Β-methyl-δ-valerolactone polymer

Abstract

A β-Methyl-δ-valerolactone polymer is represented by general formula (I).

Description

β-methyl-δ-valerolactone polymer

[0001] The present invention relates to a β-methyl-δ-valerolactone polymer.

[0002] From the perspective of global environmental conservation, there is a need in a wide range of fields to reduce the environmental impact of plastic materials used in products. To reduce the environmental impact, active development of plastic materials using polylactic acid, a type of "biodegradable plastic," has been underway. However, molded products made from polylactic acid tend to be more brittle than petroleum-based plastics, and have inferior viscosity, flexibility, and heat resistance. Furthermore, they are prone to hydrolysis, which may limit their use as resin materials. Therefore, molded products have been developed by blending polylactic acid with a biodegradable aliphatic polyester to form resin compositions, which improve the drawbacks of polylactic acid while imparting various physical properties. For example, Patent Document 1 discloses a biodegradable string containing a lactic acid-based polymer, a biodegradable aliphatic polyester other than the lactic acid-based polymer, and a lubricant. It is described that the biodegradable string is biodegradable and can be continuously bound using current binding machines. Patent Document 2 also discloses a biodegradable plastic or sheet made from a polylactic acid-based polymer and a biodegradable aliphatic polyester. The above biodegradable plastic or sheet is described as having excellent impact resistance.

[0003] Furthermore, studies have been conducted to impart various physical properties to biodegradable aliphatic polyesters that are mixed with polylactic acid as described above. For example, Patent Document 3 discloses an alkyl-δ-valerolactone polyester that is thermally stable and liquid as a biodegradable aliphatic polyester.

[0004] JP 9-111107 JP 2001-115350 JP 3-181516

[0005] Patent Documents 1 and 2 describe that aliphatic polyesters obtained by ring-opening polymerization of cyclic lactones can be used as biodegradable aliphatic polyesters. However, there is no detailed disclosure of the molecular weight, viscosity, specific structure, etc., of the aliphatic polyesters. Reference Example 1 of Patent Document 3 discloses a liquid β-methyl-δ-valerolactone polymer (average molecular weight: 1,700) obtained by modifying both ends of poly(β-methyl-δ-valerolactone)diol with acetic anhydride. However, Patent Document 3 does not specifically disclose the modifying effect of the polymer on resins.

[0006] Therefore, the present invention provides a β-methyl-δ-valerolactone polymer that can be used as an excellent modifier for resins.

[0007] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the above problems can be solved.

[0008] [1] A β-methyl-δ-valerolactone polymer represented by the following general formula (I):

[0009]

[0010] In general formula (I), R １ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by the following formula (X): In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.

[0011]

[0012] R ２represents a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. １ one hydrogen atom bonded to the terminal carbon atom of the ethyl group is substituted with a group represented by formula (X), and all of the R ２ is not a methyl group. n is an integer from 8 to 1,000, and m is an integer from 8 to 1,000. R ２ When a plurality of R and m are present, they may be the same or different from each other. １ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by formula (X), or an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by formula (X). [3] The β-methyl-δ-valerolactone polymer according to item [1] above, １ is a linear or branched alkyl group having 1 to 16 carbon atoms. [4] The β-methyl-δ-valerolactone polymer according to claim 1. １ is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the formula (X). [5] The β-methyl-δ-valerolactone polymer according to the above [1]. １ is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 10 carbon atoms is substituted with a group represented by formula (X). [6] The β-methyl-δ-valerolactone polymer according to the above item [1]. ２ is a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0013] According to the present invention, it is possible to provide a β-methyl-δ-valerolactone polymer that can be used as an excellent modifier for resins.

[0014] The following describes an embodiment of the present invention. However, the embodiment described below is merely an example for embodying the technical concept of the present invention, and the present invention is not limited to the following description. Furthermore, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. For matters indicated as numerical ranges, when there are several numerical ranges, the lower and upper limits can be selectively combined to form a preferred embodiment. In this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less." When simply referring to "molecular weight," it means "number average molecular weight" unless otherwise specified. Furthermore, "viscosity" refers to the viscosity measured using an E-type viscometer.

[0015] The β-methyl-δ-valerolactone polymer of this embodiment has a structure represented by the general formula (I) above, allowing it to be used as an excellent resin modifier. Furthermore, the β-methyl-δ-valerolactone polymer of this embodiment (hereinafter sometimes simply referred to as "polymer") is a polymer obtained by ring-opening polymerization of β-methyl-δ-valerolactone, in which at least one hydroxyl group at the molecular end is modified with another functional group, resulting in a polymer with reduced thermal decomposition. Furthermore, depending on the structure and number of molecular ends, the polymer is expected to exhibit a well-balanced modifying effect, including improved hydrolysis resistance, other functions, and ease of handling. Furthermore, since the raw material for the polymer is β-methyl-δ-valerolactone, it is expected to have good biodegradability. Furthermore, the polymer of this embodiment can also have a high viscosity, making it suitable for use as a material for adhesives with good adhesive properties.

[0016] <β-Methyl-δ-valerolactone Polymer> The polymer of this embodiment is represented by the following general formula (I).

[0017]

[0018] In general formula (I), R １ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. In the case of the above-mentioned "branched alkyl group", the number of carbon atoms is 3 to 20, and in the case of the above-mentioned "branched alkenyl group", the number of carbon atoms is 3 to 20.

[0019] Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group. Examples of the branched alkyl group having 3 to 20 carbon atoms include an isopropyl group, a 1-methylpropyl group, a 2-methylpropyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a 2-ethylpropyl group, a 1,1-diethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,3,3-trimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3,3-dimethylbutyl group, a 1-propylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 4,4-dimethylpentyl group, a butylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 1-propylpentyl group, 2-propylpentyl group, 1-butylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 5,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylhexyl group, 2-propylhexyl group, 3-propylhexyl group, 1-butylhexyl group, 2-butylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 6,6-dimethylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, 5-ethylheptyl group, 1-propylheptyl group, 2-propylheptyl group, 3-propylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl group, 7, Examples include a 7-dimethyloctyl group, a 1-ethyloctyl group, a 2-ethyloctyl group, a 3-ethyloctyl group, a 4-ethyloctyl group, a 5-ethyloctyl group, a 6-ethyloctyl group, a 1-methylnonyl group, a 2-methylnonyl group, a 3-methylnonyl group, a 4-methylnonyl group, a 5-methylnonyl group, a 6-methylnonyl group, a 7-methylnonyl group, an 8-methylnonyl group, and a 3,5,5-trimethylhexyl group.

[0020] From the viewpoint of ease of handling, the linear or branched alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylbutyl group, a 3-methylbutyl group, an n-pentyl group, or a 2,2-dimethylpropyl group is preferred.

[0021] Examples of the linear alkenyl group having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3-pentenyl and 4-pentenyl), n-hexenyl (e.g., 1-hexenyl and 5-hexenyl), n-heptenyl (e.g., 1-heptenyl and 1,3-heptadienyl), n-octenyl (e.g., 7-octenyl and 2,7-octadienyl), n-nonenyl (e.g., 3-nonenyl and 3,6-nonadienyl), and n-decenyl (e.g., 1,3-decadienyl and 1,3,5-decatrienyl). n-nyl group), n-undecenyl group (for example, 2-undecenyl and 2,4-undecadienyl group), n-dodecenyl group (for example, 2-dodecenyl group), n-tridecenyl group (for example, 2-tridecenyl group), n-tetradecenyl group (for example, 2-tetradecenyl group), n-pentadecenyl group (for example, 2-pentadecenyl group), n-hexadecenyl group (for example, 2-hexadecenyl group), n-heptadecenyl group (for example, 2-heptadecenyl group), n-octadecenyl group (for example, 2-octadecenyl group), n-nonadecenyl group (for example, 2-nonadecenyl group), n-icosenyl group (for example, 2-icosenyl group), and the like. Examples of branched alkenyl groups having 3 to 20 carbon atoms include isopropenyl, 1-methylpropenyl, 2-methylpropenyl, t-butenyl, 1,1-dimethylpropenyl, 2,2-dimethylpropenyl, 1,2-dimethylpropenyl, 1-ethylpropenyl, 2-ethylpropenyl, 1,1-diethylpropenyl, 1-methylbutenyl, 2-methylbutenyl, 3-methyl- 2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethylbutenyl group, 2,2-dimethylbutenyl group, 3,3-dimethylbutenyl group, 1,3,3-trimethylbutenyl group, 1-ethylbutenyl group, 2-ethylbutenyl group, 3,3-dimethylbutenyl group, 1-propylbutenyl group, 1-methylpentenyl group, 2-methylpentenyl group, 3-methylpentenyl group, 4-methylpentenyl group, 4,4-dimethylpentenyl group, 1-ethylpentenyl group, 2-ethylpentenyl group, 3-ethylpentenyl group, 4-ethylpentenyl group, 1-propylpentenyl group, 2-propylpentenyl group, 1-butylpentenyl group, 1-methylhexenyl group, 2-methylhexenyl group, 3-methylhexenyl group, 4-methylhexenyl group, 5-methylhexenyl group, 5,5-dimethylhexenyl group, 1-ethylhexenyl group, 2- Ethylhexenyl group, 3-ethylhexenyl group, 4-ethylhexenyl group, 1-propylhexenyl group, 2-propylhexenyl group, 3-propylhexenyl group, 1-butylhexenyl group, 2-butylhexenyl group, 1-methylheptenyl group, 2-methylheptenyl group, 3-methylheptenyl group, 4-methylheptenyl group, 5-methylheptenyl group, 6-methylheptenyl group, 6,6-dimethylheptenyl group, 1-ethyl heptenyl group, 2-ethylheptenyl group, 3-ethylheptenyl group, 4-ethylheptenyl group, 5-ethylheptenyl group, 1-propylheptenyl group, 2-propylheptenyl group, 3-propylheptenyl group, 1-methyloctenyl group, 2-methyloctenyl group, 3-methyloctenyl group, 4-methyloctenyl group, 5-methyloctenyl group, 6-methyloctenyl group, 7-methyloctenyl group, 7,7-dimethyloctenyl group Examples of octenyl groups include an ethyloctenyl group, a 1-ethyloctenyl group, a 2-ethyloctenyl group, a 3-ethyloctenyl group, a 4-ethyloctenyl group, a 5-ethyloctenyl group, a 6-ethyloctenyl group, a 1-methylnonenyl group, a 2-methylnonenyl group, a 3-methylnonenyl group, a 4-methylnonenyl group, a 5-methylnonenyl group, a 6-methylnonenyl group, a 7-methylnonenyl group, an 8-methylnonenyl group, and a 3,5,5-trimethylhexenyl group.

[0022] From the viewpoint of handleability, the linear or branched alkenyl group having 2 to 20 carbon atoms is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms.

[0023] Examples of aryl groups having 6 to 12 carbon atoms include phenyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, and 2-naphthyl groups. Phenyl groups are preferred. Examples of arylalkyl groups having 7 to 12 carbon atoms include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl, and naphthylethyl groups. Phenylmethyl groups are preferred.

[0024] In addition, in the general formula (I), R １ represents, in addition to the above-mentioned substituents, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by the following formula (X): In the above formula (X), the bond represented by * is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.

[0025]

[0026] R in the above formula (X) ２ is R ２The straight-chain alkyl group having 1 to 20 carbon atoms bonded to formula (X) above can be exemplified by the same groups exemplified above as the "straight-chain alkyl group having 1 to 20 carbon atoms." The straight-chain alkyl group having 1 to 20 carbon atoms bonded to formula (X) above is preferably a straight-chain alkyl group having 1 to 15 carbon atoms, more preferably a straight-chain alkyl group having 1 to 10 carbon atoms, even more preferably a straight-chain alkyl group having 2 to 10 carbon atoms, and even more preferably a straight-chain alkyl group having 2 to 5 carbon atoms. The branched alkyl group having 3 to 20 carbon atoms bonded to formula (X) above can be exemplified by the same groups exemplified above as the "branched alkyl group having 3 to 20 carbon atoms." The branched alkyl group having 3 to 20 carbon atoms bonded to formula (X) above is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, even more preferably a branched alkyl group having 3 to 6 carbon atoms, and may be a branched alkyl group having 3 to 5 carbon atoms. Alternatively, the alkyl group may be an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to each of the terminal carbon atoms of a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by the above formula (X).

[0027] m represents the average number of repetitions and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 500, and even more preferably 10 to 300, and may be 10 to 100, 10 to 80, or 10 to 60. If m is an integer less than 8, it may be difficult to obtain the modifying effect. Also, if m is an integer exceeding 1,000, the handling and productivity of the modifier may be poor. R １ In the above formula (I), when a plurality of groups represented by the formula (X) are present, they may be the same or different from each other. ２ and m may exist multiple times. ２ When there are a plurality of m's, they may be the same or different from each other.

[0028] R １represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X), the following structure can be specifically exemplified as the above general formula (I): Example 1: R １ However, when the linear alkyl group having carbon number Q represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-a), where Q is an integer of 1 to 20.

[0029]

[0030] <Example 2> R １ However, when the ethyl group represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom in the ethyl group is substituted with a group represented by the above formula (X), the above general formula (I) is represented by the following general formula (I-b):

[0031]

[0032] R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the formula (X), the following structure can be specifically exemplified as the general formula (I): Example 3: R １ However, when all of the terminal carbon atoms of the 2-methylpropyl group represent an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-c):

[0033]

[0034] <Example 4> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), then general formula (I) is represented by the following general formula (I-d):

[0035]

[0036] <Example 5> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylbutyl group is substituted with a group represented by formula (X), then general formula (I) is represented by the following general formula (I-e):

[0037]

[0038] <Example 6> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each terminal carbon atom of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (If):

[0039]

[0040] R １ From the viewpoint of easily obtaining a modifying effect, is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by formula (X) above, or an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by formula (X) above.

[0041] In general formula (I), R ２ represents a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. In the case of the above-mentioned "branched alkyl group", the number of carbon atoms is 3 to 20, and in the case of the above-mentioned "branched alkenyl group", the number of carbon atoms is 3 to 20. R ２ The linear or branched alkyl group having 1 to 20 carbon atoms represented by R can be exemplified by the same groups as those exemplified above as the "linear or branched alkyl group having 1 to 20 carbon atoms". ２From the viewpoint of handleability, the linear or branched alkyl group having 1 to 20 carbon atoms represented by the formula (I) is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylbutyl group, an n-pentyl group, or a 2,2-dimethylpropyl group is preferred.

[0042] R ２ The linear or branched alkenyl group having 2 to 20 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "linear or branched alkenyl group having 2 to 20 carbon atoms". ２ From the viewpoint of ease of handling, the linear or branched alkenyl group having 2 to 20 carbon atoms represented by R is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms. ２ The aryl group having 6 to 12 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "aryl group having 6 to 12 carbon atoms". ２ The aryl group having 6 to 12 carbon atoms represented by R is preferably a phenyl group. ２ The arylalkyl group having 7 to 12 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "arylalkyl group having 7 to 12 carbon atoms". ２ The arylalkyl group having 7 to 12 carbon atoms represented by R is preferably a phenylmethyl group. ２ is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, from the viewpoint of easily obtaining a modifying effect.

[0043] The polymer of this embodiment is a polymer having the general formula (I) above, R １ In the ethyl group, one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by the above formula (X), and all of the R ２ and are not simultaneously methyl groups. That is, the polymer of this embodiment is not a polymer represented by the following general formula:

[0044]

[0045] When the bond (linker portion) connecting the repeating unit n and the repeating unit m is relatively short, the modifying effect on hydrolysis resistance tends to be reduced. Furthermore, when the two terminals are acetyl groups, the modifying effect and the heat resistance of the polymer tend not to be fully achieved. On the other hand, when the linker portion is branched and the number of terminal acetyl groups increases, a modifying effect with a good balance of functionality and handleability, such as improved hydrolysis resistance and compatibility with resins, tends to be achieved. In particular, the smaller the molecular weight of the polymer represented by the above general formula (for example, a number average molecular weight of less than 2,000), the more difficult it tends to be to achieve the effect as a modifier.

[0046] n represents the average number of repetitions and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 600, even more preferably 10 to 500, and still more preferably 10 to 300. If n is an integer less than 8, it may be difficult to obtain the modifying effect. On the other hand, if n is an integer exceeding 1,000, the handleability and productivity as a modifying agent may be poor.

[0047] (Number Average Molecular Weight) From the viewpoint of easily obtaining a modifying effect, the number average molecular weight of the polymer is preferably 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. Furthermore, from the viewpoint of handleability during molding and productivity, the number average molecular weight of the polymer is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. That is, the number average molecular weight of the polymer is preferably 2,000 or more and 100,000 or less. All "number average molecular weights" described in this specification are number average molecular weights calculated in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement. Detailed measurement methods can be performed according to the methods described in the Examples.

[0048] (Weight Average Molecular Weight) The weight average molecular weight of the polymer is preferably 3,000 or more and 200,000 or less. A weight average molecular weight of 3,000 or more is likely to exhibit good viscosity. A weight average molecular weight of 200,000 or less is likely to result in excellent handleability and productivity during molding. The weight average molecular weight of the polymer is more preferably 3,700 or more, and even more preferably 4,500 or more. The weight average molecular weight of the polymer is more preferably 160,000 or less, even more preferably 125,000 or less, and even more preferably 100,000 or less. In this specification, the weight average molecular weight of the β-methyl-δ-valerolactone polymer is the weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0049] (Viscosity) In the present invention, "viscosity" refers to the viscosity of a polymer measured using an E-type viscometer. The measurement temperature can be optimized depending on the molecular weight, etc. The preferred viscosity range varies depending on the application of the polymer. However, from the viewpoint of fully exhibiting functions such as substrate retention, strength, and adhesiveness, a viscosity of 400 mPa·s or more at 80°C is preferred, and a viscosity of 1,000 mPa·s or more at 80°C is more preferred. The upper limit of the viscosity of the polymer is not limited as long as it is measured using an E-type viscometer. Note that, when measuring using an E-type viscometer, for example, if the molecular weight of the polymer exceeds approximately 25,000, the viscosity becomes too high and measurement becomes difficult even when the measurement temperature is increased. For example, by having a viscosity of 400 to 150,000 mPa·s at 80°C, the polymer is suitable as a modifier for resins such as polylactic acid. Furthermore, by having a viscosity of 400 to 150,000 mPa·s at 80°C, the polymer can also be expected to be used as a material for adhesives with good adhesive properties. Furthermore, when measuring a polymer with an E-type viscometer, the measurement temperature can be set depending on the molecular weight, etc. In another preferred embodiment, the polymer has a viscosity of, for example, preferably 3,500 to 150,000 mPa s, more preferably 4,000 to 150,000 mPa s, at 30°C. In another preferred embodiment, the polymer has a viscosity of, for example, preferably 650 to 150,000 mPa s, more preferably 800 to 150,000 mPa s, at 60°C.

[0050] <Production Method> The method for producing the polymer of this embodiment is not particularly limited. On the other hand, from the viewpoint of productivity and simplicity, or when producing a high-molecular-weight polymer, it is preferable to employ a production method including a step of adding a terminal modifier to a reaction solution obtained by reacting β-methyl-δ-valerolactone, an alcohol compound or water, and a base catalyst to perform a terminal modification reaction (hereinafter also referred to as the "reaction step"). The above production method is characterized in that the terminal modifier is added directly to a reaction solution obtained by reacting β-methyl-δ-valerolactone, an alcohol compound or water, and a base catalyst. That is, after ring-opening polymerization of β-methyl-δ-valerolactone, the terminal modifier can be added to the reactor in which the ring-opening polymerization was performed without first removing the ring-opened polymer, thereby performing terminal modification of the ring-opened polymer. Since the reaction step involves performing the ring-opening polymerization reaction and the terminal modification reaction in one pot, the above production method can be considered a simplified process. Note that the polymer of this embodiment is not limited to being produced by the above production method.

[0051] Reference Example 1 of Patent Document 3 describes that terminal modification reduces the molecular weight. Typically, β-methyl-δ-valerolactone undergoes a ring-opening polymerization reaction to become a ring-opened polymer having terminal hydroxyl groups. Having terminal hydroxyl groups in this manner makes the ring-opened polymer more susceptible to depolymerization. Once isolated, the terminal modification of the ring-opened polymer is carried out at a relatively high temperature (approximately 100°C), which tends to increase the thermal decomposition rate, and it is believed that the ring-opened polymer undergoes depolymerization and reduces its molecular weight. On the other hand, with the above-described production method, a high molecular weight polymer can be obtained without lowering the molecular weight, despite the terminal modification.

[0052] [Alcohol Compound or Water] The alcohol compound that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. Examples of alcohol compounds include linear or branched aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, aromatic hydrocarbon alcohols having 6 to 12 carbon atoms, and alkylaromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group. Note that the above-mentioned "branched aliphatic hydrocarbon alcohols" have 3 to 20 carbon atoms. Furthermore, the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol or a trihydric alcohol. The water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. For example, tap water, distilled water, ion-exchanged water, industrial water, deionized water, etc. can be used.

[0053] [Base Catalyst] Examples of base catalysts that can be used in this embodiment include metal catalysts such as alkali metals and alkali metal compounds, as well as organic base compounds. A single base catalyst may be used alone, or two or more may be used in combination. Examples of alkali metal compounds include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydrides, with organic lithium compounds such as butyllithium being preferred. Examples of organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton. Metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as base catalysts. In the reaction step, it is preferable to add 0.005 to 1.5 molar equivalents of the base catalyst relative to the hydroxyl groups of the alcohol compound. When water is used, it is preferable to add 0.005 to 3.0 molar equivalents of the base catalyst relative to the water.

[0054] [β-Methyl-δ-valerolactone] β-Methyl-δ-valerolactone that can be used in this embodiment can be produced by known methods. For example, it can be produced by known methods using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (see, for example, Japanese Patent Publication No. 6-53691). Furthermore, commercially available β-methyl-δ-valerolactone can be used, and it can be derived from either petrochemicals or biomass. In the reaction step, it is preferable to add 5 to 1,500 molar equivalents of β-methyl-δ-valerolactone relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, it is preferable to add 5 to 1,500 molar equivalents of β-methyl-δ-valerolactone relative to the water.

[0055] [Terminal Modifier] Examples of terminal modifiers that can be used in this embodiment include acid anhydrides and acid halides (acid halides are also referred to as "halogenated esters"). The acid anhydrides and acid halides are not particularly limited as long as the effects of the present invention can be obtained. For example, acid anhydrides and acid halides having at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms can be used. Note that in the case of the above-mentioned "branched alkyl group," the number of carbon atoms is 3 to 20, and in the case of the above-mentioned "branched alkenyl group," the number of carbon atoms is 3 to 20.

[0056] Specific examples of acid anhydrides include acetic anhydride, oxalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, glutaric anhydride, methacrylic anhydride, butyric anhydride, isobutyric anhydride, 1,8-naphthalic anhydride, trifluoroacetic anhydride, and cyclohexanecarboxylic anhydride. Specific examples of acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and benzoyl bromide. In the reaction step, it is preferable to add 1.0 to 20.0 molar equivalents of a terminal modifier relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, it is preferable to add 1.0 to 20.0 molar equivalents of a terminal modifier relative to the water.

[0057] [Co-catalyst] In the reaction step, a co-catalyst may be added as necessary. Examples of the co-catalyst that can be used include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, and 4-dimethylaminopyridine. In the reaction step, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the water.

[0058] [Solvent] The reaction step can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction. Examples of the solvent include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0059] [Reaction Conditions] In the reaction step, the reaction temperature when reacting β-methyl-δ-valerolactone with an alcohol compound or water and a base catalyst is usually 20 to 100°C, and the reaction time is usually 1 minute to 24 hours. In addition, in the reaction step, the reaction temperature when carrying out the terminal modification reaction after adding a terminal modifying agent to the reaction solution is usually 20 to 80°C, and the reaction time is usually 1 minute to 24 hours.

[0060] <Post-treatment step> The polymer of this embodiment can be produced by going through the above reaction step. If necessary, a post-treatment step may be carried out to isolate the produced polymer. As the post-treatment step, a suitable method can be adopted from known methods. For example, the reaction mixture after the reaction step can be washed with a reaction solvent or water, concentrated, and purified by a method typically used for separating and purifying organic compounds, such as distillation.

[0061] <Uses> The polymer of this embodiment is suitable as a resin modifier. Other uses of the polymer of this embodiment include, for example, pressure-sensitive adhesives and adhesives. When the polymer of this embodiment is used as a resin modifier, examples of the resin to be modified include biomass resins, biodegradable resins, and general-purpose thermoplastic resins. In particular, a more excellent modification effect can be expected for biomass resins and biodegradable resins.

[0062] Examples of the biomass resin or biodegradable resin include polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA) [e.g., polyhydroxybutyrate (PHB), polyhydroxybutyrate valerate (PHBV), 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyester, etc.], cellulose acetate (CA), and starch polyester (Mater-Bi (registered trademark)).

[0063] Examples of the general-purpose thermoplastic resin include thermoplastic resins and thermoplastic elastomers with a suitable processing temperature of approximately 200°C or less. Examples of the thermoplastic resin include polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polyethylene terephthalate (PET), and polyethylene terephthalate succinate (PETS). Examples of the thermoplastic elastomer include olefin-based, styrene-based, ester-based, urethane-based, acrylic-based, PVC-based, amide-based, and fluorine-based thermoplastic elastomers. Specific examples include polyester elastomer (TPC) and thermoplastic polyurethane (TPU). Examples of the general-purpose thermoplastic resin include thermoplastic resins with high heat resistance at temperatures exceeding approximately 200°C (also referred to as "high heat-resistant resins"). Examples of the high heat-resistant resin include polyamide (PA), polyacetal (POM), fluororesin (e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.), polycyclohexylene dimethylene terephthalate (PCT), polymethylpentene (PMP), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT). The resin to be modified using the polymer of this embodiment is not limited to the biomass resin, biodegradable resin, and general-purpose thermoplastic resin.

[0064] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0065] <Measurement and Evaluation Methods> Various physical properties were measured or evaluated by the following methods.

[0066] [Number average molecular weight] and [Weight average molecular weight] The polymers obtained in the examples and comparative examples were used as samples, and the number average molecular weight (Mn) and weight average molecular weight (Mw) were determined by gel permeation chromatography (GPC) using standard polystyrene equivalent molecular weights. The specific measurement methods are as follows.

[0067] <When Mn is less than 15,000> Samples with an Mn of less than 15,000 were measured as follows to determine Mn and Mw. A tetrahydrofuran (THF) solution was used as the eluent. 10 mg of the sample, calculated as resin, was weighed out and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows: (Measurement conditions) Apparatus: HLC-EcoSEC8320GPC (manufactured by Tosoh Corporation) Column: Three columns, KF-803, KF-802.5, and KF-802 (manufactured by Showa Denko K.K.), were connected in series. Eluent: tetrahydrofuran Flow rate: 0.9 mL / min Sample injection volume: 30 μL Column temperature: 40° C. Standard polystyrene: PSt Oligomer Kit (molecular weight 589 to 98,900) manufactured by Tosoh Corporation was used for cubic approximation. Detector: RI detector

[0068] <For Mn of 15,000 or More> Samples with an Mn of 15,000 or more were measured as follows to determine Mn and Mw. A tetrahydrofuran (THF) solution was used as the eluent. 1.0 mg of the sample, calculated as resin, was weighed and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows. (Measurement Conditions) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSK-gel SuperMultipore HZ-M (manufactured by Tosoh Corporation) columns connected in series. Eluent: Tetrahydrofuran Flow rate: 0.35 mL / min Sample injection volume: 10 μL Column temperature: 40°C Standard polystyrene: Polystyrene molecular weight standard (molecular weight 580 to 1,214,000) manufactured by GL Sciences Inc. was used for cubic approximation. Detector: RI detector

[0069] [Viscosity] The viscosity (unit: mPa·s) of the polymer was measured at the measurement temperatures shown in Table 1 using an E-type viscometer (product name: TVE-25 type viscometer, manufactured by Toki Sangyo Co., Ltd.).

[0070] [Thermogravimetric analysis (5% weight loss temperature)] Using a thermogravimetric analyzer (product name: TGA / DSC1, manufactured by Mettler Toledo), the temperature at which a 5% weight loss occurred was measured when the temperature was raised from 50°C to 500°C at a rate of 10°C / min under a nitrogen atmosphere (flow rate: 100 mL / min).

[0071] <Modification Evaluation> The polymers obtained in the Examples and Comparative Examples were evaluated as modifiers as follows. [Glass Transition Temperature] (1) Preparation of Kneaded Product 100 parts by mass of polylactic acid (NatureWorks, trade name INGEO 2500HP; melting point 177°C) and 10 parts by mass of the polymer obtained in the Examples or Comparative Examples were kneaded for 5 minutes at 210°C and 50 rpm using a Labo Plastomill (device name: 3S150, manufactured by Toyo Seiki Seisaku-sho, Ltd.). (2) Glass Transition Temperature Using a differential scanning calorimeter (device name: DSC25, manufactured by TA Instruments), the resin kneaded above was heated from 30°C to 220°C at a rate of 10°C / min under a nitrogen flow rate (100 mL / min), held at 220°C for 5 minutes, and then cooled to -70°C at a rate of 10°C / min. After holding at -70°C for 5 minutes, the temperature was raised to 220°C at a rate of 10°C / min, and the glass transition temperature was evaluated.

[0072] [Tensile elongation] (1) Preparation of test piece for elongation evaluation The resin kneaded in (1) Preparation of kneaded product above was decompressed to -0.1 MPaG using a reduced pressure hot press (device name: IMC-183B, manufactured by Imoto Machinery Co., Ltd.) using an oil rotary pump, preheated at 200°C for 5 minutes, and then pressed at 70 kN for 3 minutes. Thereafter, the resin was subjected to a pressure of 70 kgf / cm using a cooling press equipped with water flow cooling. ２The specimens were pressed at 100°C for 3 minutes to prepare 0.5 mm thick press plates. JIS No. 3 dumbbell-shaped test specimens were punched out from the obtained press plates and subjected to crystallization treatment in an 80°C thermostatic chamber for 16 hours. (2) Elongation Evaluation The dumbbell-shaped test specimens prepared above were stored at 23°C and 49% humidity for 24 hours or more, and the breaking strain values ​​were measured using a universal material testing machine (instron 5900R-5666, manufactured by Instron) at 23°C, 49% humidity, and a tensile speed of 5 mm / min. The measured value was the average of 5 measurements.

[0073] [Impact strength] (1) Preparation of impact resistance evaluation test piece The resin kneaded in (1) Preparation of kneaded product above was reduced in pressure to -0.1 MPaG using a reduced pressure hot press machine ("IMC-183B" manufactured by Imoto Machinery Co., Ltd.) using an oil rotary pump, preheated at 200°C for 5 minutes, and then pressed at 50 kN for 3 minutes. Thereafter, the resin was subjected to a pressure of 70 kgf / cm using a cooling press machine equipped with water flow cooling. ２ The specimen was pressed at 100°C for 3 minutes to produce a 3.0 mm thick press plate. An 80 x 10 mm strip was cut out from the obtained press plate and crystallized for 16 hours in an 80 °C constant temperature bath. A V-notch (remaining width 8 mm, tip radius 0.25 mm) was applied to the center of the long side to produce a notched strip test piece. (2) Impact Resistance Test The prepared notched strip test piece was stored at 23 °C and 49% humidity for 24 hours or more, and the impact strength was evaluated using a Charpy impact tester ("DG-CB" manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 23 °C and 49% humidity with a hammer load of 2 J. The measured value was the average of 10 measurements.

[0074] Example 1 A 500 mL four-necked glass flask was purged with nitrogen, and 7.9 g (90 mmol) of isoamyl alcohol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 11.0 g (108 mmol) of acetic anhydride and 0.55 g (4.5 mmol) of 4-dimethylaminopyridine dissolved in 5.5 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 155 g (0.04 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I), and R １ , R ２ , n are as shown in Table 1.

[0075] Example 2 A 500 mL four-necked glass flask was purged with nitrogen, and 1.6 g (18.2 mmol) of isoamyl alcohol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.35 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60°C for 60 minutes. Next, 2.3 g (22.5 mmol) of acetic anhydride and 0.11 g (0.9 mmol) of 4-dimethylaminopyridine dissolved in 1.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 162 g (0.016 mmol) of polymer. The obtained polymer was a polymer represented by the aforementioned general formula (I), R １ , R ２ , n are as shown in Table 1.

[0076] Example 3 A 1,000 mL four-necked glass flask was purged with nitrogen, and 1.6 g (18.2 mmol) of isoamyl alcohol and 623 g (5,460 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.34 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 2.2 g (21.8 mmol) of acetic anhydride and 0.11 g (0.9 mmol) of 4-dimethylaminopyridine dissolved in 1.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 450 g (0.016 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I), and R １ , R ２ , n are as shown in Table 1.

[0077] Example 4 A 1,000 mL four-necked glass flask was purged with nitrogen, and 0.9 g (10 mmol) of isoamyl alcohol and 627 g (5,500 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.41 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 1.2 g (12 mmol) of acetic anhydride and 0.06 g (0.5 mmol) of 4-dimethylaminopyridine dissolved in 1.0 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 470 g (0.01 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I), and R １ , R ２ , n are as shown in Table 1.

[0078] Example 5 A 3,000 mL four-necked glass flask was purged with nitrogen, and 0.9 g (10 mmol) of isoamyl alcohol and 913 g (8,000 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.45 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 1.2 g (12 mmol) of acetic anhydride and 0.06 g (0.5 mmol) of 4-dimethylaminopyridine dissolved in 1.0 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 620 g (0.008 mmol) of polymer. The obtained polymer was a polymer represented by the aforementioned general formula (I), R １ , R ２ , n are as shown in Table 1.

[0079] Example 6 A 500 mL four-necked glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60°C for 60 minutes. Next, 34.2 g (216 mmol) of butyric anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 158 g (0.04 mmol) of a polymer. The obtained polymer was represented by the aforementioned general formula (I-b), and R １ , R ２ , n, and m are as shown in Table 1.

[0080] Example 7 A 500 mL four-necked glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60°C for 60 minutes. Next, 48.9 g (216 mmol) of benzoic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 153 g (0.05 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I-b), and R １ , R ２ , n, and m are as shown in Table 1.

[0081] Example 8 A 500 mL four-necked glass flask was purged with nitrogen, and 8.1 g (90 mmol) of 1,4-butanediol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60°C for 60 minutes. Next, 22.1 g (216 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 155 g (0.04 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I-a) (Q is 4), and R １ , R ２ , n, and m are as shown in Table 1.

[0082] Example 9 A 500 mL four-necked glass flask was purged with nitrogen, and 14.4 g (90 mmol) of 1,9-nonanediol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.80 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60°C for 60 minutes. Next, 22.1 g (216 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 150 g (0.04 mmol) of polymer. The obtained polymer was a polymer represented by the aforementioned general formula (I-a) (Q is 9), R １ , R ２ , n, and m are as shown in Table 1.

[0083] Example 10 A 500 mL four-necked glass flask was purged with nitrogen, and 21.8 g (90 mmol) of cetanol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 11.0 g (108 mmol) of acetic anhydride and 0.55 g (4.5 mmol) of 4-dimethylaminopyridine dissolved in 5.5 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 158 g (0.04 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I), １ , R ２ , n are as shown in Table 1.

[0084] Example 11 A 500 mL four-necked glass flask was purged with nitrogen, and 14.2 g (90 mmol) of decanol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.80 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 11.0 g (108 mmol) of acetic anhydride and 0.55 g (4.5 mmol) of 4-dimethylaminopyridine dissolved in 5.5 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 151 g (0.04 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I), and R １ , R ２ , n are as shown in Table 1.

[0085] [Example 12] A 500 mL four-necked glass flask was purged with nitrogen, and 12.1 g (90 mmol) of trimethylolpropane and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60 ° C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 60 ° C. for 60 minutes. Next, 33.1 g (324 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60 ° C. for 60 minutes to obtain a reaction solution containing a polymer. The resulting reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 145 g (0.04 mmol) of polymer. The resulting polymer is represented by the above-mentioned general formula (I-e), １ , R ２ , n, and m are as shown in Table 1.

[0086] Example 13 A 2,000 mL four-necked glass flask was purged with nitrogen, and 12.1 g (90 mmol) of trimethylolpropane and 1,064 g (9,324 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 33.1 g (324 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 873 g (0.08 mmol) of polymer. The obtained polymer was represented by the aforementioned general formula (I-e), and R １ , R ２ , n, and m are as shown in Table 1.

[0087] Comparative Example 1 A 500 mL four-necked glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.78 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 60°C for 60 minutes. Next, 22.1 g (216 mmol) of acetic anhydride was added to the four-necked glass flask and stirred at 100°C for 6 hours to obtain a reaction solution containing a polymer. The obtained reaction solution containing the polymer was extracted with toluene and water and purified by distillation to obtain 114 g (0.06 mmol) of polymer. The obtained polymer is represented by the following general formula, where n and m are as shown in Table 1.

[0088]

[0089] Comparative Example 2 A 500 mL four-neck glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction. The reaction solution containing the obtained polymer was extracted with toluene and water and purified using a thin-film evaporator, yielding 135 g (0.04 mmol) of polymer. The obtained polymer is represented by the following structural formula (II), where n and m are as shown in Table 1.

[0090]

[0091] [Comparative Example 3] A 500 mL four-neck glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60 °C. 0.78 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60 °C for 60 minutes to carry out a ring-opening polymerization reaction. The reaction solution containing the obtained ring-opened polymer was purified by extraction with toluene and water, reprecipitation into a large amount of hexane, and drying under reduced pressure at 80 °C. 1,500 mL of dichloromethane was placed in a 3,000 mL four-neck glass flask as a solvent, and then the purified ring-opened polymer, 22.7 g (270 mmol) of 3,4-dihydro-2H-pyran, and 0.9 g (3.6 mmol) of pyridinium paratoluenesulfonate were added. The mixture was stirred at 25 °C for 5 hours to obtain a reaction solution containing the polymer. The resulting polymer-containing reaction solution was extracted with dichloromethane and water and purified by distillation to obtain 114 g (0.06 mmol) of polymer, which is represented by the following structural formula (III), where n and m are as shown in Table 1.

[0092]

[0093] Comparative Example 4: A 500 mL four-neck glass flask was purged with nitrogen, and 7.9 g (90 mmol) of isoamyl alcohol and 231 g (2,025 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction. The resulting reaction solution containing the ring-opened polymer was extracted with toluene and water and purified using a thin-film evaporator. 1500 mL of dichloromethane was placed in a 3,000 mL four-neck glass flask as a solvent, and then the purified ring-opened polymer, 11.4 g (135 mmol) of 3,4-dihydro-2H-pyran, and 0.45 g (1.8 mmol) of pyridinium paratoluenesulfonate were added. The mixture was stirred at 25°C for 5 hours to obtain a reaction solution containing the polymer. The resulting polymer-containing reaction solution was extracted with dichloromethane and water and purified by distillation to obtain 130 g (0.04 mmol) of polymer, which is represented by the following structural formula (IV), where n is as shown in Table 1.

[0094]

[0095] The results of the aforementioned measurements and evaluations of the various physical properties of the polymers obtained in the Examples and Comparative Examples are shown in Table 1. For reference, Table 1 also shows the glass transition temperature, tensile elongation, and impact strength of the polylactic acid alone.

[0096]

[0097] The notations in Table 1 are as follows: １ In the column, "X" represents the above formula (X). ２ In the column, "n-Pr" indicates an n-propyl group. ２ In the viscosity column, "Ph" indicates a phenyl group. In the viscosity column, "impossible to measure" means that the viscosity of the polymer was so high that it could not be measured even when the viscosity measurement temperature was raised to 80°C.

[0098] Table 1 shows that the polymers obtained in the examples have better glass transition temperatures, tensile elongation, and impact strength than the polymers obtained in the comparative examples, and are well-balanced in modifying performance. It can also be seen that the impact strength in Examples 1 to 13 is superior to that of polylactic acid alone and that of Comparative Examples 1 to 4. In particular, a comparison between Examples 1 to 11 and Comparative Example 2 shows that the structure of this embodiment significantly improves thermal stability. A comparison between Example 1 and Comparative Example 4, and between Examples 6 and 7 and Comparative Example 3 shows that resin compositions using the polymers obtained in the examples have good tensile elongation and impact resistance. Therefore, it can be seen that the polymers of this embodiment are useful as modifiers.

[0099] The polymer of this embodiment can be used as a resin modifier, and is particularly suitable as a modifier for polylactic acid.

Claims

1. A β-methyl-δ-valerolactone polymer represented by the following general formula (I): 【Chemical 1】 [In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by the following formula (X). In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. 【Chemistry 2】 R ２ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. However, R １ one hydrogen atom bonded to the terminal carbon atom of the ethyl group is substituted with a group represented by formula (X), and all of the R ２ but at the same time it is not a methyl group. n is an integer from 8 to 1,000, and m is an integer from 8 to 1,000. R ２ When a plurality of m's are present, they may be the same or different from each other.

2. The R １ is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with the group represented by formula (X), or an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with the group represented by formula (X).

3. The R １ The β-methyl-δ-valerolactone polymer according to claim 1, wherein is a linear alkyl group having 1 to 16 carbon atoms or a branched alkyl group having 3 to 16 carbon atoms.

4. The R １ is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X).

5. The R １ is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 10 carbon atoms is substituted with a group represented by formula (X).

6. The R ２ The β-methyl-δ-valerolactone polymer according to any one of claims 1 to 5, wherein is a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.

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