JP2820982B2 - Alkyl-δ-valerolactone polymer and method for producing the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel alkyl-δ-valerolactone polymer and a method for producing the same. (Wherein, R ¹ represents an m-valent hydrocarbon group having 1 to 18 carbon atoms;
R ² represents an alkylene group having 2 to 4 carbon atoms, and Y represents 2 carbon atoms.
To 6 and represents an alkylene group, and
40 mol% or more is an alkyltetramethylene group having 5 or 6 carbon atoms, m represents an integer of 1 to 3, and the average value of n is
1-m to 87 / m) and an alkyl-δ-valerolactone polymer represented by the formula:

The alkyl-δ-valerolactone polymer of the present invention is
Since it is a liquid polymer having high thermal stability, it is useful as a plasticizer for resins such as polyvinyl chloride.

[Conventional technology]

A liquid terminal obtained by subjecting a monomer containing at least 50 mol% of β-methyl-δ-valerolactone to a ring-opening polymerization reaction using an alcohol such as methanol, ethylene glycol or trimethylolpropane as an initiator, and having a hydroxyl group at a terminal end. In a composition comprising a β-methyl-δ-valerolactone-based polyester and an organic carbodiimide compound such as dicyclohexylcarbimide, the disadvantage that the polyester is originally susceptible to thermal open polymerization is improved. Therefore, it is known that the composition is useful as a plasticizer for resins such as polyvinyl chloride (see JP-A-63-225653).

[Problems to be solved by the invention]

According to the study of the present inventors, an alkyl-δ-valerolactone-based polyester having a hydroxyl group at a liquid end, such as a β-methyl-δ-valerolactone-based polyester having a hydroxyl group at the end, and an organic carbodiimide compound When such a composition was used as a plasticizer for the resin, it was found that the resin sometimes became cloudy due to the organic carbodiimide compound and that the resin exhibited skin irritation. Therefore, if a derivative having improved thermal stability of an alkyl-δ-valerolactone-based polyester having a hydroxyl group at a terminal can be obtained, a plasticizer having the above-mentioned disadvantages caused by an organic carbodiide compound can be provided. This is very desirable.

Die Makromolek
Vol. 82, pp. 41-52 (1965), δ-valerolactone-based polyester diol which is a ring-opening polymer of δ-valerolactone produced using ethylene glycol as an initiator is disclosed as acetic anhydride. It was reported that the hydroxyl groups at both ends of the δ-valerolactone-based polyester diol were respectively acetylated by reacting with acetic anhydride under heating and refluxing, and in the acetylated product thus obtained, It is reported that, unlike the δ-valerolactone-based polyester diol, which is a precursor, it is hardly subjected to depolymerization by heat. The present inventors attempted to acetylate the terminal hydroxyl group of an alkyl-δ-valerolactone-based polyester having a hydroxyl group at the terminal according to the acetylation method described above, and as shown in Reference Example 1 described below, It has been found that it is difficult to reproducibly produce an acetylated product having a desired molecular weight because depolymerization occurs under the conditions.

Thus, one of the objects of the present invention is to provide a liquid derivative having high thermal stability, which can be produced from an alkyl-δ-valerolactone-based polyester having a hydroxyl group at a terminal without depolymerization. To provide. Another object of the present invention is to provide a method for producing a liquid derivative having excellent thermal stability of an alkyl-δ-valerolactone-based polyester having a hydroxyl group at a terminal from the polyester without the polymerization. is there.

[Means for solving the problem]

According to the present invention, the above object has been attained by providing an alkyl-δ-valerolactone-based polymer represented by the general formula (I). (Wherein R ¹ , Y, m and n are as defined above) in the presence of an acidic catalyst. (Wherein R ² is as defined above, R ³ represents a hydrogen atom, R ⁴ represents a hydroxyl group or a lower alkoxyl group, or R ³ and R ⁴ together represent a single crystal) This is achieved by providing a process for producing an alkyl-δ-valerolactone-based polymer represented by the general formula (I), characterized by reacting with a cyclic ether represented by the following formula:

The m-valent hydrocarbon group having 1 to 18 carbon atoms represented by R ¹ in the above general formulas (I) and (II) is
It is roughly classified into a monovalent hydrocarbon group, a divalent hydrocarbon group having 1 to 18 carbon atoms, and a trivalent hydrocarbon group having 1 to 18 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and octyl. Group, 2-ethylhexyl group,
Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, alkyl group such as octadecyl group; alkenyl group such as 2,7-octadiethyl group; cyclohexyl group etc. A cycloalkyl group; an aralkyl group such as a benzyl group; Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, hexamethylene, and 3-methyl. Alkylene groups such as pentamethylene group, 2-methyloctamethylene group and nonamethylene group; cycloalkanediyl groups such as 1,2-cyclohexylene group, 1,3-cyclohexylene group and 1,4-cyclohexylene group; phenyl Ethylene group, o-xylene-α, α′-diyl group,
m-xylene-α, α'-diyl group, p-xylene-
An arylalkanediyl group such as an α, α'-diyl group is exemplified. Examples of the trivalent hydrocarbon group having 1 to 18 carbon atoms include a 1,2,3-propanetriyl group, A group represented by the formula A group represented by the formula And alkanetriyl groups.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ² in the general formulas (I) and (III) include an ethylene group, a trimethylene group, a propylene group, a 1-methyltrimethylene group,
Examples thereof include a 2-methyltrimethylene group and a tetramethylene group.

Examples of the alkylene group having 2 to 6 carbon atoms represented by Y in the general formulas (I) and (II) include an ethylene group, a 1,1-dimethylethylene group, a tetramethylene group, a 1-methyltetramethylene group, -Methyltetramethylene group, 2-ethyltetramethylene group, pentamethylene group and the like. In the molecule of the alkyl-δ-valerolactone-based polymer represented by the general formula (I) or the hydroxyl group-containing polymer represented by the general formula (II), m × n Ys are contained on average, The alkylene group having 2 to 6 carbon atoms represented by Y is not limited to one kind, and may be two or more kinds. However, 40 mol% or more of Y contained in the molecule of the polymer is 2
It must be a C5 or C6 alkyltetramethylene group such as -methyltetramethylene group, 1-methyltetramethylene group, 2-ethyltetramethylene group. Carbon number 2 represented by Y in the general formula (I)
In a polymer corresponding to the case where the ratio of the alkyltetramethylene group having 5 or 6 carbon atoms in the alkylene group having from 6 to 6 is less than 40 mol%, the crystallinity becomes high and the ability to plasticize the resin is insufficient. May be. In the general formula (I), Y is two or more alkylene groups having 2 to 6 carbon atoms, and two or more types of alkyl-δ-valerolactone-based polymers contained in the molecule of the polymer. (Wherein, Y is as defined above). The sequence of the structural units represented by
It may be in the form of a random copolymer or in the form of a block copolymer.

The average value of n in the general formulas (I) and (II) is 1 /
It is a number between m and 87 / m, but preferably between 8 / m and 44 / m. In a polymer corresponding to the case where the average value of n in the general formula (I) is smaller than 1 / m, the resin is not suitable for use as a plasticizer because it is easily leached from the compounded resin. On the other hand, a polymer corresponding to a case where the average value of n in the general formula (I) is larger than 87 / m has insufficient ability to plasticize the resin. The average value of n in the general formula (I) and the general formula (II) and the ratio of the alkyltetramethylene group in Y are respectively the alkyl-δ-valerolactone-based polymer represented by the general formula (I) or General formula (II)
Is a value determined based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the hydroxyl group-containing polymer represented by.

Among the alkyl-δ-valerolactone polymers represented by the general formula (I), (Wherein R ¹ , R ² and m are as defined above, and Y ¹
Represents a linear alkylene group having 2 to 5 carbon atoms, the average value of l ₁ is a positive number, the average value of l ₂ is a number of 0 or more, and
The average of l _{1 and} the average of l ₂ are respectively the average of l ₁
Relationship where the sum of l _{2 and} the average value is a number from 1 / m to 87 / m and l ₁
Average and l ratio of the average value of l ₁ to the sum of the mean value of ₂ is a number satisfying a relation of 40 mol% or higher) with β- methyl -δ- valerolactone polymer represented in,
Especially the general formula (Wherein R ¹ , R ² , m and n are as defined above), are particularly excellent in the plasticity of the resin even at a low temperature. It is preferable because it can exhibit chemical conversion ability.

Examples of the β-methyl-δ-valerolactone-based polymer represented by the general formula (I ′) include a β-methyl-δ-valerolactone-based polymer group represented by the following general formula.

(Wherein, R ⁵ represents an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an octadecyl group, and the average value of n ₁ is a number of ₁ to 87) (Wherein, R ⁵ and n ₁ are as defined above) (Wherein, R ⁵ and n ₁ are as defined above) (Wherein, R ⁶ is an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 3-methylpentamethylene group,
Hexamethylene group, nonamethylene group, represents an alkylene group having 2 to 10 carbon atoms such as a 2-methyloctamethylene group,
The average of n ₂ is a number between 0.5 and 43.5) (Wherein R ⁶ and n ₂ are as defined above) (Wherein R ⁶ and n ₂ are as defined above) Wherein R ⁷ is a 1,2,3-propanetriyl group, A group represented by the formula Represents an alkanetriyl group having 3 to 10 carbon atoms such as a group represented by, and the average value of n3 is a number of _1/3 to 29) (Wherein R ⁷ and n ₃ are as defined above) (Wherein R ⁷ and n ₃ are as defined above) Examples of the hydroxyl group-containing polymer represented by the general formula (II) used as a raw material in the production method according to the present invention are represented by the following general formula: Hydroxy group-containing polymers may be mentioned.

(Wherein, R ⁵ and n ₁ are as defined above) (Wherein R ⁶ and n ₂ are as defined above) (Wherein R ⁷ and n ₃ are as defined above) In the production method according to the present invention, R in the general formula (III) represents a cyclic ether to be reacted with the hydroxyl group-containing polymer represented by the general formula (II) ^The lower alkoxyl group which may be represented by ⁴ includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and the like. The cyclic ether represented by the general formula (III) has the general formula (Wherein R ² is as defined above), a hydroxyl group-containing cyclic ether represented by the general formula: (Wherein, R ² is as defined above, and X represents a lower alkoxyl group). (Wherein R ² is as defined above). Examples of the hydroxyl group-containing cyclic ether represented by the general formula (III-1) include tetrahydro-4-methyl-2H-pyran-2-ol, tetrahydro-2H-pyran-2-ol, and tetrahydrofuran-2-ol. General formula (III
The lower alkoxyl group-containing cyclic ether represented by -2) includes tetrahydro-2-methoxy-4-methyl-2H
-Pyran, tetrahydro-2-ethoxy-4-methyl-
2-lower alkoxy-tetrahydro-4-methyl-2H-pyran such as 2H-pyran and tetrahydro-2-propoxy-4-methyl-2H-pyran; tetrahydro-2-methoxy-2H-pyran, tetrahydro-2-ethoxy- 2H−
2-lower alkoxy-tetrahydro-2H-pyran such as pyran, tetrahydro-2-propoxy-2H-pyran; 2
Examples thereof include 2-lower alkoxy-tetrahydrofuran such as -methoxytetrahydrofuran, 2-ethoxytetrahydrofuran, and 2-propoxytetrahydrofuran. Examples of the unsaturated cyclic ether represented by the general formula (III-3) include 3,4-dihydro-4-methyl-2H-pyran, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran. Is exemplified. In order to obtain the alkyl-δ-valerolactone-based polymer represented by the general formula (I) with high purity, the entire amount of the hydroxyl group-containing polymer represented by the general formula (II) is consumed in the reaction system. It is desirable not to leave the unreacted hydroxyl group-containing polymer in the polymer. From this viewpoint, it is preferable to use the cyclic ether represented by the general formula (III) in an amount of equimolar to 200 times the molar amount of the hydroxyl group of the hydroxyl group-containing polymer represented by the general formula (II). preferable. When the unsaturated cyclic ether represented by the general formula (III-3) is used, the unsaturated cyclic ether is used in an equimolar amount or 1.3 times the molar amount of the hydroxyl group-containing polymer represented by the general formula (II). It is more preferable to use the amount in the range. When a hydroxyl group-containing cyclic ether represented by the general formula (III-1) is used as the cyclic ether represented by the general formula (III), water is generated as the reaction proceeds, and the cyclic ether represented by the general formula (III) is used. When a lower alkoxyl group-containing cyclic ether represented by the general formula (III-2) is used as the cyclic ether, a lower alcohol is generated as the reaction proceeds. In these cases, the reaction is carried out while excluding the water or lower alcohol generated during the reaction from the reaction system, but the hydroxyl group-containing cyclic ether represented by the general formula (III-1) or the general formula (III-
Even when the lower alkoxyl group-containing cyclic ether represented by the formula (2) is used in a relatively small amount within a range of from equimolar to 1.3 times the mol of the hydroxyl group-containing polymer represented by the formula (II), the formula (I) ) Is desirable from the viewpoint of increasing the conversion to the alkyl-δ-valerolactone-based polymer. Examples of a method of removing generated water or lower alcohol from the reaction system during the reaction include, for example, a method of distilling water or lower alcohol out of the reaction system as it is or as an azeotrope with an organic solvent described below. . A reaction method in which water or a lower alcohol that produces a hydroxyl group-containing cyclic ether represented by the general formula (III-1) or a lower alkoxyl group-containing cyclic ether represented by the general formula (III-2) is not removed during the reaction. When these are used, these cyclic ethers can be converted into a hydroxyl-containing polymer represented by the general formula (II) from the viewpoint of increasing the conversion to the alkyl-δ-valerolactone-based polymer represented by the general formula (I). It is desirable to use it in an amount which is in the range of 40 to 150 times the molar amount to the above.

Examples of the acidic catalyst to be present in the reaction system in the reaction between the hydroxyl group-containing polymer represented by the general formula (II) and the cyclic ether represented by the general formula (III) include mineral acids such as sulfuric acid and phosphoric acid; calcium chloride; Metal halides such as zinc chloride; organic acids such as p-toluenesulfonic acid, benzoic acid, and cation exchange resin; inorganic solid acids such as activated clay, acidic clay, and diatomaceous earth; and the like, of which activated clay is preferred. The use amount of these acidic catalysts is not particularly limited, but when the reaction is carried out in a stirred tank, the amount of the acidic catalyst is 0.1 to the reaction mixture.
Desirably, it is between 1 and 10 weight percent.

The reaction between the hydroxyl group-containing polymer represented by the general formula (II) and the cyclic ether represented by the general formula (III) is preferably performed at a temperature in the range of 10 to 150 ° C, more preferably 20 to 100 ° C.

The reaction according to the production method of the present invention can be carried out in the absence of a solvent, but can also be carried out in the presence of an organic solvent that does not adversely affect the reaction. Specific examples of such an organic solvent include hexane, heptane, octane, decane, cyclohexane, benzene, toluene,
Hydrocarbons such as xylene; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; diethyl ether, dibutyl ether, tetrahydrofuran,
Ethers such as dioxane; ketones such as acetone and methyl ethyl ketone. In particular, the general formula (III
When the reaction is carried out using the hydroxyl group-containing cyclic ether represented by -1) or the lower alkoxyl-containing cyclic ether represented by the general formula (III-2), water or a lower alcohol produced during the reaction is reacted with the reaction system. In order to facilitate distilling out, it is desirable that an organic solvent capable of forming an azeotropic mixture with water or a lower alcohol such as a hydrocarbon as in the above specific examples be present in the reaction system.

The reaction apparatus that can be used in the reaction according to the production method of the present invention is not particularly limited. Examples of such a reactor include a stirred tank reactor, a fixed bed reactor, and the like.

After the completion of the reaction, the obtained reaction mixture is subjected to neutralization or filtration as required to remove the acidic catalyst, and further washed with water as necessary. The alkyl-δ-valerolactone-based polymer represented by the general formula (I) can be separated and obtained by distilling using an evaporator such as an evaporator, a centrifugal evaporator, and a stirring film evaporator. .

The hydroxyl group-containing polymer represented by the general formula (II), which is a raw material in the production method of the present invention, is prepared, for example, according to the methods described in JP-A-60-55026 and JP-A-63-225623. Using an alcohol represented by the general formula R ¹ OH) _m (IV) (wherein R ¹ and m are as defined above) as an initiator, (Wherein Y ² represents an alkyltetramethylene group having 5 or 6 carbon atoms), or ring-opening polymerizing an alkyl-δ-valerolactone represented by the following formula:
δ-Valerolactone and general formula (Wherein Y ³ represents an alkylene group having 2 to 6 carbon atoms excluding an alkyltetramethylene group having 5 or 6 carbon atoms) and a lactone represented by the following formula: It can be obtained by polymerizing.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to the present invention, but the present invention is not limited to these examples. In the following Examples and Reference Examples, the average molecular weight of a polymer is a value obtained based on quantitative analysis of hydrogen atoms in ¹ H-NHR measurement of the polymer.

Example 1 In a 500 ml four-necked flask equipped with a liquid-liquid separator equipped with a thermometer, a stirrer, a dropping funnel and a condenser, (Wherein, k ₁ and the average value of k ₂ is Sozo is a 9) poly (beta-methyl -δ- Bararorakuton) diol represented by (average molecular weight: 2100) was 100g was dissolved in toluene 100 ml, obtained 2 g of activated clay was added to the solution. While refluxing toluene in the solution under heating and stirring, tetrahydro-4
13.9 g of methyl-2H-pyran-2-ol in 50 m of toluene
l was added dropwise over 3 hours. During the dropping, generated water was removed from the reaction system using a liquid-liquid separator. The reaction was continued for another hour from the time when generation of water was no longer observed (total reaction time: 4 hours). After completion of the reaction, activated clay was removed from the obtained reaction mixture by filtration, and most of toluene was distilled off from the filtrate using a rotary evaporator. From the obtained residue, toluene and unreacted tetrahydro-4-methyl-2H-pyran-2-
By completely distilling off all using a stirred membrane evaporator (evaporator dimensions: 60 mm (inner diameter) x 200 mm (height)) under reduced pressure of 5 mmHg at 150 ° C, the formula (Wherein, k ₁ and k ₂ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 2300) was obtained 105 g (yield: 96%) .

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Inner book Standard (hexamethyldisiloxane) solvent _{(CDCl 3) δ0.75~1.10 (m,} 60H) 1.24~2.50 (m, 100H) 3.10~4.30 (m, 44H) 4.62~4.72 (m, 2H) is obtained After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the amount of β-methyl-δ-valerolactone generated and β-methyl-δ-
When examining the molecular weight change of the valerolactone polymer,
The amount of β-methyl-δ-valerolactone generated was only 0.4% by weight relative to the polymer, and almost no change in the average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was observed. Never

Example 2 Tetrahydro-4-methyl-2H-pyran-2-ol
The reaction and treatment of the reaction mixture were carried out as in Example 1 except that 12.3 g of tetrahydro-2H-pyran-2-ol were used instead of 13.9 g, whereby the formula (Wherein, k ₁ and k ₂ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 2300) was obtained 104 g (yield: 95%) .

The results of ¹ H-NMR (90 MHz) analysis of the resulting β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) solvent _{(CDCl 3) δ0.88~1.10 (m,} 54H) 1.22~2.52 (m, 102H) 3.13~4.26 (m, 44H) 4.42~4.63 (m, 2H) resulting After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the β-methyl-
When the amount of generated δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, β
The amount of -methyl-δ-valerolactone generated was only 0.4% by weight relative to the polymer, and the change in average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was hardly observed, and Was.

Example 3 Tetrahydro-4-methyl-2H-pyran-2-ol
11.5 g of tetrahydrofuran-2-ol instead of 13.9 g
The reaction and treatment of the reaction mixture were carried out in the same manner as in Example 1 except that (Wherein k ₁ and k ₂ are as defined above), and 103 g of a liquid β-methyl-δ-valerolactone-based polymer (average molecular weight: 2300) was obtained (yield: 94%) .

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valrolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) Solvent (CDCl ₃ ) δ 0.83 to 1.10 (m, 54H) 1.20 to 2.50 (m, 98H) 3.05 to 4.26 (m, 44H) 4.93 to 5.12 (m, 2H) After heating the β-methyl-δ-valerolactone-based polymer at 200 ° C. for 0.5 hour in a glass sealed tube, the amount of β-methyl-δ-valerolactone generated and β-methyl-δ-
When examining the molecular weight change of the valerolactone polymer,
The amount of β-methyl-δ-valerolactone generated was only 0.4% by weight relative to the polymer, and almost no change in the average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was observed. Never

Reference Example 1 In a 500 ml three-necked flask equipped with a thermometer, a stirrer, and a condenser, (Where k ₁ and k ₂ are as defined above) 9.96 g of acetic anhydride was added to 100 g of poly (β-methyl-δ-valerolactone) diol (average molecular weight: 2100). The mixture was heated to 100 ° C. and stirred for 4 hours. After the reaction,
Toluene and acetic acid were distilled off from the obtained reaction mixture by a rotary evaporator. From the obtained residue, β-methyl-δ-valerocraton produced by decomposition was completely removed at 150 ° C. under a reduced pressure of 5 mmHg using the same stirred membrane evaporator as used in Example 1. By distilling off, the formula (In the formula, the average values of k ′ ₁ and k ′ ₂ are respectively 7.) 81 g of a liquid β-methyl-δ-valerolactone-based polymer (average molecular weight: 1700) was obtained.

Reference Example 2 Formula (Wherein k ₁ and k ₂ are as defined above) in a glass sealed tube at 200 ° C. for 0.5 hour at an average molecular weight of 2100.
After heating for a period of time, the amount of β-methyl-δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone polymer were examined. And the average molecular weight of the polymer was reduced to 1900.

Example 4 In a reactor similar to that used in Example 1, the formula (Wherein the average value of k ₃ is a 8) poly represented by (beta-methyl -δ- valerolactone) monool (average molecular weight: 940) and 100g was dissolved in hexane 100 ml, acidic the resulting solution 2 g of clay was added. While refluxing hexane in the solution under heating and stirring, tetrahydro-
13.9 g of 4-methyl-2H-pyran-2-ol was treated with hexane 5
A hexane solution dissolved in 0 ml was added dropwise over 4 hours. During the dropping, generated water was removed from the reaction system using a liquid-liquid separator. The reaction was continued for another hour from the time when generation of water was no longer observed (total reaction time: 5 hours). After completion of the reaction, acidic clay was removed from the obtained reaction mixture by filtration, and most of hexane was distilled off from the filtrate with a rotary evaporator. Hexane and unreacted tetrahydro-4-methyl-2H-pyran-2 were obtained from the obtained residue.
By completely distilling off all at 150 ° C. under a reduced pressure of 5 mmHg using a stirred membrane evaporator similar to that used in Example 1. (Wherein, k ₃ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 1000) was obtained 100 g (yield: 94%).

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) Solvent (CDCl ₃ ) δ 0.88 to 1.10 (m, 27H) 1.22 to 2.52 (m, 45H) 3.13 to 4.26 (m, 21H) 4.42 to 4.63 (m, 1H) After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the β-methyl-
When the amount of generated δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, β
The amount of -methyl-δ-valerolactone generated was only 0.5% by weight with respect to the polymer, and the change in the average molecular weight based on the quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was hardly observed and Was.

Example 5 In a reactor similar to that used in Example 1, the formula (Wherein the average value of k ₄ , k ₅ and k ₆ is 6) 100 g of poly (β-methyl-δ-valerolactone) triol (average molecular weight: 2200) is dissolved in 100 ml of benzene to obtain Sulfonic acid (H ⁺ ) type cation exchange resin [Rohm and Haas, USA]
Amberlyst 15] 1.5 g was added.
While stirring the obtained mixture at room temperature, a benzene solution in which 9.9 g of 3,4-dihydro-2H-pyran was dissolved in 50 ml of benzene was added dropwise over 0.5 hours. After the completion of the dropwise addition, the reaction was continued for another 3.5 hours (total reaction time: 4 hours). After completion of the reaction, the cation exchange resin was removed from the obtained reaction mixture by filtration, and the obtained benzene solution was washed three times with 50 ml each of distilled water. Most of the benzene was distilled off from the washed benzene solution using a rotary evaporator.
Benzene and unreacted 3,4-dihydro-2H-pyran were completely removed from the resulting residue at 150 ° C. under a reduced pressure of 5 mmHg using a stirred membrane evaporator similar to that used in Example 1. By distilling off, the formula (In the formula, k ₄ , k ₅ and k ₆ are as defined above) 105 g of a liquid β-methyl-δ-valerolactone-based polymer (average molecular weight: 2400) was obtained (yield: 95%).

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) solvent _{(CDCl 3) δ0.79~1.16 (m,} 57H) 1.30~2.56 (m, 110H) 3.10~4.30 (m, 48H) 4.44~4.66 (m, 3H) resulting After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the β-methyl-
When the amount of generated δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, β
The amount of -methyl-δ-valerolactone generated was only 0.6% by weight with respect to the polymer, and the change in average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was hardly observed, and Was.

Example 6 In a 500 ml three-necked flask equipped with a thermometer, a stirrer and a condenser, the formula was Wherein k ₁ and k ₂ are as defined above. 100 g of poly (β-methyl-δ-valerolactone) diol (average molecular weight: 2100) and 3,4-dihydro-
10.4 g of 2H-pyran was dissolved in 100 ml of toluene. 0.5 g of p-toluenesulfonic acid was added to the obtained toluene solution,
The mixture was stirred at room temperature for 4 hours. After completion of the reaction, the obtained reaction mixture was washed three times with 100 ml each of distilled water. From the obtained toluene solution, unreacted 3,4-dihydro-2H-pyran and toluene were removed from a rotary evaporator, and then to a stirred film evaporator (150) similar to that used in Example 1.
C. under a reduced pressure of 5 mmHg). (Wherein k ₁ and k ₂ are as defined above), and 103 g of a liquid β-methyl-δ-valerolactone-based polymer (average molecular weight: 2300) was obtained (yield: 94%) . The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone-based polymer are shown in Example 2.
The results were the same as the analysis results for the β-methyl-δ-valerolactone-based polymer obtained in the above.

Example 7 In a 500 ml three-necked flask equipped with a thermometer, a stirrer and a condenser, the formula was (In the formula, k ₁ and k ₂ are as defined above) 100 g of poly (β-methyl-δ-valerolactone) diol (average molecular weight: 2100) is represented by the formula:
After dissolving in 350 g of methoxy-4-methyl-2H-pyran, 2 g of activated clay was added to the resulting solution, and the mixture was heated to an internal temperature of 80 ° C. and stirred for 4 hours. After completion of the reaction, the activated clay was removed from the obtained reaction mixture by filtration, and methanol and most of unreacted tetrahydro-2-methoxy-4-methyl-2H-pyran were distilled off from the filtrate by a rotary evaporator. From the obtained residue, tetrahydro-2-methoxy-4-methyl-2H-pyran was completely distilled at 150 ° C. under a reduced pressure of 5 mmHg using the same stirred film evaporator as used in Example 1. By leaving, the expression (Wherein, k ₁ and k ₂ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 2300) was obtained 102 g (yield: 93%) . The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone-based polymer are shown in Example 1.
The results were the same as the analysis results for the β-methyl-δ-valerolactone-based polymer obtained in the above.

Example 8 In a 500 ml four-necked flask equipped with a liquid-liquid separator equipped with a thermometer, a stirrer, a dropping funnel and a condenser, (Wherein, k ₇ and the average value of k ₈ are each 9) poly (beta-methyl -δ- valerolactone) diol represented by (average molecular weight: 2200) was 100g was dissolved in toluene 100 ml, resulting 2 g of activated clay was added to the solution. While refluxing toluene in the solution under heating and stirring, tetrahydro-4
14.0 g of methyl-2H-pyran-2-ol in 50 m of toluene
l was added dropwise over 3 hours. During the dropping, generated water was removed from the reaction system using a liquid-liquid separator. The reaction was continued for another hour from the time when generation of water was no longer observed (total reaction time: 4 hours). After completion of the reaction, activated clay was removed from the obtained reaction mixture by filtration, and most of toluene was distilled off from the filtrate using a rotary evaporator. From the obtained residue, toluene and unreacted tetrahydro-4-methyl-2H-pyran-2-
By completely distilling off all at 150 ° C. under a reduced pressure of 5 mmHg using the same stirred film evaporator as used in Example 1, the formula was obtained. (Wherein, k ₇ and k ₈ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 2400) was obtained 106 g (yield: 97%) .

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) Solvent (CDCl ₃ ) δ 0.75 to 1.11 (m, 63H) 1.23 to 2.51 (m, 105H) 3.09 to 4.29 (m, 44H) 4.61 to 4.72 (m, 2H) After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the β-methyl-
When the amount of generated δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, β
The amount of -methyl-δ-valerolactone generated was only 0.5% by weight with respect to the polymer, and the change in the average molecular weight based on the quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was hardly observed and Was.

Example 9 In a 500 ml four-necked flask equipped with a liquid-liquid separator equipped with a thermometer, a stirrer, a dropping funnel and a condenser, the formula was added. (Wherein, k ₉ and the average value of k ₁₀ is 20, respectively) poly (beta-methyl -δ- valerolactone) diol represented by (average molecular weight: 4700) was 100g was dissolved in toluene 300 ml, resulting 2 g of activated clay was added to the solution. While refluxing toluene in the solution under heating and stirring, tetrahydro-4
6.5 g of methyl-2H-pyran-2-ol in 50 ml of toluene
Was added dropwise over 3 hours. During the dropping, generated water was removed from the reaction system using a liquid-liquid separator. The reaction was continued for another hour from the time when generation of water was no longer observed (total reaction time: 4 hours). After completion of the reaction, activated clay was removed from the obtained reaction mixture by filtration, and most of toluene was distilled off from the filtrate by a rotary evaporator. From the obtained residue, toluene and unreacted tetrahydro-4-methyl-2H-pyran-2-
By completely distilling off all at 150 ° C. under a reduced pressure of 5 mmHg using the same stirred film evaporator as used in Example 1, the formula was obtained. (Wherein, k ₉ and k ₁₀ is as defined above) beta-methyl -δ- valerolactone polymer liquid represented by (average molecular weight: 4900) was obtained 100 g (yield: 96%) .

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) solvent _{(CDCl 3) δ0.72~1.20 (m,} 126H) 1.20~2.51 (m, 224H) 3.09~4.29 (m, 88H) 4.60~4.72 (m, 2H) resulting After heating the β-methyl-δ-valerolactone-based polymer in a glass sealed tube at 200 ° C for 0.5 hour, the β-methyl-
When the amount of generated δ-valerolactone and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, β
The amount of -methyl-δ-valerolactone generated was only 0.4% by weight relative to the polymer, and the change in average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was hardly observed, and Was.

Example 10 In a 500 ml four-necked flask equipped with a liquid-liquid separator equipped with a thermometer, a stirrer, a dropping funnel and a condenser, (Wherein the average value of k ₁₁ is 40) poly (beta-methyl -δ- valerolactone) monool (average molecular weight: 4800) represented a 100g was dissolved in toluene 300 ml, the resulting solution was added active 2 g of clay was added. While refluxing the toluene in the solution under heating and stirring, tetrahydro-
3.2 g of 4-methyl-2H-pyran-2-ol in toluene 50
A toluene solution dissolved in ml was dropped over 3 hours. During the dropping, generated water was removed from the reaction system using a liquid-liquid separator. When the generation of water was no longer observed, the reaction was continued for another hour (total reaction time: 4 hours). After completion of the reaction, activated clay was removed from the obtained reaction mixture by filtration, and most of toluene was distilled off from the filtrate using a rotary evaporator. From the obtained residue, toluene and unreacted tetrahydro-4-methyl-2H-pyran-2-ol were reduced at 150 ° C. under a reduced pressure of 5 mmHg using the same stirred membrane evaporator as that used in Example 1. By completely distilling off below, the formula (Wherein, k ₁₁ wherein as is defined) in β- methyl -δ- valerolactone polymer liquid represented (average molecular weight: 4900) was obtained 97 g (yield: 95%).

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisiloxane) Solvent (CDCl ₃ ) δ 0.72 to 1.20 (m, 126H) 1.20 to 2.52 (m, 237H) 3.10 to 4.30 (m, 84H) 4.59 to 4.71 (m, 1H) Example 11 In a 500 ml three-necked flask with thermometer, stirrer and condenser, the formula (Where k ₁₂ , k ₁₃ , k ₁₄ and k _{15 have} an average value of 4.
5) random copolymer of β-methyl-δ-valerolactone and ε-caprolactone (average molecular weight: 2100) 1
00g and 3,4-dihydro-4-methyl-2H-pyran 12.0
g was dissolved in 100 ml of toluene. 0.5 g of p-toluenesulfonic acid was added to the obtained toluene solution, followed by stirring at room temperature for 4 hours. After completion of the reaction, the obtained reaction mixture was washed three times with 100 ml each of distilled water.

From the obtained toluene solution, unreacted 3,4-dihydro-4-methyl-2H-pyran and toluene were converted into a rotary evaporator and then a stirred membrane evaporator (150 ° C., By completely distilling using a reduced pressure of 5 mmHg), the formula (In the formula, k ₁₂ , k ₁₃ , k ₁₄ and k ₁₅ are as defined above) 104 g of a liquid β-methyl-δ-valerolactone-based polymer (average molecular weight: 2300) was obtained ( Yield: 95%).

The results of ¹ H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (tetramethylsilane) solvent _{(CDCl 3) δ0.77~1.10 (m,} 33H) 1.24~2.50 (m, 127H) 3.10~4.30 (m, 44H) 4.61~4.74 (m, 2H) resulting β After heating the -methyl-δ-valerolactone-based polymer at 200 ° C for 0.5 hour in a glass sealed tube, β-methyl-
When the amount of δ-valerolactone and ε-caprolactone generated and the change in the molecular weight of the β-methyl-δ-valerolactone-based polymer were examined, the amount of β-methyl-δ-valerolactone generated was slightly 0.3% by weight, and no generation of ε-caprolactone was observed. Furthermore, almost no change in the average molecular weight based on quantitative analysis of hydrogen atoms in ¹ H-NMR measurement of the polymer was observed.

〔The invention's effect〕

According to the present invention, as is evident from the above examples,
There is provided a liquid alkyl-δ-valeroctone polymer represented by the general formula (I) having high thermal stability. The alkyl-δ-valerolactone polymer represented by the general formula (I) is produced from the corresponding hydroxyl group-containing polymer represented by the general formula (II) without depolymerization.

Claims (2)

(57) [Claims] (1) General formula (Wherein, R ¹ represents an m-valent hydrocarbon group having 1 to 18 carbon atoms;
R ² represents an alkylene group having 2 to 4 carbon atoms, and Y represents 2 carbon atoms.
To 6 and represents an alkylene group, and
40 mol% or more is an alkyltetramethylene group having 5 or 6 carbon atoms, m represents an integer of 1 to 3, and the average value of n is
An alkyl-δ-valerolactone-based polymer represented by the following formula: 1 / m to 87 / m). 2. The general formula (Wherein R ¹ , Y, m and n are as defined in claim 1), and a hydroxyl group-containing polymer represented by the general formula (Wherein R ² is as defined in claim 1, R ³
Represents a hydrogen atom, R ⁴ represents a hydroxyl group or a lower alkoxyl group, or R ³ and R ^{4 taken} together represent a single bond). The method for producing the alkyl-δ-valerolactone-based polymer described in the above.