Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a ⁇ -methyl- ⁇ -valerolactone copolymer and a resin composition containing the ⁇ -methyl- ⁇ -valerolactone copolymer.
• ⁇ -valerolactone polymers synthesized from ⁇ -valerolactone are known as biodegradable materials. Biodegradable materials are used in a wide range of fields due to growing environmental awareness. Therefore, ⁇ -valerolactone polymers are being improved to give the biodegradable materials physical properties according to their applications.
• Patent Document 1 a technology has been disclosed relating to a (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with a reaction product of ⁇ -methyl- ⁇ -valerolactone and a compound having one hydroxyl group in the molecule.
• Patent Document 1 describes that the (meth)acrylic acid ester has a fast curing rate, the coating obtained by curing is flexible, has a low glass transition point, and does not crystallize even at temperatures below 0° C.
• Patent Document 1 also describes that a resin composition containing the (meth)acrylic acid ester is suitable for coating optical glass fibers for optical transmission.
• Patent Document 2 also disclosed is an alkyl- ⁇ -valerolactone polymer obtained by reacting a hydroxyl group-containing alkyl- ⁇ -valerolactone polymer with a cyclic ether (Patent Document 2).
• Patent Document 2 describes that the alkyl- ⁇ -valerolactone polymer is a liquid derivative having high thermal stability and can be used as a plasticizer.
• Reference Example 1 of Patent Document 2 discloses a liquid ⁇ -methyl- ⁇ -valerolactone polymer in which both ends of poly( ⁇ -methyl- ⁇ -valerolactone)diol are modified with acetic anhydride.
• Patent Document 1 describes that the coating obtained by using the above (meth)acrylic acid ester is flexible and has a low glass transition point.
• the above (meth)acrylic acid ester is mixed with a thermoplastic resin to form a resin composition
• the obtained resin composition has low plasticity.
• the polymer obtained by modifying the hydroxyl group at the end of poly( ⁇ -methyl- ⁇ -valerolactone)diol as described in Patent Document 2 has room for improvement as a plasticizer for thermoplastic resins. Therefore, an object of the present invention is to provide a ⁇ -methyl- ⁇ -valerolactone copolymer capable of imparting good plasticity to a resin composition, and a resin composition having good plasticity and a production method thereof.
• the present inventors have found that the ⁇ -methyl- ⁇ -valerolactone copolymer and resin composition disclosed herein can solve the above problems. That is, the present invention is as follows.
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the following formula (Y), a 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 is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• n 2 to 1,000
• m 2 to 1,000
• p 2 to 1,000
• R 1 is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R 2 is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a group represented by the formula (X), a linear alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to a terminal carbon atom is substituted with a group represented by the formula (Y), or a linear or branched alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is substituted with a group represented by the formula (Z).
• R 2 is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a group represented by the formula (X), a linear
• [4] The ⁇ -methyl- ⁇ -valerolactone copolymer according to any one of [1] to [3], wherein R 3 is a linear alkylene group having 2 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms.
• [5] The ⁇ -methyl- ⁇ -valerolactone copolymer according to any one of [1] to [4] above, having a number average molecular weight of 500 to 200,000.
• [6] The ⁇ -methyl- ⁇ -valerolactone copolymer according to any one of [1] to [5], wherein the content of the block (E) represented by the following formula in the general formula (I) is 5 to 95 mass%.
• a resin composition comprising the ⁇ -methyl- ⁇ -valerolactone copolymer according to any one of [1] to [6] above and a thermoplastic resin.
• the resin composition according to [7] comprising 0.1 to 100 parts by mass of the ⁇ -methyl- ⁇ -valerolactone copolymer per 100 parts by mass of the thermoplastic resin.
• the resin composition according to [7] or [8], wherein the thermoplastic resin comprises a polyester.
• the thermoplastic resin comprises a biodegradable resin.
• the method for producing a ⁇ -methyl- ⁇ -valerolactone-based copolymer includes a step (2) of adding a terminal modifying agent to the reaction solution and carrying out a terminal modification reaction to obtain the ⁇ -methyl- ⁇ -valerolactone-based copolymer.
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the following formula (Y), a 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 is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• n 2 to 1,000
• m 2 to 1,000
• p 2 to 1,000
• n, m, A, p, R 1 , R 2 and R 3 are present, they may be the same or different from each other.
• the polymerization catalyst is a base catalyst.
• the present invention provides a ⁇ -methyl- ⁇ -valerolactone copolymer that can impart good plasticity to a resin composition, as well as a resin composition with good plasticity and a manufacturing method thereof.
• the present embodiment is merely an example for embodying the technical idea of the present invention, and the present invention is not limited to the following description.
• preferred embodiments are shown, but a combination of two or more of the individual preferred embodiments is also a preferred embodiment.
• the lower limit value and the upper limit value can be selectively combined to form a preferred embodiment.
• a numerical range is stated as "XX to YY", it means “XX or more and YY or less”.
• ⁇ -methyl- ⁇ -valerolactone copolymer >
• the ⁇ -methyl- ⁇ -valerolactone copolymer of the present embodiment is represented by the following general formula (I) or (II).
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• linear alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.
• the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 16 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 8 carbon atoms.
• methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, etc. are preferred.
• Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl, 1-methylpropyl, 2-methylpropyl, t-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, 2-ethylpropyl, 1,1-diethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,3,3-trimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 3,3-dimethylbutyl, butylbutyl group, 1-propylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 4,4-dimethylpentyl group, 1-ethylpenty
• the branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 16 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 8 carbon atoms.
• an isopropyl group, a 1-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, a 2-ethylhexyl group, etc. are preferred.
• aryl group having 6 to 14 carbon atoms examples include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2-naphthyl group, etc.
• the aryl group having 6 to 14 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.
• arylalkyl group having 7 to 14 carbon atoms examples include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylmethyl group, a naphthylethyl group, etc.
• the arylalkyl group having 7 to 14 carbon atoms is preferably an arylalkyl group having 7 to 12 carbon atoms, and more preferably a phenylmethyl group.
• R 1 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and even more preferably a linear alkyl group having 1 to 3 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the following formula (Y), a 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 is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which
• Examples of the "linear alkyl group having 1 to 20 carbon atoms”, “branched alkyl group having 3 to 20 carbon atoms", “aryl group having 6 to 14 carbon atoms”, and “arylalkyl group having 7 to 14 carbon atoms” represented by R2 are similar to the groups exemplified as the “linear alkyl group having 1 to 20 carbon atoms", “branched alkyl group having 3 to 20 carbon atoms”, “aryl group having 6 to 14 carbon atoms”, and “arylalkyl group having 7 to 14 carbon atoms” represented by R1 described above.
• the bond indicated by *2 is bonded to a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. Specifically, it is bonded to the terminal carbon atom of the linear alkyl group having 1 to 20 carbon atoms or the terminal carbon atom of the branched alkyl group having 3 to 20 carbon atoms.
• the linear alkyl group having 1 to 20 carbon atoms bonded to the bond indicated by *2 is a linear alkyl group having 1 to 20 carbon atoms in a "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 (Y)".
• the branched alkyl group having 3 to 20 carbon atoms bonded to the bond indicated by *2 is a branched alkyl group having 3 to 20 carbon atoms in a "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 formula (Y)".
• R 1 in the group represented by formula (Y) has the same meaning as the above-mentioned R 1. Furthermore, n and A in the group represented by formula (Y) have the same meaning as n and A described below.
• the linear alkyl group having 1 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" represented by R 1 described above.
• the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 16 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• the branched alkyl group having 3 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "branched alkyl group having 3 to 20 carbon atoms" represented by R 1 described above.
• the branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 16 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• the bond indicated by *3 is bonded to a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. Specifically, it is bonded to the terminal carbon atom of the linear alkyl group having 1 to 20 carbon atoms and the terminal carbon atom of the branched alkyl group having 3 to 20 carbon atoms.
• the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms bonded to the bond indicated by *3 is the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms in the "group in which one hydrogen atom bonded to at least one carbon atom in the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by formula (Z)".
• R 1 in the group represented by formula (Z) has the same meaning as R 1 described above.
• R 3 , n, m and A in the group represented by formula (Z) have the same meaning as R 3 , n, m and A described below.
• the linear alkyl group having 1 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" represented by R 1 described above.
• the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 16 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• the branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 16 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• R2 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a group represented by the above formula (X), a linear alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to a terminal carbon atom is substituted with a group represented by the above formula (Y), and a linear alkyl group having 1 to 16 carbon atoms or a branched alkyl group having 3 to 16 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is substituted with a group represented by the above formula (Z), and more preferably a carbon atom.
• R2 is preferably a group represented by the above formula (X).
• R 3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• Examples of the linear alkylene group having 2 to 20 carbon atoms or the branched alkylene group having 3 to 20 carbon atoms include an ethylene group (-(CH 2 ) 2 -), an n-propylene group (-(CH 2 ) 3 -), an isopropylene group (-CH 2 -CH(CH 3 )-), an n-butylene group (-(CH 2 ) 4 -), a 1-methylpropylene group (-CH 2 -CH 2 -CH(CH 3 )-), a 2-methylpropylene group (-CH 2 -CH(CH 3 )-CH 2 -), a dimethylethylene group (-CH 2 -C(CH 3 ) 2 -), an ethylethylene group (-CH 2 -CH(CH 2 CH 3 )-), an n-pentylene group (-(CH 2 ) 5 -), a 2-methylbutylene group (-CH 2 -CH 2 -CH( CH3 ) -CH2-
• R 3 is preferably a linear alkylene group having 2 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms, more preferably a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, even more preferably a linear alkylene group having 2 to 5 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms, and still more preferably a linear alkylene group having 2 to 5 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group (—NH—), and from the viewpoint of excellent biodegradability, A is preferably an oxygen atom.
• n, m, and p each represent the average number of repetitions.
• n is 2 to 1,000.
• n is preferably 2 to 800, more preferably 4 to 500, and even more preferably 4 to 200.
• n is preferably 3 to 1,450, more preferably 3 to 250, even more preferably 3 to 100, and even more preferably 3 to 40.
• m is 2 to 1,000.
• m is preferably 2 to 400, more preferably 4 to 200, and even more preferably 4 to 50.
• m is preferably 3 to 1,450, more preferably 3 to 100, even more preferably 3 to 50, and even more preferably 3 to 40.
• p is 2 to 1,000. In one embodiment of the present invention, p is preferably 2 to 200, more preferably 4 to 100. In another embodiment of the present invention, p is preferably 3 to 1,450, more preferably 3 to 200, and even more preferably 3 to 50.
• m and n can be calculated from the 1 H-NMR spectrum of the ⁇ -methyl- ⁇ -valerolactone copolymer. Specifically, when A is an oxygen atom, in the spectrum obtained by 1 H-NMR measurement of the ⁇ -methyl- ⁇ -valerolactone copolymer, m and n can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom in the block (E) described later and the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom of the ether bonded to the ⁇ -methyl- ⁇ -valerolactone unit. A detailed calculation method of m and n can follow the method described in the Examples.
• the above " ⁇ -methyl- ⁇ -valerolactone unit” means a structural unit derived from a ⁇ -methyl- ⁇ -valerolactone unit, and means a unit repeated with an average repeat number n.
• the content (mass %) of block (E) represented by the following formula is preferably 5 to 95 mass %.
• the ⁇ -methyl- ⁇ -valerolactone copolymer can more reliably achieve both compatibility with thermoplastic resins and a plasticizing effect, and the crystallization rate of the resin composition is further improved, which is preferable.
• the ⁇ -methyl- ⁇ -valerolactone copolymer tends to have higher compatibility with thermoplastic resins, making it easier to suppress bleed-out.
• the content (mass %) of the block (E) represented by the following formula in general formula (I) is more preferably 5 to 50 mass %, and even more preferably 10 to 40 mass %, from the viewpoints of achieving both compatibility with a thermoplastic resin and a plasticizing effect, and of improving the crystallization rate of the resin composition.
• the content (mass %) of the block (E) represented by the following formula in general formula (I) is more preferably 5 to 80 mass %, further preferably 10 to 80 mass %, and even more preferably 10 to 50 mass %, from the viewpoints of achieving both compatibility with a thermoplastic resin and a plasticizing effect, and of improving the crystallization rate of the resin composition.
• the content ratio of block (E) is the ratio of the molecular weight of block (E) to the molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content ratio of block (E) can be calculated from the molecular weight calculated by 1 H-NMR measurement of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content ratio of block (E) can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom in block (E), the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom of the ether bonded to the ⁇ -methyl- ⁇ -valerolactone unit, and the peak intensity of the hydrogen atom bonded to the carbon atom at the ester ⁇ -position of the ⁇ -methyl- ⁇ -valerolactone unit.
• the detailed method for measuring the content of the block (E) can be according to the method described in the Examples.
• the weight average molecular weight of the block (E) represented by the above formula is preferably 100 to 40,000, more preferably 100 to 10,000, even more preferably 100 to 5,000, and still more preferably 500 to 5,000.
• the weight average molecular weight of the block (E) can be calculated from the following formula.
• Weight average molecular weight of block (E) in ⁇ -methyl- ⁇ -valerolactone copolymer represented by general formula (I) Weight average molecular weight Mw of ⁇ -methyl- ⁇ -valerolactone copolymer ⁇ Content (mass%) of block (E) in general formula (I)/100
• the weight average molecular weight Mw of the ⁇ -methyl- ⁇ -valerolactone copolymer is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the content (mass %) of block (F) represented by the following formula is preferably 5 to 95 mass %.
• the ⁇ -methyl- ⁇ -valerolactone copolymer can more reliably achieve both compatibility with thermoplastic resins and a plasticizing effect, and the crystallization rate of the resin composition is further improved, which is preferable.
• the ⁇ -methyl- ⁇ -valerolactone copolymer tends to have higher compatibility with thermoplastic resins, making it easier to suppress bleed-out.
• the content (mass%) of block (F) is the molecular weight of block (F) relative to the molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content of block (F) can be measured in the same manner as for block (E) above.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer is preferably 500 to 200,000, more preferably 500 to 110,000, even more preferably 1,000 to 66,000, and still more preferably The number average molecular weight is preferably 1,000 to 33,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 6,000.
• the viscosity of the valerolactone copolymer is not too low, improving the ease of handling during molding and the productivity.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer is a number average molecular weight calculated as standard polystyrene by gel permeation chromatography (GPC). The method can be followed.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer is preferably 720 to 400,000, more preferably 720 to 220,000, even more preferably 1,600 to 132,000, and still more preferably The weight average molecular weight is preferably 1,600 to 66,000, more preferably 1,600 to 20,000, and even more preferably 1,600 to 12,000.
• the viscosity of the valerolactone copolymer is not too low, improving the ease of handling during molding and the productivity.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer is a number average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The method can be followed.
• the molecular weight distribution (Mw/Mn) of the ⁇ -methyl- ⁇ -valerolactone copolymer is preferably 1.0 to 3.0, more preferably 1.1 to 2.0, and even more preferably 1.2 to It's 1.8.
• the molecular weight distribution of the ⁇ -methyl- ⁇ -valerolactone copolymer is a value calculated from the number average molecular weight and weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the preferred viscosity range varies depending on the application of the ⁇ -methyl- ⁇ -valerolactone copolymer, but from the viewpoint of functions such as handleability, substrate retention, strength, and adhesiveness, as well as from the viewpoint of exhibiting a more excellent modifying effect on thermoplastic resins, it is preferably 500 to 600,000 mPa ⁇ s, more preferably 700 to 500,000 mPa ⁇ s, and even more preferably 900 to 150,000 mPa ⁇ s at a measurement temperature of 30° C.
• the viscosity at a measurement temperature of 60° C. is preferably 5,000 to 600,000 mPa ⁇ s, more preferably 50,000 to 600,000 mPa ⁇ s, even more preferably 100,000 to 400,000 mPa ⁇ s, still more preferably 150,000 to 250,000 mPa ⁇ s, and still more preferably 170,000 to 220,000 mPa ⁇ s.
• the "viscosity" described in this specification is the viscosity of the ⁇ -methyl- ⁇ -valerolactone copolymer measured by an E-type viscometer. The detailed measurement method can be according to the method described in the Examples.
• the method for producing a ⁇ -methyl- ⁇ -valerolactone copolymer according to this embodiment is a method for producing a ⁇ -methyl- ⁇ -valerolactone copolymer represented by the following general formula (I) or (II).
• the method includes a step (1) of reacting ⁇ -methyl- ⁇ -valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the ⁇ -methyl- ⁇ -valerolactone to obtain a reaction liquid, and a step (2) of adding a terminal modifying agent to the reaction liquid and performing a terminal modification reaction to obtain the copolymer.
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the following formula (Y), a 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 is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• n is 2 to 1,000
• m is 2 to 1,000
• p is 2 to 1,000.
• steps (1) and (2) it is possible to easily produce a ⁇ -methyl- ⁇ -valerolactone copolymer that can be imparted with good plasticity.
• the step (1) is a step of reacting ⁇ -methyl- ⁇ -valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the ⁇ -methyl- ⁇ -valerolactone to obtain a reaction liquid.
• the reaction liquid obtained in the step (1) contains a ring-opening polymer of ⁇ -methyl- ⁇ -valerolactone, unreacted ⁇ -methyl- ⁇ -valerolactone (which has not undergone ring-opening polymerization), unreacted initiator, polymerization catalyst, and the like.
• the step (1) is preferably carried out under basic conditions.
• ⁇ -methyl- ⁇ -valerolactone ( ⁇ -methyl- ⁇ -valerolactone) ⁇ -Methyl- ⁇ -valerolactone produced by a known method can be used, for example, it can be produced by a known method using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (JP-B-6-53691, etc.).
• ⁇ -methyl- ⁇ -valerolactone may be a commercially available product, and may be of petrochemical or bio-origin.
• ⁇ -methyl- ⁇ -valerolactone is added in an amount of preferably 5 to 1,500 molar equivalents, more preferably 5 to 1,200 molar equivalents, and even more preferably 10 to 600 molar equivalents, based on the hydroxyl groups of the initiator.
• the initiator used in this embodiment is preferably an alcohol, and more preferably a polyether having at least one hydroxyl group.
• the carbon number in the structure constituting the repeating unit in the ⁇ -methyl- ⁇ -valerolactone-based copolymer is a hydroxyl group-containing polyether having preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms.
• the polyether having a hydroxyl group may be either linear or branched, but is preferably linear from the viewpoint of obtaining a ⁇ -methyl- ⁇ -valerolactone copolymer capable of imparting good plasticity.
• Examples of polyethers having a hydroxyl group include polyether monools and polyether polyols.
• An example of the polyether monol is a polyoxyalkylene monol.
• polyether polyols examples include polymers obtained by ring-opening polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, etc., either alone or in a mixture of two or more kinds, using a compound having an active hydrogen atom as a catalyst.
• Specific examples include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol (PGL), etc.
• polyethylene glycol is preferred from the viewpoint of obtaining a ⁇ -methyl- ⁇ -valerolactone-based copolymer that can impart good plasticity.
• examples of the initiator include polyethers having at least one amino group and polyethers having at least one thiol group.
• examples of polyethers having at least one amino group include triethylene glycol amine, diethylene glycol bis(3-aminopropyl) ether, and poly(ethylene glycol) diamine.
• An example of a polyether having at least one thiol group is poly(ethylene glycol) dithiol.
• the step (1) is preferably carried out under a basic condition, and the polymerization catalyst that can be used in this embodiment is preferably one that has a catalytic action under a basic condition.
• the polymerization catalyst having catalytic activity under basic conditions include base catalysts.
• the base catalyst may be a known base catalyst, for example, a metal catalyst such as an alkali metal or an alkali metal compound, or an organic base compound.
• the alkali metal compound include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydride compounds, and among these, organic lithium compounds such as butyllithium are preferred.
• the organic base compound include amine compounds having an amidine skeleton or a guanidine skeleton.
• the base catalyst metal catalysts such as organomagnesium compounds and organozinc compounds can also be used.
• the polymerization catalyst may be used alone or in combination of two or more kinds.
• the base catalyst is added in an amount of preferably 0.005 to 1.5 molar equivalents, more preferably 0.007 to 1.2 molar equivalents, even more preferably 0.007 to 1.0 molar equivalents, still more preferably 0.007 to 0.8 molar equivalents, and even more preferably 0.007 to 0.6 molar equivalents, relative to the hydroxyl groups of the initiator.
• solvent Step (1) can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction.
• the solvent include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.
• toluene is preferred from the viewpoints of solubility and stability (low risk of reaction with the polymerization catalyst).
• step (1) the method of mixing ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst is not particularly limited, but from the viewpoint of operability, it is preferable to mix ⁇ -methyl- ⁇ -valerolactone and the initiator, raise the temperature to the reaction temperature when reacting ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst described below, and then add a solution containing a solvent inert to the ring-opening polymerization reaction and the polymerization catalyst dissolved in the solvent.
• the reaction temperature when reacting ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst is preferably 20 to 100° C., more preferably 30 to 90° C., even more preferably 30 to 80° C., and even more preferably 40 to 80° C. If the temperature is within the above range, an appropriate reaction rate is achieved, depolymerization can be suppressed, and production efficiency is improved without a decrease in the raw material conversion rate.
• the reaction time is preferably 1 minute to 24 hours, more preferably 15 minutes to 12 hours, and even more preferably 30 minutes to 6 hours.
• the reaction of ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst is preferably carried out under an inert gas in order to prevent the deactivation of the polymerization catalyst.
• the inert gas include nitrogen gas, helium gas, neon gas, argon gas, krypton gas, and carbon dioxide gas, with nitrogen gas being preferred from the viewpoints of availability and versatility.
• Step (2) a terminal modifying agent is added to the reaction solution to carry out a terminal modification reaction to obtain a ⁇ -methyl- ⁇ -valerolactone copolymer.
• step (2) it is preferable to add the terminal modifier to the reaction solution obtained in step (1) without taking out at least one selected from the ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst.
• the terminal modifier to the reactor in which the ring-opening polymerization was performed to modify the terminals of the ring-opened polymer of ⁇ -methyl- ⁇ -valerolactone without taking out at least one selected from the ⁇ -methyl- ⁇ -valerolactone, the initiator, and the polymerization catalyst, or to take out only the ring-opened polymer of ⁇ -methyl- ⁇ -valerolactone and place it in a separate reaction vessel, without adding the terminal modifier to the reaction vessel.
• the ring-opening polymerization reaction and the terminal modification reaction can be performed in one pot, so that the product can be produced by a simplified process.
• Terminal Modifier examples of the terminal modifying agent that can be used in this embodiment include acid anhydrides, acid halides, etc. Among these, acid anhydrides are preferred from the viewpoint of reducing the environmental load.
• an acid anhydride and acid halide for example, an acid anhydride and an acid halide having at least one group selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 14 carbon atoms can be used.
• 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, cyclohexanecarboxylic anhydride, etc.
• acetic anhydride is preferred from the viewpoint of availability.
• acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, benzoyl bromide, etc.
• acetyl chloride is preferred from the viewpoint of availability.
• the terminal modifier is added in an amount of preferably 1 to 20 molar equivalents, more preferably 1 to 10 molar equivalents, and even more preferably 1 to 8 molar equivalents, relative to the hydroxyl groups of the initiator.
• a promoter may be added, if necessary.
• the co-catalyst that can be used include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, and 4-dimethylaminopyridine.
• 4-dimethylaminopyridine is preferred from the viewpoint of realizing high catalytic activity even in a small amount.
• step (2) the cocatalyst is added in an amount of preferably 0.001 to 10 molar equivalents, more preferably 1 to 10 molar equivalents, and even more preferably 1 to 8 molar equivalents, based on the hydroxyl groups of the initiator.
• Step (3) The ⁇ -methyl- ⁇ -valerolactone copolymers represented by the above general formulas (I) and (II) can be produced through the above steps (1) and (2). If necessary, step (3) for isolating the produced ⁇ -methyl- ⁇ -valerolactone copolymer may be carried out.
• step (3) a suitable method can be adopted from among known methods.
• the reaction mixture containing the ⁇ -methyl- ⁇ -valerolactone copolymer obtained in step (2) can be washed with a solvent or water, concentrated, and purified by a method typically used for separating and refining organic compounds, such as distillation.
• the solvent those described in (solvent) in [step (1)] above can be used.
• the resin composition of the present embodiment contains the above-mentioned ⁇ -methyl- ⁇ -valerolactone copolymer and a thermoplastic resin.
• thermoplastic resin examples include polyester, biodegradable resins other than polyester, and general-purpose thermoplastic resins.
• the thermoplastic resin may include polyesters, including non-biodegradable and biodegradable polyesters.
• polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polytrimethylene terephthalate (PTT), polyethylene adipate (TP26), polybutylene isophthalate (TP41), polyethylene terephthalate succinate (PETS), polyester made of cyclohexane dimethanol and sebacic acid (TP CH10), copolyester made of hexanediol, isophthalic acid and terephthalic acid (TP 6I/6T), copolyester made of bisphenol A, isophthalic acid and terephthalic acid (TP BAI/BAT), copolyester made of ethylene glycol, cyclohexane dimethanol and terephthalic acid (or its este
• polyesters that are biodegradable resins 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 hexanoate (PHBH), polyhydroxybutyrate valerate (PHBV), 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyester, etc.), starch polyester (Mater-Bi (registered trademark)), and the like.
• PLA polylactic acid
• PCL polycaprolactone
• PBS polybutylene succinate adipate
• PBAT polybutylene adipate terephthalate
• PEF polyglycolic acid
• PEF polyethylene furanoate
• the polyester is preferably a biodegradable resin such as polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA), etc.
• the thermoplastic resin preferably contains a biodegradable resin, and preferably contains a polyester, which is a biodegradable resin.
• thermoplastic resin is preferably a biodegradable resin
• biodegradable resin is preferably a polylactic acid polymer
• the polylactic acid polymer is a polymer having at least a structural unit derived from lactic acid.
• the polylactic acid polymer used in this embodiment include at least one selected from the group consisting of a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, a copolymer of L-lactic acid and D-lactic acid, and a polymer of lactide, which is a cyclic dimer of lactic acid.
• the polylactic acid polymer may be a copolymer of lactic acid and at least one selected from the group consisting of an aliphatic hydroxycarboxylic acid other than lactic acid, an aliphatic dicarboxylic acid, an aliphatic diol, and an aromatic dicarboxylic acid.
• the copolymer preferably contains structural units derived from lactic acid in an amount of 70 mol % or more, more preferably 90 mol % or more.
• a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid is preferable, and a homopolymer of L-lactic acid is more preferable.
• the structural units derived from L-lactic acid in the polylactic acid polymer are preferably 0.1 to 99.9% by mass, more preferably 1 to 99% by mass, and even more preferably 2 to 98% by mass, and the structural units derived from D-lactic acid in the polylactic acid polymer are preferably 0.1 to 99.9% by mass, more preferably 1 to 99% by mass, and even more preferably 2 to 98% by mass.
• the polylactic acid polymers may be used alone or in combination of two or more kinds. Commercially available polylactic acid polymers may be used.
• Examples of commercially available products include “INGEO series” manufactured by Natureworks, “Luminy series” manufactured by TOTALENERGIES CORBION, “Revode” series manufactured by Zhejiang Hisun Biomaterials Co., Ltd., and “SUPLA” manufactured by SUPLA Material Technology Co., Ltd.
• the weight average molecular weight of the polylactic acid polymer is preferably 50,000 to 600,000, more preferably 100,000 to 400,000, and even more preferably 150,000 to 300,000. If the weight average molecular weight of the polylactic acid resin is within the above numerical range, the moldability and compatibility with ⁇ -methyl- ⁇ -valerolactone copolymers are good, which is preferable.
• the weight average molecular weight of the polylactic acid polymer (polylactic acid resin) can be determined by gel permeation chromatography (GPC) measurement in terms of standard polystyrene. When a commercially available product is used, the value listed in the catalog may be used.
• thermoplastic resin may contain other thermoplastic resins than the above polyesters.
• examples of other thermoplastic resins include biodegradable resins other than the above polyester biodegradable resins, and general-purpose thermoplastic resins.
• biodegradable resin other than the above-mentioned polyester biodegradable resin is cellulose acetate (CA).
• thermoplastic resins include thermoplastic resins and thermoplastic elastomers with a suitable processing temperature of 200°C or less.
• thermoplastic resins 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), and polycarbonate (PC).
• PMMA polymethyl methacrylate
• PVA polyvinyl alcohol
• EVA ethylene vinyl acetate copolymer
• PE polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PS polystyrene
• ABS acrylonitrile-butadiene-styrene copolymer
• PC polycarbonate
• thermoplastic elastomers examples 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), thermoplastic polyurethane (TPU), etc.
• the above-mentioned general-purpose thermoplastic resin includes a thermoplastic resin (also called a "high heat-resistant resin") that has high heat resistance at temperatures exceeding 200°C.
• the above-mentioned high heat-resistant resin is preferably a thermoplastic resin with a melting point exceeding 200°C.
• the above-mentioned high heat-resistant resin include polyamide (PA), polyacetal (POM), fluororesin (e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.), polymethylpentene (PMP), etc.
• thermoplastic resins may be used alone or in combination of two or more kinds.
• the thermoplastic resin contained in the resin composition of this embodiment is not limited to the above-mentioned polyesters, biodegradable resins other than the above-mentioned polyester biodegradable resins, and general-purpose thermoplastic resins.
• the resin composition preferably contains 0.1 to 100 parts by mass of a ⁇ -methyl- ⁇ -valerolactone-based copolymer per 100 parts by mass of the thermoplastic resin, more preferably contains 1 to 30 parts by mass, even more preferably contains 1 to 15 parts by mass, and even more preferably contains 1 to 10 parts by mass.
• the resin composition preferably contains 1 to 30 parts by mass of ⁇ -methyl- ⁇ -valerolactone-based copolymer per 100 parts by mass of thermoplastic resin, more preferably contains 2 to 20 parts by mass, even more preferably contains 4 to 16 parts by mass, and even more preferably contains 7 to 13 parts by mass.
• the total content of the ⁇ -methyl- ⁇ -valerolactone copolymer and the thermoplastic resin in the resin composition is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more.
• the total content of the ⁇ -methyl- ⁇ -valerolactone copolymer and the thermoplastic resin in the resin composition may be 100% by mass or less. The above content ratios will more significantly exhibit the effects of the present invention.
• the content of block (E) in the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the general formula (I) in the resin composition of this embodiment is preferably 0.3 to 10.0% by mass, more preferably 0.3 to 8.0% by mass, and even more preferably 0.5 to 7.0% by mass.
• the resin composition of the present embodiment may contain additives in addition to the above-mentioned ⁇ -methyl- ⁇ -valerolactone copolymer and thermoplastic resin.
• additives include inorganic fillers, softeners, heat aging inhibitors, antioxidants, hydrolysis inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, brightening agents, ultraviolet absorbers, lubricants, etc. These may be used alone or in combination of two or more.
• the content of the additives in the resin composition may be appropriately determined depending on the desired physical properties of the resin composition.
• the number average molecular weight of the resin composition is preferably 1,000 to 1,000,000, more preferably 10,000 to 600,000, and even more preferably is preferably 30,000 to 500,000, more preferably 50,000 to 350,000, even more preferably 60,000 to 250,000, and even more preferably 80,000 to 150,000.
• the number average molecular weight of the resin composition is preferably 500 to 300,000, more preferably 700 to 200,000, and even more preferably 1,000 to 180,000.
• the number average molecular weight of the resin composition can be determined by gel permeation chromatography (GPC) measurement in terms of standard polystyrene, and in detail, is a value measured by the method described in the examples.
• the weight average molecular weight of the resin composition is preferably 500 to 500,000, more preferably 700 to 300,000, and even more preferably 1,000 to 250,000.
• the weight average molecular weight of the resin composition is a number average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The detailed measurement method can be according to the method described in the examples.
• the ⁇ -methyl- ⁇ -valerolactone copolymer of the present invention can lower the glass transition temperature of a thermoplastic resin.
• the glass transition temperature of a resin composition containing the ⁇ -methyl- ⁇ -valerolactone copolymer of the present invention and a thermoplastic resin can be adjusted by the addition ratio of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the glass transition temperature of the resin composition is preferably lower by 2°C or more than the glass transition temperature of the thermoplastic resin, preferably lower by 70°C or less, more preferably lower by 65°C or less, and even more preferably lower by 60°C or less. That is, it is preferably lower by 2 to 70°C, more preferably lower by 2 to 65°C, and even more preferably lower by 2 to 60°C.
• the glass transition temperature of a resin composition containing the ⁇ -methyl- ⁇ -valerolactone copolymer of the present invention and a thermoplastic resin is lower than the glass transition temperature of the thermoplastic resin, thereby improving the plasticity and elongation of the resin composition.
• ⁇ Method of producing resin composition There is no particular limitation on the method for producing the resin composition of the present embodiment, and it is sufficient to uniformly mix the ⁇ -methyl- ⁇ -valerolactone copolymer, the thermoplastic resin, and, if necessary, the additives.
• the mixing method include a method of melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a heating roll, a Brabender, various kneaders, etc., or a method of feeding each component through a separate inlet and melt-kneading the components. Alternatively, the components may be preblended before melt-kneading.
• Examples of the preblending method include a method using a mixer such as a Henschel mixer, a high-speed mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender.
• the temperature during melt-kneading can be arbitrarily selected, preferably within the range of 140 to 220° C., taking into consideration the melting point and decomposition temperature of the thermoplastic resin.
• the molded article of the present embodiment is a molded article made of the above-mentioned resin composition.
• the shape of the molded body may be any molded body that can be produced using the resin composition of this embodiment.
• Examples of the molded body include molded bodies of various shapes such as pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rod-shaped bodies, fine particles, particulate bodies, and foams.
• the method for producing the molded body is not particularly limited, and it can be molded by various molding methods, such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.
• the resin composition can have good plasticity, and therefore the above-mentioned ⁇ -methyl- ⁇ -valerolactone copolymer can be used as a modifier for thermoplastic resins.
• the resin composition of this embodiment can be used for various purposes.
• the resin composition can be used for the following purposes: Food utensils such as food bags, food caps, food trays, straws, cutlery, food containers, etc.; Closures, cap liners for containers for storing food, beverages, medicines, etc.; Single-layer or multi-layer films and sheets for electronic component packaging materials, pharmaceutical packaging materials, food packaging materials, agricultural materials, civil engineering and construction materials, industrial materials, etc.; Fibers such as woven fabrics and nonwoven fabrics; Solvent-type, hot melt-type, heat-stretching-type and other pressure-sensitive adhesives and adhesives; Coating agents such as aqueous, solution, emulsion, and dispersion types; Filament for 3D printers; developing toner; Support material for hydraulic fracturing and water leakage prevention agent for drilling; Anti-vibration rubber, mats, sheets, cushions, dampers, pads, mount rubber, and other various vibration-proofing and vibration-damping materials; Components for household appliances such
• ⁇ -methyl- ⁇ -valerolactone copolymer is a compound containing a structure represented by the following formula (1) in which R 3 in the above general formula (I) is an ethylene group (-(CH 2 ) 2 -).
• R 3 in the above general formula (I) is an ethylene group (-(CH 2 ) 2 -).
• * represents a bond.
• the content of block (E) in the ⁇ -methyl- ⁇ -valerolactone copolymer was calculated from the ratio of the sum of the peak intensity (3.6-3.8 ppm) derived from the proton at the y position in formula (1) and the peak intensity (3.6-3.7 ppm) derived from the proton at the z position in formula (1) multiplied by the molecular weight per structural unit derived from ⁇ -methyl
• Content (mass %) of block (E) ((((peak intensity at proton at position y+peak intensity at proton at position z)/4) ⁇ molecular weight per structural unit derived from ethylene glycol 44.03)/((((peak intensity at proton at position y+peak intensity at proton at position z)/4) ⁇ molecular weight per structural unit derived from ethylene glycol 44.03)+((peak intensity at proton at position x/2) ⁇ molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12))) ⁇ 100
• the ⁇ -methyl- ⁇ -valerolactone copolymer obtained in Production Example 10 is a compound containing the following formula (2) in which R 3 in the general formula (I) is an n-butylene group (-(CH 2 ) 4 -).
• the ⁇ -methyl- ⁇ -valerolactone copolymer obtained in Comparative Production Example 6 is also a compound containing a structure represented by the following formula (2).
• * represents a bond.
• the content of (E) in the ⁇ -methyl- ⁇ -valerolactone copolymer was calculated from the ratio of the sum of the peak intensity (3.5-3.6 ppm) derived from the proton at position v in formula (2) and the peak intensity (3.3-3.5 ppm) derived from the proton at position w in formula (2) multiplied by the molecular weight (114.12) per structural unit derived from ⁇ -methyl- ⁇ -valerolactone to the sum of the values multiplied by the molecular weight (72.11) per unit. Specifically, it was calculated according to the following formula.
• Block (E) ((((peak intensity at proton at position v+peak intensity at proton at position w)/4) ⁇ molecular weight per structural unit derived from butylene glycol 72.11)/((((peak intensity at proton at position v+peak intensity at proton at position w)/4) ⁇ molecular weight per structural unit derived from butylene glycol 72.11)+((peak intensity at proton at position u/2) ⁇ molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12))) ⁇ 100
• m and n were calculated from the 1 H-NMR spectrum measured when calculating the content ratio of the block (E).
• m was calculated by dividing the number of protons at the z position in formula (1) (3.6-3.7 ppm) by the number of protons at the y position in formula (1) (3.7-3.8 ppm), and then adding 1 to the result.
• n was calculated by multiplying the value obtained by subtracting the content ratio of the block (E) obtained from 100 by m and the molecular weight of the block (E), and dividing the result by the molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone.
• y position and “z position” mean “y position” and "z position” in the formula (1).
• m ((number of protons at z position/4)/(number of protons at y position/2)) + 1
• n (m x molecular weight per structural unit derived from ethylene glycol 44.03 x (100 - content ratio of block (E)) / 100) / molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12
• m and n were calculated from the 1H-NMR spectrum measured when calculating the content ratio of the block (E).
• m was calculated by dividing the number of protons at the w position in formula (2) (3.3-3.5 ppm) by the number of protons at the v position in formula (2) (3.5-3.6 ppm) and adding 1 to the result.
• n was calculated by multiplying the value obtained by subtracting the content ratio of the block (E) obtained from 100 by m and the molecular weight of the block (E), and dividing the result by the molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone. Specifically, it was calculated by the following formula.
• v position and "w position” mean “v position” and "w position” in the formula (2).
• m ((number of protons at w position/4)/(number of protons at v position/2)) + 1
• n (m x molecular weight per structural unit derived from butylene glycol 72.11 x (100 - content ratio of block (E)) / 100) / molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12
• n ((number of protons at t position)/(number of protons at s position)) + 1
• Mn and Mw were determined according to the following measurement.
• a tetrahydrofuran (THF) solution was used as the eluent. 10 mg of a sample was weighed out in terms of resin and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 ⁇ m membrane filter to prepare a measurement sample.
• THF tetrahydrofuran
• the measurement conditions were as follows: Measurement conditions: GPC device: HLC-EcoSEC8320GPC (manufactured by Tosoh Corporation) Columns: Three columns, K-803 (manufactured by Resonac Corporation), K-802.5 (manufactured by Resonac Corporation), and K-802 (manufactured by Resonac Corporation), were connected in series. Eluent: tetrahydrofuran Flow rate: 0.9 mL/min Sample injection volume: 30 ⁇ L Column temperature: 40°C Standard polystyrene: PSt Oligomer Kit (molecular weight 589 to 98,900) manufactured by Tosoh Corporation was used and approximated by a third order equation. Detector: RI detector Mw/Mn was calculated from the obtained Mn and Mw.
• GPC device High performance liquid chromatograph LC-20A (Shimadzu Corporation) Columns: Three columns, KG 4A (manufactured by Resonac Corporation) (1 column) and K-806M (2 columns) (manufactured by Resonac Corporation), were connected in series. Eluent: chloroform Flow rate: 1.0 mL/min Sample injection volume: 100 ⁇ L Column temperature: 40°C Standard polystyrene: Polystyrene standards (molecular weight: 2,880 to 6,570,000) manufactured by Agilent Technologies were used and approximated by a quintic equation. Detector: RI detector
• the viscosity of the polymers obtained in the Production Examples and Comparative Production Examples was measured in accordance with JIS K 7117-2: 1999. Specifically, the viscosity (unit: mPa s) of the ⁇ -methyl- ⁇ -valerolactone copolymer was measured using an E-type viscometer (product name: TVE-25 type viscometer, manufactured by Toki Sangyo Co., Ltd.) at the measurement temperatures shown in Table 2.
• E-type viscometer product name: TVE-25 type viscometer, manufactured by Toki Sangyo Co., Ltd.
• Glass transition temperature (Tg) of resin composition The resin compositions obtained in the examples and comparative examples were heated from 30° C. to 220° C. at a rate of 10° C./min under a nitrogen flow rate (100 mL/min) using a differential scanning calorimeter (TA Instruments, “DSC25”), held at 220° C. for 5 minutes, and then cooled to ⁇ 70° C. at a rate of 10° C./min. The glass transition temperature was evaluated when the temperature was raised to 220° C. at 10° C./min after holding at ⁇ 70° C. for 5 minutes.
• Tg Glass transition temperature
• VG No obvious bleeding out or stickiness was observed.
• G At least one phenomenon selected from the group consisting of slight bleeding out and stickiness is observed, but is at a level that does not cause any practical problems.
• NG At least one phenomenon selected from the group consisting of significant bleeding out and significant stickiness is observed, and the composition is not suitable for practical use.
• CH 3 -PEG200 Tetraethylene monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Tetraethylene monomethyl ether” (weight average molecular weight: 208.25)
• CH 3 -PEG550 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene Glycol Monomethyl Ether 550” (weight average molecular weight (median value of catalog value): 550, weight average molecular weight (catalog value): 525 to 575)
• CH 3 -PEG1,000 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene Glycol Monomethyl Ether 1,000” (weight average molecular weight (catalog value median): 1,000, weight average molecular weight (catalog value) 950 to 1,050)
• CH 3 -PEG 2,000 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene Glycol Mono
• Polylactic acid polymer 1 Natureworks, trade name "INGEO 2500HP” (weight average molecular weight: 200,000, melting point: 177°C, copolymer of L-lactic acid and D-lactic acid, content of structural units derived from L-lactic acid: 99% by mass)
• n-Butyllithium FUJIFILM Wako Pure Chemical Industries, Ltd., product name "1.6 mol/L n-butyllithium hexane solution”
• Acetic anhydride Fujifilm Wako Pure Chemical Industries, Ltd. 4-Dimethylaminopyridine: Tokyo Chemical Industry Co., Ltd. Acrylic anhydride: Tokyo Chemical Industry Co., Ltd.
• Ethylene glycol Tokyo Chemical Industry Co., Ltd.
• Toluene Kishida Chemical Co., Ltd. (special grade)
• Water Ion-exchanged water (water obtained by ion-exchanging tap water using the "Autostill WA500 pure water production device" (manufactured by Yamato Scientific Co., Ltd.).
• Example 1 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL four-neck glass flask was purged with nitrogen, and 87.9 g of CH 3 -PEG550 as an initiator and 268 g (2.351 mol) of ⁇ -methyl- ⁇ -valerolactone were added and heated to 60° C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 2 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL volume four-neck glass flask was purged with nitrogen, and 37.7 g of CH 3 -PEG200 as an initiator and 185 g (1.623 mol) of ⁇ -methyl- ⁇ -valerolactone were added and heated to 60° C. 1.2 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 185 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 3 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL volume four-neck glass flask was purged with nitrogen, and 74.5 g of CH 3 -PEG1,000 and 113 g (0.993 mol) of ⁇ -methyl- ⁇ -valerolactone were added as initiators and heated to 30° C. 2.1 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 60 minutes to obtain a reaction liquid.
• n-butyllithium 1.6 M hexane solution
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 165 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 4 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL capacity four-neck glass flask was purged with nitrogen, and 40.2 g of PEG400 and 210 g (1.843 mol) of ⁇ -methyl- ⁇ -valerolactone were added as initiators and heated to 60° C. 2.0 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• PEG400 and 210 g (1.843 mol) of ⁇ -methyl- ⁇ -valerolactone were added as initiators and heated to 60° C.
• 2.0 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 212 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 5 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL capacity four-neck glass flask was purged with nitrogen, and 103 g of PEG 1,000 and 150 g (1.313 mol) of ⁇ -methyl- ⁇ -valerolactone were charged as initiators and heated to 60° C. 1.3 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• n-butyllithium 1.6 M hexane solution
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 199 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 6 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL four-neck glass flask was purged with nitrogen, and 40.2 g of CH 3 -PEG2,000 and 208 g (1.818 mol) of ⁇ -methyl- ⁇ -valerolactone were added as initiators and heated to 60° C. 1.8 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• n-butyllithium 1.6 M hexane solution
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD") to obtain 202 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 7 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL volume four-neck glass flask was purged with nitrogen, and 14.2 g of CH 3 -PEG2,000 as an initiator, 179 g (1.564 mol) of ⁇ -methyl- ⁇ -valerolactone, and 73.3 g (796 mmol) of toluene were added and heated to 30° C. 2.1 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 60 minutes to obtain a reaction liquid.
• n-butyllithium 1.6 M hexane solution
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD") to obtain 166 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 8 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 1,000 mL capacity glass four-neck flask was purged with nitrogen, and 63.4 g of PEG 20,000 as an initiator, 150 g (1.316 mol) of ⁇ -methyl- ⁇ -valerolactone, and 61.9 g (672 mmol) of toluene were added and heated to 30° C. 1.6 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 120 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD") to obtain 191 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 9 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL capacity four-neck glass flask was purged with nitrogen, and 150 g of PEG1,540 and 74.4 g (0.652 mol) of ⁇ -methyl- ⁇ -valerolactone were added as initiators and heated to 30° C. 1.8 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 210 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 10 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL capacity four-neck glass flask was purged with nitrogen, and 91.0 g of PTMG1,000 as an initiator and 102 g (0.896 mol) of ⁇ -methyl- ⁇ -valerolactone were charged and heated to 30° C. 0.8 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 178 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 11 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL four-neck glass flask was purged with nitrogen, and 87.9 g of CH 3 -PEG550 as an initiator and 268 g (2.351 mol) of ⁇ -methyl- ⁇ -valerolactone were added and heated to 60° C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• Example 12 (1) Production of ⁇ -methyl- ⁇ -valerolactone copolymer A 500 mL four-neck glass flask was purged with nitrogen, and 87.9 g of CH 3 -PEG550 as an initiator and 268 g (2.351 mol) of ⁇ -methyl- ⁇ -valerolactone were added and heated to 60° C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60° C. for 60 minutes to obtain a reaction liquid.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), thereby obtaining 190 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the following structural formula (A), where n is as shown in Table 1.
• the reaction solution was extracted with toluene and water, and the volatile components were removed by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g (0.19 mmol) of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), thereby obtaining 159 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned structural formula (A), and n is as shown in Table 1.
• the reaction solution containing the obtained polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 532 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned structural formula (A), and n is as shown in Table 1.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution containing the obtained polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 170 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the following structural formula (B), where m and n are as shown in Table 1.
• the reaction solution containing the obtained polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 300 g of a ⁇ -methyl- ⁇ -valerolactone-based copolymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer were measured as described above, and the results are shown in Table 2.
• the resulting ⁇ -methyl- ⁇ -valerolactone copolymer is represented by the following structural formula (C), where m and n are as shown in Table 1.
• Example 6 is compared with Comparative Example 3
• Example 7 is compared with Comparative Example 4
• the ⁇ -methyl- ⁇ -valerolactone copolymer of this embodiment greatly lowers the glass transition temperature of the thermoplastic resin, thereby imparting good plasticity to the thermoplastic resin, even though the weight-average molecular weights of the polymers are similar.

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