tosoh corporation of Japan)

A chromatographic column: TSK gelG4000H + G2500H (supra)

A detector: RI (Ri)

Eluent: tetrahydrofuran (THF)

Standard substance: polytetramethylene ether glycol

Injection amount: 100 μ L

Flow rate: 1.0 mL/min

And (3) measuring the temperature: 40 deg.C

[ method for measuring color number of copolymer of five-membered cyclic ether and lactone ]

The color number of the present invention can be determined by the method of JIS K4101-1993-13.

[ examples ]

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.

[ example 1]

[ Synthesis of THF-polycaprolactone copolymer ]

63.3g (0.56 mol, 50 mol% based on the total mol of the five-membered cyclic ether (A) and the lactone (B), manufactured by Tokyo Kasei Co., Ltd.), 40.0g (0.56 mol, 50 mol% based on the total mol of the five-membered cyclic ether (A) and the lactone (B), 1.7g (0.02 mol) of 1, 4-butanediol (C), 1.6 mol% based on the total mol of the five-membered cyclic ether (A) and the lactone (B), manufactured by Nippon Kasei chemical Co., Ltd.) were added to a 500mL four-necked separable flask, phosphotungstic acid (catalyst) 0.6g (0.0003 mol, 0.02 mol% based on the total mol number of the five-membered cyclic ether (A) and the lactone (B), manufactured by Nippon Metal Co., Ltd.) was charged, and a thermometer, a nitrogen seal and a stirring device were attached. After stirring at 25 ℃ for 15 minutes, 6.4g (0.11 mol, 10.0 mol% relative to the total mole number of the five-membered cyclic ether (A) and the lactone (B), manufactured by Nihon chemical Co., Ltd., Japan) of propylene oxide (D) was added thereto, and the mixture was stirred at 25 ℃ for 4 hours. Then, THF100mL and an ion exchange resin IRA-96S50g (manufactured by Organo corporation) were added to the reaction mixture as a washing solvent, and the mixture was stirred for 2 hours. The reaction mixture was filtered, and THF was removed from the filtrate by distillation under the reduced pressure to obtain a polymer. The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 2]

[ Synthesis of THF-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same manner as in example 1 except that ε -caprolactone in example 1 was changed to 37.7g (0.33 mol) and THF was changed to 55.5g (0.77 mol). The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 3]

[ Synthesis of 3-methyl-THF-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same operation as in example 1, except that THF40.0g (0.56 mol) of example 1 was replaced with 3-methyl-THF 48.2g (0.56 mol). The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 4]

[ Synthesis of Dioxolane-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same manner as in example 1 except that 40.0g (0.56 mol) of THF in example 1 was replaced with 41.5g (0.56 mol) of 1, 3-dioxolane. The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 5]

[ Synthesis of THF-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same operation as in example 1 except that 0.6g (0.0003 mol) of phosphotungstic acid in example 1 was replaced with 1.5g (0.01 mol, manufactured by Sigma Aldrich Japan) of boron trifluoride tetrahydrofuran complex. The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 6]

[ Synthesis of THF-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same operation as in example 1 except that 1.7g (0.02 mol) of 1, 4-butanediol of example 1 was changed to 2.4g (0.03 mol). The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 7]

[ Synthesis of THF-polycaprolactone copolymer ]

Polymerization was carried out under the same conditions and in the same operation as in example 1 except that 1.7g (0.02 mol) of 1, 4-butanediol of example 1 was changed to 3.2g (0.04 mol). The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

[ example 8]

< Synthesis of THF-polycaprolactone copolymer >

Polymerization was carried out under the same conditions and in the same operation as in example 1 except that 1.7g (0.02 mol) of 1, 4-butanediol of example 1 was not used. The types of THF, the combination ratio of each raw material, the reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

Comparative example 1

< Synthesis of THF-polycaprolactone copolymer >

Polymerization was carried out under the same conditions and in the same manner as in example 1, except that the reaction temperature in example 1 was changed to 60 ℃. The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

Comparative example 2

< Synthesis of THF-polycaprolactone copolymer >

Polymerization was carried out under the same conditions and in the same manner as in example 1 except that the amount of the catalyst added in example 1 was changed to 2.1 mol%. To the obtained reaction mixture, THF100mL and an ion exchange resin IRA-96S50g (manufactured by Japan organic Co., Ltd.) were added as a washing solvent, and stirred for 2 hours, and the reaction mixture was filtered. The filtrate was cloudy and the pH was acidic, indicating significant catalyst remaining. Therefore, 100g of ion-exchanged water was added to the filtrate, and after stirring at 60 ℃ for 1 hour, the mixture was left to stand for 1 hour, and the aqueous layer was separated and discarded. This operation was repeated three times. The resulting oil layer was stirred for 2 hours while adding an ion exchange resin IRA-96S50g (manufactured by Organo corporation). The reaction mixture was filtered. THF was removed from the filtrate by distillation under the reduced pressure to obtain a polymer. The combination ratio of each raw material, reaction temperature/stirring time, and the yield, number average molecular weight (Mn), and color number of the obtained polymer were analyzed, and the results are shown in table 1.

TABLE 1

Abbreviations described in table 1 are described below.

CL: epsilon-caprolactone

3Me THF: 3-methyl-tetrahydrofuran

DOX: 1, 3-dioxolanes

PO: propylene oxide

[ Industrial availability ]

As is apparent from the examples and comparative examples, the molecular weight of the polymer obtained by the production method of the present invention can be easily controlled by changing the amount of the initiator (C) to be added. Further, even when the heteropoly acid which is a catalyst is added in a small amount, and the metal or nonmetal halide (1 mol% or less based on the total mole number of the five-membered cyclic ether (a) and the lactone (B)), the copolymerization reaction can be smoothly performed, and when 2 mol% or less based on the total mole number of the five-membered cyclic ether (a) and the lactone (B), the residual catalyst, i.e., waste acid can be easily and completely removed by the ion exchange resin, and then the copolymer can be obtained only by distilling off unreacted THF. In addition, the reaction proceeds at normal temperature, and therefore a copolymer with less coloring or impurity formation and a satisfactory color number can be obtained. The production process of the present invention is an excellent production process which is industrially very simple and free from waste and which enables obtaining a high-quality polyether.